Functionalization of some cyclic bisureas (glycolurils) and their methylol derivatives was investigated with the goal to obtain new azaheterocycles. The modification of tetra-N-methylglycoluril gave unknown before tetra-N-methylbisimidazolium tetrachloride and provided a possibility of the synthesis therefrom of glycoluril tetrafluoro derivatives.

Previously unknown amidophosphorous acid derivatives were prepared by transamidation of tert-butyl N,N-diethyl-N′-(4-phenylthiazolyl)phosphorodiamidite with 2-amino-4-phenylthiazole, and their reactions with acetyl and benzoyl chloride were studied. These reactions are shown to proceed regioselectively according to the Arbuzov scheme to give the corresponding ketophosphonates. The reaction of the phosphorodiamidite with acetyl chloride in a 1:2 molar ratio involves formation of acetophosphonate that reacts in the enol form to give the corresponding (1-acetoxy)vinylphosphonate.

The N-acylation of glycoluril with 1-haloacetyl halides was studied. The optimal conditions and reaction regioselectivity, as well as the effect of reagent molar ratios, base nature, temperature, and reaction time on the yield of the target product were established. It was shown that the chemical modification of the synthesized bis(bromoacetyl) derivative of glycoluril by phosphorylation by the classical Arbuzov reaction gave a previously unknown bis(diethylphosphonoacetyl) derivative of glycoluril. The consecutive silylation and hydrolysis of the latter derivative gave the corresponding bis(phosphonoacetyl) derivative which presents interest as a potentially biologically active compound.