Hofmann Degradation (Hofmann Bromamide Reaction)

It is the conversion of an amide (R–CONH₂) into a primary amine (R–NH₂) with one carbon less using Br₂ + KOH/NaOH.


Overall Reaction

RCONH2+Br2+4KOHRNH2+K2CO3+2KBr+2H2ORCONH_2 + Br_2 + 4KOH \rightarrow RNH_2 + K_2CO_3 + 2KBr + 2H_2O

Key point: Chain length decreases by one carbon


Stepwise Mechanism

Step 1: Formation of N-bromoamide

Amide reacts with bromine in basic medium:RCONH2+Br2+OHRCONHBr+H2ORCONH_2 + Br_2 + OH^- \rightarrow RCONHBr + H_2O


Step 2: Deprotonation

RCONHBr+OHRCONBr+H2ORCONHBr + OH^- \rightarrow RCONBr^- + H_2O

Step 3: Rearrangement (Key Step )

  • Alkyl group (R) migrates from carbonyl carbon → nitrogen
  • Br⁻ leaves

Forms isocyanate (R–N=C=O)RCONBrRN=C=O+BrRCONBr^- \rightarrow R–N=C=O + Br^-

Step 4: Hydrolysis of Isocyanate

RN=C=O+H2ORNHCOOHR–N=C=O + H_2O \rightarrow RNHCOOH

Step 5: Decarboxylation

  • RNHCOOHRNH2+CO2RNHCOOH \rightarrow RNH_2 + CO_2

Final Product

Primary amine (R–NH₂)
CO₂ released

Important Features

  • ✔ One carbon less than starting amide
  • ✔ Always gives 1° amine
  • ✔ Rearrangement step is key (migration)

Quick Trick“CONH₂ → NH₂ (minus one carbon)”

Exam Points

  • Migration order:

3>2>1>CH33^\circ > 2^\circ > 1^\circ > CH_3

  • Works only for primary amides
  • Intermediate: Isocyanate (very important)

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