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Beckmann Rearrangement

The Beckmann rearrangement, named after the German chemist Ernst Otto Beckmann
(18531923), is an acid-catalyzed rearrangement of an oxime to an amide. Most commonly
used catalysts are Conc.H
2
SO
4
, HCl, PCl
5
, PCl
3
, SOCl
2
,ZnO, SiO
2
, PPA (Poly phosphoric
acid). Aldoximes are less reactive than ketoximes. Cyclic oximes yield lactams.



Mechanism of Beckmann rearrangement:
Initially the -OH group of the oxime is protonated. Then 1,2 shift of alkyl group (R
1
)
onto electron deficient nitrogen and the cleavage of N-O bond occurs simultaneously.
Always the alkyl group which is 'anti' to the -OH group on nitrogen undergoes 1,2 shift which
indicates the concerted nature of the beckmann rearrangement.


Where is it used?
This reagent is useful in ring enlargement of cyclic ketone. A very good example is the
industrial conversion of cyclohexanone to caprolactam, which is used in the manufacture of
Nylon-6, involves Beckmann rearrangement

Mechanism of this rearrangement is given below


Also relative migratory aptitude comes in place when there are two different groups as shown
below.

Above two isomers for the unsymmetrical oxime are possible. When these oximes are
rearranged mixture of products are formed and the ratio in which they form is same as the
isomer ratio in oxime.

Oximes derived from aldehydes are not good for Beckmann rearrangement because of the
poor yields for primary amides. Tosyl chloride forms oxime tosylate which eliminates the
stable tosylate anion. PCl
5
and SOCl
2
induce rearrangement by converting OH to a better
leaving group.

Certain ketoximes (oximes of alpha-diketones, alpha-keto acids, alpha-dialkylamino ketones,
alpha-hydroxy ketones, beta-keto ethers) can be converted to nitriles by the action of proton
or Lewis acids via fragmentation reactions, which are considered side reactions, often these
are called as abnormal or second order Beckmann rearrangements.



N-Substituted thioamides were accessed from ketoximes by utilising PSCl
3
as a uniquely
capable reagent to induce Beckmann rearrangement as well as to capture the
intermediate nitrilium ion.





The Beckmann rearrangement of cyclododecanone oxime, the monomer for the production
ofNylon 12, was successfully accomplished using a wide range of micro
mesoporous catalysts, under microwave conditions, affording the selective production of -
laurolactam in high conversions after a short period of time (typically 5 min).