First examples of stable polyfluorinated bis- and tris-(alkoxy)methyl cations
摘要:
Stable polyfluorinated bis- and tris-(alkoxy)methyl cations were prepared by the reaction of the corresponding difluoroformals (RfO)(2)CF2 (R-f = -CH2CF3, -CH(CF3)(2), -CH2CF2Cl) with an excess of SbF5. Although the cation (CF3CH2O)(2)CF+ (1a) is stable at ambient temperature, the chlorinated analog (ClCF2CH2O)(2)CF+ (3a) can be generated only at low temperature in SO2ClF solvent and rapidly decomposes at ambient temperature. Although the salt [(CF3)(2)CHO](2)CF+SbnF5n+1- (2a) is slightly more stable than the salt of cation 3a, at ambient temperature it undergoes rapid disproportionation with formation of equal amounts of [(CF3)(2)CHO](3)C+SbnF5n+1- (2b) and CF3OCH(CF3)(2) (2c). Stable solid salt 2b (n = 2) 2b (n = 2) was isolated and fully characterized by H-1, F-19 and C-13 NMR spectroscopy and its structure was confirmed by single crystal X-ray diffraction. (C) 2005 Elsevier B.V. All rights reserved.
Synthesis of fluorinated tertiary diamines and diazanes
作者:Nimesh R. Patel、Robert L. Kirchmeier、Jean'ne M. Shreeve
DOI:10.1016/s0022-1139(00)80224-9
日期:1990.7
A variety of fluorinated and partially fluorinated tertiary diamines and diazanes have been prepared from 1-[bis(trifluoromethyl)amtno]tetrafluoro-2- azapropene, which is obtained from the dimerization of 2-azapropene in the presence of CsF. Addition of ClF results in the formation of the tertiary diamine (CF3)2NCF2N(Cl)CF3. Insertion of alkenes and nitriles into the nitrogenchlorine bond, as well