Nucleophilic reactions of fluorinated alkenes

Chambers, Richard D.; Vaughan, Julian F. S.

doi:10.1007/bfb0119264

Cited by 27 publications

(24 citation statements)

References 97 publications

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“…The reaction was initiated with benzoyl peroxide and carried out at 60 1C for 72 h, yielding soluble polymers containing 18-crown-6 moieties in the polymer main chain. The highest molecular weight obtained was 5.5Â10 4 . The reaction takes place as shown in Equation (8).…”

Section: Radical Polyaddition Of Perfluoroisopropenyl Compoundsmentioning

confidence: 99%

“…The yield of the 2:1 addition product of BPFP with diethoxydimethylsilane was found to be higher than that of BPFP with dimethoxydimethylsilane. The polyaddition of BFP with diethoxydimethylsilane was successful, affording fluorinated hybrid polymers possessing fluoroalkyl and alkylsilyl groups in the polymer main chain with a maximum molecular weight of 1.4Â10 4 . The reaction takes place as depicted in Equation (11).…”

Section: Radical Polyaddition Of Perfluoroisopropenyl Compoundsmentioning

confidence: 99%

“…Soluble fluorinated hybrid polymer was obtained from BFP with tetrafunctional tetraethoxysilane (Si(C 2 H 5 O) 4 ) initiated by di-tert-butyl peroxide and proceeded at 120 1C for 72 h, as shown in Equation (12). The highest molecular weight obtained was 8.2Â10 3 and the yield was fairly high.…”

Section: Radical Polyaddition Of Perfluoroisopropenyl Compoundsmentioning

confidence: 99%

“…The addition of BPFP with triethylamine afforded ordinary yields as compared with many reports on the radical addition of trifluorovinyl compounds with amine derivatives. 4 The radical polyaddition of BFP with triethylamine was then examined to yield a polymer of 6.3Â10 3 as the highest molecular weight following initiation with benzoyl peroxide and reaction at 60 1C for 72 h, as shown in Equation (9), although the yield of polymer was very low. To increase the fluorine content of polymers obtained from BFP with 1,4-dioxane, the copolymerization of BFP and bis(1-trifluoromethyl-2,2-difluorovinyl) 2,3,5,6-tetrafluoroterephthalate (CF 2 ¼C(CF 3 )OCO-C 6 F 4 -COOC(CF 3 )¼CF 2 ) with 1,4-dioxane was investigated and shown to afford polymers of molecular weight 1.1Â10 4 following initiation with di-tert-butyl peroxide and reaction at 80 1C for 72 h, as shown in Equation (10).…”

Section: Radical Polyaddition Of Perfluoroisopropenyl Compoundsmentioning

confidence: 99%

“…Radical addition reactions of fluorinated vinyl monomers with cyclic ethers and alcohols have also been reported as these vinyl compounds are generally good radical acceptors. 4 Therefore, facile carbon-carbon bond formation reactions could be achieved by anionic and radical additions of a wide variety of organic compounds to fluorinated vinyl compounds. These reactions could then be developed into the formation of carbon-carbon bonds from carbon-hydrogen bonds as functional groups in an aliphatic compound.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of novel fluorinated polymers: facile carbon–carbon bond formation aided by fluorine substituents

Narita

2011

Polym J

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The review article summarizes my work as a macromolecular synthetic chemist to leave it on the sands of time. Fluorinated vinyl compounds with high addition reactivities toward anionic and radical species were demonstrated to allow facile preparation of fluorinated polymers. Novel anionic addition polymerization of fluorinated vinyl monomers, which generally show poor homopolymerization reactivities under radical conditions, has been developed. Measurement of pseudo first-order rate constants, k¢, demonstrated the order of reactivity of 18 fluorinated acrylates and methacrylates by the reaction with diethyl(ethyl cyanoacetato)aluminum. The new field, anionic polyaddition, was accomplished by the double Michael addition of bis(2-trifluoromethylacrylate)s to active methylene compounds. Radical addition reaction of several fluorinated vinyl compounds with organic compounds possessing carbon-hydrogen bonds afforded fluorinated organic compounds. By developing the novel radical addition, the polyaddition reaction was achieved to incorporate fluorinated vinyl monomers into polymer main chains with organic compounds possessing carbon-hydrogen bonds, the first use for these polymers as starting materials of macromolecular syntheses. Facile carbon-carbon bond formation reactions were made possible with the aid of fluorine substituents under anionic and radical conditions. These reactions were then developed into the formation of the carbon-carbon bond from a carbon-hydrogen bond as a functional group in aliphatic compounds.

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Section: Radical Polyaddition Of Perfluoroisopropenyl Compoundsmentioning

confidence: 99%

Section: Radical Polyaddition Of Perfluoroisopropenyl Compoundsmentioning

confidence: 99%