INTRODUCTION

 Crude drugs (herbs) & galenical products or

phytomedicinals are widely used in "complementary
medicine " [about 50% of the total drug market].

 "Pharmacognosy" = "knowledge of drugs" gives "a

scientific description of natural materials used in medicine
(herbs, animal products & inorganic materials)".

 "Phytochemistry" studies "the chemistry, distribution,

isolation, identification, quantitative determination,
biosynthesis, metabolism & biological activity of plant
constituents."
 Role of natural products in modern
medicine
 Useful drugs which cannot be commercially produced by
synthesis e.g. opium, ergot & cinchona alkaloids, digitalis
glycosides & most antibiotics.

 Basic compounds, which could be modified to be more

effective or less toxic e.g. morphine molecule.

 Models for production of synthetic analogues with

similar physiological activities, e.g. procaine.

 Starting materials for production of potent drugs e.g.

hydrocortisone & steroidal hormones from stigmasterol
& saponins.
 Different forms of plant products
:Different forms are supplied based on
♣ Aim of use
♣ Nature of active ingredients
♣ Economic factors

1. Fresh plant materials [especially in perfume industry].

2. Dried plant materials: [flavoring agents, spices & drugs where
dosage is not critical].
3. Acellular products : materials derived directly from plants [gums,
resins, & fixed & volatile oils].
4. Galenical preparations: [plant extracts & tinctures]
5. Processed extracts : standardized to contain a certain concentration
of the active principle.
6. Pure compounds : most required in pharmaceutical formulations as
they facilitate proper standardization of biological activity &
quality control
 Primary & secondary plant metabolites
Plant metabolites : organic substances formed &
accumulated by plants.
1. Primary metabolites : essential for life & present in all
organisms e.g. carbohydrates, proteins, fats, & nucleic
acids

2. Secondary metabolites: formed as a defense against

predators, attractants (volatile or colored) or detoxifying
agents. Mostly pharmacologically active & found in
specific organisms or group of organisms.

Some metabolites could be included in both divisions e.g.

certain fatty acids & sugars.
 Nomenclature of plant constituents
Systematic nomenclature is difficult due to complexity of
structure. Naming is based on trivial nomenclature.
Root names are derived from:
1. Name of the discoverer e.g. Pelletierine alkaloid after
Pelletier

2. Common name of the plant e.g. vinca alkaloids,

(vincristine & vinblastine), ergot alkaloids (ergometrine
& ergotamine)

3. Latin name of the plant e.g. visnagin from Ammi visnaga

& digitoxin from Digitalis lanata

4. Biological action e.g. emetine alkaloid which produces

emesis
 Classification of plant constituents

Plant constituents occur as:

Single chemicals e.g. glycosides & alkaloids

……..

Mixtures of compounds e.g. gums, fixed

oils, fats, waxes, volatile oils, resins & resin
combinations.
Classification of plant constituents may
:be according to
A. Pharmacological activity [analgesics,
laxatives, cardiotonics etc……..]

B. Biosynthetic origin, solubility properties &

key functional groups

C. Chemistry & common physical properties

 B.According to biosynthetic origin, solubility
properties & key functional groups:
1. Phenolics: e.g. flavonoids & their glycosides, phenyl
propanoids, anthocyanins, xanthones, tannins &
quinones
2. Terpenoids: e.g. carotenoids, steroids & the major
constituents of volatile oils
3. Organic acids & lipids: e.g. simple organic acids (citric,
oxalic & ascorbic), fatty acids (in the form of esters in
fixed oils, fats & waxes)
4. Nitrogenous compounds: e.g. alkaloids & cyanogenic
glycosides
5. Water-soluble carbohydrates & their derivatives: e.g.
monosaccharides, oligosaccharides & water-soluble
glycosides
6. Macromolecules: e.g. proteins & polysaccharides
 C.According to chemistry & common physical
properties

This classification will be adopted for convenience,

the major groups are:

1. Volatile oils, Resins & Resin combinations

2. Carbohydrates
3. Bitter Principles
4. Tannins
5. Alkaloids
6. Glycosides
VOLATILE, ETHEREAL or ESSENTIAL OILS
 "Volatile" or "ethereal": as they easily evaporate
on exposure to air at room temperature (volatile,
from the Latin "volare" i.e. to fly & ethereal =
ether-like in their volatility)

 "Essential": as they mostly represent the

"essences" or principal active principles of the
plants in which they occur.

They differ entirely from "fixed oils“ in both

chemical & physical properties.
 Major Differences between volatile & fixed oils

Property Volatile oil Fixed oil

Volatilization at Volatile Non-volatile
ordinary temperature

Solubility Soluble in organic Limited solubility in

solvents (ether, organic solvents,
CHCl3) & alcohol almost insoluble in
alcohol
Stain on filter paper Transient Permanent & greasy

Composition Complex mixtures of Triglycerides of fatty

hydrocarbons & acids e.g. palmitic,
oxygenated ..……stearic, oleic
compounds
Response to long Resinification Rancidity
exposure to air & light
(oxidation)
Saponification with Negative Positive
caustic alkali (KOH)
 Historical

 In ancient Egypt: embalming process (antibacterial

properties of essential oils & resins).

 In the Roman culture: aromatic essences in massage &

baths.

 Incenses: [in temples, churches & mosques] consist of

resins rich in volatile oils

 In folk medicine: inhalation of aromatics as tranquilizers

(e.g. incenses in case of irritability) or stimulants (e.g.
onions in case of fainting)
 Distribution & Occurrence

:Animal sources :Botanical sources

 Musk, musk-like  Mainly in higher plants

products (civet,
castoreum) & ambergris  Especially in Pinaceae,
Lauraceae, Rutaceae,
 Secretions produced for Myrtaceae, Labiateae,
attraction or protection Zingiberaceae,
Umbellifereae, &
Compositeae.
 Free & Combined Forms of Volatile Oils

They may be present :

1. Free  aromatic characteristic odor, or

2. Combined with:
 Sugars  glycosides

 Gums, resins or both  oleo-gums, oleoresins

or oleo-gum-resins.
 Location in the plant
They may be:
 Diffused in all plant tissues (e.g. Pinaceae, Conifers)
 Accumulated in specialized secretory structures usually on
or near the surface of the plant e.g.:

1. Modified parenchyma or oil cells:

(Lauraceae & Zingiberaceae)
2. Glandular hairs: (Labiateae)
3. Oil tubes or Vittae: (Umbellifereae)
4. Oil glands: (Rutaceae & Pinaceae)
 Distribution in plant organs

V. O. may accumulate in all types of plant

organs:
 Flowers e.g. rose
 Leaves e.g. eucalyptus & peppermint
 Barks e.g. cinnamon
 Woods e.g. sandalwood
 Roots e.g. vetiver
 Rhizomes e.g. ginger
 Fruits e.g. umbelliferous & citrus
 Seeds e.g. cardamon
Variation in composition of v. oils from different
organs of the same plant
1. Cinnamon tree:
 bark oil rich in cinnamaldehyde
 leaf oil rich in eugenol
 root oil rich in camphor

2. Bitter orange tree:

 "Bitter orange oil": from the fresh pericarp of the fruit
(rind or zest),
 "Neroli oil": from the flowers
 "Petit grain oil": from the leaves, twigs & unripe
fruits.

These oils are different in composition & aroma

 Physiological role of V.O. in the plant

1. Waste products of metabolism (detoxifying

agents)
2. Energy producers in case of deficiency from CO2
assimilation
3. H+ donors in certain metabolic reactions
4. Protectants against predators: e.g. insect
repellents & antifungals (i.e. for defense).
5. Pollinators: attracting insects during cross-
pollination (due to their nice odors).
 Common Physical Characters
1. Colorless, pleasant smelling liquids, volatile at
room temperature
2. Steam distillable
3. High refractive index
4. Mostly optically active
5. Density < water (i.e. lighter than water) except
for few ones
6. Immiscible with water, but sufficiently soluble to
impart a fragrance to water  aromatic waters
[hydrosols]
7. Soluble in alcohol & common organic solvents
8. Darken in color if exposed to air & light
(resinification)
 Exceptions
1. Oils of cinnamon, clove & winter green
are heavier than water

2. Oils of anise & rose solidify just below

room temperature (15 & 18oC,
respectively)

3. Oils containing azulenes are colored (e.g.

oil of chamomile is blue).
 Chemical Composition
 V. O. are complex mixtures of hydrocarbons &
oxygenated compounds [alcohols, phenols, ethers,
aldehydes, ketones, oxides, peroxides & esters]. All of
these contribute to the odor & physiological activity of
the oil.
 Few oils consist of one main component e.g.
1. Oil of mustard (93% allylisothiocyanate)
2. Oil of clove (85% eugenol)
 Most V. O. constituents belong to 2 main groups:
1. Terpenoids [derived from acetate] &
2. Phenylpropanoids [aromatic compounds, derived
from phenylpropane]
 Variation in Physico-Chemical
Characteristics

Most important influencing factors are:

The environmental conditions under which

the plant is grown

The method used for preparation of the oil

 .Medicinal & Commercial Uses of V.O

1. Therapeutic & medicinal uses: local stimulants, carminatives,

diuretics, mild antiseptics, local irritants, anthelmintics,
parasiticides …

2. Spices & condiments: in food seasoning (to impart aroma &

flavor) or as preservatives

3. Flavoring agents: in food (e.g. beverages, soups, bakery

products, confectionery) & pharmaceutical industries

4. Aromatic agents: in all types of perfume industries (cosmetics,

soaps, deodorizers, household cleaners, polishes & insecticides)
 Me tho d s o f Pre pa ra tio n o f Vo la tile Oils

Dis tilla tio n S c arific a tio n & Expre s s io n Extra c tio n Enzyma tic
Hydro lys is
Wa te r Dis tilla tio n S p o n g e Me tho d Extra c tio n w ith Vo la tile
S o lve nts
S te a m Dis tilla tio n Ec ue lle a p iq ue r
Me th o d Extra c tio n w ith No n -Vo la tile
S o lve nts
Wa t e r & S t e a m Exp re s s io n o f Ra s ping P ro c e s s
Dis t illa t io n Enfle u ra g e Me t ho d
Ma c hine P ro c e s s e s P n e u m a t ic Me t h o d
Dire c t S t e a m
Ma c e ra t io n Me t h o d
Dis t illa t io n
 Selection of the suitable method is done according
to :

1. The condition of the plant material (moisture content,

degree of comminution)

2. The localization of the oil in the plant (superficial or deep)

3. The amount of the oil

4. The nature of the oil constituents

 Distillation methods
Principle

 Most volatile oil constituents boil between 150-300ºC. In

order to reduce decomposition, volatile oils are distilled in
the presence of water.

 The mixture will boil below 100ºC [Dalton’s law of partial

pressure : “When 2 immiscible liquids are heated together,
they will boil at a temperature below the boiling point of
either one”].

 The oil is carried over with steam in the form of vapor

 Distillation methods
Application: preparation of thermostable oils, present in
large amounts & not rich in esters (e.g. oils of turpentine,
peppermint, cardamon, anise, eucalyptus)

Types of distillation:
1. Water-distillation
2. Steam distillation
 Water-and-steam distillation
 Direct-steam distillation
 Distillation: Terminology
 Hydrodiffusion = process by which water or steam
penetrates the plant tissues to take over the oil

 Aromatic water = Hydrosols = distilled aqueous layer

saturated with oil e.g. rose, orange flower & peppermint
waters

 Cohobation = return of aromatic water to the distillation

chamber, in water distillation, in order to recover the
dissolved oil.
 Distillation methods
Steam Distillation
H2O Distillation H2O & Steam Direct Steam

Plant material Dried & fresh (petals), Dried & fresh, Fresh ( i.e. containing
not injured by boiling injured by direct boiling moisture)
with H2O with H2O

Commercial Oils of turpentine & rose Oils of clove, cinnamon & Oil of peppermint
preparations citronella

Mode of charging Plant material dipped in -H2O present but not in
H2O contact with the plant.
-Steam is generated in the
still & penetrates the drug
-Dried material is
moistened before charging
-H2O is absent.
-Steam is introduced by pipes &
forced through the plant
material placed on perforated
trays

Steam pressure  atmospheric Can be modified

Temperature  100ºC Can be modified

Rate & yield Relatively low Better The best

Advantages -Least expensive
-Cohobation is allowed
Disadvantages -Esters are hydrolyzed. -
H2O sol. & high b.p.
constituents are not
distilled
Hydrolysis is reduced Method suitable for oils rich in
esters & high b. p. constituents
-Not suitable for powders, efficient if material entire or
crushed
-Hydrodiffusion may be reduced due to lumping or channeling
 Distillation apparatus
Consists of 3 parts:
1. The distillation chamber
made of stainless steel free
from any Fe+++ ions to
avoid degradation of the oil
constituents  darker oils.
2. The condensing system
3. The receiver e.g.
Florentine receivers which
allow separation of the oily
layer from water in the
distillate (oils lighter or
heavier than water)
Florentine Receivers
Purification (Rectification) of
distilled oils

Bad smelling or dark

colored oils are purified
by:
1. Redistillation or dry
distillation under reduced
pressure
2. Dehydration by passing
over anhydrous sodium
sulphate
 Remarks
1. Distillation should be done just after comminution [ i.e. reduction in size,
crushing, powdering)  prevent loss by evaporation or deterioration of
the oil.
2. Coarse comminution  increase "Hydrodiffusion"  oils with better
yield & quality.
3. High temperature & water  distilled oils differing in composition from
natural oils [artifacts].
4. Insufficient distillation time (shorter)  fractionation of the oil.
5. Hydrolytic products (e.g. lower alcohols & acids) are water-soluble &
remain in the distillation chamber.
6. Steam volatile impurities e.g. amines & furfural (degradation product of
carbohydrates) contaminate the final product.
7. Sensitive constituents could be affected by boiling water e.g.
 Esters  hydrolyzed.
 Tertiary alcohols  dehydrated  hydrocarbons.
 Unsaturated hydrocarbons  polymerized.
 Scarification & Expression Methods
Principle
Mechanical procedures carried at room
temperature & based on puncturing &
squeezing of the plant material to liberate
the oil, which is collected.

Applications
Preparation of heat sensitive oils, present in large amounts
in outer peels of fruits e.g. Citrus fruits (Rutaceae) as
orange, lemon & bergamot.
Scarification & Expression Methods
The peel of Citrus fruits consists of 2 distinct layers:
1. Outer colored zone (waxes + pigments + oil glands)
2. Inner white zone (pectin + cellulose).
 Scarification & Expression Methods

The process involves 3 steps:

1. Squeezing of the peel under a stream of
water  emulsion (volatile oil + water +
pectin + cellulose + pigments + traces of
waxes).
2. Centrifugation (to remove water + pectin
+ cellulose)
3. Strong cooling (to remove waxes)
 Scarification & Expression Methods
A- Sponge Method

Based on squeezing the removed peels e.g. orange

1. Fruits washed, cut into halves & fleshy parts removed.

2. Peels soaked in water, turned inside out then pressed between a
convex projection & a sponge.
3. Sponge (saturated with oil emulsion) periodically squeezed in a vessel

The tissue of the sponge serves for:

1. Collection of the oil

2. Filtration of the product from any particles of the inner white zone of
the peel.
 Scarification & Expression Methods

B- Ecuelle-à-piquer method
 Based on puncturing (scarifying) the surface of whole fruits (lemon),
the oil exudes from the outer zone of the peels in the form of emulsion.

 The instrument is funnel-shaped, formed of a

shallow bowl with a tubular projection at the
center. The bowl bears numerous pins which
scarify the oil glands to release the oil.

 The tubular part serves as:

1. Handle to rotate the instrument.
2. Receiver to collect the oil.
 Scarification & Expression Methods
C- Expression of rasping process
 Based on removal of the outer layer of the peel with a
grater, collecting the rasping in special bags then strong
pressing.

 The oil emulsion is collected in large vessels

D- Machine processes
 Based on the same principles as the above 3 traditional
methods A, B & C but carried out by machines.
 Solvent extraction methods
Principle
Based on extraction of the volatile oil from the plant
material with a suitable solvent

According to the nature of the solvent used, three

types are distinguished:

1. Volatile solvent extraction

2. Non-volatile solvent extraction
3. Supercritical fluid extraction
 Solvent extraction methods-Application

Preparation of delicate flower oils

e.g. jasmine, violet, tuberose &
narcissus which are:

1. Present in very small amounts,

not easily obtained by
distillation or expression

2. Oils formed of thermolabile

constituents (i.e. easily
decomposed by heat)
 Volatile solvent-extraction
Preparation of "floral concretes"
1. Solvents used: petroleum ether & n-hexane
2. Extraction (“percolation” or “maceration” at room temperature,
“continuous hot extraction” in a Soxhlet apparatus at constant temperature)
3. Solvent removal (distillation under reduced pressure)

Percolator

Soxhlet apparatus
 Volatile solvent-extraction
Floral concrete = Fragrant constituents + Fats + Waxes +
Albuminous matter + Fat soluble pigments e.g. "floral
concrete" of jasmine is semi-solid & yellowish-orange in
color.

Floral absolute = consists mostly of the oxygenated

constituents of the oil.
 More expensive & purified than the corresponding concrete.
 Preparation: repeated extraction with absolute alcohol
 Impurities: removed by strong cooling & filtration
 Solvent removal : by distillation.
 Non-volatile solvent extraction
Application: Preparation of natural flower oils
producing the finest perfumes.

Principle: based on the liposolubility of volatile oils

Solvents:
Lipids of high degree of purity e.g.
 Fats (lard : tallow in a mixture 2:1)
 Fixed (olive oil)

Techniques:
 Enfleurage (hot & cold)
 Pneumatic method
 Maceration (in fixed oils)
 Enfleurage Process- Preparation of jasmine oil

 Equipment:
Great number of glass plates closely arranged in wooden
frames (or chassis).
 Procedure:
1. Spread the mixture of fat (lard / tallow 2: 1) on both surfaces of
each glass plate.
2. Cover the top of each plate with flowers or petals, so that each layer
of flowers is enclosed between 2 layers of fat.
3. Replace old flowers by fresh ones every 2-3 days
4. Repeat the process until the fat is saturated with the oil
5. Remove the last charge of flowers from the fat ("Defleurage")
6. Scrap & collect the fat layers, warm, filter through gauze & cool 
“Enfleurage product” or “Floral pomade”
 Enfle urag e Pro c e s s

Flo we r Pe tals
Add fat mixture
[Lard & ta llo w (2 : 1)]

1) Enfle ura g e Prod uc t (flo ral po made )

[Fat s a turate d w ith o il]
* Add abs o lute a lc ohol
* Triple e xtrac tio n
* Co oling (re mo ve mos t of fat)

2) Trip le e xtrac t
[alc . s o lutio n of vo l. oil + pig me nts + trac e s o f fats ]

Eva poration o f alc o hol Dilution with

or fra c tio na l dis tillation H2 O + NaCl

3)Abs o lute of Enfle urag e 4)Vola tile oil

[S e mi-s olid, alc o ho l-fre e pro duc t] Jasmine flowers
Enfleurage” Process“
Cold Enfleurage

Hot Enfleurage
 Super critical fluid extraction
Principle: based on using liquefied gases e.g. CO2 under
specific temperatures & pressures as extracting
solvents. Under these conditions these gases are liquids
but maintain the penetrating properties of gases &
allow more efficient extraction. The oils obtained are of
closest composition to the natural oils.
 Process Applications Advantages Disadvantages

Distillation For dried & fresh Cheapest method High temperature

material, rich in volatile (apparatus, solvent & & presence of water
oils with thermostable source of heat) may affect the
constituents constituents.

Scarification & For preparation of oils -Carried at room Expensive due to need
Expression present in large amounts temperature of high number of
in outer peels of fruits & workers
rich in heat-sensitive -Yields oils with more
constituents. natural odors.

Extraction Suitable for fresh -Carried at room or Expensive due to use of

material with heat- low temperature solvent & / or high
sensitive oils present in number of workers.
small amounts -Yields oils with more
natural odors
 Methods based on enzymatic hydrolysis of
glycosides
Glycosides with volatile aglycones are found in: Gaultheria sp.

1. Volatile oil-containing plants e.g. mint, rosemary,

Pinus spp., cinnamon & celery.
2. Plants devoid of volatile oils e.g. Gaultheria spp.,
black mustard & bitter almond.

Black mustard

The volatile aglycones are known as the

"essential oils" of the plants e.g.

1. Methyl salycilate = oil of wintergreen

2. Allyl isothiocyanate = volatile oil of black
mustard
3. Benzaldehyde = volatile oil of bitter almond
Bitter almond
 Methods based on enzymatic hydrolysis of
glycosides: Principle

1. Plant material + enzymatic hydrolysis  volatile

aglycones in the hydrolysate
2. Hydrolysate + distillation or extraction with
organic solvent  volatile aglycone

Fixed oil if present in large amount in the plant material

should be removed by expression before hydrolysis
 Examples of glycosides with volatile aglycones

Non-volatile Other hydrolytic Hydrolytic

Plant name Volatile aglycone
Glycoside products enzyme

Gaultheria Gaultherin Methyl salicylate Primeverose (Xylose + Gaultherase

procumbens Glucose)
(Ericaceae) &
Monotropin Methyl salicylate Glucose
Betula lenta
(Betulaceae)

Geum urbanum Gein Eugenol Glucose -Glucosidase

(Rosaceae)

Brassica nigra Sinigrin Allyl isothiocyanate Glucose + Potassium acid Myrosin

(Brassicaceae) sulfate

Vanilla planifolia Glucovanillin Vanillin Glucose -Glucosidase

(Orchidaceae)

Amygdala amara Amygdalin Benzaldelhyde Gentiobiose (2 Amygdalase &

(Prunus glucose units) + HCN Emulsin
amygdalus,
Rosaceae)
 Preparation & purification of volatile oil
of bitter almond
1. Seeds crushed & fixed oil removed by expression
2. Cake macerated in water for few hours, at 40ºC in a closed vessel
Amygdalin  hydrolysis (Amygdalase + Emulsin)  Benzaldelhyde + 2
glucose + HCN
3. Steam distillation  benzaldehyde + HCN (free state or as benzaldehyde
cyanohydrin)
 Purification of bitter almond oil or "Removal or fixation of HCN"
By transformation to the non-volatile Ca2Fe(CN) 6 : Impure
distilled oil + Ca (OH)2 +FeSO4+ redistillation
 Detection of residual HCN in the purified oil
Prussian blue test: Oil + NaOH (t.s.) & shake, if any traces of HCN 
NaCN + FeSO4 (traces of Fe+++ ions) + HCl & warm  Fe4 Fe (CN)6]3
(ferric ferro cyanide), bluish black in color.
2 HCN + Ca (OH) 2 Ca (CN)2 + 2H2O
Volatile Non-volatile

3 Ca (CN) 2 + FeSO4 Ca2 Fe (CN)6 + CaSO4

Non-volatile
 Determination of percentage
of volatile oil in plant Miscibility with alcohol
material

1. Most volatile oils are miscible

with absolute alcohol.

2. Oils highly miscible with alcohol

of low concentrations are usually
rich in oxygenated constituents.

3. Decreased miscibility with alcohol

of low concentrations 
adulteration with non-polar
solvents e.g. petroleum ether
(turbidity) or fixed oils

% v/w = Vol of oil × 100 / Wt of drug

 Physical Examination: helps in evaluation of the oil sample & detection
of adulterants
Odor Optical rotation [Apparatus: Polarimeter ]
Detection of any abnormal odor (by smelling 1 or 2 1. Determination helps in detection of
drops of the oil applied on a filter paper)  adulteration & identification of the variety of
adulteration or deterioration during storage the sample e.g.
e.g. orange oil acquires a caraway odor on bad  French oil of turpentine is levorotatory [l (-)]
storage due to autoxidation of limonene to as it contains l-pinene in high concentration.
carvone & carveol  American oil of turpentine is dextroratory [d
Solubility (+)] as its major constituent is d-pinene.
1. Oils are soluble in non-polar solvents as 2. Gives indication on the method of
benzene, carbon disulfide & light petroleum. preparation of the volatile oil isolate:
2. Any turbidity  moisture  All synthetic compounds are racemic (dl).
Specific gravity  Natural compounds are generally optically
active present in (l) or (d) forms.
Apparatus: pycnometer (specific gravity
Example: natural camphor is (l) or (d) while
bottle)
synthetic camphor is (dl).
Sp. gr. gives an indication on composition
1. Oils with sp. gr. < 0.9, rich in hydrocarbons &
Refractive index [Apparatus: Refractometer]
aliphatic compounds
Refractive Indices of volatile oils range from
2. Oils with sp. gr. > 1.0, rich in aromatic & S
compounds. 1.4- 1.6 any deviation  adulteration
3. Oils with 0.9 > sp. gr. < 1.0, contain different
types of constituents
Pycnometer

Polarimeter

Abbe refractometer
 Chemistry of volatile oils constituents

Types of constituents detected in volatile oils:

V. O. are complex mixtures formed of:
1. Terpenoids (mainly mono- & sesquiterpenoids)
2. Phenyl propanoids (C6-C3, aromatic)
3. Aliphatic compounds (acyclic, straight chain compounds which
may be terpenoids).
4. Miscellaneous compounds e.g. organo-nitrogen & organo-sulfur
compounds.

 Each group includes non-oxygenated (hydrocarbons) &

oxygenated compounds.
 Oxygenated constituents are generally responsible for the
characteristic odor of the oil.
 Removal of terpenoid hydrocarbons

 Oils rich in terpenoid hydrocarbons deteriorate rapidly on storage

due to oxidation & polymerization  bad smelling (with turpentine-
like odor) & resinified products.
 Removal of most terpenoid hydrocarbons  "terpeneless-oils" by
any of the following methods:
1. Fractional distillation under reduced pressure: hydrocarbons
have lower b.p. than oxygenated compounds, they distill first &
are rejected.
2. Column chromatography on silica gel: hydrocarbons are eluted
with n-hexane then oxygenated compounds with absolute alcohol.
3. Selective extraction oxygenated components with dilute alcohol
followed by distillation.
 ”Terpeneless oils“ “Volatile oil isolates”
Oils from which most terpene  An isolate is a single
hydrocarbons are removed chemical substance
1. More expensive than natural isolated from the oil
oils “Oleoptene & Stearoptene”
2. Richer in oxygenated
1. Stearoptene = solid fraction
compounds.
separating on cooling a v.o.
3. More soluble in low-strength
(previously known as
alcohols.
camphors), consists of 1 or
4. Used in smaller amounts to give more solid (mainly oxygenated )
the same strength of odor. compounds
5. More stable being less liable to 2. Oleoptene = remaining liquid
deterioration fraction, mainly formed of
hydrocarbons
 Isolation of volatile oil constituents

 Physical methods (cooling, fractional distillation,

fractional crystallization & preparative gas
chromatography)

 Chemical methods depend on:

1. Solubility differences in acids or alkalis
2. Derivatization (due to presence of functional groups).
3. Adduct formation (specific for certain compounds).
 Chemical methods for isolation of V.O. constituents
Solubility in alkalis:
1. Compounds containing -COOH group (strongly acidic) + mild alkali (Na 2CO3) 
water soluble Na salts (decomposed by acids).
2. Phenolic compounds (mild acids) + aqueous NaOH or KOH (strong alkalis)  water
soluble Na or K phenates (decomposed by acids)  phenol.

Derivatization:
1. Alcohols  esterification  phenyl urethans or acid phthalates
2. Carbonyl compounds  derivatives e.g. crystalline bisulfites, semicarbazones, phenyl
hydrazones & oximes.

Formation of crystalline additive products

1. Geraniol, benzyl & cinnamyl alcohols + anhydrous CaCl2.
2. Carvone + H2S gas in presence of NH3.
3. Cineole + strong acids (e.g. H3PO4) & resorcinol
4. Unsaturated terpene hydrocarbons + HCl, HBr & NOCl (nitrosyl chloride or
Tilden’s reagent).
5. Azulenes +
 Strong mineral acids e.g. H3PO4 and H2SO4
 Ferrocyannic acid
 Terpenoids (Terpenes)
 They constitute the largest known group of secondary metabolites.
 The term “terpenes” should better be used to indicate the
unsaturated hydrocarbons
 All yield isoprene as final product of destructive distillation (=
pyrolysis).
 Isoprene, a 5 carbon-atom unit, is the building unit of all terpenoids

1 CH h
2
4 t Abbreviated structure
H2C 3 C 2 h=head, t=tail
C CH3

Isoprene, 2-methyl 1:3 butadiene, 1,3 isopentene

 Isoprene rule for formation of terpenoids
 Theoretical biogenetic rule which states that: “Each group of
terpenes originates from the head-to-tail condensation of a variable
number of isoprene units”.
Is o pre ne

Bic yc lic
Is o p re ne Mo no c yc lic Mo no te rp e ne
Ac yc lic
m ono t e rpe ne mo no te rpe ne

Is o pre ne
Is o pre ne

Is o pre ne Ac yc lic s e s quite rpe ne Mo no c yc lic s e s quit e rpe ne

Coupling of isoprene units to yield mono- & sesquiterpenoids

 Terpenoids in Essential Oils
 Thousands are identified in essential oils
 Mainly mono- or sesquiterpenoids (volatile & of low
molecular weight)
 Acyclic (i.e. aliphatic) or Alicyclic (i.e. with non-aromatic
ring-structures)
 Hydrocarbons or oxygenated (alcohols, aldehydes, ketones,
esters, ethers, oxides or peroxides)
 Often optically active occurring as d-, l- & dl isomers

Monoterpenoids (C 10)
1. Most abundant class of essential oil constituents.
2. Consist of 2 molecules of isoprene
3. Hydrocarbons have the empirical formula C10H16
4. Acyclic or alicyclic (mainly mono- & bicyclic)
 Terpenoids in Essential Oils
Sesquiterpenoids (C15)
1. Present in the high boiling point fractions of the oils (250-280 oC).
2. Mostly viscous liquids or may be crystalline.
3. Consist of 3 molecules of isoprene
4. Hydrocarbons have the empirical formula C15H24
5. Acyclic, monocyclic or polycyclic.
6. Occur in more than 100 different skeletons with ring size ranging from 4,
7, 8, 10 & 11 C atoms.
Azulenes (C15H18)
1. Usually discussed under sesquiterpenoids because they have the same
number of C atoms & distill in the same boiling range.
2. But, they possess aromatic properties due to high conjugation & are
highly colored (generally blue, green or violet) e.g. Chamazulene in oil of
chamomile.
 Nomenclature of terpenoids
 Chemical names are derived from the corresponding saturated hydrocarbon
skeleton

1. The acyclic monoterpenoids are 2, 6-dimethyl octane (myrcane) derivatives.

2. Most monocyclic monoterpenoids are para-menthane rarely meta-menthane
derivatives.
3. Bicyclic monoterpenoids are thujane, carane, pinane, camphane or fenchane
derivatives.
4. Acyclic sesquiterpenoids are trimethyldodecane derivatives.
5. Mono- & polycyclic sesquiterpenoids are bisabolane, humulane, elemane,
germacrane cadinane, santalane, cedrane derivatives etc…
6. The number & position of the double bonds are indicated e.g. a double bond
between C1 & C2 by 1 ; while a double bond between C1 & C6 by 1(6)

 Trivial names are better adopted for facility.

 Saturated hydrocarbon skeletons of mono- &
sesquiterpenoids
MONOTERPENOIDS
S ES QUITERPENOIDS

Myrc a ne p-Me nthane m-Me nthane

Trime thyldode c ane Bis abo la ne Ele ma ne

Thujane Ca ra ne Pinane

Ge rmac ra ne Humulane Ca dinane

Bo rna ne (Campha ne ) Fe nc hane is o-Camphane

 Isomerism of Monoterpenoids

 Structural isomerism due to

shift in the double bonds, e.g.

Myrcene Ocimene Limonene Terpinene

 Structural isomerism due to

shift in the position of a
substituent group e.g. p-
menthadiene & m-menthadiene
derivatives.

Limonene Sylvestrene
 Isomerism of Monoterpenoids
 Geometrical isomerism: e.g. the cis-trans isomeric alcohols, nerol & geraniol.

CH2 OH H
H
CH2 OH

Ge ranio l Ne ro l

 Optical isomerism: due to the presence of one or more asymmetric C atoms e.g.
dipentene occurs in d, l & dl forms due to asymmetry at C 4 (not involved in a
double bond), while terpinene is optically inactive.
 Strainless ring isomerism: chair & boat configurations more stable than
planar configuration.
 Isomerism due to molecular rearrangement of the ring structures: e.g.
from pinane to camphane etc….
 Phenyl propanoids (C6-C3) or
Aromatic constituents
 Less common than terpenoids.
 Contain a C6 phenyl ring to which is attached a C3 propane
side chain
 Many are phenols (e.g. eugenol), phenol ethers (e.g.,
anethole, safrole, apiole) or aldehydes (e.g.,
cinnamaldehyde).
 The propane side chain may be formed of 2 C (C6-C2) or 1
C (C6-C1) e.g. vanillin, methyl salicylate & methyl
anthranilate.
 Certain aromatic C10 compounds e.g. p-cymene, thymol &
carvacrol can be described under monoterpenoids.
Examples of phenyl propanoids in volatile oils
OH

OH

p-Cyme ne Thymo l Carvac ro l

OCH3 OH O O
OCH3 O H CO O
3

OCH3

Ane thole Eug e no l S affro le Apiole

OH
O
OCH3 CHO
OCH3 CH2 OH

OH
CHO
Vanillin Cinnamalde hyde Me thyl s a lyc ilate Phe nyl e thyl a lc ohol