Nitroxide Chemistry. Part 18. Reaction of Bistrifluoromethyl Nitroxide with Some Ethers

Article abstract of DOI:10.1039/P19810001068

Treatment of the methyl ethers MeOX (X = Me, Ph) with a stoicheiometric amount of bistrifluoromethyl nitroxide <(CF3)2NO^. = R^.> at room temperature converts them efficiently into their bistrifluoromethylamino-oxymethyl counterparts, RCH2OX; the bis-derivative (RCH2)2O is a minor by-product in the case of dimethyl ether (X = Me).Multiple hydrogen-abstraction increases in importance with diethyl ether as substrate, the expected products RCHMeOEt and (RCHMe)2O being accompanied by a bis-derivative (RCH2CHROEt) arguably produced via the αβ-dehydrogenation 2R^. + Et2O -> 2RH + CH2=CHOEt.The halogeno-ether MeOCF2CHFCl reacts slowly with the nitroxide at 50 deg C to yield a 7 : 1 mixture of the derivatives RCH2OCF2CHFCl and RCFClCF2OMe, hydrolysis of which gives the esters RCH2OCOCHFCl and RCFClCO2Me, respectively.The latter ester is best obtained via treatment of methyl chlorofluoroacetate with bistrifluoromethyl nitroxide.