D K Bhattacharyya - Perfumery Materials - Production & Applications-Studium Press (2009)

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Perfumery Materials :
Production & Applications
D.K. Bhattacharyya
Former Professor & Head and
Emeritus Fellow (AICTE),
Department of Chemical Technology,
University Colleges of Science & Technology,
University of Calcutta, Kolkata, India
2009
www.studiumpress.com
Perfumery Materials :
Production & Applications
©2009
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FOREWORD
The book embraces all relevant aspects and recent developments of

chemistry, technology and applications of natural and synthetic
perfumery materials.
Apart from containing major essential oils the book covers also new
sources. The book has dealt with advanced technological processes such
as 'supercritical', 'microwave' and 'enzymatic for the extraction of
essential oils, revealing advantageous over the traditional methodologies
in respect of yield and quality.
The book demonstrates the scopes of certain specific reactions and
raw materials in producing new synthetics. The enormous scopes of
biotechnology involving bio-conversion processes' with isolated enzymes
and by fermentation biotechnology involving selective microorganisms
have been indicated in making synthetics. The applications of natural
aromatic oils in aromatherapy, food, cosmetics/toiletries, imitation
perfumery and allied sector have been included.
Standardisation and evaluation of natural aromatic (essential) oils
and the incidence of their adulteration have been elaborated in order
to ascertain their quality and authencity for sustaining the business in
industry.
The book is first of its kind covering all aspects and it will prove
useful to students and researchers and all those who are interested in
advancing research and promoting the growth of perfumery industry.
Prof. (Dr.) R.N. Mukherjee

Dr. rer. nat. (Stuttgart)
Former Prof. & Head
Department of Chemical Engineering,
University of Jadavpur,
Kolkata, India
ABOUT THE AUTHOR
Born 1936. Acquired M.Sc.(Tech.) and Ph.D.(Sc.) degrees

in Applied Chemistry, from Calcutta University. Had over
30 years, teaching and over 40 years research experience
'0 in the disciplines of Oils and Fats and Perfumery
Chemicals. Had Post-Doctoral experience in the BFMIRA,
U.K. and in the Biochemistry and Nutrition Department
of Mehary Medical College at Nashville, Tennessee, U.S.A.
Served as Sir Rashbehary Ghosh Professor of Applied
Chemistry, Calcutta University and as the Head of the Department of
Chemical Technology, Calcutta University. Was Emeritus Fellow (AICTE)
and now Adjunct Professor in the School of Community Science and
Technology, Bengal Engineering and Science University (formerly B.E.
College). Prof. Bhattacharyya has 212 publications mostly in foreign Journals
and has guided 34 students for Doctorate Degrees of the University of
Calcutta. Has received many Awards from O.T.A.I. for outstanding research
contributions. Has participated in and presided over numerous National
and International Conferences, and professionally associated as Life Member
and Adviser to various professional and technical associations, known
nationally and internationally for his research contributions in Lipid
Technology. His research interests are in the areas of Perfume Technology
and Food Processing.
PREFACE
Perfumery materials obtained not only from natural sources but also
produced synthetically are costly items of commerce. Their volume
production has been increasing to meet the demand gap and usage
pattern. New natural sources are being extensively examined to find
out newer applications and also extending the existing applications.
A new area of application that has been receiving considerable
attention includes "aromatherapy" that is being increasingly adopted
for the treatment of almost all kinds of ailments, as many essential
oils act as therapeutic agents for having unique constituents. The
usage pattern of natural perfumery materials in the areas of food,
drugs, cosmetics and toiletries, agricultures, and other areas has
also been highly attractive and commercially important.
Many technological advances have emerged in recent years to
provide economic benefits to perfumery industry. Mention must be
made of Biotechnology particularly biocatalyst (enzyme) technology,
supercritical extraction technology, microwave technology, which
indicate enormous potential in the perfumery industry. Biotechnology
provides new opportunities in synthesizing perfumery ingredients
from diverse kinds of raw materials in the preference to chemical
methodologies to yield the targeted products. Microwave technology
promises to be an excellent process for extracting essential oils.
Supercritical extraction process also yield superior qualtiy oils. It is
also envisaged that an appropriate combined process would soon be
developed for highly efficient extraction of aromatic oils.
Since the publication of the famous books by E. Guenther in 1948;
by T.P. West, H.J. Strausz and D.H.R. Barton on "Synthetic Perfume"
in 1949; and W.A. Poucher famous books published in 1974 and 1984,
only a very limited number of books have since then been published.
A compilation by D.H. Pybus and C.S. Sell has been published by the
Royal Society of Chemistry, U.K., in 1999.
The author makes an attempt to publish this textbook. Five chapters
have been included, dealing with the latest developments and
progresses made in the perfumery field during the last few decades.
The book is expected to be of much interest to the students,
researchers, and industry people who are involved in the pursuit of
chemistry, technology, and application aspects of natural and synthetic
perfumery materials.
ACKNOWLEDGEMENTS
I acknowledge with deepest gratitude the financial support from the

Department of Science and Technology under the Ministry of Science and
Technology, Government of India, New Delhi for this text book. I
acknowledge gratefully the authorities of Calcutta University for offering
all kinds offacilities.
Sincere acknowledgement with deep gratitude is expressed to the authors
and publishers, whose books, research publications, presentations in the
International and National Seminars and review articles served as valuable
sources of information and materials for this book. Wherever assistance
has been taken from any publication, it has been acknowledged. Eminent
and pioneer authors, namely, E. Guenther, T.P. West, H.J. Strausz, D.H.R.
Barton and W.A Poucher and the authors of eminence namely, E. Stahl,
D.H. Pybus, C.S. Sell, C. Anselmi, AK. Menon, R. Ratan, B.D. Mukherjee,
M.A Ferhat, S.D. Mestri, W.S. Brud and J. Gora and other distinguished
authors are deeply acknowledged for using their contributions in this book.
The publishers, namely, Van Nostrand Company, Inc., London, Chapman
and Hall Ltd., London, Edward Arnold & Co., London; The Royal Society of
Chemistry, u.K., Council of Scientific and Industrial Research, New Delhi;
FM'sAromatherapy and Statutory bodies like BIS, lP, BP and Analytical Methods
Committee are most gratefully acknowledged. The proceedings of the
International Congress of Essential Oils, Fragrances and Flavours (1989),
National Seminar on New Policy and Fragrance and Flavour Industry (1993),
and Journals published by Elsevier and others are also gratefully acknowledged.
I acknowledge with immense pleasure my wife, Sriparna Bhattacharyya,
for continuously inspiring me to undertake the assignment of writing the
book and completing it. The blessings of my Gurupatni Mrs. Bharati
Chakrabarty is most respectfully acknowledged.
I recognise the support from faculty members, especially Dr. S. Ghosh

and Dr. (Mrs.) M. Ghosh and research scholars in the Chemical Technology
Department, Calcutta University, and my former Ph.D. students, Dr. Sakina
Khatoon, Dr. Sanghamitra Bandyopadhyay, and Dr. Soma Das for providing
materials for this book. I appreciate the encouragement from my classmate
Dr. S.K. Sanyal and acknowledge to Ms. Soma Das for typing this book and
Mr. Ramkrishna Haldar for drawing the diagrams with care.
D.K. Bhattacharyya
CONTENTS
Foreword v
Preface vu
Introduction 1
CHAPTER 1
Natural Perfumery Materials: Sources, Characteristics,
Extraction, and Uses of Natural Perfumes
(Essential/Aromatic Oils)
Flowers 4
Grass 16
Leaves 21
Bark, Seed, Herb, and Rhizome 30
Wood 39
Fruits 42
Tropical Fruits 47
Gums 50
Animal 53
References 55
CHAPTER 2
Natural Perfumery Materials Production Technology
Introduction 61
Steam Distillation 62
Expression 69
Enfleurage 70
Maceration 71
Solvents 71
Liquid Carbon dioxide 75
Enzymatic 77
Microwave 78
x Perfumery Materials : Production and Applications
Adsorption 80
Combined Process 80
Postextraction Treatment of Recovered Essential Oils 81
Fractionation of Essential Oils 83
Concentrated, Terpeneless, and Sesquiterpeneless
Essential Oils 85
References 86
CHAPTER 3
Synthetic Perfumery Materials: Production and
Applications
Introduction 87
Correlation Between Odour Characteristics, and
Chemical Constitution 91
Terpene Alcohols and their Esters 95
Synthetic Geraniol 96
Biotechnological Method for Geraniol 97
Geraniol Esters 98
Geranyl Acetate 98
Other Esters of Geraniol 102
Perfumery Uses of Geraniol and Geraniol Esters 102
Citronellol and its Esters 103
Synthetic Citronellol Chemical Route 104
Biotechnological Route of Citrinellol Synthesis 105
Chemical Synthesis of Citronellol Esters 106
Biotechnological Route of Citronellol Esters 107
Perfumery Uses of Citronellol and its Esters 108
a-Terpineol 108
Chemical Synthesis 108
Biotechnological Synthesis 109
Perfumery Uses of a-Terpineol 110
Terpinyl Acetate 111
Other Terpinyl Esters 112
Biotechnological Route of Synthesis of a-Terpineol Esters 112
Linalool and its Esters 113
Linalyl Acetate 115
Contents Xl
Esters of Linalool, Uses 116

N erol Esters and Uses 117
Menthol and its Esters 117
Odoriferous Non-Terpene Alcohols 122
Perfumery Uses of n-Alcohols 122
Unsaturated Non-Terpene Alcohol 123
Odoriferous Non-Terpene Aldehydes 123
Perfumery Uses of the Aldehydes 125
Linear Ketones 126
Linear Lactones 126
Aldehydes, Ketones, and Lactones
(Five or Six-Membered Rings) 127
a-n-Amyl Cinnamaldehyde 127
Vanillin 128
Vanillin by Biotechnological Process 131
Heliotropin 132
Hydroxy Citronellal 134
Terpene Ketone 136
Ionones 136
Methyl Ionones 139
Five and Six-Membered Ketones 141
Jasmone 142
Benzyl Acetone 144
Acetophenone 145
Terpene Aldehydes 145
Citral 146
Citronellal 147
Perfumery Materials from Benzene 148
Toluene 150
Napthalene 151
Phenol 152
m-Cresol 153
Styrene 154
Styrene Oxide 154
Perfumery Materials from Cyclopentanone and
Dicyclopen tadiene 155
xii Perfumery Materials: Production and Applications
Synthesis of Isoborneol, Borneol, and Camphor

from a-Pinene 157
Perfumery Chemicals from p-Pinene 157
Bioflavors 158
Large Ring Ketones and Lactones 167
Civetone 168
Muscone 172
Exaltone 173
Large-Ring Lactones 174
Exaltolide 174
Artificial Musks 176
Polycyclic and Macrocyclic Musks 181
Macrocyclic Musks 183
Essential Oil Analogues 183
Artificial Floral and Fruity Perfumery 188
Perfumery Materials for Multipurpose Applications 191
References 191
CHAPTER 4
Applications of Perfumery Materials
In trod uction 196

Imitation Perfumes 197
Blending of Perfumes 197
Base 197
Blending Agent 198
Modifier 198
Fixative 198
Jasmine Floral Perfume 199
Rose 200
Tuberose 200
Essential Oils in Aromatherapy 200
Essential Oils as Antimicrobial Agents 202
Bactericidal Applications 203
As Insect Repellent 203
In Agriculture 204
Contents xiii
Composition of Fruit Flavors 205

Pineapple Beverage 207
Pineapple Jelly Crystals 207
Perfumery Products in Toilet Soaps and Cosmetics 208
Cosmetics/Toiletries 212
Incense and Fumigants Products 215
Miscellaneous Applications 217
References 218
CHAPTER 5
Standardisation and Evaluation
Introduction 219
Standards of Essential Oils (BIS) 220
Standards of Essential Oils (lP) 223
Standards of Essential Oils (BP) 229
Analysis of Essential Oils 235
Physical Analysis 235
Chemical Analysis 238
Analysis by Chromatography 244
Thin-Layer Chromatography 244
Column Chromatography 247
Gas-Liquid Chromatography 247
GC-MS in Perfume 248
GLC Analysis (Polar and Non Polar Phase) 249
Capillary GC Analysis 252
Spectroscopic Analysis 259
Adulteration of Essential Oils 263
Adulteration with Cheaper Essential Oils 263
Adulteration with Synthetic Addition 264
Methodologies for Detection of Adulterants 265
Physical Methods 265
Chemical Methods 266
Detection of Adulteration by Chromatography 266
References 267
Subject Index 269
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Introduction
Perfumery materials had been in use from the early days of human
civilization even without having any knowledge of their chemical
nature. The people, irrespective of their origin, caste, creed, religion,
and sex, have been greatly fascinated by the aroma characteristics of
numerous natural perfumery materials, like the variety of exotic
flowers, leaves, grasses, barks, fruits (peels and seeds), etc. The
communities of both sexes were the major consumers of natural
perfumery materials, called aromatic oils or essential oils, making
their applications on body, hair, and other parts as fancy perfumes.
These usage patterns set the modern concept of more extensive uses
of essential oils.
The demand for natural perfumery materials has increased sharply

and immensely as a result of their increasing uses in products like
fancy perfumes, toilet soaps, cosmetics and toiletries, food products,
and pharmaceuticals. Beside these major applications, the scope and
application of natural perfumery materials in sectors like
aromatherapy, agriculture, metallurgy for ore dressing and for uses
as antimicrobial and bactericidal agents are increasing day by day.
The term "perfumery" came from the Latin word "per" meaning
"through" and "fumare" meaning "smoke". The perfumery deals with
the preparation of perfumes or materials, which are pleasing to the
sense of smell. Perfumes are divided into two classes, namely, natural
perfumes derived from the plant or animal kingdom, and the definite
chemical compounds synthetically made. Animal perfumes are limited
in number, while those obtained from 'plants' origin are numerous.
The concepts of chemistry and technology of perfumery materials
appeared very attractive and absorbing, and enormous developments
have eventually taken place on both chemical and technological
aspects of perfumery materials. The basic nature of the various
natural aromatic (perfumery) materials became established as the
"Terpenoid" derivtives, and the determinations of the exact molecular
structures of the constituents of aromatic oils (essential oils) were
2 Perfumery Materials: Production and Applications
characterized and identified by reputed organic chemists. The

chemistry of essential oils is complex, as they may consist of
numerous constituents, broadly categorized as terpenes, esters,
aldehydes, ketones, alcohols, phenols, and oxides.
Correlations could be established between the perfumery (or aroma)
characteristics of vegetable or animal origins and their molecular
structures. Natural perfumery materials (essential or aromatic oils)
are known to be commercially produced by extraction processes such
as steam distillation, enfleurage, expression and solvent
methodologies. The extraction technology of the natural perfumery
materials has also advanced considerably in recent years in order to
obtain higher yield and superior products. However, adaptation of
the new processes needs a very critical evaluation in practical
application.
A great deal of interest for the syntheses of chemical compounds
that would resemble the odor characteristic of natural perfumery or
essential oils eventually enabled substitution of the natural aromatics.
The appropriate blending of natural essential oils and synthetic
perfume materials was the simplest approach to make pleasing aroma
of many kinds for fragrant materials. In making perfumery products
for various applications, the role of the individual essential oils and
synthetics was also investigated. This led to the syntheses of large
number of compounds that had distinct and specific odor and functional
properties, and proved to be indispensable as components of perfumery
products.
The synthetic routes of production of perfumery materials from

terpenes and allied derivatives have also undergone remarkable
advancements. Biotechnology is one such advanced technology in
making perfumery chemicals. A large number of prokaryotic
microorganisms produce enzyme(s) that catalyze reactions like
oxidation, reduction (hydrogenation), esterification, interesterifications,
hydrolysis, etc., thereby help produce biotransformed products with
distinct perfumery properties. The biogenesis of the natural perfumery
molecules from selective terpene derivatives by the enzymes from
prokaryotic microorganisms is well established. These developments
explore the syntheses of the perfumery chemicals by microbial
fermentation biotechnology and bioconversion technology. In fact, a
number of microbial enzymes isolated from fungi, yeasts, and bacteria
are extremely useful for carrying out the syntheses of perfumery
chemicals of specific molecular structures and flavors. Literature survey
shows that biotechnology involving various biotransformations have
much promise and prospect for the perfume industry.
Introduction 3
Significant advances are made in the syntheses of natural

essential oil analogs or artificial products such as the flavors from
flowers, fruits, wood, etc. Also there has been a great deal of global
interest to tap new sources for producing natural perfumery or the
essential oils.
The applications of both natural and synthetic perfumery materials
have been already extensive in a variety of products. The perfumery
industry is a multibillion dollars/rupees worth business worldwide
where India also shares significantly. Total flavor and fragrance sales
in cosmetics and toiletries are expected to reach over billions of
rupees globally. The Indian market size for perfumery industries is
reportedly estimated at 2% of world total and is likely to be growing
at an annual rate of 10%.
Above aspects are desired to be elaborated from academic and
industrial perspectives in the form of a textbook by consulting
textbooks of world-renowned authors and published review articles
and research papers.
Natural Perfumery Materials:
Sources, Characteristics, Extraction and Uses of
Natural Perfumes (Essential/Aromatic Oils)
INTRODUCTION
Natural perfumes are actually the well known essential oils or

aromatic oils, which are almost exclusively of plant origins, belonging
to different botanical or plant families, and derived from exotic
flowers, grasses, leaves, fruits, seeds, barks, woods, roots, and gums.
Certain animal organs also contain perfumery chemicals.
The content of essential oils is generally low, varying from about
0.02% to 5.0%, irrespective of the nature of source materials. The
essential oils from various sources are characterized by distinct
chemical composition, physical properties, and aroma. The aromatic
oils from animal sources also exhibit low oil content, specific molecular
nature and composition pattern, and aroma features.
The present chapter refers to the various source materials for
essential oils (natural perfumes) and their physical and chemical
characteristics along with the brief outline of their extraction
processes and uses.
FLOWERS AS A SOURCE OF ESSENTIAL OILS
A large variety of flowers occur in nature that possess oils of distinct

aroma (odor), owing to their specific chemical compositions. Among
the flowers that are most particularly recognized and commercially
Sources, Characteristics, Extraction and Uses of Natural Perfumes 5
important and attractive are the jasmine, rose, neroli, lavender,

gardenia, tuberose, etc. A number of relatively less known flowers
also deserve to be examined as important source of essential oils.
The details of each flower in respect to oil content, composition,
extraction, and uses are elaborated hereunder.
CARNATION
(Dianthus caryophyllus, Caryophyllaceae)
Oil from carnation 1 flower oil is well known throughout Europe

(mainly France and Italy), but its familiarity in India is lacking.
Hundreds of varieties of carnation exist in nature but the white
carnations are the preferred varieties from the point of view of
odor.
Oil Content: The oil content of carnation flowers is extremely

low, yielding 0.003% of oil.
Composition: The carnation oil contains eugenol 30%, phenyl

ethyl alcohol 7%, benzyl benzoate 40%, benzyl salicylate 5%, and
methyl salicylate 1 %, ~-citronellol, cinnamyl alcohol, coumarin, thujyl
alcohol and a/~-ionone, a-pinene, and geraniol.
Extraction: Carnation oil is produced by solvent extraction process

with a volatile solvent.
The carnation flower oil is a pale green solid having an intense

odor reminiscent of aliphatic aldehydes (C 4 and 40-aldehydes). On
dilution (extreme) the true flower odor is developed.
Uses: The carnation absolute is used in the most exclusive

perfumes.
CASSIE
(Acacia farnesiana, Leguminosae)
Cassie 2 flower (Acacia farnesiana) is a native of India and the East,

but is cultivated in Italy, France, Algiers, Egypt, and Syria.
Oil from Cassie flower is obtained from several species of acacia

with typical cassie odor, principally from A. farnesiana, A. cavenia, A.
giraffe, and A. corrida.
Oil Content: Cassie flowers yield 0.4% of concrete and 0.1% of

absolute.
6 Perfumery Materials : Production and Applications
Composition: Oil from cassie flower contains components

like anisaldehyde, benzaldehyde, cuminic aldehyde, decyl
aldehyde, methyl salicylate, benzyl alcohol, farnesol, linalool,
geraniol, traces of p-cresol, and two ketones, one resembling
menthone and the other having an odour recalling violet, eugenol
and methyl eugenol.
Extraction: Cassie flower oil is produced by maceration process
using hot fat or by volatile solvents. The floral aroma can also be
recovered by absorption in spermaceti followed by ethanol extraction.
Uses: Cassie flower oil finds use in fine violet perfumes. The oil
resembles both violet and orange blossoms.
CLARY SAGE
(Salvia sclarea Linn., Labiatae)
Oil from clary sage 3 is obtained from the flowering tops of the beautiful
plant. The plant grows in the Alps. The plant grows in Kashmir due
to the introduction of a Bulgarian strain of clary sage.
Oil Content: The yield of oil is reportedly 0.117%.
Composition: Clary sage oil contains linalool 6.5% to 24%, linalyl

acetate 56% to 78%, sclareol 0.4% to 2.6% as the main constituents.
Extraction: Clary sage oil is produced by the steam distillation

process of the flowering tops of the plant.
Uses: Clary sage oil is one of the costly essential oils used III
high-grade perfumes and cosmetics.
Clary sage oil has a number of uses in aromatherapy. It acts as

a powerful relaxant and provides emotional effects. The oil is helpful
in relieving depression, anxiety, tension, mental fatigue, and general
debility.
It is calming and anti-inflammatory. It reduces high blood pressure.
The oil is used in inhalations, vaporisers, bath, or massage.
GARDENIA
(Gardenia jasminoides, Rubiaceae)
India has the best variety of gardenia 4 -6 , Gardenia jasminoides, but

so far no oil has been extracted from this flower. Another potential
raw material is the tiara gardenia, Gardenia taitensis, which grows
in India and whose oil has a fascinating floral fruity odor of strong
diffusivity.
There are many Gardenia species, bearing beautiful and highly

perfumed flowers. Among these are the Gardenia grandiflora,
Coronaria radicans, and Citriodora. Gardenia florida's odor
characteristics during day and night time have been investigated. At
night, frgrance is more and attracts the insects.
Depending on the species, the gardenia oil has odor characteristic

like that of orange blossom or of jasmine.
Oil Content: The average oil content varies between 0.07% and
0.1%.
Composition: Gardenia oil contains components like benzyl
acetate, linalyl acetate, methyl anthranilate, styrolyl acetate, linalool,
terpineol, and traces of benzoic acid as ester. Styrolyl acetate also
known as Gardeniol 1 is the chief odorous constituent and benzyl
acetate is the major compound, while phenyl methyl carbinyl acetate
known as Gardeniol 2 is detected.
Gardenia florida (night) contains, as determined by GC-MS
constituents like verbenol, linalool, nerol, geraniol, neral/geranial,
caryophyllene, and a-farnesene.
Extraction: The oil is extracted by enfleurage process using liquid

paraffin and subsequent alcohol extraction. The oil may also be
obtained by solvent like petroleum ether.
The absolute is brown in color, semi-liquid consistency, and has
an odor resembling that of a mixture of the absolutes of jasmine,
orange blossom, and tuberose.
Uses: The oil is used extensively in perfumery.
JASMINE
(Jasminum officinale, Oleracea)
Jasmine 7 - 10 flower occurs mostly in India, China, Arabia, France,

Africa, and America. It has a large number of species and varieties
and depending on the varieties the oil quality varies. The white
variety of Jasmine (Jasminum officinale) is well known and contains
oil of exquisite odor. The Jasminum grandiflorum yields extracts,
which are used to make perfume. Flowers appear in July and last
until October. The plants mature fully in course of 4 years, and last
for 14 to 15 years. In India, jasmine flowers are cultivated and oil is
produced magnificently. There are other jasmine flowers from which

essential oils should be produced to impart new note for the fragrance
industry. In India, jasmine variety known as Jasminum sambac,
locally called Mallika or Mograw, yields oil that has a green diffusive
floral, odor. Another Indian jasmine species Jasminum nitidum,
commonly known as Mukhri or Chammelli has a strong diffusive
odor quite different from that of either Jasminum grandiflorum or
Jasminum sambac.
Oil Content: Jasmine flowers contain around 0.4% oil as concrete

or 0.2% as absolute.
Oil Composition: Jasmine oil is composed of 65% benzyl acetate,

7.5% linalyl acetate and other terpence esters, 6% benzyl alcohol,
15.5% free linalool, 2.5% indole, 3.5% jasmone, and 0.5% methyl
anthranilate. Other minor components are eugenol, geraniol, nerol,
cis-3-hexenol, trans-2-hexenol, jasmine lactone cis-3-hexenyl benzoate,
benzaldehyde, R-terpineol, etc. In fact, over 100 constituents have
reportedly been found in jasmine oil.
Extraction of Jasmine Oil: The oil can be extracted from jasmine

flowers by simple extraction with a volatile solvent (petroleum ether)
or by the enfleurage process that gives increased yield by 2 to 3
times to that obtained by solvent extraction and has better aroma!
fragrance characteristics. The solvent process is, however, economical,
as it recovers practically all odorous constituents and also saves
labor charges. The concrete from the solvent process is treated with
high proof alcohol to separate out the waxes and thereby yields the
absolute of jasmine.
Uses: Jasmine oil has a warm, floral scent, and musky undertone.
Jasmine absolute is dark amber and slightly viscous. Jasmine oil is
exclusively used in soaps, toiletries, hair oil, and other cosmetic products
directly and is also used in combination with other natural and synthetics.
The oil from Jasminum sambac flowers is frequently used as a deodorant.
The oil has a green diffusive floral odor. Jasmine oil blends well with
bergamot, rose, and sandalwood and citrus oils. Jasmine oil has
aromatherapy uses in reducing depression, nervous exhaustion and stress-
related conditions, and stretch marks and other scars.
KAMINI FLOWER OIL

(Murraya exotica, Rutaceae)
Kamini (M. exotica) flowers ll - 12 grow in West Bengal and in the

plains of northern India. These flowers contain essential oil.
Oil Content: The oil content of Kamini flowers has not been
reported so far presumably due to very low content of volatiles.
Composition: The essential oil of Kamini flower has been analyzed
by GC-MS resulting in the identification of 72 constituents in the
flower oil. The flower oil of North India origin shows (E,E,E)-a-
springene 23.8%, (E)-nerolidol 18.7%, (E,E)-a-farnesene 13.2%, methyl
palmitate 6.8%, and germ acre ne B 5.9% as the major constituents l l .
The flower oil from West Bengal shows the occurrence of verbenol,
linalool, nerol/geraniol, a-pinene, camphene, caryophylene,
phenylethyl alcohol, and a-methyl-4-dimethyl-3-pentenyl-oxirane
methanol 12 .
Extraction: Kamini flower oil is extracted from fresh M. exotica
flowers by steam distillation or by solvent process.
Uses: The oil can be used in making fresh perfumes. The oil from
flowers can be used as a strong antifungal agent and a modest
antibacterial agent.
LAVENDER
(Lavandula officinalis, Labiatae chaixsyn. L. Vera, DC.)
Lavender13 (Labiatae family) flowers grow in the European countries

like France, England, Yugoslavia, and Bulgaria. France produces the
best quality flowers. India should consider producing oils from various
lavender species. India is producing its own lavender oil in the
Kashmir valley. The Kashmir variety yields 80%-100% more oil than
the Bulgarian strain. The oil obtained is of much better quality.
Oil Content: The oil content is from 1.4% to 1.6% of flowers.
French lavender flowers yield 0.5% to 0.9% and English 0.8% to 1.7%
on fresh weight basis. Kashmir plants yield 2% to 4% oil from dry
flowers.
Composition: There are two main types of lavender of the genus,
Lavandula, French and English. Each has its own characteristic odor,
which is due to major compositional differences between the two
species. A comparative analysis of the volatiles of living French
Lavender (Lavandula dentata) and English (Lavandula angustifolia)
is shown overleaf:
Extraction: Lavender oil is obtained by steam distillation of the
fresh flowering tops of Lavandula officinalis.
Uses: Lavender oil is a pale yellow liquid with a pleasant odor. Its
perfumery value depends on its ester Oinalyl acetate) content.
French lavender (%) English lavender (%)
Limonene 18 6
1-0cten-3-o1 7
Hexyl acetate II 2
Eucalyptol 9 3
Linalool 7
cis-3-Hexenyl acetate 17 13
Borneol 2
Cryptone 6
Lavender oil is used in toilet soaps, toiletries, and cosmetics, and as

odoriferant and as fixative in soaps and shaving creams. Lavender
oil is valuable for its aromatherapy applications. It has excellent
uses in emotional, respiratory, skin-balancing, digestive, circulatory,
muscular, and gynaecological cures. Lavender oil has a variety of
therapeutic properties.
The therapeutic properties of lavender oil are antiseptic, analgesic,

anti-convulsant, anti-inflammatory, antiviral, bactericide, carminative,
cholagogue, decongestant, deodorant, hypotensive, sedative, and
diuretic.
NEROLI
(Citrus bigaradia, Rutaceae Risso)
Neroli oiF4-16 is obtained from the fresh flowers of sweet and bitter
oranges.
Oil Content: The essential oil content is about 0.3%.

Composition: The constituents of this oil are limonene, linalool,
esters of geraniol, linalool, nerol, phenyl ethyl alcohol, methyl
anthranilate, and indole. The following composition has been reported:
terpenes (chiefly dipentene, pinene, and camphere -35%, l-linalol
30%, geraniol and nerol 4%, D-terpineol 6%, l-linalyl acetate 7%,
neryl and geranyl acetates 4%, methyl anthranilate 0.6%, and other
trace constituents.
Extraction: Neroli oil is obtained by steam distillation of fresh

flowers of sweet and bitter oranges.
Uses: Neroli oil is widely used in perfumery. The aqueous portion

of the distillate obtained after the separation of the oil is the orange
flower water of commerce used in the toilet and perfumery industry

and in pharmacy.
The oil has aromatherapy uses. The oil can be used for skin care,
stretch marks, palpitations, anxiety, depression, shock, and stress-
related disorders.
ROSE
(Rosaceae, Rosa damascus Mill.)
Rose flowers 17 . 18 grow and are cultivated in mass farms almost

throughout the globe. The notable rose producing countries are
Bulgaria, France, Hungary, Germany, Persia, and India. Among the
many forms of rose only few forms act as source materials for
making rose oil. In India, rose is cultivated maximum in the UP
belts and the Indian roses yield attar of rose, which is different
from the Bulgarian rose. Many roses are found in India with
interesting odors. Among them, mention may be made of rose oils
such as Rosa centifolia and hybrid tea roses, for potential markets
in the fragrance industry. Tea roses are grown near Delhi and
many types of modern hybridized tea roses could be grown in India.
Each has its own characteristic rose odor and is different from that
of otto of rose Bulgarian.
Oil Content: Rose oil content varies from 0.020% to 0.4% (w/w)
on weight of rose, depending on the red or white rose used. It must
be mentioned that the yield of oil depends on the climatic conditions
during the time of recovery.
Oil Composition: Rose oil consists chiefly of two terpene alcohols,

namely, geraniol and citronellol with farnesol and nerol 5% to 10%.
Rose oil also contains components like phenylethyl alcohol 1%,
nonylaldehyde 1%, linalool 1%, eugenol 1%, and some esters of
alcohols and stearoptene 7% to 25%, l-citronellol 24-64%, total
alcohols as geraniol 63% to 84%.
Extraction: Rose oil is produced by extraction of the red or the

white rose before the flowers are fully opened by steam distillation
process or by solvent extraction with volatile solvents or by
maceration process of pomade.
Uses: Rose oil finds extensive use in fragrance industry. Rose oil
also has aromatherapy uses such as skin care, eczema, palpitations,
depression, and stress-related disorders.
TUBE ROSE
(Polianthes tuberosa, N.O. Amaryllidaceae)
Tuberose 19 is a well-known Indian flower, and is used extensively in

perfumery. India produces good quality of tuberose absolute. Tuberose
is cultivated during August-October. Oil of tuberose is obtained from
this flower of Polianthes tuberosa.
Oil Content: The oil content varies from 0.066% to 0.08%,
depending on the extraction process adopted.
Composition: The tuberose contains methyl anthranilate 5.1%,
methyl benzoate, benzyl benzoate, methyl salicylate, benzoic acid,
and tuberone 10%, butyric acid. The oil also contains benzyl alcohol,
geraniol, nerol, eugenol, and farnesol.
Extraction: The oil is obtained by enfleurage process or by solvent
extraction with volatile solvents. The enfleurage process in the cold
gives a higher yield. A concrete and absolute is extracted by solvent
extraction from the fresh flowers before their petals open.
Tuberose oil has a slightly spicy, heavy, and sweet fragrance.
Uses: The oil is used as a component of good quality perfumes.
YLANG-YLANG
(Cananga odorata var. genuina, Anoanaceae)
Ylang-ylang 20 -21 (Cananga) oil is obtained from the flowers of Cananga

odorata (Lam.) Hook.f. & Thomas trees. Most of the oils is produced
in Madagascar, Reunion, and the Comoros Islands.
Oil Content: The flowers of cananga yield an essential oil from
0.4% to 2.25%, depending upon the quality of flowers.
Composition: Alpha pinene, benzoic acid, cadinene, caryophyllene,
cresol, eugenol, 5% to 7% linalyl acetate, 8% to 10% linalyl benzoate,
30% to 32% linalool, and geraniol.
Extraction: The oil is produced by water or steam distillation of
the best quality flowers. The first fraction of the distillation is usually
the best and is marketed as ylang-ylang oil. The second fraction is
cananga oil. These two oils are obtained in almost equal quantities.
Uses: Ylang-ylang has a vastly superior fragrance when the
commercial grade known as ylang-ylang extra is used. Ylang-ylang
oil is much used in high-class perfumery. Cheaper grades are used
in cheap perfumery and soaps.
The oil has special aroma therapy applications. It promotes hair

growth, high blood pressure, depression, nervous/tension, stress-
related disorders, etc.
A pale yellow liquid with an intensely sweet, floral scent reminiscent

of a blend of jasmine and almonds. Its odor effect is intoxicating and
antidepressant.
SOME EXOTIC FLOWERS AS SOURCES OF

ESSENTIAL OILS
CHAMPACA
(Michelia champaca L. or M. longifolia, BI, Magnoliaceae n.o.)
Champaca 22 . 24 is a golden colored flower with a wonderful strongly
diffusive exotic floral odor. It grows in India (Himalayan region) but
no extract or oil of this flower is available in India. The flower is
native of Java and the Philippines. M. longifolia produces white
flowers.
Oil Content: The yield of oil is 0.03% to 0.2%.
Composition: The oil contains benzaldehyde, benzylalcohol, a

trace of benzoic acid and cineole. The major components are linalool
0.2-11.0%, methyl benzoate 1-5%, benzyl acetate 0.1-4.0%, cis-linalool
oxide pyranoid 0.2-7.0%, phenyl acetonitrile 0.1-4.3%, 2-phenethyl
alcohol 2.0-34.0%, dihydro-p-ionone 0.3-10.0%, a-ionone 0.1-6.8%, p-
ionone 0.2-3.4%, dihydro-p-ionol 0.3-3.8%, methyl anthralilate 1.4-
9.0%, indole 2.5-12.0%, methyl palmitate 1-3.0%, ionone oxides 1-
3.0% and methyl linoleate 1.0-18.0%. More than 250 compounds
including trace components have been identified.
Extraction: The oil is obtained by solvent extraction with

petroleum ether (pentane) of the fresh flowers.
Uses: The oil may be used in making floral perfumery.
MIMOSA FLOWER
(Acacia dealbata, A. floribunda, Leguminosae)
Mimosa flower 25 -26 oil is obtained from the flowers of above varieties
belonging to the family Leguminosae. Mimosa, Acacia decurrens, has
a strong green floral odor. The flower grows in southern France,
which has the same climate as parts of India. Acacia /Zoribunda
perfume approaches that of cassie. The perfume from A. dealbata is

slightly coarser and resembles ylang-ylang.
There are many more species and in recent years, the oil content
and compositions of the flower oils of some species, namely, A. caven
(Mol.) Mol. var. Caven, A. aroma Gill. ex Hook, have been reported.
Oil Content: The yield of oil as concrete is 0.7% to 0.8% and

about 0.14% to 0.16% of absolute.
Composition: Mimosa oil contains components like unsaturated
aliphalic hydrocarbons, primary alcohols, anisic acid, palmitic acid,
and acetic acid esters.
Extraction: The oil is obtained by solvent extraction of the flowers.

Uses: The oil has aromatherapy uses in nervous exhaustion and
stress. Its odor effect is calming.
ORANGE BLOSSOM WATER FLOWERS

(Citrus aurantium L. ssp. aurantium)
Orange blossom water27 is produced from the fresh flowers from C.

aurantium subspecies aurantium native to the Mediterranean areas.
Oil Content: The yield of oil varies between 0.04% and 0.06% of
orange blossom water.
Composition: The essential oil extracted from orange blossom
water contains mainly linalool 40-60% and a-terpineol 15-25%,
phenylethyl alcohol 0.5-5%, Benzyl nitrile 1-5%, Methyl anthranilate
1-6%, terpinen-4-ol 0.5-1.5%, cis-linalool oxide 1-5%, trans-linalool
oxide 0.5-3%, 6-methyl-5-hepten-2-one 0.5-6%, etc.
Extraction: Orange blossom water is produced by steam

distillation of the fresh flowers.
Uses: Orange blossom water is traditionally used in food to flavor

cakes and beverages.
The oil is used as a medicine and for skin care. It is suitable for
oily and acneric skin due to its astringent properties.
It has carminative activity in the digestive tract and calming effect

and has a kind of sleep inducing effect. Orange blossom water is
claimed to be effective in children with attention deficit hyperactive
disorder (ADHD) when used both topically and internally.
PLUMERIA FLOWER
(Plumeria rubra Linn., Frangipani)
Plumeria rubra 28 , also known as frangipani, exists in white, yellow

and pink varieties. This flower grows in India. The white variety has
the best exotic tropical floral odor of strong diffusivity. Unfortunately
no oil of this flower is available. Three Plumeria species as occurring
in Malaysia, P. acuminata Ait (white flower), namely, P. rubra Linn.
(reddish-orange flower) and P. rubra Linn. (red flower) have been
analyzed recently.
Oil Content: The oil content varies from 0.03% to 0.12% on a dry
weight basis depending on the flower species.
Composition: The oil of P. acuminata Ait white flower consists
predominantly of benzyl salicylate 39.0%, benzyl benzoate 17.2%,
trans-nerolidol 10.6%, neryl phenyl acetate 10.5% and linalool 8.9%.
P. rubra reddish-orange flower oil contains phenyl ethyl benzoate
12.3%, dodecanoic acid 11.8%, hexadecanoic acid 9.3%. P. rubra Linn.
red flower contains 27.2% hexadecanoic.
Extraction: The oils are extracted from the fresh flowers by
hydrodistillation process.
Uses: The oil has an odor reminiscent of jasmine. It finds use in
making fragrances.
WATER LILY FLOWER

(Nymphaea)
and
GINGER LILY
(Hedychium coronarium)
The water lily29 of the genus Nymphaea grows in India in fresh

water ponds. Each variety of water lily possesses its own unique
watery floral odor. This type of new floral note will give opportunity
to create new fragrances. The ginger lily is an exotic Indian flower,
which possesses a strong, diffusive jasmine-like odor.
ORCHIDS AND OTHER INDIAN FLOWERS
More than 30,000 varieties of orchids 29 can be found from the foothills
of the Himalayas to the tropical rain forests. India appears to have
many very exotic species with unusual and pleasant odors which
cannot be found in any other part of the world.
Narcissus, a tiny white flower, grows aboundantly in local Indian

gardens. The flower by extraction with hexane yields an oil having
sensuous note. The sensuous note has been utilized to create the
best women's fragrance in the United States. When extracted by
solvent the narcissus yields about 0.3% concrete and about 30% of
absolute from the concrete. The oil contains benzyl benzoate, methyl
anthranilate, esters of cinnamic acid (particularly the methyl ester),
indole, and probably linalool.
Courouptia, Couroupita guianensis, also known as cannonball

flower, grows in India and has a very unusual exotic spicy floral
note, which could be of great importance in fragrance industry of
India.
GRASSES AS A SOURCE OF ESSENTIAL OILS
Some grasses are recognized for containing essential oils, and are
commercially exploited for their production and applications. They
belong to the different plant families and they have unique aromatic
fragrance due to the occurrence of specific oxygenated terpene
derivatives as major constituents in the essential oils. Mention may
be made of citronella, lemongrass, palmarosa, and vetiver as the
major essential oil bearing grasses.
CITRONELLA GRASS
(Cymbopogon nardus Rendle, Graminaceae,
Lena batu of matara)
Citronella grass 30 occurring in various forms constitutes an important

kind of a natural essential or aromatic oil.
Ceylon and Java are the major grower of citronella grass and
producer of citronella oil. Ceylon citronella oil is produced principally
from the grass lena batu [Cymbopogon nardus (L.) RandleJ. Java
citronella oil is obtained from cymbopogon winterianus Jowitt
citronella grass. China, Argentina, and South America also produce
citronella oils.
Oil Content: The oil content is about 0.4% of the fresh grass.
Oil Composition: Citronella oils contain mainly two important
constituents, namely, the alcohol (geraniol) and the aldehyde
citronellal. The oils, however, contain citronellol 6.15-11.47% and
other compounds such as linalool 0.56-0.86%, borneol 0.05-5.23%, a-
terpineol 0.05-1.05%, decanal 0.09-0.18%, a-terpinyl acetate 0.01-
0.35%, citronellyl acetate 0.97-1.97%, bornyl acetate 0-0.42%, geranyl

acetate 2.40-5.07%, citronellic acid 0-0.17%, and a number ofterpenes
like limonene, a-pinene, camphene, myrcene, 8-3-carene, a-terpinene,
etc. In trace amounts eugenol 0-2.45%, elemol 1.14-5.58%, eis-a-and
trans-a-farnesol, etc., also occur. In addition, there is also a series of
trace 0.01% components in some citronella oils particularly in Chinese
citronella oil. The geraniol content of the Java citronella oil is 23.2%,
whereas that of the Ceylonese has 20.9%. Citronellal content is 34.79%
in Java oil, while its content in the Ceylon oil is 6.09%.
Extraction: Citronella oil is produced by steam distillation of the

fresh, partly or wholly dried citronella grass in stills. Two stills are
being used; one still is emptied and recharged, while the second one
is distilling. Normally, each charge requires 6 hours, and two charges
are completed in a day.
Uses: It is used extensively as a fragrance in soaps and household

cleaning products. It is also used as a starting material for production
of several fragrance compounds. The oil has only minor use in food
or beverage flavoring. The oil is much used in aromatherapy. The oil
vapors help reduce fatigue, headaches, and migranes, as well as
cases of neuralgia and depression.
Citronella oil acts as antiseptic, antibacterial, antidepressant,
antispasmodic, anti-inflammatory, deodorant, fungicidal, stimulant,
stomachic, and tonic.
It is useful with rheumatism and arthritis pain. The oil has the
ability to cure colds and flu and is very helpful with excessive
perspiration and in conditioning oily skin and hair.
GINGER GRASS
[Cymbopogon martini (var. Sofia), Gramineael
Ginger grass 31 oil is obtained from C. martini (var. Sofia), another

variety of Indian grass very closely related to C. martini (var. Motia).
The grass grows in the forest of Melghat (Khandesh district), Yeola
(Nasik district), Dohand and Jholad (Panch Mahal district).
Oil Content: The yield of oil varies from 0.15% to 1%.
Composition: The ginger grass oil contains a mixture of alcohols

like geraniol and dihydrocuminic alcohol.
The oil contains phellandrene dipentene and limonene, carvone

and an aldehyde reminiscent of heptaldehyde and citronellal in odor.
Extraction: Ginger grass oil IS obtained by hydro-steam

distillation of the grass.
Uses: The oil is used in perfume blends for scenting cheaper

soaps. The oil has a good fixative power.
LEMON GRASS
[Cymbopogon flexuosus Stapt (Steud Watts) Andropogon
nardus var. flexuosus. Hack., Gramineael
Lemon grass 32 is indigenous to India mostly in the southern states

like Madras and Kerala. Two types of lemon grass, namely, white
grass and red grass are available. The bulk of Indian lemon grass oil
is produced from the red grass. India is a major producer of lemon
grass oil. Improved agronomic practices have now made possible to
cultivate lemon grass on farmers and the genetic improvement of
the lemon grass has yielded several varieties to give 50% more yield
than the best cultivated varieties. A strain of Cymbopogon pendulus
has been developed by the Central Institute of Medicinal & Aromatic
Plant (CIMAP), which has more than 85% of citral and gives 100%
more oil yield. It is suitable for marginal and sub-marginal soils
including wasteland.
Oil Content: The yield of lemon grass oil varies from 0.25% to
0.5%.
Oil Composition: Lemon grass oil contains a major component

citral between 41% and 85%. In general, the citral content of the oil
is 70%-85% and it is adjusted to 75%-77% for export purpose.
The oil also contains citronellal, farnesol, geraniol, limonene,

linalool, methyl heptanol, myrcene, n-decylaldehyde, and nerol.
Extraction: Lemon grass oil is produced by the process of hydro-

steam distillation of leaves of tropical grass.
Uses: Lemon grass oil is a basic raw material for producing

aromatic chemicals, which find application in perfumery, in many
pharmaceutical preparations such as pain balm. Ionones required for
use in perfumery soap and cosmetic industries are prepared from
lemon grass oil. The oil is used for the synthesis of vitamin A.
The oil has aromatherapy uses. It is very good antiseptic and

detoxifying agent. It helps recovering temperature.
PALMAROSA
[Cymbopogon martini (Roxb.) Stapt Watts var. motia,
(Gramineae) Grass]
Palmarosa 33 -34 , mostly cultivated in central (Madhya Pradesh),

Maharashtra, and Andhra Pradesh, India, and also in the Central
American states and Brazil and Africa and Madagascar is an important
tropical grass. This exotic grass provides unique source of a natural
perfumery material. India produces a very high quantity of palmarosa
oil in the world market. India exports palmorosa oil worth over
rupees 2.5 million out of its annual production of 90 tones. Improved
varieties have been developed and released in India that give 40-50%
higher yield of oil.
Oil Content: Palmarosa grass contains on fresh weight basis up

to 0.83% or 1%. The genetic improvement can yield improved varieties
that can give 40-50% higher yield of oil.
Oil Composition: The principal, constituent of palmarosa oil also

known as 'Rosha oil', 'Rusha' or 'Ni mar' oil is geraniol which occurs
between 75 and 90%. Some 40 other compounds, mostly terpenes
occur to contribute to the typical odour of the oil. More than 100
compounds have been identified by modern analytical techniques.
The improved varieties of palmarosa as stated above yield oil, which
contains more than 95% of geraniol.
Extraction: Palmarosa oil is produced from the whole plant of

the grass preferably of the fresh or semi dried grass by the steam
distillation process in direct fired stills with perforated bottoms. Water
distillation is also done to extract palmarosa oil.
Uses: It is an excellent material for soap perfumery. The oil is

extensively used as a base for perfume and cosmetics.
The oil has wonderful aromatherapy applications. It provides

remedy for skin conditions like acne, boils, and wrinkles. It has a
natural antiseptic and bactericide property. The oil is also a wonderful
remedy for broken veins.
Palmarosa has a soft, lemony-fresh green scent with hints of

geranium and rose. Palmarosa oil is recommended for neuralgia,
lumbago, sciatica, and rheumatic pains.
Combined with lavender, Tea tree and geranium essential oils,

palmorosa oil can often assist in cleaning genitor-urinary infections,
such as cystitis, urethritis, and vaginitis.
Palmarosa oil acts as a cardio-tonic and nervous relaxant by helping

to stabilize both the heart and nervous system.
VETIVER GRASS
(Vetiveria zizanioides, Stapf, Andropogon muricatus, Retz.)
The leaves of vetiver grass 35 -36 are odorless. It is the roots that
have a strong scent. Vetivers are known in India as Khus-Khus.
The grass grows wild in Uttar Pradesh, Punjab, Bharatpur, and
parts of Assam. It is cultivated as a crop in Kerala state, East
Godavari, and Kurnool district of Andhra Pradesh. Once Bharatpur
was the biggest center of Vetiver (Khus) in North India. Now there
is hardly any Khus available in Bharatpur. Also no Khus industry
is available there. Other centers are Biswan, Musanagar, Nawabganj,
and Utarpura in u.P.
Oil Content: The yield of oil from cultivated plants and the
cultivated roots is about 1% as compared to 0.2%-0.4% from wild
roots. The high-yielding strains have been developed which yield
1.4% oil and 30-40% higher yield of roots. The yield of oil from dry
roots is about 2%. Two hybrid strains released by Indian Council of
Agricultural Research give more than 1% oil as compared to the wild
strain, which gives 0.2%-0.5% oil.
The oil content of North India roots increased up to growth period

of 24 months, whereas the content of Kerala variety did not show
any appreciable increase after 12 month roots. The oil content from
Kerala roots showed dextro rotation, while the oils from other places
were found to be laevo rotatory. The oil content of the Kerala variety
was the least compared to other varieties.
Composition: The constituents of the oil include an alcohol
vetivenol (C 15 H 24 0), vetivene (hydrocarbon). The vetivernol or
vetivenol 51-66% comprises the total alcohol.
Extraction: The vetiver (Khus) oil is obtained by steam distillation
of the roots, which are first coarsely ground and soaking with water.
Uses: Vetiver oil is a strong fixative and is used in the blending

of perfumery for cosmetics and toilet soaps. The oil is one of nature's
best moisturizers.
The oil has aromatherapy applications in bath, facial care, hand
care, and massage for hard wrinkled shine. It imparts a sense of
calm and peacefulness during stress, tension, and physical or mental
exhaustion.
LEAVES AS SOURCE OF ESSENTIAL OILS
Leaves from a number of plants constitute a major source for aromatic

or essential oils of distinct aroma (odor) characteristics. Some of the
more well-known leaves have been identified and projected here.
BASIL LEAVES
(Ocimum species, Labiatae)
Basil leaves 37 -4o from various Ocimum species on distillation yield

aromatic oil called basil oiL As many as 60 Ocimum species occur in
nature and there are also several hybrids of Ocimum species, the
oils of which are more or less similar to those of the parent plants.
The oil is obtained mostly from Ocimum basilicum L. species although
other species of Ocimum, namely O. cannum, O. americanum, O.
gratissimum, and O. kilimandscharicum, yield the oiL
Oil Content: The oil content varies from 0.4% to 0.7% although
in case of O. gratissimum species the leaves yield 0.1% of oiL
Composition: The composition of basil oils varies depending on
the variety of Ocimum species from which these oils are extracted.
The oil from Ocimum basilicum (sweet basil) is classified as methyl
cinnamate type of basil oiL In fact, methyl cinnamate is the major
component of basil oil from O. basilicum. Ocimum basilicum (sweet
basil) of methyl chavicol and eugenol types are also available. O.
basilicum (methyl chavicol type) termed as Indian Basil has become
a commercial crop for oil production. O. basilicum Oinalool type and
methyl cinnamate type) hold promise as economic crops for their
essential oils. The basil oil from O. basilicum (album) after
rectification contains 20.85% terpinene, 4.36% linalool, and methyl
cinnamate 56.67%.
The oil of O. canum species has the principal constituent like
methyl cinnamate or D-camphene or the citral depending on this
variety of O. canum species. The oil of Indian species contains as
much as 50% citral and over 68% of aldehydes calculated as citraL
The oil of O. gratissimum contains 66.7% citral and 25.7% geranioL
The basil oil (French) from O. basilicum has camphor, cineole,
estragol (or methyl chavicol), eugenol, linalool and pinene as the
principal constituents.
A comparative analysis of the volatiles of various types of living
basil (Ocimum species) is indicated below.
Component % in %in % in % in % in
purple Italian Indian green African
basil sweet basil basil (sacred) tulsi blue
O. basilicum O. sanctum (O.s.) basil
O. sp.
Aftbasil Estragole 1 45 2
Ocimene Trace 2 64 34
cis-3-Hexenyl Trace 4 46 23
acetate
Linalool 14 27 Trace Trace 41

Eugenol methyl 42
ether
Each oil has a different major constituent. India should consider

making various basil oils.
Extraction: Basil oils are produced by steam distillation of leaves

of various species of Ocimum.
Basil oils have good aroma having a fine lavender odor or having
lemon odor.
Uses: The oil is used in blending soap perfumes and cosmetics as
a flavoring agent.
Basil oils have aromatherapy (therapeutic) uses in mascular aches
and pains, respiratory disorders, colds, and flu as, expectorant, anxiety,
and depression.
CAMPHOR LEAVES
(Cinnamomum camphora Linn.)
Camphor oi1 41 is obtained from the leaves of Cinnamomum camphora

Linn. tree which is cultivated at Dehra Dun, Saharanpur, Nilgiris,
and Mysore and also in China, Japan, Ceylon, and California, Brazil,
Java, etc.
Oil Content: Total volatile oil contained III dry leaves is 1.43%
and the yield of camphor is about 1%.
Composition: The camphor oil of commerce is the oil from which
camphor is removed. Camphor oil contains safrole as a major
component.
Extraction: Camphor oil is extracted from leaves on steam

distillation. The oil is treated to remove camphor thereby yielding
the camphor oil of commerce.
The oil is pale yellow in color.
Uses: Camphor oil contains safrole and is used as the commercial
source of safrole.
CINNAMON LEAF
Cinnamon leaf42 oil is obtained from the leaves of Cinnamomum

zeylanicum Brien. The leaves are mostly grown in Malabar, South
Kanara and adjoining districts of Mysore state.
Oil Content: The leaves yield 1.7-1.8% by weight of sun-dried
leaves as essential oil.
Composition: Cinnamon leaf oil contains about 85% eugenol and
traces of cinnamic aldehyde. The oil is different from cinnamon bark
oil that contains about 75% of cinnamic aldehyde and a small amount
of eugenol.
Extraction: Cinnamon leaf oil is produced by steam distillation.
Uses: Cinnamon leaf oil is largely consumed in the flavoring and
pharmaceutical industry as well as in perfumery. The oil is known
for its aromatherapy uses.
CURRY LEAF
(Murraya koenigii, Rutaceae)
Curry leaf43 is well known in India and it acts as a source of essential

oil. The plant is widely found in hills of Uttaranchal, Sikkim, W.
Bengal, Assam, Central India, Western Ghats, Tamil nadu, and Kerala.
The plant is also cultivated in Owma, Ceylon, China, Australia, and
the Pacific islands.
Oil Content: Curry leaves when fresh yield 0.24% of essential
oil.
Composition: Curry leaf essential oil contains over 30 compounds
consisting of about 97% of the oil. The major constituents are a-
pinene 51.7%, sabinene 10.5%, p-pinene 9.8%, p-caryophyllene 5.5%,
limonene 5.4%, bornyl acetate 1.8%, terpinen- 4-01 1.3%, R-terpinene
1.2%, and a-humulene 1.2%. The oil also contains caryophyllene oxide
0.7% and spathulenol 0.4%.
There is, however, a variation III the chemical composition of

curry oils.
Extraction: The essential oil of the fresh leaves of M. koenigii is

extracted by the conventional hydro distillation process.
Uses: The oil may be utilized for flavoring oil and as a source of
natural a-pinene. The oil has antimicrobial, antifungal, and pesticided
activities.
EUCALYPTUS LEAVES
Eucalyptus oil 44 -45 is obtained from the leaves of Eucalyptus globulus

(blue gum tree) growing in India on Nilgiris, Annamalais, Palni Hills,
Simla Hills, and Shillong.
There are over 500 species of the genus Eucalyptus most of them
being utilized for the production of aromatic oils. Australia is the
largest producer of eucalyptus oil.
Oil Content: The leaves yield 0.9-1.2% of the essential oil. The
leaves of E. citriodora yield 0.5-2.0% essential oil.
Composition: Cineole or eucalyptal (70-80%) with various
aldehydes, ketones, sesquiterpinic alcohols and terpenes comprise E.
globulus oil. The oil from E. citriodora has different composition. It
contains 65-85% citronellal, 15-20% citronellol, and esters.
Extraction: The oil is produced by steam distillation of the leaves

taken in the digester and steam from a boiler (10 psi) being passed
in the digester.
Uses: The oil of Eucalyptus is strong natural antiseptic that may

be effective against a wide range of bacterial and viral infection. The
oil is largely used as a mosquito and verminlinsect repellent and as
an ingredient of germicidal and disinfecting preparation. The oil is
also used in ore flotation process. The oil is used in perfumery for
scenting soaps, etc.
The oil can be used as a motor fuel. The oil from E. citriodora is
employed as a soap perfumery and as a source of citronella that
inturn, is used in the manufacture of citronellol, hydroxy citronellal,
and menthol. This oil imparts a pleasing odor when added to
germicidal and disinfectant preparations because of its pleasant odor
in small quantities. The oil is known for its aromatherapy uses. The
oil has uplifting and invigorating emotional effects. It stimulates the
brain. The eucalyptus oil is antiseptic and decongestant. The oil has
unique applications in respiratory, circulatory, skin, and muscular
treatments.
GERANIUM LEAVES
(Pelargonium species, Geraniaceae)
Oil of rose geranium 46. 47 commonly known as oil of geranium, is

obtained from the leaves of Pelargonium species (P. graveolens!P.
odoratissimum) cultivated in the Nilgiris and Shevaroy Hills near
Salem (Tamil Nadu). Other countries are Reunion Island, Algeria,
Belgium, Congo, South of France, and some parts of Russia.
Oil Content: The best yield 0.17% is obtained from the distillation
of leaves.
Composition: The principal constituents of the oil are geraniol
(total alcohols about 75%) and geranyl tiglate. The oil from the
Algerian variety contains 30.5% esters calculated as geranyl tiglate
as composed to 43.3% from the Bourbon variety.
Extraction: The oil is obtained by water or steam distillation of

good-quality leaves.
Uses: The oil is mostly used in soap perfumery and in the

perfumery. Geranium oil is consumed in India for flavoring purposes.
Terpeneless geranium oil is a perfume, which is used, in floral
bouquets. Rhodinol and its esters are prepared from this oil. Geranium
oil along with Khus (vetiver) and patchouli oils forms the basis of all
good perfumes.
Geranium oil has a number of aromatherapy uses. It has emotional

uplifting. The oil is useful against stress and alleviates depression
and anxiety. The oil is used in inhalations, vaporizers, baths, and
massage. The oil plays an important role in respiratory cleaning and
calming; fights cold and flu; relieves throat and mouth infections;
used in mouthwashes and gargles. The oil is skin-astringent and a
digestive-tonic. Geranium oil acts as circulatory-astringent, stimulant
and antiseptic.
PATCHOULI LEAVES
(Pogostemon cablin sp.)
Patchouli oi1 4s . 49 is obtained from the leaves of Pogostemon cablin,

Benth.
The plant is cultivated in India, Malaysia, Java, Philippines,

Sumatra, Singapore, Madagasker, Paraguay, Sao Paulo, etc. In India,
plants are cultivated particularly in Western Ghats, districts of
Malabar, South Kanara, some parts of Madhya Pradesh, Assam, and
West Bengal.
Oil Content: The yield of oil is 2.0-3.5% on the basis of dry

leaves.
Composition: Patchouli oil contains components like Patchouli

alcohol (Patchoulol>, cinnamic aldehyde, benzaldehyde, eugenol, an
alcohol, and a ketone. Patchouli oil from some cultivars has been
reported to contain patchouli alcohol (20.77-49.14%) in most of the
oils.
Extraction: Patchouli oil is obtained by direct steam distillation

of the dried patchouli leaves in a number of stills that are connected
to a main boiler in which the steam pressure is raised to about 75
lb per square inch.
Use: Patchouli oil IS one of the finest fixatives known for the
heavy type of perfumes such as amber, chypre, fougere, etc. It is also
used in traces in white rose bouquets. The oil is also largely employed
as the basis of toilet powder perfumes and in the cosmetic industry.
Patchouli oil is a very useful soap perfume. It blends well with
geranium palmorosa, clove, cassia oils, terpineol, etc.
Patchouli oil acts as a bactericide and can help rejuvenate the

skin. The oil is a stimulant, effective against fever, epidemics, and
many other illnesses.
Patchouli oil is an emotional balancing, sensual, and relaxing agent.

It is helpful in freeing the mind from past. It is used in inhalations,
as vaporizers, baths and other applications or massage.
The oil is recommended for many skin conditions, allergies, herpes,

bedsores, burns, cracked skin, haemorrhoids, and eczema.
PEPPERMINT LEAVES
(Mentha piperita Linn. and its varieties)
Peppermint oiI 50 -51 , the most important amongst mint oils, is derived
from the above botanical sources, which are commercially cultivated
on a wide scale in Europe, USA, and Japan. Peppermint in commerce
is also known as black mint (M. piperita var. Vulgaris) and white
mint (M. piperita var. Officinalis). The plant is now indigenous to

India.
Oil Content: The oil yield is from 0.74% to 1.0% of oil (on dry
basis) from the plant of M. piperita. The yield of oil from plants
grown at Jammu and Katra is nearly 2%.
Other important species, which produce mint oil include M.
aruensis Linn., M. pulagium Linn., M. syluestris Linn., and M. uiridis
Linn., all growing in the Kashmir valley. M. arrensis yields 0.45% of
essential oil from the dried leaves and flowering tops. M. syluestris
gives 1.2% oil with minty odor. M. uiridius yields an oil known as
spearmint oil. The oil yield from the freshleaves anf flowering tops
is 0.25%.
Composition: The peppermint oils from all varieties contain
as their chief constituent free I-menthol and also certain
preparations of esters of menthol as acetate and iso-valerate and
valuable amount of l-menthone. The oils from Jammu and Katra
contain 70-80% menthol similar to those of the Japanese and
Brazilian oils.
The oil from M. pulgium Linn. contains 85-96% pulegone which
can be converted to menthone and menthol. This particular plant
needs to be cultivated on a large scale in India. M. syluestris oils
contains 20% carvone.
Extraction: The oil is obtained by steam distillation of the fresh
leaves and flowering tops.
Uses: Peppermint oil is one of the much commonly used essential

oils. It forms an ingredient of tooth pastes, dental creams,
mouthwashes, cough drops, chewing gums, tobacco, etc. as also
confectionary, liqueurs, and medicinal preparations for flavoring.
Peppermint oil has aroma therapy uses. It stimulates and
strengthens emotion and is useful in shock treatment. The oil is
helpful for neuralgia and relief of headaches and migraines and is
antiseptic and antispasmodic. The oil has a number of gynaecological
therapeutic applications.
PETITGRAIN LEAVES
(Citrus aurantium var. Amara)
Petitgrain 52 . 53 is obtained from the leaves and young shoots of citrus

plants, specially of C. aurantium.
Oil Content: The oil yield is about 0.2%.

Composition: Petitgrain oil is composed of geraniol and geranyl
acetate, limonene, linalool, linalyl acetate and sesquiterpene, nerol,
terpineol, furfural, pyrrol, etc.
Extraction: Petitgrain oil is produced by the steam distillation

process of the leaves and twigs of Citrus aurantia.
The oil is a pale yellow liquid with a fresh, bittersweet scent
simulating that of neroli. Its odor effect is refreshing and uplifting.
Uses: Petitgrain oil has aromatherapy uses. It is helpful to

maintain oily skin condition, nervous exhaustion, and stress-related
disorders.
The oil is used as perfume for skin creams and also in eau-de-
cologne especially of fancy types. The oil is used for perfuming soaps.
ROSEMARY OIL
(Rosmarinus officinalis L. N.O. Labiatae)
Rosemary oil 54 . 55 is obtained from the flowering tops or from the

leaves of Rosemarinus officinalis L. It is indigenous to the
Mediterranean region in the southern parts of Europe and in North
Africa.
Oil Content: The oil yield is 0.38-0.5% of the leaves. The leaves
may yield about 1-2.5% essential oil.
Composition: Rosemary oil contains Cineole 30-46.6%, Borneol

16-20%, and a-Pinene max. 25% as the principal constituents. The
oil also contains camphor 15-25% and camphene, and 7% bornyl
acetate.
Extraction: Rosemary oil is produced by steam distillation of

either the flower tops or the leaves or both.
Uses: Rosemary oil has a slightly camphoraceous, warm, and

pungent aroma. Rosemary oil is used in cheap perfumery hair washes
and soaps. English and French oils are employed for blending in eau-
de-cologne. In soap perfumery, rosemary oil will blend with lavender
to produce a cheap and refreshing odor. Rosemary blends well with
basil, thyme, cedarwood, spices, like nutmeg or cardamom and many
more. Rosemary oil has aroma therapy uses. It stimulates the memory.
It is marked for its strongly antiseptic and stimulating actions. It is
also a gentle analgesic. The oil has circulatory effects, helping in low
blood pressure, improve circulation, and reduce lymphatic congestion,

etc. The oil has gynaecological applications.
Rosemary oil has antioxidant activity that is higher or comparable

to that of a-tocopherol at the highest concentration.
SPEARMINT OIL
(Mentha viridis L., Labiatae)
Spearmint56 oil is obtained from the fresh flowering spearmint, grown

in Europe and USA, and also in India.
Oil Content: The fresh leaves and flowering tops of plants growing
in KashmirlU.P. yield a pale yellow oil (0.25%).
Composition: Spearmint oil from UK or USA consists principally
of carvone about 60%, phellandrene, limonene 2-25%, and either
dihydrocarveol acetate or dihydrocuminic acetate. Indian spearmint
oil contains 20% carvone and spearmint oil from one source, however,
does not contain carvone. The cineole content of the oil varies from
31-34.6%.
Extraction: Spearmint oil is produced by steam distillation of the
fresh leaves and flowering tops of the plants.
Uses: Spearmint oil is an excellent flavoring agent III dental
preparations and in chewing gum.
TEA TREE LEAF

(Melaleuca alternifolia, Myrtaceae)
Tea Tree 57-58 oil is obtained from the leaves of M. alternifolia tree
leaves, native to Australia.
Oil Content: The oil content is from 1.5% to 2% by weight of the
leaves.
Oil Composition: The tea tree leaf oil (M. alternifolia) contains
pinene 1-6%, a-terpinene 5-13.0%, p-cymene 0.5-2.0% terpineol 1.5-
8.0%, and cineole 15% terpinen-4-ol 30.0% minimum, y-terpinene 10-
28.0%, limonene 0.5-4.0%, and sabinene <3.5%.
Extraction: The oils are recovered by steam distillation of the

leaves of the two varieties of the tea tree trees.
Uses: Tea tree oil can be blended with lavender, bergamot, etc.,
to make an excellent spray in halls and auditoriums.
The oil has high germicidal value and it is, therefore, used in
medicated soaps and dentrifies.
The oil has remarkable contraceptive properties. It is very powerful

antiseptic, being 12 times as strong as carbolic acid (phenol) and
effective against a range of bacterial, viral, and fungal conditions.
The oil fights cold and flu, alleviates sore throats, tonsillitis, and
gum disease. The oil eases bronchitis, chesty coughs, and congestion.
The oil has skin applications in cleansing, cooling, and anti-fungal

actions. It relieves boils and rashes. The oil is bactericidal, anti-
viral, and anti-fungal. It calms diarrhoea and relieves gastroenteritis.
The oil has also gynaecological applications.
WINTER GREEN LEAF

(Gaultheria procumbens, Ericaceae)
Wintergreen 59 oil is obtained from the leaves of G. procumbens L.,

plant native to Canada and USA.
Indian winter green, G. fragrantissima wall, grows freely in the

Nilgiris and particularly in Assam.
Oil Content: The winter green leaf contains 0.7-1.0% oil.

Composition: Methyl salicylate is the main constituent of the oil
of winter green. It amounts to 90-99%.
Extraction: The oil is obtained by steam distillation of the leaves

of evergreen flowering shrub after maceration for 24 hours in hot
water in order to produce the fermentation, which releases the
essential oils.
Uses: Winter green oil has camphoraceous smell with a note of

vanillin.
The oil has aroma therapy uses like antiseptic, diuretic, stimulant,
and antirheumetic cases.
BARK, SEED, SEED FRUIT, HERB, AND RHIZOME

AS SOURCES OF ESSENTIAL OIL
Bark, seed, seed fruit, and herb from some trees and plants yield
essential oils of commerce. Some of the important source materials,
and their essential oil characteristics, uses, etc., are included.
BARK SOURCE
CINNAMON BARK
(Cinnamomum zeylanicum Brien, Lauraceae)
The bark of the tree Cinnamomum zeylanicum 60 , Breyn, yields

Cinnamon oil of commerce. The tree is cultivated in Sri Lanka,
India, and Madagascar.
Oil Content: Generally, cinnamon bark yields from 0.5% to 1.0%

of a pale-to-dark yellow oil.
Composition: Cinnamic aldehyde (60-70%) is the major constituent

of the oil. The oil also contains eugenol (4-10%). Other minor
components include cymene, linalool, pinene, phellandrene, etc.
Extraction: The oil is obtained by the steam distillation of the

bark chips from the small tree.
Uses: Used as a spice oil, widely used as a flavor in dental

preparations, and in small quantities in certain types of carnation.
The oil has aromatherapic uses. It can be used in the vaporizer

as an antidepressant room scent, as an antibiotic, and antiviral
fumigant during infectious illness.
CARDAMOM POD
(ZingiberaceaeISaitaminae, Elettaria cardamomum, Maton)
The oil is obtained from the whole fruit (the ripe pod) of Elettaria
cardamomum, Maton61 ,62 a bush which grows in the Western Ghats,
Kerala, Mysore, and Tamilnadu. Apart from India, countries like Sri
Lanka, Tanzania, Papua New Guinea, Costa Rica, El Salvador, and
Guatemala also produce cardamom.
Oil Content: The seeds yield about 2-5% of essential oil. The oil
content of Indian cardamom is higher than that of Ceylon cardamom.
Composition: The principal constituents are 1,8-cineole and
terpineol, a-terpenyl acetate, with a little limoneneor myrcene and
linalool.
Extraction: Cardamom oil is obtained by steam distillation of the
dried ripe fruit (Pod). The oil can also be extracted by the solvent
free microwave extraction of cardamom seed, although the cardamom
seeds may be destroyed.
Uses: The oil is used for flavoring curries, cakes, bread, liqueours,
and other culinary purposes. Cardamom oil is usually olfactory desired
as a sweet, spicy, warm, lightly camphorated, and citrusy.
The oil has uses in aroma therapy in digestive disturbances,

chemical fatigue, nervous/exhaustion, stimulating, etc. In traces, the
oil gives a note characteristic to eau-de-cologne, jasmine, and chipry
perfumes. It is also a useful component of the lily of the valley
perfumes.
Cardamom oil seems to have antibacterial, antiseptic, carminative,

and antispasmodic effects. The oil is insect repellent.
DAVANA HERB
(Artemisia pallens Wall.)
Davana 63 ,64 is an Indian essential oil plant and its oil is obtained
from the herb. The plant is cultivated in the neighborhood of Pune.
Due to the improvement of the agronomic practices of the plant, per
hectare yield of oil has increased 5-6 kg in place of 1 kg, and two
crops can be obtained in a year instead of only one crop. There are
other varieties of Artemisia in India.
Oil Content: The oil from the herb is 0.1-0.3% only.

Composition: The major constituent of davana oil is a
sesquiterpene ketone, davanone 30-65%, but it is practically odorless
and acts as natural fixative and synergist. The odoriferous constituents
of the oil are reported to be davana ether 1.5%, davana furans 1.0%,
and hydroxy dihydrosefuran. N erol and geraniol are minor
constituents. Methyl and ethyl cinnamates and geranyl acetate also
occur in davana oil.
Extraction: The oil is obtained by steam distillation of the herb.

Uses: The essential oil is used mainly as a food flavor and as a
constituent of high-grade perfumes. The oil is valued for its exquisite
and delicate aroma. It is used in expensive perfumes.
GINGER
(Zingiber officinale Roscoe, Scitaminae N.O.)
Ginger oi1 65 is obtained from the root (rhizomes) of the plant native
to India, China, Srilanka, Jamaica, and other parts of Southern Africa
and Japan.
Oil Content: Ginger contains from 1% to 3% of volatile oil of

light yellow color. About 55 tonnes of ginger oil is produced annually.
Composition: The main constituent of ginger oil is the

sesquiterpene hydrocarbons (50-60%). Zingiberene accounting for
about 30% and others are camphene, phellandrene, isoborneol, and
linalool. In all, more than 110 different compounds have been
isolated and identified in ginger oil. Citral levels are normally up to
4% but may be much higher than this in ginger oil. Citral levels
are normally 0.5-4% but may be much higher than this in some
Australian oils.
Extraction: Ginger oil is produced commercially by steam

distillation of the unpeeled, dried, and ground root (rhizomes) of the
plant Zingiber officinale Rose. Some oil is also extracted by liquid
CO 2 •
Uses: Ginger oils differ significantly in organoleptic character
depending source and method of extraction. Ginger oil is used for
flavoring confectionery and condiments. The oil has aromatherapic
uses. It relieves arthritis, muscular aches and pains, rheumatism,
catarrh, coughs, sore throats, nausea, travel sickness, colds and flu,
nervous exhaustion, and debility.
The oil is pale yellow or amber liquid with a warm, peppery-spicy

scent. Its odor effect is warming and stimulating. Differences in odor
profile appear to be more due to relative compositional differences
than to the presence of specific components.
TURMERIC RHIZOMES
(Curcuma longa L., Zingiberaceae)
Turmeric 66 oil is obtained from the dried rhizomes of Curcuma longa

L. It is a major cultivated material in India, China, and other tropical
countries.
Oil Content: The yield of the oil IS 3-5% of turmeric oleoresin

extracted from turmeric rhizomes.
Composition: Turmeric oil mainly contains a ketone turmerone

of a mixture of sesquiterpene ketones (40-60%) of turmeric oil. It
also contains phellandrene.
Extraction: Turmeric oil is obtained by solvent extraction (with
petroleum ether) of the dried rhizomes. It is also extracted through
hydrosteam distillation of fresh rhizomes.
Uses: The essential oils show marked antimicrobial activity against

gram-negative and gram-positive organisms. The essential oils exhibit
fungistatic activity. Curcuma oil is an effective mosquito repellent.
In fact, the oil exhibits a wide range of biological activities, e.g.,
antibacterial, anti-inflammatory, hypolipidemic, hepatoprotective,
lipoxygenase, cycloxygenase, and protease inhibitory effects. It is
effective against oxygen species scavengers and lipid peroxidase
inhibitors, lowers cholesterol, platelet aggregation is reduced, inhibits
proliferation of cancer cells and improve digestion by increasing the
flow of bile from the gallbladder.
SEED SOURCE
AJOWAN SEED
(Trachyspermum ammi (Linn.) Sprague
syn. Carum copticum Benth & Hook.f.)
Ajowan seed 67 fruit grows in many parts of India.

Oil Content: Ajowan seeds yield 2-4% of oil, the average being
about 2.5%.
Composition: Ajowan oil contains 35-60% thymol, the rest being
thymene, which is a mixture of p-cymene, a-pinene, dipentine, y-
terpenene, etc.
Extraction: The oil is produced by steam distillation of crushed
ajowan seeds.
Uses: The oil is used in small quantity for perfuming disinfectant
soaps and as an insecticide.
ANISEED
(ANI SE Pimpinella anisum, Umbelliferae)
The essential oil 68 is obtained from the seed fruits of a tender annual
plant from orient also known as sweet cumin. The seed is mainly
cultivated in Russia.
Oil Content: The average yield of oil is from 2% to 3.5%.
Composition: The aniseed oil contains 80-90% anethole with
little aldehyde, anisic acid, methyl chavicol, cineole, safrole, terpineol,
pinene, phellandrane, dipentene, l-limonene as the constituents.
Extraction: The oil is produced by steam distillation of crushed
aniseed.
Uses: Aniseed oil is a popular flavor for dental preparations;

especially if carefully blended with peppermint. The oil has
aromatherapic use acting as digestive.
CARAWAY SEED
(Carum carvi L., Umbelliferae) oil
Caraway oi1 69 is obtained from the above variety of seed. The seed
grows mostly in Europe and Northern Africa.
Oil Content: Caraway seed can yield 4-6.5% of oil.

Composition: The oil consists of 50-60% carvone and also contains
carvacol, carvene, and limonene.
Extraction: The oil is produced by steam distillation of the crushed

seed from the herb.
Uses: The oil has application in toilet soap manufacture. Caraway

oil is a mild antiseptic. It is excellent for digestive problems like
flatulence, pain, dyspepsia, colic and colitis.
CARROT SEED
(Daucus carota, Umbelliferae)
Carrot seeds act as a source of essential oil.
Oil Content: Carrot seeds yield 1-1.5% of volatile oil.

Composition: Carrot seed oil contains acetic acid, aliphatic
aldehyde arotal, cineol, ~-carotene, formic acid, limonene, pinene,
and terpineol.
Extraction: Carrot seed oil is extracted by expression process.

Uses: Carrot oil is good for skin.
CORIANDER SEED
(Coriandrum sativum L., Umbelliferae)
Coriander seed 70 ,71 is cultivated in India, Russia, Cyprus and Morocco,

German and Northern Africa.
Oil Content: The coriander seed contains 0.2-1% of oil. The

seeds of German and Russian origin yield about 1% of essential
oil.
Composition: Coriander seed oil of German and Russian OrIgm

consists principally of linalool (up to 90%). The oil also contains
components like geraniol and I-borneol with their acetate esters, n-
Cw-aldehyde, and terpenes like dipentene, cymene, terpinene and
pinene. Phellandrene is also present. The alcohol component has
been named as coriandrol (60-65%) also.
Extraction: Coriander seed oil is obtained by steam distillation.

Uses: Coriander seed oil is used as a flavoring agent in medicine
and also in the Cocoa and chocolate industry. The oil finds limited
use in fine perfumery being used as a substitute for linalool where
a more flowery first note is desired as in lily. The oil is also used for
special effects in cologne when traces only are necessary.
The oil has aromatherapic uses in curing arthritis, muscular ache

and pains, digestive problems, colds and flu, mental fatigue, and
nervous exhaustion.
CUMIN SEED OIL

(Cuminum cyminum, Umbelliferae)
Cumin seed 72 is available from a plant cultivated in Arabia, India,

and China, the chief supplies being from Morocco, Malta, and Iran.
In fact, Iran is the main supplier of cumin seed oil, while India is
only a minor producer.
Oil Content: Cumin seed yields on average between 3% and 4%

of oil.
Composition: The main odorous constituent of the cumin oil is

cumic aldehyde between 30% and 40%. It contains cymene.
Extraction: The oil is obtained by the steam distillation of the

crushed cumin seeds.
Uses: The oil can be used in trace quantity in making synthetic

cassie and may replace cuminic aldehyde. The oil may relieve
dyspepsia, diarrhoea, and hiccups. India has enough opportunity to
compete in the market for the cumin seed oil.
DILL SEED
(Anethum graveolens L. Umbelliferae)
Dill oiF3-74 is obtained from the seeds and also herb of the plant,
which is found through out India (tropical and south tropical) and
cultivated as a source of essential oil. Dill seeds grow in Kashmir

during summer and as winter crop in Jammu.
Oil Content: The dill herb yields 0.62% of volatile oil while the
dill seed yields 1.3-3.5% oil.
Composition: The oil from the seed contains D-limonene, 9%; D-
carvone, 46.5%; and dill-apiol, 39.6%, and traces of anethol, anisic
aldehyde, eugenol, and thymol.
The oil from the herb contains 12-15% carvone.
Extraction: The dill oil is recovered by steam distillation of the

seeds of the plant.
Uses: The oil is used for flavoring purposes and the herb oil due
to much less carvone content is preferred. In fact, the low carvone
containing dill oils have the finest and highly pronounced herb odor.
The oil is used for flavoring soaps, sauces etc.
The oil has aromatherapic uses. Dill seed oil is used in babies
gripe water. It helps the flow of bile, thus aiding digestion, and is
useful for cattarhal conditions like bronchitis.
MUNG-BEAN SEED AROMA

(Vigna radiata)
Mung bean (seed)75 is of considerable commercial interest in India.

Certain strains of unusually good aroma-bearing mung bean (Sona
cultivar) are famous in West Bengal (Malda, Lalgola, and Ranaghat).
The most pleasant aroma is desired from that of Malda and Lalgola
samples.
Oil Content: The oil content has not been reported so far
presumably because the real aroma generates during its frying or
boiling.
Composition: Brahmacharya and Ghosh have identified for the
first time the molecules, which impart a most desirable and
characteristic aroma to certain varieties of mung bean of Bengal -
a valuable indigenous natural product.
In boiled, or fried mung bean of the two best strains, strong
evidence for the presence of 2-acetyl-1-pyroline, the molecule
responsible for the aroma of Basmati rice and one component of
tiger pheromone, has been obtained by GLC and GC-MS studies.
Extraction: The extraction of mung bean (seed) aroma involves

boiling of fried, or non-fried mung seed is followed by collection of
steam distillate and this is shaken with ether, hexane, and carbon
tetrachloride to extract aroma components in these solvents. In
preliminary experiments CC1 4 appear to be advantageous.
NUTMEG SEED
(Myristic a officinalis or fragrans Houtt., Myristicaceae)
Nutmeg 76 is the aromatic Kernel of the fruit of Myristica fragrans,

found extensively in Indonesia and in limited quantity in the Kerala
state. The mace or aril, covering the fruit, is also a source of aromatic
(essential) oil.
Oil Content: The essential oil content of nutmeg Kernel vanes

from 7% and 16%, while that of mace, from 4% to 15%.
Composition: The oils contain myristicine with small quantities

of borneol, camphene, cymol, dipentene, geraniol, linalool, pinene,
safrole and terpineol, and acetic, butyric, caprylic, and myristic acids.
Extraction: The nutmegs or Kernels are first pressed to extract
the fat part (25-30%) and the defatted material is steam distilled to
recover the essential oil.
Uses: Oil of nutmeg is used in certain types of perfumes and
flavoring denitrifies and as a soap perfume. The oil has distinct
aromatherapic uses. It acts as a digestive, stimulating agent. Nutmeg
is a tonic, good for the heart, and for convalescence.
VALERIAN ROOT
(Valeriana officinalis L.!V. wallichii D.C., Valerianaceae)
Valeriana officinalis L.77, grows wild, and is cultivated in Northern

Europe and Asia. The Valeriana wallichii D.C., root grows in India.
Oil Content: About 0.5-2.4% of oil is obtained from the fresh
roots.
Composition: The valerian oil contains isovaleric acid/valeric
acid, formic and acetic acids. It also has borneol and a terpene,
C lO H 16 • The constituent responsible for the aroma is the bornyl-
isovalerate.
Extraction: The oil is extracted by steam distillation of the fresh

well dried roots.
Uses: The oil is known for its aromatherapy uses. It is used for
calming effect on the nervous system.
CEDAR-WOOD
(Juniperus species; Juniperus virginiana, Coniferae)
Cedar-wood oiF8 is obtained from the wood of various species of

Juniperus, particularly Juniperus uirginiana. The wood is available
mainly from North American tree, although Morocco, Lebanon, Syria,
Turkey, Cyprus, and India have cedar.
Oil Content: The oil content occurs to the extent of 2-4%.
Composition: Terpene hydrocarbons, a little cedrol and cadinene,
a sesquiterpene comprises the cedar-wood oil.
Extraction: Cedar-wood oil is produced from the wood parts by

steam distillation.
Uses: Cedar-wood oil is a colorless, or slightly yellow, viscid liquid
with a characteristic Cedar-like odor. The oil has a top note and
pleasant fragrance characteristics.
Cedar-wood oil is used as a perfume in the soap industry. The oil

finds uses in violet perfumes.
Cedar-wood oil has therapeutic actions. The oil is very effective
for skin problems like eczema, rashes, and skin eruptions. Cedar-
wood oil has therapeutic action for hair and scalpy problems like
alopecia falling hair and dandruff.
CLOVE
(Eugenia caryophyllata, Myrtaceae)
The clove tree (Eugenia caryophyllata, Thunberg)79 is a source of an

important essential oil known as the clove oil.
Clove tree grows mostly in Zanzibar and Indonesia. They also are
cultivated in India particularly in Kerala state.
Oil Content: Clove oil is obtained from the matured crimson
colored unopened flower buds. Cloves contain from 16% to 19% of
the volatile oil.
Composition: Clove oil extracted from whole buds contains 85-
97% eugenol. The oil also contains components like acet-eugenol,
benzyl alcohol, methyl salicylate, a-methyl furfurol, a-dimethyl
furfurol, furfuralcohol, methyl-n-amyl carbinol, terpene caryophyllene,

methyl-n-heptyl alcohol.
Extraction: Clove oil is produced from the crimson red unopened

buds by distillation either in water or with steam. The water-distilled
oil is of lower specific gravity and contains a smaller proportion of
eugenol (84-88%). The oil obtained with steam is of slightly higher
eugenol content (88-92%) and higher specific gravity.
Uses: Clove oil is used in soap and other perfumery in confectionery
and in medicine. Because of its flavor and disinfectant properties,
clove oil is much used in dental preparations such as toothpastes and
mouth washes.
Clove oil has aromatherapic uses. It can be used as a fumigant

during infectious illness. It is used as a first-aid mean for
toothache.
SANDAL WOOD
(Santalum album Linn., Santalaceae)
Sandalwood oi1 80 ,81 is obtained from the roots and heartwood of

Santalum album Linn. tree of the highland forests of Mysore, Coorg,
Madras, and Bombay. Indian production of sandalwood oil is of the
order of 60 tonnes/annum. Australian sandalwood (S. spicatum) is
also well known; the two species differ in the concentrations of
constituent chemicals, and, thus, in odor. West Indian sandalwood
(Amyris balsamifera) is neither Indian nor in the sandalwood family.
It is in the rue family.
Oil Content: The yield of oil varies from 3% to 6%. In Mysore

the yield varies between 4% and 6%, while in the Dutch Indies it
varies from 3% to 5%.
Composition: Sandalwood oil contains over 90% of Santalols (both

a-and ~-). It is a complex oil having over 90 chemical entities. At
least 50 components have been identified. The minor components
represent the hydrocarbons, alcohols, aldehydes, ketones, acids,
phenols, and heterocycles.
Extraction: Sandalwood oil is obtained by steam distillation of

the heartwood and roots containing the oil. Water distillation of
Sandal wood oil is also practised.
Uses: Sandalwood oil is valued in perfumery for its sweet, warm,

precious-wood fragrance of great tenacity.
Sandalwood oil is used in soap and hair oil perfumery. It has

excellent fixative properties and is used as one of the most important
constituents of perfumery.
The oil acts as a good blending agent with heliotropin, coumarin,

vetivert, and musk ambrette. It is used as base, in the traditional
attars of India.
Sandalwood oil has aromatherapy uses. Sandalwood oil is calming

and soothing in effect. It has sedative and relaxing effects. It is
beneficial for relieving anxiety, tension and lifting depression. The
oil is used in bronchitis inhalations, vaporizers, baths, application or
massage.
TURPENTINE
(Pin us varieties, Coniferae)
Turpentine oi1 82 is obtained from the oleoresin, an exudate obtained

by wounding trees, of various conifers by distillation. The oleoresin
contains 14-20% of oil.
The principal source of Indian turpentine oil is Pinus longifolia

Roxb., syn. Pinus roxburghii Sargent (Chir pine), is important
Himalayan conifer.
Oil Content: The oil obtained from the oleoresin, an exudate

obtained by wounding various conifer trees, varies from 14% to 20%.
Composition: The compostion of turpentine oil varies depending

on the species of pine trees. The compostion of Indian oil is different
from that of American oil, but resembles that of Russian oil in Carene
content.
The turpentine oil is mostly composed of terpenes, chiefly the
pinenes. The chief is a-pinene (formerly australene) although \3-pinene
occurs in varying proportions.
The Indian turpentine oil contains a- and \3-pinene, (8-30%), \3-

and ~3-carene, 37.6-60.0%, and longifolene, 5-20.3%.
It is claimed that ~3-carene is responsible for the poor-keeping

quality of the oil.
Extraction: Turpentine oil is obtained by steam distillation of

the oleoresin or by direct fire in a large copper still. A mixed method
of direct heat followed by injection of steam and water is also adopted.
The distillation can be done by steam in steam-jacketed vessels.
The distillation of the oleo-resin in vacuo and in oil-heated stills

in also practised.
Uses: Turpentine oil is an extremely important material for

preparing synthetics like a-terpineol, camphor, borneol, p-cymene,
dipentene, etc. Menthol and thymol can be made from carenes present
in turpentine oil. Indian turpentine is used in the manufacture of
varnishes, lacquers, disinfectants, and paints.
Turpentine oil is used as a source of longifolene.
ESSENTIAL OILS FROM FRUITS
Flavors derived from fruits are unique in character and can be

important for both flavor and fragrance industries although limited
in number. In India, tropical fruit extracts can be very important for
both flavor and fragrance industries. India does not appear to produce
any citrus oils although there is enough potential. Essential oils of
citrus fruit, flower and leaf are important to industry. Some citrus
fruit sources are described below.
CITRUS OILS
Many citrus materials (fruits) act as a source of some well-known

essential oils more popularly known as citrus oils. The some well
known citrus oils are bergamot, lemon, and lime, derived from peels;
neroli oils from the flower of sweet and bitter oranges; and various
petitgrain oils from the leaves and twigs of citrus plants.
BERGAMOT
(Citrus bergamia, Rutaceae)
Bergamot oi1 83 is obtained from the fresh peel of Citrus bergamia

(Risso) fruits (Bergamot orange).
Oil Content: The yield of oil is nearly 0.5% on the weight of

fruits.
Composition: The oil contains up to 50% linalyl acetate,

bergamotine, bergaptene, d-limonene, and linalool.
Extraction: The oil is obtained by expression of the rind of the
small orange like fruit.
Uses: Bergamot oil contains chlorophyll, and has a green to
greenish brown color, and a very pleasant odor. The oil has a light
green essence with a citrus aroma with a hint of spice. The oil is
refreshing and uplifting to the emotions. The oil is used in cold and
flu, fever, infectious illness, anxiety, and depression.
Bergamot oil is used to a very large extent in perfumery. Bergamot

oil from the peels of bergamot orange is used in the manufacture of
Eau-de-cologne and Lavender water. It is also used far scenting toilet
soaps and in mixed perfumes.
FENNEL SWEET FRUIT

(Foeniculum vulgare Mill., Umbelliferae)
Oil of fenne1 84 is obtained from the fruit of Foeniculum vulgare Mill.,

cultivated in India and Japan. Musk of the oil is produced in many
parts of Europe (Hungary, Bulgaria, Germany, France, Italy, and
Greece).
Oil Content: The oil content is around 4-5%.

Composition: The oil contains chiefly anethole (60-90%). The
other constituents are fenchone (contributing camphoraceous odor),
pinene, dipentene and camphene.
Extraction: The oil of fennel is produced by the steam distillation.
Uses: The oil finds use in soaps. The aromatherapic uses of the
oil include bruises, fluid retention, loss of appetite, flatulence, and
menopausal problems.
JUNIPER BERRY
(Juniperus communis, Coniferae)
Juniper oi1 85 is obtained from the ripe berries of Juniperus communis,

which is native to India (Northwards from the Himalayas), North
America, and Europe (Hungary, Italy, Russia, and Sweeden).
Oil Content: The yield of oil varies from 0.2-2% depending on

the source and the extraction process.
Composition: Pinene and cadinene are the principal constituents

of the oil. Terpineol also occurs in the oil. The principal components
are reported as about 69% monoterpene hydrocarbons with about
10% of sesquiterpenes. The oxygenated constituents are terpene 4-
01 (9.6%) together with some a-terpeneol, bornyl acetate, and a-
cadinol.
Extraction: Essential oil of Juniper Berry is produced by the

process of steam distillation or by CO 2 extraction. The CO 2 extraction
process yields more oil (2%).
Uses: Juniper berry oil is known for its aromatherapic uses.
The oil has antiseptic and diuretic properties. The oil has calming
and tonic effects, quite helpful in overcoming anxiety, insomnia, and
mental fatigue. The oil has applications in relieving indigestion,
flatulence, and diarrhoea. It is beneficial for skin particularly oily
skin, dandraf and eczema.
Juniper Berry oil is stimulant and leftful to lower blood pressure

muscular ache and pains and rheumatism. The oil has gynaecological
in irregular or painful menstruation.
Juniper Berry oil has application opportunities in toiletries and
various fine perfumes and colognes giving a clean, sweetly woody
nuance.
The oil is used as a soluble essence in the flavoring of alcoholic
beverages, particularly gin.
LEMON FRUIT
(Citrus medica L.)
Lemon oil 86 ,87 is obtained from the peel of the nearly ripe fruit of
Citrus medica L. var. l3-limonum, Hooker filius, a small tree of the
Rutaceae family. The fruit is cultivated in India and in almost all
countries.
Oil Content: The oil yield is 0.4-0.5%.
Composition: Citral is the main aldehyde component of lemon

oil (4-6%). The remainder of the oil constitutes d-limonene, traces
aldehydes (CS & C9), citronellal, methyl heptenone, phellandrene,
terpineol, linalyl, and geranyl acetates, etc.
The terpeneless oil contains about 50% of citral and about 20% of
esters in genuine oils.
Extraction: Lemon oil of pleasant odour is obtained by expressing

the peel of the nearly ripe fruit of Citrus medica L. (var. l3-limonum)
Uses: Lemon oil is widely used in toilet soaps and hand lotion
(liquid) soaps. Lemon oil blends well with benzyl acetate, palmarosa,
clove, and geranium oils and is much used along with citronella and
lemongrass oils as a verbena perfume. Lemon oil is used in Italy as

a substitute for oil of turpentine.
The oil has therapeutic values as digestive, as a blood cleanser

and as helping sweeten the breath after a heavy meal. It is a tonic,
stimulant, carminative, and diuretic.
LIME FRUIT
(Citrus aurantifolia, Christmas)
Lime oil 88 is obtained from the fresh rinds of the fruit of Citrus
aurantifolia (Christmas). Plants cultivated in many parts of India
(Madras, Bombay, Bengal, Punjab, and Mysore). Lime oils are also
produced in USA (Florida), Cuba, Mexico, and Italy.
Oil Content: The oil content is on average 0.3% of the fruits.

Composition: The oil contains d-limonene, linalyl acetate,
linalool, phellandrene, citral (chief aldehyde), a sesquiterpene as
bisabolene (limene)
Extraction: Lime oils of commerce are produced by expression of

the peels of the unripe fruits. Also oils are produced by steam
distillation.
Lime oils are a pale yellow or green liquid with a fresh, citrus
aroma.
Uses: The aroma of the expressed distilled lime oil is used in soap
and disinfectant industries. It is now largely used as a flavoring
agent. The odor effect is uplifting and refreshing.
The oils have aromatherapic uses in respiratory disorders, colds

and flu, and depression.
MANDARIN OIL
(Citrus reticulata, Blanco)
Mandarin or Tangerine oi1 89 ,9o is obtained from the peels of the fruit
Citrus reticulata, Blanco found mostly cultivated in India and China,
and in European countries like Italy, Spain, Cyprus, and Greece.
Oil Content: The yield of oil is about 400 from 1000 fruits.
Composition: The oil contains methyl anthranilate, limonene,
geraniol, terpen aldehydes.
Extraction: The oil is produced by the expression process of the

peel of the fruit.
The odor of Mandarin oil is sweet and citrus resembles sweet

orange oil.
Uses: Its odor effect is soothing and uplifting. The oil is used in
eau-de-cologne preparations.
The oil has aromatherapic uses in controlling stretch marks, fluid

retention, digestive problems, insomnia, nervous, tension.
ORANGE FRUIT AS SOURCE OF ESSENTIAL OIL
ORANGE OILS
Orange oil (sweet)91,92 is obtained principally from the peels of Citrus

sinensis (Linn.). Osbeck fruit cultivated in the Indian subcontinent
and Far East.
Oil Content: The yield of oil is around 0.4% of the peels.
Composition: The oil contains up to 90% monoterpene

hydrocarbons with limonene as the most major component. It contains
aldehyde citral, citronellol, nerol, geraniol, linalool, methyl
anthranilate, nonyl alcohol and terpineol, decanal, etc.
Extraction: The oil is normally produced by expression, or by

hydro-diffusion of the fresh ripe peel of the fruit. A combination of
microwave heating and distillation at atmospheric pressure without
any water can be tried.
The oil is pale yellow liquid with a warm, sweet citrus scent.
Uses: It is used in perfumes and flavoring extracts and as a drug.

The oil is also used in preparation of eau-de-cologne.
The oil has aromatherapic uses in palpitations, respiratory

ailments, colds and flu, nervous, tension, stress and depression.
Orange oil from bitter orange (Citrus aurantium Linn.) is

indigenous to India (Guntur of Andhra Pradesh).
The bitter oil is different from that obtained from sweet orange.
It has a fine and piercing odor.
Bergamot orange (C. aurantium var. bergamia) a form of sour

orange is used in the manufacture of eau-de-cologne and lavender
water. It is also used for scenting toilet soaps and in mixed perfumes.
Bergamot oil is a powerful germicidal agent.
Other important varieties of Citrus grown in India are C. limon

(Linn.) Burm.f., C. media Linn., and C. paradise Mac.
PEPPER FRUIT
(Piper nigrum L., Piperaceae)
Pepper oi1 93 •94 is obtained from the unripe pepper fruit of Piper nigrum
L. Most of the oil is produced in India. It is also produced in Europe
and the USA from imported materials. Black pepper is the usual
article of commerce.
Oil Content: The yield of pepper oil is 1-3%.
Composition: Pepper oil contains phellandrene, camphene,

dipentene and caryophyllene, limonene, myrcene, bisabolene,
sabinene, linalool, pinocarveol, a-terpineol.
Extraction: The oil is produced by steam distillation of the grown

black pepper. The oil can also the obtained by solvent extraction.
Uses: Pepper oil is pale, slightly greenish liquid with the

characteristic odor of pepper, reminiscent of phellandrene. The smell
is stimulating and charming.
It is used in the flavoring of sausages, soup, canned meats, table

sauces and certain beverages and liquors. The oil is used in perfumery,
particularly in bouquets of the oriental type imparting spicy notes.
The pepper oil has aromatherapic uses. It is helpful in muscular

aches and pains, loss of appetite, nausea, colds and flu, lethargy,
mental fatigue, etc.
TROPICAL FRUITS
Tropical fruit extracts can be very important for both flavor and
fragrance industries in India. Some of the more interesting
possibilities include mango, jackfruit, and pineapple, etc. Other
important varieties of Citrus grown in India are C. limon (Linn.)
Burm.f., C. media Linn., and C. paradisi Mac.
MANGO FRUIT AROMATIC OIUAROMA

(Mangifera indica L.)
Mango fruit 95 · 96 is known as one of the most popular tropical fruits

due to its delicious flavor (aroma). Several hundred cultivars of
mango fruits are known that differ greatly in their flavor
characteristics. India is one of the largest produces of mango fruits
in the world.
Oil Content: The total concentration of volatiles has been reported

to be 18-123 mglkg of fresh fruit, depending on cultivars and maturity
stage of the fruit.
Composition: Mango aroma compositions from ripe fruits have

been studied in many cultivars. Nearly 300 compounds have been
identified in mangoes. Pino et al. and Pino and Mesa have made
significant contribution in this area. Monoterpene and sesquiterpene
hydrocarbons have been reported as the most aboundant mango
volatiles. Certain esters and lactones also occur and contribute to
the flavor of certain cultivars. Lactones such as y-octalactone and y-
decalactone make a contribution to mango aroma. Among the
carnonyls, (E)-2-hexenal and hexanal have been reported in mango
aroma. a-pinene, 8-3-carene, Limonene, a-phellandrene, myrcene, p-
cymene, and terpinolene, occur and contribute to the odor of some
mango cultivars.
Esters that contribute to aroma have been reported in the aroma

from many cultivars as ethyl 2-methyl propanoate, ethyl butanoate,
methyl benzoate, and methyl anthranilate depending on the cultivars.
These esters are responsible for the fruity character in mango. In
addition, (E)-j3-ionone, decanal and 2,5-dimethyl-4-methoxy-3(2H)-
furanone also occur in mango aroma.
Extraction: Mango aroma can be extracted by steam distillation

of the mesocarp (fleshy art) portion of the fully ripened mango fruits
after removing the top skin cover and separating the mesocarp by a
suitably designed stripper. The aroma isolation can be also made by
solvent extraction, simultaneous distillation extraction and solid-phase
extraction.
Uses: Mango aroma finds use in ice cream and milk products like
pudding and confectioneries. It is used in soft drink to impart mango
aroma.
PINEAPPLE FRUIT AROMATIC OIUAROMA

[Ananas comosus (L.) Merr.]
Pineapple fruits 97 an important tropical fruit principally grow in

countries like India and the subcontinent, the Philippines, Thailand,
Malaysia, Hawaii and other tropical belts.
Composition: The analysis of fresh pineapple fruit volatiles by
HRGC-MS methodology has revealed more than 130 constituents.
Several methyl esters and some characteristic sulfur-containing
esters, various hydroxy esters and their corresponding acetoxyesters
as well as a number of lactones being responsible for the typical
pineapple flavor profile have been reported. The pineapple cultivars
show considerable variations in their amounts of volatiles. Methyl-
2-methyl butanoate, methyl 3-(methylthio)-propanoate, 2,5-dimethyl-
4-methoxy -3(2H)-furanone (mesifurane), and 2, 5-dimethy1-4-hydroxy-
3(2H)-furanone as the major compounds of pineapple fruits.
Extraction: The volatiles of pineapple fruit is isolated by

continuous liquid-liquid extraction, using pentane-dichloro methane
mixture (l+l[v/v] at 30 QC for 48 hr of the juice produced from the
fresh pineapple fruits after their peeling, slicing and homogenising
and separating out the pulp by centrifugation (300 g). The extracts
are dried, filtered and carefully concentrated at 45 QC using a Vigrepux
column.
Uses: Pineapple volatiles can be used in soft drink, pudding, ice

cream, and sweet products imparting fascinating pineapple aroma.
JACKFRUIT AROMATIC OIL

(Artocarpus heterophyllus Lam.)
J ackfruit 98 is a traditional fruit of many tropical countries indigenous

to India, Bangladesh, Burma, Sri Lanka, Malaysia, Indonesia,
Philippines, Brazil, and other countries. Very little research work
has been done on the flavor volatiles of jackfruit when fully ripened.
Composition: A total of 23 compounds have been reported in
jackfruit with esters as the major compound group contributing to
its flavor. The esters are butyl acetate and 3-methyl butyl acetate,
propyl isovalerate, butyl isovalerate, isoamyl isovalerate, 3-hydroxy-
3-methyl butanoate, ethyl-3-hydroxy-3-methyl-butanoate, hexyl
isovalerate, methyl dodecanoate, isopropyl myristate, and 3-phenyl
propyl ester. Other compounds detected are butanol-3-methyl butanol,
benzaldehyde, isovaleric acid, octadecane, and 3-phenyl propanol.
The nature of the compounds and their relative proportions vary

with the ripening period of the fruit.
Extraction: Extraction of flavor compounds is made from

principally the edible yellow-colored bulbs of the fully ripened fruit.
The bulbs are blended with distilled water. The blended material a
kind of suspension is solvent extracted with dichloromethane or by
pentane by stirring for 2 hr at 125 ppm. The emulsion formed is then
centrifuged at 9820 g at 4°C for 15 min. The liquid extract is poured
into a separator. The suspended material (sediment) is re-extracted
twice with solvent. The liquid (solvent) extract is concentrated to a
certain minimum volume (e.g. 1 mL) in a rotary vacuum evaporator
and by purging of nitrogen gas.
Uses: Jackfruit aromatic oil is used in ice cream, pudding and

milk-based sweetmeat products as jackfruit aroma is liked by many.
GUMS AS A SOURCE OF ESSENTIAL OILS
A number of gum exudes are available from the trees of different

plant families that act as a good source for essential oils. Some of
the commercially important sources are outlined below embracing
source, oil yield, composition, isolation and uses.
BENZOIN
(Styrax benzoin)
Benzoin is the kind of gum resin that exudes from the bark of the
trees native to Thailand and Sumatra Styrax benzoin belonging to
Styraceae.
Oil Content: The content of volatile oil is about 1%.
Composition: Styrax benzoin contains 20-25% cinnamic acid,

vanillin, coniferyl benzoate, benzoic acid.
Extraction: The benzoin is obtained by steam distillation of the

gum resin exudes.
Uses: The benzoin is an excellent fixative and the gum benzoin

is used in making deodorized alcohol. The benzoin has aroma therapy
uses in skin care particularly for eczema and psoriasis, bedsores,
wounds and skin ulcerations. It is also useful for catarrh and chest
infections.
ELEMI
(Canarium luzomicum)
Elemi trees 99 belonging to the plant family Burseraceae exude gum

that has distinct aromatic oil. The trees are mostly native to the
Philippines and the Moluccas.
Oil Content: The oil content is as much as 25-30% of the elemi

exude.
Composition: The oil that is a pale yellow or colorless liquid

contains exclusively terpene hydrocarbons, namely phellandrene,
dispentene, limonene, and pinene.
Extraction: Steam distillation of the gum exudes yields the

essential oil.
Uses: The oil has aromatherapic applications in rheumatic and

respiratory disorders, skin infections and nervous exhaustion.
The oil has a strong, spicy-balsamic aroma, which can be utilized

in citrus-geranium note. The odor effect is tenacious, stimulating,
and warming.
FRANKINCENSE
(Boswellia carterii)
Frankincense 99 gum is exuded from the small tree native to northeast

Africa belonging to the plant family Burseraceae.
Oil Content: The yield of oil is from 5-10 %.

Composition: The Frankincense gum yields an oil (known as oil
of olibanwn) that contains as the principal constituents a ketone
alcohol (olibanol), camphene, dispentene, (X- and ~-pinene.
Extraction: Steam distillation of the gum exudates yields the

aromatic oil.
Uses: The oil is colorless to pale yellow possessing a warm,

balsamic fragrance and a note of camphor. The oil may be used in
perfumes in the preparation of incense and fumigating preparations.
It has excellent fixative properties. The oil has aromatherapy uses
in skin care, scars, wounds, respiratory ailments, colds and flu, anxiety
and stress, and meditation.
GALBANUM
(Ferula galbaniflua)
The galbanum gum 100 exudes from the large herb (Umbelliferae plant)
native to the Middle East and Western Asia. The Levant variety is
commercially exploited.
Oil Content: The galbanum (Levant variety) yields about 10% of

volatile oil.
Composition: The oil from the galbanum gum contains 50-60%

carvone, sesquiterpene alcohol (cadinol), and terpenes Oimonene and
pinene) as the principal constituents.
Extraction: The oil is obtained by water or steam distillation of

the gum.
Uses: The oil that is an amber-colored liquid has a green-woody

scent and soft balsamic undertone. The oil has a calming effect.
The oil has aromatherapy uses in scars, wounds, muscular acts

and pains, rheumatism, respiratory oilments, nervous, tension and
stress-related disorders.
MYRRH
(Commiphora myrrha Holmes, Burseraceae)
The oleo-gum-resin of the Commiphora myrrha lOl tree native to

Northeast Africa and Southwest Asia contains the volatile oil.
Oil Content: The oil yield is 6-7% of the oleo-gum-resin.

Composition: The oil of Myrrh contains formic acid, acetic acid,
and palmitic acid, terpenes like pinene, dipentene and limonene,
aldehydes like cumic and cinnamic, phenol like eugenol and m-cresol,
and myrrholic acid. A tricyclic sesquiterpene called heeaboline is
detected in the oil.
Extraction: The oil of Myrrh is obtained by the steam distillation

of the gum.
The oil of Myrrh is a light yellow viscid liquid with a balsamic

odor. The odor effect of the oil is warming and relaxing.
Uses: The oil has a number of aromatherapy uses in skin care,

arthritis, respiratory disorders, gum infections, nervous, tension.
PERU BALSAM
(Myroxylon pereirae, Klotzsch)
Peru balsam 102 is obtained from the bark of M. pereirae, Klotzsch

tree of leguminosae family. The tree is actually subjected to a kind
of beating and scorching to yield a pathological product, the Peru
balsam.
Composition: The oil of Peru balsam consists chiefly of benzyl

benzoate and benzyl cinnamate. The oil contains also vanillin,
coumarin, and nerolidol as an ester.
Extraction: The oil is obtained by distillation of the product

obtained from the bark or trunk.
Uses: The oil is employed as an excellent fixative in perfumery

and especially for tobacco perfumes. It is a good base for oriental
perfumes when blended with coumarin, vanillin, musk, and civet.
It is used in soap compounds and incense sticks. It is used also in

lipsticks perfumes for its soothing qualities and in face powders as
a component of perfume with warmth characteristic.
TOLU BALSAM
(Myroxylon toluifera H.B. and K., Leguminosae)
Tolu balsam 102 , a resinous material is obtained from M. toluifera,

H.B. and K., tree. The balsam is collected by making deeply cut V-
shaped notchin the bark and the exudation product is collected in
cups. The balsam becomes in due course of time hard and brittle.
The product is commercially known as the Peru balsam.
Composition: The balsam obtained as above contains about 80%

of resin, together with benzoic and cinnamic acids, vanillin, benzyl
benzoate and benzyl cinnamate, and a small quality of volatile oil.
The balsam has sweet hyacinth like fragrance.
Uses: It is an excellent fixative. It is used in soap perfumery. It

is also used in high-class perfumery on dilution with alcohol.
ANIMAL AS ESSENTIAL OIL-BEARING MATERIALS
Essential (aromatic) oil-bearing materials occur in a very limited

number of animals unlike the vast multitude of the plant origins.
Among the animals, civet cats, musk deers, and sperm whale have
been recognized as animal species and sources of aromatics.
CIVET
(Viverra civetta, V. zibetha, V. rasse and V. tangalunga)
Civet caP03 both male and female of the above species and native to
Abyssinia Guinea, and Senegal secretes a material called civet that
has the distinct and characteristic odour.
Composition: The odor of civet is due to the occurrence of a

ketone called Zibetone (Civetone) having the formula.
Extraction: Civet is obtained in market as absolute. The absolute

is made by extracting the animal product with a volatile solvent,
filtering off the insoluble matter, removing the dissolved fats by
crystallization at low temperature and concentrating the solution in
vacuo to a black or deep brown viscous liquid having the typical odor.
Uses: Civet is used exclusively as a fixative.
MUSK DEER
(Moschus moschiferus L., Ungulata)
Male Musk deer 103 of the above species and also of other species (M.
chrysogaster, M. sifanicus, and M. sibiricus) and living in the
Himalayan ranges and the Atlas act as only source of an aromatic
material. Commercially, there are four varieties of Musk namely
Tonquin Cabardine, Yunnan, and Assam and Nepal yield a secretion
product that is known as the Muskodour.
Oil Content: The odor material occurs at around 2%.
Chemical Composition: The odor material (a dark brown volatolic
oil) of the male Musk deer is a ketone that has been named Muscone
whose molecular structure is
Extraction: The dried secretion from the anal glands of the musk
deer when extracted with ethanol yields the odoriferous material.
Uses: The musk as above is used in perfumery as an excellent

fixative that is necessary in blending all of the perfume components
for retaining an harmonious odor by regulating the evaporation of
the ingredients.
SPERM WHALE EXCRETA AS A SOURCE
The sperm whale produces ambreine in its intestinal tract and excretes
it out as lumps into the sea. The lumps in course of time in the
presence of salt water, air, and sunlight makes the ambreine
transformed into a mixture known as ambergris, which is a valuable
perfumery material.
Composition: About 80% of the ambergris consists of ambrein a
triterpene. The ambergris has the structure as
Q5> Ambergris
Extraction: The ambergris extract (tincture) is isolated by

alcoholic extraction of the produced degradation product of ambreine.
The alcoholic extract is allowed to mature and following filtration

and removal of alcohol, the ambergris product could be obtained.
Uses: Ambergris is mostly used in the preparation of fine perfumes.

It acts as a strong fixative as well.
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London I: 126-127, 1974.
Natural Perfumery Materials ••
Production Technology
INTRODUCTION
The natural perfumery materials are actually the naturally occurring

aromatic or essential oils from various source materials (viz., flowers,
grasses, leaves, barks, wood, fruit, etc.) having distinctive aroma
and varied nature of essential oils in addition to structural diversity
of source materials.
A number of extraction processes for producing various natural
perfumes are available. The selection of an extraction process
depends primarily on the quality of the aroma characteristic of the
essential oil to be recovered. The process selection also depends on
the stability of the oil or its constituents during the extraction
conditions, particularly under the influence of temperature. The
processes also take into account the enzymatic activity that may be
allowed to persist in certain essential-oil-bearing materials to
synthesize more oil.
The following processes have been developed for the extraction of
essential oils from various oil-bearing materials:
(1) Steam Distillation Process
(2) Percolation Process with Steam
(3) Expression Process
(4) Enfleurage Process
(5) Maceration Process
(6) Solvent Extraction Process with Volatile Solvents
(7) Liquid Carbon dioxide Process

(8) Enzymatic Process
(9) Microwave Process
(10) Adsorption Process
(11) Combined Process
The processes mentioned above are briefly outlined here. A

comparison of the quality of the essential oils obtained by above
processes is also made to indicate the differences in the content and
aroma characteristics.
STEAM DISTILLATION PROCESSl
The steam distillation process is applicable to many kinds of source

materials and it is therefore mostly used method for producing natural
perfumes or the natural essential oils of commerce.
The steam distillation process is generally carried out at
atmospheric pressure, although the process can be conducted at low
pressure (i.e., under vacuum) or at higher pressure. The steam
distillation process is also conducted at varying temperatures whereby
the process has been classified into:
• Hydro-steam distillation
• Superheated steam distillation
Each above-mentioned distillation process and also hydro distillation
process are described herein briefly alongwith its principles.
Principle of Distillation Processes
Essential (aromatic) oils are volatile in nature and have substantial

vapor pressure. The vapor pressure of the essential oils increases
further in contact with water vapor or steam vapors, thereby build
up the total pressure equal to the ambient atmospheric pressure.
The continuous availability of water or steam vapors in direct contact
with the essential oil vapors facilitates the separation of the essential
oil phase from a source material. In fact, the ratio between the
weights of the two vapor components, and therefore of the two liquids
in the distillation, is expressed by the ratio of the partial vapor
pressures multiplied by the ratio of their molecular weight.
w
H,O PH,Om H"O
----=--x--
woil ~)Jl moil
Production Technology of Natural Perfumery Materials 63
Where,
wHO is the weight of water in the distillate (condensate),

2
Wail is the weight of oil in the condensate,
p~o is the vapor pressure of water at still temperature,
Pail is the vapor pressure of oil at still temperature,
mHO IS the molecular weight of water, and

2
mail IS the molecular weight of oil
The ratio of water to oil in the condensate can be changed by

changing the operating pressure and this ratio is determined from
the above relationship.
In hydrodistillation of all kinds, the sum of PH 0 and Pail will equal

2
the operating pressure and the still temperature will influence this
condition accordingly. Thus, the lowering of the operating pressure
below the atmospheric pressure will result in the decrease of the
still or operating temperature.
The vapor pressure of water decreases more slowly with the

temperature than that of the vapor pressure of an essential oil. As
a result, the weight ratio of water to oil increases.
The distillation at reduced pressure although results in a lower

operating temperature, the steam required is however, more per
unit weight of the material (essential oil) recovered. At elevated
pressure (at high pressure), there is much less amount of steam
required per unit weight of oil as the operating or still temperature
is higher. As long as the quality of the oil is not affected, the use of
high-pressure steam is gainful. It should be remembered that the
steam used is neither saturated nor superheated.
The above theoretical concept points out that superheated steam

can be used in recovering essential oils with some advantages. In fact,
the distillation with superheated steam results in a lower ratio of
water to oil, thereby saving steam consumption. This is the case
because the increase of temperature increases more the vapor (partial)
pressure of the oil.
The above basics have been utilized in developing the distillation

processes involving steam usage for the extraction of essential
oils.
Hydrodistillation Process (Water Boiling Process)
The process consists of first charging of the properly sized and/or

dried (sun or mechanical) aroma bearing source material (grass,
leaves, flowers, etc.) in requisite quantity into the extraction vessel
and then adding water in adequate volume to properly submerge the
source material. The proportions of the source material and water
should be so chosen that water can diffuse through the material
rather freely on boiling.
Afterwards the vessel is heated (direct) by electrical means or by
controlled gas flame to achieve a kind of boiling of water.
The volatiles comprising aroma material and water vapor are

allowed to pass through a water-cooled condenser and collected in
the receiver fitted with the condenser. After sufficient time of settling
in order to break the emulsion formed, the aromatic oily layer is
separated. Fig 1 shows a typical hydrodistillation unit.
The water layer known as the water of "cohobation" is recycled to
the extraction unit to aid recovery of the essential oil along with the
Watert-
Water+
plant Q~~(rj1:[,
material ---00-0'
000:. : ...... "4----, Water
-QaD:~
Heating
o DTI GO ,
(Gas flame)
Distillation water
Fig 1. Hydro-distillation unit

fresh charge of aromatic material. Alternatively, the distillation waters

(water containing some of the dissolved or finely dispersed essential
oil) are redistilled separately in round stills efficiently provided with
a steam jacket or closed steam oil. Indirect heating is preferred to
reduce the volume of water in the still in case live steam is injected
into the still. The redistillation of distilling waters can be effective
if the water containing the oil is saturated with sodium chloride.
The essential (volatile) oil can be recovered from the distillation
water by saturating the extract with salt (sodium chloride) and then
extracting twice with a volatile solvent (e.g., petroleum ether). The
solvent is removed from the total extract (containing the essential
oil) and from the water drawn off.
Hydro-Steam Distillation Process
In this process, water is charged in the extraction vessel charged

previously with the source material (properly sized) to facilitate the
release of the aromatic molecules in much greater amount than the
water distillation alone because of the need to increase the vapor
pressure of the higher boiling constituents of the aromatic oil when
Water ~--+--I--+-t+- Water
Inlet
00000000
0cU'2.2~8.2_ ~ Oil
14-----1: _____ _
--
- --
----
---
Distillation water
Fig 2. Hydro-steam distillation unit

heated by steam. The rest of the process is conducted III the same
manner as described in the water distillation process.
The material is actually taken on a perforated grid or screen that
is located at a suitable distance above the bottom of the still. Water
is charged in the lower part of the still to a level somewhat below
the grid.
The water is heated by closed steam coil or by using a steam

jacket, or by open or perforated steam coil. The steam of low pressure
formed from the water due to heating actually rises through the
material.
The vapors of steam and volatile oil are collected via a condenser
into the receiver. The essential oil is separated and the water layer
IS recycled as usual.
The process can be carried out under reduced or increased

pressure. The use of reduced pressure gives excellent results. Fig 2
shows the hydro-steam distillation unit.
Steam Or Direct Steam Distillation Process 1 ,2
This process involves the injection of live or dry steam saturated or

superheated from a boiler through the material already charged in
the extraction unit (still pot) (Fig 3). The technology for recovery of
the essential oil is the same as outlined in the case of water and
steam distillation process except that no water is taken or kept in the
bottom of the still. Fig 3 shows a still charged with the source material
and provided with a steam inlet. The condensation arrangement with
cooling coil to circulate cooling water is also shown. The essential oil
and water are collected after condensation in a flask called florentine
flask. The waters of cohobation are recycled to the still pot.
The operating temperature will be around 100 QC at atmospheric
pressure. The distillation can be conducted at reduced pressure,
atmospheric pressure or at high pressure. The high-pressure steam
distillation reduces the distillation time by improving the transfer of
the latent heat required to vaporise the oil and increases the total
yield of oil (e.g., sandalwood, clove).
The equipments of the process include
(i) a retort, or still pot;

(ii) a condenser; and
(iii) a receiver for the condensate.
The equipments also include a boiler for generating steam.
The direct steam distillation is better than both water distillation

and water and steam distillation with respect to cost, distillation
rate, and capacity of production.
Advantages and Disadvantages of Distillation Processes
Hydro-distillation Process
Advantages
1. Hydrodistillation process is readily adaptable.

2. Applicable to processing almost all materials including the
powdered materials without formation of agglomerates/
lumps.
3. Applicable to material that cannot be processed by steam
distillation or water and steam distillation process.
Disadvantages
1. Extraction of essential oil is never complete as the

hydrodistillation process cannot volatilize the high-boiling
constituents. As a result, the yield of oil is low and the
properties as well as composition are different.
2. Distillation time is high and the productivity is low.
3. Decomposition products occur in the oil.
Hydro-Steam Distillation Process
Advantages
1. The danger of overheating the source material is low as the

rate of distillation is relatively high because of more heat.
2. The products of decomposition are much less compared to the
water distillation process.
Disadvantage
1. Require long hours of distillation as more steam is

required for vaporizing high-boiling constituents of oils.
Steam Distillation Process
Advantages
1. Accomplishes more quantitative recovery of essential oils.

2. Productivity of the process is much more than the other
distillation processes.
3. The quality of oil is good.
Disadvantage
The process is much more capital intensive than the other kinds of
distillation process.
To stack
l----- Steam
DODO
DODO
DODO
Water
Water
Ikm
+--~ Oil
Oil receiver
Fig 3. Schematic representation of steam distillation unit
PERCOLATION (HYDRODIFFUSION) PROCESS

WITH STEAM3
Percolation (hydrodiffusion) process with steam is a highly

interesting process with most of the extracted oil having an aroma
nearer to that in the plant stage. The process is primarily used for
seeds.
Unlike CO 2 extraction, the extraction equipment is simple and

the process quicker than distillation. The plant material is kept
in contact with the steam for a much shorter time.
The extraction unit is like a coffee percolator. The steam passes

through the plant material from top to bottom of the container. The
percolator has a grid to hold the plant material. The steam is
condensed below the vessel.
The oil and condensed steam (water) is collected in a vessel and
the oil that separates as the upper layer or lower layer is removed
to yield the essential oil.
EXPRESSION PROCESS4
This process is adopted almost exclusively with citrus fruits, where

the essential oil needs to be pressed out from the sacs just under the
surface of the rind.
Expressed oil is obtained from the fresh peels of the fruits that
are processed by a factory producing fruit juice.
Cold pressing yields special quality citrus oils. Often the fruit
peels after cold pressing is steam distilled to recover even more oil
(although of poorer quality).
Three processes are practised for recovering citrus oil from the
fruit peels, namely, sponge process, Ecuelle process, and "Machine
process". Among these processes, the sponge process is adopted in
case of lemon and orange oils. The machine process is commercially
applied for the production of citrus oils (bergamot, lemon). The
sponge process is often applied to produce lemon oil. Ecuelle method
is not practised for obtaining citrus oils any more.
Sponge Process
In the sponge process, the peels from the fruit are first prepared and
steeped in water for quite some time (ca, 5-6 hours) to facilitate the
removal of oil. The steeped peel material is then hand pressed against
a sponge when the oil sepamtes out. The oil is collected, filtered,
and stored.
Ecuelle Process
The process involves the treatment of fruits by rolling in hollow

vessels provided with spikes on the walls of the vessel. The oil
tissues get ruptured, and the liquid flows out at the bottom and
collected and clarified.
~achine Process
Machine process is actually a mechanical adaptation of the sponge

process, involving the use of a lever to build up the required pressure
for obtaining the citrus oil from sponge.
In the modern process, centrifugal separators are used. The whole
fruits after cleaning by washing are crushed with a fine spray of
water in a mill between two pairs of rollers, one below the other in
vertical position in a water tight casing. The mass is discharged from
the lower part of the mill on to a wooden grating. The crushed fruit
is retained and the liquid with suspensions ejects out freely. This
liquid suspension is passed over a number of strainers to remove the
coarser paticles of skin or pulp. Then liquid is passed through a pairs
of centrifuge. The clear essence is discharged from the upper cock of
centrifuge and collected appropriately in a container.
The oil obtained by this process is of good quality compared to the

other expression processes.
ENFLEURAGE PROCESS4
Enfleurage process is based on the solubilization of the aromatic

(essential) oils from the oil-bearing materials in a fat phase by means
of suitable contact, and later dissolving out the aromatic oil from the
fat phase in alcohol. The left over fat phase can be reused. The alcohol
is recovered to yield the aromatic (essential oil).
The process consists of spreading an appropriate fat layer (e.g.,

completely refined lard or tallow or palmstearin) uniformly on both
sides of the surface of "chassis" or trays (glass or steel), and the
material (fresh) to be extracted (usually a flower) is then spread over
the fat surface. Each chasis so prepared is placed in tiers so that the
flowers (petals) are enclosed between two layers of fat, both the
upper and lower fat phase absorbing the perfume released. After the
appropriate contact time period (days), the process is renewed
periodically until the fat charge becomes saturated with the perfume
of the natural material (e.g., the flower). The flavor (aroma) rich fat
produced is known as "Pomade" in commerce. The pomade is next
extracted with deodorized ethanol to recover the aromatic oil from
the fat phase. The "concretes" are obtained after removal of the
alcohol and the "absolutes" are made by crystallization from alcohol.
Often, the "concretes" are steam distilled and the recovered purified
"concretes", free from the fat used, are purified by crystallization
from alcohol to yield "absolutes".
The residual flowers are often further extracted with appropriate

volatile solvents to recover the remaining perfume material for use
in making artificial flavor. In India, sesame seeds are used instead
of a hard fat for recovery of aromatic oil from flowers (e.g., Jasmine).
The seed is mixed with flower in a hand-driven or electrical-driven
ghani and crushed in a manner similar to the crushing of seeds.
During crushing, the rotating pestle grinds the sesame seeds that in
turn gets mixed with the flavor components of the flower and absorb
the perfume by contact. The oil that comes out is perfumed oil. In
the case of jasmine flower, the oil is called "Chameli" oil and is used
in perfumed hair oil. The perfumed oil can be treated with ethyl
alcohol to solubilize the essential oil in a manner similar to that of
the conventional fat-based enfleurage process.
The process presents a few disadvantages. The amount of the
aromatic (odorous) oil is low. The fat used is not a pleasant material
to handle, and it becomes rancid after a number of uses.
MACERATION PROCESS
Maceration process is a variation of the Enfleurage process for recovery

of essential oil from flowers, leaves, etc. Unlike the Enfleurage
process, the maceration process is carried out at 50-70 QC.
The material (properly sized and dried) is stirred with an
appropriate fat (purified lard or palmstearin) or a stable liquid oil
(like olive or sesame) in a vessel at 50-70 QC for few hours.
After the extraction the source material is filtered off on perforated
screens and the fat-phase containing the aroma is collected. This fat-
phase is mixed once again with fresh charge of flower in the extractor.
The process is repeated till the aroma content of the source material
is highly depleted.
The aroma is eventually isolated from the fat phase by several
extractions with deodorized ethyl alcohol as done in the case of the
traditional enfleurage process.
Extraction with Volatile Solvents 4
Principle of Extraction with Solvents
Essential (aromatic) oils are readily soluble in both polar and apolar
organic solvents and this property has been utilized in developing
the simple solvent extraction process of most plant materials for
obtaining from them the necessary aromatic oils.
Extraction with volatile solvents demand that the solvent that

will be used must possess the following characteristics:
(i) The solvent should dissolve only the odoriferous components
quickly and completely, with a trace amount of inert matter.
(ii) The solvent should be of low boiling point.
(iii) The solvent should be chemically inert to the odoriferous
materials.
(iv) The solvent should evaporate completely without leaving any
residue.
(v) The solvent should be cheap and noninflammable.
The solvent extraction of oil-bearing materials for the recovery

of essential oils using low-boiling organic solvents nowadays is a
commercial process. Traditionally, the organic solvents like
petroleum ether (40-60 QC), hexane (64-70 QC), dichloromethane,
chloroform, carbon disulphide, methanol, ethanol, acetone, ethyl
acetate etc., are used. The use of butane as a solvent is very
interesting and it has opened up a new dimension in the solvent
extraction process in the production of "concretes" (also called
resinoids) and also "absolutes" of high quality from the concretes.
The solvent that has been most generally used is petroleum ether
(b.p. 40-60 QC) free from aromatics, olefins and sulfur compounds.
The polar solvents like methanol, ethanol, and acetone are not
much used because of the high proportion of water in the aromatic
materials.
The details of the solvent extraction process are outlined as:

(i) The properly cleaned and sized (and/or dried) materials
are charged into the extractor (batch-type), fitted with a
leak proof (hermetic ally sealed) stirrer, a heating
arrangement and an efficient condenser to facilitate reflux
of the miscella.
(ii) The appropriate solvent (3-5 volumes) is added to the extractor
and stirred at ambient temperature or nearly at the boiling
point of the solvent.
(iii) The extraction is continued till the miscella reaches an
equilibrium state of the essential oil content.
(iv) The miscella is taken out from the bottom of the extractor
into the distilling still to recover the solvent.
(v) The essential oil from the distilling unit is discharged into
the receiving unit.
The essential oil recovered by the solvent process contains in

trace amount the residual solvent, which needs to be recovered and
in fact, is removed by low heat under high vacuum. This process
steps lead to the loss of certain low-boiling components. The solvent
extracted oils invariably have a higher content of high-boiling
components compared to the traditional methods.
The solvent extraction process can also be carried out as outlined
below:
• The extraction unit consists of battery of percolators.

• Each percolator is fitted with several trays or perforated
cylinders.
• The flowers or the materials to be extracted are placed on the
trays or the perforated cylinders.
• The percolators are hermetic ally sealed and connected between
them by means of tubes in series.
• The percolators at one end are connected with the solvent
tank and at the other end with a vacuum still.
• The solvent flows through the material slowly and it is distilled
off when it reaches the vacuum still, and the solvent recovered
is returned to the solvent tank for recycle.
• The aroma (perfume) is left behind in the retort (vacuum still).
• The solvent continues to pass through the unit until the source
material is completely exhausted.
• Fresh materials are fed to the extraction unit and the extraction
and recovery process steps are carried out.
• The concretes (the products) or resinoids are isolated and further
processed with ethanol to yield absolutes.
• The concretes may be distilled to give the essential oils.
Extractors of rotary types are also used in solvent extraction
process.
In the rotary process, oil is extracted on the counter current
principle. The rotary process utilizes steam jacketed drums which
revolve around a horizontal axis and are divided into compartments
by perforated plates at right angles to the axis. The source material
(e.g., flower) and the solvent (petroleum ether, b.p. 40-60 CC) are
charged into the first drum. The drum is rotated for about an hour
at ambient temperature and then for half an hour with steam in
the jacket.
Solvent Solvent Solvent Solvent

tank tank tank tank
. - - - Plant matenal
H,O
SolutIOn Solution SolutIOn Solution

tank tank tank tank
§~lml
cone ete
Fig 4. Sehematic diagram of a solvent extraction unit
The saturated solvent is pumped to the recovery still and the

material in the drum are treated with once - used solvent and finally
fresh solvent from the recovery still. The exhausted material is blown
with steam to recover the adhering solvent. The bulk volume (90%)
of the solvent is recovered at atmospheric pressure and rest being
recovered under vacuum.
After solvent removal, the essential oil is obtained. The oil contains
waxes, resins, and coloring matter from the source material.
The product is known as concrete, and it is treated with alcohol

to remove waxes and resins from the essential oil. The alcoholic
solution contains the essential oil and some coloring matter. The
alcohol on removal yields the absolute of essential oil.
EXTRACTION OF ESSENTIAL OILS BY LIQUID

CARBONDIOXIDE5
Principle of Supercritical Extraction Technology
Recently, there has been a great deal of interest in the use of

carbondioxide as an extraction solvent in supercritical or subcritical
condition. This process of extraction has recently become a reality
in the perfumery industry for recovering the natural perfumery
materials from various sources. Carbon dioxide under supercritical
or subcritical condition is capable of behaving like organic solvents
and therefore extracting the perfume (terpenes and terpene
derivatives) material.
The extraction of essential oils direct from fresh materials, using

liquid carbondioxide at low temperatures, yields essential oils having
no loss of volatiles. The aroma profiles hence more closely resemble
those of the original plant materials.
The recovery of volatiles from such materials as herbs, spices,

and vanilla by this supercritical or subcritical carbondioxide extraction
IS preferred.
The pressure required to liquify carbondioxide at ambient

temperature is considerable and thus the necessary equipment is
expensive. This is reflected in the cost of the oils produced.
Carbondioxide in both liquid state and supercritical fluid state is
used for the single-stage extraction of essential oils as an alternative
solvent of the traditional volatile organic solvents at a low
temperature. A two-stage process involving at first liquid
carbondioxide and the supercritical carbondioxide has also been
developed for the recovery of flavoring materials (V.S. patent no.
V.S. 4, 490, 398: 25-12-84).
The process details consisting of the sequence of production steps
are briefly outlined below:
(i) The properly sized material is taken in the extraction units

(1-4 units connected in series).
(ii) Carbondioxide at 60-70 bar and at 5-10 QC is pumped through
the extraction units in the case of liquid CO 2 process.
(iii) In the case of supercritical CO 2 process, a pressure of
90-300 bar and a temperature of 60-70 QC or more are
maintained in the extraction units in order that the
supercritical CO 2 behaved like a fluid, having capability of

recovering essential oils.
(iv) The extraction is continued for 3-4 hours.
(v) The miscella is taken out into a separator (evaporator) where
the CO 2 is evaporated rapidly to the gaseous state, which is
recompressed and recycled.
(vi) The product recovered is solvent free.
The CO 2 extraction process particularly the liquid CO 2 process
offers a number of advantages over the existing organic-sol vents-
based extraction process, as enumerated below:
(i) The production of fine-quality essential oils.
(ii) No solvent residues in the extracted essential oils.
(iii) The process being carried out at a low temperature, the heat
sensitive oils is well protected and there is no generation of
off-odors and the odor characteristics are more natural.
CO, Balloons
-0
D C B A Transfer
tank
Chiller
Fig 5. A diagrmatic representation of a liquid CO 2 plant

Table 1 : Yields of oil from some spices by steam distillation and liquid
CO 2
Essential oil yield (%; w/w)
Spice Origin Steam distillation Liquid CO 2
Ginger Nigeria 1.5 - 3.0 3

Clove bud Comores 15 - 17 16
BlackPepper Sarawak 1.0 - 2.6 2
(iv) No still notes (off-odors) but more top notes.

(v) More back notes because CO 2 extracts the character of an
absolute.
(vi) Concentration of aromatic components (more concentrated oil).
The extraction process is shown diagramatically in Fig 5.
Some time it is advantageous to use an organic solvent to act as
a co solvent, such as ethanol, to modify the polarity balance and to
aid the penetration of liquid CO 2 into the plant tissues.
Some time it may be advantageous to digest the source material

with appropriate microbial enzymes to readily release more oil before
carrying out the extraction with liquid carbondioxide.
A comparison of the yields of aromatic (essential) oils between the

steam distillation and liquid CO 2 extraction processes and also of the
physico-chemical properties (Tables 1 and 2) indicates clearly some
advantages of the liquid CO 2 process.
ENZYMATIC EXTRACTION OF ESSENTIAL OILS
Increased attention is now being paid to the enzymatic extraction of

essential oils. The enzymes particularly the microbial enzymes,
Table 2: Physical properties between steam distilled and liquid CO 2

extracted ginger oil
Physical Steam Liquid CO 2 CO 2 extracted

property distilled extracted oil (terpeneless)
(at 20 'C)
Specific gravity 0.871 to 0.882 0.940 to 0.975 0.875 to 0.88

Optical rotation _28 0 to _45 0 _100 to 30 0 _25 0 to _40 0
Refractive index 1.488 to 1.494 1.500 to 1.510 1.465 to 1.495
namely, cellulase and pectinase or amylase, individually and in

combination, are getting lot of interest for the recovery of essential
oils from a variety of materials as the use of enzymes increases the
yield of essential oils compared to the other extraction processes
without employing enzyme treatment.
The process steps involved are:

(1) The proper sizing of the oil-bearing material and adjustment
of its moisture content between 15% and 30% (on weight of
the material), if necessary.
(2) The treatment of the above material with 1-5% by weight of
the ambient material cellulase, pectinase, or amylase
individually or in combination by digestion for 4-8 hours at
a temperature of 50-60 QC and pH of 4-7.
(3) The enzyme-digested material is water distilled or steam
distilled or extracted with liquid CO 2 or with organic solvent
after adjustment of the water content.
The increased release of oil from cold pressed citrus fruits is

observed by treatment with cellulase and pectinases at 0.02-0.15% of
dry weight levels for 4-6 hours before pressing.
MICROWAVE EXTRACTION PROCESS6
Microwave energy, with a frequency of 2.45 GHz, when applied to

the essential oil-bearing plant materials, ruptures their cells and
glands more rapidly than the conventional hydrodistillation. As a
result, the volatile constituents occurring in the plant materials get
released and instantly vaporized and the vaporization is further
facilitated by the steam vapors generated as a result of rupturing
from the plant materials.
A process has been eventually conceived for trying to recover

essential oils from natural perfumery materials.
Infact microwave process has been now applied in extracting

essential oil. The microwave heating accelerates water
distillation of the perfumery material. The method offers
important advantages over traditional hydrodistillation. The
process does not require additional water and the extraction
time is much shortened (e.g., 30 minute against 3 hours for
hydrodistillation). The yield of the oil also improves and the
process is more ecofriendly and of lower cost. The oil has a
better aroma characteristic.
The process needs, however high level of safety and attention.

The microwave process has been receiving attention in up scaling
for the production of essential oils particularly the heat-sensitive
ones.
The microwave process can be understood from the diagram

(Fig 6) that clearly demonstrates the design, mode of operation in
the treatment of the source material, and the isolation of the
essential oil.
The material is charged in the microwave reactor. The reactor is

provided outside with a condenser and a receiver for collecting the
volatile phases. Ultimately, the essential oil is obtained from either
upper layer or the lower layer depending on the density of the oil.
Excess water is refluxed to the extracting vessel to restore the water
to the plant material.
Cooler
Essential oil
Aqueous phase
Fig 6. Microwave clevenger

The microwave-assisted solvent (water) extraction is a viable

alternative to conventional techniques for such matrixes (essential
oil source materials).
A comparative evaluation of the properties (physical and

organoleptic) of the essential oil recovered by microwave and
hydrodistillation methodologies is included in the table below for
orange peel oil.
Physical Microwave Hydrodistillation

properties process process
Specific gravity, d 20 0.86 0.86

Refractive index n D20 1.475 1.475
Optical rotation in degree [a]D 2O 38.00 39.00
Organoleptic properties
Color Colorless Pale yellow
Odor Fresh light and Fresh, pungent,
sweet, citrusy different from
fresh fruit
Other aspects Mobile liquid Mobile liquid
Extraction time (min) 30.00 180.00

Electric consumption (kwh) 0.25 4.33
CO 2 rejected (g) 200.00 3464.00
ADSORPTION PROCESS
In recent years, the use of a selective adsorbent for the extraction

of aromatic oils or fractions is being made.
Some synthetic polymeric adsorbents are being employed with
useful results for industrial application. It is claimed that the
extraction technology carried out with polymeric adsorbents would
be useful.
The process may be used for the deterpenation of some essential

oils.
COMBINED PROCESS
The technology of extraction of essential oils by appropriate

combination of process has not been reported so far even though

there is much scope of adaptation. It is envisaged that the combination
of appropriate extraction process will enable to recover more yield of
essential oil compared to the individual processes when applied to
recover the oil.
The following combined processes are suggested for the recovery

of aromatic oils in greater yield.
(1) Enzymatic digestion and liquid carbondioxide extraction.

(2) Enzymatic digestion and microwave extraction.
(3) Enzymatic digestion and organic solvent extraction.
POST EXTRACTION TREATMENT OF THE

RECOVERED ESSENTIAL OILS7,8
The essential oils recovered by the various extraction processes vary

in quality. They require postextraction treatment or rectification to
upgrade their quality. Some oils are of extremely good quality without
requiring any post-treatment. Some of the essential oils particularly
produced by the solvent extraction process need post-treatment to
upgrade their quality as the solvent extracted oils contain
sesquiterpenes that tend to behave like waxes in alcohol medium.
The solvent extracted oils also contain pigments that need to be
removed.
The solvent extracted oils or the concrete oils as they are known
can be treated with strong alcohol at low temperature to crystallize
out the waxes followed by separation by filtration The absolute is
obtained by distilling off the alcohol in vacuo. The addition of salt to
the alcoholic solution also is helpful to separate out the pure essence
at the top when it is collected.
The pigments, particularly the chlorophylls may be satisfactorily

removed by the little addition of acid-activated earth (e.g., tonsil
earth optimum F) in the solvent phase before distillation of the
solvent. The acid-activated earth destroys the chlorophyll almost
instantaneously. The treated miscella is filtered and the solvent is
removed by distillation of the solvent in vacuo.
The pigment can also be removed by distillation either with steam

in vacuo, or with ethylene glycol. The use of ultra-violet rays is also
helpful in removing pigment.
The rectification of the essential oils that are recovered by the

various extraction technology can be achieved by the total
distillation of the odoriferous constituents by molecular distillation,
leaving behind the pigments, and the long-chain terpenes. The
rectification of essential oils can also be achieved by steam
distillation process that distills off the total flavor components of
the oil leaving behind the high-boiling materials and pigment in
the distilling unit.
Membrane process may be used for removing the undesirable

terpenes like monoterpenes and sesquiterpenes. Partitioning of the
extracted oils between two immiscible solvents like a nonpolar
solvent (e.g., pentane or hexane) and aqueous ethanol (70-80%; vi
v) can be useful in improving the quality of the extracted aromatic
oils.
Thermometer ...
Manometer
: . To vacuum pump
Drain Condensate Condensate
Fig 7. Essential oil fractionation unit

FRACTIONATION OF ESSENTIAL OILS

The essential oils directly or after rectification are further processed
to isolate their major constituents for better perfumery applications
or the major components thus recovered are derivatized to new kinds
of perfumery materials (synthetics) for better uses or for new
extended applications. The fractionation can also be helpful in
removing the sesquiterpene hydrocarbons, which are undesirable
components in the aromatic oils.
Essential oil
..,.....---. Heating oil out
Internal condenser
-----l~ Heating oil jacket
Heating oil in
receiver
Diatillate (fraction)
receiver
Fig 8. Fractionation of essential oil by molecular distillation
The fractionation can be carried out in a properly designed

distillation unit provided with heating and high vacuum (low
pressure) arrangements and fraction collectors. This process of
distillation 2-10 mm in vacuo is widely adopted in the essential
oil industry. The fractionation unit is shown in Fig 7 that indicates
the essential parts and arrangement for fractionation. The
essential oil is charged in the still and it is raised to the
appropriate range of temperature under varying vacuum (low
pressure) for achieving targetted fractionation. The vapors are
allowed to ascend the distillation column packed with Raschig
rings. The exact vacuum and temperature at the top of the packed
column is noted and the vapors are allowed to condense in a
vertical condenser. The condensate, which is a product of
fractionation is collected. There are a series of receivers to collect
the different fractions.
The short path or molecular distillation can be adopted to

fractionate essential oils efficiently below their boiling point into
fractions corresponding to their molecular size at low pressures.
Fractionation of some essential oils by molecular distillation is shown
below along with a diagram (Fig 8).
FRACTIONATION OF SOME ESSENTIALS OILS:

PALMAROSA OIL, LEMON GRASS OIL,
CITRONELLA OIL
1. Palmarosa Oil
Composition as determined by GC Geraniol 75.02%

Linalool 2.77%
Linalyl acetate 15.85%
Others 6.13%
Fraction I (yield 37 g) is collected at 2 mmHg pressure and 45 QC

Temperature, rich in geraniol, mixed with linalol.
Fraction II (yield 45 g) is collected at 2 mmHg pressure and 55 QC
contains a mixture of geraniol and linalyl acetate.
Residue (15 g) rich in color components, polymerized, and
resinified products
Total oil taken for processing: 100 g.
2. Lemon Grass Oil

Composition of citral as determined by GC is 75%.
Fraction I (yield 15 g) is collected at 2 mmHg pressure and 50 QC
temperature, rich in a-citral.
Fraction II (yield 68 g) is collected at 2 mmHg pressure and 50 QC
temperature, ~-citral and other constituents.
Residue (yield 16 g) mostly color components and resinous
products.
Total oil taken for processing: 100 g.
3. Oil of citronella
Composition as determined by GC Too many impurities
Citranellal 25%
Geraniol 30%
Fraction (yield 37 g) is collected at 2 mmHg pressure and 40 QC
temperature.
Molecular distillation data provide evidence of both fractionation

and rectification of the three essential oils. The fractions of each
essential oil obtained as above on mixing yield better quality essential
oils than the original one in respect of aroma characteristics. However,
the extent of fractionation and the composition of the fractions demand
for more critical optimisation of the process parameters like pressure
and temperature during distillation for obtaining high degree of
rectification and high-quality fractions enriched in individual
components that contribute towards the distinctive and specific aroma.
Technology of Production of Concentrated, Terpeneless, and

Sesquiterpeneless Essential Oils 9
Many essential oils contain terpenes, sesquiterpenes, diterpens,

etc., and even waxes. These components undergo oxidation and
rancidification and spoil the odor and flavor characteristics. They
also reduce the solubility of essential oils in alcohol.
It is therefore important that these undesirable components
are removed from essential oils so that the oils contain only the
oxygenated compounds and become more soluble in alcohol and
become much stronger in odor and retain most of the odor and flavor
characteristics of the original oils.
The removal of the terpenes, sesquiterpenes, etc., can be by

fractional distillation in vacuo or by extraction of the oxygenated
compounds (the constituents of essential oils) with dilute alcohol.
REFERENCES
1. Guenther, E., The Essential Oil D. Van Nostrand Company, Inc. London,
1: 112-113, 123, 1948.
2. Charles S. Sell, The Chemistry of Fragrances, Compiled by David H.
Pybus and Charles S. Sell, Published by the Royal Society of
Chemistry, UK, pp. 33-34, 1999.
3. Ratan, R., FM's Handbook of Aromatherapy, First Edition, Published
by FM's Aromatherapy, p. 9, 1997.
4. Poucher, W.A., Perfumes, Cosmetics & Soaps. Chap man and Hall,
London, Eighth Edition 2: 25-28, 31-33, 1984.
5. Moyler, D.A. and H.B. Heath in the Proceeding of the 10 th International
Congress of Essential Oils, Fragrances and Flavors: A World
Perspective; Washington, D.C., USA, Edited by B.M. Lawrence B.D.
Mukherjee and B.J. Willis 16-20 November, pp. 41-48, 1986.
6. Ferhat, M.A., B.Y. Meklati, J. Smadja and F. Chemat. Journal of
Chromatography A, 1112, pp. 121-126, 2006.
7. Bhattacharyya, D.K., Private Communication.
8. Poucher, W.A., Perfumes, Cosmetics & Soaps, Eighth Edition, Chapman
and Hall 2: 34-36, 1984.
9. Guenther, E., The Essential Oil, D. Van Nostrand Company, Inc, London,
1: 218-223, 1948.
Synthetic Perfumery Materials ••
Production and Applications
INTRODUCTION
Synthetic perfumery materials of various kinds of molecular

structures referred as "nature identical" have well-established
recognition for having very specific and characteristics aroma
and applications directly as well as in combination with the
natural aromatic (essential) oils in the multitude of perfumery
products. Natural oils are costly, whereas the synthetic materials
are cheaper thereby allowing these materials to find more uses
in industries.
The ingredients or the starting materials for most of the

synthetics are the terpenes and oxygenated terpene derivatives as
occurring in the natural aromatic or essential oils. The terpenes,
which are used mainly as feedstock are the so-called
"Monoterpenes". The monoterpene hydrocarbons are actually the
dimer of the basic C5 "isoprene" unit and contain accordingly CIO
monoterpenes acting as the key terpenes and the derivatives that
have been identified include geraniol-nerol, linalool, citronellal,
and citral. In fact, these terpene derivatives are most important
terpenes for the perfume industry. Moreover, these terpene
derivatives can be interconverted by simple reactions like
isomerization, hydrogenation, and oxidation.
The structures of the important oxygenated terpene derivatives

as stated earlier are shown below:
Geraniol (E) + Nerol (Z) Linalool Citronellol Citronellal
Two monoterpenes namely, a- and ~-pinene are also important

bulk feedstock for conversions into valuable synthetics. These two
pinenes are also interconvertible. Two more hydrocarbons, myrcene,
and dihydromyrcene Ccitronellene) are feedstocks for other fragrance
ingredients. Monocyclic monoterpene hydrocarbons like d-limolene,
terpinolene, a-phellandrene, and p-cymene are important materials
as well.
The structures of the monoterpene and monocylic monoterpene

hydrocarbons are as follows:
a-Pinene ~-Pinene Myrcene 8-Limonene Terpinolene a-Phellandrene p-Cymene
Cyclic Cmonocyclic) monoterpenes like I-menthol, l-carvone, and

a-terpineol are also important materials of commerce. Their
structures are given below:
I-Menthol I-Carvone a-Terpineol
The above kinds of terpenes and their derivatives are extremely

important materials for producing perfumery materials for the flavor
and fragrance industries.
Synthetic Perfumery Materials: Production and Applications 89
Aromatic hydrocarbons like benzene, toluene, xylenes, and

naphthalene also act as ingredients for making perfumery materials.
Phenol is also an important ingredient for synthesizing perfumery
materials.
The use of the above kinds of aromatic molecules in producing

perfumery materials has been assuming considerable commercial
importance, as evident from the literature showing a number of
perfumery synthetics.
The syntheses of various terpene derivatives having distinct aroma

from various terpene molecules and from the major ingredients of
various aromatic oils by chemical methods involving reactions like
oxidation, reduction, esterification, and interesterificationare already
well known to the fragrance industry. Even now, research activities
in the synthesis of either new kind of perfumery derivatives by
existing chemical knowledge or by developing new chemical reactions
are taking place extensively worldwide.
In recent years, biotechnology is gaining a lot of interest

significantly in the synthesis of various monoterpene derivatives based
on the biochemical transformations of monoterpene (acyclic and cyclic)
derivatives using isolated biocatalysts (isolated enzymes) and using
whole-cell microorganisms.
The majority of microbial (biochemical) transformations of

terpenoids has been performed on monoterpenoids. It is known that
monoterpenoids and their derivatives are widely occurring in nature
and they are the main constituents of many essential oils. In fact,
various monoterpenes, such as a-pinene, citral, citronellal, geraniol,
limonene, etc., are used in large quantities in the flavor industry for
the production of more valuable terpenoids.
The microbial transformation processes for terpenoids that have

been developed to date include a variety of oxidations, reductions,
esterifications, hydrolyses, and transesterifications. The resolution
of racemates by microbial enzymatic hydrolysis is also an important
development that cannot be achieved chemically.
Some microorganisms are listed along with their main activities:
The use of enzymes from above microbes on an industrial scale is

practised now. In fact, different enzymes are available in amounts
suitable for use in industrial scale. The use of isolated enzymes can
result in high-purity products by inhibiting the side products.
Microorganisms Bioconversions
Prokaryotes bacteria
Bacillus Hydroxylations, resolution of racemates
Corynebacterium Hydroxylations
Mycobacterium Oxidations, resolution of racemates
Pseudomonas All kinds of oxidative degradation
Streptomyces Hydroxylations, epoxidation, cyclization
Yeasts
Candida hansenula Resolution of racemates
Rhodotorula saccharomyces Steroselctive reductions
Candida cylmdracea Hydrolysis, esterification
Candida antarctica Esterification
Candida tropicalis Oxidation
Higher fungi
Aspergillus Oxidative degradation esterification,
transesterification, epoxidation, redox
reactions
Mucor Redox reactions, hydroxylation
Penicillium trzchoderma Resolution of racemates
Immobilized enzymes have technical advantages of handling,

recycling, and stability and are preferably used in many bioconversion
processes.
Various bioreactors with different mode of operations to improve

the production yield have been developed, namely, the stirred tank
reactor, fluid-bed reactor, packed bed reactor, air lift reactor, and
membrane bioreactor. Many bioconversions have been carried out in
these reactors with isolated enzymes and by microbial fermentation
in batch, fed-batch, and continuous operations.
Natural aromatic or essential oils are not always stable and they
develop odor and color problems when used in many scented products.
The synthetic materials are more stable only when used in products
by virtue of retention of their odors more tenaciously.
Economic considerations play a very important role in
the flavor and fragrance industries. Efforts are always made to produce
synthetics at a competitive cost so as to be affordable by
industry in their products. Many countries prefer to import
synthetics at reduced price. In India also, many synthetics used

to be imported but owing to high import (customs) tariffs the industries
are cutting down imports. This kind of situation has been motivating
Indian industries to utilize as much the natural essential oils or their
major constituents as possible in making targeted products by innovative
and by the most cost-effective methodologies or processes.
Essential oil analogs or the artificial flavors simulating the natural
odors derived from flower, fruit, wood, etc., have also been synthesized
by developing new syhthetic routes. Considerable interest and
importance still persist in this particular perfumery technology.
An interesting concept has been evolved correlating between the
odor characteristics and the chemical constitutions of the fragrant
materials. This understanding has made significant contributions in
synthesizing a variety of fragrant molecules.
The present chapter describes various kinds of synthetic perfumery

materials and essential oil analogues (artificial flavors) made from raw
materials, both naturally occurring essential oils or their major
constituents, and other ingredients adopting the chemical and
biotechnological methodologies. The chapter also includes a brief account
of the structure-odor relationship of various chemical substances.
CORRELATION BETWEEN ODOR CHARACTERISTICS

AND CHEMICAL CONSTITUTION: STRUCTURE-ODOR
RELATIONSHIPS
The odor characterisitics of a vast majority of the natural essential oils

from plant sources and from animal sources perplexed and mystified
the chemists who were engrossed in establishing their chemical
constitution and were making efforts to correlate between odor
characteristics and chemical constitution. Some interesting correlations
were drawn between structure and odour relationships (SORs).
Molecules of different functional groups (osmophores) may exhibit
nearly identical odors. Examples cited include benzaldehyde,
nitrobenzene, benzonitrile, and phenyl azoimide and found to have
practically identical odors.
There are, however, exceptions to this general concept, for example,

Methyl and ethyl ethers of J3-napthol have the odor of neroli,
whereas the methyl ester of anthranilic acid has the
odor of orange blossoms but ethyl anthranilate has a light odor,
and the isobutyl ester is odorless.
Among the same homologous series, the chain length plays an

important role irrespective of the functional groups. For example,
the lower aldehydes have unpleasant odors, while the aldehydes with
10 carbon atoms have delicate scents and the higher members are
odorless.
A chemical reaction does not necessarily lead to a change in the
odor characteristics, for example, hydro cinnamic aldehyde obtained
by the reduction of cinnamaldehyde smells of jasmine and lilac.
The position of the substituent groups in the benzene nucleus

affects odor. Although the meta compounds are odorless, the ortho or
para compounds display odour. Thus p-methoxy acetophenone has a
pleasant odor, the meta compound is odorless, o-aminoacetophenone,
o-amino benzaldehyde, and o-nitrophenol have strong odours, while
the meta and para bodies are odorless.
Among the three kinds of trinitrobenzenes only the symmetrical
form gives origin to perfumes. In fact, all trinitro derivatives of
aromatic hydrocarbons possess a musk like odor.
Some ring ketones and lactones, depending on their carbon
number, have interestingly specific odors. In fact, the structure-odor
relationship (SORs) could distinctly demonstrate that some large-
ring ketones and lactones have specific odors including pure civetone
and muscone odor. Some of the ketones and their od or characteristics
are shown below.
Ketones Odor characteristic
C9-C12 Camphor like

CI3 Cedar wood-like
CI4 Mixture of musk and cedar wood
CI5 Pure mu scone od or
CI6 Muscone and dihydrocivetone
CI7 Identical with dihydrocivetone
CI8 Slight civetone-like odor
CI9 Almost no odor
Based on the SORs, the synthesis and properties of the desired

large-ring compounds having strong natural musk odor have been
achieved.
A benzene ring with appropriate alkyl substituents and nitro groups

develops odor characteristics that resemble the odors of the natural
and synthetic musks although structurally the products are different.
The concept of molecular structures and musk odor relationship has
been produced by Baur, as illustrated below:
R
x x
x
where R ~ CH3 ; X ~ No 2 ; R' ~ C 4H lO ;
C5 H ll ; C3H 7 ; R-CO- ~ R is CH3
The attribution of the type of odor is of utmost importance for the

attribution of SORs. The sophisticated analytical methodologies, such
as spectroscopic (NMR, FTIR, DV). Chromatographic (GLC, HPLC)
and GC-MS technique have enabled over the years to elucidate
precisely the complex structures and composition of flavor molecules
(both natural and synthetic) and the attribution of SORs. Much more
attribution of SORs will be forthcoming for newer sources of essential
oils and synthetics to evaluate applications.
During the last decade, numerous papers and reviews related to

structure-odor relationship have been published highlighting subject
matter based on new theoretical concepts.
Chastrette and Rallet 1 have studied, based on hydrogen bonding

and dispersion theory (HBD), with emphasis on geometrical
constraints, structure-odor relationships for the minty note using a
set of 150 compounds (68 minty and 82 not minty) with known olfactory
descriptions and chemical structures.
Dimoglo et al. 2 have investigated by means of the electron-

topological method (ETM) using perfected software on the SOR for
ambergris odor, involving a series of 201 compounds with decalin and
nondecalin type skeletons (nearly 50% of them possessing ambergris
odor and 50% having no ambergris odor). A structural fragrant of
activity has been identified and the fragment consists of an oxygen
atom and five carbon atoms situated in both decalin and cyclohexane
parts of the molecules.
Zakarya et az.3 have established structure of sandalwood odor

relationship with neural networks (NNS) using descriptors known to
be responsible for sandalwood odor. As many as 85 compounds (39
sandalwood and 46 nonsandalwood odorants) with 7 acyclic, 19
cyclohexyl, 21 norbornyl, 32 campholenyl, and 6 decalin derivative.
The chosen chemical structures represent the main categories of
compounds developing sandalwood fragrance.
According to the authors, a compound should posses a minty odor

if its molecular structure needs several structural and geometrical
requirements.
An alicyclic ring (mostly with six carbon atom) and an oxygenated

functional group (hydroxy or carbonyl) located on C2 or on C3 to
accept a hydrogen bond are essential for the interaction between
molecules and the minty receptor sites.
Anselmi et al. 4 have investigated the relationship between chemical
structure and floral odor, based on the synthesis and the odor
evaluation of some spirane derivatives, designed on conformation
models. The authors report on the synthesis of a great variety of
potential floral odorants correlating the influence of the following
structural elements on the floral odor:
(i) Size of the alkyl group in tetrahydropyranyl ethers (THP)

derivatives of p-substituted phenols
(ii) Replacement of the benzene ring with a cyclohexane; effect
of the position of the alkyl group (limited to a methyl) on the
cyclohexane ring
(iii) Replacement of the THP group with a tetrahydrofuranyl (THF)
(iv) Substitution of either one or both of the oxygen in THP and
THF ethers with Sulfur
(v) Substitution of either one of the two oxygens in THP and
THF ethers with carbon
The authors, in fact have reported on representative examples to

indicate the effect of each type of modification of the floral odor. The
first series of odorants include THP ethers of p-substituted phenols
with alkyl groups of increasing size from methyl to tert-butyl, All the
compounds exhibit a pleasant floral odor. The typical note of white
flowers (lily of the valley, Muguet) is more pronounced in the isopropyl
and tert-butyl derivatives, and the odour intensity decreases with
increasing carbon number. The derivatives have hydrophobic region
similar to lilial and related molecules.
Synthetic Perfumery Materials.' Production and Applications 95
The substitution of the THP with the smaller THP ring does not
affect on average the odor of the corresponding derivatives. The
replacement of the benzene ring with the corresponding saturated
cyclohexane gives also pleasant odor. However, cis/trans isomers differ
in their odors.
The authors have also studied the effects of structural changes or
molecules in respect of their functional groups, the subtitution of an
oxygen with an atom of sulfur, the size and shape of the hydrophobic
part of the molecule, etc., on the odor aspects.
PRODUCTION AND USES OF SYNTHETIC PERFUMES

A: TERPENE ALCOHOLS AND THEIR ESTERS
Introduction
Certain terpene alcohols, as occurring in some natural essential oils,

are unique in character for having distinct aroma characteristics as
such and also when appropriately derivatized to esters. The more
notable terpene alcohols, which have recognition in commerce for
specific aroma, properties and usage pattern, are geraniol, citronellol,
nerol, linalool, menthol, a-terpineol, etc.
The terpene alcohols cited earlier and having commercial
importance have been described embracing their molecular structure,
source, isolation, properties, synthetic preparations, their
derivatizations into appropriate esters, and uses.
Geraniol and its Esters
Geraniol is a primary alcohol (C lO H 18 0; molecular weight 154) and

its structure is depicted as:
H,C ______
H C _ _ _ _ _ C=CH(CH,),C.C~;
,
HCCH,OH
or
or
CH,
H,C""
H,cAcH C(CH,),C·CH,
H;C / 11
H'C~~H,oH HCCH,OH
H;C CH,
Geraniol occurs as the main constituent (80-90%) of the oil

extracted from palmar os a grass (Cymbopogon martini var. motia) by
the steam distillation process. It also occurs in Java and Ceylon
where citronella oils are recovered from grass. The content in Java
oil is 26-40% and that in Ceylon oil is 30-40%. Geraniol (31%) also
occurs in geranium oil.
Isolation of Geraniol
Geraniol can be isolated in pure form from the individual essential

oils like palmarosa or geranium having high content of geraniol by
fractional distillation under vacuum collecting the fraction boiling at
114-115 °C at 12 mmHg.
Geraniol can also be isolated from an essential oil as a calcium
chloride addition compound in a low-boiling hydrocarbon solvent that
keeps in solution the other constituents/components of the source
oil. The solid addition compound is separated by filtration. The addition
compound is next decomposed by warming with water and the geraniol
released is finally recovered by steam distillation. The recovered
geraniol is further purfied by vacuum distillation or in a molecular
distillation unit.
Properties of Geraniol
Geraniol has the following properties:
Boiling point (OC) 114-115/12 mmHg, and
229-2301757 mmHg
Density, d15 (OC) 0.883
Refractive index n D 20 (OC) 1.4766
Synthetic Preparation of Geraniol

Geraniol can be synthesized by chemical and biotechnological methods.
In both methods, however, reduction reaction is involved.
In the chemical method, geraniol oil is made by reduction of citral
by in situ hydrogenation process treating citral with sodium amalgam
in a dilute alcoholic solution of acetic acid. The reaction is as follows:
H,O~ [H] H,C
/c = CH - (CH.) •. C - CH., - - - - - - ; » C = CH.(CH) •. C. CH,
H,C/ 11 H3 C
HC. CHO '" HC.
11 CH2 • OH
/'
Citral is also reduced to geraniol by treatment with methanolic

sodium borohydride first at 0 QC for 1 hour and then for 3 hours at
room temperature 5 .
lHJ NaBH,
H,C'-..,. MeOH H,C~
/ C = CH - (CH,),. C -CH, 1 hr. O"C and 3 hr » /C=CH. (CH,),.C-CH,
H,C 11 H,C 11
HC. CHO at room temperature
CH.CH,OH
The product is isolated by treating the reaction mass with cold

2(N) HCL to pH at 4.0. The product mix is then taken into water,
washed with brine and the oily layer is dried over anhydrous Na 2 S0 4 .
The distillation of the oily layer in a molecular distillation unit
yields the geraniol.
Biotechnological Method 6 of Geraniol Preparation
Biotechnological conversion of citral to geraniol can be achieved by

treating citral in suitable medium with a typical yeast preparation
like Saccharomyces cerevisiae 2415. The bioreduction is catalyzed
by the whole-cell organism in liquid medium containing maltose,
yeast extract, peptone, and mineral salts at pH 5.2 and at a
temperature of 30-32 QC. The optimum time, temperature, pH, and
growth of the organism with respect to yield of geraniol have been
established. In actual practice, the culture medium is sterilized and
it is inoculated with cells taken from the culture maintained on
agar slants (2%; w/v) incubated at 30-32 QC for 48 hours.
Bioreduction is carried out by adding 0.8% (w/v) of citral to the

48-hour oil culture, and the flasks are shaken at 30-32 QC
~C
S. cerevisiae
~C
30-32 QC, 3 days
Citral
Geraniol
for 3 days. After the cultivation, yeast cells are removed by

centrifugation (1200 g) for 10 minutes. The supernatant is extracted
with ethyl acetate three times. The combined extracts are washed
with distilled water. The organic phase is dried over anhydrous
magnesium sulphate and finally fractionally distilled.
The yield of Geraniol is 64% on the basis of citral.
Synthetic Preparation of Geraniol Esters 7
Geraniol esters of formic, acetic, propionic, butyric, and even benzoic

acids are well-known perfumery compounds. The preparation of these
geraniol esters can be achieved by both chemical and biotechnological
methodologies as cited below.
Geranyl Formate
Geranyl formate is best prepared by treating two parts of geraniol

with one part of anhydrous formic acid at ordinary temperature for
a long period of 7-8 days. The excess formic acid is washed out with
water to make the ester neutral. The ester is recovered by distillation
under vacuum at 104-105 QC at 12 mm or at 88 QC at 3 mm.
Chemical Route of Geranyl Acetate 7

The ester can be prepared by direct esterification of geraniol with
acetic acid using a mineral acid as catalytic agent or by reacting with
acetic anhydride and sodium acetate.
Geranyl acetate can also be prepared from linalool in a two-step

process. The first step involves the conversion of linalool to boric
acid ester. In the second step, the boric acid ester is heated with
acetic acid. The product is recovered by distilling under vacuum
(110-115 QC 110-11 mm) after washing out excess acetic acid and
boric acid.
Enzymatic Synthesis of Geranyl Acetate (Biotechnological Route)

In recent years, enzymatic synthesis with lipases as catalysts has
been used to produce terpene alcohol esters in anhydrous organic
solvents by trans-esterification reaction and by direct esterification
reaction as well.
The nature of the acyl donor used plays an important

role in the trans-esterification or esterification methodologies in the
presence of lipase as catalyst. Thus, yields of geranyl acetate are low

when acetic acid is used as an acyl donor in both trans-esterification
and esterification reactions.
Lipases from Mucor miehei and Candida antarctica have been

found to be efficient for geranyl acetate synthesis. The effects of
substrate concentration, temperature, enzyme concentration, time,
and solvents have been investigated.
Enzymatic Esterification Process 8 ,9
In the synthetic preparation of geranyl acetate, pure geraniol is

reacted in solvent-free approach by magnetic stirring in a flask
Enzymic esterification of geraniol of palmarosa oil with n-butyric acid

in heptane at 24 hours using Lipozyme IM9a
Variables % Esterification
Temperature (OC)
30 ± 2 89.0
40 95.1
50 94.3
60 92.0
70 86.5
Time (in hours) At 40°C
2 27.7
4 46.2
6 58.4
8 70.0
10 76.0
12 80.7
14 81.2
16 84.4
18 87.7
20 89.6
22 90.8
24 95.1
Lipozyme concentration (%, w/v)
10 85.5
20 95.1
30 95.3
40 96.8
Effect of acid concentration on esterification of geraniol of palmarosa oil

with n-butyric acid at 40 ·C / 24 hours
Amount of n-butyric acid (mL) % Esterification
1 48.0
2 87.0
3 95.1
4 94.5
5 78.0
Effect of different lipases on esterification of geraniol of palmarosa oil

with n-butyric acid in n-heptane
Lipases (1 g) % Esterification
24 hours 48 hours
Lipozyme lM 95.1 100.0

N ovozyme 388 22.0 31.6
Lipase A "Amano" 6 31.0 89.0
Lipase MAP-lO 60.0 83.0
with excess acetic acid at 60 QC in the presence of immobilized Candida

antarctica lipase (3%; w/w) on the weight of the reactants. The flask
is fitted with a condenser. The reaction is continued till the analysis
of the reaction mixture indicates a constant conversion by GLC.
The product is isolated by filtering off the enzyme and washing
the filtrate with water to remove acetic acid. The washed material
is dried with a desiccating agent (anhydrous sodium sulfate). After
the removal of sodium sulfate, the product is fractionally distilled
and the pure geranyl acetate is collected at 110-115 QC/IO-11 mm in
about 90% yield.
The synthesis of geranyl acetate by using acetic anhydride as acyl
donor in the presence of Pseudomonas sp. Lipase as catalyst has
been achieved at 97% of yield under optimum reaction conditions as
reported by Yee and Akoh 9 .
Mestri 9a has investigated enzymic esterification reaction variables
in making esters of geraniol as shown in the tables ahead:
The author has also studied the enzymic esterification
process using a packed-bed reactor and investigating the parameters
like the effects of acid concentration, temperature, and flow rate of
Variables % Esterification
Amount of butyric acid in mL (at 35 :t 2 ·C/S hr)

Flow rate 2 mUmin
1 77.2
2 86.5
3 96.5
4 96.0
5 100.0
6 94.0
7 84.3
Temperature (·C)
35 :!: 2 96.5
40 100.0
45 100.0
50 79.0
55 45.0
60 42.7
Flow rate (mL/min)

2 96.5
3 94.9
4 94.6
5 94.3
6 94.6
7 94.4
8 93.5
9 92.4
10 91.8
reactants on esterification of geraniol of palmarosa oil with n-butyric

acid with upward flow through the reactor as above.
Enzymatic Alcoholysis Process 10
The reaction is carried out using the geraniol and the acyl donor like
the acetate of methyl, ethyl, and butyl alcohol by stirring for 8 hours
with 10% (w/w) of the reactants Mucor miehei immobilized lipase at
40-60 QC depending on the molecular size of the acetate.
After the reaction, the lipase is recovered by filtration for re-

use. The geranyl acetate along with the acyl donor are distilled
under vacuum to remove the acyl donor, excess geraniol

(unconverted), and the geraniol acetate in pure form.
The yields of geranyl acetate are 76.4%, 76.6%, and 77.1%,

respectively, using methyl, ethyl, and, butyl acetates as acyl donors.
Mucor miehei (10%; w/w) HoC

ROAC (R = Me, Et, Bu); • H,C
40-60 °C; 8 hr
H,C CH, H,C
Geraniol Geranyl acetate
Other Esters of Geraniol
The geraniol esters of propionic, butyric, and valeric acids can be

prepared by chemical and biotechnological means adopting the
esterification process using the appropriate acids/anhydrides with or
without the adition of metal acetate for chemical process and with
the aid of lipases in the biotechnological process.
The geraniol esters of propionic and butyric acids have been
prepared by esterification in a solvent free system with Candida
antarctica lipase as described in the case of acetic acid (8) in about
100% yields.
Geranyl benzoate
The ester is readily prepared by treating geraniol with benzoic

anhydride in the presence of a catalyst like camphorsulfonic acid.
Perfumery uses of Geraniol and Geraniol Esters 7
Geraniol and its esters are recognized materials for perfume

applications. Geraniol has a distinct rose odor and it finds use in a
number of floral perfume compositions and in fancy perfumes.
Because of its stability in alkaline condition, geraniol is used in
soap perfumes.
The esters of geraniol possess rose-like odors or roseleaf odor,

depending on the nature of the acyl part of the ester molecule.
Geranyl formate has an odor simulating rose leaf fragrance and when
used in a perfume composition imparts a "floral" lift. The addition of
2-5% of geranyl formate in terpeneless petitgrain oil develops an
odor representing neroli oil.
Geranyl acetate for having a sweet typical roseleaf odor finds use
as an excellent sweetening agent in floral and fancy perfumes.
Geranyl propionate, butyrate, and valerate possess rose-like odors.

They are also used as modifiers in perfumes.
Geranyl benzoate has a mild rose-like odor and is an useful fixative

in rose perfumes.
The esters of geranyl acetate, propionate, and butyrate are used

as food flavors.
Citronellol and its Esters
Citranellol (C lOH 20 0; Mol. wt. 156) like geraniol is a primary alcohol

having the structure as:
CH3 CH,
H2C~ I
'} CH-CH2 (C~)2.CH.C~.CH20H

H,C CH'!CH,
HC"'
3
or or H2C
CH 20H
CH 3 CH,
H3C~ I CH
~'"
/ C = CH. (CH2)2.CH.CH2.CH20H
H3 C H 2C CH,
Citronellol occurs III rose, palmarosa, citronella, and Spanish

verbena oils.
Isolation of Citronellol
Citronellol is best produced by distillation under vacuum in a well-

designed fractionating column from its various natural source materials.
The fraction collected at 5-12 mm Hg pressure and 99-115 QC represents
the D-, L- or DL-citronellol.
Physical Properties of Citronellol
Citronellol occurs in D- and L-forms as well as in DL-form and

therefore varies in properties and aroma characteristics as indicated
below:
D-citronellol L-citronellol DL-citronellol
Boiling point (OC) 103°/5 mm 114-115°/12 mm 99°/10 mm
Density (d) 0.8604-0.8629 0.856-0.862 0.8988/17.5°C
Refractive index 1.4565-1.4579 1.4561

00'
[a] D n D -- -2.70 to +2.32° _4.2°
Synthetic Preparation of Citronellol
Citronellol can be synthesized by chemical and by biotechnological

routes.
Chemical Routes l l
Chemically citronellol can be made from geraniol by reduction with

freshly cut sodium in inert solvent in presence of preferably hydrogen
gas.
Appropriate quantity of geraniol is dissolved in a solvent like

xylene or benzene (1:6; w/w) and fresh sodium (20% of geraniol; w/
w) is added. Hydrogen gas is introduced and the entire reaction mass
heated to boiling and maintained so, for about 6 hours. Then the
mass is cooled in the hydrogen atmosphere and the xylene solution
is separated from the sodium used by drawing off from the top.
The xylene solution IS washed with water and later
steam distilled. After removing the solvent, the citronellol is purified

by fractionation (yield 70%).
Citronellol can be prepared from citral by hydrogenation in alcohol
with platinum black as a catalyst along with ferrous sulfate as a
promoter, at first to geraniol and continuing the reaction with more
hydrogen to citronellol.
Citronellol can be produced from citronellal by its reduction in

absolute n-butanol with aluminium shavings at 50-80 QC for 3-6
hours. After cooling the product mixture, water by nearly equal
volume of butanol is added when there is a separation of two layers.
The alcohol (butanol) layer is separated and distilled in vacuum to
separate the n-butanol from the citronellol (yield 80-55% on
theoretical).
Citronellal can be reduced to citronellol by silica supported nickel
catalyst and hydrogen gas at 80-100QC (yield: 60-70% of the
theoretical) or by electrolytic reduction.
Citronellal can be reduced to citronellol by sodium borohydride in

methanol first at 0 QC for 1 hour and then at room temperature for
3 hours2.
CH, CH,
H,C~ I NaBH. H~ , I
/C=CH. (CH,l,.CH.CH,CHO -------.~ )C=CH. (CH), CH.CH,CHPH
H,C/ MeOH, 0" C, 1 hr; H~ /
Citronellal 3 hr room temperature Citronellal
Biotechnological Route of Citronellol Synthesis 6
Citronellal can be converted to citronellol by biohydrogenation.

Microbial transformation by biohydrogenation of (±)-citronellal to (+)-
citronellol is carried out by adding 0.8% (w/w) of (±)-citronellal to the
48 hr old culture of the yeast strain Saccharomyces cerevisiae - 2415
taken in the flasks for the biomass growth. The flasks are shaken at
30-32 QC for 3 days. After the cultivation, yeast cells are removed by
centrifugation (12000 g) for 10 min. The supernatant is extracted
with ethyl acetate three times. The ethyl acetate solution is washed
with water and the organic phase is dried over a desiccant. The
solvent is removed to obtain the crude reaction products. The pure
citronellol is obtained by either column chromatography or by
distillation under reduced pressure. The crude products are passed
through a silicic acid (60-120 mesh) column and eluted with n-hexane-
diethyl ether solvent system, using appropriate volume to separate
the excess citronellal from the citronellol produced. The crude
products can also be isolated by fractionation by distillation at low

pressure when citronellal can be obtained at 90 QC/14 mm and
citronellol could be obtained at 103-115 QC/5 mm.
The yield of high purity (+ )-citronellol is 68%.
Several yeasts including Candida reukaufii AHU 3032 and

Rhodotorula minuta can stereoselectively reduce p-( -)-citronellal to
p-( -)-citronellol.
~HO
Candida renlwufi
AHU3032
~
~~OH
~-I- )-citronellol
Synthetic Preparation of Citronellol Esters l l
Citronellol esters can be synthesized by both chemical and

biotechnological routes involving alcoholysis reaction.
Chemical Route
Citronellol ester like citronellyl acetate can be best prepared by

alcoholysis reaction involving citronellol and individual low molecular
monohydric alcohol like methyl, ethyl and butyl alcohol ester of
acetic acid, as acyl donor in the presence of an alkoxide catalyst like
sodium methoxide or sodium ethoxide by agitating the mixture of
citronellol and corresponding acyl donor at 40-70 QC depending on
the nature of the acyl donor for a period of 30 minutes.
Reactions are carried out using terpene alcohol and acyl donor in
molar ratio of 1:5 in the presence of 0.2-0.4% sodium methoxide in
methanol on weight of charge as a catalyst. The catalyst is destroyed
by calculated amount of acetic acid. The product is next subjected to
fractional distillation to remove the individual esters of citronellol
from free citronellol (unreacted) and excess acyl donor.
The yields of citronellyl acetate are 81.4%, 87.2% and 92.3%,

respectively, using methyl acetate, ethyl acetate, and butyl acetate
and an alkoxide catalyst like sodium methoxide or sodium ethoxide
by agitating the mixture of citronellol and corresponding acyl donor
at 40-70 QC depending on the nature of the acyl donor for a period
of 30 minutes.
~~6::~H
~\
CH
NaOMe/MeOH
MeOAC, EtOAc BuOAc

KC t
H2CVCH20AC
CH
~\
CH,
H 2C CH.,
H 2C CH,
Citronellol Citronellyl acetate
Biotechnological Route 10 ,12
Citronellyl esters of acetic, propionic, and butyric acids can be

prepared by a microbial lipase catalyzed esterification reaction and
by alcoholysis reaction involving citronellol and appropriate
monohydric alcohol ester of each of the above acid.
Citronellol and alcohol ester of each acid are taken in a stirred

reactor in definite molar proportions with the alcohol ester being in
excess between 20% and 50% to aid the solubility of the reactants
and the product. A definite temperature, depending on the molecular
nature of the alcohol part of the ester of 40-50 QC or 55-60 QC is
maintained during the alcoholysis reaction.
After continuing the reaction to the stage of maximum conversion
as indicated by the TLC separation, the lipase is recovered by
filtration. The citronellyl esters are isolated from the filtrate by
fractional distillation.
CH,
H,C 0. CH,
"~ I
/ CH-CH,(CH,),CHCH,CH,oOCCH,
H,C
< Citronellyl acetate
Perfumery uses of Citronellol and its Esters
Citronellol has a distinct fine rose-like odor and is therefore an

important component of rose perfumes. It is also a constituent of
Lily-of-the-Valley perfumes. It serves as an useful sweetener in flower
and fancy perfume compositions. The rose-like odor of pure l-citronellol
has higher value than that of the o-citronellol in perfumery. It is
interesting that citronellol having methyl, ethyl, and phenyl groups
intensify the rose odor.
Citronellyl acetate has an odor resembling a mixture of lime and

bergamot oils. It is used in rose and carnation compounds. Citronellyl
butyrate imparts the odor of moss roses when used with oak moss
resin. Citronellyl propionate has a fruity-rose odor and it is used as
a modifier in rose perfumes. Citronellyl caproate has a fine rose
odor. Citronellyl valerianate is a liquid of peculiar rosaceous bouquet.
Citronellyl benzoate has an odor of dried rose petals. It is an excellent
fixative in all rose compounds.
C1oH1SO
or,
Terpineol
(X-
Synthetic Preparation 13
a-Terpineol is synthetically made from turpentine oil, which contains

a-pinene as the major component, and ~-pinene by a two-step process.
Step I: Conversion of pinenes to terpin hydrates. Turpentine oil

(1 part) is agitated vigorously in a stirred reactor in an inert
atmosphere (N 2 or CO 2 ) with 23% (w/w) dilute sulfuric acid (2 parts)
for about 4 days when the terpin hydrate formed crystallizes out. It
is separated by centrifuging and later it is purified further by washing.
Step 11: Conversion of terpin hydrate to terpineol. The terpin

hydrate is dehydrated to terpineol by treatment with a mineral
acid like sulfuric acid of appropriate strength. The process is
Synthetic Perfumery Materials : Production and Applications 109
carried out as follows: purified terpin hydrate (100 parts) is added to

an aqueous solution (5%; w/w) of sulfuric acid. Then adequate amount
(lOO parts) of benzene is added and the mixture is refluxed with
agitation at about 75°C for 4 hours or a period so when till the
terpin hydrate crystals are not visible when cooled to room
temperature. After the desired period of reflux, the mass is cooled to
30-40 °C and the supernatant layer of benzene-terpineol is separated.
The reactions are shown below:
C.CH"
// '
// / /C "
/
HC /'CH H"C/ ;'CH
I H C-C-CH
3 3 \ + I H C-C-CH, I
1
He C
~ /
CH 2
H2C~ \ /CH"
~CH/ ~CH/
a-Pinene ~-Pinene
Major constituents of turpentine oil
Dehydration
reaction
Terpin hydrate u-Terpineol
Biotechnological Route of Synthesis of a-TerpineoP4
a-terpineol has been synthesized by biochemical route from a-pinene,

the major constituent of terpentine oil, by bio-oxidation utilizing the
oxygenase enzyme occurring in Candida tropicalis yeast strain.
The process consists of adding the a-pinene utilization and the

nature of the transformation products are examined with time at
an appropriate temperature (30°C). The reaction is completed in
4 days. The isolated product is characterized by TLC and IR
spectroscopy and 13C NMR analysis. Pure a-terpineol is isolated
by column chromatography and eluting with 99:1 (v/v) hexane-
diethyl ether.
CH,
I
C
/ ''-'''~,
H2C~
HeC, CH z
rH
Candlda tropical is
"",CH,/
30"C, 4 days
I
COH
a-Pinene (+ )-a -Terpineol
a-Terpineol can be synthesized from limonene by Pseudomonas

gladiolus.
Pseudomonas gladiolus
H3C CH,
a-Terpineol
Perfumery uses of a-Terpineo[13

Pure a-terpineol is an important constituent of the lilac-type perfume,
as it resembles lilac in its odor. It is a very useful ingredient in soap
perfumes because of its resistance to alkali. a-Terpineol is used almost
exclusively in many flowery and fancy bouquets as a blending agent
as it blends well with many synthetics and essential oils.
rH,
C
HCOCH~
H 2C CH,
CH
I
C.O.COCH,
H,C / "CH d
Terpinyl acetate
Terpenyl acetate is synthetically made from turpentine oil by in

situ conversion of its major constituent pinene into terpineol and
then into the acetate derivative under a specific condition of treatment
of the oil with acetic acid containing a definite strength of sulfuric
acid at a particular temperature range and for a period of several
hours.
The product is isolated after removing the last traces of acid and
later fractionating under reduced pressure.
The details are as follows:
Step I: In situ conversion of turpentine oil into terpinyl acetate.

The acetylating agent is prepared first by mixing acetic acid (2 kg)
with sulphuric acid (0.05 kg) and water (0.05 kg).
The reagent is mixed in part (0.2 kg lot) with terpentine oil (1 kg)
at room temperature. The addition of the reagent is continued till
the oil becomes miscible. The temperature during the mixing period
tends to increase but is not allowed to exceed 50 QC.
The whole reaction mass is allowed to remain at 30-40 QC for
several hours. It is next diluted with water till there is a separation
of the oil phase. The oily material is treated with sodium carbonate
solution to neutralize the oil completely.
Step 11: Isolation of terpinyl acetate
The oily layer separated as above consists of terpenes and
terpinyl acetate. It is fractionally distilled. The fraction collected
at 110-115 QC at 10 mm pressure is the terpinyl acetate.
Uses of Terpinyl Acetate and Other Terpinyl Esters 15
Terpinyl acetate resembles linalyl acetate in odor. Being stronger,

harsher, and cheaper than acetate, terpinyl acetate is used to
strengthen the odor of artificial bergamot and lavender oils for soap
perfumes.
Other esters such as terpinyl formate, butyrate, iso-butyrate,
propionate, valerianate, anthranilate, and cinnamate are prepared
and used as perfumery materials.
Terpinyl propionate having odor nearly to that of French lavender
is used in making cheap lavender. Terpinyl valerianate prepared
synthetically is useful for blending in tobacco flavors.
Terpinyl anthranillate made synthetically is a liquid having an
odor almost close to that of lily of the valley and orange blossom.
Terpinyl cinnamate having a fragrant and persistent odor is useful
in making ideal perfumes in combination with rose and bergamot oils.
Biotechnological Route of Synthesis of a-Terpineol Esters16
a-terpineol esters of low molecular organic acids can be prepared by

enzymatic/ enzymic esterification process as an alternative of the
chemical process that requires specialized esterification conditions.
Esterification of a-terpineol with acetic anhydride or propionic
acid mediated by Rhizomucor miehei lipase has been dealt with.
Optimization of conditions for the esterification in terms of enzyme/
acid ratio, a-terpineol concentration, and incubation period are
investigated using response surface methodology.
The esterification reaction is carried out as follows
Equimolar concentration of a-terpineol and the organic acid in n-
heptane solvent are taken in a stoppered conical flask. The required
amount of the lipase is added. The reactants are agitated in a rotary
shaker at 37 QC.
The reaction is followed by determining periodically organic acid

content titrimetrically with 0.01 M NaOH and the percentage
esterification is calculated.
The unreacted acid is washed out with saturated solution of sodium
bicarbonate. The product mixture is next distilled and the a-terpinyl
esters are obtained.
The boiling point of a-terpineol is 220 QC, while the boiling point
of a-terpinyl acetate is 140 QC at 40 mm, and that of a-terpinyl
propionate is 190 QC.
Between acetic anhydride and propionic acid, the former shows

better yields at lower enzyme/substrate ratios than the latter. a-
Terpineol, which initially binds to the enzyme, can be more easily
replaced by acetic anhydride than by propionic acid. It is important
to note that for the a-terpinyl propionate system, differences in yields
up to 3.5 fold are observed for the same a-terpineol concentration
when higher amount of enzyme is used.
Linalool and its Esters
Linalool (C lO H 1S O; Mol. wt. 154) is a secondary alcohol and can be

represented as:
H,C
H,C
> OH
C=CH. (CH.,JCH= CH,

I
or
HC
'~
H,C
/ c.CCH 2)3·
CHa
I
I·
CH
CH =CH,
CH,
Linalool occurs in a number of essential oils in the free state as

well as in the ester forms. Two essential oils, namely, cayenne linaloe-
oil (Bois de Rose) with 80% linalool content and coriander oil having
60-70% linalool in the free state are the main sources for linalool.
Isolation of Linalool
Linalool is isolated from natural sources by fractionation like fractional

distillation in vacuo directly or after hydrolysis of the esters with
alcoholic potassium hydroxide solution in a well-designed fractionating
column. The fraction at 85-90 QC/20 mm Hg represents 8-linalool and
that at 86-87 QC/14 mm represents the l-linalool.
Properties of Linalool
5-Linalool I-Linalool
Boiling point (OC) 198-200 °C/760 mm 197-200 °C/756 mm

and 85-90 °C/20 mm and 86-87 °C/14 mm
Density (d20) 0.8679 0.8622
Refractive index 1.4652 1.4604
Specific rotation [alD
114 Perfumery Materials .. Production and Applications
Linalool can also be synthesized from a-pinene involving

hydrogenation, peroxidation, reduction, and pyrolysis steps in sequence
as indicated below 17 :
CH,
CH,
Hydrogenation catalyst
HC CH ~
H,C
CH
Pinane
a-Pinene
1
(1) Oxidation
(2) H/Catalyst
OH
OH
Pyrolysis
l1li
Heat
Linalool
Synthetic Preparation of Linalool
Linalool is synthetically prepared by certain distinct routes. One

important synthetic route, which is commercially promising, involves
the preparation of methyl heptenone, which in turn is reacted with
acetylene to give dehydrolinalool. This on hydrogenation yields the
linalool.
Linalool is also prepared from myrcene. It is first converted to

linalool acetate, which is afterwards hydrolyzed to free linalool. The
alcohol is recovered in pure form by distillation under vacuum.
The process is detailed as follows:
Step I: Preparation of myrcene hydrochloride.

Myrcene hydrochloride (1 mole) is prepared by treating B-pinene
pyrolysate (1 mole) with hydrogen chloride gas (1 mole) and 0.2%
cuprous chloride at about 10 QC for a period of 24 minutes.
Step 11: Conversion of myrcene hydrochloride to linalyl acetate.

Myrcene hydrochloride (1 mole) is mixed with anhydrous
ammonium acetate (1.3 mole) by stirring in course of 4 minutes.
After the mixing, the temperature is raised to 90 QC and maintained
at 90-95 QC for 6.5 hours by vigorous stirring.
The linalyl acetate (ca. 42%) is recovered as oily layer after treating
with cold water the myrcene hydrochloride and separating in a
separator. The other constituents comprise terpinyl acetate (10.3%)
and geranyl, and neryl acetates (35.7%).
The total yield of the linalyl and geranyl acetates is 77.3%.

Step Ill: Conversion of linalyl acetate to linalool and its isolation
in pure form.
Linalyl acetate is first obtained in pure form by distillation at 22-

25 mm and collecting the fraction boiling at 115-116 QC. This fraction
is hydrolyzed with alkali to free linalool, which is purified by
distillation under vacuum and collecting the fraction at 85-90 QC/20
mm.
Esters of Linalool
Formic, acetic, propionic, and benzoic acid esters of Linalool are

important derivatives for perfumery uses. One of the methods of the
production of Linalool esters involve the treatment of Linalool with
the particulate acid in the presence of chemical catalyst like a mineral
acid (hydrochloride or sulfuric) at low temperature. A mixture of
acetic acid and phosphoric acid can be an effective catalyst.
Synthetic Preparation of Linalyl Acetate 18
The simplest approach is to reflux linalool with acetic anhydride in

presence of fused sodium acetate for 1 hour. Afterwards the excess
acetic anhydride is removed by water washing. The material is next
distilled and the pure linalyl acetate fraction is collected at 95-97Q
and 8 mmHg. The yield is about 58%.
Linalool-rich oil containing 70% linalool when heated with acetic
anhydride in presence of acetic acid-phosphoric acid catalyst system
undergoes the acetylation reaction almost instantly resulting in
the rise in temperature (38-40 QC) that requires cooling to maintain
the temperature at about 40 QC. The reaction mass is stirred for
2 hours and left to stand at room temperature for 12 hours and
acetic acid as well as phosphoric acid. The product is fractionated

and the fraction collected at 95-115 °C at 10 mm is the linalyl
acetate with 85-92% converts. The oil is washed free of acetic
anhydride.
Esters of Linalool: - U ses 18
Linalyl esters like formate, acetate, propionate, butyrate and

isobutyrate, benzoate, cinnamate, anthranilate, and phenyl acetate
have distinct odor characteristics and therefore find specific
perfumery uses.
Linalyl formate with its bergamot-like odor is a sweetening

component of perfumes. Linalyl acetate is useful in artificial
perfumes, such as jasmin, ylang-ylang, cheap cologne. It is also
used in soap perfumery. Linalyl propionate is used in eau-de-cologne
and Jasmines for imparting freshness. Linalyl butyrate is useful
for blending in making lavender-type perfumes. Linalyl isobutyrate
has a strong odor of the lavender type and is useful in artificial
lavenders. Linalyl benzoate is similar to that of tuberose and it is
used as a blender in tuberose perfume. Linalyl cinnamate has a
sweet and persistant odor of lily-jasmin type. It is a valuable
constituent in jasmines, tuberose, and rose compositions. Linalyl
anthranilate has an intense odor or orange blossom type. It finds
much use in synthetic neroles, orange blossom, and jasmin. Linalyl
phenyl acetate has a fine fougere odor and blends well with
coumarin compounds.
Nerol and Its Esters
HaC)
H,C C."CHCH'.CH,.~.CH'
or
CH.CH 20H
Nerol Nerol
Nerol occurs in natural essential oils like rose, petitgrain, ylang-

ylang, champaca, neroli, and in many highly fragrant blossom oils.
Nerol is isolated from neroli oil and also from rose and petitgrain
oils.
Synthetic Preparation of Nero[19
N erol is synthetically produced from linalool and citral. Linalool

when boiled with acetic anhydride in equal parts in the presence
of sodium acetate for a long period (5-10 hours) yields geraniol
and nerol esters. The esters on saponification produce geraniol
and nerol which are separated by reaction with phthalic acid or
anhydride from excess (unconverted) linalool. The phthalates are
decomposed and the liberated geraniol and nerol mixtures are
treated with calcium chloride that forms an addition compound
with geraniol.
The nerol is separated by filtration and finally obtained in high
purity by distillation and collecting the distillate at 125 °C/25 mm.
Nerol is synthesized from citral (citral-a and citral-p) by reduction
with almunium isopropoxide in isopropanol. A typical case study
involves a reduction of citral (500 g) with a solution of aluminum
isopropoxide in isopropanol. As much as 70% by weight of citral used
the mixed alcohols (geraniol and nerol) have been obtained.
The two alcohols are separated as usual by the calcium chloride
treatment. The geraniol is removed as its calcium chloride addition
compound and the nerol isolated by filtration.
As much as 220 g nerol is obtained and 120 g geraniol.
Nerol is ultimately distilled and the fraction of pure nerol is

collected as usual at 125 °C/25 mm.
Nerol Esters
Neryl esters like formate, acetate, propionate, and isobutyrate are
important perfumery products.
Synthetically they are made by the esterification route similar to
the geranyl esters of the above acyl donors.
Perfumery uses of Nerol and Nerol Esters
Nerol and nerol esters (acetate, propionate, and isovalerate) possess

flowery and rose odor. The esters are used as best perfume for all
rose compositions.
Menthol and Its Esters
Menthol occurs in the free state between 40% and 50% in peppermint
oils. It also occurs in geranium oil.
Menthol
Synthetic Preparation of MenthoZ 20
Synthetically menthol is made from menthone by in situ

hydrogenation. The pure menthone, free from menthol and terpenes
is reduced by process using freshly cut sodium and ethyl alcohol.
The menthol is isolated after distilling off the alcohol and removing
sodium and alkoxide formed by water washing and crystallizing the
oily liquid at low temperature.
The process steps are detailed as follows:

Step I: Reduction of menthone to menthol
Pure menthone (L-) dissolved in 96% ethyl alcohol to form a 50%
solution by weight is charged into a closed steam jackated copper
still fitted with a stirrer. An inert atmosphere of nitrogen is
maintained in the still. Metallic sodium (5% by weight of menthone)
is added as small pieces in the still. After the entire sodium is
dissolved, the temperature in the still is raised to 80-90 QC slowly,
maintaining a vigorous stirring.
Step 11: Recovery of the product.
The alcohol is first recovered by distillation as much as possible.
The product (liquid form) is taken out from the still and cooled to
room temperature. The material is carefully washed with water until
neutral. The oily liquid is now cooled to -10 QC when crude menthol
(L-) is crystallized out in 70% yield.
Step Ill: Purification of Menthol (L-)
Menthol from above is purified when recrystallized from alcohol
yielding white crystalline needles of 34-36 QC melting point of menthol
(L). Synthetic L-menthol is also produced from the d-citronellal
occurring 40-60% by weight in natural citronella oil.
Another process for producing menthol in good yields comprises

dehydrogenating citronellol in presence of a copper-chromite catalyst
at 150-260 QC in hydrogen atmosphere maintaining a pressure of 0-
5 kg!cm 2 to produce menthone. Menthol is next produced by
hydrogenating the menthone produced at 110-130 QC and 10-50 kg!
cm 2 hydrogen gas pressure.
Menthol can also be produced by hydrogenating geraniol and
citronellol mixture to citronellol and later dehydrogenating the total
citronellol to menthone and next hydrogenating as usual to obtain
menthol.
In all cases, menthol is isolated in pure state by distillation under

reduced pressure.
A New Synthetic Method
An entirely new method of synthesis of menthol has been described

by Sell. It involves addition of propylene to m-cresol producing thymol.
Hydrogenation with copper chromite catalyst of thymol gives a mixture
of isomers. The hydrogenation product is optically inactive, having
been composed of 1- and I-isomers in equal amounts of all the four
conformational isomers. Menthol (62-64%), neomenthol (18-20%),
isomenthol (10-12%) and neoisomenthol (1-2%) constitute the
composition of the product. At atmospheric pressure, d, I-menthol
boils at 216.5 QC d, l-isomenthol at 218 QC and d, l-neoisomenthol at
214.6 QC. d, I-menthol has been obtained from the mixture by efficient
distillation.
The d, I-mixture is resolved by first making benzoate ester and

later being fractionally crystallized. The crystalized benzoate ester
has been saponified. Recrystallization of the saponified product gives
pure I-menthol.
The conversion steps are shown later:
Although above process uses cheap raw materials, it becomes costly

since a large number of process steps are involved.
Preparation from fJ-Pinene
I-Menthol can also be made from ~-pinene21. The process involves

conversion of ~-pinene to myrcene that acts as the actual material
for I-menthol. Myrcene is acted with diethyl amine and a strong
base. The product formed is N,N-diethylgeranylamine. On
~;!;o~:n~lOn ~ ~
CHl
OH Treated with
~ I ~ I ~
&
propylene H,. Distillation.
~I
~
m-Cresol
CH]
AI
•
HlC
5::
"
Thymol
CH
OH
CHI
Catalyst
copper
chromite
d,l M~nthul
.l.nd160mers
°
H
"
d.l-Menthol
OH
Converted to
( 1) FractIOnal
crystallizatIOn
..
(2) HydrolysIs 1 benzoate ester
Ester product
Pure I-Menthol d-Menthol I-Menthol
isomerization with the rhodium 2,2-Cdiphenyl phosphino)-l, I-binapthyl

complex, the enamine of citronellal is produced. Hydrolysis of the
enamine gives d-citronellal, which is cyclized into isopulegol by using
a Lewis acid catalyzed reaction. This can be hydrogenated to 1-
menthol.
I-menthol IS commercially produced in India to the tune of 200
tonnes per annum by camphor and allied company from
carene from Indian turpentine 21 . The process involves the
conversion of careen to d-isoterpinolene by isomerization,
~ ~) ~~
Treated wIth Isomenzed by rhodIUm
dlethylamme complex,
(PyrolysIs) and a base
• • I ~
[Rh[BINAIIIJCIQ
•
b-Pinene
Myrcene
n,n-Dlethylgeranyl amine
~OH ..
~o
ZnCI,
CH" HydrolysIS
(CyciIsed)
I-Isopulegol d-Cltronellal d-Cltronellal-n,n-Dlethylenamme
CH,
~OH
Hydrogenated
Wlth Raney
mckel
•
I-Menthol
pyrolysis, and again isomerization sequences. The d-isoterpinolene is

hydrogenated using a poisoned catalyst to d-3-p-menthene. The said
menthene is next epoxidized and the epoxidized product being
rearranged to a mixture of l-menthone and d-isomenthone. The
menthone mixture is epimerized with base to increase the percentage
of the I-isomer (l-menthone). The epimerized mixture is hydrogenated
to yield the d-and I-menthols, with the I-menthol in major amount.
The product mixture is next distilled to recover the d-menthol and
P ?
I-menthol.
2
Car-3-ene
_ _ _•
IsomerizatlOn
Catalyst
Car-2-ene
_--..
Heat I~ I somenzatlOn
d-tra n s-Llmonene
. •
d-Isoterplllolene
Eplmenzed with H/catalyst

1. Base Epoxldation with
Peracid and H' Hydrogenated
2. Hydrogenated iH/catalyst)
lH,'catalyst) 0
I-Menthol d-3-p-Menthene
(Major I-Menthone
+ d-Isomenthone
component)
d-Isomers
I-menthol is also commercially produced from d-pulegone 21 . On

hydrogenation, d-pulegone, is converted to l-menthone and d-
isomenthone mixture, which on distillation separated the two isomers.
The l-menthone is next reduced to I-menthol.
~
1 Separated by
dlsllllallon
2. LiNH,
• 98'6'1b)
-78"C OH
l-Menthene H
hydrogenated
d-Pulegone d-isomenthone I-Menthone I-Menthol
Synthesis of Menthol Esters

Menthyl acetate is an important ester of menthol (1-). It is very
readily synthesized by reacting with acetic anhydride in the presence
of fused sodium acetate. Generally equivalent amounts of menthol
0-) are boiled with the acetic anhydride and sodium acetate. Menthyl
acetate is isolated by distillation under reduced pressure. It distills
at 109 QC at 10-11 mmHg.
Use of Menthol and Menthyl Acetate
Pure I-menthol and pure D-L-menthol display a persistently pleasant

peppermint-like odor and flavor. Menthol finds extensive use in many
dental and oral preparations like toothpaste, tooth powder,
mouthwashes. It imparts remarkably a cooling effect on cold-sensitive
oral nerves and tissues.
Menthol is also used largely in medicinal preparations and in
confectionery. It is often used in coconut-soap perfumes as a
component.
Menthyl acetate has a peppermint-like odor and flavor and is used

like menthol.
Odoriferous Nonterpene Alcohols 22
Certain non terpene alcohols possess distinct flowery odors and find
perfumery uses.
The nonterpene alcohols are mostly the long-chain alcohols of
aliphatic series. Among these alcohols, mention may be made of n-
hexyl alcohol, n-nonyl alcohol, and n-decyl alcohol.
n-Hexyl alcohol (n-hexanol; CH 3 (CH2)4-CH20H) that has a typical

fruity odor is synthetically produced from ethyl-n-hexanoate (ethyl
alcohol ester of C 6 .0 acid) by Bouveault-Blanc reduction of methyl or
ethyl ester of n-nonaoic acid.
n-nonyl alcohol is also produced by catalytic hydrogenation of n-

nonaldehyde using an appropriate nickel catalyst followed by fractional
distillation after removal of catalyst. N-Nonanol is obtained at around
75% of theoretical yield of n-nonyl alcohol (b.p. 107.5/15 mm).
n-Decyl alcohol is also produced by Bouveault-Blanc reduction of

ethyl ester ofn-decanoic acid or by the high-pressure high-temperature
hydrogenation in the presence of a copper-kieselguhr catalyst. The
pure product (alcohol) is obtained by fractional distillation after
removing the catalyst. The alcohol is obtained at 120 °C/12 mmHg.
Perfumery uses of n-Alcohols
All the alcohols find extensive use in flower and fancy perfumes. n-
Hexanol has a typical fruity odor. It is often used as a modifier in
flowery bouquets. N-Nonyl alcohol has a rose-like odor like that of
citronellol and is used in artificial rose perfumes. As a modifier, it

finds use as a sweetening modifier and diluent for rose otto.
n-Decyl alcohol also has a sweet flowery odor similar to citronellol

and orris oil mixture.
It is an important material for artificial flowery perfumes like
rose, neroli, and cassie. It also is used in many fancy bouquets
providing a sweet note.
Unsaturated Non-terpene (Aliphatic) Alcohol 23
cis-Hex-3-enol is an unique unsaturated aliphatic (nonterpenic) alcohol

that has very distinct green odor. This alcohol occurs in natural
sources like freshly cut grass and strawberries.
It is synthetically made as outlined below. But-2-yne is reacted
with ethylene oxide in the presence of a strong base. The product is
hydrogenated over a Lindar catalyst to cis-hex-3-enol.
C i - - - - -...... F'Lj0H
OH
Ethylene HydrogenatIOn
Oxide • Lindlar Catalyst
C1S -Hex-3-ynol C1S -Hex-3-enol
cis-Hex-3-enol has a green odor resembling foliage and stems of

plants. It is characteristic of cut grass and is used to add a fresh
green top note to fragrances.
The esters such as the acetate and salicylate also find uses.
Odoriferous Non-terpene Aldehydes 24
Certain aliphatic (non-terpene) aldehydes have characteristic and

typical odors which make their use in the preparation of perfumes.
n-Heptaldehyde [n-heptanal, CH3(CH2)5CHO] is one of the aldehydes

of commerce having extremely limited use as a perfumery component.
n-Octylaldehyde (n-octanal, CH3(CH2)6CHO) and n-nonyl-aldehyde [n-
nonanal, CH3(CH2)7CHO] and n-decylaldehyde which occur in certain
essential oils have specific odor features and hence perfumery uses.
n-Dodecylaldehyde has odor feature suitable for certain formulations.
The production of the fatty aldehydes is made in commerce
adopting specific technology.
n-Heptaldehyde
n-Heptaldehyde is produced from castor oil by the process of pyrolysis

of the oil or its alkyl esters preferably followed by re-distillation of
the fraction collected during pyrolysis.
The methyl or ethyl ester preferably the methyl ester of castor

oil is heated under vacuum at high temperature (450-500 QC) when
the decomposition of the ricinoleate begins and distills over and
collects in a reserver.
The fraction is actually a mixture of n-heptaldehyde and undecenoic

acid. The two components are separated by fractional distillation.
The undecenoic acid is obtained at 140-170 QC/12 mm.
The heptaldehyde fraction is collected at 44 QC/9 mm in about 90%

purity and the yield of the aldehyde is about 25%.
n-Octaldehyde
n-Octaldehyde is technically produced from coconut oil which contains

n-octoic acid (caprylic acid) that comprises 5-10% of the fatty acids.
The oil is first methylated by alcoholysis process which involves

refluxing coconut oil with anhydrous methanol in presence of
potassium hydroxide as a catalyst. Normally, the amount of methanol
required in the reaction is in excess of the theoretical requirement.
The catalyst is used between 0.1% and 0.2% of the charge. The
reflux is continued at ca.70 QC for a couple of hours. After cooling,
the glycerol layer is washed to remove soaps formed. The soap-free
ester layer is fractionally distilled and the fraction collected at 85 QCI
25 mm is the methyl n-octanoate.
The methyl n-octanoate is converted to n-octanol by Bouveault-

Blanc reduction using metallic sodium and anhydrous ethyl alcohol.
The octanol is recovered after removing excess alcohol and sodium
derivatives (sodium ethoxide, sodium hydroxide) by fractional
Q
distillation and collecting the fraction at 96 CI17 mm.
The n-octanol is next oxidized by common oxidant like potassium

dichromate and sulphuric acid to the n-octaldehyde. The purification
of the aldehyde is done by the bisulphate addition compound formation
followed by decomposition of the addition compound to the free pure
n-octylaldehyde and further purified by distillation at reduced pressure
and collected at 60-61 QC/9 mm.
noN onylaldehyde
It is produced from high-purity oleic acid by ozonolysis-reaction-based

process. The oleic acid is brought in contact with ozone. The ozonide
is decomposed by hydrolysis under reducing conditions (hydrogen
atmosphere). The decomposition products on fractional distillation
yields 60-70% nonanol.
A classical method involves the dehydrogenation at 240 QC of n-
nonanol by passing it in the vapor phase at 3-5 mm pressure over
a copper spiral, coated with a layer of freshly reduced copper powder.
The unconverted alcohol after separation is recycled for further
dehydrogenation to increase the yield. In fact, 90% conversion to the
aldehyde (nonaldehyde) is achieved.
n-Dodecylaldehyde
It is produced from n-dodecyl alcohol by the usual dehydrogenation

process as described above. The n-dodecyl alcohol (Lauryl alcohol) is,
in turn, produced by the hydrogenolysis process of the methyl ester
of Lauric acid (Methyl laurate) obtained from coconut oil or palm
kernel oil by methanolysis reaction using a chemical catalyst (NaOMe)
or a biocatalyst like lipase.
The separation of the aldehyde as a pure product IS made by

distillation at reduced pressure.
Perfumery uses of the Aldehydes
n-Heptaldehyde is not recognized as perfumery chemical of

importance. It is only used in trace quantity in certain rose and
orange perfumes.
n-Octylaldehyde that occurs in lemon and lemongrass oils and in
certain other essential oils possesses a lemon odour and it produces
a flowery note to synthetic jasmine and rose perfumes.
n-Nonaldehyde is present in the oils like lemongrass, lemon,

cinnamon, and tangerine displays a characteristic rosy odor. It is
used accordingly in artificial rose ottos and also in fancy bouquets to
get rose, jasmine, and orange tones.
n-Decylaldehyde is a constituent of a number of essential oils

including neroli, lemon, lemongrass, coriander, cassia, and orris root.
It is used in perfumery because of its spicy and orange-like odor. The
aldehyde is a very useful component in synthetic floral ottos such as

jasmine, rose, neroli, cassie, and liquid orris. This aldehyde enhances
the pleasing flowery note.
n-Dodecylaldehyde in very low dilutions (below 0.5%) imparts

pleasant odor simulating the odor of the wild violet and its leaves.
It is used in violet perfumes and in certain pine oil bath perfumes
to impart a fresh note.
Some Linear Ketones and Lactones
An insight into the odor characteristics of linear ketones and lactones

points out that certain linear ketones and ketones have some kind
of odor.
Linear Ketones
Methyl-n-amyl ketone, ethyl-n-amyl ketone, and methyl-n-hexyl

ketone are reported to have odor.
Methyl-n-amyl ketone occurs in clove oil and in cinnamon bark

oil. Ethyl-n-hexyl ketone is detected in French lavender oil. Methyl-
n-hexyl ketone does not occur in nature. It has a fresh geranium-
like odor.
The above ketones have virtually no or very limited use in

perfumes. Methyl-n-amyl ketone is a useful modifier, when used in
artificial cassie oil. Ethyl-n-amyl ketone is an important component
of artificial lavender oil composition. Methyl-n-hexyl ketone is rarely
used in perfume mixtures.
Linear Lactones
Among the linear lactones, y-undecalactone is an important

perfurmery material. It is also known as peach lactone because of its
fruity odor. The aroma very strongly resembles that of coconut-like
odor. It is prepared from undecyclenic acid (~10-n-undeca acid) produced
from castor oil by pyrolysis process at high temperature (350-450 QC)
under vacuum with strong acid (e.g., conc. H 2 S0 4 ) or water both
yields y-undecalactone.
H+
H 2C=CH-(CH 2)K-COOH - - - . H,C(CH2)h-CH-CH2-CHcCO
~o~
y- U ndecalactone
Undecalactone is used for imparting a fruity note to all kinds of

fancy bouquets. It finds application in flower perfumes like jasmine
and roses.
Some special aliphatic ketones and lactones are synthesized by
biotechnology.
Aliphatic ketones, such as 3-octanone, used in lavender notes can
be prepared by using the fungus Phlebia radiata in the presence of
short-chain fatty acids.
2-Heptanone can be produced using immobilized Penicillium

roqueforti from octanoic acid.
y-Decalactone can be obtained by semi continuous fermentation of
Tyromyces sambuccus supplemented with ricinoleic acid.
Odorous Aldehydes, Ketones and Lactones (Five or Six-

Membered Ring)
Quite a large number of aldehydes, ketones, and lactones have distinct

odor and find use as constituent of perfume compositions. The odor
characteristics and perfumery applications depend on their molecular
structures. The linear aldehydes, ketones and lactones appear to
have odor characteristics different from the aldehydes and ketones
having five- or six-membered rings.
Aldehydes Having Ring Structure
Alpha-n-amyl cinnamaldehyde is best produced by condensing

heptaldehyde with benzaldehyde in presence of alkali catalyst
like sodium or potassium hydroxide, sodium methoxide, sodamide,
etc.
CRO CH=C-(CH2 )4-CH3
©l
-H,O
© 6RO
Benzaldehyde Heptaldehyde a-n-amyl Cinnamaldehyde

Technical Method of Preparation 25
The a-n-amyl cinnamaldehyde is produced on a technical scale by

adding an appropriate quantity (200 parts) of n-heptaldehyde dropwise
in course of 5 hours to benzaldehyde (600 parts) previously mixed
with an alcoholic solution (960 parts alcohol) of potassium hydroxide
(40 parts).
The product is isolated by removing the condensing agent and

alcohol and later distilling under reduced pressure and the fraction
collected at 140-141 QC at 5 mmHg pressure.
Yield: The yield of a-n-amyl cinnamaldehyde is about 80% of
theoretical.
Perfumery use
eHO
©oc~
OH
Vanillin
(m-Methoxy-p-hydroxy benzaldehyde)
Alpha-n-amyl cinnamaldehyde has a distinct jasmine odor. Its use in

making a perfume having jasmine odor is a compulsory choice. Its
use with jasmine produces the desired jasmine odor, while jasmine
fails to bring out the jasmine odor.
Vanillin is Commercially Produced from Eugenol as Occurring in Clove

Oil 26
The first step involves the conversion of eugenol to isoeugenol by

simple isomerization reaction by its treatment with potassium
hydroxide at a high temperature of around 230 QC. The isoeugenol
after isolation is acetylated to make acetyl derivative of isoeugenol.
The acetylated isoeugenol is oxidized to convert the side-chain

hydrocarbon to aldehyde group. The product is actually the acetyl
vanillin.
The acetyl vanillin is next treated with sodium bisulphite to

form sodium bisulphite addition compound, which is separated and
decomposed with dilute sulfuric acid to generate pure acetyl

vanillin.
Vanillin is obtained by alkali treatment of the acetyl vanillin
followed by acid treatment.
Finally vanillin is purified by crystallization from water at 60 cC.
The reactions are as follows:

The actual steps leading to the production of vanillin are described
in detail as follows:
CH,-CH;CH,
©lOCH,
OH
KOH ~
230C
CH;CH-{;H,
©lOCH,
OH
Ac9
~ ©::H
O-CO-{;H,
K,Cr,O. •
H,SO,(+O,J
CHO
~OCH'
O-CO-{;H,
Eugenol Isoeugenol Acetyl isoeugenol Acetyl vanillin
/H /H
CHO
~:N' ~:N'
~OCH'
NaHSO, ~ H,SO, BOIhng
• o OCH,
~
H,O
o OCH,
OH
OH O-CO-{;H,
Vanillin
Vanillin bisulfite Acetyl vanillin
bisulfite compound
Step 1: Isomerisation of eugenol to isoeugenol

Pure eugenol isolated from clove oil is isomerized by heating with
potassium hydroxide at 230 cC (1 part eugenol and 3-4 parts alkali).
The reaction mass is acidified in water medium. The oily layer that
separates out is further washed with water. The oily material is
distilled when pure isoeugenol is isolated.
Step 2: Acetylation of isoeugenol
Isoeugenol is acetylated by heating with acetic anhydride and fused

sodium acetate. Acetyl derivative of isoeugenol is isolated by distilling
off the acetic anhydride, washing out the excess anhydride, and sodium
acetate with water. The acetyl isoeugenol, if required, can be distilled
and collected as a colorless oil.
Step 3: Oxidation of acetylated isoeugenol
The oxidation of acetyl isoeugenol is carried out with dichromate
and sulfuric acid mixture and using either sulfanilic acid or p-
aminobenzoic acid to control the oxidation reaction.
Step 4: Separation of the acetyl vanillin and its purification by

sodium bisulfite treatment
The acetyl vanillin is either extracted preferable with benzene or

it is washed with water till free from the oxidant. The acetyl vanillin
is next converted to the bisulfite addition compound by treating with
sodium bisulfite solution (35%).
Step 5: Liberation of the acetyl vanillin
The sodium bisulfite solution of acetyl vanillin when boiled with

water removes the acetyl group and yields the sodium bisulfite
addition compound of vanillin in aqueous solution.
Step 6: Decomposition of the bisulfite derivative of vanillin to

vanillin
The aqueous solution of the bisulfite compound is boiled with

dilute sulfuric acid till there is no more evolution of sulfur dioxide.
The vanillin is obtained as a brownish-yellow solution.
Step 7: Purification of vanillin
The purification involves crystallization and distillation under

reduced pressure. The brownish-yellow solution is crystallized in the
usual earthenware vats. The crystallized vanillin is washed,
centrifuged, and dried. The dry vanillin is distilled under vacuum
and collected at 168-172 QC at 12 mmHg.
The product is further purified by recrystallization from water at

60 QC in the presence of sulfur dioxide and activated carbon. Vanillin
is obtained as a white product.
Vanillin can be produced from isoeugenol by ozonolysis. Vanillin

can be also made from phenol.
Vanillin is also produced from waste sulfite pulp liquor that contains
ligninsulfonic acid involving its hydrolysis.
OH
OH OH
~ ~I
~ FormYlatlOn~
9r
oMO
6
Phenol Catechol
V
Guaiacol
OMe
Guruacol
CHO
Vanillin
Yield of Vanillin
The yield of vanillin is 65% of the theoretical quantity of isoeugenol

used.
Physical and Odor characteristics and usage pattern of

vanillin
Vanillin is a white substance that crystallizes in needles. It has a

melting range 81-84 QC depending on its purity.
Vanillin is an important perfumery sustance. It is used as a fixative,

modifier, and blender. Vanillin finds extensive use in many food
products including chocolates and ice creams.
Vanillin by Biotechnological Process 27 ,28
Isoeugenol is utilised by Rhodococcus rhodochrous when it is grown

in a suitable medium containing isoeugenol for 3 days at 30 QC.
OH OH
© OCH
CH=CH-CH 3
3
Rhodococcus
rhodochrollS,
30 °e/3 days
©CHO
OCH
3
Isoeugenol Vanillin
Aspergillus niger
Vanillin can be made from ferulic acid by bioxidation process 28 .
OH
Bioxidation
CH=CH-COOH CHO
Vanillin production from Ferulic acid by biotechnological

process
Ferulic acid is recognized as a suitable precursor for vanillin

production by biotransformation using bacteria, fungi, plant cells or
genetically engineered microbes.
The biotransformation of ferulic acid to vanillin has been studied

and optimized.
Narbad and Gasson 29 have reported that a strain of pseudomonas
is capable of growth on ferulic acid converting it to vanillin. A novel
metabolic route is proposed in which CoASH and ATP are required
for initial C2 cleavage of the side chain.
CH=CHCOOH CH=CH-CO-SCA CHO
~~, ~,u ~orn'

CoASH Cleavage
~ ~ CH,.CO·SCoA
ATP+ l'ilgh activity
ferulate COA
lIgase
OH OH OH
Feruhc aCId Ferulo)'I-CoA Vamlhn Acetyl-CoA
Hue et ai.30 have elucidated a successful fedbatch biotransformation

strategy using Streptomyces sp. strain V-I and an adsorbent resin to
enhance vanillin production from ferulic acid. Several macroporous
adsorbent resins have been used to adsorb vanillin in situ during the
bioconversion. Resin DMII has been found to be the best which adsorbs
the most vanillin and the least ferulic acid. When 8% resin DMII
(wet w/v) with 60-70% water content is added in the biotransformation
system, 45 g/1 ferulic acid could be added continuously and 19.2g/1
vanillin was obtained within 55 hr, which was the highest vanillin
yield by bioconversion process until now. The resin in which vanillin
is adsorbed is collected and eluted with butyl acetate (1:2; w/v).
Desorption is performed shaking at 200 rpm for 2 hr. at 30 QC. 100%
of the adsorbed vanillin is released.
eHO
<?-1.
Heliotropin (piperonal)
Heliotropin (piperonal) is prepared from safrole, a major component

of sassafras oil, by isomerization of safrole to isosafrole and later
oxidizing the isosafrole to heliotropin (piperonal).
CH=CHCH, CHO
Isomerized with Oxidation

~
KOH (alcohohc) o Dichromate and
o sulfonic aCid
O-CH,
I O-CH,
I
Isosafrole Heliotropin
Safrole
(also called piperonal)
Step 1: Isomerization of safrole to isosafrole 31

Safrole (60 kg) is refluxed with an alcoholic solution of sodium
hydroxide (40 kg dissolved in 100 kg of 96% alcohol) for as long as
22 hours.
Step 2: Isolation of isosafrole
The above reaction mass is distilled to recover alcohol as much as
possible. Water is added to the vessel in sufficient quantity and
discharged into another vessel where the isosafrole separates as an
oil after some hours. The oily matter is washed and purified by
distillation. The fraction is collected at 123 QC and 12 mmHg as pure
isosafrole.
Step 3: Oxidation of isosafrole
Isosafrole is oxidized to heliotropin by potassium dichromate and
sulfuric acid or by chromic acid in acetic acid. The oxidant solution
is added dropwise to the required quantity of isosafrole with stirring
maintaining a temperature between 50 and 60 QC in the presence of
p-aminobenzoic acid and salts of iron, cobalt, and manganese. The
oxidant solution is prepared by mixing potassium dichromate and
sulfuric acid in appropriate amounts.
The oily layer is separated and treated with sodium bisulfite to
form the bisulfite additive compound. The unreacted isosafrole IS
removed by benzene extraction.
The water-soluble heliotropin bisulfite addition compound is boiled
with dilute sulfuric acid till the evolution of sulfur dioxide ceases.
The heliotropin liberated is extracted with benzene. The benzene
is removed by distillation and the heliotropin is obtained
between 54% and 61% of theoretical as white crystalline compound

having 35-36 QC melting point.
Heliotropin can be produced from phenol via catechol.
6 6t
Phenol
H,O,
Fe'· salt
~
Catechol
Formylation
~
&+
Methylene of
catechol
Heliotropin
Odor Characteristic and Perfumery Use
Heliotropin resembles the odor of the essential oil of heliotrope

flowers. It is an important synthetic perfumery chemical. Heliotropin
can be utilized in preparing further derivative having a distinct floral
note by aldol reaction between heliotropin and propionaldehyde,
followed by hydrogenation to give the hydrocinnamaldehyde derivative
known as Helional or AquanaP2.
Hydroxy citronellal
HlC)
HC C(OH)-CH 2-CH2 -CH-CH-CH
2 2
-CHO
a I
CHa
Hydroxy citronellal is prepared from citronellal after converting it

into the citronellal bisulfite addition compound, which is then hydrated
to the hydroxy citronellal under the suitable conditions of hydration.
The steps are indicated below:

The details of the synthetic preparation are described stepwise.
Step 1: Sodium bisulfite addition compound formation (preparation)

Citronellal of technical quality having 80% citronellal is taken as
the raw material. A 30% aqueous solution of sodium bisulfite is
made.
A definite quantity of the bisulfite solution is added to the

citronellal (definite quantity) and mixed by stirring. The whitish
bisulfite addition compound is isolated after filtration and washing
the filter cake with a benzene-toluene mixture (1:1; v/v) till the cake
is low in water content reaches a certain weight.
Citronellal bisulfite addition compound
1 Sulfuric acid hydration
H3 C )
H3 C
C(OH)-(CH2)2-CH-CH2-CH
I
< OS03 Na
OH
CH3
Hydroxy bisulfite addition compound
1 Na,CO, decomposition
H3 C )
C(OH)(CH2)2-CH-CH2-CHO
H3 C I
CH3
Hydroxy citronellal
Step 2: Hydration of the bisulfite addition product (cake)
The cake obtained in the above step is hydrated by treatment

with a definite amount of 50% sulfuric acid at low temperature
between 0 and -5 QC.
Step 3: Isolation of the hydrated (hydroxylated) product

The hydroxylated compound is neutralized with sufficient
sodium hydroxide solution (10% aqueous solution) by stirring at 15-

20 QC (below room temperature) when the bisulfite compound is
decomposed.
The hydroxy citronellal thus liberated remains soluble in benzene-

toluene mixture.
Step 4: Final recovery of the hydroxycitronellal
The crude hydroxycitronellal is obtained by recovering it from the

solvent by removing it by distillation.
The crude hydroxycitronellal is purified by fractional distillation

and collecting the distilled product at 108-109 QC and 3 mmHg
pressure.
Yield: The high-purity hydroxycitronellal is obtained III nearly

64% yield.
Perfumery Use
Hydroxy citronellal is an excellent component of perfume mixtures

of the flowers like Lily-of-the-Valley, lilac, and lime blossom, jasmin,
magnolia, and hyacinth. In small quantities it is used in perfumes
reproducing the odor of cassie, lavender and in some fancy perfumes.
It has, however, limited use in soap perfumes for its instability in
contact with alkali. It is a useful modifier in all perfumes. It is also
a fixative.
Terpene Ketones
Terpene ketones do not appear to occur in nature. Synthetic terpene
ketones also are a few in number only having characteristic odor.
Ionones, methyl ionones, and irone are important and well-known
synthetic terpene ketones.
Ionones (0.- and po)
Ionones both a and P forms are exclusively made from citral, a
terpene aldehyde.
Citral is first converted to pseudoionones by reaction with acetone
in the presence of alkaline condensing agents. The pseudoionones
after isolation in the pure form are cyclized in the presence of an
acid catalyst like conc. H 2 SO 4 for p-ionone and in the presence of
conc. H 3 PO 4 and formic acid for a-ionone.
,
H,C" / C H
C~CH =CH-CO-CH,
H2C/ CH
I
H2 C
I
C
"-CH./'''-
CH,
C l1H 200 a-Ionone ~-Ionone
The two isomeric ionones are separated through their bisulfite

addition compound formation and steam distillation when the ~-isomer
decomposes and gets steam distilled. The a-isomer remains in the
residue as the bisulfite derivative which is next decomposed and
recovered by distillation.
Finally, the two ionones are purified by re crystallization separating
one isomer in preference to the other one that remains in solution.
The reactions are shown below:
Preparation details 33 ,33a
Step 1: Pseudoionone preparation from citral (lemongrass oil).

Lemongrass oil containing 65-80% citral is mixed with equal parts
by weight acetone and the mixture is stirred in the presence of a
condensing agent like sodium hydroxide as 10% solution. The
ternary mixture is stirred for 72 hours at a temperature not
exceeding 35 QC in an appropriate vessel. Afterwards the lower
layer is removed and the upper reddish-brown oily layer that
contains the pseudoionone, the unconverted citral, and acetone is
washed with water.
The reddish-brown oily layer is now fractionally distilled under
vacuum. The fraction collected at 135-150 QCJ3 mmHg is the
pseudoionone with quantitative yield.
Step 2: Cyclization of pseudoionone to a- and ~-ionones
Pseudoionone is cyclized to a- and ~-ionones together in different

proportion when treated with 60% sulfuric acid under the condition
of specific temperature control.
Pseudoionone (1 part) is cooled to ca. -10 QC and the 60% sulfuric
acid solution (3 parts) is also cooled to -10 QC by stirring.
CH3
H:lC> I
C=CH( CH2)2-C-CH-CHO+CH3-CO-CH3
H3 C . .
Acetone
Citral
1 Condensing agent (NaOH)
Pseudoionone
1 CycHzaHon by add cataly,'
C"H,,,O a-Ionone ~-Ionone
The cold acid is added to the cooled pseudoionone at a rate till

there is a gradual rise in temperature. Afterwards, when the
temperature rises to about 30 QC, there is a sudden change in
dark brown color. The mixture is heated rapidly to 42 QC and
poured on to crushed ice. The crude ionones separate as a brown
oily material.
The cyclization reaction of pseudoionone may proceed at high
temperature (100-150 QC) with use of catalytic amounts of acids (0.05-
0.2 mole/mole, phosphoric acid preferably). Ionones are obtained with
high yields and consist of a and P isomaers. This method is also the
best one from ecologic consideration 33a .
The aqueous acid layer is extracted with benzene. The organic

layer and the crude ionones are mixed and washed with water till
neutral. Finally the crude ionones are separated and purified.
Step 3: Separation and purification of the ionones

The mixture of crude ionones, benzene, terpene by-products, and
water are now distilled under vacuum. The first fraction is collected
at 100 QC and 10-12 mmHg to remove the components other than the
two ionones. At 2-3 mm, the a-ionone gets distilled at 118-125 QC and
the ~-ionone distills at 130-135 QC.
Yield: The ionones produced contain 80-90% a-ion one and 10-
20% ~-ionone. The yield of the total ionones is about 40% of the
weight of lemongrass oil used or 70% on the citral content.
Odour characteristics and Perfumery Applications 33
The ionones have a violet odor.

In fact, the ionones are important constituents in violet perfumes.
The ionones find perfumery use as valuable ingradients of artificial-
lily-of-the-valley, tuberose, jasmin, cassia, and of almost all fancy
perfume compositions.
Unlike citral, the ionones are stable in soap alkalinity and serve
as valuable constituents of many soap perfumes.
a-Ionone has a sweeter and lighter "top-note" odor than ~-ionone

and has therefore a preference in perfume compositions. ~-Ionone
when diluted produces an odor which is less sweet and heavier and
resembles to both violet leaves and violet blossoms.
Methyl ionones
n-Methyl ionones (a and ~) are prepared from citral and methyl ethyl
ketone by first condensation and later by cyclization and separation
in a similar manner like the a- and ~-ionones.
H3C"", /CH 1 H,C"", / CH,
/C"", /C"'"
Hr ,H-cH=cH-cocH2-CH3 Hr ~-CH=CH-COCH2-CH3
H,C C-CH3 H,C C-CH,
"CH./' "CH/
a-n-Methyl ionone ~-n-Methyl ionone

The reactions are depicted as follows:

Condensation reaction
(CH,),C=CH=CH,-CH,-C=CH-CH=CH-C-CH 2-CH, + H 20
I
CH, o"
n-Methyl pseudoionone
Cyclization reaction
n-Methyl pseudoionone
! H 2 SO.
H;C" /CH,
/C"
H'I ~-CH=CH-CO-CH'-CH'
CH,C C-CH,
"'-CH/
,
~-n-Methyl ionone
orusing
H,C" /CH,
1 H 3P0 4
/c"
H'f IH-cH=cH-cocH,-cH,
H,C C-CH,
"'-CH,/'
a-n-MethyllOnone
During the condensation reaction, isomethyl pseudoionone is

produced as a product having the structure as follows:
Isomethyl pseudoionone
Isomethyl pseudoionone on cyclisation yields the two isomethyl

ionones as shown below:
Isomethyl pseudoionone
/~
H,C"", / C H , H,C~ / C H ,
H'f
/C~
lH-CH=C(CHJ-CO-CHl H'f
/~
C
r CH =C(CH,l-CO-CH3
H,C C-CH, H,C C-CH3

- "-CH.!' "-CH.!'
2
a-Isomethyl ionone ~-Isomethyl ionone
Isolation of the 4 Methyl Ionones
The 4-methyl ionones are first converted to their semi-carbazones

which are isolated by crystallization.
FIVE AND SIX-MEMBERED KETONES
Jasmone is a five-membered ring ketone and possesses the

characteristic jasmine odor. In fact, five- and six-membered ring
ketones with an alkyl group on a carbon atom close to the ketone
group (> CO) exhibit jasmine odor. The actual and the strongest
jasmone odor is associated with five-membered ring ketone.
CH 3
I C
H,C
/'\ C-CH2-CH=CH-CH,-CH3
I
H,C---CO
I
Jasmone
The six-membered ring ketone like the 2-n-pentylidene cyclohexane-

I-one possesses a pronounced jasmone note.
Some five- and six-membered ketones as shown below posses the

typical jasmine odor:
/CH,\ /CR",
CH
/ "'- H,C CR HC CH
H,C CR
I I 11 I
I I H,C CH, HC C=R
H,C CO
"'co/ '\.co/
2 3
R in 1 = (CH2)5CH3 has a jasmine, flowery smell;

R in 2 = -(CH2)4CH3 has a jasmone, aromatic note.
Synthetic Preparation of Jasmone 33
Jasmone can be made from ~3-hexene-I-ol and from an appropriate

y-diketone.
(A) ~3-Hexene-I-ol
is converted to the acid chloride, which is
brominated to form a tribromoester, which is then
condensed with laevulinic ester in the presence of zinc, to

yield a lactone. The lactone is cyclized to a ketone that is
recovered as a semicarbazone derivative.
The ketone regenerated displays odor similar to the natural
jasmone.
HBr
CH J -CH2 -HC = CH. CH2 CH 2 0H -------l~~ CH 3-CH2 -CH=CH-CH2 CH2 CH,Br
to.' -hexene-l-ol In acetic acid
KCN SOC!,
R-CH,Br -------.~ R-CH2 CN ~ RCH,-COOH -. R-CH,COCI
Br,
R-CH,-COCI ----1~~ CH 3-CH,CHBr-CHBr CH,CHBrCO,C,H,
CH CH,CHBrCHBr CH,CHBrCO,C H + CH ,-CO-CH -CH,COOC,H,+ Zn

3 2 5 2
CH,-C-CH(C02 C,H 5 )CH,-CH = CH CH,-CH,
I'O~ Cyclized with sodium, and treatment

CH,-CH,-CO
Lactone
1
CH,
with dilute mineral acid
I
/c,
H'i rCH,-CH,CH-CH,-CH,
H2 C CO
Jasmone
(B) Jasmone can be synthesized from y-diketones by ring closure

and cyclization as detailed below.
CH 3CO-( CH2)2CO-CH2R
y-Diketone
(A) Alkaline treatment using aqueous or

Alcoholic alkali or an organic base or even
alkaline material like borax or sodium
acetate, to achieve Ring closure;
/c"-
r
(B) Further processed by treating at low or H 2C C-R
room temperatures with alkali alkoxide
(alcoholic) to achieve cyclization;
H 2C
I I
CO
Odour characteristic and perfumery use of five- and six-

membered Ketones
Five-membered ketone such as Jasmone has the characteristic jasmine

flower odor. Some six-membered ketones exhibit jasmine note.
Benzyl acetone
Synthetic Preparation 34
It is prepared readily by alkaline hydrolysis of a-benzyl acetoacetic

ester or of benzylacetonoxalic ester:
2KOH
-----+~ H3C-CO-CH2+ ~C03 or N~C03
2 NaOH
Benzyl
acetone
+2KOH
----+~ H3C-CO-CH2 + ~C03 + C2H 5 0H
I
H 2 C-C 6H 5
Benzyl acetone
Benzyl acetone is also obtained by heating ethyl benzyl acetoacetate

with water in a closed reactor at 250 QC for 30 minutes. The yield
of benzyl acetone is around 88%.
Perfumery use
Benzyl acetone because of its similarity with benzyl acetate is much

closer to jasmin and hence it is used in soap perfumes. It is useful
in certain gardenia and hyacinth perfume mixtures.
CO=CH J
©
Acetophenone
Synthetic preparation 34
An elegant process for the synthetic preparation of aceto phenone

involves heating on a water bath a mixture of benzene and acetic
anhydride in presence of anhydrous aluminum chloride until hydrogen
chloride ceases to evolve.
After cooling the reaction mass, the product is treated with ice
water and hydrochloric acid and subjected to steam distillation to
recover acetophenone and excess benzene together. The mixture is
extracted with benzene and fractionally distilled under reduced
pressure.
The fraction collected at 94-95 °C/20 mmHg is pure acetophenone

(85-92%/yield).
(CH3CO)20 + AlCl 3 ----. CH 3-CO-Cl + CH 3- COOAlCl 3

CH 3-CO-Cl + AlCl 3 + C6H6 ----. CH 3COC 6H 5-AlCl 3 + HCL
CH 3-COOAlCl 3 + AlCl 3 + C6H6 ----. CH3COC6H5-(AlCl2)20 + HCL
CH3COC6H5(AlCl2)20 + 2HCl ----. CH 3COC 6H 5 + 2AlCl 3 + H 20
Perfumery Use
It is used chiefly in toilet soap perfumes because it does not cause

darkening of soaps. In this respect, it is preferred to coumarin for
use in white and light-colored soaps.
TERPENE ALDEHYDES
Terpene aldehydes of CIO acyclic monoterpene occur in a limited

number of armatic oils. Two well-known terpene aldehydes are namely,
citral and citronellal. These two aldehydes are produced commercially

from the natural essential oils and are also synthetically made.
These two aldehydes have distinct perfumery uses.
Citral
Citral ClOH160 has the following structure:
C
H3 )
HC C=CH-CH 2-CH 2 -TI-CH 3
(or)
J HC-CHO
Citral occurs predominantly in lemon grass oil between 65% and

80%. Citral can be produced from lemon grass oil either by molecular
distillation or by molecular distillation of the citral isolated in nearly
pure form as the sodium bisulfite addition compound.
Isolation of Pure Citral from Lemon Grass Oil 35

1. Treatment of lemon grass oil by sodium sulfite.
Pure lemon grass oil (appropriate quality 1 kg) is added to the
aqueous solution of Ca. 2 kg sodium sulfite and 0.6 kg sodium
bicarbonate cooled to 5-10 QC by vigorous mixing and
continuing the mixing for around 4 hours. The citral present
in the oil is converted to water soluble dihydrodisulphonic
acid derivative. The unconverted (unreacted oil) oil is extracted
out by solvent like petroleum ether (b.p. 40-60 QC) or diethyl
ether.
2. Regeneration of citral from the disulphonic acid derivative.
Citral is regenerated from the dihydro disulphonic acid
derivative by its treatment with dilute solution of sodium
hydroxide in the presence of ether as aolvent to complete
neutrality or to alkaline pH. The ether layer contains the
liberated citral.
3. Purification of the citral solution.
The ether solution of citral is very rapidly worked with dilute
solution of tartaric acid and with water alternately.
The ether solution after drying and removal by distalltion

yields about 80% of Citral at 110-111 °C/11 mm.
Synthetic Production of Citral
Citral is synthetically produced by oxidation of geraniol by chemical

catalyst or by biocatalyst process as shown below:
Pseudomonas sp.
Cultured
Cells of Rosa centifolw

Geramol Citral
Uses: Citral is used mainly for preparing ionones, which find

better perfumery applications particularly in fine perfumery compared
to citral. It is also used for imparting lemon odor in perfumes.
Citronellal
Citronellal C lO H 1S O has the structure as
C
HJ )
C=CH-CH2-CH2-iH-CH2-CHO (Or)
H,C CH
"
Citronellal occurs predominately in Java citronella oil (40%).
Citronellal can be isolated from its natural source like Java

citronella oil by the fractional distillation process and collecting the
second fraction as the citronellal at 90 °C/14 mm. The first fraction
is the terpenes, and the residual fraction is the Geraniol.
Citronellal can be isolated by forming its sodium bisulfite addition
compound and later decomposing with sodium hydroxide and steam
distillation as outlined below:
1. Bisulfite Addition Compound Formation
The citronella-rich oil is added to a saturated solution of sodium

bisulfite in water by vigarously stirring at cold. Caustic soda solution

is now added, maintaining the temperature at 0 QC or below for 1
hour. A pasty mass is formed which is further treated.
H. Treatment of the Bisulfite Addition Compound
The pasty bisulfite addition compound is mixed by stirring with

benzene for several hours to remove the unreacted oil part. The
pasty mass is kneaded with benzene and pressed.
IH. Final Isolation of Citronellal
The solid cake formed above is steam distilled in alkaline condition

when the pure citronellal is obtained.
The citronellal is finally fractionally distilled to get the pure
citronellal at 90 QC/14 mm.
Synthetic Production of Citronellal
Citronellal can be produced by chemical or biochemical methods of

oxidation of citronellol.
Uses: Citronellal is used only in cheap soap perfumes. It is an

important material for the preparation of citronellol and
hydroxycitronellal.
Synthetic Perfumery Chemicals from Certain Aromatic

Hydrocarbons and their Oxygenated Derivatives
Aromatic hydrocarbons such as benzene, toluene, and naphthalene,

and oxygenated derivatives like phenol and cresols act as important
ingredients in the synthesis of perfumery materials. Styrene oxide is
also regarded as an important material for synthesizing fragrance
chemicals.
The commercially important fragrance chemicals synthesized from
the above ingredients are discussed.
Perfumery Materials from Benzene 36
Benzene as an ingredient enables to synthezis'e some fragrance

chemicals like phenyl ethyl alcohol, styrallyl alcohol esters,
Hydrocinnamic aldehydes as outlined below:
Phenyl ethyl alcohol
Benzene is straight way converted to 2-phenyl ethyl alcohol by

reaction with ethylene oxide involving Friedel-Crafts reaction process.
o
OH
Ethylene oxide
AlCl 3 catalyst
2-Phenyl ethyl alcohol
Use: The compound is a major component of rose oils and is

widely used in perfumery for its blending qualities.
Styrallyl Alcohol Esters 36
Benzene is converted to ethyl benzene that in turn oxidized by air

to the hydroperoxide, which is later reacted with propylene and an
appropriate catalyst to yield styrallyl alcohol.
Styrallyl alcohol is now esterified with low molecular weight

monobasic acids to yield a number of esters.
The esters are used in perfumery, the acetate being more

particularly used.
Hydrocinnamic aldehydes 36
Benzene is utilized as an ingredient for synthesizing
o
Benzene
+ Isobutpne
Alkylanon
~
to
'/ I
~
(I) Acrolem Dlacetate addItIon
!Ill HydrolysIs
~ ~o
V ~ ,
(R=H)
t-Butyl benzene
~lPrOPYlene
R=Me
Hydroctnamlc aldehydes
o
0,;"
-.:
1 (J) Methacrolem
'mH,."",~.
DI3cetate~
Cyclamen aldehyde
Cumene
hydrocinnamic aldehydes. Benzene is first alkylated with isobutene

to t-butyl benzene, which is next reacted with either acrolein or
methacrolein diacetate. The addition compounds are enol esters, which
when hydrolyzed gives the hydrocinnamaldehyde.
The hydrocinnamic aldehydes possess fresh, white-floral notes
reminiscent of muguet Oily-of-the-valley) and cyclamen.
Perfumery Materials from Toluene
Toluene can act as an important material for making perfumery

materials. Benzyl acetate is present as a main constituent in Jasmine
oil. It is synthetically produced by two routes.
In one process, the product is made from benzyl chloride and
sodium acetate by heating at 150-200°C in presence of copper powder.
CH2 CI CH2-O-CO-CH3
6 + NaO-CO-CH"
CuPowder
150-200 QC ·6
Benzyl acetate
+ NaCI
In another process, the product is produced from benzyl alcohol

by acetylation:
6~:~
Benzyl acetate
Benzyl chloride is produced from toluene by chlorination reaction.

The production of benzyl alcohol is made from benzyl chloride by its
hydrolysis.
OH
Hydrolysis
uv
Toluene Benzyl alcohol
Uses: Benzyl acetate is invariably used in making Jasmine blend.

The ester is used in fine and soap perfumery as it has excellent
blending properties. It is used in many floral perfumes.
Perfumery Materials from N apthalene
Naphthalene has been used as a material for producing some

perfumery products.
Naphthalene has been converted to naphthol that, III turn, IS
transformed into ethers of naphthol as shown below.
Acetylation, OH
~ Sulfonation ~I
~ Alkyl
~ Alkalifusio! ~ Sulfate unde~
basic condition
R=Me
Naphthol R=Et
The product napthyl methyl ether is known in commerce as Yara

Yara, while the napthyl ethyl ether is known as Nerolin (Bromelia).
These two ether products are characterized by distinct floral odors
(Neroli). Napthylethyl ether has a finer neroli like odor than the
methyl ether.
Napthalene is convertible to a ketone molecule that also possesses

a floral odour (fine neroli-odor). The synthesis is outlined below.
o
~
OH
Acetylation. ~
~ CHdCOCl,
AICl.,
Naphthol Methyl naphthyl (P) ketone
Methyl anthranilate is also an important perfumery material made

from naphthalene. The process involves.
CO
00 CC
~
OXIdation. O:::CO,H Ammonia. Hoffmann •
~ h ~ CO,H
I CO)NH rearrangement
Naphthol Phthahc aCId Phthalmnde
COOMe COOH
~NH
Methyl anthramlate
OIl
EstenficatJon
R-OH & BF,-l\leOH &NH'
~I
Anthrarnhc aCId
Perfumery Ingredients from Phenol
Some important perfumery ingredients that can be produced from

phenol are described.
1. Diphenyl oxide (D.P. 0; Diphenyl ether / Phenyl ether)37
Diphenyl oxide m.p.O) also known as diphenyl or phenyl ether (D.P.E

or P.E.) is synthesized
(A) by reaction between aryl halide and Sodium phenate in the

presence of copper catalyst under specific conditions:
Copper catalyst
300°C
(-Xis Cl) Sodium phenate

Chlorobenzene
(B) by dehydration of phenol over Thoria catalyst as:
-c-a-t-a-ly-s-t-4-3-0-(-JC~·~
Thoria 0-: ---{J
0n
D.P'O.
~
Uses of D.P.O.
D.P.O can be directly used in detergents, personal care products, and

other industrial fragrances. It has odor reminiscent of geranium
leaves. It is also used as a constituent of rose perfumes in soaps. It
has a good stability and it is a low-price product. D.P.O. also is used
in artificial geranium. It is also used as a fixative as it lowers the
rate of evaporation in fragrance competition.
2. Butylated Cyclohexanol Acetates
Alkylation of phenol and hydrogenetion of the alkylated phenols yields

cyclohexanols that can be esterified to produce the acetates. The
acetates are very important fragrance ingredients.
o-t-Butyl cyclohexyl acetate has an apple odor with some fresh
woody notes. p-t-butyl cyclohexyl acetate has a warm, sweet, fruity,
woody character. The eis-isomer of p-t-butyl cyclohexyl acetate has a
desirable jasminic floral character.
OH OH
OH
cO
Phenol
Isobutene
• Or
o-Butyl phenol
+ Q
p-Butyl phenol
OAc
o-t-Butyl
cyc10hexyl
acetate
9 p-t-Butyl
cyclohexyl
acetate
(1) Hydrogenation
(2) Acetylation
Perfumery Material from m-cresol
m-Cresol is an important raw material in making perfumery material

like thymol. m-Cresol can be alkylated (isopropylated) on treatment
with propylene to give a high yield of thymol in the presence of acid-
activated earths.
Thymol is mostly used in cosmetic dentifrices and mouth washes

as a germicide and as a constituent of artificial lavender.
OH
A ~
Alkylation with propylene
HC~
3
AI
or acid activated earth (e.g., tonsil) J:'OH
Thymol
The synthesis of m-cresyl acetate by porcine pancreas lipase from

m-cresol and acetic acid has been separated by Manohar and Divakar
using response surface methodology 38.
The important process parameters namely m-cresol concentration,
enzyme/ substrate ratio, incubation period, pH, and buffer were
examined to arrive at the optimum esterification conditions for the
synthesis of m-cresyl acetate by porcine pancreas lipase.
The reaction was conducted in a stirred reactor from 6 to 54 hr
in the presence of choloroform as solvent at 59 QC by maintaining
reflux. After 54 hr incubation, the reaction mixture was filtered to
remove the enzyme used and washed with sodium bicarbonate to
remove unreacted acid and dried over anhydrous sodium sulfate.
Solvent was next evaporated off and the ester was separated by
distillation from the unreacted m-cresol.
The products were characterised by IH NMR by recording IH
NMR spectra on a Briiker AMX 500 instrument operating at 500 MHz
for proton at 20 QC.
A
~OH
---p-a-nA-c C_r:-:-i:-:l-~;-·
54 hr incubation,
0.2 Inl (pH 8) buffer
:-s-e-,--""'· !r,
V ... OAc
EnzYIne / substrate m-Cresyl acetate
ratio: 0.83 Au/In Inol (6.4 m mol yield)
m-Cresyl acetate is used as food additive in baked food and chewing

gum, as food flavour.
Perfumery Ingredients from Styrene/Styrene Oxide
Styrene can be used as a material for making perfume

ingredients. It is first converted to styrene oxide that can be used,

in turn, to produce fragrance materials. Some of the perfumery
materials that can be synthesized from styrene or styrene oxide are
mentioned.
Phenyl Ethyl Alcohol
C~-C~OH
©
Phenyl ethyl alcohol is now commercially made from styrene oxide
by hydrogenation reaction.
Hydrogenation
180°C, Ni catalyst
Styrene Oxide Phenyl ethyl alcohol
Uses of Phenyl Ethyl Alcohol

It is used in making rose water and also in artificial rose oil and
some fancy perfumes. It is also used in soap perfume because of its
stability to alkali.
Phenyl Acetaldehyde and Esters of Phenyl Ethanol
Styrene epoxide can be rearranged to phenylacetaldehyde.

Phenyl acetaldehyde has a green top note of narcissus and is used to
create a narcissus like effect in floral perfumes. The phenylethanol
esters find use in perfumery.
Perfumery Materials from Cyclopentanone and

Dicyclopen tadiene 39
Cyclopentanone has been used in making products having jasmine

like odors. The process involves the following steps:
(Q)
Styrene Styrene oxide Phenyl acetaldehyde
1 HydrogenatIOn
2-phenylethanol
l EsterIfication
Esters (acetate, isobutyrate, etc )

of 2-phenylethanol
trR
u 0 0 0
O,R-CHO ~R
HvdrogenJted El>tenfic..atlOn
erR
Aldol H./cdtalvl>t H'COH
('lmden'>atl(Jn,
ba<;t:'
C') ciopE'ntanone 2-Alk,J c..vdopf'ntannne
,A, ,B, ,C,
trR
0 U 0
2-Alkyhde-nf'
~R
6f'~." ~"
cyciopentanom> lIydrol)ol>Il> &
I:.IJrnerIzed CH.(eO.Mp) DecarboxylatIOn
b, aCid (H-' BaRe
'B, 2-Alkyl Qclopent-2-ennne

2- \Ikyhdenecvciu-
('01l,\p
penw.nune (,()M~
IC, ,0,
The Compounds [C] and [D] have Jasminic, Fruity Floral Odors
in Fragrances
Dicyclopentadiene acts as a raw material in the synthesis of perfume

ingredients as dicussed below:
Treated with RCOoH

- ~ R
)~ 0
(Hr
Dicyclopentadiene Acid catalyst

R= Me; Jasmacyclene
(fruity, jasnune like odor and
used by the fragrance industry)
Synthesis of Isoborneol, Borneol, and Camphor from a-Pinene 4o
Isoborneol can be synthesized from a-pinene via camphene preparation

by acid catalyzed rearrangement followed by acid-catalyzed addition
of acetic acid to camphene.
0 H>
----+
~
Acetic aCId In
the presence of
acid catalyst
•
4 r NaOH
HydrolysIs
~ won
a-Pinene Camphene Isobornyl acetate Isoborneol
CH,
4m<)H
Borneol
~
Reduced
with alcohol
and sodium
eY
Camphor
0 [0]
+----
Borneol is made from a-pinene by passing hydrochloric acid into

it (a-pinene) at 50°C, in the absence of water, when a solid derivative,
pinene hydrochloride (m. pt. 125°C) is obtained. The product when
treated with magnesium in a current of oxygen yields a compound
which when decomposed with water produces borneol.
CH3 CH3
I I
CCI C
CDCHOH
a-Pinene
HCI
G
Pinene hydrochloride
(1) Mg/02
(2)~O
Borneol
Perfumery Chemicals from ~-pinene41
~-Pinene is an established ingredient in producing I-menthol. It can

be utilized also as an useful ingredient in making special perfumery
material like Nopol esters, which have a sweet woody-fruity odor.
The synthesis is outlined as follows:
158 Perfumery Materials,' Production and Applications
~O:"terifi,"t;on ,~th £O~

~-Pinene
Prins reaction
HCHO,H'
~
W
Nopol
AVAcOH
•
Nopyl acetate
~-pinene can be pyrolyzed to myrcene that in turn can form a

mixture of geranyl, neryl, and linalyl chlorides by reaction with
hydrogen chloride. The hydrochlorides are reacted with acetate anion
to yield the acetate esters. The esters when fractionally distilled
yield the various acetate ester products.
\~
~ ~
CI
"=
t
Heated to HCI ~
~ Cl
500'C +
p-Pmene I I
Myrcene
Geranyl-neryl chlorIde Linalyl chlorIde
Acetate anion
Individual acetates of FractIOnal distillatIOn

geraniol, nerol, and linalool .. Geranyl. Neryl. and Lmalyl acetates
Synthesis of Low-molecular Bioflavours (Low-Molecular

Fragrant Aldehydes, Ketones, Lactones, and Esters) by
Enzymatic Reactions Route 42 . 44
Fragrant aldehyde, ketone, and lactone can be produced by microbial

fermentation biotechnology using microbes like yeast, fungus, and
bacteria of appropriate strains. Low molecular weight esters of low
molecular monocarboxylic acids and low molecular weight alcohols
have been produced by enzymatic esterification process.
Flavour Aldehyde (Aliphatic)
Ethanol is converted to acetaldehyde by oxidation in the presence of

the food grade yeast Candida utilis in good yield.
A strain of Zymomonas mobilis having altered alcohol dehydro-
genase activity produces acetaldehyde from glucose via pyruvate.
The process of producing acetaldehyde directly from fermentable

sugars is very attractive as the separate fermentation to make ethanol
is not required.
Flavour Ketone
Aliphatic ketone, such as 3-octanone, can be prepared by using the

fungus Phlebia radiata and short-chain fatty acid as the substrate.
The 3-octanone finds use in lavender notes.
2-Heptanone can be produced using immobilized Penicillium

roqueforti from octanoic acid.
Flavor Lactone
Aliphatic lactone such as y-decalactone can be obtained by

semi continuous fermentation of Tyromyces sambuceus in the presence
of ricinoleic acid.
U sing octanoic acid, Gregory and Eilerman 42 accomplished the

bioconversion in Mucor sp. to o-y-octalactone. Farbood et al. 43 obtained
a mixture of saturated and unsaturated y-decalactones using y-keto
acid as the substrate; the acid is reduced to y-hydroxy acid, which
ultimately cyclised to y-Iactones.
Flavour Esters 44
Low molecular weight esters of C2-C6 monocarboxylic acids and

different low molecular weight alcohols can be prepared by
bioesterification process in the presence of certain lipase like the
Rhizopus arrhizus, Candida cylindracea, and Lipozyme IM (Mucor
miehei).
A semicontinuous esterification process has been developed when

the appropriate acid and alcohol are fed by a suitable pump in the
esterification kettle and the water formed is removed by adsorption
in a column packed with 4A molecular sieve.
The variables such as the effects of concentration of both acid and

alcohol, the water content, and temperature on the ester yield have
been critically investigated (Figs 1-3).
The acid:alcohol molar ratio of 1:3 and maintaining the water

content at 0.4% constant water content after 6 hours reaction offer
very high yield of esters.
Examples include the synthesis of Isoamyl acetate, propionate,

and butyrate, Ethyl butyrate, and Isopropyl butyrate in high yields
(92-97%).
A pilot plant run has been carried out with a 50 I reactor. Acid to
alcohol, molar ratio is kept constant by adding alcohol continuously
in the reaction mixture. The initial acid concentration of the reaction
mixture is adjusted to about 75% of the acid concentration causing
substrate inhibition. The acid and alcohol are supplemented
continuously at a rate of their consumption. The water produced is
removed by passing the reaction mixture continuously and at a
controlled rate through a column filled with 4A zeolite.
The reaction charge consists of 6 mol acetic acid, 18 mol isoamyl

alcohol, and 30 I hexane in the reactor. The water content of the
reaction mixture is adjusted to 0.4% by adding distilled water. The
reaction mixture is heated to 40 DC under stirring. Lipozyme 1M
60 (1 kg) is added to the reaction mixture whereupon esterification
set in.
The reaction mixture is simultaneously circulated through the

zeolite column so as to adjust the water content of the reaction
mixture between 0.3% and 0.4%. After adding the enzyme, the
continuous feed of 66 mol acetic acid and 60 mol isoamyl alcohol is
started just to supplement the reactants consumed. After 16 hours,
the addition of acid and alcohol is stopped and the reaction is conducted
further for 2 hours. The yield of isoamyl acetate obtained is about
8.45 kg (93.5% yield).
Adopting the same procedure, other low molecular weight flavour

esters such as ethyl butyrate, isopropyl butyrate, isoamyl propionate,
isoamyl butyrate are produced with 92-97% yields.
The above low molecular weight esters have a fruity flavor and
used for the preparation of pineapple, banana, and apple flavor in the
food industry.
Some Synthetic Odoriferous Terpene Derivatives by

Biotechnology
Many essential oils contain dominantly monoterpene hydrocarbons.
Some monoterpens can be used as ingredients for the production

of valuable fragrance and perfumery components by biotechnology
route such as microbial transformations.
100
B---8--- 8 -----Ei-
80 g . fl· -0 _ ---"
.!;l "
/A-.. _ .. -f;.,._ .. C:,__ 1:1,
.......
'tJ."
" 'D',
"
60
" '. - '"13,- . .
, A.. ,. '-----__ ~_~_.
40
'" '. "
b."
20
--
[3----------{] Butync aCId
G- - - -0 PropJOmc acid
G-- . . --El AcetIc aCId
o
0.0 0.2 0.4 0.6 0.8 1.0
Acid concentration (mo till
Fig 1. Effect of acid concentration on ester yield (alcohol:isoamyl alcohol,

acid:alcohol molar ratio: 1:3, t=6 hr, T=40 QC, solvent: 50 mLn-hexane)
100
80
60
40
20 D---~D Without water removal
0-- -0 With water removal (0.4%)

D- - - - - - - - {] With water removal (0.2%)
o
o 1 2 3 4 5 6
Reaction time (hr)
Fig 2. Effect of water content on isoamyl acetate yield (acid:alcohol molar

ratio: 1:3; T=40 QC)
100
80
60
40
EJ··-··-··-[] 1: 1
8-----8 1:2
20
8-----1d 1:3
g--Q 1:8
o
o 1 2 3 4 5 6
Reaction time (hr)
Fig 3. Effect of acid:alcohol molar ratio on isoamyl acetate yield
The monoterpenes of commercial importance are a- and ~-pinene

and limonene.
Microbial Transformations of a_Pinene 45 ,46
The biotransformation of a-pinene obtained commercially from pine

oils (1,60,000 tonnes) has considerable commercial importance.
The enzyme of a-pinene hydroxylase involved in a-pinene

conversion to verbenol was NADPH dependent.
Optimization of growth conditions and media conditions can

enhance the yield of verbenone from a-pinene using Penicillium sp.
Depending on the nature of the microbe used, a-pinene can be

converted to different kinds of perfumery products as indicated
below:
Hydroxylation of a-pinene by Aspergillus niger has been reported

by Bhattacharyya et al. 45 - verbenol and verbenone were obtained.
Verbenone could be a product of autoxidation and verbenol was formed
by microbial oxidation.
~ ~o ~OH
Aspergillus niger
~ +
NCIM 612
a-Pinene (+)- Verbenone

(+ )-cis-verbenol
~
a-Pinene
Pseudomonas
Strain NCIB 11671
~
L-Carvone
~
OH
O)JY
Pseudomonas
~ +
Strain P xl
(NCIB 10684)
a-Pinene ( + )-trans-carveol
(+ )-cis-thujone
~
a-Pinene
Oxidation
~
Qj
a-Pinene oxide
--+ +
NOVO 1 NOVO 2
I I
Acyclic monoterpenoid
aldehydes referred to as
biofragrances NOV01
and NOVO 2
Microbial Transformations of Limonene 47,48
Limonene because of its availability in abundance from cold pressed

citrus peel oil has been the most popular transformation substrate in
recent years.
Limonene can be converted to products like carveol and carvone

and also to a-terpineol and perillyl alcohol by microbial route using
Penicillium italicum, Penicillium digitatum, Pseudomonas gladiolus,
Pseudomonas putida and Aspergillus niger.
Penicillium italicum and Penicillium digitatum produce major
products like carveol and carvone 47 . Limonene is also converted to
a-terpineol by Penicillium digitatum 48 .
Penlcllltum lialzcum
or P dlg/tatan!
Llmonene Carvol Carvone Penllyl alcohol
Corynbactenum
Hydrocarbodasturn
LlnlOIlene Carvone
2
Pseudomonas
~
gladwli
P. dlgltotl/m
~
DSM 62840
(RH + )Llmonene a-Terpmeol Perrihc aCld
Pseudomonas putlda
~
30'C 5 days
Llmonene Penl1yl alcohol p-Menth-l-ene-6.8-dlOl
! MIcrobes
~OH
Limonene-1.2-diol
Conversion of linolenic acid
j photooxidation
Hydroxy acids (A) + (B)
OH
I
CH3-CH2-CH=CH-CH2-CH-CH=CH-CH=CH-(CH2)7-COOH
13-Hydroxy linolenic acid
(A)
+
CH3-CH2-CH=CH-CH2-CH-CH=CH-CH=CH-(CH2)7-COOH
I
OH
12- Hydroxy linolenic acid
(B)
P. ohmeri
(A)
1
(R)-o- Jasmolactone
P. stipitis
(B)
2
(R)-r-J asmolactone
The concentration of limonene plays an important role. The

quantity of end-products decreases with increase in limonene
concentration. Addition of sucrose increases microbial growth but
the conversion is low.
The conversion of limonene to carveol seems to be a single-step

reaction, involving addition of a hydroxyl group at C-3.
The conversion of limonene to perillyl alcohol by Pseudomonas

putida has been reported 5 .
Microbial Synthesis of Jasmolactones 49
The perfumery compounds like 8-jasmolactone and y-jasmolctone have

been made by combination of photoxidation and intramolecular
transesterification by fungi such as Penicillium ohmeri and Penicillium
stipitis.
The transformations shown in the preceding page involve linolenic
acid:
Microbial Hydroxylation of Some Terpene and Terpene

Derivatives49
Aspergillus niger hydroxylates the acetates of citronellol and geraniol

as shown.
Citronellol acetate
A niger
~
9 HOA
OH
'
Hydroxylation Site
CH,OAc
A niger
~
Geranyl acetate Hydroxylation Site
a-Cedrene can be hydroxylated to give a series of diols of which

one had the desired odoriferous properties as shown below:
Beauverite
-------~~ Various Diols
sulfuroscens
Microbial Conversion of Patchoulol to nor-patchoulenol49
Patchoulol is a major constituent (30-45%) of patchouli oil but it has,

however, no odor value. The key aroma constituent is nor-
patchoulenol, which is present in small quality (0.3%). This aroma
constituent can be synthesized by biotechnological route by microbial
hydroxylation, oxidation to the carboxylic acid, later on
decarboxylation and oxidation. The hydroxylation is performed by
the soil fungus Penicillium rubrum FX-318 selectively in 80% yield.
Microbial
-------l~~ lO-Hydroxy patchoulol
Hydroxylation
! Oxidation
Patchoulol
Carboxylic acid derivative
(1) Decarboxylation
1 (2) Oxidation
Nor-patchoulenol
Large-Ring Ketones and Lactones 50
After the odor and perfumery characteristics of civetone and muscone

became well established, the elucidation of their molecular nature
and structures became the matter of extensive research and
eventually both civetone and muscone having natural musk odor
were characterized to be structurally large ring ketones having a

distinct carbon number. In fact, the structures odor relationship
investigation could distinctly demonstrate that some large-ring
ketones and lactones have interestingly specific odors including pure
civetone and muscone odor. Some of the ketones and odour
characteristics are shown below.
Ketones Odour characteristic
C9-C12 Camphor like

C13 Cedar-wo od-like
C14 Mixture of musk and cedarwood
C15 Pure mu scone odor
C16 Muscone and dihydro-civetone
C17 Identical with dihydrocivetone
C18 Slight civetone-like odor
C19 Almost no odor
Based on the structure-odour characteristic relationship, the

syntheses and properties of the desired large-ring compounds having
strong natural musk odor have been achieved due largely to the
invstigations by Ruzicka and coworkers.
Some of the large-ring ketones and lactones of commercial
importance are described below involving their molecular structure,
synthesis, and properties.
Civetone
Civetone having a distinct natural musk-like odor is obtained.
Synthetic Preparation of Civetone
Civetone can be prepared chemically from raw material like aleuritic

acid (9,10,16 trihydroxy plamitic acid), occurring in shellac. It can be
made from methyl oleate by chemical route. Civetone can also be
made by biotechnology route from oleic acid.
Civetone from Aleuritic Acid 50

Civetone preparation from aleuritic acid involves a series of reaction
steps. The first step is the bromination of aleuritic acid to tribromo
(9,10,16) palmitic acid. In the second step, the bromo compound is
subjected to debromination reaction to form 16 bromo palmitoleic
acid. This is next converted to acid chloride (16 bromo plamitoleic
acid chloride) that is condensed with the sodio-derivative of acetoacetic
ester. The acetoacetic ester condensate is hydrolyzed and re-esterified
to give methyl trans-18-bromo-3-keto-octadec-11-enoate.
The keto enoate is converted to the 18-iodo compound by treatment
with sodium iodide. The iodo compound is treated with potassium
carbonate in boiling methanol to give methyl a-civetone carboxylate.
On hydrolysis the product civetone is obtained.
The steps of the preparation of civetone are shown in details on
next page:
A NEW PROCESS OF PREPARATION OF CIVETONE

FROM METHYL OR ETHYL OLEATE BY CHEMICAL
ROUTE51,52
Civetone can be prepared from methyl oleate or ethyl oleate by

metathesis reaction. High-purity methyl oleate undergoes a kind of
metathesis reaction when treated with a homogeneous catalyst like
tungsten hexachloride (WC16) and tetramethyl tin Sn(CH 3)4 or with
a heterogeneous catalyst like rhenium oxide or aluminium oxide
(Re 2 0 7 /A1 2 0 3 ) modified with alkyl tin compounds.
Van Dam et aZ. 51 and Tsuji and Hashiguchi 52 described the synthesis
of civetone, an important base material in the perfumery industry,
from diethy-1-9-octadecene dioate by cyclocondensation and
decarboxylation.
Methyl oleate is heated with the homogenous catalyst at 110 DC
for 2 hours. The catalyst and the hydrocarbon produced as one of the
products are removed by distillation.
The dibasic acid (dioic) obtained by hydrolsis of the ester is next
converted by cyclocondensation and decarboxylation to civetone.
where A is CHsCCH2)7-CH = CH(CH2)7CH3'

and B is H3COOC(CH2)7CH = CH(CH2)7-COOCH3
Step 1: HO-CH,-(CH,),-CHOH-CHOH-ICH,),-COOH
I Bromination by treatment with HBr in

.. acetic acid solution
Br-CH/CH,)5-CHBr-CHBr (CH')7-COOH
I Debromination by heating with zinc dust .

.. Distilled at 199 QC/1 mmHg.
Step 2: Br-CH,--{CH,),CH = CH (CH,), COOH

I Acid chloride by treatment with Thionyl
.. chloride tIll SO, evolution ceased
Step 3: Br.CH,.(CH,),.CH = CH (CH,\COCI
! Reacted with the Sodio derivatiYe of aceto

acetic ester
/ COCH,NaTCH,COCHOOC,H.,l
Step 4: Br.CH,.(CH')5.CH = CH (CH')7COCH"",
COOC2H.,
1 Hydrolyzed and reesterified with methanol
= CH(CH,),CO.CH, COOCH,
l
Step 5' Br.CH,.(CH,), CH
Treated with sodium iodide to iodo compound
Step 6: I.CH,.(CH,)., CH = CH rCH,),CO-CH,-COOCH,
I CyclizatlOn with K,CO.l III bOlhng methanol.

.. Distilled and fraction collected at 153 °C'O.3 mmHg
Step 7: CH-CCH.J. _______

11 fV\ /' CHCOOCH,
CH-CCH,),-CO
l Hydrolysis and Decarboxylation
Step 8:
CH--{CH,);-CO
11
CH--{CH,);-CO
> CO
Civetone from aleuritic acid

Step 2: B is cyclized and decarboxylated to civetone
/ " (CH.),COOCH 3
.
/" (CH.)'X /" (CH,),)
HC HC HC
HC
" He
" • 11
HC
co
'-... (CH ),COOCH,
2 '-... (CH), COOCH 3 '-... (CH,),
Properties and Odor Charactristics of Civetone
Civetone has 31-32 QC melting point, boiling point 1450 QC /0.5 mmHg,
refractive index 1.4822, density 0.9137. It crystallizes in white needle-
shaped crystals.
Perfumery use: Civetone has a musk-like odor. It is an excellent
fixative in perfumery blends.
Biotechological Methodology for Making Civetone 53
The methodology involves the oxidation of highly pure oleic acid to

C-18 unsaturated dicarboxylic acid with the double bond of oleic acid
being retained at 9,10 position by bioxidation process with Candida
tropicalis M 2608 as a biocatalyst. The dicarboxylic acid is later
decarboxylated to civetone.
H3C-(CH2)7CH = CH-(CH2)7 COOH
t Bioxidation
HOOC-(CH2 )7-CH
11
HOOC-(CH~)7-CH
t Decarboxylated
CH-( CH
11
2)7) CO
CH-(CH)7
Through this fermentation technology, one can produce readily

hydroxy acid or the dibasic acid. These could then be easily
cyclized to the corresponding musk. Palm oil can be oxidized to
hydroxy palmitic acid or to dibasic acid and eventually to musk

compound 5 .
Alleuritic acid can also be converted to ambrettolide, a musk

compound 54 .
o
Alleuritic acid
~
Ambrettolide
CH3-(CH2)14-COOH
Palmitic acid
1 Enzyme
HOOC-( CH2)lCCOOH
~ Cyclohexadecanolide
~
Cyclopentadecanone
Muscone
Muscone is exclusively prepared from an appropriate aliphatic dinitrile

by first reduction by lithium derivative of a secondary amine to
cyanoketimide that is eventually converted to the cyclic ketone by
acid hydrolysis.
The steps are enumerated as below:
Step 1:
if
HCN
IIH2
CH,CN
IH2
LfH
C=NH (CH)lI i=NH
(i Reduced with
•
(CH,)"
Lf
)1I
+
LiN(C,H),
HCN
CH-CH,-CN
I CH
CH-Ca, I
CH,
CH,
A B
n-Aliphatic dinitrile
Cyanoketimides
I co
Acid hydrolysis (CH,)u I
Step 2: A+B
L
Muscon ..
CH'
lH-cH,
PROPERTIES OF MUSCONE
Muscone is a colorless viscous liquid possessing a very strong musk

odor. The natural muscone is laevorotatory (L form) and synthetic
mu scone is DL (racemic) form.
PERFUMERY APPLICATION
Because of its very strong musk odour, synthetic muscone is

traditionally a perfumery constituent. It is mainly used as a fixative
agent.
EXALTONE 55
CH,
Exaltone is prepared synthetically in the same manner as muscone

is prepared. The aliphatic dicyano derivative of proper carbon number
is first reduced to cyanoketimide which on acid hydrolysis gives the
desired ketone exaltone.
The steps are enumerated below:
Step 1: Reduction of the aliphatic dicyano derivative
.------CN C=NH
I
(CH),;
1: 14-dicyanotetradecane
LCH,-CN
2-Cyanocyclopentadecanone
hnide
Step 2: Hydrolysis of the imide
.------ C=NH co
Acid
hydrolysis
Exaltone
Large-ring Lactones 55
Large-ring lactones, with musk odor, have been synthesized by Ruzicka

and Stoll. The large-ring lactones that have received commercial
importance are the exaltolide and ambrettolide.
Exaltolide
Exaltolide is synthetically prepared from exaltone by converting it

into 15-hydroxypentadecoic acid by a specific oxidation reaction. The
oxidized product is later converted to the lactone.
Step 1: Exaltone is oxidized to hydroxy acid
Oxidized with
---------+~ HO-CHc(CHz\.l-COOH
peracides, potassium
persulphate in cone. H,SO,
Exaltone
Step 2: Hydroxy acid dehydrated to lactone
---.~ CH2-(CHz)13-CO
Lo-..-J
Exaltolide
Process step 1 involves oxidation reaction and this is carried out

by treating a known quantity of exaltone solution in benzene with an
aqueous solution of an oxidizing agent like potassium persulphate
dissolved in concentrated sulphuric acid and water. The reaction
temperature is kept within 50 QC.
The reaction mixture is allowed to stand for several hours and

later it is poured over ice. The benzene layer containing the oxidation
product and unconverted exaltone gets separated. The benzene
solution is washed with sodium carbonate solution that removes the
acid reaction products. The neutral constituents are treated with
semicarbazide solution that reacts with the unchanged exaltone to
form the semicarbazone.
The neutral constituents are treated with petroleum ether and
the readily soluble lactone (exaltolide) is extracted. The lactone is
recovered by removing the solvent and purified by distillation under
reduced pressure (14 mm). The fraction collected at 175 QC solidifies
mostly into crystals (m.p. 30 QC).
The fraction of the exaltolide is based on the analytical data that

corresponds with the lactone of 15-hydroxypentadecoic acid, C15H2802'
The yield of exaltolide is 47% of theoretical amount.
Characteristics of Exaltolide
Exaltolide has a relative low melting point 30 QC. It has a boiling

point 175°C at 14 mmHg. The density and refractive index are

0.9383 and 1.4633, respectively. It crystallizes as white crystalline
needles.
Exaltolide resembles mu scone in odor characteristic and also closely
ambergris. It shows excellent blending and exalting properties in
perfumes. The compound is of great tenacity.
Exaltolide is a widely used fixative in top-quality perfumes.
Exaltolide provides unique odor effects when it is combined with
natural or synthetic mu scone and ambergris.
Arnbrettolide 55
CH2 (CH 2 \-CH = CH-(CH2 )s-CO

I 0 I
Ambrettolide is synthetically prepared from 16 hydroxy 1-,.7_
hexadecenoic acid by first converting it into 16-bromo 1-,.7_
hexadecenoic acid. The bromo compound is converted into silver
salt which is later distilled at 16 mmHg pressure and the fraction
collected at 180-190 °C contains mainly the ambrettolide. The
fraction is redistilled at 185-196 °C and at 16 mmHg and the purified
ambrettolide is collected as a colorless viscous oil.
Physical and Od or Characteristics
Ambrettolide is a colorless and viscous oil. It boils at 185-190 °C/16

mmHg Its density at 20°C is 0.938.
Ambrettolide possesses a strong and persistent musk odor. It acts
as an "exalting" agent in trace quantity in finest perfumes and
ambergris colognes.
Artificial Musks 56
Artificial musks are synthetic perfumery chemicals, which are

structurally different but resemble the odor characteristics of the
natural and synthetic musks.
Chemically, the artificial musks contain a benzene ring with
appropriate alkyl substituents and nitro groups. A. Baur first
synthesized a musk compound that provided the chemical basis
Synthetic Perfumery Materials : Production and Applications 177
of synthesizing compounds having distinct musk odor. The number of

nitro of the alkyl chain in the ring does not influence the odor of the
artificial musks. Baur produced first the concept of molecular
structures and musk odor relationship as illustrated below:
x:({x R' --7 C4~ or CSHll or C3H7
RY R
' R --7 CH3
X --7 (N0 2)3
X R.Co --7 R-CH3
or R-CO
In fact, all trinitro derivatives of aromatic hydrocarbons possess

a musk-like odor.
The artificial musks which have established themselves as
extremely valuable musk-like odor molecules are musk xylene, musk
ambrette, and musk ketone.
The syntheses of the above three artificial musks and their odor
characteristics are described.
Synthetic Preparations of Some Artificial Musks of Commerce 56
Musk xylene
CH
O,N*NO, 3
H,C 0 C(CH,'
NO,
meta-xylene is first alkylated with isobutylchloride by means of
Friedel-Crafts reaction to m-tertiary butylxylene. This is separated
from the excess reactants and the pure m-tert-butyl xylene is nitrated
to give musk xylene that is finally isolated in pure form.
The process details are described hereunder.
Alkylation Process
A definite quantity of m-xylene (45 kg), 3 parts by weight, isobutyl

chloride (15 kg) 1 part by weight, and a mixture of sublimed
aluminium chloride 0.5% (0.3 kg) by weight and defatted aluminium

filings (0.12 kg) 0.2% by weight are taken in the desired number of
reaction vessels in series with connected gas pipes and fitted with
reflux. Dry hydrogen chloride that is passed slowly through the
vessels initiates the alkylation reaction vigorously. The temperature
that rises fast is invariably maintained below 67 DC. The alkylation
reaction slows down remarkably after 2 hours when the supply of
hydrogen chloride is discontinued. Afterwards steam is circulated
for a couple of hours.
The contents of the vessels are next poured into ice-cold water
when an oily layer separates. The separated layer is next washed in
sequence with dilute hydrochloride acid, sodium carbonate solution,
and water. Eventually, the oily material is dried and distilled at
ordinary pressure and the fraction boiling between 196-212 DC is
collected. This fraction is redistilled under vacuum to yield the
alkylated product, m-tert-butylxylene.
Nitration
The nitration is carried out by adding fuming nitric acid (2.5 parts
by weight) with vigorous stirring in small proportions to m-tert-butyl
xylene (1 part by weight) in a vessel provided with a reflux
arrangement. The temperature is not allowed to rise as far as
practicable. Fuming sulphuric acid is now added slowly with continued
stirring. The mass is next heated to 70 DC for 3 hours and poured on
to ice and left standing overnight. The crystalline mass that forms
is separated and purified by recrystallization from benzene and alcohol,
respectively.
Yield: Musk xylene as light yellow crystals (m.p. 112-113 DC) is

13 kg.
Musk ketone
C(CH,J,
meta-Xylene is first alkylated with isobutyl chloride to the tert-butyl

m-xylene as described earlier in synthesizing musk xylene.
The tert-butyl-m-xylene is next converted to acetyl derivative by

Friedel-Crafts method.
The keto compound is nitrated to its dinitro derivative that

possesses a strong musk odor.
The synthetic steps are shown as follows:
H.,C>
+ CH-CH 2 Cl
H3 C
m-Xylene Isobutyl chloride (A)
CH. 1
Friedel-Crafts {)
------.~ H,C V C (CH')J
CO-CH,
4-Acetyl derivatIve
Nitration
O>NO NO,C
H-l
(E) H,C~C(CH,).
CO-CH,
Musk ketone
The process details are described below:

Acetyl derivative preparation by Fridel-Crafts acylation method:
Appropriate quantity of tert-butyl-m-xylene is mixed with a known
quantity of the acylchloride like acetyl chloride in the presence of a
definite amount of aluminium chloride.
The mixture is gently warmed till the evolution of hydrochloric
acid gas ceases. The reaction product is next poured into ice. The
oily layer that separates out is isolated. It contains excess tert-butyl-
m-xylene and the acetylated product. The hydrocarbon derivative is
removed by steam distillation.
The material left behind (the residue) is fractionated and the
fraction that distills at 260 QC is collected as the methyl ketone
(acetyl derivative). It has been characterized by its solubility in alcohol
and benzene and by its melting point (48 QC).
Nitration of the Acetyl derivative (Methyl Ketone)
The nitration of the acetyl derivative is smoothly carried out by

adding it to nitric acid (100%) at 0 QC. The dinitro derivative is

readily soluble in alcohol but less soluble in 60% acetic acid. The
product is crystallized from 60% acetic acid.
The melting point of musk ketone is 136 QC.
Musk Ambrette
meta-Cresyl methyl ether is alkylated with isobutyl chloride by

Friedel-Crafts method.
The 4-tert-butyl derivative IS nitrated to yield musk Ambrette.

The synthetic steps are provided below:
Friedel
Isobutyl chloride + HCI
crafts catalyst
AlCI, anhydrous
C(CH,l,
m-Cresyl methyl ether
CH,
Nitrated
with fuming nitric acid

Q,N©ocH,
C(CH,l, C(CH,l,
Musk ambrette
The process details for producing the musk ambrette are provided
below:
Alkylation Process
A definite quantity of both m-cresyl methyl ether and isobutyl chloride

are heated together with an appropriate amount of anhydrous
aluminium chloride on a water bath. The reaction is stopped when
the evolution of hydrogen chloride ceases.
The product is steam distilled and the alkylated molecule, namely,

the tert-butyl-m-cresyl ether is isolated eventually by fractionation
and collecting the colorless liquid at 222-224 QC.
Nitration
The ether derivative is nitrated with fuming nitric acid. The ether
is slowly added to definite parts (6-10) of fuming nitric acid and
heated on a water bath. The nitration is stopped when the nitrated
sample solidifies in contact with ice or with water.
Isolation of the Product
After the nitration is over as indicated by its solidification behaviors

as above, the product is poured into water and washed with dilute
sodium carbonate solution. The product is finally crystallized from
alcohol yielding yellowish white needles with musk odor and having
m.p. 84-86 QC.
Perfumery Characteristics and Usage Pattern of the Artificial

Musks
The artificial musks are quite extensively used as synthetic perfumes

for having natural musk odor.
Musk xylene is used mostly in cosmetic and toilet soaps to provide

indefinable sweetness. Musk ketone is used mainly in fine perfumery
admixed with natural musk. Musk ambrette is most widely used in
soap perfumery because of its tenacity and peculiarity of its odor.
Musk xylene along with musk ketone or musk ambrette is used in
very fine toilet soaps. All the three artificial musks have extraordinary
fixing properties and also blending properties. These special properties
make them blend excellently with soap perfumes and consequently
impart to soaps indefinable sweetness.
Polycyclic and Macrocyclic Musks 57
Entirely different kinds of musks have been synthesized that are

known as the polycyclic and macro cyclic musks instead of the
traditional nitro musks.
The polycyclic musks are structurally different and have indane,
tetralin (hydrogenated naphthalene) or isochroman structures with
alkyl groups like methyl or other chains.
182 Perfumery Materials.' Production and Applications
Some of the important polycyclic musks are 6-acetyl-1; 1,2,4,4,7-

hexamethyltetralin; 4,6,6,7 ,8,8-hexamethyl-1,3,4,6, 7 ,8-hexahydro-
cyclopenta (g) liso chromene.
The isochroman derivative also known as galaxolide has been

synthesized from cumene as shown below:
Cumene
Isoamylene
•
-90 '- I
......"
Propylene
oxide
•
~
HeHO
Galaxolide (isochroman)
The synthesis of a tetralin-type polycyclic musk more commonly

termed as Tonalid in the trade, has been made as follows:
~AcetYlation,
5: Neohexene
:::::-....
I •
Friedel-Crafts:::::-""
p-Cymene
reaction
I
Hexamethyl tetralin
AcX
AcX AlCl s
•
)~
Tonalid
Another synthetic of the trade name extralide has been made as

indicated:
9 Dehydrogenation
•
2
I /.
2'3-DimethYl-but-2-ene~
T i4C l . I ~ +
OH Hexamethyl tetralin Isoporpyl tetra
!
a -Terpineol p-Cymenol methyl indane
Acylation AcCVAlCl
)~+)~
Extralide
Macrocyclic Musks 57
Macrocyclic musks are normally the long-chain lactones or ketones,

some of which have been discussed earlier in the section on large-
ring ketones and lactones.
One of the largest macrocyclic musk is cyclopenta decanolide which
has been synthesized as follows:
Tetrahydrofuran Methyl undecylenate

Methyl=11-(2'-tetrahydro furyl)
undecanoate
(1) Heated
(2) H/catalyst (hydrogenated)
(3) Hydrolyzed
Cyclopentadecanohde
(macrocychc musk) 15-Hydroxy pentadecanOlc aCId
Another interesting way of synthesizing macro cyclic musk is shown

below:
Butadiene
Polymerized
------~~ Cyclododecatriene C.A ~
Cyclodocecanone
~
(1) Epoxidized with
H 2 0jNaOH Methyl acrylate
+ - - - - - . .-
(2) Converted to the Addition
hydrazone with o
Muscone methane sulphonyl
Bicyclic ketone
hydrazine
MeSO,-NH-NH2
hydrogenated
Synthesis of Essential Oil Analogues 58, 58a, 58b
Essential oils from various natural sources are quite costly and do
not possess the right aroma or fulfill the aroma characteristics as
required in many areas of their applications. There has been
worldwide research investigations in the synthesis of odoriferous
materials that are structurally different but equivalent to or better
than the natural oils in terms of odor and functional properties.

These kinds of synthetics are regarded as the analogues of the
essential oils and also known as the artificial aromatic oils.
Some of the analogues resembling the aroma of floral, woody, and
fruity characters and more suitable to meet the requirements of
applications are briefly highlighted.
The chemistry lies in the selection of certain base molecules,

which may be non-terpentine, followed by their applicable substitution
in their structure/molecule by alkyl subtituents and functional groups,
the two together become responsible for generating the typical aromas
by a kind of relationship between the molecular (chemical) structure
and the odor of the products synthesized.
The effect of the size of the alkyl group acting as subsistent, the
effect of the position of the alkyl group (limited to a methyl group)
and replacement of the oxygen atoms by sulfur or carbon enable to
produce some floral odor analogues 58 , 58a, 58b.
Anselmi et al. 58 synthesized and screened a series of 38
tetrahydropyranyl ethers. Two compounds, namely,
and
having a white floral odor and reminiscent of hydroxy citronellal and

Lilial have been synthesized.
A white, floral odor analogue is cyclamen aldehyde that has been

synthesized, remiscent of wild cyclamen. This odor molecule is stable
in alkaline condition and nonirritating to the skin unlike the hydroxy
citronellal. It is often, therefore, used in place of the hydroxy
citronellal.
The t-butyl analogues, namely,
xV°Y) and
Lilial Bourgeonal
have improved floral odor and have a more pronounced muguet floral
odor.
Berends and van der Linde 59 synthesized 24 analogues of cyclamen

aldehyde.
[Rl=CH(CH 3 )2 devoloping Cyclamen character,

R2=CH 2C(CH 3 )2 developing more Muguet odor]
The artificial flavors, resembling cedarwood, sandalwood, and

Vetiver oils have been synthesized.
Thus, cedarwood odors 60 has been made from isolongifolene as
shown below:
Paraformaldehydrade
m formIc aCId, 90 °C/16
hr, fractIOnally dIstIlled
at05mmHg
IsolongJfolene
paraformaldehYdradel Cl' Formates recovered at 110-120 QC

InacetIc aCId WIth
sulphunc aCId, 60°C, J J
fractlOnahty dIstIlled
Cedarwood-Vetiver
*
C"Acetates (Cedarwood vebver odor)
Saponified distilled
Cedarwood odor, resembhng that of cedrol

~ Saponified dIstilled
Cedarwood odor, resembling that of cedrol
Sandalwood oil aroma is now made artificially having reminiscence

of sandalwood oil odor. This artificial sandalwood is relatively
cheaper and is available in more quantity compared to
the natural oil and can be used as replacements of extenders.
Threo-isomer Erythro-isomer
(3-trans-Isocamphylcyclohexanols) (3-trans-isocamphylcyclohexanols)
The exact structures of the compound as shown earlier and also

below responsible for the sandalwood note could be established.
Osyrol
In course of investigations, several new sandalwood aroma

compounds have emerged as indicated below along with trade names:
~ OH
OH
Sandalore Bacdanol Dragoco
OH
Dragoco Ionosantalol Methyl sandeflor Givaundal
It has been reported that a-compholenic aldehyde serves as a

valuable building block for the elaboration of sandalwood aroma
compounds.
Lewis acid
CHO
a-Pinene oxide a-Compholenic aldehyde
Synthesis of compounds likely to have sandalwood aroma has been

made from appropriate aldehyde and suitable ketones as depicted
below:
QCHO +
~ Base 40% methanolic KOH or NaOH
OH
.;:- . . . . . .1 '" R' lR)

H, Catalyst xy~
Raney NI '::5>Z R'lR)
Alcohol (A)
Unsaturated ketone
Alcohol (E)
Among the alcohols (A) and (B), only two compounds possess
sandalwood fragrances as shown below:
and
OH
OH
(Cl
The process 61 of Hall and Wiegers replacements or extenders

involves the following course of preparation involving catechol and
camphene as the starting raw materials:
OH
Friedel-Crafts
(y +~
0H
<?I Catalyst (BF,
~ u
120-175 C,
Catechol Camphene AIel,) 5-12 hr
(A) (El
(A) + (E)
Hydrogenation
225°-250°C,
200-2500 psi,
RaneyNi
9 R
+
Compounds having intense

sandalwood oil aroma
A compound has been synthesized that is known as Khusimone

having the odor of vetiver oil. Its synthesis is outlined below:
~ 1
097 6
IsomenzatlOn 6,7,7-'Ihmethyl-
tricyclo-( 6.2.1.01,5)
Sunlight 0,
1 undec-5-en-2-one reducing agent

o 5
3 4
°
Tricyc\o carbmol
6,6,7-Trimethyl- H
~
tricyclo [5.2.2 0 "]
Reduction
undec-8-en-2-one
°
7,7-Dimethyl-6-methylene tricyclo
[6.2.1.0'"] undecan-2-one (Khuslmone)
Artificial Floral and Fruity Perfumery62-65

Products have been synthesized having reminiscences of floral odors
like those of rose, lavender, gardenia, jasmine, lilac from certain
specific alcohols or from their esters.
The alcohols which have been utilized are almost exclusively the
nonanols and nonenols and the monocarboxylic acids used are the
linear aliphatic saturated acids of the carbon numbers CI-C7 or the
unsaturated (one double bond) aliphatic monocarboxylic acids of C3-
C7 carbon number and carboxylic acids like cyclopentane and
cyclohexane carboxylic acids, salicyclic acid, cinnamic acid, etc_ 62 .
Synthetic Perfumery Materials,' Production and Applications 189
The process is based on the simple esterification reaction between

the appropriately chosen nonanol or nonenol alcohols and the
respective carboxylic acids as such or in the form of anhydrides or
acid chlorides. The products are isolated by washing, drying, and
distillation under vacuum and at appropriate temperatures.
The products like 3-methyl-nonan-3-yl-acetate and 3-methyl-1-
nonen-3-yl-isobutyrate have been made for use in Gardenia perfume
composition. Similarly, the ester like 3-methyl-nonan-3-yl-cyclohexane
carboxylate has been synthesized for lilac type floral composition.
The molecule like 3-methyl-l-nonen-3-yl-isovalerate has been prepared
for use in making jasmine perfume composition.
Analogs of natural rose oil constituents originating from structure-
odour considerations have been produced, some of which are
commercially available and mentioned below:
a-Damascone A-Damascone I) -Damascone
Some synthetics have been developed possessing molecular

structures like octadiene derivatives, which simulate the fragrances
of some well-known flower/floral extracts. Thus, 2,7-dimethyl-5,7-
octadien-2-ol enable to obtain rose odor. The acetate derivative of
this compound yields Gardenia fragrance. The structures are
represented as follows:
CH, CH 3 CH 3
I I Hydration I
H,C=C-CH,-CH,-CH=CH-C=CH, ~ H 3 C-C-CH,-CH,-CH=CH-C=CH,
I I
2,7-Dimethyl-l ,3, 7-Octatriene OH CH,
2,7-Dimethyl 5,7 -octadiene-2-ol

(rose odor)
CH, CH,
I I Esterification
H,C-C-CH,-CH,-CH=CH-C=CH,
I
OR
where R-Acetyl group (Gardenia odorl
Some sulfur compounds of the type a-oxy (oxo) sulfides have

floral or fruity odor. The more common oxosufides have been
prepared, namely, 3-methyl or propyl thio-4-heptanol (floral note),
3-isobutyl thio-2, 6-dimethyl-4-heptanol (floral note like that of
hyacinth and narcisse), and 3-methylthio-2, 6-dimethyl-4-heptanone
(floral and fruity) etc. 64 .
The syntheses of some of the above compounds are outlined briefly

as follows:
Methanolic
o solution of o
11 sodium methoxide 11
CH J-( CH, ),C-CH-CH 2-CH J CH,,-(CH) ,C-CH-CH,-CH,
I N aOMe+methanolic I
Cl solution of methyl SCH"
mercapton CH,-SH
3-chloro-4-heptanone 3-Methyl thio-4-heptanone
(rose floral)
o OH
11 Reduction I
(E) CH,,-(CH,l,C-CH-CH,-CH, CH,,-{ CH, ',C-CH-CH,-CH"
1
using NaBH,in 1 I
SCH, anhydrous ethanol H SCH,
3-Methylthio-4-peptanol
(floral N arcisse)
Some a-oxy (oxo) mercaptans have been made with characteristic

fruity odor by Evers et aZ. 65 as mentioned below:
(A)
o o o
11 11 NaSH 11
CH,-lCH,l,C-CH,-CH,CH, CH,(CH,),-C-CH-CH,CH, ---I.~ CH,lCH,),-C-CH-CH,CH.,
25-30°C
4-heptanone
2-3 hr
1 1
Cl SH
3-Chloro-4-heptanone 3-l\lercapto-4-heptanone
(grape fruit odor)
(El
o SodlUm borohydride OH
11 in ethanollreductlOn) 1
CH,lCH,),-C-CH-CH,CH, CHJ CH, ),-C-CH-CH.CH,
1 11 -
SH H SH
3-Mercapto-4-peptanol
(Grape frUIt and Bnchu odor)
There are few more mercapto alkanones and alkanols having

distinct fruity fragrance.
Synthesis of Perfumery Materials for Multipurpose

Applications 66
Many perfumery materials have been synthesized which have diverse

molecular structures but unique flavor and fragrance characteristics
and which have accordingly applications in a variety of perfumed
articles and products.
Some CIO-terpene ethers better known, as terpenyl ethers have
been synthesized by Mussiman et al. 66 with structures shown below:
Geranyl butyl ether Carvyl ethyl ether 8-p-Cymenyl-

(floral rose, citrus Fenchyl ethyl ether
(Parsley-like, celery-like, ethyl ether
flavor, floral aroma) and grape fruit-like aroma)
The production of the above CIO-terpenyl ethers involves reaction

at reflux conditions of the terpenyl alcohol with low-molecular alkanol
using an acid catalyst like p-toluene sulphonic acid.
The production is also carried out by reacting a terpenic alcohol

with the appropriate alkyl sulfate and sodium hydride under certain
specific conditions.
The above terpenyl ethers have been used in many materials to
augment flavor aroma characteristics.
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Applications of Perfumery
Materials
INTRODUCTION
The fragrance and flavor industry is a multibillion dollar/rupees

worth business worldwide. India also shares significantly in this
industry. Total flavor and fragrance sales in cosmetics and toiletries
alone are expected to reach over $1 billion in the beginning of the
21S t century.
Natural and synthetic flavors and fragrances, individually or in

combinations have enormous extent of applications. The major
applications, with very substantial consumption of fragrances, include
the products like "imitation" perfumes, soaps, shampoo, shower, and
bath gel, other cosmetics, toiletries, detergents and the incense sticks.
It is the fragrance that actually makes the difference of these products
to the consumers. The demand for fragrance has been increasing and
is bound to grow in the areas of the above applications.
The use of flavoring agents in foods has been increasing to impart
characteristic flavors to foods. The essential oils have therapeutic
uses. They also have other applications. The natural perfumes
(essential oils) have limited availability and high prices. They could
not be used in large volumes and slowly synthetics materials started
replacing (partially or fully) the natural perfumery products. Synthetic
aroma chemicals are often more stable than natural products.
The Indian market size is estimated at $100 million (2% of world
total) and is likely to be growing at an annual rate of 10%1.
Applications of Perfumery Materials 197
Some major applications in the perfumery and non perfumery areas

of various natural and synthetic perfumery materials are briefly dealt
herewith:
A. IMITATION PERFUMES (SIMULATING NATURAL

ODORS)
Among the perfumery applications, the volume production and actual

consumption of floral perfumes that can simulate the natural odors
derived from the various kinds of flowers occupy a major market.
Irrespective of the pattern of the applications of floral perfumery
products, there is invariably a need for the blending of selective
natural essential oils and synthetics in appropriate proportions. The
selection of both natural and synthetics depends on some important
concepts. In fact, the blending of perfumes constitutes a fascinating
and challenging practice, and it forms an important subject matter
in the perfumery industry.
The art of blending is based on a precise scientific approach instead

of the trial and error approach followed earlier. The "Blending of
Perfumes" for applications in various kinds of products requiring
specific flavours and fragrances is elaborated in brief.
Blending of Perfumes
The most important element in the perfumers art is the blending of

the odoriferous materials (odor principles) to form a mixture, which
gratifies the sense of smell. In fact, the various perfumes of commerce
are actually blends of naturally occurring essential oils and synthetic
perfumery chemicals. The individual essential oils and synthetics
are classified from efficient blending point of view as base, blending
agent, modifier, and fixative. These four terms are well recognized
in the blending of perfumes. It may be pointed out that an essential
oil or a synthetic can function as base, blending agent, modifier, or
as a fixative in a perfume.
The above four terms as used in making perfumes by utilizing the
blends of natural and synthetic flavors and fragrances are defined
below:
Base
The natural and synthetic aromatics that are used in producing the
characteristic prime odors are regarded as the base of a perfume.
Blending Agent
Some natural and synthetic aromatic ingredients, when used

individually or in combination in perfumery formulations, required
to harmonize the odors of the various perfumery ingredients into the
resultant odor or final odor are termed as the blending agents. These
are the ingredients that smooth out the transitions of a perfume
between layers or bases. Common blending agents include linalool
and hydroxy citaonellal.
Modifier
The ingredients/aromatics both natural and synthetics that are used

to obtain the final odor in perfect state are known as modifiers. The
ingredients alter the primary scent to give the perfume a certain
desired characters, e.g., fruit esters in floral primary base creating
fruity floral odor.
Fixative
The natural and synthetic ingredients that help in reducing the

volatility of a perfume thereby making the perfume last longer are
regarded as the fixatives. Fixatives are the substances having lower
volatility than the perfume oils. All fixatives are classified into four
groups, viz., animal fixatives, resinous fixatives, essential oil fixatives,
and synthetic fixatives.
Some common fixatives are castor or castoreum oil (exudate of

the perineal gland of beaver and consists of benzyl alcohol,
acetophenone, I-borneol, and resinous substance castorin) and civet
oil (secreted from the perineal gland of civet cat and contains a cyclic
ketone known as civetone). Musk is the most useful animal fixative
(secreted from the preputial glands of the male musk deer) comprising
a cyclic ketone known as muscose. Ambergris, musk zibata (obtained
from the glands of musk rat) contains macro cyclic ketones.
Hard resins (e.g., benzoin), soft resins (e.g., labdanum), moderately

soft resins (e.g., peru balsam and tolu balsam), oleoresins (terpenoids
and extract from resins (e.g., ambrein) are important resinous
fixatives, which are exudates of certain plants.
Clary sage, vetiver, orris, sandalwood, etc., are the various

essential oils that we used as essential oil fixatives in addition to
odoriferous substances.
Synthetic fixatives are generally of two types. The high-boiling

odorless esters such as glyceryl diacetate, ethyl phthalate, benzyl
benzoate, etc., constitute one class of fixatives to replace some of the
animal fixatives.
The class of synthetics that act as fixatives are some odoriferous

substances to impart fragrance to the perfume as well. These
synthetics are amyl benzoate, musk ketone, musk ambrette,
benzophenone, vanillin, coumarin, indole, skatole, acetophenone,
cinnamic acid esters, cinnamic alcohol ester, etc.
It needs to be stated that an ingredient can function both as a

fixative and as a blending agent, a base constituent can also be a
blending agent, while a component used as a modifier also acts as a
fixative.
Many natural and synthetic aromatics, embracing the above

concepts and functions have been utilized as ingredients in making
many perfumes that simulate the natural perfumes specially the
floral oils. Some typical floral perfumes are exemplified overleaf,
which have immense acceptance to consumers for personal use, and
to industry for use in many products.
JASMIN 2
Base Modifier
Benzyl acetate 200 Hydroxy citronellal 250

Jasmin absolute 30 Phenyl acetaldehyde 10
a-Amyl Isojasmone 10
Cinnamaldehyde 30 a-Ionone 50
Indole 1
Phenylethyl alcohol 100
Linalool 100
Blending agent Fixative
Ylang-ylang oil 20 p-cresyl phenyl acetate 30

Benzyl salicylate 50 Musk ketone 20
Decylic aldehyde 10% Civet absolute 5
Phenyl ethyl isobutyrate 90
Octyl isobutyrate 1
ROSE 2
Base Modifier
Phenyl ethyl alcohol 280 Nonyl aldehyde 10

Citronellol 170 Hydroxy citronellal 30
Rhodinol 380
Blending agent
Rose oil (Bulgarian) 60

a-Ion one 10
Linalool 60
TUBEROSE 2
Base Modifier
Methyl benzoate 40 Neroli oil Bigar 20

Isobutyl salicylate 20 Tuberose absolute 30
Geraniol 300 Heliotropin 20
Jasmin absolute 15
Blending agent Fixative
Cannanga oil 200 Civet absolute 5

Benzoin 30
Styrax 20
B. ESSENTIAL OILS IN HUMAN THERAPY

(AROMATHERAPY) 3
Essential oils have nonperfumery applications as therapeutic agents

in curing many diseases, some of them being universal, namely,
basil, rosemary, sage, sandalwood, thyme. The table gives the list of
some essential oils and their therapeutic uses. It can be stated here
that a number of references are available to evidence the therapeutic
claims and accordingly applications.
It may be marked that the majority of the essential oils cater to

aroma therapy in the disease like antiseptic, sedative,
cerebroneutropica, stomachia, cardiaca, hypnotica, diuretic, analgetica,
antirheumatic, antigrippe, bronchodilantia, biostimulation,
carminative, stimulativa, etc.
Table: Aromatherapy uses of natural perfumery materials (essential oils)
Aromatherapy Essential oils

application
1. Antiseptic Bergamot, Cedar wood, Eucalyptus, Geranium,

Juniper, Lavender, Rose, Rosemary, Sandalwood,
Peppermint, Pine, Thyme, Turpentine
2. Analgesic Cinnamon, Clove, Eucalyptus, Geranium,

Jasmine, Juniper, Lavender, Lemon, Marigold,
Rosemary, Thyme, Turpentine, Mint, Melissa
3. Antirheumatic Benzoin, Camphor, Mint, Rosemary, Thyme,

Sage, Turpentine
4. Anti-grippe Basil, Camphor, Cederwood, Cinnamon,

Eucalyptus, Frankincense, Juniper, Lavender,
Pepper, Rosemary, Thyme
5. Anthelmintica Bergamot, Cinnamon, Clove, Cumin, Eucalyptus,

Lemon, Mint, Thyme
6. Bronchodilantia Anis, Basil, Benzoin, Bergamot, Camphor,

Cedarwood, Eucalyptus, Jasmine, Lemon
Lavender, Mint, Melissa, Rosemary, Sandalwood,
Thyme
7. Carminative Anis, Cumin, Fennel
8. Cardiac Anis, Benzoin, Cinnamon, Cumin, Juniper,

Lavender, Lemon, Marigold, Pepper, Rose,
Rosemary, Thyme, Valeriana, Ylang-ylang
9. Diuretic Anis, Benzoin, Camphor, Cedarwood, Cumin,

Eucalyptus, Fennel, Frankincense, Geranium,
Juniper, Lavender, Lemon, Pine, Rosemary,
Sandalwood, Thyme
10. Digestive (Stomachia) Anis, Basil, Bergamot, Cinnamon, Clove,

Coriander, Cumin, Dill, Eucalyptus, Fennel,
Geranium, Lemongrass, Marigold, Mint, Nutmeg,
Pepper, Rose, Rosemary, Sandalwood, Thyme
11. Sedative Benzoin, Cedarwood, Jasmine, Lavender,

Lemongrass, Patchouli, Rose, Rosemary,
Sandalwood, Thyme, Valeriana, Ylang-ylang
12. Stimulation Bergamot, Cinnamon, Eucalyptus, Geranium,

(Biostimulating) Juniper, Lavender, Peppermint, Rosemary, Sage,
Thyme
Table : Continued ...... .
Aromatherapy Essential oils

application
13. Hypnotic (Sleeping) Basil, Juniper, Lavender, Neroli, Orange, Rose,

Sandalwood, Ylang-ylang
14. Stimulativa Basil, Bergamot, Camphor, Geranium, Ginger,

(Stimalating Jasmine, Juniper, Lemon, Melissa, Patchouli
energigingl Pepper, Peppermint, Rosemary, Sandalwood,
Verbena, Ylang-Ylang
15. Cerebroneutropica Basil, Clove, Dill, Eucalyptus, Juniper, Mint,

(Brain & nervous Nutmeg, Rosemary, Thyme
system mental abilities)
C. ESSENTIAL OILS AS ANTIMICROBIAL AGENTS3
Some essential oils are uniquely characterized for their antimicrobial

activity against selected microorganisms when used at low
concentrates. The table shows some typical examples.
The essential oils from turmeric show marked antimicrobial activity

against gram- negative and gram-positive organisms. The curry leaf
oil has antimicrobial, antifungal and, pesticidal activities.
Table : Antimicrobial activity of essential oils in pg/cm 3 microbe
Essential oil
Microbe O. grati- P. roseum Mppe P. patch-

ssimum ouli
Staphylococcus aureus 200 * * 200

E. coli * * * *
Proteus vulgans * * *
Klebsiella pneumonia * * 40c
Pseudomonas aeruginosa * * * *
Enterobacter cloacae * * * *
*Means concentrations higher than 400 ).lg/cm 3
D. BACTERICIDAL APPLICATIONS OF ESSENTIAL

OILS3
Essential oils have bactericide properties and are used for disinfection
of air, sometime the mixture of oils provide synergistic activity against
bacteria.
A few examples of the above features are exemplified below:
Bactericide activity of some essential oils on Koch bacillus in air
Oil name VN (%) in air
Thyme 0.1
Peppermint 0.4
Marjoram 0.2
Phenol 0.8
The essential oils when blended with antibiotics display even more
bactericide activity as indicated below:
Oil + Bacteria Bactericide concentration

antibiotic tested pg/cm 3
Separately Mixture
Basil oil I-form 100 50

Erythromycin Streptococcus 0.2 0.02 (basil + erythromycin)
Bactericide activity of essential oils is also utilized in conserving

food. Geranium oil and citronella oil in 0.1% concentration extends
the shelf life of citrus fruits by two to three times respectively,
being effective against Penicillium digitatum and Penicillium
stabilum.
E. ESSENTIAL OILS AS INSECT REPELLENTS3
Some essential oils have distinct insect-repellent properties affecting

their life span. A list of some of the important essential oils is listed
below having repellent activity.
Insect Repellent Oils
Cocroach (Periplaneta americana) Eucalyptus

Flies (Calliphora) Eucalyptus
Mosquitoes Basil +eucalyptus
Longer earthworm and leeches Geranium, rose oil
Croton bug Spearmint
Gnat Citronella, clove, eucalyptus
The essential oils are used as natural insecticides (bioinsecticides).

The oils of cumin, coriander, thyme are strong insecticides. The
synergistic effect is obtained when a mixture of basil and eucalyptus
oils kill 100% of mosquito larve at a concentration two to six times
lower than individual oils. A mixture of peppermint (50%), camphor
(25%) and, coumarin (25%) is used as a very effective home fumigant.
Dill oil is antifidant for the desert locust. Artemisia oil kills larvae
of anophele (Anopheles stephensi) at a concentration of 0.016%, while
the same effect is obtained with 0.014% DDT.
F. ESSENTIAL OILS IN AGRICULTURE3
The essential oils find a great deal of applications in agriculture to

enhance productivity of agri materials by acting as insect repellents
both in the air and soil. Some essential oils also inhibit the
productivity by slowing down or stopping germination of plants and
vegetables. Oils of coriander, angelica, and fennel can be toxic to
numerous cultivated vegetables.
Terpene alcohols like geraniol, citronellol, menthol, and a-terpineol
are highly toxic totally stopping germination of some plant materials.
Pulegone and camphor also appear to be toxic in regard to plant
protection.
Basil and mint are beneficial for the good growth of cabbage.
G. APPLICATIONS IN FOOD AND PHARMACEUTICAL

PRODUCTS
Perfumery materials both natural and synthetic find use in a number

of food products to impart specific flavor to the food products thereby
creating a kind of preferential fascination to the consumers. Most

food products have in general typical and appealing flavor
characterized only as the Maillard reaction products. The natural
and synthetic perfumery materials on addition generate extra and
more favorite flavor/aroma in the food products. Orange blossom
water has been traditionally used in food to flavor cakes and
beverages. Lemongrass oil adds an exquisite flavor to thai salads,
with seafoods and meats in them.
Many fruit flavors are being simulated in actual fruit drinks/juices 4 .
The fruit flavors like those of apple, banana, grape, pineapples,
strawberry, etc., have been already developed and discussed.
Beverages are the largest market segment for added flavors,
accounting for about one-third of the worldwide flavors~les. Around
Composition of some fruit flavors 4
Apple flavor Pineapple flavor
Amyl valerianate 30 Amyl butyrate 50

Ethyl malonate 20 Ethyl butyrate 20
Acetaldehyde 10 Ethyl acetate 5
Chloroform 5 Acetaldehyde 6
Geranyl butyrate 4.5 Chloroform 5
Ethyl acetate 20 Lemon oil 2
Vanillin 0.5 Ethyl methyl phenyl glycidate 1
Glycerin 10.0 Propyl valerianate 10
100 Vanillin 1
100
Banana flavour Grape flavour
Amyl acetate 30 Acetaldehyde 5

Amyl butyrate 10 Amyl butyrate 5
Benzaldehyde 1.5 Chloroform 5
Benzyl propionate 4.0 Clary sage 1
Ethyl butyrate 40 Ethyl acetate 40
Ethyl sebacate 10 Ethyl oenanthate 20
Clove oil 2 Ethyl pelargonate 3
Petitgrain oil 2 Ethyl formate 5
Vanillin 0.5 Methyl salicylate 1
100 Succinic acid 3
Cognac oil 1
Octyl valerianate 0.5
Vanillin 0.5
Glycerine 10
100
90% of the flavors added to beverages in the EC and the US are

natural. The savoury products contain about 80% naturals and
percentages for flavored dairy products are 50-75%.
Certain low-molecular aliphatic alcohols, aldehydes, esters, terpene
alcohol esters, aromatic aldehydes, and some essential oils are used.
Other components/materials used act as a vehicle or as a diluent or
to improve the taste.
The esters mostly used are ethyl acetate, amyl acetate, ethyl
formate, ethyl butyrate, amyl butyrate, ethyl sebacate, ethyl malonate,
ethyl oenanthate, ethyl pelargonate, propyl valerianate, benzyl
propionate, octyl valerianate, methyl salicylate, ethyl methyl phenyl
glycidate, Geranyl acetate. Vanillin, benzaldehyde, acetaldehyde,
essential oils like clove oil, Petit grain oil, clary sage, cognal, and
lemon oil, succinic acid, glycerin, chloroform are also in regular use.
Compositions of some well-known fruit flavors, namely, apple,
banana, pineapple, and grapes duly imitated or formulated from
appropriate synthetics only or from blends of synthetics and natural
essential oils have been provided by Poucher 4.
A formula for imitation pinapple flavor is shown below:
Pure compound (%) Essential oils (%)
Allyl caproate 5 Oil of sweet birch 1

Isoamyl acetate 3 Oil of spruce 2
Isoamyl isovalerate 3 Balsam peru 4
Ethyl acetate 15 Volatile mustard oil 1
Ethyl butyrate 22 Oil cognac 5
Terpinyl propionate 3 Concentrated orange oil 4
Ethyl croton ate 5 Distilled oil of lime 2
Capric acid 8 19
Butyric acid 12
Acetic acid 5
81
Mestri 4a has reported that isoamyl butyrate has a fruity flavor

and it can be widely used in the food industry for preparation of
pineapple, banana, and apple flavors. Similarly, geranyl butyrate and
citronellyl butyrate having a high rosaceous fruity character are
widely used in the preparation of fruity flavors. These three flavor
esters along with other constituents have been utilized in pineapple
flavor preparation. Pineapple base has been prepared using the
following formulation:
Ethyl acetate 1.5

Ethyl butyrate 3.0
Ethyl valerate 4.0
Amyl acetate 1.5
Allyl caproate 22.0
Allyl heptonte 18.0
Ethyl vamillin 1.5
Phenylethyl alcohol 7.5
Propylene glycol 41.0
100 parts
Mestri 4a has also prepared pineapple beverage and pineapple jelly

crystals using pineapple flavor prepared as above.
Pineapple Beverage
11 g of sugar and 0.25 g of citric acid is dissolved in 100 mL of water,

to which 5 mg of tatrazine col or is added and the prepared pine apple
flavor (0.1 mL) is added.
Pineapple Jelly Crystals
Sugar (75 g) is mixed with 0.05 g of tatrazine color and 0.5 mL of

prepared pineapple flavor. Gelatin (20 g) is mixed with 0.9 g of citric
acid, 0.4 g of sodium citrate and 0.2 g of NaCI and then added to
flavored and colored sugar. It is mixed to get uniform dry powder.
Then it is dissolved in 400 mL of boiled water, heated, cooled and
then refrigerated.
The perfumery materials particularly the natural essential oils
are added in food products to provide antioxidants for the purpose of
increasing their shelf life specially when the food products contain
highly unsaturated fatty acids that are indispensable for our nutrition
and health benefits. The oils are Rosemary, spice oils like clove,
cinnamon, coriander, ani se, cardamom, etc.
The perfumery materials also provide protection against microbial

growth in food as indicated earlier and offers therapeutic values.
Drugs and pharmaceutical industry also employ perfumery
materials both natural and synthetic. A number of natural essential
oils have been listed in Pharmacopea helvetica, British pharmacopea,
United States Pharmacopea; and Indian Pharmacopea.
A number of standard medicaments contain essential oils. For

examples, the isolates like menthone, a-pinene. Camphene, borneol,
cineol, menthol are used for the treatment of gall stones, gall bladder
infections, liver insufficiency, urocystitis, minor tract infections, renal
infections. It may be mentioned that isolates like anethol, fenchon are
also used for the urocystitis and the above tract and renal infections.
The oils like eucalyptus, anis, camphor, pine, thyme, and menthol
are used for the treatment of cough and bronchitis and to promote
expectoration. The oils like eucalyptus, cedar wood, camphor,
turpentine, and menthol are also used for the treatment of cattarh,
colds, headaches, etc. The oils like camphor, peppermint, eucalyptus,
clove, cinnamon, and menthol find extensive use for the treatment
of colds, headaches, rheumatic, and muscular pains.
Essential oils can be used for the treatment of almost all diseases
including cancer as evident from the table showing the aromatherapy
uses of various essential oils.
H. PERFUMERY PRODUCTS IN TOILET SOAPS

AND COSMETICSITOILETRIES
Many natural aromatic (essential) oils and synthetics individually as

well as in the form of appropriate blends find extensive use in toilet
soaps and in a variety of cosmetic products. Infact, soaps and
cosmetics/toiletries are the major consumer of the natural and
synthetic perfumery materials. The cost of toilet soaps and cosmetics
depends on the price of the perfume contained in them.
Toilet Soaps
The most important types of perfumes used in toilet soaps are floral
in character, namely, carnation, gardenia, heliotrope, jasmin,
lavender, lilac, lilly-of-the-valley lime blossom, mimosa rose, and
violet. Mention may be made of sandalwood, citronella, basil,
bergamot, cassia, clove, eucalyptus, geranium, palmarosa, patchouli,
rosemary, thyme, vetivert etc. The synthetics mostly used include
amyl cinnamic aldehyde (useful in jasmine soaps), anisic aldehyde,
benzaldehyde (almond soaps), benzyl acetate (to most soaps, useful
in jasmin), heliotropin (in colored soaps), geranyl acetate, ionone,
methyl benzoate, methyl salicylate (used in fern and chypre soaps),
Phenyl ethyl alcohol, a-terpineol, musks, and other appropriate
synthetics. A number of other essential oils are used. Each of the
above soap perfume type formulation utilizes a number of essential
oils acting as base, blending agent, modifying agent, and fixative as
well as a number a synthetic perfumes for similar functional
properties in appropriate proportions.
The ingredients used in the most important soap perfume types

and classified already as base, blending agents, modifying agents,
and fixatives are worth reporting for appraisal about the selection of
materials for soap perfumes mentioned below.
Carnation Soap
Base: Amyl salicylate, eugenol, isoeugenol, clove oil.

Blending agents: Pepper oil, phenyl ethyl alcohol, terpineol.
Modifying Agents: cinnamon leaf oil, Ylang-ylang Oil,
bromostyrene, ionone, heliotropin, cyclamen aldehyde.
Fixatives: Peru balsam, tolu, benzoin, geranium, vanillin, musk
xylene.
Jasmine Soap
Base: Benzyl acetate, amyl cinnamic aldehyde, phenyl ethyl alcohol,

linalool, methyl anthranilate, indole.
Blending agents: Cananga oil, Petitgrain oil, linalyl acetate,
benzyl propionate, benzyl salicylate, geraniol.
Modifying agents: Sweet orange oil, undecalactone, ionone, scatole.

Fixatives: Styrax, benzoin, civet, resinoids, musk xylene.
Lavender Soap
Base: Lavender oil, spike oil, lavender resinoid.

Blending agents: Bergamot oil, rosemary oil, geranium oil,
linalool acetate, linalool, linalyl propionate, terpinyl acetate, benzyl
propionate, vetiveroyl acetate.
Modifying agents: Clary sage oil, peppermint oil, thyme oil,
borneol, methyl ionone, vetivert, oakmoss, resinoids.
Fixatives: Coumarin, musk xylene, patchouli, orris resin, sandal,
resinoids, labdanum.
Mimosa Soap
Base: Anisyl acetate, anisaldehyde, Ylang-ylang oil, methyl

acetophenone.
Blending agent: Mimosa concrete, cananga oil, Cassia oil,

hydroxy citronellal, terpineol, ionone, geraniol.
Modifying agents: Methyl ionone, Amyl cinnamic aldehyde,

Isoeugenol, methyl methylanthramilate, bromostyrene, indole, methyl
phenyl carbinol, cuminic aldehyde, nonylene aldehyde.
Fixatives: Heliotropin, musk ketone, resinoids, orris, styrax, tolu,

peru balsam, myrrh, Civet.
Musk Soap
Base: Synthetic musk, Castoreum resinoid

Blending agents: Cedarwood oil, cassia oil, geranium oil, ginger
grass oil, sandal oil, terpineol, benzyl salicylate.
Modifying agents: p-Cresyl phenyl acetate, methyl cinnamate,

amyl salicylate, lauryl alcohol.
Fixatives: Resinoids, labdanum, cinnamon, clove, vetovert, tolu,

peru balsam.
Rose Soap
Base: Geranium oil, geraniol, citronellol, rhodinol, phenyl ethyl

alcohol, nerol.
Blending Agents: Geranyl, citronellyl and phenylethyl esters,
linalool, terpineol, Ionone, methyl ionone, nonyl alcohol.
Modifying agents: Palmarosa oil, linaloe oil, clove oil, sandalwood

oil, patchouli oil, methyl cinnamete, benzyl acetate, nonyl aldehyde,
vanillin, hydroxy citronellal.
Fixatives: Resinoids, geranium, styrax, benzoin, Peru balsam.
Sandal Soap
Base: Sandal oil (east Indian), sandal resinoid.

Blending Agents: Sandalwood (West Indian) oil, cedarwood oil,
cananga oil, linaloe oil, geraniol, patchouli oil.
Modifying Agents: Clove oil, cassia oil, ylang-ylang oil, bergamot

oil, Peru balsam, heliotropin, vanillin, a rose complex.
Fixatives: Synthetic musk, coumarin, resinoids, orris, vetivert,

geranium, civet.
Numerous branded toilet soaps are commercially available and
one can visualize the volume consumption of perfumery materials,
especially that of the natural essential oils. It may be mentioned
that the perfume added in a toilet soap varies between 0.5% and 2%
by weight of the soap. Deodorant soaps deodorant sticks contain 1-
2% of perfume and aerosol deodorants have 0.5% perfume. The
composition of some floral perfumes duly compounded for use as
soap perfumery are briefly discussed.
The toilet soap perfumes are made either from essential oils or
from the various synthetics or their blends. The more well-known
floral perfumes compounding have been elaborated by Poucher 4.
Antiseptic and Medicated Soaps 5
Thyme oil 50 Cassia oil 100

Clove oil 100 Eucalyptus oil 50
Rose geranium oil 200 Vetivert oil 20
Rosemary oil 80 Lavender oil 200
Lemon oil 200
Carnation Soap Perfume Composition
A B
Based on the use of more Based on the use of more

of natural (essential) oils of synthetics
Amyl salicylate 100 Benzyl acetate 100

Geraniol, Java 100 Terpineol 100
Eugenol or clove 450 Bromostyrole 20
Geranium, Bourbon 50 Phenyl ethyl alcohol 60
Cassia 30 Amyl salicylate 100
Orris resin 50 Geraniol, Java 100
Iso-eugenol 70 Clove 400
Musk xylene 30 Cassia 50
Pepper 20 Iso-eugenol 70
Peru balsam 100 Musk xylene 30
1000 Styrax resin 30
1000
Amyl salicylate, benzyl acetate, eugenol, isoeugenol act as base, while phenyl ethyl
alcohol, pepper oil, and terpineol act as blending agents. Bromostyrole, serves as
a modifying agent; Peru balsam, Styrax, Musk xylene, Geranium, act as fixatives.
Jasmine Soap Perfume Composition 5
A B

Benzyl acetate 200 Benzyl acetate 200

Rose wood 100 Rose wood 200
Petitgrain para 80 Terpineol 100
Phenyl ethyl alcohol 100 Petitgrain para 150
Bergamot 100 Amyl salicylate 50
Amyl salicylate 70 Cananga 50
Sweet orange 20 Ionone 50
Cananga 100 Methyl anthranilate 50
Clove 50 Clove 20
Civet absolute 3 Amyl cinnamic aldehyde 50
Orris resin 50 Musk xylene 30
U ndecalactone 2 Styrax resin 50
Amyl cinnamic Aldehyde 40 1000
Liquidambar resin 50
Musk xylene 30
1000
When benzyl acetate, phenyl ethyl alcohol, amyl cinnamic aldehyde, methyl
anthramilate, act as base. Canaga oil and petitgrain oil and rosewood are blending
agents while sweet orange, Undecalactone, Ionone serve as modifying agents.
Styrax, civet, musk xylene, ambar resin, orris resin, are the fixatives.
CosmeticslToiletries
The cosmetics/toiletries, which have developed extravagantly to meet

the requirement and demand pattern of the consumers, use a variety
of natural and synthetic perfumery to impart the desired fragrance
and therapeutic functions besides providing customers delight and
psychology satisfaction.
The volume consumption of the perfume materials used is

enormously high and will be continuously increasing in view of
the expected growth of the cosmeticltoiletries industry (body
powder, shampoos, creams, lotions, bouquets, skin care/toners,
toothpastes, etc).
Detergents industry has been growing by leaps and bounds globally
for fabric washings and for use in cosmetics/toiletries. The detergents
Lavender Soap Perfume Composition 5
A B

Bergamot 70 Benzyl acetate 50

Geraniol, Java 50 Rose wood 70
White thyme 20 Petitgrain para 30
Spike lavender 100 Terpinyl acetate 100
Lavender 130 Spike lavender 200
Rosemary 100 Lavendin 100
Clove 10 Rosemary 50
Orris resin 30 Coumarin 100
Benzoin resin 70 Musk xylene 40
Coumarin 50 Oakmoss 10
Musk xylene 30 Vetivert 50
Okemos 30 1000
Patchouli 10
Santal 30
1000
Lavender oil, spike oil, lavendin are base; bergamot oil, rosemary oil, terpinyl
acetate act as blending agents; Thyme oil, okemos serve as modifying agents; and
coumarin, musk xylene, patchouli, orris resin, benzoin, santal, resinoids act as the
fixatives.
invariably are scented with certain fascinating fragrances that include

a variety of natural perfumes (essential oils) and specific synthetics.
Shampoos, shower, and bath gels are major materials and require
certain perfumery raw materials providing the fragrance and
maintaining the thixotropy of the product and behaving as nonreactive
ingredients to guard against the chemical changes of the ingredients
of shampoo and protection against hair and skin. The top-quality
shampoos contain 0.5-1.0% of fragrance material imparting herbal,
fruit, and floral odors. Shower and bath gels also contain 0.5-1.8% of
perfume. Hair oils are scented with floral perfumes like jasmine,
rose, lavender, ylang-ylang, sandalwood oil, etc.
Antiperspirant products specially aerosol antiperspirants require

fine fragrance formulation at 1-1.5% by weight of the aerosol product.
The cosmetic products like lipsticks contain 1-4% of perfume. The

face powders contain 1-3% of perfume.
Rose Soap Perfume Composition5
A B

Citronellol 200 Benzyl acetate 30

Phenyl ethyl alcohol 200 Phenyl ethyl alcohol 300
Geraniol Palmarosa 200 Diphenyl oxide 30
Verbena 20 Palmarosa 350
Ionone 50 Citronella, Java 100
Clove 10 Ethyl cinnamate 10
Geranium, Bourbon 150 Cassia 10
Orris resin 50 Ginger grass 50
Musk xylene 30 Benzophenone 10
Santal 50 Musk xylene 30
Tricholar phenyl 30 Patchouli 10
Methyl carbinyl acetate Phenyl acetic acid 20
Vetivert 10 Styrax resin 50
1000 1000
Geranium oil, geraniol, phenyl ethyl alcohol, and citronellol act as base. Ionone
acts as blending agent. Palmarosa oil, clove oil, ethyl cinnamate, benzyl acetate,
patchouli oil serve as modifying agents, while resinoids, styrax, benzoin, musk
xylene as fixatives.
Dental powders and creams contain 1-3% of perfume, while mouth

washes use 2-10% of aromatics as they contain 60-80% of alcohol.
The flavor of a good mouthwash producing the freshness of the mouth
is an essential feature. Methyl salicylate (oil of Winter green),
peppermint, menthol, eugenol, etc., are commonly used flavors which
gives a feeling of freshness.
Massage oils use 0.2-0.5% of perfume. Sun-tan oils contain 1-3%

of perfume. Shaving preparations of various kinds such as creams,
sticks, powders, aerosols, and lotions use 0.5-1.0% of perfume.
Normally, the soap compatible perfumes are used.
The essential oils commonly used in lipsticks are of the light

floral or the other oils like basil, bergamot, carrot, cederwood,
cinnamon, clove, clary sage, coriander, cumin, eucalyptus, lavender,
juniper, lemon, orange, tangerine (Mandarin), neroli, palmarosa rose,
sandalwood, vetivert, ylang-ylang, etc. Rose alcohols and their esters
are often used.
Creams use bergamot, coriander, eucalyptus, geranium, lavender,

neroli, Palmarosa, patchouli, petitgrain, rose, rosemary, sandalwood,
winter green, ylang-ylang, etc.
Aftershave lotions use 1% of perfume and an aerosol after-shave
lotion contains 0.5% of perfume.
The flavor of a toothpaste influences the consumer acceptance,
conventionally, flavors have been based on the oils of spearmint and
peppermint, often fortified with menthol to give cooling effect or
with clove, winter green, eucalyptus, anise, anethole, cinnamon, etc.
The toothpastes contain 1.0-1.5% of the perfume (flavor).
Toothpowders also contain the above types of flavor components

being used in much lower amount.
Toilet waters, also known as fragrant waters, are produced for
skin care and hair wash principally and for therapeutic and hygienic
purposes as well. Toilet waters of commerce are available that
contain between 5% and 20% essential oils. Many well-known
branded products that are used by consumers, notably eau-de-
colognes lavender water, rose water, almost exclusively contain
natural perfumery materials (essential oils). The citrus oils (e.g.
bergamot, lemon, sweet orange, mandarin), and oils like rosemary,
peppermint, verbena, clove, lavender, nutmeg, coriander, neroli,
meliasa, clary sage, rose geranium, thyme, rose, otto, vetivert,
terpeneless lime oil, petitgrain, mimosa, ylang-ylang, patchouli
oil, rose absolute, jasmin absolute are extensively used in
formulation.
The products also contain synthetics musks, resinoids, styrax,
benzoin, vanillin, coumarin, ethyl acetate, isobutyl salicylate, linalyl
acetate, terpenyl acetate, phenyl ethyl alcohol, methyl cinnamate,
methyl ionone, heliotropin, a-ionone, geranyl acetate, hydroxy
citronellal, decyl aldehyde, etc.
INCENSE AND FUMIGANT PRODUCTS6
Incense and fumigant products particularly the incense stick industry

(also called the Agarbathi) occupies a distinct position in India and in
this subcontinent.
A number of perfume materials are used in incense sticks between
20% and 30% level of the incense sticks. Not all perfumery materials
are suitable in incense sticks as many when burnt generates smokes
and changes into something else.
216 Perfumery Materials .. Production and Applications
Materials such as methyl anthranilate, y-nonalactone, methyl

napthyl ketone, benzyl acetate, sandalwood oil, benzoin resin,
patchouli oil, citronellol, vanillin, geranium oil, musk xylene, amyl
cinnamic aldehyde, tetralin musks, etc., are needed. Most of the
aliphatic aldehydes burn very well in agarbathi.
Phenyl ethyl alcohol is widely used because of its rose odor and
low price. However, the burning note recommends the use of phenyl
ethyl acetate in preference to the alcohol as the acetate displays a
far richer and cleaner burning signal.
Synthetic linalool is also widely used. However, its bad burning

note suggests its replacement with tetrahydrolinalool or terpinyl
acetate provided price permits.
A number of chemical suppliers can give some finished perfumes
of excellent fragrances for use as agarbathi fragrances having the
following fragrance notes:
(i) A fresh fruity note
(ii) A strong geranium, Sandalwood note
(iii) A strong fruity apple rose note
(iv) A floral honey pineapple note
(v) A tart fruity sweet note
(vi) A new sweet musk note
(vii) A herbal note
(viii) A fresh ozone sea note
(ix) A warm sage note
(x) A rich woody amber note
A typical formulation of perfume used as a perfumed incense is

exemplified below that shows clearly that a number of essential oils,
gum resins, and synthetics are utilized in a regular manner.
Perfumed Incense Composition
A. Essential oils/powders
Bergamot oil 30 Patchouli oil 10
Neroli oil 20 Cassia oil 15
Clove oil 5 Sandalwood (Powder) 300
Cardamon (Powder) 40 Cascarilla (Powder) 150
Cubebs (Powder) 35
B. Gum - resins
Siam benzoin 150
Myrrh (Powder) 10
Peru balsam 30
Orris - oleoresin 10
Grain musk 5
c. Synthetics
Iso-butyl cinnamate 30
Methyl ion one 10
D. Other constituents
Charcoal (Willow) 120
Saltpetre 30
Aromatic or essential oils are burnt as fumigants in sickrooms

and as perfumes for apartments.
APPLICATION OF PERFUMERY MATERIALS IN

MISCELLANEOUS PRODUCTS7
Perfumery materials both natural and synthetics find applications

relatively in low volume in the products like perfumed sachets, floral
cachous, gelled perfumes, fragrant, or toilet waters.
Perfumed sachets consist of a powder composed of a mixture of

vanillin, musk, etc; contained in an ornamental silk sac. Such powders
are spread after being made into a paste with a little glycerin upon
card or chamois leather or flannel. The cards after dry up and covered
with various parti colored silks are ready for sale. The odor of the
cards is retained for years unimpaired.
Floral cachous are perfumery products of commerce containing

essential oils as flavor embedded in a suitable hard base such as
tragacanth or mixture of acacia and tragacanth. The base also contains
icing sugar and starch. A solution of glucose is also used. The floral
cachous available are jasmine, rose, heliotrope, etc.
Essential oils are used in the manufacture of lacquers, inks,

varnishes, greases, lubricating, oils, etc.
Essential oils also find much use in the industries like adhesive,
animal feed, automobile, household products, paper and printing,
rubber, leather, textile and tobacco for imparting specific perfumery
effects.
REFERENCES
1. Parelkar, P.A. and S.R. Iyer, XI National Seminar on New Policy and
Fragrance and Flavour Industry, 18 th and 19 th April, 1993, Hotel
Taj Bengal, Calcutta, p. 49.
2. Prakticum des Modernen Parfumeurs, Printed by J.W. Arrowsmith
Ltd; Bristol, pp. 61, 73, 76, 1954.
3. Brud, W.S. and J. Gora, Proceeding of the 11th International Congress
of Essential Oils, Fragrances and Flavours, 12-16 November, 1989
2: 13-23, Edited by S.C. Bhattacharyya, N. Sen and K.L. Sethi,
Oxford & IBH Publishing Co. Pvt. Ltd, New Delhi.
4. Poucher, W.A., Perfumes Cosmetics & Soaps, Vol. 2, Eighth edition,
Chapman & Hall, London, 1984, pp. 353-354, 356-358.
4a. Mestri, S.D., Ph.D. Thesis, University of Bombay, November 1996,
p. 113, 197.
5. Poucher, W.A. Perfumes Cosmetics & Soaps, Vol. 2, Eighth edition,
Chapman & Hall, London, 1984, pp. 289-290, 301-302, 311-312,
341.
6. Conboy, F.E. XI National Seminar on New Policy and Fragrance &
Flavour Industry, 18 th and 19 th April, 1993, Hotel Taj Bengal,
Calcutta, pp. 60-62, Perfumes & Flavours Association of India.
7. Perfumery - Love To know 1911 on line Encyclopaedia @ 2003, 2004.
Standardization and Evaluation
INTRODUCTION
Essential oils are known for their distinct odor and physico-chemical
characteristics. In these respects, they also differ significantly.
Evaluation of quality and authenticity of various essential oils is
important. Standardization of the physical and chemical parameters of
essential oils is highly imperative in order to establish identity,
authenticity, and quality of essential oils.
Essential oils vary in physical properties like specific gravity,
refractive index, optical rotation, and solubility in alcohol. Essential
oils also possess specific chemical characteristics like acid value,
ester value, carbonyl value, specific and major constituents such as
alcohols, aldehyde, esters, ketones, etc.
Both physical and chemical characteristics have been accepted for
characterizing and evaluating essential oils. In fact, analytical data,
both physical and chemical, have been accepted as standard data for
essential oils. Accordingly, standards or specifications/requirements
are laid down for essential oils for the purpose of their standardization
and evaluation in actual practice.
India not only produces huge amount of essential oils but also
exports a large volume of it. Accordingly standard specifications are
essential for providing quality certification. In fact, the oils produced
are exported under AGMARK quality standards by Directorate of
Inspection and Marketing. Bureau of India Standards (BIS) has
formulated Indian standards or standard specifications for essential
oils to guarantee quality and authenticity. International standards
for essential oils under ISO/TC54 of International Organization for

Standardization (ISO) have helped formulating Indian Standards.
Standards (standard specifications) laid down by Indian Pharmacoepia
(IP), British Pharmacopeia (BP), Codex, AFNOR, FMA, EOA, etc., have
been accepted for standardisation of quality and purity of essential oils.
Essential oils being high-priced materials are wilfully adulterated
with relatively much cheaper nonfragrant materials having properties
close to those of the essential oils and by the addition of cheaper
essential oils and adjuncts.
Routine analytical determinations point out some unusual
characteristics, but do not reveal adulterants in essential oils.
Standards and analysis is one part of standardization and evaluation
of essential oils. Available standards for essential oils covering various
parameters and factors are included in the chapter to corroborate
standardization and evaluation of essential oils.
Standard specifications as laid down for essential oils by BIS, IP
and BP have been mainly shown in tabular forms for information
and reference.
Standards of Essential Oils as prescribed by the Bureau of

Indian Standards 1
Standard requirements for oillemongrass (east Indian oil of lemongrass)
S. No. Characteristic Requirements
(i) Color and appearance Dark yellow to light brown-

red mobile liquid
(ii) Odor Lemon-like
(iii) Specific gravity at 30 DC/30 QC 0.888 to 0.898
(correction for change in temperature
is 0.00062 for each degree centrigrade)
(iv) Refractive index at 30 QC 1.4786 to 1.4846
(Correction factor is 0.00044 for each
degree centrigrade change)
(iv) Optical rotation _3° to +lQ
(vi) Citral content, percent by volume, 75
minimum adopting bisulfite method
(30%; w/v solution)
(vii) Solubility in alcohol Soluble in 2 to 3 volumes of
ethyl alcohol (70%; v/v)
IBureau of Indian Standards, IS: 327-1961, pp. 6; IS: 526, 1968, pp. 7; IS: 528,
1970, pp. 6; IS: 329, 1961, pp. 5; IS: 1177, 1969, p. 6.
Standardization and Evaluation 221
Standard requirements for oil of palmarosa
SI. Characteristic Requirements

no.
(i) Color Light yellow to yellow
(ii) Odor Rosaceous, with a characteristic

grassy background
(iii) Specific gravity at 30 QC/30 QC 0.8740 to 0.8860

(iv) Q
Optical rotation -2Q to +3
(v) Refractive index 30 QC 1.4690 to 1.4735
(vi) Acid value, max 3
(vii) Ester value 9 to 36
(viii) Ester value after acetylation 266 to 280
(ix) Total alcohols, calculated as geraniol, 90.0
percent, min.
(x) Solubility in alcohol Soluble in 2 volumes of ethyl

alcohol (70%; v/v)
Standard requirements for oil of Ginger grass
SI. no. Characteristic Requirements
(i) Color and appearance Brownish yellow to brownish

red, hazy
(ii) Odor Sharp but pleasant odor
(iii) Specific gravity at 30 QC/30 QC 0.8960 to 0.9250
(iv) Optical rotation -14° to + 54°
(v) Refractive index at 30 QC 1.4740 to 1.4820

(vi) Acid value, max 6
(vii) Ester value 13.5 to 34
(viii) Ester value after acetylation 140 to 180
(ix) Total alcohols, calculated as 36 to 60

geraniol, percent, min.
Standard requirements for oil of peppermint

no.
Type.1 Type-2
Color and appearance Colorless, pale yellow Pale yellow

or greenish yellow
liquid
n Odor and taste Characteristic strong Characteristic minty,

minty, herbal followed intense herbal
by cooling sensation followed by cooling
sensation
iii Relative density at 0.8750 to 0.9100 0.890 to 0.9100

30 °C/30 °C
iv Optical rotation _30° to _43° _17° to _35°
v Refractive index at 1.4550 to 1.4630 1.4500 to 1.4620

30°C
vi Free alcohols, as 68 40
menthol (mol. wt.
156.26), percent by
weight, min.
VII Solubility (B.P. 2007, Miscible with alcohol Miscible with alcohol
Vol. 11, p. 1605) and with methylene and with methylene
chloride chloride
viii Acid value CB.P. 2007, max. 1.4 max. 1.4

Vol. 11, p. 1605)
ix Ester, as menthyl 3 to 15 6 to 25
acetate (mol. wt.
198.26), percent by
weight.
x Total alcohols, as 75, min. 45 to 55

menthol (mol. wt.
156.26), percent by
weight.
xi Ketones, as menthone 6 to 22 11 to 45
(mol. wt. 154.25),
percent by weight
Standard specification (requirement) for oil of sandalwood

no.
(i) Color and appearance Nearly colourless to golden

yellow, somewhat viscid oily
liquid
(ii) Odor and taste Pleasant, sweet, woody, and

persistent
(iii) Specific gravity at 30 °C/30 °C 0.962 to 0.976
(iv) Optical rotation
(v) Refractive index at 30°C 1.4990 to 1.5060
(vi) Esters calculated as santalyl acetate 2

(C 17 H 26 0 2 ), percent by weight, min.
(vii) Free alcohols, calculated as santalol 90

(C 15 H 24 0), percent by weight, min.
Standards of essential oils as prescribed by Indian Pharmacoepia Ip2

Standard specification of clove oil

no.
(i) Color Clear, colorless or pale yellow liquid

when freshly distilled, becoming
darken, and thicker by ageing or
exposure to air
(ii) Odor Odor as of clove
(iii) Weight per mL 1.038 g to 1.060 g (1.030-1.063)
(iv) Refractive index at 20°C 1.527 to 1.535
(v) Optical rotation 0° to -1.50° (00 to _2°)
(vi) Phenolic substances, expressed Minimum 85.0% w/w and
as chiefly eugenol, percent by maximum 95.0% w/w
weight
(vii) Heavy metals 0.5 g complies with the limit test for
heavy metals
(viii) Solubility in alcohol 1.0 mL is soluble in 2.0 mL or more
of alcohol (70%; v/v)
2Indian Pharmacoepia, IP 2007, p. 2031, 2032-2033, 2051-2052, IP 1966, pp. 529-

530, 335, 373, 305, 173, 145, 135, 110, 42.
Standard requirements for oil of vetiver roots

(Cultivated and Khus)

no.
Type-1 (cultivated) Type-2 (Khus)
(i) Color and appearance Light to reddish Light to reddish

brown, sometimes brown, sometimes
greenish, viscous greenish, viscous
liquid. liquid.
(ii) Odor Characteristic and Characteristic and

persistent aroma persistent aroma
with pleasant with pleasant
woody odor woody odor
(iii) Specific gravity at 0.992 to 1.015 0.990 to 1.032

30 °CI 30°C
(iv) Optical rotation 100 to 25 0 _50° to -130°
(v) Refractive index at 1.516 to 1.530 1.512 to 1.523

30°C
(vi) Acid value, max. 35 40
(vii) Ester value calculated 25 to 50 25 to 80

on (C 15 H 22 0), (mol.
wt. 218)
(viii) Ester value after 125 to 155 145 to 200

acetylation
(ix) Carbonyl value, min 55 24
(x) Total alcohols 55 70

(calculated on mol.
wt. 220), percent by
weight, min
Standard requirements of mentha oil
(i) Color Colorless or pale yellowish, clear liquid
(ii) Odor Characteristic and pleasant
(iii) Weight per mL 0.892 g to 0.910 g
(iv) Specific optical rotation -18° to _33°

Standard specification of eucalyptus oil
( i) Color Colorless or pale yellow liquid

(ii) Odor Aromatic and camphoraceous
(iii) Weight per mL 0.897 to 0.924 g
(iv) Refractive index 1.457 to 1.469
(v) Optical rotation
(vi) Cineole content, percent (w/w) Minimum 60
(vii) Solubility in alcohol Soluble in 5 volumes of ethanol
(70%; v/v).
Standard specification of turpentine oil
(i) Color Colorless, limpid liquid

(ii) Odor Characteristic
(iii) Solubility Soluble in 5 volumes of alcohol
(iv) Weight per mL at 25° 0.854 to 0.868 g
(v) Refractive index at 25° 1.467 to 1.477
(vi) Optical rotation Optically active but the rotation is variable
Standard specification of nutmeg oil
(i) Color Colorless or pale yellow liquid
(ii) Odor Odor of nutmeg
(iii) Solubility Soluble in 3 volumes of alcohol
(iv) Weight per mL at 25° 0.880 g to 0.910 g for east India oil and
0.854 to 0.880 for west India oil
(v) Refractive index at 20° 1.4740 to 1.4880 (east India oil)

1.4690 to 1.4760 (west India oil)
(vi) Optical rotation +8° to + 30° (east India oil)

+25° to +45° (west India oil)
Standard specification of lemon oil
(i) Color Pale yellow or greenish yellow liquid
(ii) Odor That of lemon
(iii) Solubility Soluble in 3 parts of alcohol and miscible

with alcohol.
(iv) Refractive index at 25° 1.4711 to 1.4761
(v) Weight per mL at 25° 0.849 g to 0.855 g
(vi) Optical rotation +57° to +65°
Standard specification for fennel oil
(i) Color Colorless or pale yellow oil.

(ii) Odor Odor characteristic
(iii) Solubility Soluble in 1 part of alcohol (90%), and in
8 parts of alcohol (80%)
(v) Weight per mL at 25° 0.953 to 0.973
(vi) Optical rotation at 25° +12° to +24°
Standard specification of dill oil
(i) Color Colorless pale yellow liquid, darkening with

age
(iil Odor That of the fruit
(iiil Solubility Soluble in an equal volume of 90% alcohol
at 15.5 °C, and in 10 volumes of 80% alcohol.
(vi) Optical rotation +70° to +80°
Standard specification of coriander oil
(i) Color Colorless or pale yellow liquid

(ii) Odor That of coriander
(iii) Solubility Soluble in 3 volumes of alcohol (70%)
(vi) Optical rotation
(vii) Acid value, Max (B.P. 2007, 3.0
Vol. 1, 599-600)
Standard specification of cinnamon oil
(i) Color Yellow liquid when freshly distilled,

gradually becoming reddish-brown with age
(ii) Odor Cinnamon odor
(iii) Solubility Soluble at 15.5 °C in 3 volumes of alcohol

(70%), the solution showing not more than
a slight opalescence
(vi) Optical rotation
Standard specification of cinnamon leaf oil
(i) Color Dark brown, limpid liquid

(ii) Odor Cinnamon od or Penetrations, fragrant,
resembling those of cinnamon and clove
(vi) Optical rotation -2.5 to +2.0° (Ceylon cinnamon leaf oil)
Standard specification of cassia oil
(i) Color Yellowish or brownish, becoming darker

and thicker on keeping
(ii) Odor Characteristic od or
(iii) Solubility Soluble in alcohol (equal volume), in 2

volumes of 70% alcohol and in an equal
volume of glacial acetic acid
(v) Weight per mL at 25° 1.045 to 1.063 g
(vi) Optical rotation at 25°C
Standard specification of anise oil
(i) Color Colorless, or pale yellow liquid
(ii) Odor That of the fruit
(vi) Optical rotation _2° to +1°
Standard specification of ajowan oil
(i) Color Colorless, or brownish liquid becoming

darker on keeping
(ii) Odor Resembling thyme
(iii) Solubility Soluble in 4 parts of alcohol (90%)
(vi) Optical rotation 0° to +2°

Standards of essential oils as prescribed by British Pharmacoepia, Bp3

Standard of rosemary oil
SI. no. Characteristic Standard
(i) Color Clear, colorless to pale yellow liquid

(ii) Odor Characteristic odor
(iii) Relative density 0.895 to 0.920
(v) Optical rotation _50 to +8 0
(vi) Acid value Maximum 1.0
3British Pharmacoepia, BP 2007, vol. 11, pp. 1819-1820, 1829-1830, 1933, 1997-1998,
1221-1222, 1187-1188; 1453-1454, 1530-1531; BP 2007, Vol. I, p. 383,367-368.
Standard of sage oil
(i) Color Colorless to brownish yellow liquid, usually a

pale yellow
(v) Optical rotation -26 0 to _100
Standard of spearmint oil
(i) Color and appearance Colorless, pale yellow or greenish-yellow

liquid when recently distilled, but becoming
darker and viscous on keeping
(ii) Odor That of spearmint
(iii) Weight per mL. 0.917 - 0.934 g (American type)
0.935 - 0.952 (Chinese type)
(v) Optical rotation _45 0 to _60 0 (American type)

_50 0 to _620 (Chinese type)
(vi) Solubility in ethanol Soluble at 20 0, in 1 part of ethanol (80%).
The solution may become cloudy when
diluted.
Standard of tea tree oil
(i) Color and appearance Clear, mobile, colorless to pale yellow liquid
(iii) Relative density 0.885 - 0.906
(v) Optical rotation +5° to +15°
Standard of lavender oil
(i) Color and appearance Colorless to pale yellow, clear liquid
(iii) Relative density 0.878 - 0.892
(v) Optical rotation -12.5° to -7.0°
Standard of juniper oil
(i) Color and appearance Mobile, col or less to yellowish liquid
(iii) Relative density 20°C 0.857-0.876
(iv) Refractive index 20 °C 1.471-1.483
(v) Optical rotation _15 0 to -0.5 0
(vi) Peroxide value Maximum 20

Standard of cardamom oil
(i) Color and appearance Clear, colorless or pale yellow liquid

(ii) Odor That of cardamom fruit
(iii) Weight per mL 0.917 to 0.940
(iv) Refractive index 20°C 1.461 to 1.467
(v) Optical rotation +20° to +40°
(vi) Ester value 90 to 156
(vii) Solubility in ethanol Soluble at 20 °C in 6 volumes of ethanol (70%)
Standard of orange oil
(i) Colour and appearance Yellow to yellowish brown liquid
(ii) Odour That of orange
(iii) Specific gravity Between 0.842 and 0.848
(iv) Refractive index 1.472-1.476 at 20°C
(v) Optical rotation +94° and +99°
(vi) Solubility in ethanol Soluble at 20 °C m 7 volumes of ethanol

(90%)
(vii) Content of aldehydes Not less than 1.0% (w/w) calculated as

decanal, C lO H 20 0
Standard of rose oil
(i) Color and appearance Clear liquid
(iil Odor Characteristic

(iii) Specific gravity 0.848-0.863 at 30 °C compared with water
at 15°C
(iv) Refractive index 1.457-1.463 at 30°C
(v) Optical rotation _1° to _4°
(vi) Residual solvents Meets the requirements

Standard of neroli oil
(i) Color and appearance Clear, pale-yellow or dark-yellow liquid

(v) Optical rotation +1.5 to +11.5
0 0
(vi) Acid value, max. 2.0
Standard of sweet orange oil
(i) Color and appearance Clear, pale-yellow to orange, mobile liquid

which may become cloudy when chilled
(ii) Odor Characteristic odor of fresh orange peel
(v) Optical rotation
(vi) Peroxide value Max 20
Standard of caraway oil
(i) Color and appearance Clear, colorless or yellow liquid

(ii) Odor Characteristic
(v) Optical rotation +65 0 to +81 0
(vi) Acid value Max 1.0
Standards are published also by August bodies like Food Chem. Codex, EOA (25 °C),
AFNOR, FMA, AMC/EO, BPC 73, ISO 1342, etc.
Standards published by some of the above bodies of essential oils like cumin
(fruits), ginger, and rosemary are mentioned below.
Standards of essential oil of cumin (Egypt)4
SI. Property Food EOA AFNOR FMA AMC/

no. Chem. (25°C) EO
Codex
(i) Relative density Min. 0.905 0.905 0.905 0.908 0.920

at 20 °C/20 °C Max.0.925 0.925 0.930 0.928
(ii) Refractive index Min. 1.501 1.501 1.490 1.501 1.501

at 20°C Max.1.506 1.506 1.506 1.506
(iii) Optical rotation Min. + 3° +3° +1" +3° +4°

at 20°C Max. + 8° +8° +8° +3°
(iv) Miscibility with 1 in 8 1 in 10 1 in 8

80% (v/v) ethanol
at 20°C
(v) Carbonyl value 45-52 4-58 45-52

expressed as
cuminal
EOA Essential Oils Association now Fragrance Materials Association (FMA)
of Amaila.
AFNOR Association Francais de Normalisation.
BPC The British Pharmaceutical Codex.
4Analyst, July 1993, Vol. 118, p. 1092, 1095, 1097.
Standards of essential oil of ginger (Nigeria)
SI. Property Food EOA FMA AMCIEO

no. Chem. (25°C) sample
Codex
(i) Relative density Min. 0.871 0.878 0.879 0.920

at 20 °C/20 °C Max.0.882 0.888 0.882
(ii) Refractive index Min. 1.488 1.488 1.488 1.501

at 20°C Max. 1.494 1.494 1.494
(iii) Optical rotation Min. _28° -28° _28° _32°

at 20°C Max. _45° -45° _45°
Standards of essential oil of rosemary4
SI. Property Food BPC AFNOR ISO AMCI

no. Chem. 73 1342 EO
Codex sample
(i) Relative density Min. 0.894 0.893 0.895 0.895

at 20 °C/20 °C Max. 0.912 0.910 0.910 0.920
(ii) Refractive index Min. 1.467 1.466 1.467 1.467

at 20°C Max.1.476 1.474 1.474 1.474
(iii) Optical rotation Min. _5° _5°

at 20°C Max. +10° +10°
(iv) Esters as bornyl Min. 1.5

acetate (%; m/m)
(v) Alcohols as bornyl Min. 8

alcohol (%; m/m)
(vi) Miscibility with 1 in 1 1 in 10 1 in 10 1 in 10 1 in 8

80% (v/v) ethanol (90%)
at 20°C
(vii) Acid value 1.0 1.0 0.5

(max.) (max.)
(viii) Ester value 2-20 2-20 15
(ix) Ester value 30-55 30-76 46

after acetylation
4Analyst, July 1993, Vol. 118, p. 1092, 1095, 1097.
Standards for the various essential oils have become possible

due to the development of sophisticated analytical methodologies,
which are based on the progress of the chemistry and technology of
terpene derivatives. New standards are expected in order to maintain
the quality and authenticity of natural essential oils for continuing
their applications in food, cosmetic, and related products, with
complete safety and without any aroma problems.
ANALYSIS OF ESSENTIAL OILS
Essential oils have well-defined physico-chemical properties. A

number of analytical methodologies have been developed and
practised for essential oils to establish their physical characteristics
and determine their chemical compositions with a view to ascertaining
quality.
The physical characteristics that are usually tested include

refractive index, specific gravity, optical rotation, solubility in alcohol
congealing point, melting point, boiling point, and evaporation residue.
The chemical properties include determination of acid value,
saponification value, ester value and content of total alcohols,
aldehydes, phenols, cineole, etc.
Chemical analysis includes also identification and determination

of the major and minor constituents of essential oils.
Physical Analysis of Essential Oils 1
Among the many physical methods adapted for characterization of

essential oils, mention may be made that solubility test, optical
rotation, specific gravity, refractive index are considered imperative
for examination. These analytical methods are elaborated briefly
here.
Solubility Test
Essential oils, by virtue of their compositions exhibit ready solubility

in polar solvents like alcohols (monohydric, namely, methanol,
ethanol, isopropanol, butanol, etc., dihydric and trihydric alcohols
(e.g. diethylene glycol, glycerol>; chlorinated compounds like
methylene chloride, chloroform; aromatic solvents like benzene,
toluene; and non-aromatic hydrocarbon solvents like petroleum ether
(b.p. 40 QC-60 QC), n-hexane (b.p. 69 QC-70 QC), cyclohexane, etc.
Oils are also soluble in solvents like carbon disulphide, supercritical
carbon dioxide. However, it is the solubility of essential oils in
ethanol such as absolute (>95% alcohol), rectified alcohol (90%), or
in 70-80% alcohol that is accepted for characterizing the solubility
of essential oils and quality.
The solubility of natural essential oils in 70% ethanol at a particular

temperature (20 QC) is normally accepted as satisfactory for accepting
solubility character of essential oils.
Method
The method consists of adding gradually 2, 3, 5 or 10 vol. alcohol of

a definite strength to 1 volume of essential oil taken in a graduated
stoppered test tube and mixing thoroughly.
The appearance of cloudiness or haziness or turbidity or the
separation of either oily layer or a wax deposit with alcohol of varying
strength is noted with time of settling to indicate the purity or
autheticity of an essential oil and its solubility in alcohol.
Specific or Optical Rotation
Most essential oils have optical activity and show specific rotation
property when placed in a beam of polarized light. The specific rotation
and its direction (right or dextrorotatory and left or laevorotatory)
depend on the nature of essential oils. These values are highly specific
and are, therefore, regarded as criteria of purity.
Method
The method consists of taking in a polarimeter an essential oil after

being duly purified by filtration to remove suspended impurities and
dried with anhydrous sodium sulfate removing the water occurring
in small amount.
The polarimeter is next placed between the polarizer and
analyzer. The analyzer is slowly turned until both halves of the
field show equal illumination intensities when viewed through the
telescope.
A kind of rotation to the right or to the left can be observed
making a distruct in equality in the illumination intensities of the
two halves of the field. If the analyzer is turned counter clockwise
from the zero position to get the final reading, the rotation is
laevo (-) and when turned clockwise, dextro (+).
After establishing the direction of rotation, the analyzer is carefully
adjusted again to obtain equal illumination of the two halves of the
field. The eye piece of the telescope is adjusted to give a clear, sharp
line between the two halves of the field. The rotation, the degree,
and the minutes precisely using two-fixed verniers.
The duplicate reading is taken with a variation not beyond ± 5'
from the first reading.
Refractive Index
Refractive index of essential oils is an important determinant which

varies depending on the composition of essential oils and the values
are used in identification of their purity and authenticity.
Method
Abbe' refractometer is used in routine determination of refractive

index of essential oils at a definite temperature.
Properly clarified and dried essential oils are taken for the
determination of refractive index at a particular temperature (e.g.,
20 QC or 15 QC).
Few drops of the essential oil treated as above are placed on the
prism of the Abbe' refractometer adjusted to the particular
temperature (20 QC) and the reading from the scale is noted.
Necessary temperature correction can be made by using a factor of
0.00045 per degree.
The value is added when the determination is done above 20 QC

or deducted/subtracted when refractive index is measured below
20 QC.
Specific Gravity of Essential Oils l
Essential oils exhibit distinct specific gravity that is accepted as an

important and reliable criterion of their quality and purity.
Method
Specific gravity of an essential oil is best determined by Pycnometer.

Properly cleared Pycnometer is filled with freshly distilled and boiled
water and the Pycnometer is allowed to cool at first to about 12 QC
and later raised to 15 QC at which temperature the specific gravity
value is expressed.
The water level is adjusted to the top of the capillary side

arm, excess water with a blotter, and the ground glass cap is
placed.
The Pycnometer is removed from the water bath, dried

carefully allowed to stand for 30 min, and weighed accurately
(W 1)'
The weight of the empty and dried Pycnometer is taken (W 2 ). The

Pycnometer is next filled with the filtered and dried essential oil
cooled at 12 QC already; and then raised to 15 QC. The oil is adjusted
to the proper level as done for water and processed similarly, and
the weight of the Pycnometer plus oil is taken accurately (W 3 ).
W3 - W 2
Specific gravity at 15 I15 C =
Q Q
W1 - W2
Chemical Analysis of Essential Oils
Essential oils are characterized for their chemical properties like

acid value (A.V.), ester value (E.v.) and saponification value (S.V.).
The essential oils are also analyzed for the content of their major
constituents such as alcohols (total and primary), aldehydes, and
phenols including cineole.
Chemical Properties of Essential oils l
Acid value (A.V.) determination: Acid value is defined as the

milligram of potassium hydroxide required to neutralize the free
acids in 1 g. of essential oil.
Procedure: The method consists of refluxing a known quantity
(2-5 g) of an essential oil in a 250 mL Erlenmeyer flask with 25 mL
of neutral alcohol containing 2-3 drops of a 1% phenolphthalein
solution for 2 minutes on a steam bath, followed by titrating to red
end point with 0.1 N NaOH solution.
The acid value or acid number is calculated from the formula
below:
5.61 x V (no. of cc. of O.IN NaOH)
Acid value (Acid number) =
Weight of essential oil taken for
titration
Ester Value (E.V.) Determination and Ester Content
The ester value (E.V.) is determined by estimating the saponification

and acid values of an essential oil.
Ester value = (S.v. - A.V.)
Procedure: Acid value is first determined to phenolphthalein end

point. Saponification value is determined by refluxing with 10, or 20 mL
of 0.5 N KOH solution for 1 hour on a steam bath, a known quantity
of essential oil (2-5 g.) is taken in a 250 mL Erlenmeyer flask, followed
by titrating the excess alkali with 0.5 N HCI or H 2 S0 4 to discharge
the pink/red color. A blank run is done during the saponification
value determination, titrating as usual to discharge as usual the
phenolphthalein color.
(A-B) x 5.61 x V (cc of 0.5 N acid)
Saponification value (S.v.) =
Weight of essential oil
where, A is the volume of 0.5 N HCI or H 2 S0 4 in blank titration,

B is the volume of 0.5 N HCI or H 2 S0 4 in case of sample.
Ester value is calculated as: Ester value (E. V.) =
(S.v.) - (A.V.)
a x m
Percent ester is calculated as: Percent ester = - - - -
20 x s
where, a is mL of 0.5 N NaOH used in S.v.,
m is molecular weight of the ester, and
s is weight of the sample in gm
Ester content: Ester content in percent is calculated as:
m (ester value or number)

Percent Ester = for monobasic acid.
561.04
Determination of the Major Constituents in Essential Oils!

Determination of alcohols: Essential oils contain in general a
variety of terpene alcohols, which may be primary, secondary, or
tertiary. Primary and secondary terpene alcohols normally occur.
The method of determination of alcohols depends on the nature of
alcohols in essential oils. Total alcohols are determined by total
acetylation while the primary alcohols are quantitated by
phthalation reaction.
Total Alcohols by Acetylation
The method involves of acetylating an essential oil by acetic

anhydride and later determining the ester content of the acetylated
product.
The percentage of alcohol III essential oil is calculated from the

formula:
a x m
20 (s - 0.021a)
where, a is mL of 0.5 N NaOH solution required for the

saponification of the acetylated oil,
s is the weight of acetylated oil in grams used in the
saponification,
m is the molecular weight of the alcohol.
Primary Alcohols in Essential Oils
Terpene alcohols having primary hydroxyl group can be determined

in essential oils by taking advantage that primary alcohols react
with phthalic anhydride to form an acid phthalate ester.
The method involves the preparation of the acid phthalate ester

and determination of the equivalent alkali required to saponify the
ester and the equivalent alkali to neutralize the equivalent phthalic
anhydride used in the actual determination. The difference in the
alkali content relates to the actual amount of phthalic anhydride
reacted with the primary alcohol.
Method
CD A known quantity of accurately weighed (about 1.2 g) of the

essential oil is taken in a 100 mL flask. Accurately weighed
about 2 g of phthalic anhydride is also taken in the flask. 2
mL, of benzene is added and the flask is heated on a steam
bath for 2 hr with occasional shaking.
(ii) The flask is cooled to room temperature for 30 min then
60 mL of 0.5 N aqueous KOH solutions is added. The
contents are mixed by shaking thoroughly for 10 min using
a stopper.
(iii) The excess alkali is titrated with 0.5 N Hel, using
phenolphthalein (1% solution) indicator, which is 'a' value.
(iv) A blank determination is conducted without the oil taking
the same amount of anhydride and benzene.
Calculation
The percentage of primary alcohol is calculated from the formula =

m (b - a)
20 w
where, m is the molecular weight of the primary alcohol,

b is the volume in c.c. of 0.5 N KOH required for the
amount of phthalic anhydride used in the determination,
a is the volume in c.c. of 0.5 N KOH consumed in the
determination.
w is the weight of oil in grams.
Aldehyde Content in Essential Oils
Adehyde content in essential oils is mostly determined by taking

advantage of its ability to form addition compound with sodium
bisulfite solution.
The principle involves reacting a known volume of an essential oil

with a saturated aqueous solution of sodium bisulfite in a Cassia
flask. After the reaction is complete and the bisulfite addition
compound goes in solution, a certain volume of the unreacted oil
separates out. The difference in volume between the volumes of the
original oil taken for the reaction and the volume of the unreacted
oil is taken as the volume of the aldehyde component occurring in
essential oil.
Method
(i) 10 mL of the essential oil is taken in the Cassia flask (150

mL).
(ii) 75 mL of a freshly prepared saturated aqueous solution of
sodium bisulfite is added gradually to the oil by mixing till
the solid or semisolid mass is formed which goes into solution
completely when placed on a steam bath.
(iii) The flask is shaken repeatedly for complete reaction. Further
volume (25 mL) of bisulfite solution is added by gradual
shaking.
(iv) The flask is allowed to remain at rest unsettled till the
unreacted oil separates out completely and clearly.
(v) Further volume of bisulfite solution is added to bring the

unreacted oil to rise to the surface within the neck of the
flask.
The aldehyde content IS calculated by means of the formula

provided below:
Percent aldehyde = 10 (10 - vol. in mL of the unreactd oil)
Aldehydes/Ketones Determination in Essential oils by

Hydroxylamine Method
Essential oils having aldehyde or ketone functional group invariably

react with hydroxyl amine used as hydroxylamine hydrochloride. An
equivalent amount of hydrochloric acid is liberated that is estimated
by standard alkali solution.
The process therefore consists of adding a known volume of a

standard hydroxylamine hydrochloride to the known weight of an
essential oil and estimating the equivalent HCI liberated. A blank
run is carried out with equal volume of hydroxylamine hydrochloride
for accurate color match.
Method
(i) A known weight of an essential oil is taken in a 100 mL

Erlenmeyer flask.
(ii) A known volume (25 mL) of 0.5 N hydroxylamine
hydrochloride solution is added.
(iii) The reaction is allowed to take place in course of 15 minutes.
(iv) The equivalent hydrochloric acid liberated is titrated with
0.5 N alcoholic NaOH solution to the original greenish shade
of the hydroxylamine solution.
(v) A blank run is conducted by titrating the same volume of
hydroxylamine hydrochloride solution for accurate color match
only.
MxV
Percentage of aldehyde or ketone = - - -
20W
where, M is the Molecular weight of the aldehyde or ketone,
V is the volume of 0.5 N NaOH solution required for
neutralization, and
W is the Weight of essential oil in grams.
Determination of Phenols
Essential oils containing phenolic constituents are evaluated by

determining the total phenolic molecules and expressing as the major
component of the oil.
The principle involved is that phenolic compounds are reactive to

alkalis like sodium hydroxide or potassium hydroxide, while the
nonphenolic constituents remain unreacted and separate as an oily
layer. The difference in the volume of the oil reacted is taken as the
total phenolics and expressed as the percentage of the major phenolic
component.
Method
(i) 10 mL of the essential oil is taken in a Cassia flask.

(ii) 75 mL of 1 N KOH (aqueous) solution is gradually added to
the oil and shaken thoroughly at room temperature for 10
minutes. Sometime it may be required to heat the flask on
a steam bath.
(iii) The entire flask is allowed to stand for 1 hr or so till the
unreacted oil separates out sharply.
(iv) An excess of the alkali solution is very carefully added to
bring the uneacted oil within the graduated scale of the Cassia
flask.
(v) The exact volume (in mL) of the unreacted oil is
measured.
Percentage of phenol = 10 (lO-V)
where, V is mL of the unreacted oil for clove oil, the phenolic

component is expressed as Percent Eugenol.
Determination of Cineole
Cineole as occurring in essential oils forms an addition compound

with phosphoric acid when appropriately treated. The addition
compound is isolated in pure form by extracting out the
unconverted oily material with a nonpolar solvent like petroleum
ether (b.p. 40-60 QC). The addition compound is decompressed
with hot water to liberate the cineole portion, which is later
measured in volume (mL) in a Cassia flask by adding gradually
water.
Method
(i) 10 mL of the oil is taken in a 50 mL beaker and cooled in

a ice and salt bath.
(ii) 4 mL of phosphoric acid is gradually mixed with the oil by
stirring carefully.
(iii) The mixture is allowed to remain in ice-salt bath for another
5 minutes.
(iv) 10 mL of petroleum ether (b.p. 40-60 QC) previously cooled
is added and the mixture is filtered off as quickly as possible
on to a Buchner funnel under suction.
(v) The cake from the Buchner funnel is broken into small
fragments and transferred into a Cassia flask.
(vi) Warm water is added to decompose the addition compound.
(vii) Water is next added to bring the cineole liberated into the
neck of the Cassia flask.
(viii) The content is cooled to room temperature and the volume
of cineole is noted.
Volume of cineole
Percentage of cineole = x 100
Volume of oil
ANALYSES OF ESSENTIAL OILS BY

CHROMATOGRAPHY
A number of chromatographic techniques such as thin layer and
column chromatography, gas-liquid and high-performance liquid
chromatography have been developed in the field of essential
oils.
Thin Layer Chromatography (TLC)2
TLC has been examined as a very elegant methodology for qualitative
detection of natural essential oils on the basis of functional groups
that show distinct adsorption pattern on the surface of silica gel and
other adsorbents.
In fact, the selection of appropriate solvent system as eluting

solvent (from Eluotropic series) and detection reagents have been
developed for separating the major and minor constituents of
essential oils.
Hexane, cyclohexane, methyl cyclohexane, ethylacetate +
toluene (5 + 95), as solvents separate the terpenes and
sesquiterpens in essential oils on silicagel G layer and other

constituents.
Benzene or chloroform resolves terpene alcohols on Silicagel G
layers. Benzene shows lower RF values while chloroform shows higher
RF values. The esters of terpene alcohols also exhibit difference in
the RF values between benzene and chloroform as eluting solvents.
The separation is also done on preparative scale and the separated

bands are isolated and examined further by spectrocopic techniques
(U.v. and LR.) to identify functional groups.
Separation pattern of terpene alcohols and their esters on Silica Gel G

layers2
Substance Solvent RF x 100
Terpene alcohols Chloroform 26-33 (Linalool-38l

Terpene alcohol acetates -do- 63-65
Terpene alcohol formates, propionates -do- 71-74
and butyrates
Sesquiterpene alcohols -do- 35-40
Separation pattern of aldehydes and ketones (as occurring in essential

oils) on Silica Gel G layers and colour reactions 2
Aldehyde/ketone RF x 100 Color reactions

(chloroform
solvent) 2,4-DNPH o-Dianisidine
Vanillin 29 Orange Yellow-Orange

Citral 56 Yellow Yellow-Brown
Piperonal 55 Orange
Cinnamaldehyde 60 Orange Orange-Brown
Benzaldehyde 59 Yellow
Cuminic aldehyde 65 Orange Yellow
Carvone 56 Orange Yellow
Methyl heptenone 56 Yellow
Methyl hexyl ketone 57 Yellow Green-Brown
Methyl nonyl ketone 57 Yellow
Menthone 60
Reversed-phase TLC technique is often adopted to suitably separate

the terpene alcohols having the same number of carbon atoms. In
practice, silica gel G layer is coated with a nonpolar phase liquid
paraffin or silicone oil and using a polar solvent such as 70% aqueous
methanol as an eluting solvent.
TLC separation patterns of the various molecular constituents as
occurring involving adsorption and reverse-phase principles have been
disscussed here as elaborated by StahI2, in tabular forms.
Terpene alcohols can be sharply separated from their esters as
evident from the differences in the RF-values. It is to be noted
that the acetate esters show somewhat lower RF-values, indicating
Reversed-phase TLC separation of terpene alcohols on Silica Gel G
impregnated with paraffin or silicone oil and using 70% Methanol as an
eluting solvent 2
Substance RF x 100
Farnesol, nerolidol, cedrol, guaiol 17-20

Geraniol, nerol, linalool, menthol, terpineol, fenchol, borneol, 42-48
isoborneol, cuminic alcohol
Cinnamyl alcohol 55
Benzyl alcohol 59
a difference III adsorption pattern on the surface of silica gel G.

Sesquiterpene alcohols show somewhat higher RF values as
expected.
It is evident that the aldehydes and ketones barring a few, show
almost identical RF-values and color reactions. The separation of
aldehydes from ketones by silica gel G TLC technique does not appear
to be achievable. In most cases, aldehydes and ketones can be isolated
together and later resolved by GLC.
Terpene alcohols and terpene aldehydes are often appropriately
derivatized and the derivatives are separated by TLC technique 2 .
Terpene alcohols can be converted to dinitrobenzoates, and
next separated by TLC using 1:1 (v/v) benzene and hexane.
Terpene aldehydes as occurring in essential oils are often
separated as their 2,4-dinitrophenyl hydrazones on silica Gel G
layers with benzene-petroleum ether (60-80 QC) in 75:25 (v/v) or
with benzene + ethyl acetate (95+5).
The TLC separations of some essential oils are exemplified
that indicate the scope of qualitative identification of the polar and
nonpolar constituents having adsorptive properties and the

constituents forming colored spots when sprayed with anisaldehyde,
or vanillin reagent and heating at 100-105 QC for 5-10 min and
viewing under day light.
Lavender oil when eluted with ethyl acetate and toluene solvent
system (5+95; v/v) on TLC silicagel plate and sprayed with anisaldehyde
solution and heated at 100 QC for 10 min, resolves into a number of
colored spots, viz., violet-red or greenwish-brown, a violet-red, violet
to brown, etc., when viewed under day light 3.
With the same TLC silica gel layer and eluting system, rosemary
oil when heated with vanillin at 105 QC for 10 min, shows a number
of different coloured spots under day light 3.
Tea tree oil on TLC silica gel separation with 20:80 (v/v) ethyl
acetate and heptane and heating with anisaldehyde solution at 105 QC
for 10 min gives on the chromatogram a number of coloured zones
also under day light3.
Juniper oil reveals also colored spots in day light. Sage oil gives
also coloured spots after spraying with vanillin reagent and heating
at 105 QC for 10 min 3.
Column Chromatography
Column chromatography (CC) is also used in separating the

constituents of essential oils into various fractions depending on the
polarity of the components. Normally silicic acid and alumina are
used as an adsorbent. The elution is done with hexane, and using
hexane and diethyl ether with increasing amount of diethyl ether
facilitate more complete separation of the polar components. The CC
methodology can be combined with GLC for more complete and
accurate analysis, and it can be combined with UV and FT-IR
techniques to confirm the functional groups.
Gas Liquid Chromatography
Gas liquid chromatography (GLC) with packed bed columns (PGC)

and preferably capillary columns (CGC) has proved to be the best
analytical method for separation, identification and quantitation of
the constituents occurring as major and minor components in various
kinds of essential oils. The application of capillary GLC has been
widely explored for establishing the composition and purity of the
essential oils very efficiently and rapidly.
GC-MS and GC-FT-IR have been adopted and applied to study

the composition of essential oils. Almost, all the known essential oils
have been extensively analyzed by capillary GC. Essential oils from
new source materials are also examined nowadays by capillary GC
and capillary GC-MS techniques.
Capillary GC enables to ascertain industrial quality control of
essential oils. The methodology also helps to detect adulteration in
essential oils by taking advantage of the finger print 'CG'
chromatogram and comparing with that of the suspect sample which
may show different kind of separation pattern.
Capillary GC columns used nowadays are almost exclusively fused
silica columns, although glass columns coated with polar or non polar
phases are used. Chiral columns (cyclodextrin capillary columns) have
been exploited for essential oil analysis particularly for identification
and authenticity control of essential oils.
The operating condition includes the programming of temperature
depending on the vapor pressure (boiling points) of the constituents
of essential oils and FID is used for the purpose of detecting the
components eluted from the column.
GC-MS in Perfume (Essential Oil) Analysis
Two-dimensional comprehensive GC indicated as GC x GC has been

now adopted for achieving unsurpassed resolution and detection
sensitivity by coupling two GC columns and allowing heart-cuts from
the first column to be analyzed on the second column. A cryogenic
or a thermal modulator is used at the point where both columns are
coupled. The initial column is a regular apolar capillary - GC column,
whereas the second column has a polar phase and "high speed"
dimensions (e.g., short length and small internal diameter and film
thickness).
All the fractions eluting from the first column are next separated
in real time by the second column. The detection is mainly performed
with the FID, but coupling to TOF-MS detectors has been
demonstrated recently.
The GC x GC analysis of vetiver and lavender essential oils have
revealed that these natural perfume ingredients are even more
complex than had been assumed on the basis of regular GC analysis.
In recent years, the MS detector is applied in the selected ion
monitoring (SIM) mode preferably thus making GC-MS very
suitable for trace analysis of essential oil ingredients.
Essential oil of cumin (Egypt) by GLC 4
Peak identity Polar stationary Nonpolar stationary

phase phase
(polyethylene glycol (methyl
20 M) polysiloxane)
RRI RPA RRI RPA

(%) (%)
a-Thujene, a-Pinene 1034 102.0 915 0.4
p-Pinene 1120 21.0 926 1.1
p-Myrcene 1160 1.1 974 21.0
a-Phellandrene 1176 1.4
a-Terpinene 1190 0.1
Limonene 1215 0.7
p-Phellandrene 1,8-cineole 1228 0.5
r-Terpinene 1261 20.0
p-Cymene 1285 9.7 1050 20.0
Terpinolene 1300 0.1 1012 9.4
Terpin-4-ol 1610 0.5 1166 0.3
p-Canyophyllene 1620 0.3 1429 0.3
a-Terpineol 1690 0.3 1174 0.4
p-Mentha-1,3-dien-7 -al 1795 11.0 1270 19.0
p-Mentha-1,4-dien-7 -al 1811 8.9 1596 0.6
Carotol 2027 0.5 1221 21.0

(cuminall
Cuminic alcohol 2098 0.2 1450 0.4

<p-farnesene)
Essential oil of rosemary (Spain) by GLC 4

phase phase
20 M) polysiloxane)
RRI RPA RRI RPA

(%) (%)
Tricyclene 915 0.8
a-Pinene 930 18.0
a-Thujene 1026 18.0
Camphene 1066 8.8 945 9.4
~-Pinene 1180 5.5 975 5.5
~-Myrcene 1158 1.0
p-Cymene 1275 2.8 1014 2.9
Limonene 1211 7.3 1028 33.0
1,8-Cineole 1219 25.0
Terpinolene 1284 0.2 1051 0.1
Fenchone 1443 0.3 1056 0.1
ISO-Fenchone 1454 0.3
Camphor 1528 16.0 1130 16.0
Linalol 1547 1.3 1086 0.4
Bornyl acetate 1589 2.0 1278 2.2
Terpinen -4-01 1600 0.3 1168 0.2
~-Caryophyllene 1608 0.4 1430 0.5
a-Terpineol 1695 1.9 1178 2.0
Borneol 1702 1.8 1158 1.4
Caryophyllene oxide 1577 0.1

Essential oil of ginger (Nigeria) by GLC 4

phase phase
20 M) polysiloxane)
RRI RPA RRI RPA

(%) (%)
Tricyc1ene 1014 0.2 911 0.2

a-Pinene 1028 3.3 926 3.0
Camphene 1072 8.8 944 8.3
~-Pinene 1117 0.5 951 (methyl 0.4
heptenone)
Sabinene 1124 0.8 963 (p-Pinene) 0.7
(p-Myrcene)
~-Myrcene 1166 1.5
~- Phellandrene 1176 0.5
Limonene 1,8-Cineole 1213 1.7
~-Phellandrene 1224 8.2 1021 9.6
r-Terpinene 1255 0.1
p-Cymene 1278 0.1
Terpinolene 1291 0.3
a-Copaene 1506 0.7
Linalol 1541 0.4
Bornyl acetate 1600 0.8
Neral 1686 1.3 1216 1.4
Borneol 1704 1.1 1152 0.8
a-Zingiberene Geranial 1741 29.0 1498 29.0
1244 1.4
~-Bisabolene 1741 5.8 1509 14.0
a-Farnesene Geranyl acetate 1755 7.3 1360 0.9
Sesqui-p-phellandrene 1784 14.0 1525 9.9
Geraniol 1848 0.4 1233 0.5
Nerol 1210 0.2
~-Elemene 1393 0.7
a-Terpineol 1176 0.3
Gas chromatography with packed-bed column containing both polar

and nonpolar stationary phases of essential oils is shown. It may be
Capillary GC analysis of lavender oil
A: Operating details
Capillary column Fused silica (60 m x 0.25 mm)
Stationary phase Macrogel 20,000 (0.25 ).lm thickness)
Carrier gas and flow rate Helium 1.5mLlmin
Split ratio 1:100
Temperature programming 70 QC 0-15 min
70 QC-180 QC 15-70 min
Injection port temperature 220 QC
FID detector temperature 220 QC
B: Percent composition (%; w/w)
Limonene <1.0
Cineole <2.5
3-0ctanone 0.1-2.5
Camphor <1.2
Linalol 20 to 45
Linalyl acetate 25 to 46
Terpene-4-0 1 0.1-6.0
Lavandulyl acetate >0.1
a-Terpineol <2.0
Capillary GC analysis of rosemary oil (Spanish)
A: Operating conditions
Column Fused silica (60 m x 0.25 mm)
Stationary phase Macrogel 20,000
Carrier gas and flow rate Helium 1mL/min
Split ratio 1:50
50 QC-200 QC 10-85 min
200 QC 85-110 min
B: Percent composition (%; w/w) (Spanish) for Moroccan and Tunisian
a-Pinene 18.0 - 26.0 9.0 - 14.0
Comphene 8.0 - 12.0 2.5 - 6.0
13-Pinene 2.0 - 6.0 4.0 - 9.0
13-Myrcene 1.5 - 5.0 1.0 - 2.0
Limonene 2.5 - 5.0 1.5 - 4.0
Cineole 16.0 - 25.0 38.0 - 55.0
p-Cymene 1.0 - 2.2 0.8 - 2.5
Camphor 13.0 - 21.0 5.0 - 15.0
Bornyl acetate 0.5 - 2.5 0.1 - 1.5
a-Terpineol 1.0 - 3.5 1.0 - 2.6
Borneol 2.0 - 4.5 1.5 - 5.0
Verbenone 0.7 - 2.5 Max 0.4
Capillary GC analysis of neroli oil
Stationary phase Macrogel 20,000 (0.25 )lm thicknessl
Split ratio 1:100
75 QC-230 QC 4-42.8 min
I3-Pinene 7.0 - 17.0
Limonene 9.0 - 18.0
Linalol 28.0 - 44.0
Linalyl acetate 2.0 - 15.0
u-Terpineol 2.0 - 5.5
Neryl acetate Max 2.5
Geranyl acetate 1.0 - 5.0
trans-Nerolidol 1.0 - 5.0
Methyl authranilate 0.1 - 1.0
(E,El-Farnesol 0.8 - 4.0
Capillary GC analysis of clove oil
Stationary phase Macrogel 20,000 <0.25 )lm thickness)
Split ratio 1:100
Temperature programming 60 QC 8 min.
60 QC-180 QC 3 QC/min.
180 QC 5 min.
I3-Caryophyllene 5.0 - 14.0
Eugenol 75.0 - 88.0
Acetyl eugenol 4.0 - 15.0
Capillary GC analysis of lemon oil
Carrier gas and flow rate Helium 1.0 mLlmin
Split ratio 1:100
45 QC-90 QC 6-21 min
90 QC-150 QC 21-39 min
180 QC 39-55 min
B: Percent composition (% w/w)
13-Pinene 7.0 -17.0
Sabinene 1.0 - 3.0
Limonene 56.0 -78.0
r-terpinene 6.0 - 12.0
13-Caryophylene Max 0.5
a-Terpineol Max 0.6
Neryl acetate 0.2 - 0.9
Geranial 0.5 - 2.3
Geranyl acetate 0.1- 0.8
Capillary GC analysis of anise oil
Carrier gas and flow rate Helium 1.0 mLlmin
Split ratio 1:100
60 QC to 210 QC 5-80 min
180 QC 80-95 min
Linalol <1.5
Estragole 0.5 - 5.0
a-terpineol <1.2
eis-Anethole 0.1 - 0.4
trans-Anethole 87 - 94
Anisaldehyde 0.1 - 1.4
Pseudoisoengenyl-2-methyl butyrate 0.3 - 2.0
Capillary GC analysis of coriander oil and cinnamon bark oil (Ceylon)
Carrier gas and flow rate Helium 1mL/min (Cinnamon bark)
Split ratio 1:65 (Coriander) or 1:100 (Cinnamon bark)
Temperature programming Coriander Cinnamon bark
0-10 min 60-190 QC

60 QC 2 QC/min
10-75 min 60-190 QC at 2 QC/min.
75-120 min 190 QC (75-200 min)

190 QC

200 QC

240 QC
B: Percent composition Coriander Ceylon Cinnamon

(%; w/w) bark oil
a-Pinene 3.0-7.0 Cineole <3.0
Limonene 1.5 -5.0 Linalol 1.0-6.0
r-terpinene 1.5 -8.0 ~-Caryophyllene 1.0-4.0
p-Cymene 0.5-4.0 Safrole <0.5
Camphor 3.0-6.0 trans-Cinnamic 55-75

aldehyde
Linalol 65.0-78.0 Eugenol <7.5
a-terpineol 0.1-1.5 Coumanin <0.5
Geranyl acetate 0.5-4.0 trans-2- 0.1-1.0

Methoxy
Cinnamaldehyde
Benzyl benzoate <1.0

Capillary GC analysis of cinnamon leaf oil (Ceylon)
Carrier gas and flow rate 1.5 mL/min
Split ratio 1:100
Temperature programming 45 DC 0-10 min
45 DC to 180 DC 10-78 min
180 DC 78-88 min
Injection port temperature 200 DC
FID detector temperature 240 DC
Cineole <1.0
Linalol 1.5-3.5
~-Caryophyllene 1.5-7.0
Satrole <3.0
trans-Cinnamic aldehyde <3.0
Cinnamyl acetate <2.0
Eugenol 70-85
Coumarin <1.0
Capillary GC analysis of eucalyptus oil
Carrier gas and flow rate Helium 1.5 mLlmin.
Split ratio 1:100
Temperature programming 60 DC 5 min
60 DC-200 DC at 5 DC/min
200 DC 5 min
Injection port temperature 220 DC
FID detector temperature 220 DC
a-Pinene Traces-9.0
~-pinene <1.5
Sabinene <0.3
a-phellandrene <1.5
Limonene Traces-12.0
1,8-Cineole Minimum 70.0
Camphor <0.1
Capillary GC analysis of peppermint oil
Column fused silica (60 m x 0.25 mm)
Split ratio 1:50
60-180 QC 10-70 min
180 QC 70-75 min
Limonene 1.0 - 5.0
Cineole 3.5 -14.0
Menthone 14.0 - 32.0
Menthofuran 1.0 - 9.0
Isomenthone 1.5 - 10.0
Menthyl acetate 2.8 -10.0
Isopulegol Max 0.2
Menthol 30.0 - 55.0
Pulegone Max 4.0
Carvone Max 1.0
Capillary GC analysis of spearmint oil

Stationary phase Macrogel 20,000 (carbonex 20 M)
Carrier gas and flow rate Helium 1.5 mL/min
Split ratio 1:100
Temperature programming 55 QC 6 min
55-180 QC at 4 QC/min
Limonene 2.0-25.0
Cineole <2.5
Menthone <2.5
Isomenthone <1.0
Menthyl acetate <1.0
Pulegone <0.5
Menthol <2.0
Carvone Max 55.0
Capillary GC analysis of juniper oil
Stationary phase Poly (dimethyl) (diphenyl) siloxane
Carrier gas & flow rate Helium 2.0 mLlmin.
Split ratio 1:50
Temperature programming 60 cC 0-1 min
60-230 cC 1-58 min
Injection port temperature 250 cC
B: Percent composition (% w/w)
a-pinene 2.0-50
Sabinene <2.0
p-pinene 1.0-12.0
p-Myrcene 1.0-35.0
a-Phellandrene <1.0
Limonene 2.0-12.0
Terpinen -4-01 0.5-IQ
Bornyl acetate <2.0
p-caryophyllene <7.0
Capillary GC analysis of tea tree oil
Stationary phase Poly (dimethyl) (diphenyl) siloxane
Split ratio 1:50
50-230 QC 1-37 min
230 QC 37-45 min
a-Pinene 1.0-6.0
Sabinene <3.5
a-Terpinene 5.0-13.0
Limonene 0.5-4.0
Cineole <15.0
r-terpinene 10.0-28.0
p-cymene 0.5-12.0
Terpinolene 1.5-5.0
Terpinen-4-0 1 Min 30.0
Aromadendrene <7.0
a-Terpineol 1.5-8.0
noted that there is a kind of difference in the separation pattern and

in percent distribution of essential oil constituents.
The separations of some essential oils as achieved by capillary gas
chromatography (CGC)3 are also shown in the tables.
HPLC analysis
High-pressure (also performance) liquid chromatography (HPLC) is
an excellent chromatographic technique, but it cannot be used
efficiently to separate complex essential oil profiles.
Reports are available on the separation of the essential oils by

HPLC without much success. In general, a normal phase HPLC
column (Hiber Li Chrosorb 60, 10 ]..lm, 250 x 4 mm id, Merck)
installed in a Perkin-Elmer 3 series apparatus equipped with an
LC 75 DV detector. The solvent system used was a gradient from
hexane to methanolltetrahydrofuran (80:20). The separations did
not occur fully. The separations actually serve as preseparation of
essential oils.
Combined HPLC and CGC
Combined HPLC and CGC methodology appear to be an elegant

approach for the analysis of highly complex essential oils. The
combined methodology offers to identify more constituent
components of essential oils.
HPLC fractions are collected and injected directly into the
capillary column of the GC that is duly temperature programmed
and detected. Each fraction could be resolved efficiently into
individual components representing the different functional
groups.
More investigations are desired to optimize the combined

methodology for analysis of essential oils.
Spectroscopic Analysis of Perfumery Materials
Spectroscopic techniques such as ultraviolet (DV), Infra-red OR), and

Nuclear Magnetic Resource (NMR) are in regular use in investigating
the chemistry and technology of natural and synthetic perfumery
materials. The techniques are very suitable for the synthetic
perfumery materials and relatively less suitable for essential oils in
view of high complex composition of essential oils. The utility of the
various spectroscopic techniques is very briefly discussed.
Ultraviolet spectroscopy is used in detecting conjugation as

maximum absorption (max) at 217-228 m).l (for acyclic dienes), 230-
240 m).l (for semicyclic dienes), and 256-265 m).l (for having double
bonds) in the same rings are obtained. The occurrence of carbonyl
system also shows UV absorption at 220-250 m).l, which is the case
with many essential oils.
IR spectroscopy especially FTIR technique is used regularly in the
detection of functional group like the hydroxyl (OH) group, carbonyl
group (CHOI>C=O), ester group, carboxyl group (COOH) and C-H
and C-C stretching in essential oils and in a host of synthetics as
well.
IH-NMR and 13C NMR spectra in deuterio chloroform (CDCI 3)
with tetramethylsilane (TMS) as internal standard are adopted in
confirming the identification of functional groups. A Brucker AM-
300L spectrometer (Rheins, Germany) operating at a frequency of
300 MH z is mostly used.
Spectral data of geraniol, geranyl acetate, citronellol, and

citronellyl acetate 5
Name of FTIR: v max IH NMR: d Mol. wt: Mt

compound (cm·I)K (ppm)b
Geraniol 3334, 2958, 2924, 5.47 (t,lH, J=6.0) 154

1458, 1373, 1057 5.15(t,lH, J=6.0)
4.20 (d.lH), 3.73(q,2H)
2.08 (m, 4H), 1,77(s,6H)
1.64 (s, 3H)
Geranyl 2924,2365, 1741, 5.39 (t, 1H, J=6.0) 196

acetate 1447, 1374,1235 5.06 (t, 1H, J=3.0) (C:H:O)
4.57 (d, 2H, J=6.0) 73.31:
2.10 (s, 3H), 2.03 (m, 4H) 10.02:
1.69 (s, 6H), 16.52
1.62 (s, 3H)
1.62 (s, 3H)
Citronellol 3333, 2958, 2924, 5.13 (t, 1H, J=6.0) 156

1456,1377,1057, 4.13 (q, 1H), 3.68 (m, 2H)
1008 2.61 (m, 2H),
2.02 (m, 2H),
1.71 (s, 6H), 1.60 (m, 1H)
1.40 (m, 2H), 0.91 (m, 3H)
Citronellyl 2957,2361, 1741, 5.06 (t, lH, J=6.0) 198

acetate 1452, 1373, 1238, 4.55 (t, 2H, J=8.0) (C:H:O)
1035,829 2.02 (m, 2H), 2.00 (s, 3H) 70.60:
1.65 (s, 6H), 1.55 (bs, 1H) 10.44:
1.30 (m, 4H), 0.89 (m, 3H) 18.64
The NMR spectra are extremely useful in following the synthesis

of perfumery ingredients from specific terpene derivatives.
Spectral data like FTIR and proton NMR (lHNH) of terpene alcohols
like geraniol, citronellol, and their esters such as acetates are shown
in the previous Table.
The FTIR spectra of geraniol and citronellol show absorption of
hydroxyl groups at t 3334 cm- I and 3333 cm-I, respectively. The FTIR
of the acetates of geraniol and citronellol lacks the absorption for
the hydroxyl group at 3333 cm- I and 3334 cm- I but show absorption
at 1741 cm- I as expected for the ester carbonyl group.
Similarly, from the IH NMR data, the resonance signal at 3.73
ppm for geraniol and 3.68 ppm for citronellol due to methylene
protons (-CH 2 ) of -CH 2 0H end group disappear in the acetates, viz.,
4.57 ppm for geranyl acetate and 4.55 ppm for citronellyl acetate.
The increase in values in the acetate products compared to starting
alcohol are due to the formation of acetate (-OCOCH 3 ) group which
shifts the methylene protons to higher frequency. The structure of
a-terpineol has been examined by FTIR, 1H NMR and 13C NMR and
GC-MS5 has been documented in the Table.
The hydroxyl (OH) group appears at 3380 cm-I. Strong C-H
stretchings are noted at 2925 cm- I and 2364 cm-I. An absorption band
Spectral data of a-terpineol
FTIR: "Ymax
a IH NMR: Sb 13C NMR: Sb GC-MS: ml2
3380, 2925 5.35 (tt, H, J=3.0Hz 136.93 (C) 154 (M+, 5.8)
2364, 1643 4.66 (bs, 1H) 120.51 (CH) 136 (48), 121 (100)
1447,1124 2.00 (m, 1H) 72.71 (C-OH) 107 (19), 93 (58),
1.70 (s, 3H) 44.97 (CH) 69 (8)
1.62 (d, 2H, J=4.5Hz) 30.98 (CH 2 )
1.40 (m, 2H) 27.29 (CH 3 )
1.19 (m, 2H) 26.96 (CH 2 )
1.15 (s, 3H) 26.23 (CH 3 )
1.14 (s, 3H) 23.95 (CH 2 )
aWave number in cm-I; bresonance signal in ppm

at 1643 cm- I is due to C=C stretching vibration. The absorption band

at 1447 cm- I corresponds to the bending vibration of C-H bonds and
at 1124 cm- I is due to the C-O stretching absorption of tertiary
alcohol.
The IH-NMR exhibits signals due to tertiary methyl groups (1.14,
1.15 ppm). The appearance of resonance signal at 4.66 ppm (D 2 0
exchangeable) indicates hydroxyl (OH) functional group.
The I3C-NMR spectrum exhibits signals due to two olefinic carbons
(120.51 and 130.93 ppm), three methylenes (23.95, 26.96, 30.98 ppm),
one methine (44.97 ppm), and one quaternary carbon (72.71 ppm)
carrying a tertiary hydroxyl group, in addition to three methyl carbons
(23.29, 26.23, 27.29 ppm).
The GC-MS spectrum of the single major peak indicates that the
peak is composed of ions at m/2 154 (M, 5.8%), 136 (154-18, 48%),121
(136-15, 100%), 107 (19%), 93 (58%) and 69 (8%). The peak at m/2 136
is due to loss of one water molecule which in turn confirms the
presence of hydroxyl group. The base peak (100%) at m/2 121 appears
by the less of one methyl (CH 3) group. The spectral data confirms
the structure of (+)-terpineol (p-menth-1-em-8-01).
The FTIR spectra of a-pinene shows only absorption of C-H
stretching (2920 cm- I and 2875 cm-I) and C-H stretching (2920 cm- I
and 2875 cm-I), and C-H deformation (1438 cm- I and 1375 cm-I),
characteristic of a typical hydrocarbon.
In a-pinene, one of the geminal methyl groups is held in a shielded
position of the double bond, and hence shows significantly lower 8
value (0.87 ppm) than its twin (1.25 ppm).
The FTIR spectra of citral shows absorption of the aldehyde
carbonyl (-CH=O) group at 1673 cm- I strong C-H stretching are
observed at 2922 cm- I and 2860 cm- I for citral. The IH-NMR spectra
of citral shows a chemical shift at 9.89 ppm, due to the presence of
aldehydic proton (-CH=O).
The appearance of resonance signal at 82.16 ppm in citral indicates
the presence of Vinylic methyl group (CH 3-C=C-).
The FTIR spectra of (±)-citronellal shows absorption band at 1723
cm-I, which is due to the presence of aldehyde carbonyl group. Strong
C-H stretchings are observed at 2921 cm- I and 1716 cm- I for the aldehyde.
The H-NMR data indicates the resource signal of the aldehydic
proton (9.73).
Although only a limited number of examples of the use of
spectroscopic methodologies have been cited, the spectroscopic
techniques are extensively followed in case of various synthetic

routes, including biotechnological routes involving fermentation
biotechnology and microbial biocatalyst technology, for making
synthetic perfumery materials from terpene derivatives and related
molecules.
ADULTERATION OF ESSENTIAL OILS: NATURE OF

ADULTERANTS AND DETECTION METHODOLOGIES
Essential oils because of high price are adulterated with materials

that are either nonfragrant in nature having characteristics in
common or fragrant materials of natural and synthetic and artificial
origins.
Nature of nonfragrant and fragrant adulterants in essential oils
is quite variable. N onfragrant adulterants are mostly the lipid
materials such as the vegetable oils and the alkyl esters of short-
chain fatty acids or dibasic acids because these lipid materials
increase the ester number of essential oils. Polyols like glycerol
and sorbitol which act as vehicle for essential oils also act as
adulterants. Mineral oil like medicinal grade paraffin oil is added as
an adulterant.
Authentic oil Adulterant
Bergamot oil Lemon oil

Cinnamon bark Cinnamon leaf
Lavender Cheaper lavandin and spike lavender. Acetylated lavandin oils
Patchouli oil Vegetable oils
Petit grain oils Fatty aldehydes, linalyl acetate, orange terpenes, etc.
Sandalwood oil Sandalwood terpenes, artificial sandalwood
Rosemary Eucalyptus
Ylang-ylang Cananga oil, reconstituted oil
Aniseed Fennel and dill
Palmarosa Ginergrass
Castor oil having about 85% hydroxy acid such as hydroxy oleic
acid (ricinoleic acid) is completely and readily soluble in ethanol and
it is therefore a common adulterant. Also, castor oil has high acetyl
or hydroxyl value and it is therefore an adulterant in oil like
sandalwood oil. Rapeseed oil in the EU is a particularly cheap
vegetable oil used as an adulterant.
Synthetic sddition Essential oil

obtained
Anethol Anise oil

Methyl chavicol and synthetic linalol Basil oil exotic
Linalol and linalyl acetate, limonene, terpinyl
acetate Bergamot oil
Synthetic cinnamic aldehyde, methyl cinnamic
aldehyde and coumarin Cassia oil
Synthetic benzaldehyde, eugenol and cinnamic
aldehyde oil Cinnamon bark
Limonene and (+ )-carvone Caraway seed oil
Linalyl acetate, 1,8-cineole, and a-terpinyl acetate Cardamom oil
Reconstituted ones, benzyl acetate, cinnamic aldehyde Jasmine absolute
Linalol and trace amounts of certain pyrazines oil Coriander seed
Cuminaldehyde Cumin seed oil
a-Phellandrene and limonene Dill seed oil
Addition of citral Lemon grass oil
Geraniol Palmarosa oil
(- l-Carvone Spearmint oil
p-Cymene and thymol Thyme oil
Methyl salicylate Wintergreen oil
Among the natural fragrant materials, cheaper essential oils are

used as adulterants 6 .
Some of the more common adulteration practices of authentic
good quality essential oils with the addition of cheaper essential oils
are also tabulated.
Addition of synthetics to upgrade poor-quality oils and sell as

regular quality ones is also commercially practised. Some examples
are cited in tabular form.
Adulteration of essential oils also include the use of a number of
solvents, some of which are cited below:
Benzyl alcohol, carbitol, diacetone alcohol, dipropylene glycol,
dipropylene glycol methyl ether, phthalate esters like diethyl
phthalate DEP and diiso-octyl phthalate DIOP, and Polyethyelen
glycols.
METHODOLOGIES FOR THE DETECTION OF

ADULTERANTS
A number of physical and chemical methodologies have been devleoped

for detecting various kinds of adulterants in essential oils, which are
discussed.
Physical Methods
(AJ Solubility Test
Among the physical methods the solubility test in polar solvent like
ethanol (95% or 70-80%) is an important approach. An essential oil
is appreciably soluble in 70-80% ethanol. The separation of any oil
phase as a lower layer indicates the presence of an ester material
such as vegetable oil or an alkyl ester of a fatty acid.
An essential oil when treated with an apolar solvent such as

petroleum ether (boiling point 40-60 QC or 60-80 QC) may separate
out a liquid phase as a lower layer that may be indicative of a
vegetable oil phase. This oil layer is likely to be castor oil, because
castor oil is rich in long-chain hydroxy acids, making it relatively
insoluble in the apolar solvent.
(E) Evaporation Residue Test and Characterisation of the

Evaporation Residue
Essential oils are volatile in nature and they show significant losses
when freely evaporated much above the ambient temperature (e.g.,
100 QC), attaining a more or less a constant weight.
The amount of evaporation residue is normally low after heating

at 100 QC. If the amount of evaporation residue from an essential oil
exceeds significantly then the sample of essential oil is a suspect.
The nature of the high-boiling material is likely to be a fatty material
or a mineral oil.
The saponification or ester value determination of the evaporation

residue, if it turns out to be quite high, then the presence of a fatty
material is indicated.
The evaporation residue may also be identified by TLC

technique. The residue separates out on a thin layer of silica gel
plate by eluting with a mobile solvent consisting of 90 volume

hexane and 10 volume diethyl ether in a chamber into a
triglyceride spot or other lipid spots as identified by comparing
the RF values of the spots with those of the standard triglyceride
and other lipid spots.
The evaporation residue may be further analyzed by GLC and

spectral techniques to establish qualitatively and quantitatively the
molecular nature of the evaporation residue.
CHEMICAL METHODS OF DETECTION OF ADULTERATION
Determination of ester number, primary alcoholic OH, phenoic -OH,

and carbonyl (-CHO) may provide an idea about adulteration in those
essential oils that are known for their ester, primary terpene alcohol,
phenolic compound, as well as a terpene aldehydic content.
Standard chemical methods as described previously are suitable

for these determinations.
Some typical examples of adulteration are mentioned here, which

can be detected by physical and chemical tests:
1. Palmarosa oil of analogous quality odor can be produced by

adultering low-grade palmarosa oil with geraniol esters like
geranyl acetate or butyrate. In this case, both ester number
determination and geraniol content will indicate the case of
adulteration.
2. Lemon grass oil adulterated with lemon oil: Determination of

aldehyde content by hydroxylamine hydrochloride method or
by sodium bisulfite method will be reduced and determination
of the terpene hydrocarbons will increase that come from
lemon oil.
3. Castor oil in sandalwood oil is based on the ricinoleic acid and

hydroxyl value from the evaporation residue.
Detection of Adulterants by Chromatography
Among the chromatography techniques, GC particlarly GC x GC

technique appears to be most reliable and sensitive for detecting
adulterants of various kinds in essential oils. The GC x GC-MS
combined methodology is regarded as the most reliable approach for
detection of adulterations in essential oils.
Certain key components which are valuable to the particular

essential oil are often quantified using suitable standards to determine
the adulteration of the essential oil. Complex essentital oils such as
peppermint oil, sandalwood oil, eucalyptus oil, geranium oil, citronella
oil, lemon grass oil, etc., are easily analyzed using gas
chromatography thereby identifying adulteration in the oils.
TLC separation of essential oils on silica gel layers into a series

of molecular components according to functional groups exhibits
considerable differences between the various kinds of essential oils.
The separated spots show unique col or when sprayed with specific
spray reagents. Since different essential oils contain different kinds
of molecular species, the spray reagents when used may reveal
differences in color formation and thereby indicate the means of
detecting adulteration of essential oils.
Combination of TLC and single or dual-column GC can also be

adapted in detecting adulterants in essential oils.
REFERENCES
1. Guenther, E., The Essential Oils, Van Nostrand Company, Inc.,
London, I: 237-241, 243-245, 249, 263, 265, 271, 279, 285, 293,
1948.
2. Stahl, E., Thin-Layer Chromatography: A Laboratory Hand Book,
Springer-Verlag, pp. 189-196, 1965.
3. British Pharmacoepias, B.P. 2007, 11: 1221, 1187, 1819, 1997, 1829.
4. Analytical Methods Committee, Royal Society of Chemistry, Analyst,
118: 1089-1096, 1993.
5. Bagchi, T., Ph.D. Thesis, Calcutta University, December, 1998.
6. Burfield, T., Presentation to the IFAAnnual AGM, London, October 11,
2003.
Subject Index
A Napthalene: 151-152
Toluene: 150-151
Acetophenone: 145 Artificial floral and fruity perfumery:
Synthetic preparation and 188-191
perfumery use: 145 Floral: 188-189
Adulteration of essential oils: Fruity: 189-190
263-267 Artificial musks: 176-181
Methodologies for the detection Musk ambrette: 180-181
of adulterants: 265-267 Musk ketone: 178-180
Nature of adulterants: 263-264 Musk xylene: 177-178
Ajowan: 34 Usage: 181
n-aldehydes: 123-125 Artificial perfumery materials for
Perfumery uses: 125 multipurpose applications: 191
Aldehydes five or six-membered
ring: 127-132
ex-n-amyl cinnamaldehyde: 127-128 B
Preparation and uses: 127-128
Vanillin preparation - chemical Bactericidal applications of essential
route: 128-130 oils: 203
Aliphatic ketones: 127 Banana flavour: 205
Biotechnological process: 131- Bark: 31
132 Base: 197
Ambergris: 55 Basil leaves: 21
Ambrettolide: 176 Benzoin: 50
Analysis of essential oils: 235-263 Benzyl acetone: 144-145
Chemical analysis: 238-244 Preparation: 144
Chromatography: 244-259 Use: 145
Gasliquid: 247-248
Bergamot: 42
GC-MS in essential oil analysis:
248 Bioflavours: 158-162
Esters: 159
Physical analysis: 235-238
Spectroscopic analysis: 259-263 Flavour aldehyde: 158
Thin layer chromatography: 244--247 Ketone: 159
Animal as essential oil-bearing Lactone: 159
materials: 53-55 Blending agent: 198
Aniseed: 34 Blending of perfumes: 197-199
Apple flavour: 205 Fixative: 198-199
Application of perfumery materials: Modifier: 198
196-218 Borneol from
Application in miscellaneous products: ex-pinene: 157
217-218 Butylated cyclohexanol acetates: 153
Aromatherapy and aroma therapy uses:
200-202
Aromatic hydrocarbons for perfumery
c
chemicals: 148-152
from Benzene: 148-150 Camphor from ex-pinene: 157
Camphor leaves: 22 D
Caraway: 35
Cardamom: 31
Davana: 32
Carnation: 5
Dicyc10pentadienc derived perfumery
Carrot: 35 chemical: 156
Carvyl ethyl ether: 191 Dill: 36
Cassie: 5 Diphenyl oxide: Preparation and use:
Cedarwood: 39 152-153
Cedarwood odour: 185 Dodecyl aldehyde: 125
Champaca: 13 Uses: 125-126
Cinnamaldehyde: 127-128
Cinnamon bark: 31
Cinnamon leaf: 23 E
Citral from lemon grass oil: 146
Synthetic production: 147 Ecuelle process: 69
Uses: 147 Elemi: 51
Citronella grass: 16 Enfleurage process: 70
Citronellal: 147-148 Essential oil analogs: 183-191
Isolation: 147-148 Cedarwood odours: 185
Synthetic production: 148 Sandal wood: 185-188
Use: 148 Vetiver: 188
Citronellol and its esters: 103-108 Essential oil applications in: Food and
pharmaceutical products: 204-208
Citronellol esters preparation: 106-107 food: 204-207
Chemical route: 105-106
Pharmaceutical: 207-208
Biotechnological: 107
Toilet soaps, cosmetics and
Perfumery uses: 108 toiletries: 208-213
Citronellol synthetic preparation: 104- Essential oils as antimicrobial agents:
106 202
Biotechnological: 105 Agriculture: 204
Synthetic: 104 Bactericidal: 203
Citrus oils: 42 Insect repellents: 203-204
Civet: 54 Eucalyptus: 24
Civetone: 168 Exaltolide: 174-176
Civetone from oleate: 169 Exaltone: 173-174
Aleuritic acid: 169-170 Expression process: 69
Oleic acid: 171 Extraction: Post treatment of recovered
Civetone synthetic: 168-171 oils: 81-82
Biotechnological: 171 Fractionation of essential oils: 83-
Clary sage: 6 85
Clove: 39 Extraction: With volatile solvents: 71-74
Coriander: 35 by adsorption: 80
Correlation between odour and by enzyme: 77-78
structure: 91 by microwave: 78-80
Cumin: 36 with liquid carbon dioxide: 75-77
Curry leaf: 23
Cyc1opentanone derived perfumery F
material: 155-156
Cymenyl ethyl ether: 191 Fenchyl ethyl ether: 191
Subject Index 271
Fennel sweet: 43 I
Five membered ketone: 141-142
Flowers: 4-16
Imitation perfumes: 197-200
Flowers exotic: 13-16
Incense and fumigant products: 215-
Fractionation of essential oils: 83-85
217
Frankincense: 51
Ionones: 136-139
Fruits: 42-47
Perfumery application: 139
Fruits flavours: 205
Preparation: 137-139
Fruits tropical: 49-50
Isoborneol from a-pinene: 157
G J
Galbanum: 52
Jackfruit: 49
Gardenia: 6
Jasmine: 7
Geraniol: 95-98
Jasmolactones: 166
Biotechnological preparation: 97
Microbial synthesis: 166
Synthetic preparation: 96
Jasmone: 142-144
Geraniol esters: 98-103 Synthetic preparation: 142-144
Geranium: 25 Juniper: 43
Geranyl acetate: 98-102
Chemical: 98
Enzymatic alcoholysis: 101 K
Enzymatic esterification: 99
Other geranyl esters: 102 Kamini: 8
Perfumery uses: 102-103 Ketones: Linear: 126
Geranyl butyl ether: 191
Ginger: 32
Ginger grass: 17 L
Grape flavour: 205
Grasses: 16-21 Large ring ketones and lactones: 167-
Gums: 50-53 176
Lavender: 9
H Leaves: 21-30
Lemon fruit: 44
Lemon grass: 18
Heliotropin: 132-134 Lime fruit: 45
Perfumery uses: 134 Linalool and its esters: 113-116
Preparation from Linalool esters: 115-116
Phenol: 134 Linalool esters uses: 116
Safrole: 133-134 Linalool synthetic: 114-115
Heptaldehyde: 123-124 Linalyl acetate preparation: 115
Herb: 31-32 Linear ketones: 126
Hydro-cinnamic aldehyde: 149 Linear lactones: 126
Hydro-distillation: 64
Hydro-steam distillation: 65
Hydroxy citronellal: 134-136 M
Perfumery use: 136
Synthetic preparation: 134-136 Maceration process: 71
Machine process: 70
Macrocyclic musks: 183
o
Mandarin: 45
Mango: 48 Octaldehyde-n: 124
Menthol and its esters: 117-122 Odorous aldehydes: 127
Menthol esters: 121-122 Orange blossom water: 14
Uses: 122 Orange fruit: 46
Menthol from menthone: 118 Orange oils: 46
from ~-pinene: 119 Orchids: 15
from carene: 121
from m-cresol: 119 p
from pulegone: 121
Menthol preparation synthetic: 118-121
Methyl ionones: 139-141 Palmarosa: 19
Microbial hydroxylation of terpene and Patchouli: 25
terpene derivatives: 166-167 Pepper fruit: 47
Microbial synthesis of jasmolactones: Pepper mint: 26
165-166 Perfumery chemicals from ~-pinene:
Microbial transformations of a-pinene: 157-158
162-163 Geranyl, neryl and linalyl acetates:
Limonene: 163-164 158
Microorganisms and bioconversion: 90 Nopyl acetate: 158
Mimosa: 13 Perfumery ingredients from phenol:
Molecular distillation of essential oils: 152-153
83-85 m-cresol: 153-154
Mungbean: 37 m-cresyl acetate by bioprocess: 154
Muscone: 172-173 Use: 154
Musk deer: 54 Perfumery ingredients from Styrene/
Myrrh: 52 Styrene oxide: 154-155
Perfumery materials: Production
N technology: 61-86
Percolation process with steam: 68
Perfumery: 1
Natural perfumery materials: 4-55
Peru balsam: 53
Natural perfumery materials:
Production technology: 61-86 Petit grain: 27
Phenyl acetaldehyde and esters of
Nerol and its esters: 116-117
phenyl ethyl alcohol: Synthesis and
Nerol esters: 117
Perfumery uses: 117 use: 155
Synthetic preparation of nerol: 117 Phenyl acetaldehyde: 155
Neroli: 10 Phenyl ethyl alcohol: 149, 155
Non-terpene alcohols: 122-123 Preparation and use: 149, 155
Preparation: 122 Phenyl/ethyl alcohol preparation and
Uses: 123 use: 155
Non-terpene alcohol unsaturated: 123 Pineapple: 49
Non-terpene aldehydes: 123-126 Pineapple flavour: 205-206
N onylaldehyde: 125 Pinepaple jelly crystals: 207
Nor-patchoulenol: 167 Piperonal: 132-134
Nutmeg: 38 Plumeria: 15
Subject Index 273
Polycyclic and macrocyclic musks: 181- a-terpineol: 108-110

183 Biotechnological: 109-110
Macrocyclic musks: 183 Perfumery uses: 110
Polycyclic musks: 181-182 Synthetic preparation chemical:
Post extraction treatment: 81 108-109
Terpene ketones: 136-139
R Terpeneless essential oils: 85
Terpenyl acetate and other esters: 111
Biotechnological: 112-113
Rhizome: 32-33 Chemical preparation: 111
Root: 38 Uses: 112
Rose: 11 Thymol: 153-154
Rosemary: 28 Toilet soaps, cosmetics and toiletries:
208-213
s Tolubalsam: 53
Tropical fruits: 47
Sandalwood: 40 Tuberose: 12
Seed: 34-38 Turmeric: 33
Sesquiterpeneless essential oils: 85-86 Turpentine: 41
Spearmint: 29
Sperm whale excreta: 55 u
Sponge process: 69
Standard requirements for essential
oils: 220-234 Unsaturated non-terpene alcohol: 123
BIS: 220-223
BP: 229-232 v
IP: 223-228
Others: 233-234
Standardisation and evaluation: 219- Valerian: 38
267 Vanillin: 128-132
Steam distillation process: 62 Biotechnological process: 131-132
Principles: 62-63 Chemical process: 128-131
Process: 66-67 Use: 131
Structure-odor relationships: 91-95 Vetiver grass: 20
Styrallyl alcohol esters: 149
Supercritical extraction technology
principle: 75
w
Synthetic perfumery materials: 87-191
Production and applications: 87-191 Water lily: 15
Wintergreen: 30
Wood: 40-41
T
y
Tea tree: 29
Terpene alcohols and their esters: 95-122
Terpene aldehydes: 145-148 Ylang ylang: 12

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This book contains information obtained from authentic and highly

All rights are reserved under International and Pan-American

The book embraces all relevant aspects and recent developments of

Prof. (Dr.) R.N. Mukherjee

Born 1936. Acquired M.Sc.(Tech.) and Ph.D.(Sc.) degrees

I acknowledge with deepest gratitude the financial support from the

I recognise the support from faculty members, especially Dr. S. Ghosh

Esters of Linalool, Uses 116

Synthesis of Isoborneol, Borneol, and Camphor

In trod uction 196

Composition of Fruit Flavors 205

The demand for natural perfumery materials has increased sharply

characterized and identified by reputed organic chemists. The

The synthetic routes of production of perfumery materials from

Significant advances are made in the syntheses of natural

Natural perfumes are actually the well known essential oils or

FLOWERS AS A SOURCE OF ESSENTIAL OILS

A large variety of flowers occur in nature that possess oils of distinct

important and attractive are the jasmine, rose, neroli, lavender,

Oil from carnation 1 flower oil is well known throughout Europe

Oil Content: The oil content of carnation flowers is extremely

Composition: The carnation oil contains eugenol 30%, phenyl

Extraction: Carnation oil is produced by solvent extraction process

The carnation flower oil is a pale green solid having an intense

Uses: The carnation absolute is used in the most exclusive

Cassie 2 flower (Acacia farnesiana) is a native of India and the East,

Oil from Cassie flower is obtained from several species of acacia

Oil Content: Cassie flowers yield 0.4% of concrete and 0.1% of

Composition: Oil from cassie flower contains components

Oil Content: The yield of oil is reportedly 0.117%.

Composition: Clary sage oil contains linalool 6.5% to 24%, linalyl

Extraction: Clary sage oil is produced by the steam distillation

Clary sage oil has a number of uses in aromatherapy. It acts as

India has the best variety of gardenia 4 -6 , Gardenia jasminoides, but

There are many Gardenia species, bearing beautiful and highly

Depending on the species, the gardenia oil has odor characteristic

Extraction: The oil is extracted by enfleurage process using liquid

Jasmine 7 - 10 flower occurs mostly in India, China, Arabia, France,

produced magnificently. There are other jasmine flowers from which

Oil Content: Jasmine flowers contain around 0.4% oil as concrete

Oil Composition: Jasmine oil is composed of 65% benzyl acetate,

Extraction of Jasmine Oil: The oil can be extracted from jasmine

KAMINI FLOWER OIL

Kamini (M. exotica) flowers ll - 12 grow in West Bengal and in the

Lavender13 (Labiatae family) flowers grow in the European countries

French lavender (%) English lavender (%)

Lavender oil is used in toilet soaps, toiletries, and cosmetics, and as

The therapeutic properties of lavender oil are antiseptic, analgesic,

Oil Content: The essential oil content is about 0.3%.

Extraction: Neroli oil is obtained by steam distillation of fresh

Uses: Neroli oil is widely used in perfumery. The aqueous portion

flower water of commerce used in the toilet and perfumery industry

Rose flowers 17 . 18 grow and are cultivated in mass farms almost

Oil Composition: Rose oil consists chiefly of two terpene alcohols,

Extraction: Rose oil is produced by extraction of the red or the

Tuberose 19 is a well-known Indian flower, and is used extensively in

Uses: The oil is used as a component of good quality perfumes.

Ylang-ylang 20 -21 (Cananga) oil is obtained from the flowers of Cananga

The oil has special aroma therapy applications. It promotes hair

A pale yellow liquid with an intensely sweet, floral scent reminiscent

SOME EXOTIC FLOWERS AS SOURCES OF