PERFLUORO TERTIARY ALCOHOLS .2. SYNTHESIS OF HIGH-MOLECULAR-WEIGHT PERFLUORINATED DIKETONES, KETO ALCOHOLS AND TERTIARY DIALCOHOLS

A variety of perfluorinated diketones, Rf1C(O)RfaC(O)Rf1 (1), keto alcohols, Rf1Rf2C-(OH)RfaC(O)Rf1 (II), and dialcohols, Ff1Rf2C(OH)RfaC(OH)Rf1Rf2 (III), R(r)1 = (CF3)2-CFO(CF2)2, (CF3)2CFO(CF2)4 and CF3O[CF2CF(CF3)O]2(CF2)2; R(f)2 = (CF3)2CFO(CF2)2 and C3F7O[CF(CF3)CF2O]2(CF2)2; and R(f)a = (CF2)2, (CF2)8, CF2OCF2CF2OCF2, (CF2)2O(CF2)5O(CF2)2 and (CF2)40(CF2)40(CF2)4, have been prepared via perfluoroalkylether lithium intermediates. In the reaction of diketones with perfluoro lithium reagents, the solvent and the nature of the R(f)a groups play important roles in determining the yield and the nature of the reaction products formed. The reaction of diketone I [where R(f)a is other than (CF2)3] with excess perfluoroalkylether lithium yielded the diol III as the principal product and keto alcohol II as the minor product. However, when R(f)a = (CF2)3, the product is exclusively keto alcohol II.