Terpenoids

PRESENTED BY:
Sayli Sawant
(F.Y. M. Pharmacy)
Department of Pharmaceutical Chemistry

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CONTENTS
1. Introduction
2. Classification of terpenoids
3. Isoprene rule
4. Isolation of terpenoids
5. General methods of structural elucidation of terpenoids

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 INTRODUCTION
 Terpenes are hydrocarbons and components of resins and also turpentine
produced from resins.

 When terpenes are modified chemically such as by oxidation or

rearrangement of carbon skeleton, the resulting compounds are known
as TERPENOIDS.

 Terpenoids are regarded as derivatives of polymers of ISOPRENE;

and are abundantly available in volatile oils. They consist of a mixture
of terpenes or sesquiterpene, alcohols, aldehyde, ketones, acids and
esters.

Isoprene unit

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 General properties:
a) Most of the terpenoids are colourless, fragrant liquids which are lighter
than water and volatile with steam. A few of them are solids e.g.
camphor. All are soluble in organic solvent and usually insoluble in water.
Most of them are optically active.
b) They are open chain or cyclic unsaturated compounds having one or more
double bonds. Consequently they undergo addition reaction with
hydrogen, halogen, acids, etc. A number of addition products have
antiseptic properties.
c) They undergo polymerization and dehydrogenation
d) They are easily oxidized nearly by all the oxidizing agents. On thermal
decomposition, most of the terpenoids yields isoprene as one of the
product.

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 CLASSIFICATION
Based on no. of Isoprene units present :
Sr. Class No. of Isoprene Molecular Example
No. units formula

1. Monoterpenoids or Terpenes 2 C10 H16 Citral, Menthol

2. Sesquiterpenes 3 C15 H24 Eugenol

3. Diterpenes 4 C20 H32 Taxol, Retinol

4. Triterpenes 6 C30 H48 Squalene

5. Tetraterpenes or Carotenoids 8 C40 H64 β-carotene

6. Polyterpenes or Rubber n (C5 H8)n Crocin, Bixin

Eugenol Retinol

Beta- carotene

d-Limonene 5
Based on the no. of rings present in the structure :
Sr. no. Class No. of rings Example

1. Acyclic Terpenoids Open structure Geraniol, Phytol

2. Monocyclic Terpenoids 1 d- Limonene, Menthol

3. Bicyclic Terpenoids 2 Manool

4. Tricyclic Terpenoids 3 Abietic acid

5. Tetracyclic Terpenoids 4

Citral Menthol Manool Abietic acid

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 ISOPRENE RULE
 In 1887, Wallach enunciated the famous isoprene rule which may be
stated as follows:
“The skeleton structures of all naturally occurring terpenoids are built
up of isoprene units.”
 The divisibility into isoprene units is regarded as a necessary condition to
be satisfied by every naturally occurring terpenoid.
 The isoprene rule has been deduced from the following facts:
a) The empirical formula of almost all the naturally occurring terpenoids is
C5H8.
b) The thermal decomposition of almost all terpenoids gives isoprene as
one of the products. For examples, rubber on destructive distillation
yields isoprene as one of the decomposition products.

Destructive
(C5H8)n nC5H8
distillation
Isoprene

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Special Isoprene Rule:
 This rule was proposed by Ingold (1925) and it tells us how the
isoprene units in the terpenoids are linked together.
 The branched end of the isoprene unit is considered as the head and
the other end as the tail. The isoprene units of terpenoids are linked in
a head to tail fashion.

H H
or H

T T
T
T

where H - Head H

T - Tail

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 It should be noted that this rule can only be used as a guiding principle
and not as a fixed rule. Therefore, there are departures and violations
of this rule in many compounds.
i. Certain terpenoids are known whose carbon content is not a multiple
of five. For example, Cryptone contains nine carbon atoms.
ii. Certain terpenoids are known whose carbon content is a multiple of
five but cannot be divided into two isoprene units.
iii. Certain terpenoids are also known in which the special isoprene rule
is violated. For example, lavandulol is composed of two units of
isoprene with the unusual linkage of tail to tail and not head to tail.

Cryptone Lavandulol

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 ISOLATION
1. Isolation of essential oils. 2. Separation of Terpenoids.

Plant part having maximum The essential oils obtained contain a

concentration of essential oil at a number of terpenoids and these are
particular time are desirable for separated by various chemical and
extraction of oil. physical methods.
Following are the methods used: Following methods are used:
a. Expression method. a. Chemical methods.
b. Steam distillation method. b. Physical methods:
c. Extraction by means of volatile • Fractional distillation method
solvents. • Chromatography
d. Adsorption in purified fats.

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1. Expression method.
Plant material is cut into small
pieces. The pieces are crushed
to get juice and larger particles
are removed.
The juice is centrifuged in a
high speed centrifugal
machine.
One half of oil is extracted and
the rest half remains with
residue.
From residue, inferior quality
of oil is obtained by
distillation.
This method is used to extract
citrus, lemon and grass oils.
2. Steam distillation method.
The plant materials are
macerated and then steam
distilled to get essential oils.
Essential oils in the distillate
are extracted by using pure
organic volatile solvents.
The solvent is then removed
by distillation under reduced
pressure.
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3. Extraction by volatile solvents

The oils from

The oil is taken this extract are
The plant
up by the separated by
material is
solvent along removing the
directly treated
with the soluble solvent by
with light petrol
colouring distillation
at 50oC.
materials. under reduced
pressure.

4. Adsorption in purified fats

The fat is warmed to The petals are This extract is cooled

50oC on glass plates. removed, the fat is to 20oC and the fat
Then the surface of fat digested with ethanol. separates out. This is
is covered with flower some quantity of fat is fractionally distilled
petals and is kept for also dissolved in under reduced
several days. alcohol. pressure.

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Separation of terpenoids
1. Chemical methods 2. Physical methods
• Essential oil containing
terpenoid are treated with
nitrosyl chloride and
chloroform, which result
in crystalline adducts
1. having sharp melting
points.
• Essential oils containing
alcohol are treated with
phthalic anhydride to form
diesters, which are
2. decomposed by alkali to
parent terpenoid alcohols.
• Terpenoid aldehydes and
ketones are separated by
forming adducts with 2,4-
dinitrophenylhydrazine,
NaHSO3 ,
3. phenylhydrazine.
• Fractional distillation
• The terpenoid-
hydrocarbon distill out
first, followed by
oxygenated derivatives.
• Distillation of residue
under reduced pressure
1. yields the
sesquiterpenoids and
these are separated by
fractional distillation.
• Chromatography
• In adsorption
chromatography, alumina
and silica gel are used as
adsorbents, specially for
separating triterpenoids.
• Gas chromatography has
2. been useful for isolating
pure configurational
forms of a given
terpenoid from mixtures
produced by synthesis.
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GENERAL METHODS OF
STRUCTURAL ELUCIDATION
 Molecular formula:
Molecular formula is determined by usual quantitative analysis and
molecular weight determination methods and by means of mass
spectrometry. If terpenoid is optically active, its specific rotation can
be measured.
 Nature of oxygen atom present:
If oxygen is present in terpenoids its functional nature is generally as
alcohol aldehyde, ketone or carboxylic groups.
o Presence of –OH group :
It can be determined by the formation of acetates with acetic
anhydride and benzoate with 3,5-dinitirobenzoylchloride.
o Presence of >C=O group:
Terpenoids containing carbonyl function form crystalline addition
products like oxime, phenyl hydrazone and bisulphite

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 Unsaturation:
The presence of olefinic double bond is confirmed by means of
bromine, and number of double bond determination by analysis of
the bromide or by quantitative hydrogenation.
Addition of nitrosyl chloride(NOCl) and epoxide formation with
peracid also gives idea about double bonds present in terpenoid
molecule.

 Dehydrogenation:
On dehydrogenation with sulphur, selenium, polonium or palladium
terpenoids converted to aromatic compounds. Examination of these
products, the skeleton structure and position of side chain in the
original terpenoids can be determined. For example α-terpenol on
Se-dehydrogenation yields p-cymene.

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 Spectroscopic studies:
All the spectroscopic methods are very helpful for the confirmation
of structure of natural terpenoids and also structure of degradation
products.
o UV Spectroscopy: In terpenes containing conjugated dienes or α,β-
unsaturated ketones, values of λmax for various types of terpenoids
have been calculated by applying Woodward’s empirical rules.
o IR Spectroscopy: IR spectroscopy is useful in detecting group
such as hydroxyl group (~3400cm-1) or an oxo group (saturated
1750-1700cm-1).
o NMR Spectroscopy: This technique is useful to detect and identify
double bonds, to determine the number of rings present, and also to
reveal the orientation of methyl group in the relative position of
double bonds.
o Mass Spectroscopy: It is used for determining mol. wt., Mol.
formula, nature of functional groups present and relative positions
of double bonds.

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