Reaction of Malonic Acid Derivatives with Acetylenic Diphosphonates

摘要

The primary addition products in the reactions of malonic esters,cyanoacetic esters,and malo-nonitrile with acetylenediphosphonates in acetonitrile in the presence of anhydrous potassium carbonate are potassium derivatives,viz.esters and nitriles of the corresponding 2-alkoxycarbonyl(or 2-cyano)-3,4-bis(di-alkoxyphosphinoyl)-2-potassiobut-3-enoic acid.Further hydrogen replacement for potassium in the nitriles is accompanied by isomerization involving double-bond shift and geometry change.(E)-and(Z)-3,4-bis(dial-koxyphosphinoyl)-2-cyano-2-potassiobut-3-enenitriles(the alkoxy groups are CH_3O and C_2H_5O)are crystalline compounds;they were isolated and characterized.