Derivatives of the triaminoguanidinium ion, 3. Multiple N-functionalization of the triaminoguanidinium ion with isocyanates and isothiocyanates

Abstract

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.

Derivatives of the triaminoguanidinium ion, 5. Acylation of triaminoguanidines leading to symmetrical tris(acylamino)guanidines and mesoionic 1,2,4-triazolium-3-aminides

“…Easily accessible by the reaction of guanidinium chloride with hydrazine [2], triaminoguanidinium chloride (TAG-Cl) offers the opportunity to serve as a C 3 -symmetrical platform for the synthesis of triaminoguanidines with multiple functionalization (see [3] and references cited there). In most studies reported so far, triaminoguanidinium salts or the neutral triaminoguanidine have been reacted with carbonyl compounds.…”

“…In most studies reported so far, triaminoguanidinium salts or the neutral triaminoguanidine have been reacted with carbonyl compounds. Reactions with aldehydes [3–7] or ketones [8–10] yielded the corresponding tris(iminyl)guanidines; cyclocondensation of pentane-2,4-dione at one hydrazinyl branch of TAG-Cl afforded a pyrazole which went on to a 3,6-di(pyrazol-1-yl)-1,2,4,5-tetrazine [11], and with 1,1,1-trifluoro-2,4-pentanedione two branches of TAG-Cl were converted into pyrazoline moieties and the third one into an enaminone [12]. …”

“…Reactions with carboxylic acids have been addressed only rarely, reactions with acid chlorides appear to be unknown. We have recently reported on the threefold carbamoylation of N , N ’, N ’’-tris(benzylamino)guanidinium salts with aryl isocyanates [3]. Concerning the reaction with carboxylic acids, it is known that TAG-Cl and formic acid on heating yield 3-hydrazinyl-4-amino-4 H -1,2,4-triazole hydrochloride ( I , R = H) (Scheme 1) [13].…”

Triaminoguanidinium-Based Ligands in Supramolecular Chemistry

“…Another method to reduce TAGX-derived ligands was described by Maas et al [14]. While the reduction of tris(2-phenylpropyl-1-iminyl)guanidinium chloride was not possible by catalytic hydrogenation, the reaction with dimethylaminoborane (DMAB) and p-toluenesulfonic acid ( pTsOH) according to Casarini et al [15] yielded the reduced tris(2-phenylpropyl-1-amino)guanidinium tosylate (Fig.…”

Sn<sup>IV</sup> and Zr<sup>IV</sup> Compounds of a <i>C</i><sub>3</sub>-Symmetric Ligand with Amine [ONN] and [ONNO] Coordination Sites

“…To circumvent this problem, the imine double bond can be reduced. Maas et al [12] reported a method to reduce TAG-based molecules with dimethylamino borane complex according to Ghelfi et al [13]. This resulted in a loss of its threefold symmetry in solid state with an enhancement of structural flexibility.…”