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Camphor is the most important constituent of the oil of camphor.

It is not widely distributed in nature. The main source is the trunk


of cinnamomum camphora..It is industrially synthesized from
pinene obtained from turpentine oil by following series of
reactions.

B o r n y l c h lo rid e C am phene Is o b o rn y l a c e ta te
P in e n e

C am phor Is o b o rn e o l

Camphor is colourless with charecteristic smell and


Taste. It is optically active.

(R)-Camphor (S)-Camphor Ocimum kilimandscharicum


* I) Molecular formula: It was found to be C10H16O.
* II) Saturated Nature: General reactions like formation of mono substituted
products; mono bromo, monochloro camphor and molecular refraction
show that it is saturated.
* III) Nature of Oxygen atom present: Nature of Oxygen atom in camphor
is found to be ketonic as it forms oxime with hydroxyl amine, and phenyl
hydrozone with phenyl hydrazine.
* Camphor when oxidised with nitric acid yields a dicarboxylic acid called
camphoric acid, without loss of carbon atoms. On reduction with sodium
amalgam it gives secondary alcohol; borneol. Thus oxo function in camphor
is cyclic ketone.
* IV) Presence of Bicyclic system: Molecular formula of saturated
hydrocarbon of camphor (C10H16O) corresponds to the general formula of a
bicyclic compound (CnH2n-2)
* V) Presence of a Six membered ring: When distilled with zinc Chloride or
phosphorous peroxide, it yields p-cymene. Formation of p-cymene confirms
the presence of six-membered ring.
6. Camphor on distillation with iodine forms carvacrol which suggests the
presence of ketonic group in camphor.

O H

I2
C am p h or

7.Oxidation of camphor with nitric acid gives camphoric acid, C10H16O6 and further oxidation
of camphoric acid gives camphoronic acid C9H14O6.

H N O 3 H N O 3
C C 9H O
10H 16O C 10 H 16 O 4
14 6

C am p h or C a m p h o r ic a c id C a m p h o r o n ic a c id

 Structure of camphor can be elucidated from the structure of its oxidative degraded
products, camphoric acid and camphoronic acids.
Structure of camphoronic acid:
a) It was found to be staturated tricarboxylic acid, with molecular formula C9H14O6 and so
the molecular formula of saturated parent carbon is found to be C9H20 corresponding
to CnH2n+2, so camphoronic acid is an acyclic molecule.
b) camphoronic acid is not easily decarboxylated under ordinary conditions its three
carboxylic acid groups are attached to three different carbon atoms.

a) camphoronic acid on distillation at atmospheric pressure it gave (1) isobutyric acid (2)
trimethyl succinic acid (3), carbondioxide, and carbon. But it does not undergo
decarboxylation under ordinary condition it shows that three carboxylic groups are
attached to the different carbon atoms.
C
O O
H

C
H3
H C C
H3
+ CO2
C HC C C
O H+
O
9H 4O
3
1 6
H H
3C C C
H3

C
amp
horo
n icacid Iso
b uty
rica
cid C
O O
H
T
rim
ethy
lsuccin
ica
cid
To explain the formation of degradation products Bredt suggested that camphoronic acid is a
α, α,β-trimethyl tricarboxylic acid.

(b ) C H 3 C H 3

C H 3
H 2 C C C O O H (a ) H C C C O O H
2
(a ) -C O 2
H 3 C C H
H O O C C (C H 3 ) 2 C O O H C O O H
p r o p a n e - 1 ,2 ,2 - t r ic a r b o x y lic a c id C O O H
C O O H + is o b u ty r ic a c id
C a m p h o r o n ic a c id C O O H
-C O C H 3
2

(b ) H C C C H
3 3 H 3 C C C O O H
H
C O O H I s o b u ty r ic a c id
2 ,2 - d im e t h y lm a lo n ic a c id
H 2 C C O O H

C O O H
m a lo n ic a c id
C H 3 C O O H

H O O C C C O O H -C O H C C H
2 3

H 3 C C C H 3 H 3 C C C H 3

C O O H C O O H
2 - m e t h y lb u t a n e - 2 ,3 ,3 - t r ic a r b o x y lic a c id
T r im e th y l s u c c in ic a c id
The bredt structure for camphoronic acid is proved by synthesis:

CH3 CH3 CH3


2C 2H 5ONa
C O Zn-CH 2BrCOOC 2H 5
C O 2CH 3 C OZnBr
H2C
Reformatsky reaction
H3C C CH3 CH3
CH2 C2H5OOC C
CH3

COOC2H5 COOH COOH


2,2-dimethyl-3-oxobutanoic acid
ethyl 3-oxobutanoate
CH3

CH3
PCl5 C OH
KCN H2C
COOH C COOH CH3
H 2C C
HCl C2H5OOC CH3
COOH CH3
HOOC C
CH3 COOH
COOH
COOH
4-(ethoxycarbonyl)-3-hydroxy-2,2,3-
trimethylbutanoic acid
Camphoronic acid
Structure of camphoric acid:
i) Camphoric acid is found to be a saturated dicarboxylic acid with a molecular formula
C10H16O4. Molecular formula of its saturated compound is C10H20 which corresponds to
CnH2n Suggesting camphoric acid is monocyclic.
ii) Camphoric acid and camphor have three methyl groups similar to that of its oxidised
product camphoronic acid. So its molecular formula can be written as Me3C5H5(COOH)2
which suggests camphoric acid is a cyclopentane dicarboxylic acid.
iii) Camphoric acid forms monoester very easily compared but diester with difficulty
indicting that the two carboxyl groups are not similar i, e one is primary or secondary and
other is tertiary. The formation of monobromo derivative suggests one of the carboxylic
groups is secondary and other is tertiary.
iv) Camphoric acid is found to be a ring- substituted glutaric acid on the basis of Blanc rule,
which states that on heating with acetic anhydride, glutaric acids give anhydrides give
anhydrides, adipic acid gives cyclopentanones and pimelic acids give cyclohexanones. Since
camphoric acid gives anhydrides it must be a glutaric acid derivative.
On the basis of the above points structure of camphoric acid can be assingned as I
C
H3
C
H3

1 1
5C C C
OOH
5
H2C C C
OOH
C
OOH
C
H3
C2 C
C
H3 C
OOH
3 4 3
4C C C
OOH H2C C C
OOH
H H
The structure of camphoric acid is proved by its synthesis

CH3 O
C O O C 2H 5 C O O C 2H 5
H 3C C CH3 +
C O O C 2H 5 C 2H 5O N a C O O C 2H 5 N a-H g
C H 2C O O C 2H 5 diethyl oxalate O
ethyl 3,3-dim ethylbutanoate
D iketocam phoric acid

HO HO O
COOH COOH N aO H C O O C 2H 5
HI

COOH COOH C O O C 2H 5
HO HO O
D iketocam phoric ester
HBr

COOH Zn COOH

COOH C H 3C O O H COOH
Br
cam phoric acid
Camphoric acid exists in two geometrical isomers, cis- camphoric acid and
trans- isocamphoric acid which cannot form anhydride, so camphoric acid is
a cis isomer.
H H H H

H C
H H C
OOH
3
C
H C
H3
C
OO
H 3
C
OO
H H H
H H

C
OO
H C
OOH C
H3
C
OOH C
OOH
C
H C
H3
3
H
OO
C
c
amp
ho
ri
c a
ci
d C
is
-Ca
m p
hor
ica
cid T
ran
s-
Iso
Camp
hor
ica
cid
I
soc
amp
ho
ri
c a
ci
d

Camphor on condensation with benzaldehyde forms a monobenzylidene derivative


Suggesting the presence of (-CO-CH2) which is also confirmed by the formation of
Isonitroso derivative with nitrous acid. So the structure of camphor is III which explains
the above reactions.

CO
CO
CO C
H
C
H C
H
8
14 8
14
8
14 CC
HC
H
6
5
CN
OHHO C
O
N H
2
C
HC
HO
6
5
O

HNO3 COOH (O ) COOH

COOH COOH

C am phor III (O )
C am phoric acid
OH
-C O 2

COOH COOH

COOH
COOH
O
C am phoronic acid
C am phonic acid
SYNTHESIS OF CAMPHOR FROM CAMPHORIC ACID

COOH OC (O ) OC
O O

COOH CO CH2
KCN
C am p h oric acid C am p h olid e
C am p h oric an h yd rid e

O COOH
H eat th e
CN
C a salt COOH
COOH
CH2
H yd rolysis
CH2

C am p h or H om ocam p h oric acid


*
Zinziberine is the important constituent of ginger oil.
 Molecular formula: C15H24
 Catalytic hydrogenation of zingiberine results in hexahydrozinziberine indicating the
presence of three double bonds.
Pt black C15H30
C15H24 + 3H2

 The molecular refraction and UV absorption spectrum at λmax-260ηm and formation


of an adduct with maleic anhydride confirm the conjugation of two of the double
bonds. This is further confirmed by the fact that zinziberine on reduction with
sodium and alcohol forms dihydrozinziberine.
Na/C2H5OH
C15H24 C15H26

 Dihydrozinziberine has the molecular refraction of 68.37 which is similar to the


calculated value 68.25 of dihydrzinziberine on the assumption that the latter has two
isolated bonds, hence dihydrozinziberine must be having two isolated double bonds
produced by reduction of one conjugated double bonds.
4. Zinziberine on dehydrgenation forms cadalene which indicates the carbon
skeleton of zinziberene.
5. Zinziberine on ozonolysis gives the same products as obtained by bisabolene,
like acetone, laevulinic acid and succinic acid indicating that the former has the same
skeleton as the latter.
Z in z ib e rin e C a d a le n e

6. The carbon skeleton of zinziberine can also bre further confirmed by the
Dehydrogenation of hexahydrozinziberine over palladised charcoal to
6-p-tolyl-2-methylheptane, I, which on oxidation with chromic acid gives acetic, oxalic,
Terephthalic acids.
C O O H
+ C H 3 C O O H
H e x a h y d r o z in z ib e r in e H O O C
P d /C
H O O C

C O O H

T e r e p h th a lic a c id
7. As acetone is formed as one of the products during ozonolysis one of the double
bonds must be present as isopropylidene group.
8. Dihydrozinziberine on oxidation with potassium permanganate gives ketodicarboxylic acid
C12H20O5which on further oxidation with sodium hypobromite forms a tricarboxylic acid
C11H18O6 along with bromoform indicating that the ketdicarboxylic acid has a -CO-CH3
group. Hence dihydrozinziberine must be having the following structure.

K M nO 4 N aO B r

COCH3 COOH
COOH COOH COOH COOH

K e to d ic a rb o x y lic a c id T ric a rb o x y lic a c id


D ih y d ro z in z ib e re n e

9. The position of the third double bond is established by the formation of 2,6 – dimethyl
Octa-2-diene II, and methylphthalate III by the pyrolysis of the adduct of zinziberine
with dimethyl acetylene dicarboxylate
COOCH 3

H 3 COOC
CCOOCH 3
ADDUCT +
+
CCOOCH 3 Pyrolysis

Dimethyl acetylene
carboxylate
Zinziberine has two chiral centres. Thecyclic chiral centre has been stereohemically related
to that in (-) α- Phellandrene and the acyclic chiral centre to that in (+) citronellal. Thus
(-) Zinziberine has the following absolute structure.

H
The structure of zinziberine is further confirmed by its synthesis from methyl heptenone

OH

O BrMg
-H 2 O
+

M gBr OC H 3
O

P- Anisyl magnesium bromide


Methyl heptenone

CH 3 M gI

Anhydrous Oxalic Acid


CH 3

-H 2 O
OH

zinziberine