Aromatic amines and their derivatives. Part 1. The reactions of 4-methyl-2-[N-(p-toluidinyl)methyl] aniline with phosphorus oxychloride and thiophosphoryl chloride. Spectroscopic investigations of the heterocyclic products, and the crystal structure of 2-chloro-6-methyl-3-p-tolyl-1,2,3,4-tetrahydro-1,3,2-benzodiazaphosphorine 2-oxide

Abstract

4-Methyl-2-[N-(p-toluidinyl)methyl]aniline, (3), reacts with phosphorus oxychloride or thiophosphoryl chloride to give 2-chloro-6-methyl-3-p-tolyl-1,2,3,4-tetrahydro-1,3,2-benzodiazaphosphorine 2-oxide, (5a), or 2-{4-methyl-2-[N-(p-toluidinyl)methyl]anilino}-6-methyl-3-p-tolyl-1,2,3,4-tetrahydro-1,3,2-benzodiazaphosphorine 2-sulphide, (5c), respectively. Under more forcing conditions the diamine (3) and thiophosphoryl chloride give the pentacycle, 3,11-dimethyl-6,14-di-p-tolyl-5,6,13,14-tetrahydro[1,3,2,4]diazadiphospheto[1,2-a;3,4-a′]{bis[1,3,2]benzodiazaphosphorine} 7,15-disulphide, (6). The ¹H n.m.r. Spectra of the above compounds are discussed. A crystal structure determination of the compound (5a) shows it to consist of hydrogen-bonded dimers. The heterocyclic rings are not planar. A tentative relation between dihedral angles, P–N–C–H, and spin-spin coupling constants, J(P–N–C–H), is drawn for compounds (5a) and (6).