Organo-phosphorus oxyhalide(s) prodn. - by reaction of aryl phosphinate or phosphonate ester(s) with phosphorus oxychloride in presence of lewis acid at 100-350 deg. C

摘要

Organophosphorus oxyhalides of formula R1-P(O)(R2)kClmCl (I) are produced by reaction of corresp. aryl phosphinate and phosphonate esters of formula R1-P(O)(R2)k(OR3)m(OR4) (II) with POCl3 (III) in the mol. ratio (III): (aryl ester residue) (1-6):1, pref. (13):1, esp. pref. 2:1, in the presence of Lewis acid (IV) at 100-350 (pref. 170-200) deg.C.; R1, R2 = opt. substd. 1-20C alkyl, 2-20C alkenyl or 6-10C aryl; R3, R4 = opt. susbtd. 6-10C aryl; k, m = 0 or 1, with k + m = 1. Amt. of catalyst (IV) is 0.01-0.1 (pref. 0.02-0.06) mol./mol. aryl ester residue, and pref. (IV) is AlCl3; reaction is carried out under pressure at 170-200 deg.C, and the prod. is worked up by distn., pref. by multi-stage distn. at reduced pressure, esp. pref. at 5-100 mbar; pref. (II) is diphenyl methanephosphonate (IIA) or ethanephosphonate. USE/ADVANTAGE - (I) are useful as intermediates for the synthesis of a wide range of cpds. The invention provides an economical process for the prodn. of (I) without the disadvantages of prior-art processes (expense of prepn. of phosphanes, dichlorophosphanes or free acids as starting materials, formation of alkyl chloride by-prods., etc.)W