The Islands of Spice

Chemistry of Essential
Oils
Dwi Setyaningsih

PROPERTIES OF
VOLATILE OILS

Almost entirely volatile without decomposition

Density: Most are less than 1g/ml
heavier Cinnamon and Clove oil
Soluble in ether, chloroform & alcohol
Slightly soluble in water: give it a characteristic odour &
taste. All are characteristic odours
Most are colourless, Most are optically active
Oxidize on exposure to air and resinify colour becomes
darker (odour changes slightly)

VOLATILE
OIL
COMPOSITION
VOLATILE OIL COMPOSITION
Mixtures of hydrocarbon and oxygenated
compounds derived from these HCs.
Oil of turpentine mainly HCs
Oil of clove mainly oxygenated
compounds
Exception: Oils derived from glycosides
( bitter almond & mustard oil)
Oxygenated compounds responsible
for the odour/smell of the oil. Slightly
water soluble
Rose water & Orange water; more
alcohol soluble
Most volatile oils are terpenoid. Some
are aromatic (benzene) derivatives fixed

CHEMICAL
COMPOSITION
CHEMICAL
COMPOSITION
Volatile oils are divided
into 2 main classes
based on their
biosynthetic origin
I.
Terpene derivatives
(acetate mevalonic
acid pathway)
II. Aromatic
compounds
(shikimic acidphenylpropanoid
route)
III. Miscellaneous
Origin

CO2
Photosynthesis
Carbohydrates
Pentose phosphate pathway
Glycolysis
Erythrase 4-phosphate

Shikimic acid
pathway

Phosphoenol pyruvic acid

Tricarboxylic acid

Aromatic amino acids

Alphatic amino acids

Nitrogen containing
secondary metabolites

Acetyl CoA
Melonic acid pathway

Mevalonic acid
pathway
IPP + DMAPP

Phenolic compounds

Terpenes

TERPENES

CLASSIFICATION

Terpenes/terpenoids, the largest

group of secondary metabolites
Constitute one of the most
diverse families of natural
products, with over 40 000

different structures of terpenoids

All formed from acetyl CoA or

glycolytic intermediates

Unsaturated hydrocarbons
Monoterpenes and
sesquiterpenes used in
flavours and fragrances
Weak odours not fully
represented they come from
Sometimes poorly soluble in
weak ethanolic solutions

Terpenoids contain only the

most volatile terpenes (MW
is not too high) mono
and sesquiterpenes
All terpenes are formed from
5-C elements
Isoprene is the basic
structural element
May occur as oxygenated
derivatives : alcohols,
aldehydes, ketones, phenols,
oxides & esters
Can oxidate or polymerise
easily changing odour and
lessening volatility

Terpenoids
Form a large and structurally diverse family of
natural products derived from C5 isoprene units
joined in a head to tail fashion
CH3
H2C
1

C
2

tail
CH
3

CH2
4

Isoprene
(2-methyl-1,3-butadiene)

head

Isoprene unit
C5

e biologically active isoprene units were identified as

e pyrophosphate esters IPP (Isopentenyl pyrophosphate)
d DMAPP (Dimethylallyl pyrophosphate)

Mevalonic acid

ORIGIN OF
TERPENES
OPP

OPP

DMAPP (C5)
GPP (C10)

Hemiterpenes (C5)

IPP (C5)

Monoterpens & Iridoids (C10)

OPP

IPP
FPP (C15)

Sesquiterpenes (C15)

OPP

IP
P

Sesterpene (C25)
Diterpenes (C20)

GGPP (C20)
2 x FPP

squalene

OPP

Triterpenes (C30)

2 x GGPP

Steroids (C18-C30)

Tetraterpens
(C40)

TERPENES
BIOSYNTHESIS
IN PLANT CELL

Terpenoids are
enzymatically synthesized
from acetyl CoA and
pyruvate provided by the
carbohydrate pools in
plastids and the cytoplasm.

Classification of Terpenes

C10-Monoterpenes :
Regular monoterpenes (EO, oleoresins,
iridoids)
Irregular monoterpenes (pyrethrins)
C15-Sesquiterpenes : essential oils, sesquiterpenoid, lactons
C20-Diterpens : retinol
C30-Triterpens & steroids : saponins, cardiac glycosides
C40-tetraterpenes : -carotenes

Terpenes
Myrcene (isolated from oil of bayberry)
is a typical terpene
CH3

CH2
CHCH2CH2CCH

CH3C

or

CH2

The Isoprene Unit

An isoprene unit is the carbon skeleton of
isoprene (ignoring the double bonds)

Myrcene contains two isoprene units

The Isoprene Unit

The isoprene units of myrcene are
joined "head-to-tail."

tail
head
tail head

REPRESENTATIVE MONOTERPENES

OH

OH

-Phellandrene
(eucalyptus)

Menthol
(peppermint)

Citral - oxygenated monoterpene

- seldom comprises > 2% of the
essential oil of lemon - largely
carries the lemon flavor

(lemon grass)

REPRESENTATIVE SESQUITERPENES

-Selinene
(celery)

REPRESENTATIVE DITERPENES

OH

OH

Vitamin A

REPRESENTATIVE TRITERPENES

tail-to-tail linkage of isoprene units

Squalene
(shark liver oil)

From 15 Carbons to 20

OPP

OPP

Farnesyl pyrophosphate is extended by another

isoprene unit by reaction with isopentenyl
pyrophosphate.

Cyclization

Rings form by intramolecular carboncarbon bond formation.

OPP
OPP
E double
bond

Z double
bond

Limonene
H

OH
H2O

-Terpineol

Bicyclic Terpenes

+
-Pinene

-Pinene

EXAMPLES OF TERPENES
LIMONENE

Structural classification: a
monoterpene hydrocarbon
Monocyclic terpene
Functional classification:
Unsaturated HC
Occurrence: Citrus fruit
The major terpene in many
or most citrus products.
Orange > 95%
Lemon ~ 65%

MENTHOL

Structural classification:
Monocyclic with hydroxyl
group
Functional classification:
Alcohol
Occurrence: Peppermint

BORNEOL
Occurrence: Cinnamon

NEROL

Cis-3,7-Dimethylocta-2,6-1-ol

OH

Colourless to pale liquid

Stable
Application: Magnolia, Neroli,
Jasmin, Lilac and other floral
perfumes
Origin: Rose, Neroli, Petitgrain,
Lavender, Lemongrass,
Palmarosa and citrus oils

GERANIOL

Trans-3,7-Dimethylocta-2,6-dien-ol
Colourless liquid
Stable
Applications: Floral and most other
perfumes
Origin: Rose, Citronella, Geranium
and Palmarosa

LINALOOL

3,7-Dimethylocta-1,6-dien-3-ol
Colourless Liquid
Stable
Applications: Almost universal
application in fragrances,
especially floral
Origin: Rose, rosewood,
Lavender, minor constituent of
others

EXAMPLES OF TERPENES

SESQUITERPENES

Contain 3 isoprene units

Acyclic Farnesol
CH2OH

Monocyclic Zingiberine

Bicyclic Chamezulene
(Chamomile)

MONOTERPENE SKELETONS

Regular

Irregular

Iridane

Iridoid

The iridan skeleton found in iridoids

is monoterpenoid in origin and
contains a cyclopentane ring which is
usually fused to a six-membered
oxygen heterocycle

Pyrethrins

EXAMPLES OF TERPENES

Apocarotenoid formation

Carotenoid substrates are oxidatively cleaved to yield the apocarotenoid

derivatives (right).

Many terpenoids are non-volatile and are involved in

important plant processes such as membrane structure
(sterols), photosynthesis (chlorophyll side chains,
carotenoids), redox chemistry (quinones) and growth
regulation (gibberellins, abscisic acid, brassinosteroids)

AROMATIC COMPOUNDS

Many phenols are

phenol esters

- Vanillin

Phenols
Eugenol
Compounds with 1 or 2
hydroxy groups, similar to
benzyl alcohols
Tend to be toxic and caustic
Prone to oxidization
Basically clean type odours

4-allyl-2-methoxyphenol
Stable
Colourless liquid
Applications: Carnation,
spicy fragrances, rose and
oriental perfumes
Origin: Clove, cinnamom
leaf oil, patchouli, Ylang
Ylang

Major classes of phenolic compound

Numbe
r of C
atoms

Basic
skeleton

C6-C1

Benzoic

p-Hydroxybenzoic
acid
Vanillic acid
Protocatechuic acid

C6-C3

Hydroxycinna
mic acids

Caffeic acid

15

C6-C3-C6

Flavoids
Anthocyanins

Cyanidin

Flavonoids
glycosides

Rutin

Iridoids

Oleuropin
Ligstroside

Class

Lignins
Tannins

Example

Alcohols
Hydroxy compunds
consisting of hydrocarbon
chains
Primary, secondary and
tertiary alcohols (i.e., no.
carbon atoms), also
aliphatic alcohols
Terpenoid alcohols very
important chemicals found
in many plants
Polyhydric alcohols (2 or
more hydroxy groups)
odourless, but solvents
Acyclic alcohols faint

Phenylethyl Alcohol

2-Phenylethanol
Colourless liquid
Stable
Sweet rosy like odour
Applications: widely
used in synthetic form
From floral to aldehydic,
chypre and fougere
Fragrances
Origins: Rose, Neroli,
Geranium and Ylang
Ylang

Eugenol

Citronellol

3,7-Dimethyloct-6-en-1-ol

Colourless liquid, Stable

Applications: used in florals

Origin: Rose, citronella oils

Benzyl Alcohol

Oct-1-en-3-ol
Colourless liquid, Stable
Strong, fatty, orange like, balsamic
Applications: In the reconstruction of
lavender and lavindin oils
Origin: in some mushrooms and savory oil

OH

Carboxylic Acids
Benzoic Acid
Organic acids with a
carbonyl and hydroxy
group
Usually derived from
aliphatic alcohols or
aliphatic aldehydes
through oxidization
Odours usually resemble
precursors

Colourless
crystaline solid
Slightly pungent
odour

Esters
Derived from alcohols
in reversible reactions

Benzyl Acetate

Fruity notes
Not very pH stable

Colourless liquid, Stable

Applications: Versitile in many fragrances,
especially jasmin and gardenia
Origin: Jasmin, Tuberose, neroli, Ylang
Ylang

Aldehydes
Fatty aldehydes have
pungent odours
Aliphatices used in
perfumery and flavours
mainly from synthetic
sources
Usually used in very
diluted forms
Aldehydes are very
reactive (oxidisation,
polymerisation and acetal
formations)

Benzaldehyde

Colourless liquid

Can oxidize to benzoic acid

Applications: In traceable
amounts in sweet florals

Origin: Bitter almond oil,

cassia

Aldehydes

Amines
Compound with one or
more hydrogen atoms of
ammonia, replaced with
hydrogen radical

Methyl Anthranilate
(Methyl 2-aminobenzoate)

3 types, primary,
secondary and tertiary
Most foul smelling
animalic

Colourless liquid
Discolouration
From many flowers
such as orange and
ylang ylang

Lactones
Naturally ocuring in many
fruits

-butyrolactone

Most often hydroxy group

of alcohols which react with
carboxylic acids

-caprolactone

Contain ester functional

group in the cyclic part of
the molecule
Important fruit flavours &
fragrances

and

FLAVONOIDS
OCCURRENCE
Flavonoids are widely distributed in the flora

they can be found in petals, crops, seeds,

leaves, stems, roots and barks
it is the reddish brownish - yellowish colour
of heartwood
flavonoids of ferns are C-methyl derivatives
glycoflavonoids can be isolated from seaweeds
microorganisms and algae species do not
synthesize

STRUCTURE OF FLAVONOIDS
Polyphenols, namely favonoids are low molecular weight
The skeleton can be represented as the C6 - C3 - C6 system Three
main groups can be distinguished on the places of phenyl ring.
The chemical structure of
flavonoids are based on a
C15 skeleton with a
chromane ring bearing a
second aromatic ring B in
position 2, 3 or 4.
The oxidation state of
propane chain means the
difference. Oxidation
degree rises from 0 to 6

REASON FOR
THEIR VARIETY

OH groups
number and position of
O-methyl, O-alkil, O-glycosyl-groups
variance of glycosyl groups, acylation
with or without conjugated double bonds

The most often occuring substituents can bond to C3 -, C5 , C7 -, C3 -, C4

atoms.
Sugars can bond:

through oxygen atom (O-glycosides)

directly to C-atom (C-glycosides)

Antocyanides are always in their glycoside forms in vacuoles (in cell fluids)
Catechines and procyanidines can be stored in their aglycone forms
(tannic acid holders, dissolved in essential volatile oils)

THE ROLE OF FLAVONOIDS IN

PLANTS

Flavonoids are the secondary metabolites of plants, and

they are providing the colour and flavour materials

protect against UV-radiation, fungus, insect and snail pests

they are signal for N-bound bacteria
they modify enzyme reactions
75% of Angiospermae contain kaempferol and quercetin and 10% of
them myricetin

kaempferol

quercetin

myricetin

SYNTHESIS OF FLAVONOIDS

Phenylpropanoid pathway : amino acid phenylalanine -- 4-coumarateCoA combined with malonyl-CoA to yield the true backbone of
flavonoids, called chalcones which contain two phenyl rings.

Conjugate ring-closure of chalcones results in the familiar form of

flavonoids, the three-ringed structure of a flavone.

 series of enzymatic modifications

flavanonesdihydroflavonolsanthocyanins
Along this pathway, many products can be formed :
flavonols, flavan-3-ols, proanthocyanidins (tannins), polyphenolics.

BIOFLAVONOIDS
flavone, flavonol, flavanone, flavanonol
2-phenyl-benzo--pyron

isoflavone
3-phenyl-benzo--pyron

catechin

anthocyanidin

High concentration of
quercetin in in vitro
causes DNA mutations
in spite of this flavonoid
prevents
atherosclerosis, infarct

ALKALOID
Boundary : contains atom which has base properties
and become part of heterocyclic ring
Classification :
1. Base on the heterocyclic N ring
2. Base on the plant source
3. Base on biogenetic origin

N
N
Isoquinoli
H
H
Isokuinolin
ne
Pirolidin
Piperidin
Pirolidine Piperidin
e

N
Kuinolin
Quinolin
e

N
Indol H
Indol

Caharacteristics of Alkaloid Structure

1. Policyclic skeleton and substituen group are not
varried
2. Nitrogen atom found as amine group (-NR2) or
C NR2
amide
not as NO2 (nitro) or N=N- (diazo)
O

3. Oksigen substituen found as phenol (-OH), metoxy

(-OCH3) or methylen dioxy (-OCH2-O) at para or para
N CH3in aromatic ring
and meta position
4. Substituen

is frequently found

THANK YOU FOR YOUR

ATTENTION