Terpenoids

The hydrocarbons represented by (C5H8)n as well as the oxygenated derivatives, ie., all the
compounds having (C5)n are known as terpenoids.
Classifications:

Terpenoids can be classified in two ways:

i) On the basis of structure
ii) On the basis of the number of isoprene units
i) On the basis of structure Terpenoids are of two types: (a) Cyclic and (b) Acyclic
ii) On the basis of the number of isoprene units Terpenoids are classified as: (a) Hemiterpene or
Isoprene, (b) Monoterpene or Terpenes, (c) Sesquiterpenes, (d) Diterpenes, (e) Triterpenes,
(f) Tetraterpenes or Carotenoids and (g) Polyterpenes or Rubber.
Isoprene Rule:
Isoprene rule was first pointed out by O’ Wallach:
The rule is: The thermal decomposition of almost all terpoenoids gives isoprene as one of the
products and this led to the suggestion that the skeleton structures of all naturally occurring
terpenoids can be built up of isoprene units.
Special Isoprene Rule:
Ingold in 1925 formulated the special type of C C
C

arrangement of the isoprene units under “special C C C C

H T
C C C C
H T
Or

isoprene rule”. The rule is: The isoprene units in C

2

terpenoids are usually joined in head-to-tail linkage H

C1 C
3

or 1,4-linkage, where the branched end of the

isoprene unit was considered as the head. 4 4
C C T
T
Explanation of the special isoprene rule with C
3

example:
The isoprene and special isoprene rule have been 2
C
of great value as a working hypothesis in the 1
C H C
structural elucidation of terpenoid compounds.
For example, in a terpenoid of
the formula C10H16 the isoprene
units are linked in the following H
H
H T

manner:
The isoprene units making up T T T
T
several naturally occurring
H
terpenoids are illustrated in the
following formulae:
H
myrcene cadinene
isoprene (2-isoprene units) (3-isoprene units)
(1-isoprene unit) (C15H24)
(C10H16)
(C5H8)
  Classes of terpenoid hydrocarbons:
Class No. of Isoprene units Molecular formula
(C5H8)
1. Hemiterpene or isoprene 1 C5H8
2. Monoterpene or terpenes 2 C10H16
3. Sesquiterpenes 3 C15H24
4. Diterpenes 4 C20H32
5. Triterpenes 6 C30H48
6. Tetraterpenes or Carotenoids 8 C40H64
7. Polyterpene or Rubber n (C5H8)n
Essential oils:
Fruits, flowers, leave; stems, barks and roots of nearly all the plants have some pleasant smell.
This pleasant smell of the fruits is actually due to the presence of certain steam volatile oils known as
essential oils. The essential oils are complex mixtures of hydrocarbons and their oxygenated
derivatives. Among the chief constituents of the essential oils are the terpenoids having carbon atom
upto C15 and their oxygenated derivatives such as alcohols, aldehydes and ketones.
Isolation of terpenoids:
As terpenoids are of wide occurrence, there is no general method for their isolation, but on the
other hand since the mono and sesquiterpenoids have a common source, ie., essential oils, their
isolation may be generalised. The isolation of mono and sesquiterpenoids is effected in two steps:
(i) Isolation of essential oils from the plants and (ii) Separation of the individual terpenoids from the
essential oils.
(i) Isolation of essential oils: Four methods have been developed for the isolation of essential oils.
(a) Expression, (b) Steam distillation, (c) Extraction by means of volatile solvents and
(d) Adsorption in purified fats.
(a) Expression methods: The plant material is crushed and the juice is screened to remove the large
particles. The screened juice is centrifuged in a high-speed centrifugal machine when nearly half of the
essential oil is extracted. The other half of the oil is generally not extracted and such residue is used
for the isolation of inferion quality of oil by distillation: citrus, lemon and grass oils are extracted by
this method.
(b) Steam distillation: This is the most widely used method. The plant material is macerated and
then steam distilled; if the essential oils go into the distillate, they are extracted by the use of pure
organic volatile solvents, like light petroleum. However, the method should be used with a great care,
since some essential oils are decomposed during distillation and some are hydrolysed to non-or less
fragrant compounds.
(c) Extraction by means of volatile solvents: Some essential oils are sensitive to heat and hence
decomposed during distillation. In such cases, the plant material is directly treated with light petroleum
at 50oC and the solvent is then removed by distillation under reduced pressure.
(d) Adsorption in purified fats: The fat taken in glass plates is warmed to about 50 oC, then its
surface is covered with petals (parts of the flower) and it is allowed to be kept as such for several days
until the fat is saturated with the essential oils for which the old petals may be replaced by the fresh
ones. The petals are then removed and the fat is digested with ethyl alcohol when the essential oils
present in fat are dissolved in ethyl alcohol and if some fat is also dissolved during digestion it is

2
removed by cooling to about 20oC. The extract having ethyl alcohol and essential oils is distilled
under reduced pressure to remove the solvent. Recently, the activated coconut charcoal is used in place
of fat owing to the greater stability and more surface as compared to fat.
(ii) Separation of the individual terpenoids from the essential oils: The essential oils obtained
in the first step generally contain a number of terpenoids belonging to mono- and sesqu- terpenoid
groups. Chemical as well as physical methods have been used for the isolation of the individual
terpenoids:
a) Chemical methods: Terpenoid hydrocarbons are treated with nitrosyl chloride in CHCl3
(Tilden’s reagent), crystalline adduct, with sharp melting points are obtained. These adducts were
separated and decomposed into their corresponding hydrocarbons. The terpenoid alcohols were
separated by their reaction with pthalic anhydride to form diesters when the primary alcohols react
readily, secondary alcohols less readily and tertiary do not react at all. The diesters were extracted with
NaHCO3 and then decomposed by alkali to give the parent terpenoid alcohol.
Terpenoid aldehydes and ketones are separated by reaction with the common carbonyl reagent, such as
NaHSO3, 2,4-dinitrophenyl hydrazine, phenylhydrazine, Grignard reagent etc.
b) Physical methods: Fractional distillation and chromatography have been used successfully
among the physical method. In the chromatographic separation, the essential oil is allowed to flow
through the proper adsorbent where the different classes of terpenoids form different chromatograms.
The individual chromatograms are then separated further subjected to chromatography when the
different terpenoids of each group will be forming different bands and thus the individual terpenoids
may be obtained by eluting the later chromatograms.
Determination of the structure of terpenoids:
In general, elucidation of structure of a terpenoid involves the following point:
i) The first step is to determine the molecular formula of a pure specimen by qualitative analysis.
ii) If the terpenoid in question is optically active, its specific rotation is measured since optical
activity is used as a means of distinguishing the two or more possible structures.
iii) The functional nature of the oxygen, if present, is ascertained. Terpenoids are found to possess
alcoholic, aldehydic, ketonic and ether groups.
iv) The C-alkyl CH3 CH2
groups are present C-methyl C CH3 , isopropylidene C and isopropenyl C .
CH CH3
frequently in the 3

terpenoid molecules. Three such important C-alkyl CrO3-H2SO4

C CH3 C COOH
groups are as shown:
The C-methyl group is detected and estimated C-methyl C-carboxylic acid
by the oxidation of the terpenoids with chromic acid
when all the C-methyl groups are converted CH3 O3 CH3
C O C
CH3COOH molecules (Kuhn-Roth method), which CH3
CH3
is estimated volumetrically. The isopropylidene
group is detected by the ozonolysis to acetone. isopropylidene acetone
The amount of acetone is estimated volumetrically
and thus the number of isopropylidene group is CH2 O3 H
determined. On similar treatment, isopropenyl C O CH2 O C
CH3 H
group yields formaldehyde. Lastly, the two groups
are distinguished by taking IR spectrum. isopropenyl formaldehyde

3
 v) Dehydrogenation of terpenoids with sulphur, selenium, platinium or palladium gives
well-known aromatic compounds and thus one can judge the carbon framework of all the molecules.
This step is generally useful only for the cyclic terpenoids.
vi) The presence and number of double bonds are Pd
C=C + H2 C C
ascertained by the common olefinic reagents,
H H
eg., hydrogens, halogen acids, per acids and nitrosyl
chloride (Tilden reagent). C=C + Cl2 C C
Addition of Tilden’s reagent is somewhat more Cl Cl
importance as it gives idea about the nature of the carbon C=C + HCl C C
atoms having double bond because if the two carbon H Cl
atoms joined by a double bond are tertiary a blue O
C=C + RCOOH C C + RCOOH
C O
C C NOCl C
C C C C per acid epoxide carboxylic
C C C C
NO Cl acid
tert. tert. C=C + NOCl C C
blue
NO Cl
H C H Tilden
C NOCl C C isomerisation C reagent
C C C C C
C C C C C
Cl NO Cl NOH
tert. sec.
coloured nitrosyl chloride derivative is
oxime (color less)
formed while if one of the carbon atoms
joined to double is tertiary and the other is secondary, a colorless nitrosyl chloride derivative is
obtained. Here the addition of nitrosyl chloride takes place according to Markownikoff’s rule: the
negative part ie., Cl- is added to tertiary carbon atom. While the positive part NO + is added to the
secondary carbon atom.
Calculation of the number of rings: With the help of the number of double bonds and the nature of the
functional groups the molecular formula of the terpenoid is converted into its fully satrurated parent
hydrocarbon and then compared with the following formulae for the various types of compounds and
thus the number of the rings in a terpenoid molecule is ascertained. For example, if a terpenoid of
molecular formula C10H16O is found to possess two double bonds and an aldehyde group,
the molecular formula of its fully saturated hydrocarbon will be C 10H22 (four hydrogen atoms from two
double bonds and two hydrogen atoms from bivalent aldehydic group) and thus it will be acyclic since
it concides with the general formula C nH2n+2. In mono-and sesqui-terpenoid hydrocarbons the double
bonds directly indicate the nature of the ring: eg.,
In monoterpenoids, presence of: whereas in sesquiterpenoids, presence of:
3 double bonds indicates Acyclic monoterpenoids 4 double bonds indicates Acyclic sesquiterpenoids
2 double bonds indicates Mono cyclic monoterpenoids 3 double bonds indicates Mono cyclic sesquiterpenoids
1 double bonds indicates Bicyclic monoterpenoids 2 double bonds indicates Bicyclic sesquiterpenoids
Zero double bonds indicates Tricyclic monoterpenoids 1 double bonds indicates Tricyclic sesquiterpenoids

The nature of the carbon skeleton Class of No. of double Molecular

particularly in sesquiterpenoids may also be sesquiterpenoids bonds refractivity
established by the value of the molecular Acyclic 4 69.5
refractivity of the individual terpenoid. Monocyclic 3 67.8
Molecular refractivity of a terpenoid is Bicyclic 2 66.1
calculated according to the following formula: Tricyclic 1 64.4
where n is the refractive index, d is the density and
M is the molecular weight of the terpenoid.
n2-1 . M
RM =
n2+2 d
4
 vii) Presence of conjugated system of double bonds is generally detected by Diel’s Alder reaction.
Sometimes optical exaltation (eg, in Zinziberene) is also used for establishing the presence of
conjugation. Optical exaltation is the difference of observed and calculated molecular refraction, as the
molecular refraction being an additive property it can be obtained by the sum of atomic and bond
refractions.
viii) The presence of conjugation in terpenoids is determined by the use of ultraviolet spectroscopy.
In simple acyclic dienes max is 217-228 nm. When the diene is homoannular, ie., the two conjugated
double bonds are in the same ring, max is 256-260 nm; while when the diene is heteroannular
(semicyclic); ie., the conjugated double bonds are not in the same ring , max is 230-240 nm.
If an -, - unsaturated carbonyl group is present, the max is 220-250 nm and there is also a weak band
at max 315-330 nm. According to Woodward the absorption maximum of diene system is dictated by
its number, type and degree of substitution. To calculate the absorption maximum from the molecular
structure of the compound a set of empirical rules was developed. Comparing this calculated value
with the experimental value the tentative structure of the terpenoids may be assigned. In continuation
to ultraviolet spectra it is also necessary to mention the application of IR spectroscopy in terpenoid
chemistry. The use of IR spectra is essentially complementary to that of ultraviolet spectroscopy, and
its applications are too numerous to be dealt here. Among the important uses are the detection of a
hydroxyl group (3650-2650 cm-1) and a >C=O group (saturated: 1750-1700 cm-1, ,  unsaturated:
1700-1660 cm-1). Moreover, the heteroannular dienes and ,  unsaturated ketones, which can’t be
distinguished by UV spectra, can be distinguished by IR spectra. Nuclear magnetic resonance has been
used to detect and identify double bonds, to determine the nature of end groups and also the number of
rings present and to ascertain the orientation of methyl groups in the molecule. Mass spectroscopy is
now being increasingly used as a means of elucidating the structure of terpenoids. It has been used for
determining the molecular weight, molecular formulae, and nature of the functional groups and the
relative positions of the double bonds.
i) Citral (C10H16O): Citral is the most important member of the acycylic monoterpenoids since the
structures of most of the other compounds in this group are based on that of citral. It is widely
distributed and occurs to extend of 70 to 80% in lemon grass oil. It is also found in oil of orange, oil of
lemon (6 to 7%) and in citronella oil.
Constituents of citral: The Constituents of citral has been deduced from the consideration of facts
and conclusions of the followings.
i) Elemental analysis and molecular weight determination show that the molecular formula of citral
is C10H16O.
ii) It reacts with two molecules of
Pd-H2 Br2
bromine to form a tetrabromide derivative. C10H20O C10H16O C10H16O.Br2
This indicates the presence of two carbon-
carbon double bonds in the citral tetrahydrocitral citral citral tetrabromide
molecules.
iii) Citral reacts with hydroxylamine to form an Ag2O Na/Hg
oxime. It also adds sodium bisulphate and reduces C10H16O2 C10H16O C10H18O
Fehling solution, so oxygen must be present as an geranic acid citral geraniol
aldehydic group. It is confirmed by its reduction to
geraniol (a primary alcohol C10H18O, and oxidation by silver oxide to geranic acid, C10H16O2, without
loss of any carbon atom.

5
 iv) The presence of two double bonds and an aldehydic group in citral C 10H16O led to C10H22 as the
molecular formula of its fully saturated hydrocarbon. Now as C 10H22 corresponds to the general
formula for acyclic compounds (CnH2n+2) citral must be acyclic compounds.
v) Citral, on heating with potassium hydrogen sulphate, gives a C C
well-known aromatic compound p-cymene and thus the carbon C
skeleton and hence the position of the alkyl groups, viz, methyl and C KHSO4
isopropyl, are established. C C

vi) On treatment with sodium bisulphate citral forms mono- as C C

well as di-bisulphite addition products, indicating the presence of C
, -unsaturated aldehydic group. The , -unsaturated aldehydic C
group in citral is confirmed by its ultraviolet absorption spectrum Carbon skeleton of citral p-cymene
(max 38 nm).
vii) The position of other double bond
and the complete structure of citral is [O] COOH COOH
established by its oxidation with alkaline CHO
O O COOH
permanganate followed by chromic acid to alkali
KMnO4/CrO3
give acetone, oxalic acid and laevulic acid.
laevulic acid
citral
viii) The above structure citral is proved
by Verley’s work that found that citral when treated with aqueous K2CO3 solution is converted into
acetaldehyde and an unsaturated ketone which was identified as 6-methylhept-5-en-2-one by its
ozonolysis to acetone and laevulic
COOH
acid. (laevulinic acid). The conversion CHO
aq. K2CO3
CH3CHO
O3
O O
of citral to methylheptenone and O
CH3CHO is actually owing to the CH3
presence of an , -unsaturated citral 6-methylhept-5-en-2-one laevulic acid
carbonyl group which whenever
treated with alkali gives an aldehyde and ketone.
ix) Finally the structure of citral has been confirmed by various syntheses. Barbier and Bouveault
(1896) converted methylheptenone into geranic ester by using Reformatsky reaction. After this
Tiemann (1898) converted geranic ester into citral by distilling a mixture of calcium salts of geranic
and formic acids.
(i) hydrolysis
(ii) distilt Ca salt
Reformatsky COOC2H5 (CH3CO)2O COOC2H5 with (HCOO)2Ca CHO
CH2ICOOC2H5 Zn
O reaction
( H2O)
OH
CH3
methyl ethyl iodoacetate geranic ester citral
heptenone

Cis-trans isomerism in citral: Careful examination of

citral shows that citral may exist in two geometrical CHO H
isomerism forms. The two forms differ in the arrangement
opf the aldehyde group about the double bond in the H CHO
2,3-position; in one the aldehydic group is cis with respect to cis-citral or citral-b trans-citral or citral-a
methylene group of the main chain, while in the other it is or neral or geranial
trans. bp. 117-118o/20mm bp. 118-119o/20mm
Both the forms are found to be present in nature and
actually the natural citral is a mixture of these two. The existence of the two isomeric citrals is also
6
proved chemically, viz. formation of two different semicarbazones and formation of geraniol and nerol
on reduction. The trans-citral gives geraniol hence it is also known as geranial or citral-a, while the
cis-citral gives nerol, and hence also known as neral or citral-b.
ii) Menthol (C10H20O): Menthol belongs to monocyclic monoterpenoids and it is an optically
active compounds; only the (–)-forms occurs naturally in peppermint oils (50-60%). (–)-Menthol,
mp. 43oC, is a saturated compound, and the functional nature of the oxygen atom is alcoholic,
as shown by the reaction that menthol forms esters. Menthol is used as antiseptic and as flavouring
agents.
Constituents of Menthol: i) The molecular formula of menthol is C10H20O.
ii) Since menthol can be easily esterified with acids it must possess
[O]
an alcoholic group. The alcoholic nature of hydroxyl group in menthol C10H20O C10H18O
as secondary one is proved by the oxiodation of the the compound to a
ketone, menthone. Hence menthone and menthols are related as a ketone menthol menthone
and secondary alcohol.
iii) Menthol yields p-cymene on dehydration followed by dehydration /
dehydrogenation
dehydrogenation, suggesting the presence of p-menthane
skeleton in the molecule. This can also be proved by the fact OH

that menthol when reduced with hydrogen iodide gives p- p-menthane

menthol p-cymene
menthane.
HI
[H]
iv) Menthone on oxidation with KMnO4 gives a keto
acid, C10H18O3, which on further oxidation
forms acetone and -methyladipic acid. KMnO4 [O]
The oxidation products can be easily explained COOH COOH
O COOH
by the following structure of menthone. O

v) Menthol undergoes dehydration with menthone keto-acid -methyladipic acid

potassium bisulphate to form 3-menthene by removal of the –OH
group from the C-3 and the hydrogen atom from C-4.
KHSO4
vi) Hence the structure for menthol will be I, which explain all OH
the reactions. eg., its formation from pulegone and its aromatisation H
to thymol via menthone by means of bromine and quinoline.
Menthol 3-Menthene

O OH Br OH
O O
Reduction [O] Br2 Heat with quinoline
( 2HBr)
Br

Pulegone Menthol (I) Menthone Dibromomenthone Thymol

7
 vii) Finally, the structure of menthol has been proved by its synthesis from m-cresol.
COOC2H5
CO COOC2H5
OH OH O O heat under
O
H2-Ni CrO3 (COOC2H5)2 reduced pressure
Na ( CO)

m-cresol
(i) C2H5ONa
(ii) Me2CHI
(i) hydrolysis COOC2H5
OH O O
H2 over copper chromite (ii) CO2

( ± )-Menthol Menthone

The (± )-menthol is resolved by means of phthalic acid.

iii) Cadinene (C15H24): It is a widely distributed sesquiterpenoid found in oleum cadinum, oil of
cubebs, galbanum oil, the oil of angostura rind and various other sources. It is an optically active
liquid, bp, 134-136oC/11mm.
Constitution: i) Its molecular formula is C15H24.
ii) On catalytic hydrogenation it takes up 2HCl 2H2
two moles of hydrogen; similarly on treatment C15H24.2HCl C15H24 C15H28
with hydrogen chloride it takes up two moles of Cadinene Tetrahydro
hydrogen chloride to form the fully saturated dihydrochloride Cadinene cadinene
corresponding compounds. This indicates that
cadinene has two double bonds and hence it must be bicyclic.
CH3
iii) Cadinene on sulphur dehydrogenation gives C
C
1,6-dimethyl-4-isopropylnapthalene (cadalene). C S
C C
The formation of cadalene from cadinene
+ 12H
establishes the carbon skeleton of cadinene. C C C
CH3
Thus the carbon skeleton of cadinene may be C C
depicted as shown in the figure.
C
iv) To ascertain the position of the double bond, H C CH3
3
cadinene on ozonolysis gives a product having the
Cadalene
same number of carbon atom as cadinene, which Cadinene
indicates that the two double bonds are present in different rings. Again since cadinene is not reduced
by sodium and amyl alcohol, the two double bonds do not form a conjugation, which is also confirmed
by the UV absorption spectral analysis and molecular refraction of cadinene.
C
C C C
C C C PhCO3H C C CH3MgI OH C C C
Se
O
C CH C
C
H CH3 ( H2O) C C CH3
C C
H

8
 Campbell and Soffer using the following method established the exact positions of the double
bonds. The general principle of the method is to convert the unsaturated compound into the methylated
compound according to the following set of reactions.
CH3 CH3
1 O 1 OH
C C C C
H3C CH3
2
C C C 7
PhCO3H C2 C 7 C
CH3MgI OH
O 6
3
C C C 6 3
C C C
CH3 CH3
C4 C5 C4 C5

C C

H3C CH3 H3 C CH3

Se
Cadinene Cadinene dioxide ( H2O)

2,7-dimethylcadalene

Thus during such conversions, the methyl groups are introduced on the unsaturated carbon atoms
having maximum number of hydrogen atoms. Cadinene on such treatment gives 1: 2: 6: 7-tetramethyl-
4-isopropyl naphthalene (2,7-dimethylcadalene as the final product, and hence the double bonds in
cadinene are in nmmm1:2- and 6:7-positions.
iv) Camphor (C10H16O): Camphor is the most important constituent of the oil of camphor. The
main source of it is Cinnamonium camphora (camphor tree), which is extensively found in Formosa. It
forms a colourless, transparent mass of characteristic smell and burning taste, mp 179 o and bp 204o. It
is optically active; (+)- and (-)-forms occur naturally, while, the racemic form is usually a synthetic
product. Camphor is mainly used as a plasticiser for the production of celluloid and photographic
films, for smokeless powder and explosives and also for medicina purposes, eg, as a mild disinfectant
and stimulant for the heart muscles. It is also used as an insect repellent.
Constitution: i) Its molecular formula is C10H16O.
ii) The nature of oxygen atom is found to be cyclic ketonic by the fact that camphor forms an
oxime with NH2OH, semicarbazone with semicarbazide, and a dicarboxylic acid having the same
number of carbon atoms on oxidation.
iii) The presence of ketonic group in camphor C10H16O led C10H18 as the molecular formula of its
saturated hydrocarbon. Since C10H18 corresponds to CnH2n-2 (general formula for bicyclic compounds),
camphor must be cyclic.
iv) Camphor on condensation with C6H5CHO forms monobenzylidene derivative suggesting the
presence of –CO–CH2–
group that is confirmed C=O HONO C8H14 C=O C6H5.CHO C=O
CH C8H14
by the formation of 8 14
C=NOH CH2 C=CHC6H5
isonitroso derivative
(oxime) with nitrous isonitroso derivative camphor monobenzylidene derivative
9
acid (isoamyl nitrite and hydrogen chloride) The presence of –CO–CH2– grouping is further confirmed
by its oxidation to a dibasic acid, camphoric acid, with the same number of carbon atoms.
The presence of –CO–CH2– grouping is further confirmed by its oxidation to a dibasic acid, camphoric
acid, with the same number of carbon atoms.
v) Camphor on distillation with zinc chloride or phosphorus pentoxide gives p-cymene.
This suggests that in camphor, one ring is six
OH
membered. ZnCl2 I2
Camphor Camphor
vi) Camphor on distillation with iodine forms
carvacrol. The presence of phenolic group in
carvacrol suggests the presence of ketonic group in p-cymene carvacrol
camphor.
vii) Oxidation of camphor with nitric acid produces camphoric acid and then camphoronic acid.
Thus for elucidating the structure of camphor first of all to know the structures of its oxidative
degraded products. ie, camphoric acid and camphoronic acid.
viii) Constitution of camphoronic acid, C9H14O6: (a) Since the camphoronic acid is found to be
saturated tricarboxylic acid, its formula C9H14O6 may be written as C6H11(COOH)3 and hence its
saturated parent hydrocarbon will be C6H14. Now since C6H14 corresponds to the general formula
CnH2n+2 for an acyclic compound, camphoronic acid must be acyclic.
COOH COOH COOH
(b) Since camphoronic acid is not easily decarboxylated under
ordinary conditions its three carboxylic groups are attached to three C C C
different carbon atroms. (c) The exact structure of camphoronic acid is
established by its distillation at atmospheric pressure when it gives isobutyric acid, trimethyl succinic
acid and CO2 as the major products.
CH3 3 CH
To explain these degradation
H2C C COOH H2C C COOH
Bredt suggested that camphoronic
acid is a , , -trimethyl COOH C(CH3)2 COOH C(CH3)2

tricarballylic acid since this COOH COOH

structure would give the required -trimethyltricarballylic acid -trimethyltricarballylic acid
decomposition products. This is
illustrated in the figure. The left
hand side molecule is imagined to CH3 CH3
break up as shown; and produced
CO2 + 2 CH3 CHCOOH CO2 + H C COOH
one molecule of carbon dioxide
and two molecules of isobytyric 2H + C C(CH3)2
acid (but there is a shortage of two isobutyric acid COOH
hydrogen atoms). The right hand trimethylsuccinic acid
side molecule breaks up to form one molecule of trimethylsuccinic acid, one molecule of carbon
dioxide, one atom of carbon and two atoms of hydrogen, which now make up the shortage of the left
hand side molecules. Finally, the structure of camphoronic acid was confirmed by synthesis.
ix) Constitution of C H Br
camphoric acid, C10H16O4: Br2
(a) Camphoric acid was C C COOH ; C C COOH C C COOH
found to be saturated C C C
dicarboxylic acid. (b) Since t-carboxyl group sec-carboxyl group monobromo derivative
its oxidized product (esterified with difficulty) (easily esterified)

10
camphoronic acid has a gem dimethyl group and a separate methyl group, camphoric acid and camphor
also must have three methyl groups.
Thus now the formula for camphoric acid may be written as
Me3C5H5(COOH)2 which leads C5H10 as its saturated parent hydrocarbon suggests that camphoric acid
is a cyclopentane dicarboxylic acid. (c) Camphoric acid forms monoester very easily but diester with
some difficulty indicating that the two carboxyl groups are not similar, ie, one is primary or secondary,
and the other is tertiary. This is confirmed by the fact that camphoric acid forms only
monobromoderivative, which is possible only when one of the carboxylic CH3
groups is secondary. (d) Camphoric acid is found to be a ring substituted 5 1
glutaric acid on the basis of Blanc Rule, which states that on heating with C C COOH
glutaric acids give anhydrides, adipic acids give cyclopentanones and pimelic 2 t-carboxyl
C
acids give cyclohexanones. Since camphoric acid gives an anhydride; it must
4 3
be glutaric acid derivative. So on the basis of these points the partial structure C C COOH
of camphoric acid should be assigned as shown in the figure. sec-carboxyl
H
Now as the camphoric acid is a cyclopentane derivative C4 and C5 must be
linked to form a cyclopentane derivative. Furthermore, since camphoronic Partial structure
acid has a gem dimethyl group it must be present on the second carbon atom of camphoric acid
in camphoric acid since other carbon atoms viz.4 and 5 are oxidized during
oxidation and hence camphoric acid may be represented as shown in figure and finally, these structure
was proved by synthesis.
CH3
1
H2 C 5 C COOH
t-carboxyl
2
H3C C CH3
H2 C 4 3
C COOH
sec-carboxyl
H
Structure of camphoric acid

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