The Formation and Deamination of Brominated m-Aminobenzotrifluorides¹

Synthesis and copolymerization of vinylidene fluoride (VDF) with Trifluorovinyl Monomers, 11

“…In contrast to the efficient telomerizations of VDF with perfluoroalkyl iodides9,13,35,36 ClCF 2 CFClI9 or α , ω ‐diiodoperfluoroalkanes,37 linked to the low dissociation energy of the CI bond, it can be assumed that similar reactions in the presence of dibrominated reactant 1 would be more difficult to achieve because of the well‐known strong CBr bond 38. However, as in the case of the CFClI end‐group,39 the CFClBr bond activated by the chlorine atom is more cleavable than the CF 2 Br extremity, which is why Tarrant and Lilyquist,22 using dibenzoyl peroxide at 100 °C to initiate this reaction, produced the telomers in 67% yields.…”

“…BrCF 2 CFClBr seems to be a more active transfer agent but, to our knowledge, only one article describes its reactivity toward VDF 22. Dibenzoyl peroxide was efficient in this telomerization process but the authors did not try thermal, photochemical or redox initiations and did not use other organic initiators.…”

Synthesis and copolymerization of fluorinated monomers bearing a reactive lateral group. XX. Copolymerization of vinylidene fluoride with 4‐bromo‐1,1,2‐trifluorobut‐1‐ene

“…The telomerization of fluorinated olefins with BrCF 2 CFClBr has already been described in the literature,7, 52, 53 just like the ethylenation of diiodofluorinated telogens 54, 55. For the radical addition of BrCFClCF 2 Br to ethylene, to our knowledge only the mechanism has been described previously 56…”

Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes

“…7 Shortly thereafter, Tarrant et al accomplished the construction of 1,1-difluorocyclopropane from 1,3-dibromo-1,1-difluoro-2-methylbutane in 39% yield mediated by excess Zn, which was the first report on the synthesis of gem -difluorinated cyclopropane in history. 8 In 1960, when the first difluorocarbene precursor (sodium chlorodifluoroacetate) was discovered to be useful for the synthesis of a nearly infinite variety of fluorinated cyclopropanes, the research into fluorinated cyclopropanes moved to a higher level. 9 Nowadays, there are many synthetic methods to obtain gem -difluorinated cyclopropanes, all of which facilitate the exploration of their reactivities (Scheme 1 ).…”