Synthesis, Properties, and Spectra of Partially Fluorinated Esters.

A solution of 0.5 mole of fluoroacid and 0.5 mole of unfluorinated alcohol in 100 ml. of benzene was refluxed in a round-bottomed flask fitted with a Dean-Stark receiver. When the water in the receiver became constant. the contents of the flask were diluted with ether and washed first with 1N sodium hydroxide and finally with distilled water until the water washes were neutral to litmus paper. The ether extract was dried (8), concentrated, and distilled. The fluoroalcohols were esterified with the addition of concentrated sulfuric acid catalyst. Trifluoroethyl butyrate was prepared in this way as well as from the acid chloride (5) and the fluoroalcohol ( 4 ) . Trifluoroethyl valerate was prepared by refluxing the acid and excess alcohol in benzene with a concentrated sulfuric acid catalyst without azeotroping the water. For the trifluoroacetate preparations, sulfuric acid was omitted, and benzene and Dean-Stark receiver were replaced by carbon tetrachloride and a distilling tube receiver, respectively.