Synthesis and Reactions of Substituted Alkyl Trifluoromethyl Ethers

Abstract

Trifluoromethyl hypochlorite has been reacted with RCH—CH2(R = S02CH=CH2, (CH30)3Si, Cl3Si, (CH3)3Si) to form isomeric mixtures of the trifluoromethyl ethers. With SbF3, CF3OCH2CH(SiCl3)Cl gave CF3OCH2CH(SiF3)Cl, and when CF3OCH[Si(CH3)3]CH2Cl was thermolyzed, the vinyl ether CF3OCH=CH2resulted. The addition product of CF3OCl with C12C==CHC1 was dehydrochlorinated to CF3OCCl=CCl2, which when chlorinated gave CF30CC12CC13. The latter could not be obtained by direct reaction of CF3OCl with tetrachloroethylene. Dechlorination of the CF30C1/C12C==CF2addition products (6a) gave CF3OCCl—CF2, which formed a bis(trifluoromethyl) ether (6c/d) with CF3OCl. The latter when dechlorinated gave (CF30)2C=CF2(6e). 1,1,1-Trifluoropropene with CF3OCl gave a 60% yield of the Markovnikov-type addition 8a, which when reacted with KOH formed m-CF3CH=CClH as a result of the loss of [CF3OH]. The former with CF3OCl produced CF3OC-H(CF3)CHC12. The yields of trifluoromethyl ethers formed by reaction of CH30C(0)CH=CH2, CH3C(0)CH—CH2, and HC(0)CH=CH2 with CF3OCl decreased from 65 to 5%. © 1986, American Chemical Society. All rights reserved.