SARDAR PATEL MAHAVIDYALAYA,

CHANDRAPUR
P.G. DEPARTMENT OF CHEMISTRY
M.SC 1 ( SECOND SEMESTER 2013-2014)

SEMINAR ON:

PINACOL-PINACOLONE REARRAGEMENT
(ORGANIC CHEMISTRY)

TOPICS

1) Pinacol- Pinacolone
Rearrangement
2) Benzil- Benzlic Acid
Rearrangement

PINACOL-PINACOLONE REARRANGEMENT

When pinacol is treated

with
dilute
on
moderately
concentration sulphuric acid (H 2SO4),
the rearrangement reaction takes
place which leads to the formation of
ketone called as pinacolone and the
rearrangement is known as pinacolpinacolone or pinacolic rearrangement.

General ReactionCH3

CH3CH3
H3C

OH OH
Pinacol (1,2(2,3-dimethyl
glycol) butane2,3-diol)

CONC.30%
CH
3

H3C

H2SO4

CH3
C

C
O CH3

Pinacolone
( (3,3-dimethyl
ketone ) butane-2one )

Mechanism
Mechanism of this reaction having following stepsStep-1

Addition of H+ to OH groupCH3 CH3

H3C

CH3

H2SO4
H+

CH3 CH3

C
C
OH OH
OH OH
+
Step-2 Removal of water molecule and forming 2
carbocation.
CH3 CH3
H3C

C
C
OH OH
+
2

CH3H2O

H3C

CH3

CH3 CH3
H3C

C
+
OH

Carbocation
(I)

CH3

Step-3 Migration of any : R , H , Ar group

CH3 CH3
H3C

CH3 Shift

H3C

CH3

CH3

C
C
OH CH3

CH3

Carbocation
(II)

Step-4 Removal of H+

H3C

OH CH3

OH

CH3

CH3
CH3

H3C

C
C
OH CH3
+

Oxonium
cation

-H

CH3

CH3

H3C

C
C
O CH3
Pinacolone

Applications:1) The reaction provide methods for the preparation of

many carbonyl compounds which are otherwise difficult
to prepare
Example :- Benzopinacol rearranges to
Benzopinacolone when heated with acetic acid in
presence OH
of iodine
or catalyst.
OH
Ph
Ph

Ph Ph
Benzopinacol

H + / I2

Ph

Ph

C
O Ph

Ph

Benzopinacolone

Benzil Benzilic Acid

Reorrangement

The transformation of diketone to hydroxy acid by

means of hydroxide is known as benzil benzilic acid
rearrangement the best known example is the conversion of
benzil into benzilic anion .

O
H5C6 C

OH

O
C C6H5

Aqua.
NaOH
Or KOH

H5C6

C
C6H5

(-DIKETONE)

Benzilic acid
anion

COO

MechanismStep- I Addition of hydroxide ion to carbonyl

carbon atom.
H

C6
CH5
5

OH-

H 5 C6

C
C6H5

Step : 2 :- migration of phenyl

groopO-

H5C6

O-

C
OH
C6 H 5

Fast
H+

OH O
H5C6
O

C-

C6 H 5
Benzilic acid anion

OH

Step 3
Protonation
OH O
H 5 C6
O

C
C6 H 5

C-

H+

OH O
H5C6
C
OH
C6 H 5
BenzilicA
cid

Applications :
- The benzil- benzilic acid rearrangement is particularly
1)
useful for the synthesis of citric acid from ketopinic acid
OH
O O
HOOCCH2
CH2COOH

KOH /
HOH

HOOC
C
CH2COOH
CH2COOH

Ketopinic
acid
2) Formation of Furilic acid from furil
O

C
O

O
H
C

NaO
H

C
O

Furil

Citric acid

H+

O
COO
H

Furilic
acid

References:1)Reaction , Rearrangment and reagents , S.N.

Sanyal , 175
2) Organic reaction mechanism , V. K. Ahluwalia ,
225
3) Advanced organic chemistry , Dr. Jagdamba
singh , Dr. L. D. S. Yadav

THANK
YOU

Guided By :Lect. Varsha

Bankar

Presented
By :Saroj B.
Yadav