Fluorinated phosphorus compounds

Abstract

Twenty nine bis(fluoroalkyl) phosphates (R F O) 2 P(O)OR were prepared in 18-75% yield by treating phosphorochloridates (R F O) 2 P(O)Cl, where R F was HCF C with methanol, ethanol, propanol and isopropanol in diethyl ether in the presence of triethylamine. The bulky chloridate [(CH 3 ) 2 CF 3 CO] 2 P(O)Cl reacted with methanol, ethanol and propanol, but not with isopropanol -even on heating in the presence of the catalyst 4-dimethylaminopyridinedue to steric hindrance at phosphorus. The relative reactivities of three of the chloridates decreased in the order [(CF 3 ) 2 CHO] 2-P(O)Cl > [(FCH 2 ) 2 CHO] 2 P(O)Cl > [(CH 3 ) 2 CF 3 CO] 2 P(O)Cl. Also described is the synthesis of phosphates (CF 3 CH 2 O) 2 P(O)OCH 2 R, where R = CH 2 Br, CH 2 Cl, CH 2 F and CHF 2 , and diphosphates [H(CF 2 ) n CH 2 O] 2 P(O)OCH 2 (CF 2 ) 2 CH 2 OP(O)[OCH 2 (CF 2 ) n H] 2 , where n = 1, 2 and 4. Crown