New Convenient Route to Polyfluoroalkenyltrialkylsilanes and Germanes

Perfluoroalkylation with Organosilicon Reagents

“…Selective monosubstitution of a chlorine atom in 1,2-dichlorooctafluorocyclohexene (Table , entry 14, n = 2) was achieved by Bardin et al. 14a Long-chain perfluorooxaalkyl iodides were used by Chen et al to obtain the corresponding trimethylsilylated adducts (Table , entries 15−17) . In the case of secondary long-chain perfluorooxa derivatives, Grignard route is also applicable but gives inferior yields compared to the modified Ruppert's method.…”

“…These authors also succeeded in the preparation of the first tris(trifluoromethyl)silane derivative, (CF 3 ) 3 SiNEt 2 . Bardin et al converted Me 2 SiClOEt into bis(pentafluorophenyl) derivative using Ruppert's protocol 14b…”

Explored routes to unknown polyfluoroorganyliodine hexafluorides, RFIF6

“…We have found that IF 7 and 2,2,2-trifluoroethyliodine tetrafluoride (27) did not react in PFP even at 25 8C over 16 h (Eq. (7)).…”

“…Products cyclo-1,3-C 6 F 7 -1-IF 4 (20), cyclo-1,4-C 6 F 7 -1-IF 4 (14), and cyclo-1-C 6 F 9 -1-IF 4 (15) [23], cyclo-1,3-C 6 F 7 -1-SiF 3 (9), cyclo-1,4-C 6 F 7 -1-SiF 3 (10), cyclo-1,4-C 6 F 7 -1-SiMe 3 (2), cyclo-1-C 6 F 9 -1-SiF 3 (11), cyclo-1-H-1,4-C 6 F 7 (12), cyclo-1,4-C 6 F 8 (6), [26], cyclo-1-C 6 F 9 -1-SiMe 3 (3) [27], and cyclo-1-H-1-C 6 F 9 (13) [28] were identified by 19 F NMR spectroscopy.…”

Dehalogenative aromatization of perchlorofluoroalicyclic compounds C6Cl6F6, C10Cl8F8 and C5Cl4F5N in the vapour phase or in solution

“…Dehalogenation with P(NEt 2 ) 3 gave a somewhat different molar ratio of 1 Sulfolane b C 10 F 8 (9), 1-C 10 ClF 7 (10), 2-C 10 ClF 7 (19), C 10 Cl 2 F 6 (33) 2 Sulfolane c C 10 F 8 (6), 1-C 10 ClF 7 (9), 2-C 10 ClF 7 (19), C 10 Cl 2 F 6 (37) 3 Diglyme c C 10 F 8 (7), 1-C 10 ClF 7 (10), 2-C 10 ClF 7 (19), C 10 Cl 2 F 6 (34) 4 DMA d C 10 F 8 (7), 1-C 10 ClF 7 (9), 2-C 10 ClF 7 (18) perhalogenated arenes derived from 1 and 3. Unlike the metal used, P(NEt 2 ) 3 can react partially with intermediate cycloalkenes at the C-F and C-Cl bonds of olefinic moiety [21] to decrease yields of desirable polyfluoroarenes.…”