Studies on the preparation of 2-(trifluoromethyl) acrylic acid and its esters from 3,3,3-trifluoropropene via hydrocarbonylation reactions

The synthesis of methyl alpha-(trifluoromethyl) acrylate (MTFMA) has been carried out in three steps starting from commercially available 3,3,3,-trifluoropropene; this route involving the cobalt-catalyzed carbonylation of 2-bromo-3,3,3-trifluoropropene (2-Br-TFP) under very mild reaction conditions, gave only about 30% yield of the desired methyl ester. 2-(Trifluoromethyl) propanal, available in 90% yield by rhodium catalyzed hydroformylation of 3,3,3-trifluoropropene, proved to be an interesting starting product for the preparation of MTFMA: while the synthetic route involving the alpha-halogenation of 2-(trifluoromethyl)propanoic acid (TFMPA) failed to give any results, the reaction scheme based on the alpha-selenenylation of the above aldehyde followed by H2O2-oxidation afforded 68% yield of 2-(trifluoromethyl) acrylic acid (TFMAA). (C) 1997 Elsevier Science S.A.