Terpenes and Terpenoids

Introduction
• Terpenes is a group of compounds containing carbon atoms in multiples of
five (C5H8)n. There are more than 20,000 such natural and synthetics
compounds exists.
• Terpenoids are oxygen-containing terpenes (alcohols, ketones, aldehydes.

• Terpenes and terpenoids are the primary constituents of the essential oils of

many types of plants and flowers. 
 Introduction

• Terpenes are a large and diverse class of organic compounds,

produced by a variety of plants, particularly conifers, and by
some insects.
 Terpenes
• The basic molecular formulae of terpenes are multiples of
that, (C5H8)n where n is the number of linked isoprene-
Isoprene-2-methyl-1,3-butadiene units. This is called
the isoprene rule or the C5 rule. 
• Terpenes are natural products that are structurally related to
isoprene.
 Isoprene-2-methyl-1,3-butadiene

Butadiene

Formula: C4H6
International Union of Pure and Applied Chemistry
IUPAC ID: Buta-1,3-diene
 Terpenes
• Compounds containing carbon atoms in multiples of 5
suggest a C5 building block - isoprene units linked in a
“head-to-tail” fashion.

2-methyl-1,3-butadiene
 Terpenes
•Myrcene (isolated from oil of bayberry) is a
typical terpene. CH CH
3 2

CH3C CHCH2CH2CCH CH2

or
 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."
head tail

tail head
 Classification of Terpenes (C5H8)n

•Class Number of carbon atoms

•Monoterpene 10
•Sesquiterpene 15
•Diterpene 20
•Sesterpene 25
•Triterpene 30
•Tetraterpene 40
 Representative Monoterpenes

OH O

-Phellandrene Menthol Citral

(eucalyptus) (peppermint) (lemon grass)
 Representative Monoterpenes

OH O

-Phellandrene Menthol Citral

(eucalyptus) (peppermint) (lemon grass)
 Representative Monoterpenes

-Phellandrene Menthol Citral

(eucalyptus) (peppermint) (lemon grass)
Representative Sesquiterpenes

-Selinene
(celery)
Representative Sesquiterpenes

-Selinene
(celery)
Representative Sesquiterpenes

-Selinene
(celery)
Representative Diterpenes

OH

Vitamin A
Representative Diterpenes

OH

Vitamin A
Representative Diterpenes

Vitamin A
 Representative Triterpene

tail-to-tail linkage of isoprene units

Squalene
(shark liver oil)
Finding the isoprene building block - cyclic compounds

Finding the isoprene building block -

sesquiterpenes (C15)

22
Finding the isoprene building block -
triterpenes (C30) -

Squalene has a natural and vital part in the synthesis of all plant
and animal sterols
animal  , including cholesterol, steroid hormones, and
vitamin D in the human body
• Finding the isoprene building block -
tetraterpenes (C40)
• Lycopene is responsible for the red color in
tomatoes and watermelon
-carotene is the compound that causes carrots
and apricots to be orange
”
C10 terpenoids

• The precursor to C10 terpenoids

(monoterpenes) is Geranyl
pyrophosphate (GPP), also known
as geranyl diphosphate (GDP), which
consists of two C5 “isoprene units” that are
joined “head-to-tail O O

•
P O P O
O O

• PP
OPP
head - tail head - tail
Geranyl pyrophosphate
 C15 sesquiterpenoids
• are derived from Farnesyl diphosphate,
diphosphate
• which consists of three C5 “isoprene units”
that are joined
• “head-to-tail”
 C20 diterpenoids
• are derived from Geranylgeranyl
diphosphate,
• which consists of four C5 “isoprene units” that
are joined
• “head-to-tail”

OPP
 Terpenoid nomenclature
• Groups and subgroups
• Based on pathways
• Classification
• IUPAC
• CAS
• Trivial name(derived from the structural
family
• Or relate to natural source)
 Examples of the co-existence of
systematics Semi-systemetic and
trivial names
•
Menthol – a cyclic terpenoid
H3C CH3
CH This terpene has been
oxidised to a terpenoid
CH OH
H2C CH

H2C CH2
CH

CH3

Menthol
(peppermint)
Absinthe – a cyclic terpenoid a potent green aniseed-
flavoured liqueur, originally made with the shrub
wormwood.(the seed of the anise, used in cooking and herbal medicine)
H3C CH3
CH This terpene has been
C oxidised to a terpenoid
H2C CH2

HC C
CH O

CH3

Thujone
(Absinthe)
Camphor – a cyclic terpenoid
CH3
H3C
C

CH
CH2 CH2
C
H2C C
H3C
O

Camphor
(Camphor tree)
 -Selinene – a cyclic terpene

CH3
CH2
3 isoprene units
CH2
H2C C CH2
15 carbon atoms
H2C CH C CH2
C CH2 C
H
CH3 CH2

-Selinene
 β-carotene – a linear terpene

H3C CH2
C CH2
CH3 CH3
H3C CH3
CH C CH2
CH CH CH
C CH C CH C CH CH C
C CH C
H2C C CH CH CH CH CH
H3C CH3
CH3 CH3
H2C C
CH2 CH3 -carotene

8 isoprene units

40 carbon atoms
 Questions
• Which unit makes up every terpene?
Isoprene Unit
• How many carbons are there in an isoprene
unit?
Five
• What is the systematic name for isoprene?
– 2-methylbuta-1,3-diene
• What is an oxidised terpene known as?
• Terpenoid
 Carvone: C10H14O
• Carvone is a member of a family of chemicals called terpenoids. It is
found naturally in many essential oils, but is most abundant in the
oils from seeds of caraway, spearmint, and dill.

• used in the food and flavor industry.

• Occurs in Enantiomeric forms
• Also known as Meridian fennel, Persian carrot
• Uses
• Carvone –Latin name for Caraway, carum carvi
• Basic carbon skeleton
• 1-isopropyl-4-methylcyclohexane common in nature the
genus mentha includes various types of mint
• saturated ketone of the p- menthane family of
monoteroenoids
• Greek letters
• Use to distinguish between isomeric terpenoids
• Depends on
• In order in which the isomers were discovered
• Their abundance
• α- Pinene ¾ component of turpentine oil
by weight
• β- Pinene next most significant
component
 Cyclic Terpenoids
• α, β, and γ refers to the location of double bond
in isomeric olefins
• α - endocyclic tri substituted double bond
• β- A tetra substituted olefinic bond
• γ- exocyclic methylene function
• Example E1 reaction

•
 α - endocyclic tri substituted
double bond
• A trisubstituted alkene is an alkene in the
molecule of which the doubly bonded carbons
are bonded to a total of three carbon atoms
excluding each other.
A tetrasubstituted alkene is an alkene in the molecule of which
the doubly bonded carbons are bonded to a total of four
carbon atoms excluding each other.
 Methylene group
γ- exocyclic methylene function
THE ROLE OF TERPENOIDS IN NATURE
• Terpenoids are produced by a wide variety
of plants, animals and micro-organisms.
• As for all metabolites, the synthesis of
terpenoids places a metabolic load on the
organism which produces them and so,
almost invariably, there is a role which the
material plays and for which it is
synthesized.
• The roles which the terpenoids play in living
organisms can be grouped into three classes:
• Functional
• Defense and (producing resins and gums
Acacia gummiferae)
• Communication.
 Examples
• Vitamin A, or retinol, is the precursor for the
pigment in eyes which detects light and is
therefore responsible for the sense of sight.

• Vitamin E, or tocopherol, is an important

antioxidant which prevents oxidative damage
to cells.
• Vitamin D2, also known as calciferol,
regulates calcium metabolism in the body
and is therefore vital for the building and
maintenance of bone.
• Chlorophyll-a is a green pigment found, for
example, in plant leaves and is a key factor of
photosynthesis through which atmospheric
carbon dioxide is converted to glucose.
Calciferol
Tocopherol
Chlorophyll
 Communication
• Terpenoids are also used as chemical messengers.
• If the communication is between different parts of the
same organism, the messenger is referred to as a
hormone.

• Giberellic acid is a hormone used by plants to control

their rate of growth.
• Testosterone and oestrone are mammalian sex
hormones.
Oesteron
 Semiochemicals
• Chemicals that carry signals from one
organism to another are known as
semiochemicals.
• These can be grouped into two main classes.
• Pheromones
• Allelochemicals
 Pheromones
• If the signal is between two members of the
same species, the messenger is called a
pheromone.
• Pheromones carry different types of
information.
• Not all species use pheromones.
• In those which do, some may use only one or
two pheromones while others, in particular
the social insects such as bees, ants and
termites, use an array (arrangement)of
chemical signals to organise most aspects of
their lives.
• Ants and termites use trail pheromones to
mark a path between the nest and a food
source.
• This explains why ants are often seen walking
in single file over long distances.
• One such trail pheromone is Neocembrene-A
which is produced and used by termites of the
Australian species Nasutitermes exitiosus..
• The social insects also use alarm, aggregation,
dispersal and social pheromones to warn of
danger and to control group behaviour.
 Allelochemicals
• Chemicals which carry messages between
members of different species are known as
Allelochemicals. Within this group,
• Allomones benefit the sender of the signal,
• Kairomones its receiver and with
• Synomones both the sender and receiver
benefit.
 Examples
• Camphor and d-limonene are Allomones in
that the trees which produce them are
protected from insect attack by their
presence.
• These trees are protected from termite attack
because the d-limonene they produce is an
alarm pheromone for termites that live in the
same area.
• Similarly, antifeedants (a naturally occurring
substance in certain plants that adversely
affects insects or other animals that eat
them.)could be considered to be Allomones
since the signal generator, the plant, receives
• the benefit of not being eaten
• Myrcene is a Kairomone, in that it is
• produced by the ponderosa pine and its
presence attracts the females of
• the bark beetle, Dendroctonous brevicomis
• Geraniol is found in the scent of many
flowers such as the rose.
• Its presence attracts insects to the flower and
it can be classified as a Synomone since the
attracted insect finds nectar and the plant
obtains a pollinator.
• They often have a strong odor and may
protect the plants that produce them by
deterring herbivores and by attracting
predators and parasites of herbivores.