Dialkyl (3-Aryl-1,2,4-oxadiazol-5-yl)phosphonates: Synthesis and Thermal Behavior - Evidence for Monomeric Alkyl Metaphosphate

Article abstract of DOI:10.1021/jo00171a015

Dialkyl (3-aryl-1,2,4-oxadiazol-5-yl)phosphonates 6a-h have been obtained by 1,3-dipolar cycloaddition of arenenitrile oxides 5a-f to dialkyl phosphorocyanidates (4a and 4b) in yields ranging between 30percent and 58percent.A standardized method for obtaining cyanidates 4a and 4b has been established.The diethyl thiophosphorocyanidate (4c) is less reactive than 4a and 4b, only the 3-(4'-nitrophenyl) derivative 6i being obtainable.While the IR and NMR spectra of 6a-6i were unexceptional, their UV spectra showed evidence of conjugative interaction in high degrees between the phosphonate and heterocyclic moieties as well as a varying conjugative interaction between the heterocyclic and aryl moieties.The oxadiazoles 6a-h are thermally labile and yield trialkyl phosphates 7 as the only identifiable products.A mechanism based on the intermediacy of monomeric alkyl metaphosphate 11 in the formation of trialkyl phosphate was postulated, and supportive evidence in the form of trapping the metaphosphate with acetophenone has been obtained.