New information on the Hofmann reaction Communication 5. Reaction of amides of n-acylatedβ-plperonyl-β-alanines with alkaline hypobromites

Summary

• 1. The Hofmann Reaction has been carried out with the amides of N-benzoyl, N-acetyl and N-carbomethoxy β-Piperonyl-ß-alanine under different conditions (heating to 65° and 80°).

• 2. It has been shown that in all cases the reaction mechanism is the same as that which occurs with the amides of of N-acylated β-phenyl-ß-alanines. The mechanism may be considered a general one for amides of N-acylated aminoacids of the aromatic series.

• 3. In all three cases 5-piperonylglyoxalidone, 5-piperonyl-l,3,4-oxadiazol-2(3H)-one and piperonylic acid were separated from the reaction-mixture; in addition the reaction with N-benzoyl-ß-piperonyl-ß-alanine yielded 1-N-benzoyl-5-piperonylglyoxalidone.

• 4. It has been shown that the separation of 1-N-benzoyl-5-piperonyglyoxalidone takes place readily under the conditions used by Rodionov and Zvorykina for amino-acids if the aliphatic series (heating to 65°), and the separation of piperonylic acid under the more drastic conditions (heating to 80° ) which we have previously used (reaction proceeding further ).

• 5. When the Hofmann Reaction was carried out on N-acetyl-ß-piperonyl-ß-alanine, a bromine-containing compound of composition C₁₂H₁₃O₄N₂Br was separated.