Abstract
Aminolysis and alcoholysis reactions of β-arylaminoacrolein and its N-acyl derivatives were studied. Acid-catalyzed aminolysis of β-(N-benzoyl-p-toluidino) acrolein (III) occurred at the β-position of III, accompaying the reversible interaction of the amine and the formyl group of III. In the reaction of III and amine in methanol under neutral conditions, aminolysis at the β-position of III and alcoholysis of the amide carbonyl group of III proceeded in parallel ; the latter reaction was catalyzed by amine. In either case, no evidence for aminolysis at the amide carbonyl group of III was obtained. The reaction of the formyl group of III proceeded mainly when III and amine were reacted in benzene solution. Thus, 1-(N-benzoyl-p-methylphenylamino)-3-(p-chlorophenylimino)-1-propene (XII) was obtained when III and p-chloroaniline were reacted in benzene. Alkaline hydrolysis of XII afforded 1-(p-methylphenylamino)-3-(p-chlorophenylimino)-1-propene (XIII), an unsymmetrical malonaldehyde dianil. Aminolysis and alcoholysis reactions of 1-arylamino-3-arylimino-1-propene (malonaldehyde dianil) and its N-acyl derivatives were also studied. Alcoholysis occurred at the amide carbonyl group of N-acyl derivatives, while aminolysis occurred at the 1-position except for the case of 1-(N-phenylcarbamoyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (XIV).
