The Beckmann rearrangement named after the German Chemist Ernst Atto Beckmann(1853-1923).

It is rearrangement of an oxime functional group to substituted amides.

The rearrangement can also be performed on haloamines, nitrones, cycloximes and
haloamines to yield lactones.
In beckmann rearrangement , migration of group does
not depend upon the migratory aptitude but upon the
orientation of the group related to hydroxyl group. Always
that group will migrate which is anti to hydorxide group
(OH) in case of beckmann rearrangement.

Oximes are compounds containing the C=N-OH group derived from aldehydes and ketones
by condensing them with hydroxylamine.

Oximes are of two types:

a. Aldoximes: Combination of aldehydes with hydroxylamine.

b. Ketoximes: Combination of ketones with hydroxylamine.

Beckmann Rearrangement is an acid catalyzed rearrangement of an oxime to N-substituded

amide. Here are some of the Beckmann Rearrangements given as;
  Open chain oximes give open chain amides.
 Cyclic oximes gives lactam.

The Beckmann solution consisting of acetic acid, hydrrochloric acid and acetic anhydride, is
widely used to catalyze the rearrangement.
Other acids such as polyphosphoric acid sulphuric acid and pentachloride can also be
used.

The reaction mechanism of the Beckmann rearrangement I generally believed to consists of;
a. An alkyl migration with expulsion of the -OH group to form a nitrilium ion. (R-C≡N+−H).
b. Followed by hydrolysis.

1. Protonation:
1ststep is the reaction of an oxime with an acid, (H+) it means lone pair of oxygen atom(OH) attack on
the H+ ion to form H2O which is good leaving group rather than hydroxide group, that’s why OH group is
protonated.

2. Dehydration:
2nd step is the removal of water and leaving behind electron deficient nitrogen.
3. Rearrangement:
3rd step is the migration of anti group (R2) on electron deficient nitrogen and making a carbocation.

4. Hydration:
4th step is addition of water in which lone pair of oxygen atom(H2O) attack on the electron deficient
carbon atom.

5. Deprotonation:
5th step involve the deprotonation and leaving behind the desired product.

6. Tautomerization:

𝑨𝒎𝒊𝒅𝒆

Beckmann rearrangement is a ring expansion rearrangement. ∴Favorskii rearrangement

Here six member ring is converted into seven membered ring. is ring contraction
rearrangement.

1. Protonation
2. Dehydration:

3. Rearrangement:

4. Hydration:

5. Deprotonation:

6. Tautomerism:
 It is used in the synthesis of caprolactam, that is used in the production of Nylon-6.
 It is used in the synthesis of paracetamol by converting a ketone to ketoxime with the
help of hydroxylamine.
 This rearrangement is also applied in the production of some other useful chloro-bicyclic
lactames.
Alicyclic ketones of all sizes undergo beckmann rearrangement of their oximes and yield lactams. A
product of considerable industrial importance is perlon which is prepared from e-caprolactam, this is
obtained by beckmann rearragement of cylcohexane oxime. It is synthesize from phenol. Reaction is
given as;

One minute: There may be the chances of errors and mistakes. So, I apologize in advance!!
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M. Azam Javeid