Terpenes

&
Terpenoids
Terpenes - class of >20,000 compounds
containing carbon atoms in multiples of five
Terpenoids - oxygen-containing terpenes
(alcohols, ketones, aldehydes
The name "terpene" is derived from the word
"turpentine"
Terpenes and terpenoids are the primary
constituents of the essential oils of many types of
plants and flowers.

rose oil (zenc 3 kereviz)

(
 Terpenes

Terpenes are natural products that are

structurally related to isoprene.

CH3

H2C C CH CH2 or

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

Myrcene (isolated from oil of bayberry)

is a typical terpene.

CH3 CH2

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

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)

20
 Finding the isoprene building block -
triterpenes (C30) -

Squalene has a natural and vital part in the synthesis of all plant and
animal sterols, 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

PP P O P O
O O

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

C
H2C CH2 This terpene has been
HC C oxidised to a terpenoid
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
• 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.