Learning objectives

 What is rearrangement?
 Types of rearrangements
 Carbonium rearrangements
– Wagner-Meerwein rearrangements
– Neopentyl rearrangement
Rearrangement
The term “rearrangement” is used to
describe organic reactions which
involve the migration of a H atom or of
a larger molecular fragment from one
part of the molecule to the other. Types
are:-
 Carbonium ion rearrangements
 Carbanion rearrangements
 Radical rearrangements
Carbonium ion rearrangements
1-Without change in carbon skeleton
 Allylic rearrangement
2-With change in carbon skeleton
 Neopentyl rearrangement
 Pinacol-pinacolone rearrangement
 Wolf rearrangement
 Rearrangement of hydrocarbons
Wagner-Meerwein
rearrangements
 The rearrangements involving change in
carbon skeleton are collectively known as
Wagner-Meerwein rearrangements
 Wagner-Meerwein rearrangements
 Wagner-Meerwein Rearrangements are [1,2]-
rearrangements of H atoms or alkyl groups in carbonium
ions that do not contain any heteroatom attached to the
valence-saturated center C-1 or to the valence-unsaturated
center C-2.
1 1
R(H) R(H)
+
C C+ C C
1' 2' 1' 2'
Example is neopentyl rearrangement
 Conversion of neopentyl bromide to amyl
alcohol
Example is neopentyl rearrangement
Example is neopentyl rearrangement
 Conversion of neopentyl alcohol to amyl
chloride
 Example:
 1-Bromopropane isomerizes quantitatively to 2-
bromopropane under Friedel-Crafts conditions.
The [1,2]-shift A→B involved in this reaction
again is an H-atom shift.

Tetrabromoaluminate
 Example:
Wagner-Meerwein rearrangement as a E1
elimination

+
OH conc. H SO OH2 H
2 4
+
_H O
2 H

Methyl shift

H H
+
_
H+
Example
 Conversion of p-xylene to m-xylene
In the presence of acid, methyl group
moves to meta position, which is
energetically more stable
 Example:

CH3 OH
HNO2
H3C CH2NH2 CH3 C CH2CH3
CH3 CH3

Methyl shift
Mechanism
CH3 HNO2 CH3 +
H3C CH2NH2 CH3 C CH2
CH3 CH3

+ OH
CH3 C CH2CH3 H2O CH3 C CH2CH3
CH3 H+ CH3
 Amylalcohol is isopentyl alcohol
 Tertiarybutyl carbinol is neopentyl alcohol
 2 methyl butanol is amyl alcohol