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KIMIA ORGANIK BAHAN ALAM
Terpenoid

Written by Dante Alighiri


The simple isoprene unit is the basis of an
enormous range and a variety of chemical
structures which we know as TERPENOIDS
1 (TERPENES)

DEFINITIONS

Isoprene is a conjugated diene. It is a colorless liquid made


by destructive distillation of rubber or from petroleum, and
used to make synthetic rubber. It is the basic unit of plant
products, including carotenoids, sterols, and terpenes
(terpenoids)

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For identification purposes, the five carbon atoms in
isoprene are numbered as follows:
1

DEFINITIONS

Carbon 1 is called the head of the molecule; carbon 4 is


called the tail.

Since the isoprene molecule has five carbon atoms, the


number of carbon atoms in the molecule of a
terpene/terpenoid is a multiple of five

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What is difference between TERPENES and
TERPENOIDS?
Bayberry fruit (Myrica gale L.)

Terpenes are hydrocarbons, whereas Terpenoids contain


oxygen.
1
Organic chemists increasingly use the words terpene and
DEFINITIONS terpenoid interchangeably.

Myrcene Geraniol
Geranium flower (Geranium L.)
(constituent of bayberry oil) (constituent of geranium oil)
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In nature, terpenoids serve a variety of purposes
including defence, signaling and as key agents in
metabolic processes
2
PURPOSES
&
FUNCTIONS Terpenoids have been used in perfumery,
cosmetics , and medicine for thousands of years
and are still extracted from natural sources for
these uses.

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 Terpenoids are defined as materials with molecular
structures containing carbon backbones made up of
isoprene (2-methylbuta-1,3-diene) units.
 Isoprene contains five carbon atoms and therefore, the
number of carbon atoms in any terpenoid is multiple of 5.
3  The generic name terpene (terpenoids/monoterpenoids)
was originally applied to the hydrocarbons found in
turpentine.
CLASSIFICATION
 The suffic –ene indicating the presence of olefinic bonds.
Each of these materials contain two isoprene units, hence
10 carbon atoms.
 Related materials containing 20 carbon atoms are named
as diterpenes (diterpenoids).
 The most basic members of the family, i.e. those containing
only one isoprene unit, came to be known as
hemiterpenoids.

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Name No. of isoprene units No. of carbon atoms
Hemiterpenoids 1 5
Monoterpenoids 2 10
Sesquiterpenoids 3 15

3 Diterpenoids 4 20
Sesterterpenoids 5 25
CLASSIFICATION Triterpenoids 6 30
Tetraterpenoids 8 40
Polyisoprenoids
>8 >40
(Polyterpenoids)
Steroids 6 30
Caretenoids 8 40

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 Terpenoids as chemicals containing a carbon skeleton formed
by the joining together of isoprene units.
 Isoprene, the building block of terpenoids is 2-methylbuta-1,3-
diene.

4
ISOPRENE RULE
head-to-tail type to produce a monoterpenoids backbone

Two or more isoprene molecules are linked to one


another. Linking between two isoprene molecules could
occur in three ways, given that the head and the tail of the
molecule are primarily involved in the linking

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1.The head of one isoprene molecule could link with the
head of another isoprene molecule.

4
ISOPRENE RULE This link is called a head-to-head or 1-1 link

2. The head of one isoprene molecule could link with the tail
of another isoprene molecule.

This link is called a head-to-tail or 1-4 link


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3. The tail of one isoprene molecule could link with the tail of
another isoprene molecule.

4
This link is called a tail-to-tail or 4-4 link
ISOPRENE RULE
 head-to-head, tail-to-tail, head-to-tail, by far the commonest
fusion is head-to-tail.

 Occasionally, a tail-to-tail coupling occurs. This is characteristic


feature of steroids and caretonoids.

 The hypothetical head-to-head fusion does not occur.

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Cyclic terpenes also contain links that are neither 1-1,
1-4, nor 4-4, which are called crosslinks. Isoprene rule
states that, in most naturally occurring terpenes, there
are no 1-1 or 4-4 links
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ISOPRENE RULE
Mrycene

Limonene

Retinol
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β-carotene
4
After formation of the C5n skeleton, the chain may be folded
ISOPRENE RULE to produce rings and functionalized by the introduction of
oxygen or other heteroatom

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4
ISOPRENE RULE

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 Families of terpenoids possessing the same skeleton
are named after a principal member of that family,
usually either the most common or the first to have
5 been discovered. Charts of these names are given in
Devon and Scott’s dictionary.
NOMENCLATURE
 The name an individual terpenoid, it is customary to
use the IUPAC or CAS systems of nomenclature.

 It is often more convenient to use either a trivial


name or a semi-systematic name derived from the
terpenoid structural family to which the material in
question belongs.

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As an example of the co-existence of systematic, semi-
systematic and trivial names.
The monoterpenoid ketone, carvone. Carvone occurs in
both enantiomeric forms in nature:
1. leavo-form in spearmint
2. dextro-form in caraway
5 Trivial name: carvone is derived from the Latin name for
caraway, Carum carvi
NOMENCLATURE
Systematic name: the basic carbon skeleton is that of 1-
isopropyl-4-methylcyclohexane
Semi-systematic name: This skeleton is very common in
nature and is particularly important in the genus
Mentha, which includes various types of mint, since it
forms the backbone of most of the important
components of mint oils. The skeleton has therefore
been given the name p-menthane
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5
Trivial : carvone
NOMENCLATURE
Systematic : 1-methyl-4-(1-methylethenyl)cyclohex-1-
ene-6-one
Semi-systematic : p-menthan-1,8-dien-6-one

To classify it, we would say it was an unsaturated ketone of


the p-menthane family of monoterpenoids

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Greek letters are used in various ways to distinguish
between isomeric terpenoids. They may indicate the
order in which the isomers were discovered or their
relative abundance in the oil. For instance:

1. α-pinene is the most significant component of


5 turpentine, usually comprising almost there quarters of
the oil by weight.
NOMENCLATURE
2. β-pinene is the next significant component of
turpentine

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In the case of cyclic terpenoids, the letters α, β, and γ
often refer to the location of the double bond in isomeric
olefins.
1. The letters α: indicates an endocyclic trisubstituted
double bond
5 2. The letters β: indicates an endocyclic
tetrasubstituted olefinic bond
NOMENCLATURE
3. The letters γ: indicates an exocyclic methylene
function

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5
NOMENCLATURE

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Functional Terpenoids as play key part in the metabolic
processes of the organism in which they are produced
1. Vitamin A, or retinol, is the precusor for the pigment in eyes
which detects light and is therefore responsible for the
senses of sight.
6
TERPENOIDS
IN
2. Vitamin E, or tocopherol, is an important antioxidant which
NATURE prevents oxidative damage to cell

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3. Vitamin D2, also known calciferol, regulates calcium
metabolism in the body and is therefore vital for the
building and maintenance of bone.

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3
TERPENOIDS
IN
NATURE
4
4. Chlorophyll-a is green pigment found, for example, in plant
leaves and is a key factor of photosynthesis through which
atmospheric carbon dioxide is converted to glucose
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Defence Terpenoids as terpenoid chemicals to protect
themselves via production of resins

1. Many plants, when damaged, exude resinous


materials as defence mechanism. Rosin is produced as
6 a physical barrier to infectious organisms, by pine
trees when the bark is damaged. Similarly, rubber is a
TERPENOIDS defensive secretion.
IN The shrub Commiphora abyssinica (Commiphora
habessinica, myrrh tree, Arabian myrrh, Yeman myrrh)
NATURE produces a resin which contains a number of
antibacteria and antifungal compounds. One of these
is the eudesmane derivative

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The role of the resin is to seal the wound and prevent
bacteria and fungi from entering and damaging the
plant. The resin has a pleasant odour and so was put
the use by man as perfume ingredient. It is known as
Boswellia sacra myrrh. Because of its antimicrobial properties, myrrh
was also used as an antiseptic and preservative
6 material, for instance, in the embalming of corpses.
TERPENOIDS 2. Frankincense, derived from trees of the genus
Boswellia, is another such resin and has been used in
IN religious rites for thousands of years.
NATURE

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3. Bufotalin, also known is a cardiac glycoside which
function as a heart stimulant. It is produced by toads
in order to prevent other animals from preying on
them; would be predators soon learn that toads do
not make good food.
6
TERPENOIDS
IN
NATURE

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4. Similarly, many plants produce terpenoids making
them unpalatable to insects which would otherwise
eat their foliage.
Azadirachtin which is produced by Melia azadirachta
6 (white cedar, chinaberry, mindi, renceh, cakra-cikri)
and also by the Indian neem tree (mimba), Azadiracta
TERPENOIDS indica.
IN
NATURE

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5. Warburganal which is produced by plants of the genus
Warburgia.
Warburganal contain two aldehyde functions and one of
these is α, β-unsaturated. Thus, it is capable of undergoing
triple alkylation of nucleophilic materials such as the
nitrogen atoms of proteins and nucleic acids. This property
6 makes it a skin sensitiser (i.e. a material which can induce an
allergic reaction in some subjects upon repeated exposure)
TERPENOIDS and carcinogen. It is therefore a doubly effective deterrent
because of its unpleasant taste and high toxicity. In the figure
IN the arrow indicate the three potential sites of nucleophilic
NATURE attack.

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Terpenoids are also used as chemical messengers. It called
as Communication Terpenoids

A. If the communication is between different parts of


the same organism, the messenger is referred to as a
6 hormone.
1. Giberellic acid is a hormone used by plants and fungi
TERPENOIDS to control their rate of growth
IN 2. Testosterone and oestrone are mamalian sex
NATURE hormones. Testosterone is a male hormone and
oestrone, a female.

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B. Chemicals that carry signals from one organism to
another are known as semiochemicals.

These can be grouped into two main classes.

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Pheromones
TERPENOIDS
IN
NATURE Semiochemicals

Allelochemicals

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1. If the signal is between two members of the same
species, the messenger is called a pheromones.
Pheromones carry different type of information.

6 Not all species use pheromones. In those which do, some


may use only one or two pheromones while others, in
TERPENOIDS particular the social insects such as bees, ants, and
IN termites, use an array of chemical signals to organize most
aspects of their lives.
NATURE
Sex pheromones are among the most widespread. Male
moths can detect female by smell at a range of many
miles.

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Androst-16-en-3-ol is a porcine sex pheromone and the
compound which produces “boar taint” in pork. (Boar taint
is flavour found in the meat of boars but not of sows). It is
produced by boars and is released in a fine aerosol when
the boar salivates and champs his jaws. When the sow
6 detects pheromone in air, she immediately adopts what is
known as “the mating stance” in readines for the boar.
TERPENOIDS
IN
NATURE

Grandisol is a sex attractant for the male boll weevil, a


serious pest for cotton growers.
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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
6 species Nasutitermes exitiosus

TERPENOIDS
IN
NATURE

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The social insects also use alarm, aggregation, dispersal,
and social pheromones to warn of danger and to control
group behaviour. For example, d-limonene is an alarm
pheromone of some Australian termites and lineatin is the
aggregation pheromone of Thrypodendron lineatum.
6
So, exposure to these two terpenoids will produce
TERPENOIDS opposite reactions in their target species, repulsion in the
IN first case and attraction in the second.

NATURE

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2. 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.
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Allomones
TERPENOIDS
IN
NATURE Alleochemicals Kairomones

Synomones

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Camphor and d-limonene are allomones in the the trees
which produce them are protected from insect attack by
their presence.

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TERPENOIDS
IN
NATURE d-limonene in the latex exuded by trees of the species
Araucaria bidwilli. These tree are protected from termite
attack because the d-limonene they produce is an alarm
pheromone for termites that live in the area. Similarly,
antifeedants could be considered to be allomones since
the signal generator, the plant, receives the benefit of not
being eaten.
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Myrcene is a kairomones , in that it is produced by the
penderosa pine and its presence attracts the females of
the bark beetle, Dendroctonous brevicomis.

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TERPENOIDS
IN
NATURE

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.

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One terpenoid which has an unsual signaling property is
nepetalactone. This is actually a mixture of two isomers.

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TERPENOIDS
IN The major being the trans, trans-isomer (1.2) and the minor the
trans, cis-isomer (1.3). Neptalactone is the principal component
NATURE of the oil catnip or cat mint (Nepta cataria), constituting 70-90%
of the oil. It is an insect repellent, which is probably why the
plant produces it. However, it has a surprising effect on all
felines, from domestic cats to lions and tigers, in that it induces
grooming and rolling behaviour in them. This is probably purely
coincidental as it is hard to see what benefit this would be to the
plant.
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Many commercial uses of terpenoids reflect their natural
uses. Those that are produced in nature because of their
biological activity may well find commercial use as drugs or
pest control agents.

7 α-santonin is extracted from Levant wormseed, Artemisia


maritima, for use as an anthelmintic.
THE USE
OF
The poisonous nature of foxglove is due to the presence of
TERPENOIDS terpenoid glycosides which have strong stimulant action on
heart muscle. Digitoxin is a glycoside of digitoxigenin and
it extracted from foxglove for use in treatment of certain
heart conditions.

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The odorous terpenoids are, of course, used as fragrance
ingredients in cosmetics, toiletries, and house-hold
products.
Cineole, extracted from various eucalyptus species, serves
both purposes since it is used in perfumery as well as a
7 nasal decongestant.

THE USE Rubber is a polymer of isoprene which is produced in the


rubber tree as a defensive secretion but is widely used by
OF humans because of its elastic properties.
TERPENOIDS
Turpentine has a long history of use as a solvent,
particularly for paints and, similarly, lac resin as varnish.
Nowadays, turpentine is also used as a feedstock for the
synthesis of other materilas of commercial interest, in
addition to a wide variety of fragrance ingredients.

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