Abstract
A series of six alkoxysubstituted diphenylmethylamines was prepared and the amines were examined for both optical and chemical instability. Compared with the carbon-oxygen bond in the corresponding alcohols, the carbon-nitrogen bond was found to be more stable (as expected). Indeed, (+)-alpha,alpha-(2,4,4'-triethoxydiphenyl)methylamine was found to be optically stable. The known instability of the intermediate diarylketoximes was encountered and further demonstrated by their novel Beckmann rearrangement at an elevated temperature. The above amine exhibited chemical instability both as its salts and as its acyl or sulphonyl derivatives, giving rise to non-nitrogenous polymers. It was not found possible to detect the expected carbonium-ion intermediates by standard methods, but both toluene-p-sulphonamide, accompanied by an aldehyde, and benzamide were isolated from the appropriate reaction mixtures. Only with derivatives of the unsubstituted amine were characterisable scission products obtained; the carbonium-ion being detected as derivatives of sym-trimethoxybenzene. This was similarly used to show that the known acid-catalysed rearrangement of N-diphenylmethyl salicylamide was inter-molecular. The decomposition of alpha,alpha-(2-hydroxydiphenyl)methylamine hydrochloride afforded a non-nitrogenous polymer and not the hitherto accepted benzoxet.