Pinacol Pinacolone
Rearrangement
Dr. Sobia Iftikhar Ali
Ph.D Scholar,Pharm. D, M.phil
1
Contents
• Definition
• General Reaction
• Introduction
• Mechanism
• Application
2
Carbocation Rearrangement
• Pinacol-pinacolone rearrangement
• Wagner-Merrwein Rearrangement
• Wolf Rearrangement
• Hoffman Rearrangement
• Beckmann Rearrangement
3
Pinacol Pinacolone rearrangement
4
Pinacol Pinacolone
rearrangement
• The pinacol rearrangement is the acid-catalyzed dehydration of
glycols, which converts the glycol into an aldehyde or a ketone.
5
Pinacol Pinacolone
rearrangement
• Pinacol Pinacolone rearrangement is a very important process in
organic chemistry for the conversion of 1,2 diols into carbonyl
compounds containing a carbon oxygen double bond. This is done via
a 1,2-migration which takes place under acyl condition..
6
General Reaction
7
Pinacol Pinacolone Rearrangement Process
• The pinacol pinacolone rearrangement process takes place via a 1,2-
rearrangement. This rearrangement involves the shift of two adjacent
atoms. This reaction is a result of the work of the German chemist
William Rudolph Fittig who first described it in the year 1860.
8
Pinacol and Pinacolone
• Pinacol is a compound which has two hydroxyl groups, each attached
to a vicinal carbon atom. It is a solid organic compound which is
white in colour.
• The IUPAC name of Pinacolone is 3,3-dimethyl-2-butanone.
Pinacolone is a very important ketone. It has a peppermint like or
camphor like odour and appears to be a colorless liquid.
9
Pinacol Pinacolone Reaction
• The pinacol pinacolone rearrangement proceeds through the
formation of an intermediate which is positively charged. The methyl
group in this intermediate proceeds to migrate from one carbon to
another. This reaction can be given by
10
Reaction Equation
11
Mechanism
• The Pinacol Pinacolone rearrangement mechanism proceeds via four
steps. Each of these steps are explained below.
• Step 1 Protonation of a hydroxyl group
• Step 2 Loss of water
• Step 3 Methyl migration
• Step 4 Deprotonation
12
13
14
15
16
Reaction Mechanism
• Step 1:
Since the reaction is carried out in an acidic medium, the hydroxide
group of the pinacol is protonated by the acid.
• Step 2:
Water is now removed from the compound, leaving behind a
carbocation. This carbocation is tertiary and therefore stable.
17
• Step 3:
The methyl group shifts to the positively charged carbon in a
rearrangement of the compound.
• Step 4:
The oxygen atom which is doubly bonded to the carbon is now
deprotonated, giving rise to the required pinacolone.
18
19
• Thus, the required Pinacolone product is generated. It is important to
note that this rearrangement is regioselective in nature. The
rearrangement of the more stable carbocation yields the major
product.
20
Uses of Pinacolone
The uses of the pinacolone product produced from the pinacol pinacolone
rearrangement include:
• Used in Pesticides, Fungicides, and Herbicides.
• Used to prepare the cyanoguanidine drug – pinacidil.
• Used in Stiripentol, which is used to treat epilepsy.
• Used to produce triadimefon which is used to control fungal diseases in
agriculture.
• The primary applications pinacolone are in the drug industry.
21
22
