Summary1,2,3-Triaminoguanidinium chloride was combined with benzaldehyde and hydratropic aldehyde to furnish the corresponding tris(imines), which were converted into 1,2,3-tris(benzylamino)guanidinium salts by catalytic hydrogenation in the former, and by borane reduction in the latter case. The resulting alkyl-substituted triaminoguanidinium salts underwent a threefold carbamoylation with aryl isocyanates to furnish 1,2,3-tris(ureido)guanidinium salts, while p-toluenesulfonyl isocyanate led only to a mono-ureido guanidinium salt. With aryl isothiocyanates, 3-hydrazino-1H-1,2,4-triazole-5(4H)-thione derivatives were obtained. Compounds 7a and 8 show interesting solid-state structures with intra- and intermolecular hydrogen bonds.

AbstractN,N′,N″-Triaminoguanidinium chloride (TAG-Cl) reacts with cyclopentanone or cyclohexanone to afford 8-(2-cyclopentylidenehydrazinyl)-6,7,9,10-tetraazaspiro[4.5]decan-8-ylium and 3-(2-cyclohexylidenehydrazinyl)-1,2,4,5-tetraazaspiro[5,5]undecan-3-ylium salts, respectively, i. e., two arms of the TAG ion were engaged in spiroaminal formation and the NH2 group of the third arm underwent imine-forming condensation. Ring-opening reactions of the cyclopentanone derived spiroaminal with aldehydes, aryl ketones, aromatic or aliphatic isocyanates give access to a variety of unsymmetrically substituted derivatives of the TAG ion.