INSECT CHEMOSTERILANTS .4. OXIDATION OF HEXAMETHYLPHOSPHORIC TRIAMIDE AND SYNTHESIS OF N-FORMYLPHOSPHORAMIDES

The chlomform-soluble products of oxidation of hexamethylphosphoric triamide with aqueous KMnO4, were identified as pentamethylphosphoric triamide, N-[bis(dimethylamino)phosphinyl]-N-methylformamide, and N-[(dimethylamino)(methylamino)phosphinyl]-N-methylformamide. When the molar ratio of permanganate/amide was high, no pentamethyl compound was isolated but N-methylformamide appeared among the products. Oxidation of N, N, N′, N′-tetramethyl-P-piperidinophosphonic diamide yielded N-[(dimethylamino)piperidinophosphinyl]-N-methylformamide but the other oxidation products were not identified. The three formylphosphoramides obtained by oxidation are examples of a new class of phosphoramides; they were also synthesized by a new formylation procedure. The pentamethylphosphoric triamide appears to be formed by the decomposition of the unstable methylol precursor rather than by the oxidative decarbonylation of the formyl compound. © 1968, American Chemical Society. All rights reserved.