Fluorinated phosphorus compounds: Part 9. The reactions of bis(fluoroalkyl) phosphorochloridates with oxygen nucleophiles

Twenty nine bis(fluoroalkyl) phosphates (RFO)2P(O)OR were prepared in 18–75% yield by treating phosphorochloridates (RFO)2P(O)Cl, where RF was HCF2CH2, HCF2CF2CH2, H(CF2)4CH2, C2F5CH2, C3F7CH2, (CF3)2CH, (FCH2)2CH and (CH3)2CF3C with methanol, ethanol, propanol and isopropanol in diethyl ether in the presence of triethylamine. The bulky chloridate [(CH3)2CF3CO]2P(O)Cl reacted with methanol, ethanol and propanol, but not with isopropanol – even on heating in the presence of the catalyst 4-dimethylaminopyridine – due to steric hindrance at phosphorus. The relative reactivities of three of the chloridates decreased in the order [(CF3)2CHO]2P(O)Cl > [(FCH2)2CHO]2P(O)Cl > [(CH3)2CF3CO]2P(O)Cl. Also described is the synthesis of phosphates (CF3CH2O)2P(O)OCH2R, where R = CH2Br, CH2Cl, CH2F and CHF2, and diphosphates [H(CF2)nCH2O]2P(O)OCH2(CF2)2CH2OP(O)[OCH2(CF2)nH]2, where n = 1, 2 and 4.