TERPENOIDS
Isomeric hydrocarbons of general formula C10H16
Occurs in turpentine oil
Their Oxygen derivative - Camphors
TERPENOIDS
• Terpenoids are naturally
occurring hydrocarbons of plant
origin of the general formula
(C5H8)n .
• The C5H8 unit is called as isoprene unit (2-methyl1,3
butadiene).
• There are two types terpenoids – Simple and Complex
terpenoids.
• Simple terpenoids occur in steam volatile essential oil and
obtained from sap and tissues of certain plants and trees.
• Complex terpenoids are not steam volatile and obtained
from gum and resins of plants.
Examples of terpenoids
Geraniol Limonene Eugeno
Citral
PHYSICAL PROPERTIES
• Terpenoids are colourless liquid.
• Soluble in organic solvents and insoluble in water.
• Most of the terpenoids are optically active.
• Volatile in nature.
• Boiling point 150 – 1800 C.
CHEMICAL PROPERTIES
• They are unsaturated compounds.
• They undergo addition reaction with hydrogen, halogen,
halogen acids to form addition products.
• They undergo polymerization and dehydrogenation in the
ring.
• On thermal decomposition, terpenoid gives isoprene as
one of the product.
ISOLATION OF TERPENOIDS
i) Isolation of essential oils from plantparts,
a) Expression method
b) Steam distillation
c) Solvent extraction
d) Adsorption in purified fats (Enfleurage)
ii) Separation of terpenoid s from essential oils by,
a) Fractional distillation
b) Fractional crystallization
c) Chromatographic technique such as TLC, GLC, HPLC and
column chromatography.
CLASSIFICATION OF TERPENOIDS
The terpenoids have general formula (C5H8)n . Based on the
value of ‘n’ the terpenoids are classified into following:
CLASSIFICATION OF TERPENOIDS
• Terpenoids are classified based on the
number of rings present in the terpenoids.
• Mono-terpenoids 3 types-
1) Acyclic terpenoids
2) Monocyclic terpenoids
3) Bicyclic terpenoid
1) MONOTERPENOIDS
i) Acyclic monoterpenoids
Eg.
ii) Monocyclic monoterpenoids
Eg.
iii) Bicyclic monoterpenoids
• The size of the first ring (six membered) in terpenoid is same in
all these terpenoids but the size of second ring is varies. Eg.
α-Pinene Camphor
• At the third level each class is subdivided on the basis of
functional group present in terpenoid.
i) Monocyclic monoterpenoid
a) Hydrocarbon- Eg. Dipentene
b) Alcohol- Eg. Menthol
ii) Bicyclic monoterpenoid
a) Hydrocarbons- Eg. α-Pinene
b) Ketones- Eg. Camphor
ISOPRENE RULE
• In 1887, Wallach proposed the isoprene rule.
• “It states that the skeleton structures of all terpenoids are built up
of isoprene units or 2-methyl 1,3-butadiene”.
CH2= CH-CH=CH2
CH3
• The isoprene rule derived from the following facts:
a) The empirical formula of almost all terpenoids is C5H8.
b)The thermal decomposition of all terpenoids gives isoprene as
one of the products. Eg: Rubber on destructive distillation yields
isoprene as the product.
Also referred to as Isoprenoid compounds
SPECIAL ISOPRENE RULE
• This rule proposed by Ingold in 1925.
• According to this rule “the isoprene units in terpenoids are
joined by head to tail linkage or 1,4- linkage ( The branched
end of isoprene unit was considered as head and other end
as the tail).
GENERAL METHODS OF STRUCTURAL
ELUCIDATION OF TERPENOIDS
1) ANALYTICAL METHOD
a) Molecular formula
b) Unsaturation
c) Nature of the oxygen atom
d) Number of rings
e) Oxidative degradation products
f) Dehydration
g) Dehydrogenation
a) Molecular Formula
• Qualitative method
• Quantitative method
• Mass spectroscopy
Optical activity
limolene carvone
b) Unsaturation
• It is determined by the formation of addition products
with reagents like hydrogen, halogen, halogen acids,
and nitrosyl chloride.
• One mole of H2 for each C=C.
General Formula Type
Cn H2n+2 acyclic terpenoid
Cn H2n monocyclic terpenoid
Cn H2n-2 bicyclic terpenoid
Cn H2n-4 tricyclic terpenoid
Cn H2n-6 tetracyclic terpenoid
• The molecular formula of citral is C10H16O, it contain 2 double
bonds and one oxygen atom as carbonyl group.
• The molecular formula C10H22 corresponds to Cn H2n+2 (general
formula of acyclic terpenoid), so citral is an acyclic terpenoid.
CONJUGATED SYSTEMS Diels Alder Reaction
PRESENCE OF C-ALKYL GROUPS IN TERPENOIDS
1. C-METHYL -C-CH3
2. ISOPROPYLIDENE
3. ISOPROPENYL
1. C-METHYL -C-CH3
Oxidation with Chromic acid
C- Methyl converted to CH3COOH
Kuhn Roth oxidation
2. ISOPROPYLIDENE
Ozonalysis
3. ISOPROPENYL
Ozonalysis
The two groups can be identified by IR
c) Nature of oxygen atom
i) Hydroxyl group
▪ ROH + ( CH3CO)2O ROCOCH3 + CH3COOH
Acetate
• Nature of hydroxyl group is revealed by the rate of
esterification.
• Primary alcohols undergo esterification more readily than
secondary and tertiary alcohols.
ii) Carboxyl group
• If terpenoid soluble in NaHCO3 and gives effervescence, it
indicate the presence of –COOH group.
R-COOH + NaHCO3 RCOONa + CO2 + H2O
• Number of –COOH group is estimated by titration against a
standard alkali.
iii) Carbonyl group
Carbonyl group : Aldehyde or Ketone
iii) –CH2CO- (oxo) group
Terpenoids form oximes with nitrous acid and benzylidene
derivative with benzaldehyde
iv) –CH2CO-CH3 (acetyl) group
• It forms haloform reaction.
R-CH2 – CO- CH3 Br2/NaoH R-COOH + CH3COOH
• On strong oxidation with CrO3 gives acetic acid.
R-CH2 – CO- CH3 CrO3 R-COOH + CH3COOH
e) Degradation products
• By studying oxidative degradation products we can find out
position of olefinic bonds and pri., sec., tert., alcohol present in
terpenoid.
➢ Alkaline KMNO4/ OsO4
• If compound contains double bond it gives diol (glycol)
R-CH=CH-R + HO KMNO4/OsO4 R-CHOH-CHOH
• Trisubstituted olefine gives ketone and acid.
• Primary and secondary alcohols are oxidised to acids while tert.
alcohol does not oxidised with KMNO4/OsO4.
➢ CrO3
It is strong oxidising agent so brings about oxidation of tert.
alcohol.
➢ Ozone
• Terpenoid react with ozone to yields carbonyl compounds
which helpful to know the position of double bond.
• Terminal alkenes gives formaldehyde as one of the product.
• Tetra substituted alkenes gives diketones.
➢ Performic acid
• Alkenes form epoxides with performic acid which on
hydrolysis gives diol.
f) Dehydrogenation
• Dehydrogenation of is carried out by heating with S, Se,
Pd, Zn and the products obtained are examined.
heat/Se
g) Dehydration
• Terpenoid are heated with dehydrating agents like potassium
bisulphate, zinc chloride, P2O5, conc. H2SO4 , mostly gives p-
cymene.
2) PHYSICAL METHOD
• Modern methods used for the structure determination of
terpenoids are-
• UV spectroscopy
• It is used for the detection of conjugation in terpenoids
• IR spectroscopy
• Used for detecting the presence of a hydroxyl group, an oxo
group.
• Used for distinguish between cis and trans isomer.
• Used for quantitative measurements (determination of no:
of methyl group).
• NMR and Mass spectroscopy
• NMR was used for structure determination and moleculer
weight was find out by mass spectroscopy.
3) SYNTHETIC METHOD
• The final structure is confirmed by its synthesis starting from
known compound in the laboratory.
ISOLATION OF TERPENOIDS
i) Isolation of essential oils from plantparts,
a) Expression method
b) Steam distillation
c) Solvent extraction
d) Adsorption in purified fats (Enfleurage)
ii) Separation of terpenoid s from essential oils by,
a) Fractional distillation
b) Fractional crystallization
c) Chromatographic technique such as TLC, GLC, HPLC and
column chromatography.
I) ISOLATION OF ESSENTIAL OILS
a) Expression method
• In this method the plant material is crushed .
• Juice obtained is filtered.
• Then juice is centrifugated, half of essential oil is obtained in
the centrifugate.
• Solid residue is used for isolation of inferior oil by
distillation..
b) STEAM DISTILLATION
c) SOLVENT EXTRACTION
• Solvents like hexane and ethanol is used to isolate essential
oils.
• It is used for the plant parts have low amount of essential oil .
• Plant material are treated with the solvent, it produces a waxy
aromatic compound called a "concrete.“
• Then it mixed with alcohol, the oil particles are released.
• Then it passess through a condenser then it separated out.
• This oil is used in perfume industry or for aromatherapy
purposes.
SOLVENT EXTRACTION
d) ENFLEURAGE
• The fat is warmed to 500C on glass plates.
• Then the fat is covered with flower petals and it kept for several
days until it saturated with essential oils.
• Then the old petals are replaced by fresh petals, it repeated.
• After removing the petals, the fat is treated with ethanol when all
the oils present in fat are dissolved in ethanol.
• The alcoholic distillate is then fractionally distilled under reduced
pressure to remove the solvent.
ROSE PETALS ENFLEURAGE
