Abstract Synthesis of symmetrical diesters derived from hydroxy methylene diphosphonic acids 1 to 8 is described either in one step or via the corresponding α ketophosphonate 1a to 8a. Study of the diphosphonates (1 to 6)→ phosphate-phosphonates (1b to 6b) isomerization has been realized. Results related to peculiar cases in connection with nonsymmetrical esters 10, 11, 17 and study of the hydrolysis reaction of diphosphonates ...