Lec-5

Some Name Reactions

Beckmann rearrangement

The Beckmann rearrangement, named after the German chemist Ernst Otto Beckmann (1853–
1923), is an acid-catalyzed rearrangement of an oxime to an amide.

Cyclic oximes yield lactams.

Generally oximes can be changed to the corresponding amide derivatives by treatment with
various acids. This reaction is called Beckmann rearrangement.

Reaction mechanism

The reaction mechanism of the Beckmann rearrangement is in general believed to consist of an

alkyl migration with expulsion of the hydroxyl group to form a nitrilium ion followed by
hydrolysis:

Example (1)
Example (2)

This example reaction starting with cyclohexanone, forming the reaction intermediate
cyclohexanonoxime and resulting in caprolactam is one of the most important applications of
the Beckmann rearrangement, as caprolactam is the feedstock in the production of Nylon 6.

Nylon 6 is synthesized by ring-opening polymerization of caprolactam. Caprolactam has 6 carbons, hence 'Nylon 6'. When
caprolactam is heated at about 533 K in an inert atmosphere of nitrogen for about 4-5 hours, the ring breaks and undergoes
polymerization. Then the molten mass is passed through spinnerets to form fibres of Nylon 6.

Applicaion of Beckmann rearrangement

Nylon 6 or polycaprolactam is a polymer developed by Paul Schlack at IG Farben to reproduce the properties of
nylon 6,6 without violating the patent on its production. Unlike most other nylons, nylon 6 is not a condensation
polymer, but instead is formed by ring-opening polymerization. This makes it a special case in the comparison
between condensation and addition polymers. Its competition with nylon 6,6 and the example it set have also
shaped the ecnomics of the synthetic fiber industry.

Synthesis
Nylon 6 begins as pure caprolactam. Caprolactam has 6 carbons, hence 'Nylon 6'.
When caprolactam is heated at about 533 K in an inert atmosphere of nitrogen for about 4-5 hours,
the ring breaks and undergoes polymerization. Then the molten mass is passed through spinnerets
to form fibres of Nylon 6.
Melt Spinning: is used for the polymeric fibers or the polymers that can be melted. The polymer
is melted and then pumped through a spinneret. The cooled and solidified molten fibers get
collected on a take-up wheel. The fibers, when stretched in both, the molten and solid states,
facilitate orientation of the polymer chains along the fiber axis. Melt spun fibers can be forced
through the spinneret in different cross-sectional shapes such as round, trilobal, pentagonal,
octagonal among others. Trilobal-shaped fibers are capable of reflecting more light which give a
sparkle to the fabrics.

Mechanism of the Beckmann Rearrangement (cyclohexanoxime to caprolactam)

Oximes generally have a high barrier to inversion, and accordingly this reaction is envisioned to proceed by
protonation of the oxime hydroxyl, followed by migration of the alkyl substituent "trans" to nitrogen. The N-O
bond is simultaneously cleaved with the expulsion of water, so that formation of a free nitrene is avoided.
Crossed Aldol condensation- The condensation reaction between two different aldehydes or
ketones or between an aldehyde and a ketone.

Aldol condensation between acetone and acetaldehyde

Friedel-Crafts Alkylation
Friedel–Crafts alkylation involves the alkylation of an aromatic ring with an alkyl halide using a
strong Lewis acid catalyst. With anhydrous ferric chloride as a catalyst.

The general mechanism is shown below.

Mechanism of the Friedel-Crafts Alkylation

More example of Cannizzaro Reaction

This redox disproportionation of non-enolizable aldehydes to carboxylic acids and alcohols is conducted in
concentrated base.

Mechanism of the above Cannizzaro Reaction