Synthesis and reactions of 5-arylamino-1,2,4-trioxans

Abstract

Eleven 5-arylamino-1,2,4-trioxans were synthesized by the reaction of arylamines, e.g., aniline, toluidines, xylidines, or mesitylamine, with aldehydes, e.g., 2-methylpropanal or 2-phenylpropanal, in the presence of atmospheric oxygen. The structures of these trioxans were proved to be similar to that of 5-(1-naphthylamine)-1,2,4-trioxan, determined by X-ray crystal structure analysis. Reductive decomposition of the trioxans with sodium borohydride afforded the N-(2-hydroxypropyl)arylamines. Pyrolysis of the trioxans gave a ketone, an aldehyde, and the N-formylarylamines. On decomposition with acid the trioxans gave a ketone, an aldehyde, formic acid, arylamines, and the N-formylarylamines. The same products were also found in the case of decomposition of the trioxans with base.