Fragrance Technologies and Applications (2012-04-04)

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Fragrance Technologies
and Applications
This eBook examines the fragrance market and its

technologies and end uses, to increase the appeal of
household, fabric and personal-care products.
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Fragrance Technologies and Applications
Dr. Peter Smallwood IntertechPira Business Intelligence
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table of contents
4 5
Executive Summary End-use Applications Future Trends
Introduction Introduction
1
Introduction and Methodology Surfactants, Micelles and Emulsions Environmental and Green Issues
Introduction Chemical Stability of Fragrances 4Sensitisation by Fragrances and Animal Testing
Methodology Perfumes 4Natural vs. Synthetic Fragrances
Definitions Air Fresheners 4Other Green Issues
4Diffusion Devices The Search for New Fragrances
2
State of the Global Fragrance Industry 4Candles 4Using Clues from Nature
Introduction 4Spray Air Fresheners 4Serendipity
Fragrance Market Personal-care Formulations 4Synthesis of Analogues
Legislation 4Soap 4Ligand-Olfactory Receptor Modelling
Self-Regulation of Fragrances 4Hair Shampoos 4Structure-Activity Relationship (SAR)
Toxicity, Sensitisation and Biodegradation 4Shower Gels Manufacture of Fragrances by Biotechnology
Analysis and Testing Of Fragrances 4Antiperspirants and Deodorants
Quantifying Fragrance 4Gels References
4Aerosols
3
Trends in Fragrance Chemistry Fabric Care Appendix
Science of Smell Household-care Products
Physical Chemistry of Smell 4Dishwashing Detergents List of Tables and Figures
Fragrance Compounds 4Bleaches
4Natural Products and Essential Oils
4Natural Products, Musks
4Aroma Compounds
4Carbon, Hydrogen and Oxygen Aliphatic
Compounds
4Terpenes
4Acyclic Terpenes
4Cyclic Terpenes
4Other Cycloaliphatic Fragrances
4Aromatic Compounds
4Heterocyclics Containing Other Elements
4Fragrances Containing Silicon
Pro-Fragrances
Encapsulation of Fragrances
Malodour Counteractants
Fragrances used as Indicators
home and personal care > e-book > fragrance technologies and applications
Executive Summary
Fragrance, aroma, smells—call them what you will—they play an companies command 63% of the business. Natural fragrances Fragrances, like
important role in our everyday emotional state: The signals from are obtained from plants, but most are made synthetically from natural essences,
our nose are processed in a section of the brain responsible for a variety of raw materials and are either identical to substances are blends of many,
memory and emotion, and so a simple aroma can induce feelings found in nature or are completely new. The fragrance houses,
of comfort and even warn us of danger. It stands to reason, then, perfumers and soap producers have teams of experts creating
perhaps hundreds,
that we like to be in places and around people that smell pleasant. fragrance blends to satisfy the preferences of contemporary of individual
We also prefer to use materials that have a nice odour, for instance, consumer (Chapter 2). compounds.
because it confirms that our washed clothes are truly clean. In this
report we investigate the use of fragrances in the care products we Fragrances, like natural essences, are blends of many, perhaps
use to clean ourselves, our clothes and our houses. hundreds, of individual compounds. They are all organic molecules,
composed of carbon, hydrogen, oxygen and a few other elements,
Humans have used perfumes that alchemists isolated from flowers, many of which are described in Chapter 3. They must be volatile,
plants and in some cases animals for thousands of years. But which limits their molecular weight (size) to less than 310. Each
they were mostly in short supply and available only to the rich. compound creates its own particular fragrance sensation in the
It was long thought that these fragrance oils were mixtures of brain, and each has different physical and chemical properties that
many ingredients, but by the 1850s organic chemists started to modify the intensity and duration of its odour. Perfumers aim to
identify individual fragrance ingredients, work out their structure create an experience that persists for a number of hours or even
and synthesise them in the laboratory. They also made fragrance days by blending individual fragrances with different properties
molecules that had not been found in nature, and the types and but complementary effects. A mixture of individual fragrances is
use of fragrances steady grew. In the 1960s the introduction of called an accord. Top notes are the more volatile compounds in a
new analytical techniques made it easier determine chemical fragrance, and they create the first olfactory sensation when the
structures, and even more new fragrances became available. In container is opened or the perfume is first applied; base notes are
1991, two researchers discovered how olfactory receptor cells (ORC) the lesser volatile compounds that provide the lingering odour. The
in our noses detected odours, enabling the discovery of still more middle notes of a fragrance are, as expected, the intermediates,
fragrance compounds; these researchers were awarded a Nobel providing a link between the top and base notes. Interestingly, the
Prize in 2004. middle and base notes make up the “theme” of the fragrance.
Today the fragrance industry is worth US$22bn a year. There are The olfactory characteristics of the molecule are affected by the
many thousands of fragrance companies, but five multinational other components of the blend, the solvents, other fragrances,
CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

Executive Summary
surfactants, etc. Fixatives are molecules that associate with Fragrances come into very close contact with the body. People
fragrance molecules, reducing their volatility. Pro-fragrances are like to use them, and they do not expect them to do them harm.
fragrance molecules chemically bound to larger, less volatile Even though they are used in very small quantities, there have
molecules, which are designed to release the fragrance at the been cases of fragrances sensitising the skin and the view persists
point of use. The rate of release of fragrances can be controlled among many consumers that artificial fragrances cause irritation.
by encapsulating them inside a protective coating. The capsule As a result of this perception, the industry has established two
can protect the fragrance from oxidation or attack from other independent self-regulating bodies to ensure fragrances are used
formulation ingredients, thereby extending its shelf-life. They can safely. They have banned the use of certain substances and
also be designed to stick to the substrate and to be brittle so that restricted the use of others. The use and labelling of products
folding or rubbing the textile releases the fragrance. containing fragrances is also tightly regulated by government
agencies (Chapter 2).
Fragrances are available in many forms. Perfumes and colognes
are solutions of fragrances in ethanol and water for applying Despite new fragrances being introduced over the last 150 years,
directly to the body. Air fresheners are designed to fragrance spaces large potential exists for developing new fragrance compounds
(the simplest devices rely on diffusion to circulate the fragrance). that are more stable chemically and can be used more flexibly,
Fragranced candles and devices that plug-in to electric sockets use to replace products that can no longer be used. It is necessary
heat to enhance circulation. Pump and aerosol can spray devices to develop new ways of formulating them, to develop new pro-
create an instant perfumed spray. Personal-care products such as fragrance and encapsulation systems to increase their stability.
soaps and shampoo are designed to cleanse the body. They are Fragrance molecules containing silicon atoms are being researched,
fragranced to make them pleasant to use and to leave the body and the first fragrances produced by the fermentation of genetically
feeling clean and smelling nice. Fragrances are added to laundry engineered microorganisms have become available (Chapter 5).
and dishwashing detergents and household cleaners for similar The industry can look forward to another 150 years as exciting as
reasons. The role of fragrances is particularly important with fabric the last.
conditioners, which are designed to leave the laundry feeling and
smelling sweet. In all of these products, the perfume is blended
with other substances. The fragrances must be designed and
blended to function effectively with other very different types of
ingredients with which they are mixed (Chapter 4).

Introduction and Methodology
1
Introduction Amphoteric surfactants A surfactant with an anionic and This report reviews
This report reviews the fragrance market and its technologies cationic group, such as a betaine the fragrance
and end uses, to increase the appeal of household, fabric and
market and its
personal-care products; it does not discuss the chemical synthesis Anionic surfactant A negatively charged surfactant
of fragrance molecules, as there are already many other excellent technologies
reviews of this topic (Sell, 2006; Rowe, 2005 and Surburg, 2006). Aromatherapy A form of alternative medicine that uses essential and end uses, to
This report does not aim to discuss perfumes and fragrances used oils and aromatic compounds to alter peoples’ emotions, state of increase the appeal
in cosmetic products or flavours used in food, although in many mind and health. of household,
cases the technology is similar. fabric and personal-
Cationic A positively charged surfactant care products
Methodology
This report is based on the results of primary and secondary Concrete The fragrance obtained from a natural product by cold
research culled from various sources. Primary research consisted extraction into a solvent such as hexane or dimethyl ether
of interviews with key ingredient and detergent manufacturers.
Additional sources of data include published literature and ECHA European Chemicals Agency, the organisation responsible
statistics, in-house market and technology reports, conference for overseeing REACH Legislation
presentations, company information, and industry associations.
Enantiomer Stereoisomer molecules that are mirror images of
Definitions each other, chiral molecules
Most of the fragrance compounds discussed in this article are
described in the list of fragrance compounds in List of fragrance Ex vivo Testing carried out outside the body
compoounds in the Appendix. As well as its name, each compound
can be identified by its unique Chemical Abstract or CAS number, Fixatives A fragrance that reduces the volatility of other
which is given in square brackets [ ] after its name. fragrances
Absolute An oily liquid that is purified from a natural extract by GRAS Generally Regarded as Safe
extraction into ethanol. Ethanol dissolves hydrophilic and some
hydrophobic compounds Hydrophilic Compounds that dissolve in and like “water.”

Introduction and Methodology
Hydrophobic Compounds that are insoluble in water, preferring to RIFM Research Institute for Fragrance Materials
dissolve in non-polar oils
SCCNFP EU, Scientific Committee on Cosmetics and Non-Food
I&I cleaning products Cleaning products that are used on a Products
large scale by industrial and institutional cleaning companies. I&I
cleaners tend to be stronger and more hazardous than domestic SDS Safety Data Sheet
formulations and are used by skilled operators using automatic
machines Stereoisomer Stereoisomers are molecules with exactly the same
molecular structure but in which the spatial arrangements of the
IFRA The International Fragrance Association groups in the molecule are different
In vitro Testing carried out on live tissue outside the organism, in Threshold concentration The lowest concentration of fragrance
the test-tube that a human beings can detect, although not necessarily identify
In vivo Testing carried out in the organism or animal
MSDS Material Safety Data Sheet TABLE 1.1 Terpene nomenclature

Name Number of isoprene units Number of carbon atoms
Muguert Lily of the valley odour Hemiterpenoids 1 5
Monoterpenoids 2 10
Sequiterpenoids 3 15
Nonionic A surfactant with no charge
Diterpenoids 4 20
Sesterpenoids 5 25
PVA Poly(vinyl alcohol) Triterpenoids 6 30
Carotenoids 8 40
PVP Poly(vinyl pyrrollidone) Source: IntertechPira
REACH Registration, evaluation, authorisation and restriction of

chemicals—European legislation to which all chemicals sold in
quantities of greater than 1 tonne must conform

State of the Global Fragrance Industry
2
Introduction notes form the main theme of the perfume. The perfumer will adjust Individual fragrance
Fragrances are used in small quantities and rarely have any other function the composition of the blend so that it will deliver the required scent compounds
besides stimulating the olfactory system. The sole purpose of perfumes, at the appropriate parts of its lifecycle. A typical fragrance blend
have their own
air fresheners and potpourri is to fragrance an individual or a space to might contain 25% top notes, 20% middle notes and 55% base
stimulate the emotions and create an ambience. Fragrances are also notes, depending on the application. particular odour
added to compositions designed to achieve other effects. They are added and evaporate and
to fabric cleaners, hard-surface cleaners and personal-care products. The Fragrance Market stimulate our senses
fragrance does not help in the cleaning process but makes the cleaner The global market for flavours and fragrances was worth about US$22 at a particular rate.
nicer to use and adds greatly to impression of cleanliness. Fragrances are billion in 2010 (see Table 2.1), and is split fairly evenly between food
very important to consumers who use it to recognise a particular product flavours (52%) and fragrances (48%). The size of the market increased
and to satisfy themselves that the product has performed well. Fragrances from US$20 billion in 2009 after three years of stagnation. The market
contribute to a feeling of well-being and luxury. is dominated by five large multinational players—Givaudan, Firmenich,
IFF (International Flavors and Fragrances), Symrise and Takasago, who
Individual fragrance compounds have their own particular odour and together hold 63% of the market. This proportion has been increasing
evaporate and stimulate our senses at a particular rate. They are not over recent years as the majors assimilate their smaller rivals.
used individually, but as with natural fragrances, are blended together
to create the required olfactory experience. Each fragrance delivers TABLE 2.1 Global flavour and fragrance market, 2010
its effect in its own way and modifies the effect of other fragrances in Company Location Sales value Market share
(US$ million) (%)
the blend. The odour of a single chemical compound is described as a
Givaudan Switzerland 4,538 20.6
note. A mixture of two or more compounds, having a single olfactory Firmenich Switzerland 3,319 15.1
theme is known as an accord. More volatile fragrance compounds IFF USA 2,623 11.9
evaporate most rapidly and are described as the top or head notes. Symrise Germany 2,107 9.6
Top notes are the fragrances that are detected most rapidly, when Takasago Japan 1,416 6.4
the container is first opened. The least volatile and most persistent Mane SA France 643 2.9
Sensient Technologies USA 583 2.6
fragrances are referred to as the base notes, which provide the depth
T Hasegawa Japan 557 2.5
and solidity to the perfume. Compounds with intermediate volatility Robertet France 484 2.2
are referred to as middle or heart notes. The middle notes provide a Frutarom Israel 451 2.1
link between the top notes and the base notes, which take longer
(perhaps 30 minutes or so) to appear. Together, the middle and base Top Ten 16,722 76
Others 5,277 24
Source: www.leffingwell.com
8

Companies that are active in flavours and fragrances can be • Phenylethanol [60-12-8], used to make many aromatic
divided into the following types: fragrances, is made from benzene or styrene.
• The large multinational fragrance houses active in both • Increasing amounts of natural fragrances and synthetic
flavours and fragrances (Table 2.1). They source and fragrance compounds are being supplied from lower-
manufacture the base fragrance chemicals, many of wage economies in the Far East, especially India and
which are sold on the open market but some of which, China.
particularly newly discovered fragrances, are retained in- • A large number of ‘Mom and Pop’ small companies,
house for formulating their own fragrance blends. Some which, together, supply a significant proportion of the
of these companies go back over a hundred years and market.
have a wealth of experience and technical resources to
develop new fragrances. Sales of fragrances are greatest in the developed countries of Europe
• Large consumer groups that are unlikely to manufacture and North America (Fig 2.1), although growth is more rapid in the
their own aroma chemicals but have teams of flavourists emerging markets of Asia, the Middle East and South America.
and perfumers to support their own businesses. These
include household and consumer groups such as Proctor FIGURE 2.1 Global sales of fragrances by region
& Gamble, Unilever, Henkel, L’Oreal and Kao, and food
groups such as Nestle, Danisco, Unilever and Kerry.
• Specialist companies, which tend to have smaller
turnover but could still be significant in certain key areas
such as Frutarom and Flavor and Fragrance Specialities.
• Mainstream chemical companies that manufacture
fragrance chemicals as part of their business (e.g. BASF,
Inospec, Rhodia, etc). They do this because they have
the feedstocks or the chemical technology needed to
make particular fragrances. For example, companies
in the wood pulp and paper industries supply terpene
raw materials. Kuraray of Japan manufactures synthetic
rubber from butadiene and isoprene and has diversified
into the manufacture of terpene aroma chemicals.
Source: IAL Consultants
9

The US$10.5 billion market for fragrances can be compared to the But fragrances also come into quite close contact with people and
value of the global market for cleaning products, which is estimated so extra care is needed to ensure the substances are safe to use.
to have been US$130 billion in 2010.
In Europe, chemicals that are manufactured or imported in
The ultimate customers are those who purchase the fragranced quantities of greater than 1 tonne must be registered under
formulation, and their tastes reflect the place in which they live REACH (Registration, evaluation, authorisation and restriction of
and the current fashion trends in that place. These need to be chemicals) regulations (http://guidance.echa.europa.eu/about_
picked up and specified by the “care” product manufacturers who reach_en.htm). REACH Legislation requires all manufacturers and
provide briefings for the fragrance manufacturer, describing the importers of a chemical that is sold in quantities of greater than 1
odours they require (Sell, 2006). They must also specify the types tonne to register it by submitting documentary evidence (a dossier)
of formulations to be fragranced, as each has its own chemical to the European Chemicals Agency (ECHA) describing the hazards,
stability and application requirements (Chapter 4). The market for if any, of using the substance. This information is used to draw up a
care products is very competitive, and even though they are used Safety Data Sheet (MSDS or SDS), informing users of the substance,
in small quantities, fragrances must be competitively priced. The how it should be handled and used. It is also used to classify and
larger care-product companies have their own perfumers developing label the compound under global CLP Regulations. The use of food
fragrance blends from compounds supplied by others. Smaller care and foodstuff additives and of biocides are covered by more specific
companies purchase ready-made fragrance blends from smaller but legislation. The objective of the legislation is to eliminate the risk to
highly competent fragrance houses. the public using the chemicals and to facilitate the free movement
of substances throughout Europe. The ECHA will restrict the use of
Larger-volume fragrance products are manufactured globally in Substances of Very High Concern, with the ultimate objective being
volumes of 5,000-6,000 tonnes per year and cost a little more to replace them with less hazardous products.
than standard petrochemicals—of which many millions of tonnes
are produced. Other fragrance compounds, particularly those Submitting a dossier on the possible toxic effects of an individual
with intense odours that are used in very small amounts, are fragrance compound requires a significant amount of testing but
manufactured in kilogram quantities and can be very expensive. that is relatively straightforward. Data from component fragrances
can then be used to assess the hazards of a fragrance blend, if it is
Legislation sold in quantities of greater than 1 tonne. Submitting a dossier on
Flavours and fragrances are chemicals, and as such, must conform the possible hazards of natural oils is more complex (Ellis, 2009).
to legislation that controls the supply and use of such substances. Natural complex substances (NCSs in REACH terminology) have,
10

by their nature, a variable composition. Individual components that Most ingredients present in amounts >0.2% must be generically
are present in concentrations of >10% should be known. If analysis named on the packaging—for example, non-ionic surfactants,
can determine their concentration to an accuracy of >90%, they bleaching agents, etc.. The ingredients must be listed in certain
are classed as a well-defined NCS. If not, they are incompletely concentration bands, say, <5%, 5-15%, 15-30% and >30%. Certain
defined NCSs, and individual ingredients should be assessed classes of ingredients—enzymes, disinfectants, optical brighteners,
separately. Industry consortia are working with the ECHA to resolve preservatives and perfumes—must be named, irrespective of their
these issues. concentration. In general, individual constituents of perfumes and
essential oils and colouring need not be specified. However, the EU
The sale of all detergents and cleaning agents in the EU is Scientific Committee on Cosmetics and Non-Food Products (SCCNFP)
governed by Regulation (EC) No. 648/2004, details of which can has listed 26 fragrances they have classed as more likely to trigger
be seen on the following website: (www.ec.europa.eu/enterprise/ an allergic response, and these fragrances must be individually
chemicals/legislation/detergents/index_en.htm named if their concentration in the rinse-off cleaning product exceeds
0.01% (100ppm), so consumers are aware of their presence. These
The regulations cover any cleaning agents—whether or not they fragrances are listed in Table 2.2; further details of the fragrances can
contain surfactants and include personal-, fabric- and home-care be seen in List of fragrance compoounds in the Appendix
products. The regulations specify that all ingredients in laundry
detergents and cleaning agents must meet certain biodegradability TABLE 2.2 The 26 potentially allergenic fragrance ingredients
and environmental standards. They also require all cleaning Ingredient CAS No
products to conform to certain labelling standards. The packaging Amyl cinnamyl 122-40-7
label must contain the manufacturers’ details and also certain Benzyl alcohol 100-51-6
Cinnamyl alcohol 104-54-1
details of the products’ ingredients. Further details must be
Citral 5392-40-5
available to the public on websites and on the products’ MSDS. Eugenol 97-53-0
Finally, the manufacturer must file more specific details of the Hydroxycitronellal 107-75-5
composition of the detergent with local medical authorities for Isoeugenol 97-54-1
use in emergencies. Medical authorities are obliged to keep this Amylcinnamyl alcohol 101-85-9
information confidential. There are certain exceptions for automatic Benzyl salicylate 118-58-1
Cinnamal 104-55-2
dishwashing detergents and industrial and institutional (I&I)
Coumarin 91-64-5
cleaners. Geraniol 106-24-1
11

Leerall/Lyral 31906-04-4 Self-Regulation of Fragrances

Anisyl alcohol 105-13-5 The fragrance industry controls the use of flavours and fragrances
Benzyl cinnamate 103-41-3 through two self-regulating bodies, the International Fragrance
Farnesol 4602-84-0
Association (IFRA, www.ifraorg.org), based in Geneva, and the
Butylphenyl 80-54-6
methylpropional/Lilial US-based Research Institute for Fragrance Materials (RIFM, www.
Linalool 78-70-6 rifm.org). These entities are independent but work closely together.
Benzyl benzoate 120-51-4 The RIFM is the scientific centre responsible for the testing and
Citronellol 106-23-0 monitoring of fragrances. It commissions and carries out tests
Hexyl cinnamal 101-86-0 on fragrances, sets out protocols and collects data from research
Limonene 138-86-3
and consumer studies. The RIFM database contains over 54,000
Methyl 2-Octynoate 111-12-6
Alpha-isomethyl ionone 127-51-5
references and holds the results of over 112,000 human health and
Oak moss extract, 90028-68-5 environmental studies. The database lists and classifies more than
Evernia Prunastri 5,100 substances; if there is a concern over the use of a substance
Extract RIFM can review its history.
Treemoss extract, n/a
Evernia Furfuracea
Extract The IFRA is worldwide industry body that develops the standards
Source: SCCNFP and protocols controlling the use of fragrances. It has developed a
Quantitative Risk Assessment (QRA) process to assess the hazards
In the US, the FDA is responsible for legislation of these types of of using particular fragrances in particular applications. Table
products. Similar legislation is being passed by other governments. 2.3 lists applications for fragrances, the public’s likely exposure
to the product and the maximum concentration of fragrances the
The US and EU label flavours and fragrances differently. Both formulation should contain. The IFRA also publishes an assessment
recognise substances of recent biological origin as natural. of each individual fragrance and specifies how and what
In Europe a synthetic substance that is identical to a natural concentration of the fragrance can be safely used in each type of
substance is classed as nature identical. In the US, the synthetic product. It publishes a “Code of Practice” that requires all members
chemical must be described as artificial flavouring, even though it and associates to comply with local and national legislation. It also
is impossible to distinguish it from the natural product. In Europe, requires that all fragrances should only be used under appropriate
only compounds that are not found in nature are described as conditions in a way that presents no risk to human health or the
artificial, and thus the term is viewed with greater apprehension. environment.
12

TABLE 2.3 I FRA/RIFM quantitative risk assessment criteria (QRA) for The most important list of flavours is the US-based Flavor and
fragrances, June 2010 Essence Manufacturers Association (FEMA). The FEMA lists more
IFRA Product Consumer SAF Max.
than 4,000 substances in their GRAS List that they generally
category exposure (sensitisation permitted
mg/cm2/ assessment fragrance recognise as safe and that are the only flavours permitted to be
day 1 factor) content 2 used in foodstuffs in the US. In the EU there is a “white list” of
1 Lip products 11.7 300 Derive approved aroma chemicals and related substances.
2 Deodourants/ 9.1 300 from safety
antiperspirants assessment
3 Hydroalcoholics 2.2 300
Toxicity, Sensitisation and Biodegradation
for shaved skin Fragrances are detected by the nose at very low concentrations, at
4 Hydroalcoholics 2.2 100 levels unlikely to be toxic. Similarly, they are not likely to be ingested
for unshaved in significant concentrations. They are only likely to affect the body
skin
5 Hand cream 4.2 100
when applied to or absorbed through the skin. Skin irritation, which
6 Mouthwash 1.4 100 usually manifests as redness and/or swelling, is unpleasant (and
7 Intimate wipes 4.4 300 is unacceptable to the consumer), but it is not dangerous as the
8 Hairstyling aids 1.0 100 2% effect disappears as soon as the fragrance is removed. A number
9 Rinse-off 0.2 100 5% of fragrances and other compounds are able to penetrate through
products
(includes soaps,
the skin to the epidermis; some of these substances can trigger
shampoos, an immune response that results in skin sensitisation. The allergic
shower gels etc.) response can take a few days to develop and can last for many
10 Hard surface 0.1 100 2.5% more days or weeks, well after the offending substance has been
cleaners
(includes
removed. Once the body has reacted to allergen, it can become
laundry sensitised to smaller quantities of the substance.
products)
11 Candles 0.00033 10 Not Because of this, the EU insists that fragrances that are potential
restricted
allergens in leave-on skin products (e.g., perfumes and deodourants)
Note: 1 Estimated highest consumer exposure; 2 Risk assessment on a particular
fragrance might indicate a lower acceptable exposure level
must be listed if their concentration is above 10ppm and if it is
Source: IFRA above 100ppm for rinse-off skin products (e.g., soaps, detergents
and shampoos) (Table 2.2). This helps consumers who are sensitive
to these fragrances to avoid using such products.
13

This labelling mandate also applies to allergens present as minor Although they are not toxic to humans, their environmental effects
ingredients in natural oils. Thus, the IFRA ensures that only oils and are being studied. Recently the EU has banned the use of musk
materials of certain purity can be used in fragrances. xylene in Europe.
The IFRA tests for skin sensitisation using skin patches containing Analysis and Testing Of Fragrances
10 times the normal concentration of the fragrance. If there are Natural and synthetic fragrances are complex mixtures of often
signs of an allergic reaction, the IFRA would determine the ‘no- small quantities of many tens or hundreds of individual chemical
effects concentration’ and will only allow the compound to be used compounds. Identifying the particular compound responsible
at a tenth of this concentration. for the fragrance or the presence of impurities in a sample for
registration purposes presents particular problems that have limited
In the 1970s it was discovered that some sunscreen formulations the development of fragrance science. Fahlbusch, et. al. (Fahlbusch,
containing coumarin [91-64-5] derivatives caused skin sensitisation 2005) have pointed out that in 1960, merely 450 food flavours
but—ironically—only when they were exposed to sunlight. The IFRA had been identified compared to the 8,000 known today as a result
subsequently restricted its use. of the availability of new analytical techniques.
Once they have permeated the skin, fragrances can affect other To identify the compounds responsible for the fragrance in a natural
body organs. Cases have been rare, but the IFRA has banned product or a shampoo, it is necessary to extract the individual
the use of Musk Ambrette [83-66-9] because of its neurotoxicity components from the blend. This is generally done using a number
and skin-photosensitisation effects. Other nitrated musks, such as of techniques to extract particular components from the blend and
musk ketone [81-14-1] and musk xylene [81-15-2] have since been then combining the results to render the complete picture.
prohibited. Tests on rats indicated that phenolethanol (phenylethyl
alcohol) in rose oil might cause reproductive effects. But more The volatiles responsible for the fragrance can be obtained by
detailed tests on the skin showed that any phenylethyl alcohol that headspace analysis, confining the plant or sample in an enclosed
did penetrate the skin was rapidly converted to phenylacetic acid, a space and then analysing the volatile gases evolved into the
natural component of blood. headspace (Fig 2.2). The volatiles can be concentrated in a trap.
Individual components can be extracted from the original sample
The discovery of nitromusks and polycyclic musks in surface water, by expression (pressing), or solvent or water extraction. Typical
fish and milk samples has highlighted their low biodegradability, solvents used include dichloromethane, pentane/diethyl ether,
which is exacerbated by their high hydrophobicity with Log P >5. freon, hexane, ethanol or acetone (Da Costa, 2005). Steam
14

distillation separates ingredients without the use of high boiling compound can be positively identified by injecting a known sample
non-volatiles, although it does involve heating the sample. The use of the same compound into the column and observing its retention
of supercritical CO2 as the extraction solvent is useful for extracting time. If the retention times are the same, it is likely that the two
fragrance components from solids or viscous liquids. Its solvating compounds are the same. The area of the substance’s peak is
power can be altered by changing the pressure. The extraction is related to its concentration.
carried out at low temperatures and thus it does not degrade the
fragrance. Unfortunately, though, the technique is time consuming. The advantage of GC is that it fractionates complex mixtures. The
particular component in a mixture responsible for the particular
A number of techniques are used to identify the individual fragrance can be identified by GC-olfactometry. The mixture is
components, many of which involve using gas chromatography injected onto the GC column. The exit gas is split into two streams.
(GC) in which mixtures can be separated into individual One is directed to the detector. The other can be sniffed by the
components. Gas chromatography involves injecting and then analyst. By relating the smell to the peaks, it is possible to identify
vapourising the sample into a stream of an inert carrier gas, usually the peak responsible for the odour.
helium, passing through a column with a high surface area. The
surface of the column is coated with a liquid stationary phase. The GC columns can be linked up to other types of detectors, such as
components in the gas stream absorb into the liquid material on mass spectrometers (GC-MS) that measure the molecular weight
FIGURE 2.2 Headspace the column wall. After a period of time the absorbed material is and fragment pattern of the component of the sample. InfraRed
method of trapping the scent eluted and returns to the gas stream. On leaving the column, the (IR) Spectroscopy provides a ‘fingerprint’ of the functional groups
of a flower in the field gas stream passes a detector. Provided conditions in the column are in the compound being analysed. Nuclear Magnetic Resonance
Note: plant in photo is maintained constant, the elution time of a particular component Spectroscopy (NMR) gives information about the number and
Pachira insignis
Source: Kaiser (2005) is constant. The elution times of the individual components in the position of atoms (particularly hydrogen and carbon) in the
original sample are different, and thus they leave the column at substance.
different times.
The column can be a long narrow silica tube with the liquid phase
coating the wall; or the column can be packed with liquid coated
beads. The composition of the liquid phase can be adjusted to
absorb particular types of compound. Various types of detectors
are used, the most common being flame ionisation detectors. The
15

FIGURE 2.3 G
C-MS of trapped scent of Turbinicarpus pseudomacrochele The fragrance analysed in Fig 2.3 is from Turbinicarpus
ssp. Krainzianus flower (insert) pseudomacrochele, a flower that lives in arid regions of Mexico.
Its scent is unusual, being described as the “Mouldiest Scent
on Earth”, associated with moist damp places. It is possible the
fragrance attracts insects looking for moisture in the desert.
Individual fragrance compounds in the flower’s scent are eluted
from the GC column at different times. The fragrance in each peak
is analysed by mass spectroscopy. GC-MS analysis of the flower’s
fragrance shows that its major component, 78% of the total, is
(+)-Dehydrogeosmin, which is responsible for the damp odour.
Using these techniques helps scientists to identify the structure of

fragrance compounds, which enables them to synthesis new actives.
But how do they quantify the fragrance?
Quantifying Fragrance
Source: Kaiser (2005)
When it comes to describing a fragrance, human beings by nature
detect and respond to sensory perceptions in very different ways.
An interesting example of the identification of floral fragrances
And so, fragrances are usually evaluated by a panel of individuals,
comes from Roman Kaiser of Givaudan. Givaudan has been
each of whom is selected for their sensitivity to smell and their
conducting a long-term study to identify the fragrance of a number
short-term odour memory. They are trained for many months
of endangered plants (Kaiser, 2005). The flower was inserted into
to enable them to perceive and recognise different fragrance
a glass bottle designed so that it would not damage the flower
standards individually and in complex mixtures and to be able to
(Fig 2.2). The scent from the flower is then drawn through an
describe what they smell.
absorption column by a battery-operated pump. The absorption
column traps 10-200μg of the volatile fragrance. The fragrance is
Humans have five senses, and each sense can influence what
then washed out of the column with a hexane/acetone solvent and
we perceive in another. Thus we can be given a drink that tastes
is sealed in a micro-ampoule. Back at the laboratory, the fragrance
of cherry, but many people will not think it is cherry unless it is
is removed from the ampoule and analysed by GC-MS.
coloured red. So in order for the panel to be able to quantify the
16

effect of a particular fragrance, it is important that there are no

other variables. The samples being tested must look and behave
in exactly the same way, the only difference being the fragrance
they contain. The fragranced sample should be tested in a room or
cubicle decorated and furnished neutrally.
Describing, reporting and quantifying the results is also difficult.

Different groups tend to develop their own way of describing
an odour, and various multi-dimensional techniques are used to
present their results. Some commercial companies offer test kits
to quantify taste and odour, but the ultimate and most important
arbiter is the customer, and fragrance companies carry out
consumer surveys and establish panels of lay consumers to help
them identify market trends.
17

Trends in Fragrance Chemistry
3
Science of Smell FIGURE 3.1 Human olfactory system it is estimated that
Human beings’ two chemical senses are taste and smell. In most the majority of
animals these are the most important senses. Some birds, primates our sensation of
and humans rely more on sight, but despite this, smell strongly
influences the way we assess our environment, and it has an
taste comes from
important influence on our emotional state. our sense of smell,
possibly because
Taste receptors are confined to the mouth and are mostly found our smell receptors
on the tongue. Taste receptor cells are found in groups of 50 to are 10,000 times
150, which make up our taste buds. Individuals have between more sensitive than
500 and 20,000 taste buds at a concentration of between 3 to
those of taste.
several thousand per cm2. These differences explain why taste
varies from individual to individual. The taste receptors respond to
the relatively high concentrations of chemicals that are present in
food, and convert them into electrical signals that are sent to the Source: Adapted from Givaudan
brain for processing. Human beings detect four basic tastes—sweet,
salt, sour and bitter, although some sources talk of a fifth—umami— We smell volatile fragrance molecules in the air we breathe through
which is a pleasant savoury taste, caused by glutamates and our noses. The mechanism of this process is still the subject of
nucleotides. With the exception of bitter substances, the chemicals active research and debate but is important to our understanding
humans taste are water soluble. Despite this, it is estimated that of the way fragrances work and in our search for new actives. The
the majority of our sensation of taste comes from our sense of following description summarises current understanding.
smell, possibly because our smell receptors are 10,000 times more
sensitive than those of taste. Many millions of smell or olfactory receptor cells (ORC) are situated
in nasal epithelium, a 2.5cm2 yellow patch of tissue on the roof of the
nasal cavity, beneath the eyes (Fig 3.1). The nasal epithelium is about
100-200μm thick and is covered in a 35μm thick layer of viscous liquid
known as the olfactory mucus. The olfactory mucus layer refreshes the
surface of the receptor cells by flowing backward over the epithelium at
a rate of about 1-6cm/min. At one end, each receptor cell has 8 to 20
18

cilia, which are 20-200μm long and contain the olfactory receptor sites. Fragrance molecules are drawn in with the air that is breathed
ORC cells are regenerated approximately every 40 days. It is interesting through the nose. Other fragrance molecules reach the olfactory
to note that an animal’s sense of smell remains active long after its epithelium in the nose, from food being eaten in the mouth. To
other senses start to fail in old age. The receptor cells pass through the reach the odour receptor cells, the fragrance molecules must pass
bone of the cribriform plate at the base of the skull. The other end of the through the aqueous olfactory mucus layer. There is evidence
receptor cells are connected to the glomeruli cells in the olfactory bulb. that hydrophobic (water-insoluble) fragrance molecules are
carried through the mucus by “odour-binding proteins” (OBP).
Like all cells, the membranes of olfactory (smell) receptor cells The fragrance molecule induces a change in the GPCR, which is
are composed of lipid bilayers that isolate and protect the transmitted through the lipid membrane into the receptor cell. The
cell’s contents from their environment. The lipid’s cell walls of change in the GPCR molecule generates an electrical potential
smell receptor cells (ORC) contain key receptor proteins, called inside the cell, which is passed via the synapse of the receptor
7-transmembrane (7-TM) G-protein coupled receptors (GPCR’s) (Fig cell onto the glomeruli in the olfactory bulb on the inside of the
3.2). The protein backbone forms 7 loops through the lipid bilayer, brain cavity (Fig 3.1). The protein receptors in the lipid are then
and they allow communication across the cell wall. deactivated and wait for the next fragrance molecule to arrive.
FIGURE 3.2 S
chematic diagram of the cell membrane of olfactory The GPCR proteins in the cell membrane in each receptor cell
receptor cells respond to odour molecules with particular combinations of
chemical and physical properties. Thus, different molecules can
trigger the same receptor cells, provided they have similar groups.
An odour molecule is also able to trigger other receptor cells.
So, each fragrance molecule triggers a particular combination of
ORCs while not affecting others. It is the triggering of a particular
combination of receptor cells that creates the smell sensation in our
brains. Molecules of different fragrances have different chemical
and physical properties and will trigger different combinations
of receptor cells. This is shown schematically in Fig 3.3, with
two fragrance molecules labelled A and B. Human beings have
about 350 to 400 types of olfactory receptor cells, and because
Source: Adapted from http://scienceblogs.com/mt/pings/49986
of this, combinatorial mechanism can detect many thousands of
19

fragrances. There is evidence that the same types of receptor cells suppressed; for example, salt can affect our interpretation of the
are connected to the same glomeruli. odour or taste of certain foods. Our brains are also able to “block”
our ability to detect odours that have been present for a number
FIGURE 3.3 S
chematic diagram of the effect of different fragrance of hours. Odour fatigue (or adaptation), occurs because when an
molecules on olfactory receptor cells odour has been present for a while and nothing bad has happened,
the cause of the odour cannot be a danger.
There is extensive debate about how fragrance molecules trigger

particular types of receptor cells and how this creates the smell
sensation in the brain (Veithen, 2010, and Sell, 2006), a topic that
is discussed further in Chapter 5.
Some fragrance molecules are also detected by the trigeminal nerve

system, which passes sensory information from the face and mouth
Source: Adapted from Sell (2006)
for processing by the higher brain.
The signals from each type of receptor cell are passed to their
Physical Chemistry of Smell
glomeruli, where they are processed and sent to two regions of
Fragrances are liquids—or perhaps solids—that are volatile and able
the brain, the hypothalamus and via the thalamus to the olfactory
to reach and trigger certain combinations of olfactory cells in our
cortex of the higher brain. The hypothalamus deals with emotion
noses to create a particular fragrance sensation in the brain. In
and memory, and its connection to the glomeruli is short, direct
order to be volatile at room temperature, fragrance molecules need
and rapid. This explains why smell has such a fast-acting effect
to have a relatively low molecular weight; all current fragrance
on emotions and memory, as our subconscious reacts to the
molecules have a molecular weight of less than 310. The type of
odour before we are even aware a fragrance has been detected.
smell perceived depends on the particular combination of receptor
The signals are also fed to the higher brain, the olfactory cortex,
cells the molecule triggers. The intensity of the fragrance depends
which processes the odour inputs. It is here that the signals from
on the concentration of the fragrance in the air and the molecule’s
the odour receptors are combined with other sensory inputs (e.g.,
effect on the ORCs. Below its threshold concentration, the fragrance
taste) to “create” the smell in the brain. The olfactory cortex has
is not detected.
the power to “edit” the stimuli. The odour can be enhanced or
20

A fragrance’s concentration in the air depends on the amount of and the lower their vapour pressure, as it becomes more difficult
the fragrance present in the formulation and its volatility, which for the molecule to break free and evaporate. Polar groups include
is primarily determined by its vapour pressure. Vapour pressure carbonyl groups (-C=O) in aldehydes, ketones and carboxylic acids
is measured in units of mm of mercury (Hg). As the temperature and hydroxyl (-OH) groups in alcohols and esters. Nonpolar groups
increases, the substance’s vapour pressure increases, it becomes such as alkyl chains (CH3-CH2-CH2-) or aromatic aryl groups have
more volatile until at its boiling point, it equals atmospheric no charge separation. They do not attract polar groups, preferring
pressure (760mmHg) and the liquid boils, becoming a gas. A to interact with other hydrocarbons. They are hydrophobic and
fragrance vapour pressure of 2mmHg at 25°C is high; most insoluble in water.
fragrances have vapour pressures that are 3 to 5 orders of
magnitude smaller (List of fragrance compoounds in the Appendix). Similar interactions occur between fragrance molecules and the
solvents in which they are dissolved. Water is a very polar solvent
Fragrances are usually blends of many individual compounds and readily dissolves polar molecules as a result of polar hydrogen
designed to achieve the desired olfactory effect, and they are bonding between the negative dipoles on the oxygen atoms and
almost always mixed with other ingredients such as solvents, positive dipoles on hydrogen.
surfactants, emollients, dyes, bleaches, enzymes, etc. Fragrance
molecules will interact with these ingredients to a greater or Alcohols and polyols are polar molecules as a result of their –OH
lesser extent and these interactions will affect, usually reduce, the groups. The lower-molecular-weight alcohols, such as methanol,
fragrance’s volatility. Despite this, the saturated vapour pressure of ethanol, isopropyl alcohol are miscible with water but contain
a particular fragrance gives a good idea of its volatility. short hydrophobic alkyl groups that are able to dissolve more
hydrophobic nonpolar molecules that are not normally soluble in
The hydrophobicity or polarity of a fragrance is its preference for water. As the proportion of fatty alkyl groups in the solvent increase
wanting to be in water or a nonaqueous oil phase, and this affects (e.g., octanol or dioctyl phthalate), they become even less polar. The
its volatility in a mixed formulation. Polarity arises because certain ultimate are hydrocarbon paraffin oils, which dissolve only nonpolar
atoms in the molecule, such as oxygen, attract electrons more than compounds and are immiscible with water.
others and become slightly more negative than its neighbours.
Electrical neutrality must be maintained, and thus another part A common measure of hydrophobicity of a fragrance is P, the
of the molecule has a slight, equal positive charge. The negative ratio of it distributed between octanol and water. Values of P for
region of one molecule is attracted to the positive region of its different fragrances vary over orders of magnitude and thus are
neighbour. The greater their polarity, the greater their attraction quoted as Log P. Experimental Log P values are not always known
21

and are often calculated and expressed as ClogP values. Methods it is used. Fragrances can also be chemically reacted with other
of calculating ClogP values are given in Howard and Meylan, 1997. molecules to increase their molecular weight and reduce their
ClogP calculations are carried out by a number of commercial volatility. These pro-fragrances can be design to hydrolyse and
companies, such as Daylight Information Systems (www.daylight. release the fragrance at its point of use. These approaches are
com). ClogP values agree well with empirical values. If the ClogP discussed later.
of a fragrance is <2, it is hydrophilic (water-soluble), or if it is >3,
it is hydrophobic. ClogP, along with the boiling point and vapour We have discussed how the intensity of the fragrance depends
pressure of a fragrance, gives an indication of its volatility in a on it volatility and interaction with ingredients in solution.
fragrance blend. Another important factor to be considered is the substantivity
or longevity of the fragrance. A perfume or cologne is applied
The volatility of a hydrophilic fragrance molecule, with a low Log directly to the skin, a shampoo to the hair, a fabric conditioner
P value, dissolved in water will be less than that of a hydrophobic to textiles, and a kitchen cleaner to a work surface. In many
fragrance molecule (high Log P), which will be more likely to applications, it is beneficial that the fragrance persists for a long
evaporate from the aqueous solution. The solubility or miscibility of period of time. Fragrances with a high substantivity adhere well
the hydrophobic fragrance molecule in water can be increased by to the substrate and persist for longer than those that are easily
solubilising it with a surfactant. removed. Skin has a low odour-retaining potential. Hair is nonpolar
with a certain porosity and is able to retain fragrance molecules.
Traditionally perfumes are stored in glass jars and bottles Fragrances with a high ClogP are hydrophobic and are more
because glass is impermeable by fragrances. Many liquid cleaning likely to stick onto surfaces, particularly if they are formulated in
formulations are stored in plastic bottles, and powdered detergents aqueous solutions. A perfume in a cleaner or a fabric softener
in cardboard boxes. Some of these containers are permeable to will be applied to the surface in a washing or cleaning step in
fragrances and require careful design to ensure their contents the presence of surfactants, and unless it is very hydrophobic, is
retain their fragrance during storage. likely to be removed with the rinse water. Different textiles will
react in different ways. Cellulose fabrics such as cotton are polar
There are ways that the volatility and performance of fragrances and hydrophilic while synthetics such as polyesters tend to be
in a formulation can be modified. Fixatives are fragrances, usually hydrophobic (Ester, 1994).
higher-boiling ones, that are added to the formulation and
associate with more volatile fragrances, reducing their volatility. Fragrance blends are designed by the skills of the perfumer using
Encapsulation can be used to physically protect a fragrance until their extensive theoretical and practical experience. As we have
22

seen, they contain a balance of volatile low substantivity top notes Natural Products and Essential Oils Traditionally, flavours and
and less-volatile, more-substantive fragrances to provide the slower fragrances have been obtained from animals and plants. Nowadays
but longer-acting base notes. very few fragrances are obtained from animals. Natural fragrances
usually contain a complex blend of ingredients, each with its own
Thus, the olfactory impact of a fragrance depends on the physical organoleptic properties. Essential oils are extracted from plant
chemistry of the fragrance and the way it interacts with the material by the following methods.
substrate. Many of these parameters, such as vapour pressure,
ClogP and substantivity, are listed in published data on fragrances Expression: Many citrus oils are obtained by applying physical
(see also List of fragrance compoounds in the Appendix). While this pressure to the plant material and collecting the oil that is expelled.
data on fragrances provides a guide to what components to use, Distillation: A number of distillation processes are carried out. High-
the final performance of the blend ultimately must be determined boiling-point wood oils, such as cade and birch, are obtained by dry
in practice. distillation—directly heating the plant material.
Fragrance Compounds Steam distillation is the most common method of extracting

Many thousands of compounds can be used as fragrances, about natural oils. It involves adding water or steam and heating the
1,000 of which are used in care products (Procter & Gamble). It plant materials. Water and oil are co-distilled, cooled, and the two
is not appropriate to list all of these here; nor is it of relevance immiscible phases separated on the basis of their density. As the
to discuss the synthesis of fragrances; more specialist texts are maximum temperature is limited to 1,000°C, less degradation
available (Rowe 2005, Surburg, 2006). This report will provide a occurs than with dry distillation. The water separated off is usually
general survey of fragrances, describing particular chemical types discarded or returned to the still. One exception is rose oil, which
and compounds that are of interest to the care industry and the is water soluble; the aqueous fraction—rose water—is retained and
issues that accompany their use. used as a perfume.
List of fragrance compoounds in the Appendix gives the structures A number of processes are used which involve breaking open the
and key properties of certain fragrances. Readers interested plant cells, releasing their contents. These include hydrodiffusion
in finding out more about particular fragrances in greater (the steam is added at the top of the still and the resultant water/
depth could start by visiting The Good Scents Website (www. oil mix is removed from the base). Microwaves have also been used
thegoodscentscompany.com), which has a fully searchable to fracture plant cells.
database of individual fragrances.
23

Sometimes monoterpenoid oils are removed from the essential oils automated. With some plants like jasmine flowers, for example,
by distillation or solvent extraction to improve the oil’s fragrance. automation is not possible and this is reflected in its price. The
price of the oils varies widely, primarily depending on their ease
Solvent Extraction: The most common solvents used to extract oils of growth and harvesting. The supply of natural fragrances is
are petroleum ether, acetone, hexane and ethyl acetate. Benzene very dependent on the success of the growing season and on the
is no longer used because of toxicity concerns. Ethanol is not weather. Table 3.1 is a list of the larger-tonnage essential oils and
widely used because of the high water content of plants, although of smaller-tonnage oils that hold particular interest of the care-
it is used to extract vanilla beans and ambergris. Ambreine is a product industries.
triterpene that forms in the intestine of sperm whales, probably to
protect it from the shells of the animals it eats. The whale expels TABLE 3.1 M
ajor essential oils, and oils of particular interest for home-
the ambreine, and it is found floating in the sea or on beaches. care products
Ethanol extract of ambreine yields tincture of ambergris.
Natural Products, Musks Musks are the dried secretion from
Supercritical carbon dioxide is used to decaffeinate coffee and an internal pouch between the hind legs of the 60cm-high male CLICK TO VIEW TABLE
in the extraction of hops, but it requires expensive, high-pressure musk deer, Moschus ssp., found in mountain forests of Southeast
equipment. Asia and Eastern Russia. The highly fragranced secretion is used to
mark territory and to attract female deer over very large distances.
Enfleurage: Enfleurage was used years ago, but is of little Unfortunately for the musk deer, humans also find its animal-like,
commercial significance today. Parts of the plant, such as the sweet and ammoniacal smell very attractive, and the male deer
petals, are pressed into a thin bed of purified fat. Over time, were hunted for their musk pods. After drying, the pods were
hydrophobic fragrances in the plant diffuse into the fat. The soaked in water to open them up and the musk was extracted with
ancients applied the fragrance fat directly to the body. More alcohol and used as tinctures in perfumes. This continued until
recently the fragrance has been extracted from the fat using 1979 when trade in musk was banned for all but a very few Asian
ethanol. Distillation removes the ethanol, yielding the perfume medical applications.
absolute.
In 1888, Albert Bauer discovered the synthetic musk (subsequently
Plants contain only a few percent of the essential oil and so it known as “Musk Bauer”) while searching for new TNT-type
makes economic sense to carry out the extraction where they are explosives. Musk Bauer (or musk toluene) became the first of a
grown. Whenever possible (e.g., with lavender), the farming is number of nitro musks. Musk xylene is cheaper and is used in
24

soaps and detergents. However, nitromusks suffer from a number Carbon, Hydrogen and Oxygen Aliphatic
of disadvantages: Their synthesis is hazardous, involving explosive Compounds Aliphatic compounds are those that contain
intermediates, and some have been found to be phototoxic, so they hydrocarbon chains, which for fragrances are up to about
have been replaced. 12 atoms long. The chains can be linear, branched,
saturated or unsaturated. The carbon chain is usually
Meanwhile, analysis of deer and animal musks led to the isolation of attached to a number of functional groups. Groups that
three components of deer musk, three of which have been synthesised are important for fragrances are shown in Fig 3.4. They
and commercialised: muscone [541-91-3], civetone (a mixture of are alcohols, carboxylic acids and their alcohol esters,
isomers) and exaltone [502-72-7], all of which are macrocylic ketones. aldehydes, ketones and acetals. Functional groups that
Musk fragrances from the plant kingdom have been found to be based contain atoms other than carbon, hydrogen and oxygen
on macrocyclic lactones (thibetolide and exaltolide [106-02-5]). (e.g., N and S) will be discussed later.
Continuing research into musk fragrances led to the discovery of a FIGURE 3.4 Functional groups found in fragrances
synthetic nitrogen-free polycyclic aromatic family of musks (PCMs).
These have been found to be stable and hydrophobic and to have
high substantivity on fabrics. Galaxolide [1222-05-5] is widely used
in fabric softeners, in detergents and in perfumes.
Note: Alcohol (left) and carboxylic acid with low and high pH (left to right)
Aroma Compounds The fragrance of natural essential oils is due Source: IntertechPira
to the individual chemical compounds they contain. Because of the
expense of isolating them and the uncertainty over their supply, Aliphatic fragrances made from natural materials are
most commercial fragrances are made by blending individual derived from natural oils. For example, octanoic acid
fragrance compounds that have been made synthetically. The [CH3(CH2)7•COOH] is obtained by reacting the glycerol
following section is a summary of the types of compounds used as esters in plants such as palm, coconut, castor oil, etc.,
fragrances. Nature-identical compounds are found in nature but with caustic soda. Octanoic acid is separated from the
have been made synthetically. Other synthetic compounds have mixture of fatty acids formed and is then converted into
useful fragrances, but have not yet been found in nature. its alcohol, aldehydes, ketones and esters. Because of
the way plants synthesise them, natural fats are made
of acids with even numbers of carbon atoms. Odd-
25

numbered carbon chains are obtained by cleaving longer Aliphatic aldehydes are widely used in fragrances. The
carbon chains. Similar compounds can be obtained from lowest, acetaldehyde, has a pleasant apple flavour and
petrochemicals. is used in fruit flavours. The lower aldehydes C2-C7 are
common in nature and have fruity and roast flavours
Pure saturated hydrocarbons with no functional groups and are primarily used as food flavourings. Their odour
(e.g., hydrocarbon oils) do not have an odour; of more becomes weaker and a fatty character develops as their
importance are their derivatives. molecular weight increases and the higher aldehydes
(>C13) are not used. Of more importance for fragrances
Ethanol (C2H5OH), an important component of alcoholic are branched chain and unsaturated aldehydes, including
drinks, is used as a solvent for many fragrances, such as two that are alkali stable and are used in soaps and
Eau de Cologne. Other flavouring and fragrance solvents detergents, trimethyl undecadienal [24048-13-3] and
that contain hydroxyl (-OH) include propylene glycol and methyl pamplemousse [67674-46-8] (List of fragrance
dipropylene glycol. compoounds in the Appendix). Acetaldehydes, particularly
saturated ones, are prone to oxidation. They can be
Unsaturated aliphatic alcohols are of more interest. The stabilised by converting them into the corresponding
most important is leaf alcohol, cis-3-hexenal [928-96-1] acetals or nitriles that have similar fragrances. Aliphatic
(see List of fragrance compoounds in the Appendix), a ketones are not widely used in fragrances.
wound compound produced by green vegetation when it
is cut that emits the very intense fragrance of cut grass. Acids react with alcohols to make esters that provide fruity
9-Decen-1-ol [13019-22-2] and 10-Undecen-1-ol [112-43- flavours and fragrances. Melon valerate [39255-32-8] is
6] are also used in detergents. 3,4,5,6,6 pentamethyl-2- used in shampoos and fabric-care products. Some esters
heptanol [87118-95-4] is a mixture of isomers sold under with no odour, such as triacetin (glyceryl triacetate) and
the trade name Kohinool (IFF), which is used to impart a triethyl citrate, are used as solvents.
woody fragrance.
Terpenes Terpenes are a family of compounds found
Aliphatic acids, such as acetic acid found in vinegar, are in plants, particularly conifers, which form the largest
used to flavour food but tend not to be used in fragrances. group of natural and synthetic odorants. They are based
The C3-C8 acids have fruity flavours; C4 and C6-C12 have on the isoprene unit C5H8 ( ), which can be
cheese flavours. linked together to form linear or cyclic structures. Their
26

nomenclature is described in Chapter 2. The most significant distillation of essential oils. For example, Linalool [78-70-6]
are the oxygenated monoterpenoids (with 2 isoprene is obtained from Brazilian and other rosewood oils. Terpenes
units). The fragrant higher terpenoids are less volatile, more can also be made synthetically from petrochemicals.
tenacious and are used in longer-lasting base notes.
cyclic Terpenes Terpenoid hydrocarbons have weak
A
Terpenes can be made from turpentine, which is obtained odours and are not used as fragrances, although they
by distilling resin from pine trees. Different pines yield are used to make other fragrances. The corresponding
turpentine with different compositions. Large quantities alcohols, aldehydes and acetals, originally isolated
of turpentine are obtained from the Kraft Process, which from essential oils, are widely used as fragrances.
manufactures paper pulp from soft woods such as pine, fir Typical linear terpenes are listed in List of fragrance
and spruce trees. Distillation of the water-insoluble liquids compoounds in the Appendix
present in the pulp yields crude sulphate turpentine,
which is rich (>70%) in α and β-pinene. cyclic (linear) terpene alcohols such as geraniol
A
[106-24-1], linalool [78-70-6] and citronellol [106-22-
FIGURE 3.5 Structure of pinenes 9] are important fragrances and are intermediates for
the synthesis of other compounds. The corresponding
aldehydes citral [5392-40-5], citronellal [106-23-0]
and dihydrocitronelle [107-75-5] are also important
(List of fragrance compoounds in the Appendix) and
are also used as derivatives for other fragrances. Citral
[5392-40-5] is the key odoriferous agent in lemon
Note: α-pinene (left) and β-pinene oil, but unfortunately it is susceptible to oxidation
Source: IntertechPira
and cannot be added to bleach. The nitriles, such as
geranyl nitrile [5146-66-7] has a similar odour but is
The nonvolatile residue is known as tall oil and contains more stable and can be used instead. Ketones are less
diterpenoids (composed of 4 isoprene units). α and important, although one is listed in List of fragrance
β-pinenes are the raw materials used to synthesise many of compoounds in the Appendix.
the terpenoid fragrances. Other natural sources of terpene
fragrances, particularly cyclic terpenes, are from the fractional L inear terpene acids are not important fragrances, but
27

some of their esters are. Most are used in perfumes, isomers of the ionones, and these molecules are being
but two, listed in List of fragrance compoounds in the actively investigated in the search for new fragrances.
Appendix are of interest here. α-Ionone [127-41-3], δ-Damascone [57378-68-4],
Isodamamascon and Piconia [23787-90-3] are listed in
C
yclic Terpenes Plant essential oils contain large List of fragrance compoounds in the Appendix as they
quantities of cyclic terpenes, some of which are used are used as fragrances. Some cyclic terpene esters are
as fragrances in their own right and others of which used in fragrances for household products.
are used to make other fragrances. Of the monocyclic
terpenes, those with a para structure such as limonene Other Cycloaliphatic Fragrances There are a
[138-86-3], terpinene [8013-00-1] and terpinolene number of other cycloaliphatic (cyclic but nonaromatic)
[586-62-9] are most important. compounds that are important fragrances for household
products and perfumes. Selected alcohols and ethers of
yclic terpene alcohols are widespread in nature, but
C importance in fabric and home care, many of which have
few are used as flavours or fragrances. Menthol is woody sandalwood odours, are listed in List of fragrance
important physiologically because of its cooling effect. compoounds in the Appendix.
Selected cyclic terpene alcohols are shown in List of
fragrance compoounds in the Appendix. The most important cycloaliphatics are the ketones such
as jasmone [488-10-8]. The esters have fruity and woody
yclic terpene aldehydes and ketones are found
C fragrances.
only in small quantities in plant oils, so commercial
quantities must be made synthetically. A few, such Cycloaliphatic acetals, including a number of “amber”
as Fenchone [1195-79-5], are used commercially chemicals because of their resemblance to ambergris from
as fragrances. List of fragrance compoounds in the the stomach of whales, are an active area of research.
Appendix gives some representative examples. The C13
terpene, α-ionone exists as three isomers, depending Aromatic Compounds Aromatic molecules are cyclic,
on the position of the double bond and as a number usually 6-membered rings, and have unsaturated -C=C-
of methyl derivatives. They have powerful, sweet, bonds alternating with saturated C-C bonds which enables
“powdery” violet aromas and were the first synthetic the valance electrons to be delocalised around the ring.
aromas to be used. The damascones are structural Aromatic flavours and fragrances can be made from
28

petrochemicals such as benzene, toluene, and phenol. Heterocyclics Containing Other Elements Cyclic
Phenolic fragrances can render off-notes. Benzene can also molecules can also contain other atoms besides carbon.
be used to make styrene, styrene oxide and styrallyl oxide, These are the heterocyclic molecules containing oxygen,
all of which are used to produce fragrances. This includes nitrogen and sulphur atoms. Some, such as furans, are
2-phenylethanol [60-12-8], a major component of rose oil, aromatic. The nomenclature and structure of heterocyclics
one of the most important perfume ingredients. Aromatic is given in Zviely, 2005. Many heterocyclics are used in
alcohols with saturated side chains are very stable and are food flavouring, only ones of interest to care products are
used in soaps and detergents. considered in this report.
Esters of lower molecular weight acids of aromatic Aldehydes tend to be unstable in strong acids and alkali
alcohols have fruity flavours and are important food solutions, limiting their use in many cleaning products;
additives and perfumes; these include benzyl acetate they are susceptible to degradation by oxidation and heat
[140-11-4], propionate [122-63-4) and isovalerate [103- as well. They can be replaced by nitriles.
38-8]. Similarly, the phenethyl esters, such as phenylethyl
acetate [103-45-7] have fruity, flowery flavours and Fragrances Containing Silicon A number of
fragrances. Rose acetate [90-17-5], unusual in being a compounds in which carbon atoms have been replaced
chlorine derivative, is used to perfume soaps, powders and by silicon are reported to be fragrances. Dimethyl(1,1,2-
bath salts. Phenylacetic acid [103-82-2], the benzoates trimethylpropyl)silyl-acetaldehyde has been reported
and phenylacetates have sweet flowery odours and as having a strong woody odour but is not used as
fragrances. Because of its stability, cinnamonitrile [4360- fragrances (Doszczak, L., 2005)
47-8] is used for perfuming soaps and detergents.
Pro-Fragrances
Salicylates derived from phenol are found in a number of Fragrances are lost from a substrate at a rate that depends on their
essential oils. Methyl salicylate [119-36-8] has antiseptic volatility and whether they bind to the substrate, their substantivity.
properties and is used in wintergreen fragrances. Hexyl The rate at which the perfume evaporates can be reduced by covalently
salicylate [6259-76-3] is used for inexpensive floral notes bonding the fragrance molecule with another to form a larger, less-volatile
and benzyl salicylate [118-58-1] is used as a fixative. pro-fragrance molecule. The pro-fragrance molecule traps the fragrance in
the perfumed formulation but is designed to release it at the formulation’s
point of use. A number of pro-fragrance systems have been patented.
29

Henkel has claimed a system in which an amine polymer, with FIGURE 3.6 Photosensitive pro-fragrance adduct
primary (-NH2) and secondary (R-NH-R) amine groups, such as
polyethyleneimine (PEI), is reacted with a modifier molecule
(WO2009153209). The PEI-modifier adduct is then reacted with an
aldehyde or ketone fragrance molecule to form the pro-fragrance.
The pro-fragrance can be blended into the formulation with other
fragrance molecules. When the formulation is used, the pH drops
and the imine releases the aldehyde fragrance.
Dial has claimed forming esters of silicic acid with OH functional

fragrances (alcohols or carboxylic acids) that are stable in liquid
detergents at pH 7 to 12.5 (WO2008/033280A). Polysiloxane Source: Procter & Gamble
esters of fragrance alcohols have also been claimed as pro-
fragrances (Momentive, US2010/120657). Encapsulation of Fragrances
By their nature, fragrances are volatile and easily lost. Many are
Procter & Gamble has patented (US6861402, 2005) a system in chemically unstable and can be deactivated by oxidation, light or
which aldehyde and ketone functional fragrances form pro-fragrances by reacting with other ingredients in their formulation. An effective
with oxazolidines, β-amino or ortho-esters. The pro-fragrances are way of preserving fragrances until they are required is to encapsulate
stable in personal-care formulations at pH>7 but hydrolyse and them in a protective coating. The filled capsules can also be designed
release the fragrance when the pH drops below 7 on the skin. to stick to the substrate (e.g., textile fibres or to kitchen work
surfaces) to increase the fragrance’s longevity. There are a number
Photo-sensitive pro-fragrances can be used in systems that are exposed of ways to encapsulate fragrances. The method chosen depends on
to light. Procter & Gamble has claimed (US2005/014663) a molecule the properties of the fragrance, its melting point, volatility, ClogP and
with the structure shown in Fig 3.6. The fragrance molecule is the –OR how it is to be used. For example, will the fragrance be formulated in
moiety, which is released in the presence of light. The rate of release a dry powder detergent or in an aqueous liquid formulation? Finally,
of the fragrance may be adjusted by altering the R1 group. Unilever it is important to consider how the fragrance will be released—by
claims to generate fragrances in laundry fabric softeners from lipid pro- mechanical means such as impact or shear, by diffusion or by the
fragrances containing one or two unsaturated aliphatic –C=C- bonds, chemical destruction of the coating. Encapsulation technologies are
using a photobleach such as phthalocyanine (WO2009/030600). also used to protect other actives such as food flavours, vitamins,
30

pharmaceuticals, pesticides and dyes. The simplest encapsulation method is to directly emulsify the water-
immiscible fragrance into droplets stabilised by a water-soluble
Water-soluble capsules can be blended into powdered detergents. polymer such as a PVA, cellulose ether, PVP or a protein. The
Dissolving the powdered detergent in the wash water will dissolve coarse emulsion can be added to aqueous formulations, but the
water-soluble coating, releasing the fragrance. fragrances, especially the water-soluble ones, are likely to diffuse
out of the droplet. Hydrophobic fragrances can be dissolved in
If the coating is resistant to the solvent, the capsules can nonpolar liquids. Emulsion droplets can be made by emulsifying the
be dispersed into liquid formulations. The capsules can be nonpolar liquid, such as fatty alcohols or acids, hydrocarbon waxes
designed to release their contents by diffusion, by destroying or polysiloxanes, containing the hydrophobic fragrance, into water
the coating mechanically, chemically, or by altering the solution with surfactants. Dow Corning says that hydrophobically modified
pH or temperature. Encapsulated fragrances in skin-cleansing waxy cyclopolysiloxane polymers make better matrices as they are
or deodourant products are often released by the action of skin more compatible with fragrances and give better sustained release
enzymes or a change in pH on contact with the skin. Other systems (US2009/180977).
can be designed to slowly release the fragrances by diffusion
through the protective coating. The active fragrances can be dispersed into a powder blend with
the matrix material, which is then extruded as narrow cylinders
Encapsulated fragrances are of two main types. They can be protected and chopped up into smaller lengths. This tends to produce larger
by a polymer shell surrounding the fragrance core, or, the fragrances cylindrical-shaped capsules up to 1000μm long.
can be dispersed in a matrix of the protective polymer (Fig 3.7).
Spray drying is a more popular method (Fig 3.8) of encapsulating
FIGURE 3.7 Structure of capsules, core-shell and matrix fragrances.
31

FIGURE 3.8 Spray-drying tower centrifugal disc and broken into small (mm sized) droplets, which
fall down a tower through a current of hot air. The hot inlet
air (100-2,200°C) rapidly cools as the water evaporates from
the droplets; because the grains are not subjected to very high
temperatures and the residence time is short, fragrance losses are
small. Dried powder containing the fragrance is separated from the
air stream in a cyclone or bag filters.
Capsule coatings can also be made by granulation. Granulation

involves spraying a liquid melt or coating solution into a fluidised
or a rotating bed of beads or particles containing the fragrance.
The liquid forms a film on the surface of the tumbling particles
and solidifies, either as a result of solvent evaporation or cooling,
leaving a protective coating surrounding the beads. It is also
possible to disperse the fragrance in the spray liquid.
The fragrances can be dissolved as a solution or dispersed in water A number of methods involve the phase separation of water-
containing the protective matrix or shell material. The matrix soluble polymers onto the surface of immiscible fragrance droplets
material can be a water-soluble polymer, such as a starch or gum dispersed in the continuous water phase. Complex coacervation
arabic, in which case, the spray-dried powder will dissolve when (Fig 3.10) was a method developed in the 1950s by NCR for
placed in an aqueous solution. manufacturing carbonless copying paper. Gelatine is dissolved
in near-boiling water and cooled to room temperature. A water-
Water-insoluble fragrances can be emulsified into water dissolved in immiscible liquid (oil) or solid particles containing the fragrance
water-immiscible liquids. The protective matrix could be a water- is dispersed in the water using an anionic water-soluble stabiliser
insoluble polymer such as a hydrophobic wax, fatty alcohol, acid or such as sodium carboxy methyl cellulose (CMC). The solution is
ester, a hydrophobically modified starch (US6200949, 2001) or a cooled to 10°C and an acid is added to reduce the solution’s pH
cyclopolysiloxane polymer. to 4.7, the isoelectric point of gelatine, at which point the protein
precipitates and forms a film on the surface of the dispersed
The solution or dispersion is then pumped through nozzles or a particles. The gelatine-coated droplets are sufficiently stable to be
32

separated from the water and dried. The coating is soft and pliable; water-immiscible liquid (Bone, 2011). The water-immiscible liquid
cross-linking it with glutaraldehyde makes the coating brittle and containing the fragrance and melamine is then dispersed into
susceptible to fracturing by shear crushing. Other methods of water as droplets. Reducing the pH triggers the polymerisation
forming a shell around the dispersed fragrance droplets involve the of the melamine (Fig 3.10) and the interfacial film is cross-linked
phase separation of water-soluble polymers by the addition of a by gentle heating. These aminoplast resin capsules are effective,
nonsolvent. Similar products can be made by mixing water-soluble but when added to detergents or shampoos are susceptible to
anionic and cationic polymers together in the presence of the attack by surfactants, and they fracture as a result of swelling
dispersed oil droplets. caused by osmotic diffusion. The capsules can be strengthened
by copolymerising an aromatic polyol comonomer into the resin,
FIGURE 3.9 Complex coacervation which also reduces the free formaldehyde content. Modifying the
thickness of the polymer layer and the size of the capsules is used
to optimise the diffusivity of the capsules. Perfume can also be
released when the capsules are fractured by rubbing them onto the
skin or the by the creases made when laundry gets folded.
FIGURE 3.10 Formation of melamine -formaldehyde capsules
Source: Adapted from Rowe (2006)
Mechanically stable protective coatings can also be produced by

interfacial polymerisation. Monomer is dissolved in the oil phase
containing the fragrance and the blend dispersed in water. The
polymerisation initiator is dissolved in water and initiates the Melamine Formaldehyde Resin coating
polymerisation of the monomer at the droplets’ surface, at the Source: IntertechPira
interface between the two phases.
Interfacial polymer coatings can also be made using thermoplastic
The in-situ polymerisation of thermosetting melamine-formaldehyde resins (e.g., polyesters and polyamides) or reacting a polyfunctional
resins is a popular method of encapsulating fragrances. Melamine- isocyanate and a polyol to give urethane.
formaldehyde pre-condensates are added to the fragrance oils in a
33

Cognis have developed a range of capsules made from chitosan, and in the genitoanal region. Many malodours are molecules
the linear cationic polysaccharide obtained from the shells of containing –NH2 (amines), -SH (thiols mercaptans) or unsaturated
crustaceans (Fig 3.11). The capsules are prepared from a “matrix” –C=C- groups. Care products use a number of methods to suppress
solution that mixes a chitosan solution with the fragrance blend unpleasant malodours. The following are but a few examples.
and any other ingredients required. This solution is then added by • Swamp the malodour with large quantities of pleasant
drops into a sodium alginate gelling solution. The anionic alginate fragrances. In the 1960s, particular combinations of
neutralises the chitosan, forming a precipitate at the interface of aldehydes and esters were recommended (Herman,
the fragrance droplets. The protected capsules are recovered by 2005).
filtration (US6534091, 2003). • Using compounds that do not necessarily smell but
that are able to react and neutralise the malodour.
FIGURE 3.11 Polysaccharides used to encapsulate fragrances Metazene is composed primarily of lauryl methacrylate,
which reacts with molecules of malodours, increasing
their molecular weight, eliminating their smell. Other
compounds act in a similar way. Meelium is a blend
of polyhydroaromatic sulfonates, Neutrolair D-7 is a
Note: Chitosan (left) and alginic acid mixture of geranyl crotanalte and dihexyl fumarate,
Source: IntertechPira Vandor B is 3,5,5-trimethylhexylanal and Forestall
(Croda) is cationic soyaethyl morpholinium ethosulfate.
The positively charged chitosan capsules are particularly useful as Zinc ricinoleate, derived from castor oil, appears to have
they adsorb and stick onto the negatively charged surfaces of hair the unique ability to react with compounds responsible
and textiles. for body odour and is available in a blend as Grillocin
(Kuhn et al, 2000). Procter & Gamble recommends
Malodour Counteractants using aliphatic aldehydes and ketones with unsaturated
Just as pleasant smells trigger a warm emotional response, bonds (e.g., ionones) (WO2006/005007, 2006).
malodours are unpleasant and signal the occurrence of a danger. Ionones react with amines, polyacrylic acid reacts with
Thus, the smell of sour milk or rotting flesh indicates danger amines and thiols.
of infection and tells us not to eat the food. Unpleasant body • Cyclodextrins, made by the action of enzymes on starch,
odours are formed by the action of skin bacteria on perspiration are composed of glucose units arranged in a cavity
from the apocrine glands situated in armpits, around the nipples structure that can encapsulate molecules of a certain
34

size, including malodours, reducing their volatility. • Cyclodextrin molecules can also be used to trap
The cyclic oligosaccharides are used in air and fabric fragrances. The fragrances are released when the
fresheners such as Procter & Gamble’s Febreze range. molecules are warmed—for example, when ironing or
The concept has been expanded to include their Lenor drying clothes or when placed on warm skin.
and Stayfresh range. • Sensory modification odour blockers: Ionones reduce
• Cyclodextrin molecules have a tapered toroid structure the ability to detect sulphur smells.
in which the external surface is hydrophilic and • Blocking the action of the bacteria that breakdown
while they dissolve in water, the internal surface is sweat. Silver has been used as an antimicrobial agent
hydrophobic and can trap hydrophobic malodour for thousands of years. It is used to impregnate textiles
molecules of a certain size (Fig 3.12). Three main-sized used in medical applications and sportswear. The action
oligosaccharides are used with fragrances, types α, of silver ions is localised, inhibiting the action of bacteria
β and γ with 6, 7 and 8 glucose units in the hoop on the fabric while not affecting skin flora (Hofer, 2011).
that trap molecules of different weights. The bonding Other antimicrobial agents have a similar effect.
between cyclodextrin and odour molecules is physical
and thus reversible. Cyclodextrins will release trapped Fragrances used as Indicators
fragrances when heated. There are applications in which foul fragrances are added to
materials as a warning.
FIGURE 3.12 Representations of cyclodextrin
The hydrocarbon gas used to provide heat domestically and
industrially was town gas produced from coal. Because of the
impurities it contained, it had a distinct unpleasant smell. Natural
gas is purer and does not smell. The gas is explosive and leaks are
very dangerous but difficult to detect. Thus, mercaptans (R-SH) and
other chemicals, with powerful distinctive rotten egg odours, are
added to natural gas to make it instantly recognisable.
Source: IntertechPira adapted from various
35

End-use Applications
4
Introduction range of personal-care products such as colognes, antiperspirants, Compared to other
Previous chapters of this report have discussed what fragrances lotions, soaps or shampoos might need to be designed to deliver ingredients, the
are and how they work. Fragrances are most often not stand-alone the same scent, even though they are formulated in different
cost of fragrances
formulations but rather used to enhance the appeal and value media, be it water, ethanol or paraffin oil. Most perfumed
of another formulation primarily designed to achieve a function formulations are stored before they are used, and it is necessary to is high and it
such as cleaning or protection. In perfumes and air fresheners, ensure the fragrance is not lost in the wait: They must be prevented is important to
the fragrance is used to add a pleasant scent to a person or area. from evaporating prematurely, they must not react chemically with optimise their
Fragrances are usually so intense they cannot be applied alone; in other ingredients in the formulation, and they must not degrade in effectiveness.
order to achieve good uniform coverage and an acceptable, less- the presence of light.
intense odour, they are diluted with substances that make them
easier to apply. Thus, fragrances in a perfume are usually dissolved This chapter will review how fragrances are formulated with the
in a solvent, and to use them to freshen an air space, it is necessary other components used in personal-, fabric- and household-care
to add a carrier to ensure uniform distribution and appropriate products.
concentration. Compared to other ingredients, the cost of the
fragrance is high and it is important to optimise their effectiveness. Surfactants, Micelles and Emulsions
Most fragrances are insoluble in water, and surfactants are
Chapter 3 discussed the way fragrance molecules trigger the ORCs required to solubilise fragrance in aqueous systems. Surfactants
to create the scent sensation in our brain. But the volatility of are low-molecular-weight compounds in which part of the
fragrance molecules is modified by the other fragrance molecules molecule is hydrophobic and the other hydrophilic (Fig 4.1). They
and solvents with which they are blended. A highly polar fragrance are surface active because they tend to migrate to interfaces,
molecule, which is very soluble and is strongly attracted to solvent reducing the interfacial tension. They improve the compatibility
water molecules, will be less likely to vapourise than an insoluble between immiscible phases by emulsifying immiscible oils and
hydrophobic, less polar, molecule. The vapourisation of a fragrance stabilising particulate dispersions. Because they adsorb onto wet
molecule will be affected by its interaction with other fragrance surfaces, displacing oils and dirt, many are essential ingredients in
molecules in the perfume. So the scent of a perfume blend changes detergents, cleaning and personal-care products. The performance
with time. Initially, the more-volatile top notes vapourise. As they of surfactants is varied by altering the proportion of the
are exhausted, the middle notes and then finally the base notes hydrophobic and hydrophilic components of the molecules.
become more apparent. Some fragrance formulations are marketed
as families of products with the same fragranced theme. Thus a
36

FIGURE 4.1 Structure of surfactants biocides. Amphoteric surfactants, such as betaines, containing
both positively and negatively charged groups are widely used as
secondary surfactants in personal-care formulations.
Unlike most chemicals, such as solvents, fragrances or

pharmaceuticals, which consist of one type of molecule, surfactants
are manufactured from raw materials, using processes that
result in them consisting of many different types of molecules.
Most surfactant molecules will have the quoted structure, but a
significant proportion will not. Thus, an alkyl ether sulphate will
contain molecules with a spread of alkyl groups and a significant
proportion of unsulfated alkyl ethoxylate. Because of the way
they work, this is usually an advantage, but when they are used in
personal-care applications and they come into close contact with
and are often left on the skin, they need to be very pure to ensure
they do not contain substances that could irritate or cause rancidity.
Surfactants are of four main types, depending on the charge on
the hydrophilic group. Anionic, negatively charged surfactants, are
In aqueous solutions, surfactant molecules associate to form
primarily sulfonates (–SO32-) as in Fig 4.1, or sulfates (-SO42-). Soap is
micelles and liquid crystal phases (Smallwood, 2011). The
an anionic carboxylate (-COO-).
hydrophobic groups escape the water phase by associating
together, surrounded by hydrophilic (water-soluble) groups, which
Most nonionic surfactants have poly(ethylene oxide) hydrophilic
stabilise nano-sized micelles and micron-sized emulsion droplets in
groups, as in Fig 4.1. More recently glucoside hydrophilic groups
water (Fig 4.2). Being much smaller than the wavelength of light,
have been introduced, as in the renewable alkyl polyglucosides
micelles are invisible, and their solutions are transparent. Larger
(APG) that are increasingly being used in personal-care products
emulsion droplets (>0.5μm) scatter light and form milky solutions.
because of their mildness and foaming properties.
Surfactant micelles and emulsion droplets solubilise water-insoluble
hydrophobic molecules in their hydrophobic cores.
Cationic surfactants are positively charged as a result of their
amine groups. They are used in fabric softeners, and some are
37

FIGURE 4.2 Schematic diagram of surfactant micelles effect of the base on its olfactory performance.
Dispersing a fragrance blend in a surfactant solution will alter

the olfactory theme of the blend. Fragrance molecules dissolved
in solution are more likely to evaporate than fragrance molecules
solubilised inside micelles and emulsion droplets.
The viscosity of concentrated emulsions and dispersions, dispersions

containing a very larger number of particles, depends on the size
and interactions between the emulsion droplets. So, additives that
affect the interaction between emulsion particles, such as salts
(e.g., NaCl), can alter the dispersion’s viscosity. Similarly, fragrance
molecules that interact with the surfactant molecules at the oil/
water interface can change the viscosity. The other way of altering
(increasing) viscosity is to dissolve high-molecular-weight polymers
to the water.
The location of a fragrance molecule in a surfactant-stabilised
aqueous emulsion will depend on its solubility. A few fragrances Not only do surfactants solubilise water-insoluble fragrance
such as phenylethyl alcohol [60-12-8] and vanillin [121-33-5] are molecules, but as will be seen later in this chapter, surfactants are
soluble in water, and most of the molecules will be in the aqueous the major active ingredients in cleaning and personal-care products.
phase. Pinene [80-56-8] with no oxygen groups is completely
hydrophobic, and most will be found in the hydrophobic core of the Chemical Stability of Fragrances
micelles. Hydroxycitronellal [107-75-5], has some surface activity Most fragrance formulations will need to be stored for months
and can displace some of the surfactant molecules surrounding or even years before they are used. It is important to ensure the
the micelle, disrupting their stability and altering the viscosity of individual fragrances remain intact, and steps need to be taken to
the dispersion (Friberg, 1999). Amyl alcohol [71-41-0], with its fatty ensure they are not degraded.
chain and hydroxyl group can partition into the surfactant liquid
crystal layers, stabilising the emulsion. Partitioning is a slow process Degradation and loss of colour on storage can be prevented a
and the fragrance dispersion will need to be aged to determine the number of ways:
38

• Heavy metal ions can destroy fragrance molecules by more stable alternative.
catalysing oxidation; they can also cause discolouration. • Occasionally fragrance compounds react with each
If contamination by heavy metal ions is likely to be a other, the most common being the reactions between
problem (e.g., when using water from a natural source an alcohol and an aldehyde to produce a hemiacetal,
rather than demineralised water), they can be removed and likewise, between a carbonyl compound (aldehyde,
by the addition of complexing agents such as EDTA. ketone or carboxylic acid) and an amine to produce an
• Oxidation can be reduced by adding antioxidants such imine (Schiff’s base). Again, the solution is to use more
as BHT (butylated hydroxytoluene), citric, tartaric or stable alternatives.
oxalic acid, either singly or together.
• Many chemicals are degraded by photons if they are Perfumes
exposed to light. One way to prevent this is to store Perfumes and more diluted eau de parfums are products whose
the formulation in an opaque container or a dark glass major purpose is to deliver the fragrance uniformly to the skin and
bottle, if possible. Photo-degradation of fragrances or clothing. So the fragrance blend is diluted in a carrier, often a blend
dyes can be reduced by adding a UV absorber such as of alcohol (ethanol) and water.
benzophenone-2.
TABLE 4.1 Typical perfume and cologne formulations
FIGURE 4.3 Stabilisers for fragrances Cologne (wt%) Perfume (wt%)
Alcohol 80 85
Fragrance blend 8 15
Distilled water 12 n/a
Surfactant n/a n/a
Benzophenone 0.5 0.5
Britex 0.0010 n/a
Note: BHT (left), benzophenone-2 (center), and citric acid Source: IntertechPira, adapted from various
The carrier solvent must have a number of characteristics:
• A number of fragrances are susceptible to degradation • The carrier will constitute the bulk of the formulation,
in the presence of strong acids (as in bleach) or strong and it should not have an odour. If it does have an
alkalis (as with many detergent formulations). This can odour, it should be a pleasant one that and contributes
only be overcome by substituting the fragrance with a to the effect of the perfume.
39

• The main purpose of the carrier liquid is to dilute from being ingested. A common very bitter denaturant is Bitrex
the fragrance. Thus, it should dissolve the fragrance. (diatonium benzoate, [3734-33-6]).
Although some fragrances are water soluble, most
are hydrophobic and do not dissolve in water. Many Water is added to reduce the cost of the perfume and to reduce
oil-soluble fragrances will dissolve in alcohol, but if the sharp odour of the alcohol. Concentrate ethanol (>60-65%)
they do not, a surfactant can be added to emulsify the can cause stinging if the skin is damaged and so aftershave lotions
fragrance as a submicron dispersion. The surfactant contain a higher proportion of water. Water should be pure so
must be chosen with care, as it will not evaporate and it does not affect skin and soft so that it does not leave mineral
will be left on the skin. deposits. Distilled water is ideal.
• The carrier liquids should be miscible (e.g., alcohol and
water) so the cologne forms a clear solution. Because ethanol is flammable, solutions containing more than 7%
• The carrier should not damage the skin. should, according to chemical-labelling legislation, be indicated as
• The carrier should rapidly disappear, leaving the highly flammable.
fragrance on the skin. Water has a high heat of
evaporation (2,257 kJ kg-1). Alcohol has a lower boiling The fragrance in the cologne must be stable for the life of the
point (78°C) and lower heat of evaporation (841 kJ product, and so it often contains oxidants and light stabilisers.
kg-1) and rapidly evaporates, cooling the substrate.
Water will evaporate more slowly, but there is a smaller Some perfumes contain small quantities of surfactants to help
amount present and it evaporates in an acceptable stabilise the fragrance molecules in solution and to act as an
amount of time. emollient.
• Attractive, transparent, colourless, low viscosity
Colognes are made up by dissolving the stabilisers and then the
The carrier is usually ethanol or other alcohols such as isopropanol, fragrances in alcohol. The water needs to be added with care, to
which can be manufactured synthetically or obtained from the ensure no precipitation occurs. The perfume should be stored in
fermentation of carbohydrates. Ethanol forms an azeotrope stainless-steel or glass containers. Pipelines and gaskets must not
containing 95% alcohol and 5% water, so it is not possible to react with the formulation. Extensive stability testing is carried out
purify the alcohol further by distillation. To obtain anhydrous to ensure the formulation will not degrade or precipitate over time.
alcohol (>99%), another solvent must be added. Finally, in
many countries, denaturants are added to ethanol to prevent it
40

Air Fresheners A typical wick-type formulation can be prepared by mixing

Devices to fragrance rooms can take a number of forms: They can the ethanol base (70%) with the fragrance blend (6%) and a
be passive evaporative/diffusion devices; they can involve heat to stabilising surfactant such as an ethoxylated castor oil or fatty
accelerate evaporation; or they can involve spraying the fragrance acid (6%) to form a clear solution and then diluting with 8% of
into the room via an aerosol or other device. demineralised water.
Diffusion Devices Traditionally, potpourri is a mixture of dried A more advanced system involves dispersing the fragrances in polymer
plant material (e.g., fragranced wood shavings, lavender, marjoram, gel. The gel is opened to the atmosphere and the fragrance allowed
rose flowers, etc.) with a pleasing fragrance placed in a bowl or sheer to evaporate slowly. The solvent-soluble polymer gel was originally
fabric in the room. Nowadays, potpourri tends to contain attractive carrageenan gum (sulphated polysaccharide polymers extracted
pieces of dried plant material impregnated with the fragrance. from red seaweed), but other gelling agents are also used, such as
carboxymethyl celluloses, alginate (polysaccharides from seaweed),
Simple diffusion devices involve the evaporation of the scent from guar gums (nonionic polysaccharides obtained from guar beans) or
a solution of the fragrance into the air and its distribution around even clays. The polymeric gel and the solvent (e.g., ethanol or propylene
the room by air turbulence. The scent is a blend of fragrance glycol) can be adjusted to control the release of the fragrance. The gel
compounds, the most volatile of which will evaporate first and the can be transparent, attractively coloured and contain fragments of
others more slowly. If each component has a different fragrance, plant leaves or fruit to make them more appealing.
the scent will change with time. Formulating the blend with
higher concentrations of the least volatile ingredients will help Some air-freshener devices involve heating. The fragrance is
maintain the relative concentration of the individual fragrances in dispersed in a matrix that is gently heated by plugging it into an
the air constant over the lifetime of the air freshener (e.g., “linear electrical socket.
fragrances”). Alternative methods to make certain that the scent
does not change with time includes ensuring fragrances with Candles Originally candles were used to provide light; now they
different volatilities have similar odours or utilising slow-release are designed to fragrance rooms. Initially, the customer chooses
technologies. The rate of evaporation of the fragrance will also which candle to buy as a result of its “cold throw,” which is its
depend on the molecule’s interaction with other fragrances, the appearance and fragrance when unlit in the shop. When lit, the
solvent, and any wick or pad. In any event, however, the amount candle should give a strong and characteristic odour that fills the
of fragrance that evaporates initially will be high and will decrease room with scent. Candles can contain up to 5% fragrance, which
over the 30- to 60-day lifetime of the device. is composed primarily of top and middle notes; base notes are not
41

required. Finally, the candle must be safe to use and should burn wax. Usually the fragrances are dissolved in a solvent, such as
smoothly; in the US it is estimated that candles are the cause of dioctyl adipate, mineral oils or capric/caprylic triglycerides.
10% deaths and injuries in fires (Hall, 2009).
The perfume must not affect the burning of the candle; ideally, it
Candles are available in a number of designs, such as tapers, should simply vapourise in the flame and fragrance the room.
votives, pillars and jars, and the wax used in each type needs to Candles also contain colourants, often azo compounds that can
be slightly different. For example, taper candles must have a high react with the fragrances, and high concentrations of fragrance
melting point so they do not distort. Various additives are used to can affect a candle’s colour. Fragrances are degraded by light, so
modify the properties of the wax. Most candle wax is petroleum candles often contain stabilisers and chelants. Long-term testing
based, although it can also be made from natural waxes. The wick is required to ensure the candle, wax, fragrance and colouring are
is a piece of string or cord that transports the melted liquid wax to stable during storage and use.
the flame by capillary action.
Spray Air Fresheners The most immediate way of distributing
The wick of the candle is lit by a flame from a match, and the a fragrance around a room is by a fine particle spray. The smaller
heat generated melts and vapourises the surrounding wax. The the liquid droplets, the longer they will remain dispersed in the air
vapourised wax is the fuel that enables the candle to continue to before settling but the more rapidly they will evaporate. Simple
burn, vapourise and consume more wax. Wick that is not emitting pump sprays can be used, but the most effect method is to use a
vapourising wax slowly burns, reducing the height of the candle pressurised aerosol-can dispenser.
and ensuring the burning and heat generation continues at a
uniform rate. The temperature of the flame varies from zone to Aerosol cans are usually made of tin plate or aluminium sheet
zone, but on average is about 1,000°C. crimped together, and the can contains the fragrance solution.
Pressure is supplied by including an odourless liquid propellant.
Paraffin waxes are nonpolar, and most fragrances are alcohols, The liquid propellants used to be chlorofluorocarbons (CFCs),
aldehydes, esters and alcohols which are slightly polar. Therefore, which have been banned since it was discovered they destroy the
care must be taken to ensure the polar fragrances are not extruded earth’s ozone layer. Nowadays the propellant is usually a volatile
from the wax with time. Fragrances that are not compatible hydrocarbon, often a blend of butane isomers and propane, which
with the wax can also sublime, depositing the fragrance on cold has the disadvantage it is flammable at concentrations in the air
surfaces. This is a particular problem with crystalline fragrances between 2 to 9 wt%. A commonly used propellant, Butane 40,
such as vanillin. The fragrance must also be soluble in the molten exerts a pressure of 40psig at 210°C. The advantage of using a
42

volatile liquid propellant is that the pressure in the can remains A typical aqueous-based aerosol formulation is shown in Table 4.2.
constant as long as the liquid is present. If a pressurised gas is The surfactant, the alcohol, fragrance blend, an odour neutraliser
used, the internal pressure will decrease with time. and corrosion inhibitors (to protect the metal in the can) are
blended together and then mixed with the water/glycol solution;
Pressing the actuator (Fig 4.4) depresses the spring cup against 40% of the aqueous dispersion is then charged with 60% of
the spring allowing the pressurised liquid to pass the value into the butane into the aerosol can.
narrow orifice where the liquid is broken down into very fine liquid
droplets that is sprayed into the surrounding air. TABLE 4.2 Typical aerosol air-freshener formulation
Ingredient Amount (%)
Surfactant (e.g. sorbitan ester) 1.5
FIGURE 4.4 Aerosol spray can
Triethylene glycol 2.5
Isopropyl alcohol 4.0
Water 90.0
Odour neutraliser 1.0
Fragrance Blend As required
Corrosion Inhibitors As required
Source: IntertechPira, adapted from various
Each can is tested in a water bath at 50°C before being

despatched to ensure it can contain the pressure.
World patent 2006/00507, assigned to Procter & Gamble,

discusses the formulation of an air-freshener fragrance.
A number of modifications to simple air sprays have been made.

Small battery devices have been developed that squirt jets of
fragrance into the atmosphere at adjustable, predetermined
intervals. More sophisticated devices are fitted with sensors to
Source: www.boxvox.net/2009/05/4-aerosol-paint-can-spin-offs.html detect the malodour and counteract it with a squirt of air freshener.
43

Personal-care Formulations Bars of soap are relatively alkaline (pH 9-10), and they must not
Fragrances are an important part of personal-care products, such discolour in sunlight. Raw vegetable carboxylate soaps are a cream-
as soaps, bath and shower gels, antiperspirants and shampoos, as yellow colour. They are rendered opaque (and whiter) by adding
they make the product nicer to use and they enhance their effect. titanium dioxide powder (TiO2). A whitener (containing a blue
pigment and a fluorescent whitening agent) can be added to make
Soap Soaps are the salts, usually the partially water-soluble sodium pure white soaps; dyes are added to make other colours.
or potassium salts, of carboxylated fatty acids. They are prepared
by reacting vegetable or animal (tallow) fats, which are fatty-acid Fragrances are added to the soap to mask the odour of the fatty
glycerides, with concentrated alkalis, usually caustic soda. The soap soap, to provide a fragrance during washing in warm water and to
is dried, formulated with emollients, colouring, possibly antibacterials leave a pleasing scent on the skin once washing is complete. The
and fragrances and made into bars. They are rubbed with water to fragrances must be alkali stable. Vanillin is totally unsuitable as it
solubilise, disperse and remove dirt and oils from the body. rapidly browns in the alkali in the presence of sunlight light. Ethyl
vanillin is also unstable, but as it has a stronger odour can be used
In many parts of the world bars of soap are used to wash laundry at lower concentrations and has less effect on colour. Vanilla cresol
by hand. But rather than soap, which forms an insoluble scum [2563-07-7] is an alkali-stable alternative with a vanillin-type odour
with hard water, the bars are made of at least some or perhaps all that could be used in its place. Other alkali unstable perfumes
synthetic sulfated detergents. include eugenol [97-53-0], isoeugenol [97-54-1], heliotropin [120-
57-0], certain mosses, Schiff’s bases, citral [5392-40-5], and indoles.
FIGURE 4.5 Soap manufacturing chemistry
Liquid soaps are made with blends of sulfate, sulfonated and
nonionic surfactants as dilute (20%-30%) solutions in water with
high concentrations of fragrances. They have a neutral pH and
are more soluble and better at cleaning than carboxylated soaps,
particularly in hard waters.
Hair Shampoos Hair shampoos are primarily designed to wash

the hair and scalp, but they also need to be easy and pleasant to
use and leave the hair feeling good and easy to comb. As they are
used on the skin and could get into the eyes, shampoos must be
44

mild. A shampoo must deal with the oils secreted by the sebaceous Polyquaterniums is the INCI name for cationic polymers, such
glands in the scalp, pollutants and particulate matter trapped in as quaternised hydroxyl ethyl cellulose (polyquaternium-10).
the hair. The isoelectric point of hair fibres lies between 5.5 and Their positive charge enables them to absorb onto the negatively
6.2; the pH of shampoos should fall within this range. charged surface of the skin and hair, reducing static. They interact
with anionic surfactants, reducing their interfacial tension. They are
A basic shampoo formulation is shown in Table 4.3. It contains a easily washed off by the shampoo and thus also act as rinse aids.
diluted blend of water-soluble anionic, nonionic and amphoteric
surfactants. The surfactants are designed to produce a stable Silicone polymers, such as ethylene oxide and amino copolymers
foam because consumers take this as an indication the shampoo of poly(dimethylsiloxane), dimethicones, are used to improve the
is working well. They are resistant to hard water and do not form feel of washed hair. They absorb onto the surface of the hair,
a scum. Its pH can be controlled by the addition of small amounts reducing static and imparting a silky feel.
of NaOH or citric acid. The viscosity of these liquid cleaners can be
affected by the fragrances that are used. Further modifications to Proteins and amino acids from vegetable sources such as
viscosity can be made by adjusting the amount of salt (e.g., NaCl) wheat, maize, soya or almond proteins are believed to improve the
added, or by using water-soluble thickeners. mechanical properties of hair.
TABLE 4.3 Typical hair-shampoo formulation Ceramides are cationic lipids that are found in cell membranes,
Ingredient Wt% Comment hair contains 0.01% of them. Synthetic ceramides absorb onto
Demineralised water ~75
damaged hair, protecting it from further mechanical and UV
Sodium lauryl sulfate 8 Anionic surfactant
Cocoamidopropyl betaine 7 Amphoteric surfactant
damage.
C12-16 fatty-acid glucoside 4 Nonionic surfactant
Lauryl alcohol 2EO 0.9 Nonionic surfactant Panthenol is oxidised in air to pantothenic acid, vitamin B12,
NaCl 3 which is important for hair growth. Panthenol also moisturises and
Perfume As required improves hair texture.
Preservative As required
Note: appearance is typically clear; pH is 5.5 and viscosity is 8,000mPas
Source: Adapted from Cognis
Glutamic acid enhances hair growth.
Other ingredients can be added to achieve other effects. These Antidandruff agents such as zinc pyrithione and piroctone
include: olamine are added to control dandruff.
45

Shower Gels The composition of shower gels is similar to that of after sports might have a fresh, minty fragrance; a gel specifically
shampoos, although they tend to contain more fragrance as the formulated for swimmers would likely contain an anti-chlorine
retention of scent by the skin is less than that of the hair. A basic fragrance with a small quantity of thiosulfate to destroy the
shower-gel formulation is given in Table 4.4. chlorine. Baby wash gels must be very mild; those formulated for
adults might have flowery aroma fragrances intended to relax the
TABLE 4.4 Typical shower-gel formulation user. Bath gels have similar formulations.
Ingredient Wt% Comments
Deionised water ~45
Antiperspirants and Deodorants Humans have between 3
Sodium laureth sulphate 30 Mild foaming surfactant, Na
(26% active) lauryl ether sulphate 1 mol EO
and 5 million eccrine sweat glands distributed over their bodies,
Cetrimonium chloride (25% 1 Emollient, conditioner particularly on the soles of the feet, the palms of the hands and
active) on the scalp. These glands work continuously to help maintain
Capryl/capramidopropyl 13.5 Mild amphoteric surfactant and the body temperature by releasing up to 2 litres of perspiration
betaine (37.5% active) conditioning agent
per day when the body is excessively hot. Perspiration is mainly
Glycerin 0.5 Humectant
Sodium cocoamphodiacetate 8 Foam booster and viscosity
composed of water (99%) and small amounts of salts, urea,
(37.5%active) builder proteins, etc. The evaporation of this water from the skin cools the
Chelate 0.1 EDTA body. Antiperspirants are used to help prevent sweating and to
Sodium hydroxide As required pH adjustment reduce the formation of unsightly and uncomfortable perspiration,
Citric acid As required pH adjustment
particularly under the arms. Deodorants, which contain biocides
Sodium chloride As required Viscosity modifier
Fragrances As required
and fragrances, act against the microorganisms present in
Dye, preservatives As required perspiration which degrade proteins producing malodours, which
Note: appearance is typically clear; pH (at 25°C) is 5.5 – 6.5; viscosity (at 25°C) are masked by the fragrance. Antiperspirants and deodorants are
is 2,500 – 3,000cps available in many forms, including sticks, roll-ons, aerosols and gels.
Source: Adapted from Stepan
It was discovered in the 1920s and 1930s that aluminium chlorides
Shower gels can be clear or cloudy. They tend to have high, often and sulphates reduced perspiration, but the salts were acidic
pseudoplastic (shear thinning) viscosities, as they are often stored and caused major skin irritation. In the 1940s, basic aluminium
in bottles that are placed upside down in the shower cubicle. chlorides or aluminium chlorohydrates (ACH) were developed with
Their formulation is varied to achieve different effects, and their a more acceptable pH of 4. Since then, a number of other, even
fragrance is adjusted to enhance these effects. Shower gels for use more effective aluminium chlorohydrate and aluminium zirconium
46

chlorohydrates (AZCH), have been developed. They are available breathing. The polymer also gives the skin a silky feel and
as aqueous solutions containing up to 50% actives, powders of helps retain the active ingredient on the skin.
different particle size, and as solutions in propylene glycol.
It is thought that the soluble aluminium-based antiperspirants work A schematic diagram of an aerosol can is shown in Fig
by diffusing into the sweat glands. Neutralisation of the ACH forms 4.4. The valve on the internally lacquered spray can needs
insoluble aluminium hydroxide-protein gels, which partially block to be modified to enable it to spray the powder dispersion.
and reduce the flow of sweat.
TABLE 4.5 Typical antiperspirant aerosol-spray formulation
Gels Antiperspirants and deodourants can be applied Ingredient Wt% Comment
Isopropyl myristate 10
to the skin in various solid, gel or roll-on forms. The
Bentonite 3.6
gel continuous phase can be water, alcohol (ethanol Volatile silicone fluid 48.6 Cyclopentasiloxane, BPt >65°C
or propylene glycol) or, more recently, silicone based. Activated ACH powder 36
Whatever their continuous phase, they are often gelled High-molecular-weight 0.5 High-viscosity dimethioconol polymer
using stearates. The ACH active can be soluble in the silicone polymer in cyclomethicone solvent.
continuous phase, or if the viscosity is high enough to Fragrance 1.2
prevent sedimentation, dispersed as particles. They often Note: aerosol fill is typically 25% concentrate and 75% propane-butane propellant
contain antibacterial agents such as triclosan.
Volatile cyclic silicone oligomers are becoming increasing A number of fragrance ingredients react in the presence
popular in the continuous phases. They evaporate rapidly of the acidic ACH and cannot be used. These include
from the warm skin without significant cooling. They also phenolics, unsaturated terpene alcohols and esters
leave a pleasant nonoily feel to the skin. (e.g., linalool [78-70-6] and linalyl acetate [115-95-7]),
unsaturated or reactive aldehydes (e.g., lilialdehyde [80-
Aerosols Antiperspirant aerosols are dispersions of 54-6], lilyall [ 80-54-6] and ligustral [68039-49-6] and
activated micronised ACH powders dispersed in a some essential oils such as bergamot, lavender, rosemary,
butane soluble, low-viscosity volatile cyclopentasiloxane citrus oils and spices (e.g., nutmeg and black pepper).
(INCI name cyclomethicone) fluid (Table 4.5). A high- Care must also be taken to eliminate metal ions that
molecular-weight silicone polymer is included to prevent could discolour fragrances.
the formation of an aerosol cloud that can interfere with
47

Once the formulation is sprayed, the more volatile top environmental impact, packaging and transport costs. Single-dose
notes will evaporate almost immediately, so particular solid tablets and liquid capsules are also used, in Northern Europe
care must be taken balancing the concentrations of and particularly in the UK.
the different notes. As usual, their interaction with the
silicone solvent will affect their volatility and thus careful Globally, the cost of a detergent is the most important factor
development is needed to formulate the correct balance that determines which brand a consumer buys. In the developed
of ingredients. markets of North America and Europe, consumers also rate
performance and convenience as important purchasing criteria.
There are interesting demographic differences in the Consumers can afford to pay for detergents that are convenient
types of products used in different regions. Consumers in and pleasant to use, and so fragrance plays an important role in
the North and South America and the UK prefer to use deciding which brand to buy. The perfume is designed to fragrance
antiperspirants and deodourants; those in continental the detergent and suppress or swamp the odour of the ingredients,
Europe prefer to use just deodourants. In the US solids but more important, to scent the clothing being washed. This is the
and roll-on products are preferred; in the UK consumers primary function of fabric conditioners—cationic systems that are
prefer aerosol-based products. incompatible with anionic/nonionic laundry detergents and must
be added separately at the end of the wash. Cationic surfactants
Fabric Care reduce static and improve the feel of the washed clothing. They are
Laundry-care products account for half of the cleaning products also heavily fragranced with a wide variety of scents to appeal to
sold, and most of these are laundry detergents—more specifically, individual consumers.
heavy-duty laundry detergents (HDD). Globally, most laundry
detergents are sold as granular powders, which in the developed Laundry-cleaning products can be divided into solids and liquids, as
world are used in washing machines (Smallwood, 2011). In the their composition and technology are slightly different (Table 4.6).
developing world, most washing is done by hand using bars of
soap, although these are slowly being replaced by powders. In the TABLE 4.6 C
omposition of typical European powder and liquid heavy CLICK TO VIEW TABLE
developed world, particularly North America, powders have been duty detergents
replaced by liquids. Liquid detergents have also gained significant
market share in Europe but not the dominance they have achieved Both types of detergents contain surfactants that solubilise dirt
across the Atlantic Ocean. There is a trend toward using compact and soil, although the types of surfactants differ (Table 4.6). Both
powders and concentrated liquid detergents to reduce their contain builders that remove the Ca2+ and Mg2+ ions present in
48

hard water that impair the surfactants. Most modern detergents Fabric softeners can contain other compounds to improve their
contain enzymes to help remove proteins, carbohydrates and fatty performance: Anywhere from 1% to 2% of sacrificial scavenging
dirt and stains. Detergents also contain other ingredients such cationic polymers (e.g., cationic polysaccharides such as guar
as polymers that complement builders, aiding the dispersion and or starches) can be added, which precipitate residual anionic
removal of dirt into the wash water, as well as optical brighteners, surfactants remaining on the textiles from the earlier main wash,
preservatives, and, of course, fragrances. preventing them from precipitating the cationic fabric conditioners.
Other fabric softening compounds such as glycerol fatty esters,
The major difference between solids and liquid detergents is that the sucrose esters and silicones can be included. Supermarket shelves
latter do not contain bleaches; the reactivity of bleach means that they contain rows of fabric softeners, all containing similar actives but
cannot be stored with the other ingredients in aqueous detergents. with different fragrances to suit individual tastes.
Fabric softeners are added during the later stages of the wash to Laundry products used by industrial and institutional (I&I) users
improve the feel and fragrance of the laundry. Softeners’ main account for 20% of the detergent market in Europe. They contain
ingredients are cationic surfactants, and they are slightly acidic with similar ingredients as fabric softeners, but are more powerful and
a pH between 4 and 7. The fatty hydrophobic group (usually a C16-C18 aggressive liquids that are not suitable for handling by hand. They
stearic group) absorbs onto the surface of the textile, imparting are used by skilled operators in large machines, in which liquid
a smooth feel. The cationic hydrophilic group reduces static by detergents and boosters are automatically metered into the wash
neutralising anionic groups and increasing surface conductance. In when required.
Europe fabric softeners contain 5% or 10% esterquats, which, because
of their ester bonds, are more biodegradable than traditional quats. Powder detergents contain less surfactants and more builders,
and as they contain very little water, they can be formulated with
FIGURE 4.6 Cationic surfactants peroxide bleaches. They are mm-size granules that are dissolved
in water immediately prior to use. They are made by spray drying
or granulation. The liquid fragrances are added in the final
manufacturing stage, along with heat-sensitive enzymes, once the hot
granules have been allowed to cool. It is important that the fragrance
does not cause lumping, which adversely affects powder flow.
Note: Esterquat (left) and quat

49

The amount of fragrance remaining on clothing that has been washed ADDs can be powders or liquids with compositions similar to
and dried in a tumble dryer can be quite small. To improve their uptake laundry detergents with more emphasis on the use of builders.
and retention, fragrances used in fabric softeners tend to be less water The move away from phosphate builders for environmental
soluble, have higher boiling points and lower volatilities so that they reasons is having a detrimental effect on their performance so the
adsorb more strongly and are retained on the fabric. Encapsulated and industry is working hard to develop effective alternatives. ADDs
pro-fragrances (Chapter 3) can be used to further enhance fragrance are just starting to contain enzymes. In Europe consumers prefer
retention. The proportion of volatile top notes in laundry detergents to use single-dose tablets. Historically, consumers added a water
tends to be relatively low (~15%). The top notes provide the fragrance softener at the start of the wash cycle, then the washing detergent
first detected when the pack of detergent is initially opened. and, finally, the rinse aid. These have been replaced by tablets
containing 3 or even 4 sets of ingredients designed to be released
Household-care Products at the appropriate stage of the wash.
There are many types of household cleaners that are used to clean
different surfaces (hard-surface cleaners) around the home; the Various other surface-cleaner formulations are available for
largest category is dishwashing detergents. cleaning different parts of the house. They are often liquids,
containing 10%-20% actives, dispensed from handheld spray
Dishwashing Detergents Hand dishwashing detergents are containers. The surface is wiped with a cloth to remove the dirt
widely used around the world. They are liquids with a similar and spent cleaner. Kitchen cleaners have a fresh fragrance and
composition to shampoos and shower gels with surfactants will contain surfactants designed to solubilise grease. Bathroom
designed to cut through grease. They must be mild on the skin, cleaners contain limescale removers (chelating agents and
produce a stable foam, and be attractively coloured and smell nice. polyacrylate polymers). Both will be fragranced and coloured, and
Many also contain antibacterial agents. some contain antibacterial agents. Other cleaners are designed
for use on floors and furniture, and there are nonstreaking
More affluent consumers can afford dishwashing machines, formulations for windows and cars, as well as multisurface products
which use automatic dishwashing detergents (ADDs). Whereas for use on many substrates (Smallwood, 2009). Most all of these
most households in the developed world have laundry washing cleaners contain fragrances.
machines, the penetration of dishwashing machines is significantly
lower (Smallwood, 2011). The statistics suggest that as well as Cleaning carpets presents special problems as fitted carpets cannot
buying ADDs for their dishwashing machines, households continue be easily removed. They are washed in place, using the minimum
to use hand dishwashing detergents. amount of water because drying them is difficult. Some carpet
50

cleaners are foaming aqueous liquid shampoos that are applied to is made by reacting chlorine with caustic soda, both of which are
the carpet and release the dirt and dry to form stable foams. Other obtained from the electrolysis of brine (common salt):
types are powder products that are sprinkled over the carpet before
being removed with the liberated soils via a vacuum cleaner. Carpet Cl2 + 2NaOH → NaClO + NaCl + H2O
cleaners are heavily fragranced to leave the room smelling pleasant. (chlorine + caustic soda → hypochlorite)
Bleaches There are two main types of bleach, those based on A slight excess of NaOH is used to keep the pH >11 as hypochlorite
chlorine such as hypochlorites and those based on peroxides. is unstable at lower pHs. Most hypochlorite bleaches have a pH of
Bleaches have two main functions. In household and industrial 12 to 13.5. At pH <4 hypochlorites evolve chlorine and thus they
care, chlorinated bleaches are used as disinfectants on heavily must not be mixed with acids. Hypochlorites are also destabilised
contaminated areas such as toilets and drains. Chlorine is also by metal ions, air and sunlight, and should be stored in opaque
widely used to kill microorganisms and purify water. In parts of bottles in a cool place.
the developing world, diluted hypochlorite solutions are used as
cleaners (e.g., floor cleaners). In other regions, household cleaners Toilet and industrial bleaches contain up to 15% hypochlorite,
are more likely to contain milder antimicrobial agents. domestic laundry bleaches are more diluted at 3% to 6%
hypochlorite. Diluted domestic bleaches are more stable and are
In laundry, bleaches are used to remove coloured stains, and dirt and easier to formulate.
soil from the textiles being washed. Because of their reactivity, bleaches
tend to be added to the wash separately. Diluted liquid chlorine Many compounds are unstable in the presence of bleach because
bleaches are preferred in North America, Southern Europe and the of its high pH and reactivity. It is also important that the bleach
developing world, peroxide-based bleaches are preferred in Northern ingredients do not destabilise the hypochlorite. Most surfactants
Europe. Peroxide bleaches and bleach activators can be incorporated are unstable; sulphates are more stable than sulfonates, so sodium
into granular powder detergents but not into liquid detergents. alkyl sulphates are used (provided alkyl chain length is <C12).
The most common surfactants used in bleaches are the alkylated
Chlorine-based bleaches are very effective and cheap, but they react diphenyl oxide disulfonates, such as Dowfax 2A1. Phosphate ester
rapidly with organic compounds and are unstable. They remove dirt surfactants are also bleach stable.
certainly, but they also react with coloured dyes on textiles, and they
attack wool, silks and synthetic fabrics (they are considered safe on Similar problems occur with fragrances, many of which are unstable
cottons). They are aqueous liquids containing hypochlorite, which in strongly alkaline solutions and in the presence of strong oxidising
51

agents. Fragrances that are stable in bleach are highlighted in List of

fragrance compoounds in the Appendix. Hypochlorite bleaches have a
strong base odour that is difficult to mask. The stability of fragrances can
be improved by encapsulation.
Careful long-term testing of the stability of the fragrance and stability

of the fully formulated bleach is very important. Its stability should be
compared with the stability of an unfragranced control as it will also
degrade with time.
Hydrogen peroxide solutions are also unstable and are not widely used,
except as bleach in hair-care applications. Metal ions catalyse their
degradation so formulations usually contain a chelating agent such as
EDTA to remove destabilising metal ions. They are most stable under
acidic conditions at pH 2 to 5. Most surfactants can be used with
hydrogen peroxide. Their viscosity can be controlled by careful choice of
surfactants and ionic salts. They can also be thickened by polacrylate
polymers.
Oxygen-based bleaches for use in laundry detergents are based on

solid percarbonates. Perborates have been phased out because of
environmental concerns over the buildup of boron in surface waters.
Laundry detergents usually contain activators that enable the formation
of active bleach species (peracids) at lower temperatures (down to
40°C). Percarbonate bleaches, and TADD and NOBS activators, can be
formulated into stable powder detergents, but because of their chemical
instability in solution, they cannot be incorporated into liquids (Table
4.6). As a result, sales of granular percarbonate detergent boosters are
rapidly increasing as consumers switch to bleach-free liquid detergents.
52

Future Trends
5
Introduction sense. Helped by the introduction of better washing machines, The protection of
The market for fragrances is like fashion, consumers’ preferences consumers are altering the way they wash to minimise water usage, our environment
change over time. The natural clean scents of a few years ago have wash temperatures and CO2 emissions. But it is clear that while and improving
been replaced by ozone and fruit fragrances and more recently consumers prefer to buy environmentally friendly products, their
exotic superfruit odours. It is for the marketers to identify the most important purchasing criteria is that the product is effective
sustainability has
fragrances of tomorrow. The industries’ task is to be able to offer and reasonably priced (Smallwood, 2010). The rapid increase in been guiding the
what the market requires and to develop new fragrances and demand for premium “green products” in 2008 and 2009 has been development of
technologies to offer the market exciting new fragrance options. replaced by a more pragmatic approach, no doubt influenced by new products for
In this chapter we will discuss how the industry is facing the the continuing recession. over a decade.
challenges of the future.
Sensitisation by Fragrances and Animal Testing The
Environmental and Green Issues concentration of fragrances in care products is very low, so the
The protection of our environment and improving sustainability environmental issues faced by the fragrance industry are different
has been guiding the development of new products for over a to those faced by detergent producers. Because the concentration
decade. Personal-, fabric- and home-care products are used in of fragrances in cleaners is so low, exposure to fragrances is low
large quantities, in close proximity to people, and the waste and toxicity and biodegradation effects are less of an issue. The
products are discharged into local water courses. Thus, toxicity and problem for fragrances is that many trigger allergic responses or
environmental issues have always been important. Sustainability skin irritation in those who use the product and wear the cleaned
improvements have been driven by consumer preferences and by clothes. It is a difficult problem to deal with as it can be triggered
the introduction of strict government regulations, which specify by very low concentrations of agents and its effect varies from
what ingredients can and more important, which cannot, be individual to individual. It is important, though, because a bad
included in formulations. Current European legislation sets strict experience will cause a customer to buy a different product.
toxicity and biodegradability criteria for all cleaning products. Thus,
all products have to conform to basic standards of good practice. The industry has tackled this problem by establishing a very
The only green issue left for products to compete on is their use of effective system of self-regulation. It is important this system
natural sustainable rather than petrochemical-sourced ingredients. continues to enjoy the respect of both regulatory authorities
Care-product producers are ensuring that their production processes and consumers; it must continue to remain effective and remain
are as sustainable and nonpolluting as possible, which not independent of the fragrance industry.
only appeals to their customers but also makes good economic
53

Future Trends
To ensure that a fragrance is safe, it needs to be tested, which from petrochemical or other fragrances, it is impossible to tell the
used to be done on animals, a practice abhorrent to most modern difference. Other synthetic fragrance molecules are completely
consumers. Registering a product for REACH requires the applicants artificial and have not yet been found in nature. The development
to submit a dossier of test results to convince the ECHA that the of synthetic fragrances has transformed the industry, allowing
compound is safe to use. This, coupled with the need to identify fragrances to become available to a much wider group of people. It
and restrict the use of allergens, is likely to increase the amount is unlikely it will be possible to return to using fragrances sourced
of testing required. It is important that animal testing is replaced naturally, except perhaps for ranges of expensive perfumes.
by alternative methods. A number of companies have developed
In Vitro test procedures using human tissue culture as models for Yet consumers are more comfortable using naturally sourced
human skin (e.g., www.matek.com, www.apredica.co.uk and www. ingredients. They feel they are better for the environment and that
ceetox.com). This type of testing will be used more widely to meet natural products are nontoxic and less likely to irritate the skin. This
the authorities demand for more test results, while satisfying the is untrue, however, as there are sensitising natural fragrances just as
consumers’ demand to cease animal testing. there a benign synthetics; in the end, each compound must be judged
on its merits, regardless of its source. Consumers still prefer naturals,
Natural vs. Synthetic Fragrances Perfumes derived from but unless they are prepared to pay significantly higher prices for that
natural products have been used for many thousands of years, preference, they will continue to buy—and use synthetics.
but the choice of materials has been limited and their lack of
availability has made them expensive. The application of science The concern over the allergenic effects of fragrances, whether they
has led to the discovery of many thousands of synthetic reasonably are natural or synthetic, is very real. These concerns have led to
priced fragrance compounds, suitable for use in a wide range of a demand for fragrance-free products, and they became widely
consumer products, in many diverse applications. available. Since then, no doubt partly a result of the industries self-
regulation, these concerns have diminished and the trend is moving
Originally fragrances were isolated from both plants and animals, in the other direction; supermarket shelves are filling up with rows of
but the use of animal fragrances stopped many years ago. fabric conditioners, identical except for their fragrance. Consumers
Many are still obtained from plants but most fragrances are clearly like themselves, their clothes and living spaces to be
now manufactured synthetically; they tend to be cheaper, are fragranced and the demand for fragranced products has increased.
available in larger quantities and their supply is more reliable.
Nature-identical synthetics are identical to the compounds Other Green Issues Biodegradation, which has become a major
obtained from plants and although they are made synthetically issue with detergent ingredients, is unlikely to affect fragrances.
54

Future Trends
They are volatile and are unlikely to reach and pollute waterways. Dihydrojasmone [1128-08-1] and methyl dihydrojasmonate [24851-
The problem of VOCs (Volatile Organic Content), especially with air 98-7]), cost $15 to $80/kg (Jenner, 2006).
fresheners, is more likely to become an issue, although the absolute
quantity of volatile fragrances used are very small. Identifying fragrances from natural products has not always been
as easy. In the 1990s headspace and vacuum headspace analysis
Improving the manufacture of large-tonnage chemicals has become of lily of the valley led to the identification of the fragrance
an important issue. Fragrances are produced in much smaller dihydrofarnesol [37519-97-4], which, although it possesses a
quantities, and thus the amount of energy, raw materials and waste strong odour, is difficult to detect because of its very low vapour
generated during their manufacture are relatively small. But it is pressure. More recently, an excellent lily of the valley fragrance, iso-
still good practice to develop manufacturing processes that are as β-bisabolol, was found in a completely different source, in Australian
environmentally friendly and as green as possible. They are likely to sandalwood oil, and it has since been synthesised (Jenner, 2006).
be more efficient and less wasteful.
Serendipity Many fragrances have been found by “luck” by
The Search for New Fragrances investigators who were sufficiently open-minded to realise what
The search for new fragrance molecules continues as companies they had stumbled upon. Such serendipitous finds include the nitro
seek to develop new odours, to develop fragrances which are musks (Chapter 3). The oil from lily-of-the-valley is not available
stable in a wider range of formulations and to develop fragrances commercially but in the 1929 synthetic hydroxycitronellal [107-
to replace those whose use has been restricted because they have 75-5] and cyclamen aldehyde [103-95-7] were chance discoveries
been identified as potentially allergenic or hazardous. Various made by the Winthrop Chemical Corporation.
search strategies are employed.
Synthesis of Analogues Once a new fragrance has been
Using Clues from Nature This report has shown how the discovered it is common to prepare a number of synthetic analogues.
identification of fragrance components in natural fragrances and This is done in the hope that a molecule that is cheaper to make,
their subsequent manufacture by synthetic routes, has led to the that has a better fragrance or that has better stability is discovered.
development of a large number of new cheaper fragrances. For It also enables researchers to learn which molecular characteristics
example, 12 tonnes per year of Jasmine absolute, isolated from are responsible for the fragrance. Finally, analogues are also made
Jasmine flowers in Egypt and Morocco, costs $5,000 to $8,000/ to ensure that all possible leads have been considered when filing
kg. Nature-identical Jasmone [488-10-8] costs $500 to $800/ a patent, to prevent competitors from identifying and patenting
kg, while simpler cyclopentanones with a similar fragrance (e.g., alternatives that were not originally disclosed.
55

Future Trends
Ligand-Olfactory Receptor Modelling Scientists always try It is rational to suppose that molecular shape—the location in
to seek explanations for their observations. By trying to explain space of the atoms in the molecule—plays a role. Many molecular
the olfactory properties of a fragrance molecule on the basis of recognitions in biochemistry require a fit between a receptor and
its chemical structure, they hope to be able to determine how an antagonist, and this is how 7-TM proteins in other types of
fragrance molecules might interact with the ORC receptors in the receptor cells function. But while there is evidence that the shape
nose, in the expectation it will lead to the design of new molecules of a molecule determines the intensity of an odour, in spite of
with interesting fragrance properties. all the evidence that is available, it has not been possible to link
molecular shape with the character of the odour, because whatever
While little is known about the way signals from the Olfactory is proposed, there are always exceptions. In pharmacology, it is
Receptor Cells (ORCs) create the sensation of odours within our common that enantiomers (stereoisomers that are mirror images
brain, the discovery by Linda Buck and Richard Axel in 1991 of of each other) have very different activities. Fragrance enantiomers
the role ORCs play in our sense of smell was a major breakthrough usually (but not always) have similar odours. Also in pharmacology,
in our understanding of the olfactory process—and in 2004 the the concept of antagonist molecules is well known. These are
team won the Nobel Prize for their work. While a lot is understood molecules that bind to the receptor group more strongly than the
about their structure and about the way ORCs work (Chapter 3), fragrance molecule, blocking the receptor site thought they have
we still do not understand the process well enough to be able to no odour themselves. One weakness of the shape hypothesis is
predict whether a molecule will have olfactory properties. It is a that fragrance antagonists were unknown (Turin, 2005). Although
very active topic of research (Jenner, 2006, and Veithen, 2010) and recently Hatt (Hatt, 2005) claims to have found one.
it seems likely that biochemists will soon determine the mechanism,
enabling the discovery of many new perfumes. An alternative theory, which has been used with some success
(Turin, 2005), is that there is a better relationship between odour of
In the meantime, we must rely on other approaches to help with a molecule and its vibrational (IR) spectra than between odour and
the design of new fragrance molecules. The first requirement is that shape. Each chemical group exhibits its own unique IR vibrational
fragrances must be volatile, and as a result their molecular weight frequency and the frequencies from all of the groups in a molecule
must be less than 310. It is known that olfactory receptors respond contribute to its IR spectra. Thus the IR spectrum of a molecule is
to particular groups on a molecule and that a particular molecule determined by the chemical groups the molecule contains. The –SH
will interact with a number of different receptors. But at present, group has a unique sulfuraceous odour and a distinctive IR stretch
we cannot be certain about the mechanism of this interaction and frequency at 2,550 wavenumbers. The B-H stretch frequency of
various theories have developed. boranes is similar, and it has a similar smell despite containing
56

Future Trends
different atoms. This line of thought has been used to develop a and its effectiveness can be related to its substantivity. Using
number of new fragrances including more acid-stable versions of technology developed in the pharmaceutical industry it is possible
the lemon fragrance citral [5392-40-5], which in air, rapidly breaks to develop mathematical descriptions of molecular properties
down into some unpleasant-smelling compounds. The instability (QSARs). These include steric properties, electronic effects, 3-D
is due to the tail double bond. Replacing the double bond with a descriptors, hydrogen bonding, hydrophobicity, branching, etc.
cyclopropane ring, which has a similar vibrational spectra but is There are a number of different techniques for doing this. The
chemically more stable, led to the development of Acitral [877-60- final step is to relate the quantified molecular properties to the
1], which degrades over a period of days, yielding sweeter-smelling molecule’s organoleptic properties. For these analyses to be
degradation products. successful, it is necessary to carefully choose at least 5 of the best
molecules for each variable included in the molecular description.
Thus, both approaches have their own merits and have yielded The compounds should exhibit a reasonable spread of olfactory
results, but neither can explain all of the observations. It would properties for a useful correlation. Modern computers make this
seem that a combination of these approaches is more likely. It is work much easier, and a number of commercial computer packages
possible the ORCs are triggered by functional chemical groups, are available to help. Once the structure of the new fragrance has
yielding particular vibration spectra, but the groups need to be been identified, organic chemists need to synthesise it, which can
arranged in a particular spatial arrangement to trigger the ORC. be difficult.
Structure-Activity Relationship (SAR) SARs is a concept These approaches have led to the development of a number of
borrowed from the pharmaceutical industry based on the idea that new fragrances, including muguet ethanol [63767-86-2], which
fragrances that have similar structural features will have similar is stable in acidic and alkali-care formulations but not in very
odours. While it is clear this is not always true, it offers another acidic bleaches. Givaudan used floral pyranol [63500-71-0] as a
potential route to identify and synthesise new fragrances. The standard for muguet modelling work, which led to the development
first problem is to be able to quantify the odour of a compound. of Rossitol [215231-33-7] in the late 1990s. As with most newly
As we have seen, this is not always easy, as different testers have discovered fragrances, initially it is being used exclusively by
been known to describe odours differently. It also requires that Givaudan. Later it will be offered on the open market.
the test compound is ultra-pure, as minute amounts of impurities
can affect its smell. The next step is to quantify the molecules’ Manufacture of Fragrances by Biotechnology
structural properties. For example, we have seen how the odour of a Fermentation of microorganisms such as yeast is being investigated
fragrance is related to its molecular weight and its vapour pressure as a method of sustainably producing chemicals from carbon
57

Future Trends
sources such as sugar and cellulose. Microorganisms can be used

to produce very complex molecules such as the enzymes used
in detergents or simple chemicals such as ethanol, succinic acid
and polyols that are used as feedstocks for the synthesis of more
complex organic compounds.
A number of companies are working to use fermentation technology

to manufacture fragrances. Allylic (www.allylix.com), a small
startup company based in California and Kentucky has genetically
engineered yeast to produce two citrus extracts, nootkatoone
[91416-23-8] and valencene [4630-07-3] when fed with sugar cane.
They also claim to be able to prepare sesquiterpenes by a similar
route (Dolan, 2010). In the Netherlands, Isobionics (www.isobionics.
com) are also offering nootkatone and valencene, primarily for use
as a beverage flavouring, using similar technology.
The larger fragrance companies understand the potential benefits

of this approach. Firmenich and Givaudan have signed separate
agreements with the Californian biotech company, Amyris (www.
amyris.com) to produce unspecified fragrances.
58

References
Author Title Source Publisher Date

Berger, Ralf G Flavours and Fragrances: Chemistry, Bioprocessing and Sustainability Springer 2007
Bone, S et al Microencapsulated Fragrances in Melamine Formaldehyde Resins Chimia 65 (3) p177 2011
Da Costa, N and Eri, S Identification of Aroma Chemicals In Chemistry and Technology of Flavors and Fragrances, Ed D J Rowe CRC Press, Blackwell 2005
Publishing
Donlan K A Allylix Sniffs Out Biotech for new Fragrances Forbes Magazine, 8th Nov 2010 2010
Doszczak, L et al Silylating Reagents: A Powerful Tool for the Construction of Isosteric Analogs In “Perspectives in Flavor and Fragrance Research” Edited by Kraft, P and Wiley-VCH 2005
of Highly Branched Odourants Swift, K A D
Ellis, Graham Special Issue 40th ISEO: Toxicological Challenges for Essential Oils in REACH Flavour and Fragrance Journal 25, pp138-144 2009
Ester, s and Oliveros, E A Quantitative Study of Factors that influence the Substantivity of Fragrance J Am Oil Chem Soc 71(1), pp31-40 1994
Chemicals on Laundered and Dried Fabrics
Fahlbusch, KG et al Flavors and Fragrances Ullmanns Encyclopedia of Chemical Technology Wiley-VCH 2005
Friberg, S et al Stability Factors and Vapour Pressure in Model Fragrance Emulsion System J Soc Cosmetic Chem 50(4), p203 ]219 1999
Hall, John NFPA 2009 http://www.nfpa.org/assets/files//PDF/Research /Fire_overview_2009. 2009
pdf
Hatt, H Molecular and Cellular Basis of Human Olfaction In “Perspectives in Flavor and Fragrance Research” Edited by Kraft P and Wiley-VCH 2005
Swift K A D
Herman, S J Applications II: Fragrance In Chemistry and Technology of Flavors and Fragrances, Ed D J Rowe CRC Press, Blackwell 2005
Publishing
Hofer,D Antibacterial silver does not Affect Skin’s Natural Bacteria Advances in Textile Technology, Feb 2011 2011
Howard, Philip H and Handbook of Physical Properties of Organic Chemicals CRC Press, Lewis 1997
Meylan, William M Publishers
Jenner, Karen The Search for New Fragrance Ingredients In The Chemistry of Fragrances, Edit C Sell RSC Publishing 2006
Kaiser, R Vanishing Flora ]Lost Chemistry: The Scents of Endangered Plants Around the In “Perspectives in Flavor and Fragrance Research” Edited by Kraft P and Wiley-VCH 2005
World Swift K A D
Kuhn, H et al Mechanism of the odour ]adsorption effect of zinc ricinoleate: A molecular J Surfactants and Detergents, 3, p335 ]343 2000
dynamics computer simulation
Ohloff, G et al Scent and Chemistry: The Molecular World of Odours Wiley-VCH 2011
Rowe, D Chemistry and Technology of Flavours and Fragrances Blackwell, CRC Press 2005
Sell, C Chemoreception In The Chemistry of Fragrances, Edit C Sell RSC Publishing 2006
Smallwood, P V Disruptive Technologies in Cleaning Products IntertechPira 2010
Smallwood, P V Liquid Detergents IntertechPira 2011
Surburg, H and Panten, Common Fragrance and Flavor Materials Wiley-VCH 2006
J
59

Turin,L Rational Odorant Design In Chemistry and Technology of Flavors and Fragrances, Ed D J Rowe CRC Press, Blackwell 2005
Publishing,
US 2008/0132437 Fabric Care Compositions for Softening, Static Control and Fragrance Benefits Procter & Gamble 2008
US2009/180977 Controlled Release Compositions Dow Corning 2009
US6200949 Process for Forming Solid Phase Controllably Releaseable Fragrance ] IFF 2001
Containing Consumable Articles
US6534091 Microcapsules Cognis 2003
van Soest, Jeroen J G Encapsulation Flavours and Fragrances: Chemistry, Bioprocessing and Sustainability, Edit Springer 2007
Berger, R G
Veithen, A et al Olfactory Receptors Perfume and Flavorist 35(1), Jan 2010, pp38-43 2010
WO2009/121831 Controlled Release Particles Akzo 2009
WO2009153209 Modified Polymeric Pro-Fragrance Henkel 2009
Zviely, M Aroma Chemicals II: Heterocyclics In Chemistry and Technology of Flavors and Fragrances, Ed D J Rowe CRC Press, Blackwell 2005
Publishing

Useful websites:
Leffingwell & Associates: www.leffingwell.com

International Fragrance Association: www.ifraorg.org
Research Institute for Fragrance Materials: www.rifm.org
The Good Scents Company: www.thegoodscentscompany.com
Procter & Gamble: www.scienceinthebox.com
60

Appendix
TABLE 7.1 List of fragrances

Common Name IUPAC Name CAS STRUCTURE Mol Formula Mol Wt SOURCE FRAGRANCE USES Log P Subs Vap Press Mpt BPt
hours mm/Hg
250C
LINEAR ALIPHATIC ALCOHOLS
Amyl alcohol pentan-1-ol 71-41-0

Leaf alcohol Cis-3-Hexen-1-ol 928-96-1 C6H12O 100 Natural Powerful freshly 1.40 4 1.04 155
cut grass

1-octen-3-ol 3391-86-4 C8H16O 128 Natural Earthy mushroom 2.60 4 0.53 174
9-decen-1-ol 13019-22-2 C10H20O 156 Natural Fresh clean citrus- Rosy floral 3.56 340 0.003 234
like odor soaps
10-Undecen-1-ol 112-43-6 C11H22O 170 Natural Fresh clean green Soaps and 4.00 152 0.004 2.5 246
citrus-like odor detergents
Amber carbinol 87118-95-4 C12H26O 186 Synthetic Floral woody odor Personal, 4.32 44 209
Kohinool fabric and
3,4,5,6,6 pentamethyl-2-
home care
heptanol
LINEAR ALIPHATIC ALDEHYDES, KETONES AND ACETALS
Trimethyl 2,6,10-Trimethyl-5,9- 24048-13-3 C14H24O 208 synthetic Aldehydic-floral Soaps, 5.04 0.0018 292
undecandienal undecadienal odour with fruity detergents
nuances and
household
products
Methyl 1,1-Dimethoxy-2,2,5-trimethyl- 67674-46-8 C11H22O2 186 synthetic Fresh fruity citrus/ Alkali stable. 3.18 2 0.214 213
pamplemouse, 4-hexene, grapefruit odour Used in
Grapefruit acetal soaps and
detergents
Methyl methyl oct-2-ynoate 111-12-6 154 synthetic Green, leafy, waxy, 3.22 240 0.125 218
2-octynoate* violet, cucumber 61

ALIPHATIC ESTERS
Melon valerate Ethyl 2-methylpentanoate 39255-32-8 C8H16O2 144 Natural Fruity-apple, Shampoos, 2.65 4 2.91 152
melon odour fabric
conditioners,
detergents,
air fresheners
and soaps
Nonisyl acetate 3,5,5-Trimethylhexyl acetate 58430-94-7 C11H22O2 186 Synthetic Woody-fruity Personal and 4.60 <3 0.47
odour fabric care
TERPENE ALCOHOLS
Citronellol* 3,7-dimethyl-6-octen-1-ol 106-22-9 C10H20O 156.2 Various Sweet rose-like Fine 3.91 56 0.02 224
isomers from odour fragrance,
essential oils personal,
fabric and
home care.
Intermediate
for other
fragrances
Geraniol* 3,7-dimethyl-trans-2,6- 106-24-1 C10H18O 154.2 Found Flowery rose-like Widely used, 2.94 60 0.013 15 230
octadien-1-ol naturally in odour does not
most terpene discolour
containing soaps. Air
essential oils. fresheners.
Intermediate
for
production
of other
fragrances
Farnesol* 3,7,11-trimethyldodeca-2,6,10- 4602-84-0 C15H26O 222 Natural Mild and delicate Body lotion, 5.31 400 0.00037 263
trien-1-ol green floral odour shampoo,
not in acid
bleaches
Linalool* 3,7-dimethyl-1,6-octadien-3-ol 78-70-6 C10H18O 154.25 Component of Flowery-fresh Is volatile 3.28 12 0.09 197
many essential odour, similar to and is useful
oils. A number lily of the valley for top notes.
of isomers It is stable
exist. Isolated in alkali and
from rosewood thus is used
oil in soaps.
62

Dihydromyrcenol 2,6-dimethyloct-7-en-2-ol 18479-58-8 C10H20O 156 Made from Fresh citrus and Fine 3.00 16 0.166 195
citronellene lime-like odour fragrances
and a lavender and soap and
note detergents
Tetrahydrogeraniol 3,7-Dimethyl-1-octanol 106-21-8 C10H22O 158 Natural Waxy, rose petal- Very stable 3.70 24 0.0386 215
Dihydrocitronellol like odour and so used
in household
products
Tetrahydromyrcenol 2,6-Dimethyl-2-octanol 18479-57-7 C10H22O 158 Synthetic Fresh citrus, lime- Good 3.51 6 0.115 200
like floral odour chemical
stability.
Used in
household
products,
especially
bleach
cleaners
Sandal octanol 3,7-Dimethyl-7-methoxyoctan- 41890-92-0 C11H24O2 188 Synthetic Sweet Top note in 1.96 112 0.0125 230
2-ol sandalwood, high- quality
soapy, floral sandalwood
woody compositions
for cosmetics,
toiletries and
soaps
LINEAR TERPENE ALDEHYDES, KETONES AND ACETALS
Citral 3,7-dimethyl-2,6-octadien-1-al 5392-40-5 C10H16O 152 Found in many Strong lemon Important 3.45 12 0.2 228
essential oils, lemon
lemon grass, flavouring.
litsea cubeba Only stable
at neutral pH,
so limited use
as fragrance.
Important
intermediate
Citronellal* 3,7-dimethyl-6-octen-1-al 106-23-0 C10H18O 154 Different Refreshing odour, Limited use 3.48 16 0.28 207
isomers are reminiscent of for perfuming
found in balm mint soaps; its
essential oils main use as
and is still raw material
an important for other
source fragrances
63

Hydrocitronellal 7-hydroxy-3,7- 107-75-5 C10H20O2 172 synthetic Flowery odour Unstable to 1.54 218 0.00318 241
dimethyloctanal reminiscent of acids and
linden blossom alkalis, thus
converted to
more alkali-
resistant
acetals
Geranyl acetone 6,10-dimethyl-5,9- 689-67-8 C13H22O 194 Found in fruits Fresh-green, Unstable to 4.13 0.0157 247
undecaadien-2-one and essential slightly acids and
oils penetrating rose- alkalis, thus
like odour converted to
more alkali-
resistant
acetals
TERPENE ESTERS
Linalyl acetate 3,7-dimethylocta-1,6-dien-3-yl 115-95-7 C12H20O2 196 Found in Distinctive Stable to 3.83 20 0.116 220
acetate lavender oil bergamot- alkali so can
lavender odour be used in
soaps
Dihydromyrcenyl 2,6-dimethyloct-7-en-2-yl 53767-93-4 C12H22O2 198 Synthetic Fresh, clean, citrus, Flowery-citric 3.90 4 0.0269 215
acetate acetate floral odour top notes in
soaps
CYCLIC TERPENES
Limonene* 1-methyl-4-prop-1-en-2- 138-86-3 C10H16 136 Exists as a Lemon-like Household 4.57 3 1.55 178
ylcyclohexene number of products
stereoisomers.
(+)-limonene
is isolated in
large amounts
from orange
peel.
terpinolene 1-methyl-4-propan-2- 586-62-9 C10H16 136 Natural Fresh woody, Fine 4.67 4 1.13 184
ylidenecyclohexene sweet, pine, citrus fragrance,
personal,
fabric and
home care
64

CYCLIC TERPENES ALDEHYDES AND KETONES
Methone p-menthan-3-one 3391-87-5 C10H18O 154 Occur naturally Minty odour Peppermint 2.63 0.256 208
as two isomers. oils. Used
to make
menthol
derivatives
Camphor 1,7,7-trimethylbicyclo[2.2.1] 76-22-2 C10H16O 152 From oil of Characteristic Used 2.38 0.65 176 204
heptan-2-one Camphor Tree minty balsamic industrially
odour and as a
plasticiser
Fenchone 1,3,3-trimethylbicyclo[2.2.1] 1195-79-5 C10H16O 152 Natural in Camphoraceous Used to make 2.13 0.463 5 193
heptan-2-one fennel oil artificial
fennel oil and
to perfume
household
products
α-Ionone (E)-4-(2,6,6-trimethyl-1- 127-41-3 C13H20O 192 Found in many Sweet floral, Highly valued 3.86 112 0.0144 237
cyclohex-2-enyl)but-3-en- natural oils. similar to violets fragrance
2-one One of a family
of ionones
α-isomethyl ionone* (E)-3-methyl-4-(2,6,6- 127-51-5 C14H22O 206 Synthetic Woody floral Economical 4.41 124 0.006 231
trimethyl-1-cyclohex-2-enyl) violet fragrance
but-3-en-2-one mainly used
in household
and cosmetic
products
δ-Damascone (E)-1-(2,6,6-trimethyl-1- 57378-68-4 C13H20O 192 Natural, a Fruity, rosy note Binds to 3.91 220 0.0102
cyclohex-3-enyl)but-2-en- number of textiles well
1-one isomers exist so used
in fabric
softeners
CYCLIC TERPENE ALCOHOLS AND ETHERS
Menthol (1R,2S,5R)-5-methyl-2-propan- 2216-51-5 C10H20O 156 The –(-) isomer Minty flavour, Cigarettes, 3.20 32 0.032 41 212
2-ylcyclohexan-1-ol is found widely imparts refreshing, foods,
in nature cooling effect sweets and
medicines
α-Terpineol 2-(4-methyl-1-cyclohex-3-enyl) 98-55-5 C10H18O 154 Natural Lilac Stable and 2.79 20 0.0283 40 215
propan-2-ol inexpensive,
used in 65
soaps and
cosmetics

cis-muguet shiseol [cis-4-(propan-2-yl)cyclohexyl] 13828-37-0 C10H20O 156 Synthetic Fresh, soft, clean Has excellent 3.24 0.0192 224
methanol floral odour of stability, used
white flowers and in soaps,
blossom detergents
and
cosmetics
Cedrol methyl ether 19870-74-7 C16H28O 236 Synthetic Cedarwood odour Perfumes, 6.16 124 0.0128 268
with distinct soaps and
amber nuance cosmetics
CYCLIC TERPENE ESTERS
Marine formate 1-(3,3-dimethylcyclohexyl) 25225-08-5 C11H20O2 184 Synthetic Fresh woody, Fine 3.74 12 0.0678 228
ethyl formate herbal seashore- fragrances,
like odour personal and
household
care
Menthanyl acetate 2-(4-methylcyclohexyl)propan- 58985-18-5 C12H22O2 198 Synthetic Citrus-fresh, pine Ester mixture 3.96 4 0.103
2-yl acetate needle, odour is very stable
and thus
is used in
household
products
Nopyl acetate 2-[(1S,5R)-7,7-dimethyl-4- 35836-72-7 C13H20O2 208 Synthetic Fresh-fruity woody Perfumes and 3.99 0.00751 253
bicyclo[3.1.1]hept-3-enyl]ethyl odour household
acetate products
Bornyl acetate (1,7,7-trimethyl-6- 76-49-3 C12H20O2 196 Natural in Pine needles Soaps, bath 3.86 0.228 27 229
bicyclo[2.2.1]heptanyl) essential oils products and
acetate room sprays
Iso-bornyl acetate [(1R,4S,6R)-1,7,7-trimethyl- 125-12-2 C12H20O2 196 Natural in Pine needle odour Perfuming 3.60 8 0.025 229
6-bicyclo[2.2.1]heptanyl] essential oils soap, bath
acetate products and
air fresheners.
Precursor in
manufacture
of camphor
Ethyl safranate ethyl 35044-59-8 C12H18O2 194 Natural Natural rose Unexpectedly 4.24 164 0.0266
2,6,6-trimethylcyclohexa-1,3- odour with stable. Floral
diene-1-carboxylate aspects of apple and fruity
cider and woody fragrances for
cider shampoos,
toiletries and 66
detergents

CYCLOALIPHATIC ALDEHYDES
leerall* 4-(4-hydroxy-4-methylpentyl) 31906-04-4 C13H22O2 210 Synthetic Soft delicate Fragrance 2.53 400 0.000029
cyclohex-3-ene-1- floral, lily, and care
carbaldehyde cyclamen products
2,4-ivy 2,4-dimethylcyclohex-3-ene-1- 68039-49-6 C9H14O 138 Synthetic Green herbaceous Perfuming 2.67 24 0.578 196
carbaldehyde carbaldehyde citrus note cosmetics
and
household
products
Citrus 4-(4-methylpent-3-enyl) 37677-14-8 C13H20O 192 Synthetic Fresh fruity citrus- Fine 4.38 244 0.00565 228
carbaldehyde cyclohex-3-ene-1- like odour. Ozone fragrance,
Myrac aldehyde carbaldehyde outdoor effect personal and
household
care.
CYCLOALIPHATIC KETONES
Fruity 2,2,5-Trimethyl-5- 65443-14-3 C13H24O 196 Synthetic Jasmine, lactonic Popular 4.39 12 0.026
Cyclopentanone pentylcyclopentanone and fruity odour. because of
Reminiscent of its floral note
peach and apricot and great
with a suggestion stability.
of lavender Body-care
products,
soaps and
detergents
Jasmone 3-methyl-2-[(Z)-pent-2-enyl] 488-10-8 C11H16O 164 Natural Strong jasmine Perfumes 2.91 68 0.0098 257
cyclopent-2-en-1-one odour, major
component of
jasmine oil
Dihydrojasmone 3-methyl-2-pentylcyclopent- 1128-08-1 C11H18O 166 Natural Jasmine-like odour Perfumes 3.25 340 0.01
2-en-1-one with fresh and
fruity undertones
67

Orris hexanone 4-tert-Pentylcyclohexanone 16587-71-6 C11H20O 168 Synthetic Powerful orris Popular 3.01 328 0.065 124
type aroma. economic
Camphoraceous, fragrance
earthy. for personal,
home, fabric
care and
detergents
Musk indanone 1,1,2,3,3-pentamethyl-2,5,6,7- 33704-61-9 C14H22O 206 Synthetic Long-lasting Fine 4.06 48 0.0027 285
tetrahydroinden-4-one diffusive, conifer- fragrance,
like musk odour personal,
fabric and
home care
Musk pentane (Z)-4-Cyclopentadecenone 14595-54-1 C15H26O 222 Synthetic Strong animal Good on 5.46 376 0.000096 337
musk note hair, skin
resembling and cloth.
natural musk Personal,
fabric and
home care
δ-muscenone 3-methylcyclopentadecenone 82356-51-2 C16H28O 236 Synthetic Powerful elegant Perfume, 5.91 356 0.1 346
musk note fabric care
reminiscent of and cleaners.
nitro musks with Adheres to
a natural animal hair, textiles,
undertone etc.
Patchouli ethanone 1-(2,3,8,8-tetramethyl- 54464-57-2 C16H26O 234 Synthetic Woody amber Soaps, 5.29 172 0.000538
1,3,4,5,6,7- colognes and
hexahydronaphthalen-2-yl) detergents
ethanone
CYCLOALIPHATIC ALCOHOLS AND ETHERS
Muguet ethanol 1-(4-propan-2-ylcyclohexyl) 63767-86-2 C11H22O2 170 Synthetic Light floral Body lotion, 3.59 196 0.00678 240
ethanol reminiscent of shampoo,
muguet with waxy soap, roll-on
elements deodorants
and cleaning
formulations.
Unstable in 68
bleach

Sandal butenol (E)-2-methyl-4-(2,2,3- 28219-60-5 C13H22O 194 One of a Powerful Household 4.43 400 0.000961
trimethyl-1-cyclopent-3-enyl) number of sandalwood products
but-2-en-1-ol synthetic odour
fragrances
developed
to substitute
natural
sandalwood oil
Sandal 2-methyl-4-(2,2,3-trimethyl-1- 72089-08-8 C13H24O 196 Another of Woody tenacious Stable 4.38 400 0.00154 261
cyclopentane cyclopent-3-enyl)butan-1-ol a number sandalwood in most
of synthetic odour household
fragrances and personal-
developed care products,
to substitute including
natural bleach
sandalwood oil
Amber dioxane 5-butan-2-yl-2-(2,4-dimethyl- 117933-89-8 C17H30O2 266 Synthetic High tenacity Fragrances, 5.36 0.00033 328
1-cyclohex-3-enyl)-5-methyl- powerful radiant soaps and
1,3-dioxane woody amber detergents.
odour Shampoos
and fabric
rinse
conditioners
CYCLOALIPHATIC ESTERS
Green acetate (2-tert-butylcyclohexyl) 88-41-5 C12H22O2 198 Synthetic. Commercial Important 3.96 8 0.103 221
acetate The 4-tert product a fruity fragrance
isomer is also agrumen-like used in soaps,
an important odour. With more bath and
household cis isomer more household
fragrance wood-camphory products
Galbanum prop-2-enyl 68901-15-5 C11H18O3 198 Synthetic Green galbanum Toiletries and 2.96 32 0.0032 282
oxyacetate 2-cyclohexyloxyacetate fruity pineapple household
products
69

Methyl (3-oxo-2-pentylcyclopentyl) 24851-98-7 C13H22O3 226 Natural Powerful floral Fine 2.50 72 0.00071
dihydrojasmonate acetate jasmine fragrance fragrance,
personal,
fabric and
home care
AROMATIC ALCOHOLS
Benzyl alcohol* phenylmethanol 100-51-6 C7H8O 108 Natural Sharp floral fruity Weak odour, 1.10 35 0.094 -15 205
mainly
used as
solvent and
as starting
material to
synthesise
other
fragrances
Phenethyl alcohol 2-Phenylethanol 60-12-8 C8H10O 122 Occurs widely Sweet, fresh, floral, Widely used 1.50 32 0.074 -26 220
in nature, main strong rose for rose
component of fragrances.
rose oils Stable in
alkali and
thus used in
soaps
Lilac pentanol 3-methyl-1-phenylpentan-3-ol 10415-87-9 C12H18O 178 Synthetic Dry-flowery lily-like Used in 3.11 304 0.0025 254
odour soaps,
cosmetics
and
detergents
AROMATIC ALDEHYDES, KETONES AND ACETALS
Benzaldehyde Benzaldehyde 100-52-7 C7H6O 106 Widely in Bitter almond Starting 1.48 4 1.27 -25 178
nature material
for many
flavours and
fragrances
Hexyl cinnamal* 2-(phenylmethylidene) 101-86-0 C15H20O 216 Mild slightly Widely used 5.33 400 0.000697 174
octanal fatty flowery in flowery
herbal odour, like formulations
jasmine when and because
diluted it is alkali
stable in soap
perfumes.
Inexpensive
and fibre
70
substantive

Cinnamaldehyde* 3-phenylprop-2-enal 104-55-2 C9H8O 132 Natural Cinnamon, spice, Mainly 2.20 212 0.0265 -7 250
Cinnamal pungent flavours
and an
intermediate
Cyclamen aldehyde 3-(4-propan-2-ylphenyl) 103-95-7 C13H18O 190.28 Found in Floral cyclamen Important 3.72 72 0.0124 270
butanal nutmeg fresh rhubarb, for forming
musty green blossom top
notes
Alpha-amyl 2-benzylideneheptanal 122-40-7 C14H18O 202 Natural Flowery, slightly Stable 4.80 256 0.00233 288
cinnamaldehyde* fatty odour. in alkali
Becomes like and long
jasmine when lasting, large
diluted quantities
used in soaps
Cyclamen propanal 18127-01-0 C13H18O 190 Synthetic Powerful green Toiletries, 3.72 104 0.00934 300
aquatic, aldehydic, soaps and
lily of the valley detergents
odour.
Galaxolide 1,3,4,6,7,8-hexahydro- 1222-05-5 C18H26O 258 Synthetic A clean powerful Alkali stable 6.23 400 0.000414
Musk 4,6,6,7,8,8- and versatile and not
hexamethylcyclopenta(g)-2- isochroman musk discoloured
benzopyran with exceptional by light. Fine
persistence fragrance,
personal,
fabric and
home care
Lilyall 3-(4-tert-butylphenyl)butanal 80-54-6 C14H20O 204 Synthetic Mild-flowery Large 4.07 236 0.0046 250
odour reminiscent quantities
of cyclamen and used in soap
lily of the valley and cosmetic
(muguet) perfumes
Hydratropaldehyde 1,1-dimethoxypropan-2- 90-87-9 C11H16O2 180.24 synthetic Floral, hyacinth, Fine fabric 2.42 12 0.123 241
dimethyl acetal ylbenzene green and personal-
care
AROMATIC KETONES
Acetophone 1-phenylethanone 98-86-2 C8H8O 120 Present in Penetrating sweet Detergents 7.00 7 0.397 19 202
many foods odour, reminiscent and industrial
and essential of orange blossom products and
oils intermediate 71
in synthesis

para-methyl 1-(4-methylphenyl)ethanone 122-00-9 C9H10O 134 natural, In Flowery-sweet Soap 2.00 20 0.187 -22 224
acetophenone Brazilian odour, milder than perfumes
rosewood and acetophenone
pepper
Benzyl acetone 4-phenylbutan-2-one 2550-26-7 C10H12O 148 In volatile Sweet-flowery Soap, 1.96 172 0.0557 235
content of perfumes
cocoa
Beta-naphthyl 1-naphthalen-2-ylethanone 93-08-3 C12H10O 170 Synthetic Orange blossom Soap, 2.00 400 0.000957 54 300
methyl ketone perfumes and
detergents.
Is a good
fixative
Musk dimethyl 1-(6-tert-butyl-1,1-dimethyl- 13171-00-1 C17H24O 244 Synthetic Musk Light, stable 5.51 400 0.000652 70 308
indane 2,3-dihydroinden-4-yl) used for
ethanone perfuming
soap and
cosmetics
Musk methyl 1-(1,1,2,6-tetramethyl-3- 68140-48-7 C18H26O 258 Synthetic Dry sweet amber Soaps and 6.14 400 0.000045
ketone propan-2-yl-2,3-dihydroinden- musk detergents
5-yl)ethanone
Musk tetralin 1-(3,5,5,6,8,8-hexamethyl- 1506-02-1 C18H26O 258 Synthetic Strong sweet Light stable 6.37 >400 0.000028 53 393
6,7-dihydronaphthalen-2-yl) amber fruity musk versatile
ethanone fragrance
used in
soap and
cosmetics
AROMATIC ACIDS AND ESTERS
Phenyl acetic acid 2-phenylacetic acid 103-82-2 C8H8O2 136 Natural Honey, rose Used in 1.35 400 0.005 77 265
fragrances.
Only
aromatic acid
used

72

Rose acetate (2,2,2-trichloro-1-phenylethyl) 90-17-5 C10H9Cl3O2 267 Synthetic Weak, very Soap 3.66 400 0.000042 190
acetate natural, lasting powders and
rose odour bath salts

Benzyl cinnamate* benzyl 3-phenylprop-2-enoate 103-41-3 C16H14O2 238 Natural White, sweet, Fixative in 4.06 243 38
balsamic-smelling perfumes and
crystals a component
of heavy,
oriental
perfumes
Hexyl salicylate hexyl 2-hydroxybenzoate 6259-76-3 C13H18O3 222 Natural Floral fruity Used in floral 4.89 40 0.000491 290
character with fragrances,
a mild sweet soaps and
herbaceous slant detergents
PHENOL DERIVATIVES
Diphenyl ether phenoxybenzene 101-84-8 C12H100 170 Synthetic Geranium leaves It has a low 4.21 156 0.0223 28 258
diphenyl oxide price and is
stable. Soap
and perfumes
Thymol 5-methyl-2-propan-2-ylphenol 89-83-8 C10H140 150 Essential oils Spicy, herbal, Dry top note 3.28 176 0.0376 50 231
slightly medical in lavender
odour reminiscent note in men’s
of thyme. Some fragrances.
antiseptic Oral health;
properties used to make
menthol
Eugenol* 2-Methoxy-4-(2-propenyl) 97-53-0 C10H1202 164 Common Spicy, clove leaf Perfumes. 2.27 52 0.0104 -11 252
phenol in cheap In dentistry,
essentials oils. used as an
Little is made antiseptic
synthetically
73

PHENOL ALDEHYDES
Vanillin 4-hydroxy-3- 121-33-5 C8H803 152 20te/yr Vanilla Reactive 1.19 400 0.00194 83 285
methyoxybenzaldehyde obtained molecule
from essential used as
oils and intermediate.
12,000te/yr Primarily
manufactured used as food
synthetically flavour
Ocean propanol 2-Methyl-3-(3,4- 1205-17-0 C11H1203 192 synthetic Green floral odour Fine 2.25 64 0.0027 283
methylenedioxyphenol) with top notes of fragrance.
propanol ozone and mown Used in care
hay products
Ethyl vanillin 3-Ethoxy-4- 121-32-4 C9H1003 166 synthetic Sweet, creamy, Flavour for 1.72 400 0.00088 77 290
hydroxybenzaldehyde vanilla, caramellic. chocolates
Like vanillin but
x3 stronger
LACTONES
Coumarin* chromen-2-one 91-64-5 C9H602 146 Found widely Sweet, Widely used
in nature herbaceous— in perfumes
warm, spicy and soaps for
spicy green
notes
MISCELLANEOUS
Amber spirolene 154171-77-4 C17H2802 264 Synthetic Woody-ambery Long lasting >392 0.012
musk fruity odour. Soaps,
cosmetics
and perfumes
74

Strawberry ethyl 3-phenyloxirane-2- 121-39-1 C11H12O3 192 Synthetic Strawberry-like Used for 1.89 312 0.00184
glycidate Special carboxylate odour creating
aldehyde C16 harmonic
fruity notes
in household
and fine
fragrances
Galbanum (2R,4S)-2-methyl-4-propyl-1,3- 59323-76-1 C8H16OS 160 Natural in Tropical green Personal, 2.31 56 0.123 218
oxathiane oxathiane passion fruit oil passion fruit note fabric and
and grapefruit-like home care
tartness
NITRILES
Waxy nitrile tridec-2-enenitrile 22629-49-8 C13H23N 193 Synthetic Powerful citrus Good stability 5.49 400 0.0023 288
tangerine note, Personal,
floral, aldehydic home and
with sea breeze fabric care,
nuance not bleaches
citronellyl nitrile 3,7-dimethyloct-6-enenitrile 51566-62-2 C10H17N 151 Synthetic Citrus, green, Alkaline 3.13 16 0.1 110
fruity, floral stable,
substitute for
citronellal
Geranyl nitrile 3,7-dimethylocta-2,6- 5146-66-7 C10H15N 149 Synthetic Citral, fresh, floral 3.37 56 0.025 220
dienenitrile
Cinnamyl nitrile 3-phenylprop-2-enenitrile 4360-47-8 C9H7N 129 Natural Spicy cinnamon 2.32 0.01 263
Leafy oxime N-(5-methylheptan-3-ylidene) 22457-23-4 C8H17ON 143 Synthetic Green, natural, Perfumes, 2.59 0.041
hydroxylamine leafy, fresh, cosmetics
powerful
Hexen-1-yl 3-[(Z)-hex-3-enoxy] 142653-61-0 C9H15NO 153 Synthetic Green, floral Personal 1.89 0.0129 Liq
oxypropane nitrile propanenitrile violet, cucumber care, acidic
cleaners, not
bleach
Floral nitrile 3-(4-ethylphenyl)-2,2- 134123-93-6 C13H17N 187 synthetic Fresh, floral, Fine 3.41 304 0.00576 311
Fleuranil dimethylpropanenitrile ozone, salted, fragrance,
basillic, herbal personal,
notes with good fabric and
diffusion home care 75
Notes: * On EU List of potential allergens. The table lists a selection of fragrances that are used by the care industries; it is not a complete list. Log P is the fragrance’s partition coefficient between octanol and water. When a
melting point is given, the fragrance is a solid at room temperature; otherwise it is a liquid. Boiling points are measured at atmospheric pressure 760mm Hg. Natural fragrances are found in nature, although many are produced
synthetically. Synthetic fragrance molecules are not found in nature. CAS Number, their Chemical Abstracts number.
TABLE 3.1 Major essential oils, and oils of particular interest for home-care products
Oil Form Source Region Tonnes per year* Fragrance Uses
Anise S Seed China, Vietnam 1,200 n/a Food, beverages, oral hygiene.
Bay S Leaf Caribbean 20 Spicy, clove-like Mild antiseptic because of phenol content. Aftershave
Camphor S Wood China 250
Cedarwood S Wood, Leaves China, USA 2,200 Cedar wood Soaps. Being replaced by synthetic oils
Citronella and S Leaves of Cymbopogon grasses Sri Lanka, Indonesia 2,300 Fresh grassy camphoraceous odour Toilet soaps, washing powders and household care
Lemongrass
Clove leaf S Leaf Indonesia, Madagascar 2,000
Cornmint S Aerial parts China, Brazil 3,000
Copaiba (Balsam) U Extruded resin Brazil 40 Aromatic balsam, slightly bitter Mainly as fixative in soap perfume
pungent
Elemi C,S Resin from Canarium luzonicum tree Philippines 10 Fresh, citrus-like peppery odour Soap
Eucalyptus S Leaves, various types Brazil, S Africa, Aust. 2,500
Geranium A,S Leaves/stem Reunion, Egypt 150 Rosy notes Soap
Grapefruit E Fruit Israel, Brazil, USA 250
Lavender S Aerial parts France, Spain, Tasmania 1,000 Soaps, perfumes, bath products
Lemon E Fruit USA, Italy, Brazil, Argentina 2,500
Lime E Fruit Mexico, Haiti 1,200
Orange (citrus oil) E Fruit USA, Brazil, Israel, Italy 30,000 Orange peel Flavouring food, cologne soaps and household
products
Peppermint S Aerial parts USA 2,200 Oral health
Peru Balsam C,S Resin from Myroxylon balsamum tree San Salvador, Brazil 45 Sweet balsam odor Fixative in soaps and cosmetics.
Allergenic
Pine S Various types of pine tree USA, Mexico, Finland, Russia 1,000 Fir leaves Soaps, bath products and air fresheners
Rosemary S Aerial parts Spain, Morocco,
Tunisa 250 Bath products shampoos
Rosewood S Wood Brazil, Peru, Mexico 250 Sweet odour similar to linalool Soaps
Sandalwood S Wood Indonesia, India 250 Sweet woody long-lasting odour
Sassafras S Roots Brazil 750 Characteristic odour of safrole Raw material
Spearmint S Aerial parts USA, China, Brazil 1,400
Tangerine E Fruit Brazil 300
Tea Tree S Leaves of Melaleuca tree Australia 10 Earthy odor Has some antiseptic properties, Aroma-therapy
Vanilla C,T Fruit Reunion, Madagascar 2,500
Vetiver S Root Reunion, Haiti, Indonesia 260 Precious wood and root-like, long-
lasting odour
Note: A=absolutes; S=steam distilled; E=expressed oil; C=resin; T=tincture
* Approximate figures from 2006
Source: Adapted from Sell (2006) and other sources
RETURN TO PAGE
TABLE 4.6 Composition of typical European powder and liquid heavy duty detergents
Ingredient Powder detergents Liquid detergents
Examples Composition (%) Example Composition (%)
Surfactants Anionic surfactants, Alkyl benzene sulphonates, alcohol sulphates, etc 10-25 Anionic and nonionic surfactants 22-48
Nonionic <5 Nonionic 20
Soaps/fatty acids Soaps (salts of carboxylated detergent acids) 5-20
Builders Zeolites, STPP, citrates, silicates, carbonate/bicarbonate, chelates e.g. EDTA 30-55 Citrates, chelates (e.g. EDTA, NTA) 0-10
Co-builders Na polycarboxylates, phosphonates 3-8 Polycarboxylates, phosphonates 4
Bleaching agents Sodium percarbonate 8-15
Bleach activators TAED 1-7
Enzymes Protease, amylase, lipase, cellulase, mannase, etc 0-2 Protease, amylase, etc. 0-3
Enzyme stabilisers Borax 0-3.5
Anti-redeposition and Cellulose ethers such as SCMC 0-1 Cellulose ethers such as SCMC 0-1
soil repelling agents
Foam regulators Soap, antifoams 0.1-4 0.1-1.0
Optical brighteners <1 <1
Preservatives <1 As required <1
Fillers/solvents Sodium sulphate 0-30 Alcohols, polyols (e.g., glycerol), solubilisers 1-15
Fragrances As required 0.2-1.5 As required 0.2-1.5
Water 5-15 5-50
pH of 1% aq soln 9.5-11 7-9
RETURN TO PAGE
List of Tables and Figures
List of Tables List of Figures

TABLE 1.1 Terpene nomenclature FIGURE 2.1 Global sales of fragrances by region
TABLE 2.1 Global flavour and fragrance market, 2010 FIGURE 2.2 Headspace method of trapping the scent of a flower in the field
TABLE 2.2 The 26 potentially allergenic fragrance ingredients FIGURE 2.3 GC-MS of trapped scent of Turbinicarpus pseudomacrochele ssp. Krainzianus
TABLE 2.3 IFRA/RIFM quantitative risk assessment criteria (QRA) for fragrances, June 2010 flower (insert)
TABLE 3.1 Major essential oils, and oils of particular interest for home-care products FIGURE 3.1 Human olfactory system
TABLE 4.1 Typical perfume and cologne formulations FIGURE 3.2 Schematic diagram of the cell membrane of olfactory receptor cells
TABLE 4.2 Typical aerosol air-freshener formulation FIGURE 3.3 Schematic diagram of the effect of different fragrance molecules on olfactory
TABLE 4.3 Typical hair-shampoo formulation receptor cells
TABLE 4.4 Typical shower-gel formulation FIGURE 3.4 Functional groups found in fragrances
TABLE 4.5 Typical antiperspirant aerosol-spray formulation FIGURE 3.5 Structure of pinenes
TABLE 4.6 Composition of typical European powder and liquid heavy duty detergents FIGURE 3.6 Photosensitive pro-fragrance adduct
TABLE 7.1 List of fragrances FIGURE 3.7 Structure of capsules, core-shell and matrix
FIGURE 3.8 Spray-drying tower
FIGURE 3.9 Complex coacervation
FIGURE 3.10 Formation of melamine -formaldehyde capsules
FIGURE 3.11 Polysaccharides used to encapsulate fragrances
FIGURE 3.12 Representations of cyclodextrin
FIGURE 4.1 Structure of surfactants
FIGURE 4.2 Schematic diagram of surfactant micelles
FIGURE 4.3 Stabilisers for fragrances
FIGURE 4.4 Aerosol spray can
FIGURE 4.5 Soap manufacturing chemistry
FIGURE 4.6 Cationic surfactants
78

Fragrance Technologies and Applications (2012-04-04)

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Fragrance Technologies and Applications (2012-04-04)

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This eBook examines the fragrance market and its

Head of editorial Business Support

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

Introduction and Methodology

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

Introduction and Methodology

In vivo Testing carried out in the organism or animal

MSDS Material Safety Data Sheet TABLE 1.1 Terpene nomenclature

REACH Registration, evaluation, authorisation and restriction of

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

Leerall/Lyral 31906-04-4 Self-Regulation of Fragrances

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

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State of the Global Fragrance Industry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

Using these techniques helps scientists to identify the structure of

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

State of the Global Fragrance Industry

effect of a particular fragrance, it is important that there are no

Describing, reporting and quantifying the results is also difficult.

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Trends in Fragrance Chemistry

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Trends in Fragrance Chemistry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

Trends in Fragrance Chemistry

There is extensive debate about how fragrance molecules trigger

Some fragrance molecules are also detected by the trigeminal nerve

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Trends in Fragrance Chemistry

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Trends in Fragrance Chemistry

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Trends in Fragrance Chemistry

Fragrance Compounds Steam distillation is the most common method of extracting

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Trends in Fragrance Chemistry

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Trends in Fragrance Chemistry

CHAPTER ES 1 2 3 4 5 TOC WWW.INTERTECHPIRA.COM

Trends in Fragrance Chemistry

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Trends in Fragrance Chemistry

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Trends in Fragrance Chemistry

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Trends in Fragrance Chemistry

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