Synthesis, structure and properties of novel N-thiophosphorylated derivatives of 1,3-dihydro-2H-benzimidazol-2-imine and imidazolidine-2-imine

The reaction of bis-thiourea o-C6H4[NHC(S)NHP(S)(Oi-Pr)2]2 (1) with iodine, KOH and ClCH2C(O)OCH3 leads to O,O′-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylideneamidothiophosphate (2) formation. The complex of the potassium salt of compound 2 with 18-crown-6, having the composition [K(18-crown-6)L], has been synthesized. Bis-thiourea [CH2NHC(S)NHP(S)(Oi-Pr)2]2 (6) forms a stable potassium salt, which oxidation by iodine leads to a product of heterocyclization, O,O′-diisopropyl-(1-{[(diisopropoxyphosphorothio)amino]carbonothioyl}imidazolidine-2-ylidene)amidothiophosphate (8), in which one of the thiourea fragments is kept.

Graphical abstractN-Thiophosphorylated thioureas are of interest as complexing agents and precursors for the synthesis of heterocycles containing exocyclic phosphorylic groups. Thus a number of reactions with their participation, leading to phosphor-containing iminothiazolidines, iminooxazolidines and thiophosphoryl(phosphonyl)aminothiozoles formation have been reported. With the presence of two thiourea fragments occupying α,β positions in a molecule, it is reasonable to expect interesting transformations leading to cyclic structures.Figure optionsDownload full-size imageDownload as PowerPoint slide