Cyclization reactivities of fluorinated hex-5-enyl radicals

Rong, Xiao; Bartberger, Michael D.; Koroniak, Henryk; Smart, Bruce E.; Yang, Zhen‐Yu

doi:10.1039/a707701g

Cited by 38 publications

(40 citation statements)

References 46 publications

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“…The functional group, which is subsequently introduced in a lateral position around the backbone of the copolymer, brings specific and complementary properties: adhesion for a carboxylic function,8 solubility from a cyclohexyl group,9 curability due to hydroxyl or epoxide function,2, 10–12 surface properties from a perfluorinated group,13 and good hydrophilicity or heat and chemical resistance from a phosphonated function 14. Various functional monomers exhibiting ω‐trifluorovinyl groups have already been synthesized 2, 11, 12, 15–20. Among them, 2,3,3‐trifluoroprop‐2‐enol (FA1), prepared by the reaction of 2,2,3,3‐tetrafluoropropanol with methyl lithium,17 is attractive.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group. XII. Copolymerization of vinylidene fluoride with 2,3,3‐trifluoroprop‐2‐enol

Guiot

Améduri

Boutevin

2002

J. Polym. Sci. A Polym. Chem.

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An improved synthesis of 2,3,3‐trifluoroprop‐2‐enol (FA1) and its copolymerization in solution with vinylidene fluoride (VDF, or 1,1‐difluoroethylene) initiated by tert‐butyl peroxypivalate are presented. A new synthesis of FA1, with NaH and lithium diisopropylamine as bases, from 2,2,3,3‐tetrafluoropropanol is described. A series of nine copolymerization reactions were investigated from initial [VDF]0/[FA1]0 molar ratios of 9.1/90.9 to 94.2/5.8. The copolymer compositions were calculated via 19F NMR spectroscopy. From the Tidwell–Mortimer method, the reactivity ratios of both comonomers were determined (rFA1 = 0.11 ± 0.22 and rVDF = 0.83 ± 0.77 at 50°C), and they showed an azeotropic point. Alfrey and Price's Q and e values of FA1 were calculated to be 0.0178 (from QVDF = 0.008), 0.039 (from QVDF = 0.015), and 0.275 (from QVDF = 0.036) and 2.74 (vs eVDF = 1.20), 2.04 (vs eVDF = 0.50), and 1.94 (vs eVDF = 0.4), respectively, and they indicated that FA1 is an electron‐accepting monomer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3634–3643, 2002

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Section: Introductionmentioning

confidence: 99%

Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group. XII. Copolymerization of vinylidene fluoride with 2,3,3‐trifluoroprop‐2‐enol

Guiot

Améduri

Boutevin

2002

J. Polym. Sci. A Polym. Chem.

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“…Finally, they can be functionalised by phosphonic acid groups [8,40,41], like diethyl perfluoro(3-vinyloxypropyl) phosphonate [41], or F 2 C=CFP(O)(OH) 2 [42]. Furthermore, various functional trifluorovinyl monomers have also been prepared, bearing either a carboxylic acid [43], or a sultone [44] group.…”

mentioning

confidence: 99%

Proton‐Conducting Polymer Electrolyte Membranes Based on Fluoropolymers Incorporating Perfluorovinyl Ether Sulfonic Acids and Fluoroalkenes: Synthesis and Characterization

et al. 2005

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This paper presents the synthesis of new polymer electrolyte membranes based on fluoropolymers incorporating aromatic perfluorovinyl ether sulfonic acids. A novel synthetic route describing the preparation of perfluorovinyl ether monomer containing sulfonic functionalities, 4‐[(α,β,β‐trifluorovinyl)‐oxy]benzene sulfonic acid (TFVOBSA), is reported. The radical (co) and terpolymerisation of 4‐[(α,β,β‐trifluorovinyl)oxy]benzene sulfonyl chloride (TFVOBSC) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF), hexafluoropropene (HFP), and perfluoromethyl vinyl ether (PMVE) is described. The terpolymers of TFVOBSC with VDF and HFP, or VDF and PMVE, were hydrolysed and also led to new fluorinated terpolymers bearing sulfonic acid aromatic side‐groups. The terpolymers were characterized by 1H and 19F NMR spectroscopies, SEC, DSC, and TGA. Membranes incorporating these functional fluoropolymers were prepared and the electrochemical properties (IEC, proton conductivity, swelling rates) were studied and discussed.

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“…Dolbier and co‐workers carried out an interesting study on the influence of fluorine substitution on the reactivity of 5‐ exo ‐ trig , 6‐ endo ‐ trig , and 6‐ exo ‐ trig cyclizations of 5‐hexenyl and 6‐heptenyl radicals , . Remarkably, the presence of fluorine at the radical center caused reaction rate increase by several orders of magnitude (Figure ), confirming the electrophilic character of these fluorinated radical intermediates.…”

Section: Transfer Of the Cf2cf2 Fragmentmentioning

confidence: 85%

Advances in the Synthesis and Application of Tetrafluoroethylene‐ and 1,1,2,2‐Tetrafluoroethyl‐Containing Compounds

et al. 2018

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In this review, we provide a comprehensive and critical perspective on the synthesis and application of 1,1,2,2‐tetrafluoroethyl‐ and tetrafluoroethylene‐containing compounds. These structures have been the focus of increasing attention as witnessed by a spectrum of new synthetic approaches, which have recently appeared in the literature. Likewise, applications of molecules containing the CF2CF2 fragment as pharmaceuticals, agrochemicals, pesticides, and advanced materials are described. It is expected that the number of successful applications of these compounds will increase in the future as a result of availability of the synthetic methods outlined here.

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Cyclization reactivities of fluorinated hex-5-enyl radicals

Cited by 38 publications

References 46 publications

Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group. XII. Copolymerization of vinylidene fluoride with 2,3,3‐trifluoroprop‐2‐enol

Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group. XII. Copolymerization of vinylidene fluoride with 2,3,3‐trifluoroprop‐2‐enol

Proton‐Conducting Polymer Electrolyte Membranes Based on Fluoropolymers Incorporating Perfluorovinyl Ether Sulfonic Acids and Fluoroalkenes: Synthesis and Characterization

Advances in the Synthesis and Application of Tetrafluoroethylene‐ and 1,1,2,2‐Tetrafluoroethyl‐Containing Compounds

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