Asked • 06/17/23

Explain Hofmann rearrangement?

The reaction of Br with Naoh forms sodium hypobromite in situ, which transforms the primary amide into an intermediate isocyanate. The formation of an intermediate nitrene is not possible because it implies also the formation of a hydroxamic acid as a byproduct, which has never been observed. The intermediate isocyanate is hydrolyzed to a primary amine, giving off carbon dioxide.[2]

Hoffman rearrangement.png

  1. Base abstracts an acidic N-H proton, yielding an anion.
  2. The anion reacts with bromine in an α-substitution reaction to give an N-bromoamide.
  3. Base abstraction of the remaining amide proton gives a bromoamide anion.
  4. The bromoamide anion rearranges as the R group attached to the carbonyl carbon migrates to nitrogen at the same time the bromide ion leaves, giving an isocyanate.
  5. The isocyanate adds water in a nucleophilic addition step to yield a carbamic acid (aka urethane).
  6. The carbamic acid spontaneously loses CO2, yielding the amine product.


1 Expert Answer

By:

Anonymous A. answered • 06/17/23

Tutor
New to Wyzant

“Get your brain in the game with a dedicated tutor by your side”

Still looking for help? Get the right answer, fast.

Ask a question for free

Get a free answer to a quick problem.
Most questions answered within 4 hours.

OR

Find an Online Tutor Now

Choose an expert and meet online. No packages or subscriptions, pay only for the time you need.