ES367109A1 - A PROCEDURE FOR THE PREPARATION OF PHOSPHONIC ACID AND DERIVATIVES OF THE SAME. - Google Patents

Abstract

A compound of the formula wherein R is an ester-forming group is obtained by reacting a phosphite ester P(OR) 3 with a compound of the formula wherein X is a halogen atom or a quaternary ammonium salt radical. The radical R may be alkyl, cycloalkyl, alkenyl, C 2 -C 5 alkynyl, cyano C 1 -C 5 alkyl, aryl, C 1 -C 5 alkyl substituted mononuclear aryl, or aralkyl, and X is halogen, e.g.Cl,Br or I or a quaternary ammonium salt radical, e.g. one having a cation of the formula +-NR1R2R3 wherein R1 is C 1 -C 5 alkyl and R2 and R3 are each C 1 -C 5 alkyl or R2 and R3 together with the N atom form a heterocyclic group, e.g. piperidino. The reaction is generally carried out in an inert solvent and the isomeric ester mixture formed can be separated, e.g. by gas- or adsorption chromatography, to yield the esters of ( ) cis- and ( ) trans - (1,2 - epoxypropyl) phosphonic acid. The esters of the ( ) cis acid can be converted to the free acid or salts thereof, which have antibiotic properties, by various defined methods and the free acid can be converted to alkali metal-or alkaline earth metal salts or to the amine salts by treatment with an appropriate base. The 1,X-1,2-propylene oxide compounds of Formula I in which X is halogen may be obtained by treating a compound of the formula CH 3 CH = CHX with an oxidizing agent, e.g. perbenzoic acid, metachloroperbenzoic acid, trifluoroperacetic acid or perphthalic acid. The compounds I in which X is a quaternary ammonium salt radical are obtained by reacting an a-halopropionaldehyde with a secondary amine, e.g. piperidine, in the presence of a base and then reacting the product with a C 1 -C 5 alkyl iodide. Tricyanoethyl phosphite is obtained by reacting #-hydroxypropionitrile in benzene with PCl 3 in triethylamine at 10 C. Tri-tert butyl phosphite is obtained similarly using tertbutanol instead of the #-hydroxy propionitrile.