Fluorinated phosphorus compounds: Part 6. The synthesis of bis(fluoroalkyl) phosphites and bis(fluoroalkyl) phosphorohalidates |
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Authors: | Christopher M Timperley Robert E ArbonSally A Saunders Matthew J Waters |
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Institution: | Defence Science and Technology Laboratory, Chemical and Biological Defence Sciences, Porton Down, Salisbury, Wiltshire SP4 0JQ, UK |
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Abstract: | Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (RFO)2P(O)H in 42-89% yield, where RF=HCF2CH2, H(CF2)2CH2, H(CF2)4CH2, CF3CH2, C2F5CH2, C3F7CH2, (CF3)2CH, (FCH2)2CH, CF3(CH3)2C, (CF3)2CH3C, CF3CH2CH2, C4F9CH2CH2 and C6F13CH2CH2. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (RFO)2P(O)Cl in 49-96% yield. The chloridate (CF3CH2O)2P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF3CH2O)2P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF3CH2O)2P(O)Br and iodidate (CF3CH2O)2P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly—its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts. |
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Keywords: | Bis(fluoroalkyl) phosphite Bis(trifluoroethyl) phosphorobromidate Bis(fluoroalkyl) phosphorochloridate Bis(trifluoroethyl) phosphorofluoridate Bis(trifluoroethyl) phosphoroiodidate |
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