Ministry of Higher Education

and Scientific Research

University of Babylon
College of Science

Rearrangement Report

Wisam Abdul Jaleel Jawad

Faculty of Science, Department of Chemistry

PhD Student

0202-0202
 Rearrangement Report
Rearrangement Reaction: A rearrangement reaction is
a broad class of organic reactions where carbon skeleton
of a molecule is rearranged to give a structural isomer of
the original molecule, and substituent moves from one
atom to another atom in the same molecule.
Carbonium ions can be rearranged through migration of
an organic group or hydrogen atom with it's pair of
electrons to cause electron deficient carbon.
All carbonium ion reactions are aimed to proride
electrons to cover electron-deficient carbon in a
carbonium ion, the electron deficient carbon is bonded to
three other atoms, so carbonium ions can be classified
into: primary, secondary and tertiary after the carbon
bearing the positive charge.

̈ , ̈
̈
Ethyl cation Isopropyl cation
(primary, 10) (secondary, 20)

Tert-Butyl cation
(tertiary, 30)
When electron-deficient carbon is happened, a neighbor
group relieve this deficiency. Other atoms besides carbon
can be electron-deficient such as nitrogen, and oxygen
and then too can get electrons through rearrangement the
common class of molecular rearrangement involve 1,2
shifts to electron-deficient atoms.
In a rearrangement, the neighbor groups carry electrons
to an electron-deficient atom and go back to where it
came from. Thus neighboring group participation is most
often revealed by a special kind of stereochemistry or by
un usually fast rule of reaction.
Rearrangements: Hofmann rearrangement
(Intramolecular or Intermolecular).
The intermolecular: the migration of group move from
one to another atom, ot the group move from one
molecule to another.
In this mechanism of Hofmann rearrangement is
intramolecular.
Hofman rearrangement is for synthesis of amines by
degradation of amides:

⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗
=

An amide
Mechanism :
̈
1- ⃗⃗⃗⃗⃗⃗⃗⃗⃗
=

=
̈ ̈
2- ⃗⃗⃗⃗⃗⃗⃗⃗⃗

=
=

̈ ̈
3- ⃗⃗⃗⃗⃗⃗⃗⃗⃗ =
=

̈ ̈

̈ ̈
4- ⃗⃗⃗⃗⃗⃗⃗⃗⃗
=

𝐻𝑂
5- ̈ ̈

Explaining of mechanism:
Step (1): halogenation of an amide, an N-halo amide
being isolated if no base is present.
Step (2): the abstraction of a hydrogen ion by hydroxide
ion.
Step (3): separation of a halide ion, which leaves behind
electron-deficient nitrogen atom.
Step (4): the actual rearrangement
Step (3) and (4) are similar to be simultaneous, the
attachment of R to nitrogen help to push out halide ion.
Step (5): the hydrolysis of an isocyanate (R-N=C=O)
To form an amide and carbonate ion.
The stereochemistry of Hofmann rearrangement
proceeds with complete reaction of configuration about
the Chiral Centre of the migration group.
A typical example the conversion of an amide into amine
containing one carbon less by the reaction of alkaline by
pubromite (Hoffmann reaction)
There a group of reactions very closely related to that of
Hofmann, all of which involve the formation of an
isocyanate by rearrangement of an intermediate.

The Curtius and Schmitt reactions are involve N2 as the

leaving group from azide intermediate, and here the
migration of R groups in concerted process.
The azide may be obtained nitrogation of an acid
hydrazide (Curtius reaction) or by the reaction of
hydrazoic acid HN3 on a carboxylic acid (Schmitt
reaction).
The stability of carbonium ion electron-deficient carbon
and attendant positive charge.
According to the laws of electronics, the stability of a
charged system is increased by dispersal of the charge,
therefore the tendency to spread out the positive charge
of the electron-deficient carbon and distribute over the
rest of the ion to stabilize a carbonium ion.
An electron releasing substituent tends to reduce the
positive charge at the electron-deficient carbon. This
dispersal of positive charge will stabilize the carbonium
ion.
References:
1- Robert Ti Morrison and Robert N. Boyd (2002) "organic
chemistry" , New York , PP: 885-892.
2- Peter Sykes (1985) "Mechanism in organic chemistry", PP:
101-128.
3- Hofmann, A. W. (1881). "Ueber die Einwirkung des Broms
in alkalischer Lösung auf Amide" [On the action of
bromine in alkaline solution on amides]. Berichte der
Deutschen Chemischen Gesellschaft. 14 (2): 2725–2736.
4- Mohan, Ram S.; Monk, Keith A. (1999). "The Hofmann
Rearrangement Using Household Bleach: Synthesis of 3-
Nitroaniline". Journal of Chemical Education. 76 (12):
1717..
5- Keillor, Jeffrey W.; Huang, Xicai (2002). "Methyl
Carbamate Formation via Modified Hofmann
Rearrangement Reactions: Methyl N-(p-
Methoxyphenyl)carbamate". Organic Syntheses. 78: 234.
6- Plagens, Andreas; Laue, Thomas M. (2005). Named
organic reactions (2nd ed.). Chichester: John Wiley &
Sons.
7- Wolff, Hans (2011). "The Schmidt Reaction". Organic
Reactions: 307–336.
8- Lang, S.; Murphy, J. A. (2006). "Azide rearrangements in
electron-deficient systems". Chem. Soc. Rev. 35 (2): 146–
156.