Acyclic polyfluoro mono and disiloxanes CF(3)CH(2)OSiMe(3) (1), CF3C(CH3)(2)OSiMe(3) (2), CH3C(CF3)(2)OSiMe(3) (3), C6H5C(CF3)(2)OSiMe(3) (4), (CF3)(2)CHOSiMe(3) (5), (CF3)(3)COSiMe(3) (6), FCH(2)CH(2)OSiMe(3) (7), HCF(2)CF(2)CH(2)OSiMe(3) (8), n-C(7)F(15)CH(2)OSiMe(3) (9), (CF(2)CH(2)OSiMe(3))(2) (10), and CF2(CF(2)CH(2)OSiMe(3))(2) (11) are synthesized by the reactions of their respective alcohols with hexamethyldisilazane. Reactions of 1 with CH2Br2, (CNF)(3), CFBr3, perfluorocyclobutene, and C6F5CN proceed readily in the presence of fluoride ion to form CH2(R(f))(2) (12), C3N3(R(f))(3) (13), C(R(f))(4) (14), CF2C(R(f))=C(R(f))CF2 (15), CF2C(R(f))=C(F)CF2 (16) and 4-R(f)C(6)F(4)CN (17) (when reacted 1:1) and (R(f))(5)C6CN (18) (when reacted with excess of 1), respectively (R(f) = OCH2CF3). Reactions of 2 with C6F5CN, C6F6, CF3C6F5, ClC6F5, NC5F5, 1,2-diiodotetrafluorobenzen and perfluorocyclobutene in the presence of fluoride ion give R(f)C(6)F(4)CN (19) or (R(f))(2)C6F3CN (20) (depending on the ratio of reactants), R(f)C(6)F(5) (21), R(f)C(6)F(4)CF(3) (22), R(f)C(6)F(4)Cl (23), R(f)C(5)F(4)N (24), R(f)C(6)F(3)I(2) (25), and CF2C(R(f))=C(F)CF2 (26), respectively (R(f) = CF3C(CH3)(2)O). Reactions of 3 with C6F5CN, C6F6 and 1,2-diiodotetrafluorobenzene with fluoride ion as catalyst form R(f)C(6)F(4)CN (27), R(f)C(6)F(5) (28) and R(f)C(6)F(3)I(2) (29), respectively (R(f) = CH3C(CF3)(2)O). Reactions of 4 with CF3C6F5, C6F5CN, perfluorocyclobutene, C6H5CH2Br and CH3I give R(f)C(6)F(4)CF(3) (30), R(f)C(6)F(4)CN (31), CF2C(R(f))=C(F)CF2 (32), R(f)CH(2)C(6)H-5 (33) and R(f)CH(3) (34), respectively (R(f) = C6H5C(CF3)(2)O). Reactions of 5 with C6F5CN and CF3C6F5 result in R(f)C(6)F(4)CN (35) and R(f)C(6)F(4)CF(3) (36), respectively (R(f) = (CF3)(2)CHO). Siloxanes 6, 7, 8 and 9 with C6F5CN form CNC6F4OC(CF3)(3) (37), FCH2CH2OC6F4CN (38), HCF2CF2CH2OC6F4CN (39) and n-C7F15CH2OC6F4CN (40). Disiloxane 10 with CH2Br2, Br2CHCHBr2, SOF2, SO2Cl2, COF2, C6F5CN, (COF)(2), POCl3, C5F5N, CF3SO2F, 1,2-diiodotetrafluorobenzene, I(CF2)(2)O(CF2)(2)SO2F, FC(O)(CF2)(3)C(O)F and 1,4-dibromotetrafluorobenzene gives polyfluorinated cyclic or acyclic ethers CF2CH2OCH2OCH2CF2 (41), CF2CH2OCHOCH2(CF2)(2)CH2OCHOCH2CF2 (42), CF2CH2OS(O)OCH2CF2 (43), CF2CH2OSO2OCH2CF2 (44), FC(O)OCH2CF2CF2CH2OC(O)F (45), 4-CNC6F4OCH2CF2CF2CH2OC6F4CN-4 (46), CF2CH2OC(O)C(O)OCH2CF2 (47), CF2CH2OP(O)FOCH2CF2 (48), NC5F4OCH2CF2CF2CH2OC5F4N (49), CF3SO2OCH2CF2CF2CH2O S O2CF3 (50), F2CH2CO(3,6-difluoro-4,5-diiodo-o-phenylene)OCH2CF2 (51), I(CF2)(2)O(CF2)(2)SO2OCH2(CF2)(2)CH2OSO2(CF2)(2)I (52), CF2CH2OC(O)(CF2)(3)C(O)OCH2CF2 (53), and (-F2CH2CO)(2)(3,6-dibromo-1,2,4,5-benzenetetrayl)(OCH2CF2-)(2) (54), respectively. Reactions of 11 with CH2Br2, COF2, SOF2, and SO2Cl2 also give cyclic and acyclic ethers CF2CF2CH2OCH2OCH2CF2 (55), FC(O)OCH2(CF2)(3)CH2OC(O)F (56), CF2CF2CH2OS(O)OCH2CF2 (57), and CF2CF2CH2OSO2OCH2CF2 (58), respectively. Ethers 17, 38-40 and CH3CH(CF3)OC6F4CN (59) are also prepared by reacting the corresponding alcohols with pentafluorobenzonitrile in the presence of alkali carbonate as the HF-acceptor. Reaction of C(6)H(5)OSiMe(3) With C6F5CN yields the polyether (C6H5O)(5)C6CN (60). When ethers 17, 38-40 and 59 are hydrolyzed in alkaline hydrogen peroxide (30%), the corresponding benzamides CF3CH2OC6CONH2 (61), FCH2CH2OC6F4CONH2 (62),HCF2CF2CH2OC6F4CONH(2) (63), n-C7F15CH2OC6F(4-) CONH2 (64) and CH3CH(CF3)OC6F4CONH2 (65), respectively, are formed.= 2?c