Pharmacognosy Lect 8 N 58 Terpenoids

Pharmacognosy I Lecture 8
Terpenoids &
Volatile Oils
Mohammed N. Sabir
•Introduction
•Uses in Plants & Medicine
•Classes of terpenoids
•Chemistry & Biosynthetic origin
•Monoterpenoids
2 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Terpenoids
Widely distributed natural products, mainly found in

higher plants.
Biosynthesized from mevalonic acid via acetate β-

Plolyketide Pathway.

In Plants, they composed from dimerization and

polymerization of single isoprene (isoprenoid) units.
About 20,000 compounds related to terpenoids discovered
CH3 CH3
CH3 CH3
H3C H3C
Head-to-tail conjugation

Biosynthetic origin of terpenoids

Mevalonic acid
OPP Hemiterpens C5
OPP
Dimethylallyl PP Isopentenyl PP
(DMAPP) C5 (IPP) C5
C10 Monoterpenes (C10)
IPP
C15 Sesquiterpenes (C15)
IPP
C20 Diterpenes (C20)
IPP
C25 Sesterterpenes (C25)
C30 Triterpenes (C30)
Steroids (C18-C30)
C40 Tetraterpenes (C40)

Carotenoids

Volatile Oils
Are terpenoids (almost mono), they are oily substances

and volatile at room temperature .

Role in Climate
Monoterpenes are emitted by forests and form that can

serve as Cloud Condensation Nuclei (CCN).
Such aerosols can increase the brightness of clouds and cool
the climate.


Functions of terpenoids in Plants
•Insect repellants
•Insect attractant (Pollinating agents)
•Defensive agents
•Plant hormones
•Signaling molecules

Medicinal Uses of terpenoids

•As flavoring agents
•Antiflactulents
•Spasmolytic
•Expectorants
•Insect repellent
•Analgesic anti-inflammatory agents
•Cough suppressants
•Local anesthetics
Terpenes
Hemiterpenes Monoterpenes Sesquiterpenes
Diterpenes
Acyclic
Monocyclic
Triterpenes
Bicyclic
OH
Tetraterpenes
HO
Classification of terpenoids
•Hemiterpenoids (one isoprene unit)

•Monoterpenoids (two isoprene units)
•Acyclic
•Monocyclic
•Bicyclic
•Tricyclic
•Sesquiterpenoids (three isoprene units)

Classification of terpenoids
•Diterpenoids (four isoprene units)

•Triterpenoids (six isoprene units)
•Tetraterpenoids & carotenoids (eight isoprene units)
•Meroterpenoids

CALASSFICATION
TYPE OF NUMBER OF ISOPRENE

TERPENOIDS CARBON ATOMS UNITS
hemiterpenes C5 one
monoterpenes C10 two
sesquiterpenes C15 three
diterpenes C20 four
sesterterpenes C25 five
triterpenes C30 six
tetraterpenes C40 eight
NOTE: hemi = half di = two

sesqui = one and a half tri = three
tetra = four

Bicyclic sesquiterpenoids

ing in carbon numbers, the possibilities of cyclization
also ed.
Therefore; a wide variety of cyclic terpenoids exists.

In addition to common six-membered ring systems

such as zingiberene, a constituent of the oil from
Ginger, cyclization of one end of the chains to the
other end can lead to macrocyclic rings such as
humulene.

Sesquiterpenes are a class of terpenes that consist of

three isoprene units and have the molecular formula
C15H24.
Sesquiterpenes may be acyclic or contain rings,

including many unique combinations.

Biochemical modifications such as oxidation or

rearrangement produce the related sesquiterpenoids.

OH
Geraniol
OH
Farnesol
Squalene
Phytoene
Taxadiene
Methanol Bisabolene

Nomenclature of terpenoids
-Oid suffix rather than ens
-ene suffix should be restricted for the unsaturated

hydrocarbon of the class
-Isoprene units are linked head-to-tail manner
-The number of isoprene units incorporated indicate

the class of the terpenoid

Named either to IUPAC (systematic) or the trivial

names…
Sometimes not only an isoprene oligomer, but rather saturated

or partially saturated isomers as well as oxygenated derivatives
such as alcohols, aldehydes, ketones, phenols, ethers and esters
are involved in the structure.

Monoterpenoids
-About 1,000 naturally occurring monoterpenoids have

been isolated from higher plants.
-Monoterpenoids are also found in secretions of

insects.

Monoterpenoids
-A characteristic feature of monoterpenoids are their

volatility and intensely pungent odor
-They are the most compounds responsible for plant

fragrance (essential oils)

Classes of monoterpenoids
A-Acyclic Monoterpenoids (Myrcane sub-class)
Is the major component of Rose oil

and occur in small quantities in
lemon essential oils

B-Cyclic Monoterpenoids
1-Monocyclic monoterpenoids
(ex. p. Menthane)
Found in:-
-Eucalyptus oil
Used in topical preparations for the treatment of

muscle spasm (analgesic activity and in insect
repellants (Citridiol©)).

2-Bicyclic monoterpenoids
Subclasses:-
-Bornane
-Carnane
-Fenchone
-Pinane
-Thujane

CH3
CH3 CH3
OPP
H 2C
OPP H
OPP
PPO
H 3C CH3 H3 C CH3
H3C CH3
DMAPP GeranylPP Linalyl PP

(Mycrane class)
Menthane
Carnane
Bornane Pinane
Fenchone
Thujane
-Most of these monoterpenoids occur in nature as

optically pure compounds. However some of which
may present in some plants as both enantiomers.
Ex:- (+) & (-) α-Pinene in Pinus spp.

Turpentine oil
(+) alpha-pinen (-) alpha pinen

-Camphor
CH3
Is a ketone obtained from
Cinnamomum camphora
O
(Fam: Lauraceae) H3C
CH3
Also Rosemarinus officinalis

Camphor = kafur
Bicyclic bornane class Camphor

Medicinal uses…
-Local anesthetic
-Anti-inflammatory
-Antimicrobial
-Antipruretic in conc. 0.1 – 3%
-Counterirritant for neuralgia & fibrositis.

-Common colds, externally applied for the chest in

cough conditions, especially in Children
-Inhalations of the aromatic vapors causes a local

anesthetic action
Vicks©, Vaporub©
Extract obtained by steam

distillation
Synthetically, made
from pinene
Cineol (eucalyptol) CH3
Found in Eucalyptus globus and in

Cajuput, Fam: Myrtaceae
Also called cajuputol O
Obtained from eucalyptus leaf oil and

H3C CH3
other sources by steam distillation.
Cineole

Medicinal Uses
•Flavoring agent
•Nasal inhalers for nasal congestion
•Antiseptic sprays
•Mild anesthetic for nose and throat
•Expectorant
•Analgesic

Menthol (menth-3-ol)
Peppermint or Mint
Is an alcohol obtained from divers mint oils and

prepared synthetically.
It is Levorotatory (-)-menthol when natural.
The synthetic are racemic mixtures [( + )-menthol]

It is prepared form Japanese peppermint oil by freezing

to (-220oC), during which the menthol crystallizes.
The liquid portion is poured off and the crystallized menthol is

passed between filter papers and subsequently purified by
recrystallization.

Also obtained by steam distillation of the flowering

tops of Mentha arvensis, M. piperita
Fam: Lamiaceae
Synthetic racemic menthol is produced by hydrogenation of

thymol CH3 CH3
+H
OH OH
H3C CH3 H3C CH3
Thymol Menthol

Menthol occurs as colorless, hexagonal crystals that are

usually needle like, as fused masses, or as a crystalline
powder.

Medicinal uses:-
•In concentrations ranging from 0.1-1.0%, found in
preparations used to treat minor burns and sunburns,
poison ivy rash, athletics' foot.

•In concentrations (1.0 – 16.0%) act as a counter

irritant.
•Combined with Camphor and Eucalyptus oil (Cineol) in
ointments, cough drugs, nasal sprays and inhalations to
relieve symptoms of bronchitis, sinusitis and nasal
congestion.

•Small oral doses act as carminative, however larger

doses have a depressant action on the heart.

Thymol
Is a phenol obtained from thyme oil (Thymus vulgaris)
[Lamiaceae]
It may be prepared synthetically from m-cresol or p-cymene.

CH3 OH
CH3
H3C CH3
m-cresol
p-Cymene
Thymol is an antifungal and antibacterial agent. It is

more powerful than Phenol, but it’s use is limited by its
low solubility in water and because of it’s irritation to
skin.

It’s included in topical antiseptic and analgesic

preparations in concentrations ranging from 0.1 – 1.0%
and oral gargles.


Volatile Oils
Are odorous principles found in various plant parts

Since they are volatilize upon exposure to air, they are
termed as volatile
Some times also called essential oils related to essence,
and also called ethereal oils

Spices are dried, fragrant, aromatic, or pungent plant

parts that contain volatile oils are primarily used in
food as seasoning rather than nutrition
Depending on the plant family, volatile oils may occur

in specialized secretary structures

Family Occurrence
Lamiaceae Glandular hair
Pipraceae Modified paranchymal cells
Apiaceae Oil-tubes (Vittae)
Pinaceae Schizogenous passages

They may be formed directly by the protoplasm

through decomposition of the cell wall, or by hydrolysis
of certain glycosides
Plant Part Plant
Conifer All tissues
Rose Petals
Cinnamon Bark and Leaves
Mints Glandular hair of stem and

leaves
Orange Flower petals
The chemical constituents of volatile oils and spices are

divided into two broad classes, based on their
biosynthetic origin:-
1. Terpenoid (acetate, mevalonic acid)

2. Aromatic compounds (Shikimate)

Common physical properties of volatile oils

1. Characteristic odor
2. High refractive index
3. Optical activity
4. Special optical rotation
5. Immiscible with water
6. Soluble in ether, alcohol and organic solvents

Differences between volatile oils and fixed oils
Volatile oils Fixed oils

Can be distillated from the Leave a permanent grease spot
natural sources on paper
Don’t become rancid Become rancid
On exposure to light they Sapponified with alkalis

oxidize and resinify
Volatile at room temperature Not volatile

Volatile oils consist of chemical mixtures
The presence of traces of the essential oils is essential

for the aroma

Cinnamon
Cinnamomum zeylanicum
Plant part: Barks

Fam: Lauraceae

Clove (Eugina) euginol
Eugina caryophyllus
E. caryophylata
Syzygium aromaticum
Plant part: Flowers

Fam: Myrtaceae

Sesquiterpenoids
Consists of three isoprene units and having the formula

C15H24.
Like monoterpenes, it may be acyclic or contain rings,

including many unique combinations.

Biochemical modifications such as oxidation or

rearrangement produce the related sesquiterpenoids.

Sesquiterpenoids
• Acyclic sesquiterpenoids • Monocyclic sesquiterpenoids
姜黄酮
¦Á
-farnesene 姜稀
¦Â
-farnesene
• Bicyclic sesquiterpenoids
H
OH H
¦Á-eudesmol guaiazulene
cadinene
Acyclic Sesquiterpenoids
When geranyl pyrophosphate reacts with isopentenyl

pyrophosphate, the result is the 15-carbon farnesyl
pyrophosphate, which is an intermediate in the
biosynthesis of sesquiterpenes such as farnesene

farnesene
farnesyl pyrophosphate
farnesol


Oxidation can then provide sesquiterpenoids such as

farnesol .
Sesquiterpenes are found naturally in plants as

defensive agents.

Monocyclic Sesquiterpenoids
Increasing chain length and additional double bonds, the number

of possible ways that cyclization can occur is also increased, there
are a wide variety of cyclic sesquiterpenes.
zingiberene
姜稀

In addition to common six-membered ring systems such as is

found in zingiberene, a constituent of the oil from ginger,
cyclization of one end of the chain to the other end can lead to
macrocyclic rings such as humulene.

Sesquiterpene lactones
The α-methylene-δ-lactone ring is essential for the

pharmacologic actions.

Example of Sesquiterpenoids
- Artemisinin
Isolated from the plant Artemisia annua.
Not all plants of this species contain artemisinin.
Used to treat multi-drug resistant strains of falciparum.


Its anti-malarial application was first described in

Zhouhou Beji Fang "The Handbook of Prescriptions for
Emergencies", edited in the middle of fourth century
by Ge Hong.

In 1972, discovered artemisinin in the leaves of

Artemisia annua

It was found that it cleared malaria parasites

from their bodies faster than any other drug in
history.

Cancer treatment is under early research and testing

lactone peroxide group which comes into contact with high
iron concentrations (common in cancerous cells), the
molecule becomes unstable and releases reactive oxygen
species. It has been shown to reduce angiogenesis and the
expression of vascular endothelial growth factor in some
tissue cultures.

Chamomile
Dried flowering tops of Matricaria recutita (Astraceae)
Bisabolol

Major constituents…
Bisabolol
Bisaboloxides
Matricin

H3C H3C
HO CH3
H3C
H3C α-(-)-bisabolol
 a natural monocyclic sesquiterpene alcohol
 a colorless viscous oil
 almost insoluble in water
 well soluble in ethanol

Has weak sweet floral aroma and used in various

fragrances.
Be used for hundreds of years in cosmetics because of

its perceived skin healing properties.
- spasmolytic
- anti-inflammatory
- anti-microbial

Feverfew
Dried leaves of Tanacetum parthenium
(Astraceae)
CH3
Contains Parthenolide
CH2
O
H3C
O
O
The drug has anti-migraine activity

• Zingiberene
姜稀
is a monocyclic sesquitepenoid which is the

predominant constituent of the oil of ginger (Zingiber
officinale), from which it gets its name.

• The name 5-(1,5-dim--ethyl-4-hexenyl)-2-methyl-1,3-

cyclohexadiene, chemical formulaC15H24
www.herbalfire.com
Diterpenes
Diterpenes are composed for four isoprene units and

have the molecular formula C20H32. They derive from
geranylgeranyl pyrophosphate .

Examples of diterpenes are cafestol, kahweol, cembrene

and taxadiene (precursor of taxol)
geranylgeranyl pyrophosphate

The first diterpenoids introduced were:-

 Abietic acid
 Gibberllins
 Podolactones
 Diesters of Phorbal
 Stevioside

Taxol (Paclitaxel) Overview

 a mitotic inhibitor used in
cancer chemotherapy
 1967, Wall and Wani
 Pacific yew tree, Taxus

brevifolia
 Bristol-Myers Squibb (BMS)
 taxol ---- paclitaxel ----

trademark 'Taxol‘

Forskolin (Colforsin)
Dried roots of the Indian herb Coleus forskohlii

(Lamiaceae)

Contains Forskolin CH3

CH2
O
OH
CH3 CH3
O
OH O
O CH3
CH3 OH
H3C

Ginkgolides
Ginkgo is a genus of highly unusual non-flowering

plants with one extant species, G. biloba, which is
regarded as a living fossil.

Ginkgolides are biologically active terpenic lactones

present in Ginkgo biloba.
They are bicyclic diterpenoids, and there are six

lactone-rings in their skeletons.

Ginkgolide B is an extract from the cultivated leaves of

the Ginkgo Tree. Clinical studies have shown ginkgo to
benefit short term memory, cardiovascular health,
respiratory health and gastrointestinal health.

Ginkgolide B is an active platelet aggregating factor

(PAF) antagonist.
All ginkgo formulas must have adequate levels of
ginkgolide B in order to successfully increase cerebral
blood flow.

Triterpenes
Triterpenes consist of six isoprene units and have the

molecular formula C30H48. The linear triterpene
squalene , the major constituent of shark liver oil, is
derived from the reductive coupling of two molecules of
farnesyl pyrophosphate.

Squalene is then processed biosynthetically to generate

either lanosterol or cycloartenol , the structural
precursors to all the steroids.
farnesyl pyrophosphate

Ginsenosides are a class of triterpene saponins, found

exclusively in the plant genus Panax (ginseng).
Ginsenosides have been the target of research, as they
are viewed as the active compounds behind the claims
of ginseng's efficacy.

Ginsenoside Rb1
• most abundant in Panax quinquefolius

(American Ginseng).
• affect the reproductive system in animal
testicles.
• recent research ---- affects rat embryo
development.
• may increase testosterone production
in male rats indirectly through the
stimulation of the luteinizing
hormone.
• inhibits chemoinvasion and angiogenesis.
Ginsenoside Rc
is recognized for producing more sedative related
results than other ginsenosides

In one particular study on breast cancer and different

ginsenosides, it was found that only ginsenoside-Rc
was capable of inhibiting the growth of these cancer
cells. This suggests that there is a possibility that
ginsenoside-Rc may have effects that prevent or limit
the development of breast cancer.

• A further study was also able to demonstrate a

possible effect of ginsenoside-Rc on the motility of
sperm. Data from this experimentation showed a
significant increase in motility when the sperm was in a
ginsenoside-Rc solution.

Ginsenoside Rg1
• Most abundant in Panax ginseng (Chinese/Korean

Ginseng).
• Improves the capability of spatial learning for mice,

plus estrogen-like activity (which could account for the
boosting of "yin" theory)

Tetraterpenes and carotenoids
•Vitamin-A
• Physiologic importance
• Deficiency

Some biologically important compounds such as retinol,

retinal, and phytol. They are known to be antimicrobial
and antiinflammatory.

CH3 CH3
H3C
CH3
H3C CH3
CH3 CH3
Β-carotene

Preparations…
- Tretinoin
- Isotretinoin


Thank you

Pharmacognosy Lect 8 N 58 Terpenoids

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Pharmacognosy I Lecture 8

2 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Widely distributed natural products, mainly found in

Biosynthesized from mevalonic acid via acetate β-

3 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

In Plants, they composed from dimerization and

About 20,000 compounds related to terpenoids discovered

4 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Biosynthetic origin of terpenoids

C10 Monoterpenes (C10)

C15 Sesquiterpenes (C15)

C20 Diterpenes (C20)

C25 Sesterterpenes (C25)

C30 Triterpenes (C30)

C40 Tetraterpenes (C40)

5 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Are terpenoids (almost mono), they are oily substances

6 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Monoterpenes are emitted by forests and form that can

7 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

8 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Functions of terpenoids in Plants

9 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Medicinal Uses of terpenoids

Hemiterpenes Monoterpenes Sesquiterpenes

•Hemiterpenoids (one isoprene unit)

12 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

•Diterpenoids (four isoprene units)

13 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

TYPE OF NUMBER OF ISOPRENE

NOTE: hemi = half di = two

14 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

15 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

ing in carbon numbers, the possibilities of cyclization

16 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

In addition to common six-membered ring systems

17 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Sesquiterpenes are a class of terpenes that consist of

Sesquiterpenes may be acyclic or contain rings,

18 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Biochemical modifications such as oxidation or

19 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

20 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

-Oid suffix rather than ens

-ene suffix should be restricted for the unsaturated

-Isoprene units are linked head-to-tail manner

-The number of isoprene units incorporated indicate

21 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Named either to IUPAC (systematic) or the trivial

Sometimes not only an isoprene oligomer, but rather saturated

22 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

-About 1,000 naturally occurring monoterpenoids have

-Monoterpenoids are also found in secretions of

23 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

-A characteristic feature of monoterpenoids are their

-They are the most compounds responsible for plant

24 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

A-Acyclic Monoterpenoids (Myrcane sub-class)

Is the major component of Rose oil

25 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

Used in topical preparations for the treatment of

26 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13

27 Terpenoids & Volatile Oils 17 ،‫ ﺷﺑﺎﻁ‬13