Perfluoro tertiary alcohols. III. (Perfluoroalkyl)- and (perfluorooxaalkyl)-trimethylsilanes in the synthesis of perfluorinated tertiary alcohols

Article abstract of DOI:10.1016/0022-1139(94)03068-5

High-molecular weight perfluorinated tertiary alcohols, R_f¹,R_f²,R_f³C(OH) f¹=n-C8F17, R_f²=CF3, R_f³=n-C6F13; R_f¹=(CF3)2CFO(CF2)4, R_f²=CF3, R_f³=n-C6F13; R_f¹=C3F7O2CF(CF3), R_f²=CF3, R_f³=n-C6F13; R_f¹=n-C8F17, R_f²=CF3O2(CF2)2, R_f³=(CF3)2CFO(CF2)2> (IIIa-d), have been prepared by the reactions of (perfluoroalkyl)- and (perfluorooxaalkyl)-trimethylsilanes (Ia-d) with fluoroketones (IIa-c).Ketones containing a trifluoromethyl group as well as higher molecular weight perfluorinated substituents have been studied under different experimental conditions.The yield of tertiary alcohol is influenced by the solvents, reaction temperatures, type and concentration of metal fluorides, and structures of the fluoroalkyltrimethylsilanes and fluoroketones.The reaction has been extended to carbonyl compounds other than ketones.While a perfluorinated secondary acid fluoride gave good yield of the ketone, no reaction was observed with esters.