Terpenoids

CAMPHOR
1. Molecular Formula : C10H16O
2. General reactions showed it is saturated.
3. Oxidation of camphor gave dicarboxylic acid of 10 C atoms
which showed the presence of a keto group.
4. Parent hydrocarbon has molecular formula C10H18 which is
CnH2n-2, hence it is a bicyclic system.
5. It forms an oxime with nitrous acid, hence it contains
CH2CO- group.
6.
7. Camphoric acid is a dicarboxylic acid which contains same
number of C atoms as camphor. Hence in the formation of
camphoric acid, the ring containing the keto group has
opened and it contains only one ring.

8. Camphoronic acid was shown to be a saturated tricarboxylic

acid and on distillation gave isobutyric acid II,
trimethylsuccinic acid III, CO2 and C.
9. Bredt suggested that camphoronic acid is ,,-trimethyl
tricarballylic acid I since this structure would give the required
decomposition products.

10. Camphoronic acid has structure I, hence camphoric acid must

contain three methyl groups. The formula can be written as
(CH3)3C5H5(COOH)2. The parent hydrocarbon of this is C5H10,
which corresponds to cyclopentane derivative.

11. Camphoric anhydride forms only one monobromo derivative

therefore there is only one -H atom. Hence one carboxylic
acid has to be at tertiary carbon (C1). The position of other
carboxylic acid has to be predicted.

=
A

p-Cymene
B

Distillation of camphor with ZnCl2 gives p-Cymene, which can be

expected from the structure B only.
When distilled with iodine camphor gives
carvacrol, VIII.

SYNTHESIS of CAMPHORIC ACID

SYNTHESIS of CAMPHOR

LONGIFOLENE
1. Molecular formula : C15H24.
2. The structure was established by the X-ray analysis of its
hydrochloride

SYNTHESIS of LONGIFOLENE
O

O
H

p-TsCl

OH

O
H

H
+

H3O

Et3N
(CH2OH)2

S
S

(CH2SH)2

Ph3CNa

1. LiAlH4

H2CrO4

2. Wolff-Kishner
reduction

BF3

MeI

O
O
MeLi
OH

SOCl2
C5H5N

OH
O

LiClO4
CaCO3
THF
OTs

OsO4

O
H

O
H

OH

Ph3P=CHCH3

(CH2OH)2

O
H

OH

ABIETIC ACID
1. Molecular Formula : C20H30O2.
2. Its a monocarboxylic acid.
3. On dyhydrogenation with S it gives
retene.
4. Retene, C18H18 was shown by
oxidative degradation to be 1methyl-7-isopropylphenanthrene
(confirmed by synthesis).

Hence the carbon skeleton present in abietic acid is :

5. It is known that on dehydrogenations with S/Se , carboxyl

groups and angular methyl groups are eliminated.
6. Oxidation of abeitic acid with KMnO4 gives a mixture of
products, among which are 2 tricarboxylic acids, C11H16O6 (II),
C12H18O6 (III). II on dehydrogenation forms m-xylene and III
forms hemimellitene. In both cases 3 carbon atoms are lost
which could be 3 carboxylic groups. Hence atleast two methyl
groups are in the meta position. One methyl group was
originally present in abietic acid in ring A, hence the other
methyl group must be an angular one and present at 12
position.

7. Vocke showed that acid II evolves two molecules of CO2

when warmed with concentrated H2SO4. This indicates II
contains 2 carboxyl groups attached to tertiary carbon atoms.
These results can be explained by assuming that one
carboxyl group in II is that in abietic acid, and since in both
cases this carboxyl group is attached to a tertiary carbon
atom, the most likely position of this group is 1.
8. Catalytic hydrogenation of abietic acid gives tetrahydroabietic
acid, C20H34O2. Thus it contains two double bonds.
9. Abietic acid on oxidation with KMnO4, among other products
gives isobutyric acid. Hence one double bond is in ring C at
6,7 or 7,8 position.
UV spectrum has indicated that the double bonds are not only
conjugated but also present in different rings.
10. If one double bond is at 6,7 position then the other double
bond will be in the same ring but if it is at 7,8 position then the
other double bond will be at 14,9 position.

SYNTHESIS of ABIETIC ACID

O
MeI
Pyrrolidine
enamine
O

O
Br

i) Raney Ni

HS(CH2)2SH

OEt

ii) Pd-C
S
O

S
COOEt

COOEt

i) RMgX
ii) Ac2O
iii) Cr3O
H
COOEt

HOOC

TAXOL