Effects of N-Acyl- and N-s-Triazinyl Groups on the Rearrangement of S-(s-Triazinyl)-2-aminothiophenols and O-(s-Triazinyl)-2-aminophenols

Abstract

Abstract S-s-Triazinyl-2-aminothiophenols (I) containing methoxyl and/or dimethylamino groups in the S-triazine nucleus gave disulfides of N-s-triazinyl-2-aminothiophenols upon the S→N migration of the s-triazinyl group in the presence of acid; the rate of S→N migration was slow compared to that of the O→N migration of the corresponding O-s-triazinyl-2-aminophenol. On acylation or s-triazinylation, S-dimethoxy-s-triazinyl-2-aminothiophenol (I–1) and O-dimethoxy-s-triazinyl-2-aminophenol (II-1) gave N-acyl-N-s-triazinyl- or N,N-bis (s-triazinyl) derivatives upon the S→N or O→N migration of the s-triazinyl group. However, S-dimethylaminomethoxy-s-triazinyl-2-aminothiophenol (I–2), S-bis[(dimethylamino)-s-triazinyl]-2-aminothiophenol (I–3) and the corresponding derivatives of o-aminophenol gave N-acyl- or N-s-triazinyl derivatives, wihtout any migration of the s-triazinyl group, by acylation or s-triazinylation. The facility of the rearrangement of these N,S-bis-(s-triazinyl)-2-aminothiophenols and N,O-bis(s-triazinyl)-2-aminophenols depended not only upon the substituents in S- or O-s-triazine nucleus, but also upon the substituents in the N-s-triazine nucleus; the substituents in the N-s-triazine nucleus of strong electron-attracting and of strong electron-donating substances were not appropriate for the rearrangement in the presence of alkali to give disulfides of N-s-triazinyl-2-aminothiophenols (III–I) or N-s-triazinyl-2-aminophenols (III–II).