Verfahren zur Herstellung von Estern, Esteramiden und Amiden der (cis-1,2-Epoxypropyl)-phosphonsäure und ihren Thioanalogen

1,267,091. Preparing (cis-1,2-epoxypropyl)- phosphonic acid and derivatives thereof. MERCK & CO. Inc. 12 May, 1969 [15 May, 1968; 16 Dec., 1968], No. 23988/69. Heading C2P. (cis-1,2-Epoxypropyl)phosphonic acid and its salts and esters and the phosphonamidate, phosphonothioate, phosphonamidothioate, phosphonodithioate, thiophosphonoamidate and diamide derivatives and analogues thereof are obtained by treating an appropriate phosphinyl- or phosphinothioyl methylide having a suitable leaving group at the methylide carbon with acetaldehyde. The methylide compound may have the formula wherein M is a sulphonium cation (R2) 2 S#, a sulphoxonium cation (R2) 2 SO#-, a phosphonium cation of the formula (R2) 3 P# or an ammonium cation (R3) 3 N#- where R2 is alkyl, aryl or aralkyl, R3 is alkyl or aralkyl, Z is O or S, and each of R and R1 is alkoxy, alkenyloxy, mono-, di-, or tri-haloalkoxy, dialkylaminoalkoxy, aryloxy, aralkoxy, phthalimidoalkoxy, dialkylamino, alkylthio, N-alkyl- N-arylamino, or acyloxymethoxy, R and R1 being the same or different, or R and R1 together are arylenedioxy, the reaction product having the formula The phosphinyl methylide may also have the formula wherein Z, R and R1 are as defined above, M A # is a cation, and M1 is halo, di-(C 1 -C 5 alkoxy)- phosphinyl, diaryloxyphosphinyl, or diaralkyloxyphosphinyl. The compounds IIa may be formed, if desired in situ, by reacting a halomethylphosphonic derivative of the formula wherein X is halo with an appropriate sulphide, amine, sulphoxide or phosphine to form a cationic intermediate which is then reacted with a base such as a sulphonylmethylide or sodium hydride. The compounds IIb in which M1 is the specified phosphinyl group may be obtained by treating III with an appropriate phosphite triester and then treating the resulting intermediate with a base, e.g. as specified above. When M1 in compounds IIb is halogen the starting compound may be obtained by treating III with a base. The halomethyl derivatives (III) may be obtained by treating HalCH 2 P(O)(Hal) 2 wherein Hal is halogen, e.g. ClCH 2 P(O)Cl 2 , with an appropriate alcohol, phenol, arylene diol, mercaptan, dialkyl amine, or dialkylaminoalkanol in one or more steps according to the product required. When a fluoromethyl phosphonic derivative (X = F in III) is required it may be obtained by treating POCl with an alcohol or other appropriate compound as defined above in the presence of a base, e.g. triethylamine, to form a chlorophosphonic de