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.
This example reaction
starting with cyclohexanone, forming the reaction intermediate cyclohexanone oxime 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.
The
Beckmann solution consists of
acetic acid,
hydrochloric acid and
acetic anhydride, and was widely used to catalyze the rearrangement. Other acids, such as
sulfuric acid or
polyphosphoric acid, can also be used.
sulfuric acid
is the most commonly used acid for commercial lactam production due to
its formation of an ammonium sulfate by-product when neutralized with
ammonia.
Ammonium sulfate is a common agricultural
fertilizer providing nitrogen and sulfur.
The Beckmann rearrangement is an organic reaction used to convert an
oxime to an amide under acidic conditions. The reaction begins by
protonation of the alcohol group forming a better leaving group. The R
group trans to the leaving group then migrates to the nitrogen,
resulting in a carbocation and the release of a water molecule. This
trans [1-2]-shift allows for the prediction of the regiochemistry of
this reaction. The water molecule then attacks the carbocation and after
deprotonation and tautomerization results in the final amide product.
-
lactam, a
monomer for the production of
Nylon 12.
SEE BELOW ILLUSTRATION IN
http://www.mdpi.com/1420-3049/17/11/13662
Upon treatment with phenyl dichlorophosphate (PhOP=OCl
2)
in acetonitrile at ambient temperature, a variety of ketoximes
underwent a Beckmann rearrangement in an effective manner to afford the
corresponding amides in moderate to high yields.