Dimethyl 3-chloroprop-1-en-2-ylphosphonate. Part 2. Alkylation of amines, phosphines and phosphites

Abstract

Dimethyl 3-chloroprop-1-en-2-ylphosphonate 1 reacted with secondary amines to give phosphorus-containing allylic amines. Interaction of the phosphonate 1 with triethylamine formed the corresponding ammonium salt which, when heated, was converted into the betaine 15. The reaction of the phosphonate 1 with triphenylphosphine also led to formation of the corresponding phosphonium salt which, when heated, underwent prototropic isomerisation to give the betaine 17. The phosphonium salt was utilised in a Wittig reaction with paraformaldehyde to form buta-1,3-dien-2-ylphosphonate. The Michaellis–Arbusov reaction of the phosphonate 1 with trimethyl phosphite led to prop-2-ene-1,2-diyldiphosphonate. Its hydrolysis gave the corresponding diphosphonic acid, which is a hydrolytically stable analogue of phosphoenol pyruvate. Alkylation of N-heterocycles, glycine and DL-alanine led to compounds having biological activity potential.