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Beckmann Rearrangement Explained

The Beckman rearrangement is an acid-catalyzed intramolecular rearrangement of ketoximes to amides or anilides. Specifically, it involves an alkyl migration from the hydroxyl carbon to the nitrile carbon, forming a nitrilium ion. This is followed by hydrolysis to yield the final amide product. The reaction mechanism proceeds through the formation of a nitrilium ion intermediate. The Beckman rearrangement allows for the preparation of amides from ketoximes and is widely used in organic synthesis.

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Maryam Khushbakhat
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75 views17 pages

Beckmann Rearrangement Explained

The Beckman rearrangement is an acid-catalyzed intramolecular rearrangement of ketoximes to amides or anilides. Specifically, it involves an alkyl migration from the hydroxyl carbon to the nitrile carbon, forming a nitrilium ion. This is followed by hydrolysis to yield the final amide product. The reaction mechanism proceeds through the formation of a nitrilium ion intermediate. The Beckman rearrangement allows for the preparation of amides from ketoximes and is widely used in organic synthesis.

Uploaded by

Maryam Khushbakhat
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Beckman rearrangement

Beckman
rearrangement
Chemical Properties
 Name of rearrangement is on the name
of a German Chemist; Ernst Beckmann
 The ketoximes by the action of acids
undergo a peculiar intramolecular re-
arrangement known as the BECKMAN
REARRANGEMENT yielding an amide
or anilide as a final product
Oximes

 OXIMES are compounds, containing


C = N-OH, derived from aldehydes and
ketones by condensing them with
hydroxylamine
+
H
R2CO + NH2OH R2C=NOH
Types of Oximes

Oximes are of two types:


 Aldoxime: obtained from aldehydes and
hydroxylamine
 Ketoxime: obtained from ketones and
hydroxylamine
RCHO + RHC=NOH
H
+ NH2OH

R2CO R2C=NOH
Isomers

 If we use aldehydes or asymmetrical


ketones, there is the possibility of
getting TWO STEREOISOMERS of
the oxime
OH HO
N N

R R' R R'
Possible Isomers

 2, p-bromophenyl ethyloxime is an
asymmetric oxime, hence two possible
products
OH HO
N N

CH3 CH3

Br Br
Beckman Rearrangement
 It is an acid-catalyzed rearrangement
of an oxime to an N substituted amide

H
Beckman Rearrangement

R1 R2 OH R2

C C

N N

OH R1
Beckman Rearrangement

 Open Chain oxime gives an open chain


amide
 Cyclic oxime gives lactam
Beckman Rearrangement

 The Beckmann solution consisting of


acetic acid, hydrochloric acid and
acetic anhydride, is widely used to
catalyze the rearrangement
 Other acids, such as polyphosphoric
acid, sulfuric acid or phosphorous
pentachloride, can also be used
Beckman Rearrangement

 The reaction mechanism of the


Beckmann rearrangement is generally
believed in to consist of:
1. An alkyl migration (trans to –OH)
with expulsion of the hydroxyl group to
form a nitrilium ion ( )
2. Followed by hydrolysis
R1 R2 R1 R2

C RCOCl C

N N
Beckman OH OCl
Rearrangement -OCl -

Mechanism R2
In the presence of R1 R2
+C
acid chlorides/acid
C
halides
N
N+
R1
H2 O

+ OH R2
OH2 R2

C
C -H+
R2CO N H R1
N
N
R1
R1
R1 R2 R1 R2

C H+ C

N N
Beckman OH OH2+
Rearrangement -H2O
Mechanism R2
R1 R2
In the presence +C
of strong acids C
N
N+
R1
H2O

+ OH R2
OH2 R2

C
C -H+
R2CO N H R1
N
N
R1
R1
Cyclic oxime
Application
 Amides can be prepared from the
Beckmann Rearrangement
 Because it is an acid catalyzed
rearrangement of an oxime to an amide
Application: Preparation of Amides

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