Novel C-phosphorylated heterodienes based on pentachloroethyl isocyanate

A preparative method for the synthesis of novel N-phosphorylcarbonyl-and N-alkoxycarbonyltrichloroacetimidoylphosphonates from accessible pentachloroethyl isocyanate was developed. Factors that determine the C/N-selectivity of the phosphorylation of trichloroacetimidoyl chlorides were revealed: phenyl substituents at the P atom and an electron-withdrawing N-alkoxycarbonyl group in imidoyl chloride favored N-phosphorylation, while reactions with silyl phosphite gave exclusively C-phosphorylation products. Dedicated to the Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2563–2566, November, 2005.