PERFLUORO TERTIARY ALCOHOLS .1. SYNTHESIS OF HIGH-MOLECULAR-WEIGHT PERFLUORINATED MONO-KETONES AND TERTIARY ALCOHOLS

A series of high molecular weight perfluoro ketones, Rf1C(O)Rf2 (II) and alcohols, Rf1Rf2Rf3COH (III) [R(f)1, R(f)2: n-C6F13, (CF3)2CFO(CF2CF2)x (x = 1 and 2), C2F5O(C2F4O)yCF2 (y = 4 and 5), CF3O[CF2CF(CF3)O]2CF2CF2 and C3F7O[CF(CF3)CF2O]2CF2CF2; R(f)3: (CF3)2CFOCF2CF2 and C3F7O[CF(CF3)CF2O]2CF2CF2 where R(f)1, R(f)2 and R(f)3 may be the same or different, has been prepared in good to excellent yields. This was accomplished by the reaction of the appropriate perfluoroorganometallic reagent and diethyl carbonate or perfluoroalkylether ester under suitable conditions to yield symmetric or asymmetric ketones (II). These ketones (II) were then reacted with perfluoroalkylether lithium, containing an oxygen atom beta to the carbon atom attached to lithium, to produce tertiary alcohols (III). The yield of alcohol is influenced by the type of perfluoroorganometallic reagents, the mode of addition and the solvents.