Generation and thermal polymerization of 1-fluoro-2-phenylacetylene

Okano, Takashi; Ito, Katsukiyo; Ueda, Teruo; Muramatsu, Hiroshige

doi:10.1016/s0022-1139(00)81946-6

Cited by 31 publications

(23 citation statements)

References 16 publications

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“…The trifluorovinyl synthetic intermediate 178 was transformed to the trifluoromethylated pyrethroids 179 by S N 2 0 type dehydroxylative fluorination with DAST [67]. This successful alkylation with 174 at room temperature contrasts sharply to the reaction of trifluorovinyl lithium, which is thermally unstable and must be handled at the temperature below À78 8C The CsF-catalyzed desilyl-defluorination of trifluorovinylsilane174b [75] and difluorovinyl silane 194 [76] is applicable to the polymerization, which is proposed to undergo via the very reactive fluoroalkyne intermediates. The vinyl silane 174b gives semiconductor fluoropolyacetylene polymer 195, which shows conductivity of 10 À9 to 10 À10 V À1 cm À1 [75] (Scheme 49).…”

Section: Trifluorovinyltrimethylsilanementioning

confidence: 99%

“…2,2-Difluoro-1-phenylethenyl(trimethyl)silane 2,2-Difluoro-1-phenylethenyl(trimethyl)silane 265 is prepared by lithiation of the bromide 266 followed by silylation with TMSCl, where 2,2-difluoro-1-phenylethenyl lithium is rather unstable to eliminate fluoride ion and to provide 1-phenylhexyne as a byproduct via a possible intermediate of 2-fluorophenylacetylene (Scheme 68) [76]. The more straightforward synthesis was reported recently as shown in Scheme 69 [97].…”

Section: 2-difluoro-1-trialkylsilylethenyl Trimethylsilyl Ethersmentioning

confidence: 99%

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Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

Uneyama

2008

Journal of Fluorine Chemistry

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Section: Trifluorovinyltrimethylsilanementioning

confidence: 99%

Section: 2-difluoro-1-trialkylsilylethenyl Trimethylsilyl Ethersmentioning

confidence: 99%

Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

Uneyama

2008

Journal of Fluorine Chemistry

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“…Arylacetylenes were polymerized with Ziegler–Natta catalyst yielding often the cyclotrimer mixture and the polymer with low molecular mass. The polymer/cyclotrimers ratio are dependent on the catalyst, solvent, and the monomer structure 33–35…”

Section: Introductionmentioning

confidence: 99%

Synthesis of poly(p‐methoxyphenylacetylene) with the vanadium acetylacetonate‐aluminum triethyl Ziegler–Natta catalyst system: Cyclotrimers/polymer ratio analysis

Rodriguez

Lafuente

Martı́n-Villamil

2005

J. Polym. Sci. A Polym. Chem.

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Poly(p‐methoxyphenylacetylene) was obtained by the reaction of p‐methoxyphenylacetylene (MOPA) with the vanadium acetylacetonate‐aluminum triethyl V(acac)3‐AlEt3 homogeneous catalyst system. The crude product was always a mixture of 1,2,4‐ and 1,3,5‐tris(p‐methoxyphenyl)benzene and poly(MOPA) of low averaged molecular weight. The 1,2,4‐ and 1,3,5‐cyclotrimers versus poly(MOPA) ratio was analyzed. The poly(MOPA) obtained under different conditions, on the basis of the spectroscopic data, always shows a cis–transoidal stereo‐regular structure. Molecular mass of poly(MOPA) was determined by vapor pressure osmometry, high pressure liquid chromatography (HPLC), and gel permeation chromatography (GPC) techniques. The kinetics of the reaction has been also analyzed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5987–5997, 2005

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“…[2] Efforts towards this motif are plentiful and span aw ide range of general synthetics trategies. They are prepared from aldehydes by am ulti-step sequence involving trifluoromethylation and deoxygenation (Scheme 1a,i ), [3,4] and also from b,b-difluorostyrenes by hydrofluorination( Scheme 1a, ii). [5] Nucleophilic displacementonavariety of activated benzylic compounds is achieved with in situ-generated "CuCF 3 " [6,7] (Scheme 1a,i ii).…”

mentioning

confidence: 99%

“…Conducting the reactions olely in water failed, but when a1 :1 mixture of acetonitrile and water (by volume) was employed, product 1a was observed in 33 % yield (entries 2a nd 3; also, see Supporting Information for complete detailso nu nivariate screening of reaction conditions). Various other solvents such as THF,1 ,4-dioxane and MeOH all gave 1a,a lbeit in lower yield than acetonitrile (entries [4][5][6]. Substituting the water co-solvent with alcohols (such as MeOH, iPrOH) caused the reactions to fail, except for tert-amyl alcohol, which led to 1a in ad ecreased yield of 15 % (entry 7).…”

mentioning

confidence: 99%

Denitrogenative Hydrotrifluoromethylation of Benzaldehyde Hydrazones: Synthesis of (2,2,2‐Trifluoroethyl)arenes

Zhao

Kevin

Legault

et al. 2019

Chemistry A European J

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Reacting hydrazones of arylaldehydes with To gni's CF 3 -benziodoxolone reagent, in the presenceo f potassium hydroxide and cesium fluoride, induces ad enitrogenative hydrotrifluoromethylation eventt op roduce (2,2,2-trifluoroethyl)arenes. This novel reactionw as tolerant to many electronically-diverse functionalg roups and substitution patterns, as well as naphthyl-and heteroarylderivedsubstrates. Advantages of this processi nclude the easy access to hydrazone precursors on al arge scale, speed and operational simplicity,a nd being transition metal-free.Organofluorine compounds play criticalr oles in many areas of modernr esearch,f rom medicinal chemistry to agrochemistry, and from materials science to medical imaging, [1] so the continued development of new fluorination methodologies is critical. Amongt he myriad important organofluorine motifs, (2,2,2-trifluoroethyl)arenes( 1)h ave received considerable attention from the synthetic community,d ue to their favorable biological properties including their increased metabolic stability over alkyl groups. [2] Efforts towards this motif are plentiful and span aw ide range of general synthetics trategies. They are prepared from aldehydes by am ulti-step sequence involving trifluoromethylation and deoxygenation (Scheme 1a,i ), [3,4] and also from b,b-difluorostyrenes by hydrofluorination( Scheme 1a, ii). [5] Nucleophilic displacementonavariety of activated benzylic compounds is achieved with in situ-generated "CuCF 3 " [6,7] (Scheme 1a,i ii). Metal-mediated cross-coupling strategies [8] between arenes or heteroarenes and (2,2,2-trifluoroethyl)-based reagents have been achieved with Cu-, [9] Ni-, [10] Co-, [11] Zn-, [12] Ir-, [13] and Pd-based [14,15] catalysts( Scheme 1a,i v) and arylboronic acids have also been effectively coupled with 2,2,2trifluorodiazoethane (Scheme 1a,v ). [16] Over the past few decades, the use of hypervalenti odine(III) (HVI) reagents in organic chemistry has undergone tremendous growth,d ue to the advantageso fm ild reactionc onditions and broad reactivity,a nd of recyclable,e nvironmentallybenignb y-products. [17] The synthesis of (2,2,2-trifluoroethyl)arenes has recently been accomplished with mesityl( 2,2,2-trifluoroethyl)-iodoniums alts, by electrophilicc oupling with arenes( Scheme 1b,i ). [18] Togni's CF 3 -containing HVI reagent (2) [19] has also been used in the synthesis of 1,throughthe radical trifluoromethylation of benzylic CÀHb onds (Scheme 1b, ii). [20] We were interested in exploitingt he electrophilic nature of 2 [21] to develop at ransitionmetal-free synthesis of 1,b ye xposingi tt oas uitable benzylic nucleophile such as ah ydrazone. [22] Arylaldehyde-derivedh ydrazones readily undergo trifluoromethylation at the azomethine carbon, [23] but to the best of our knowledge,t his reactivity has not been coupled with a denitrogenation event. Given our interest in HVI-mediated gem-difunctionalization reactions of diazo compounds and hydrazones, [24] we aimed to interrupt aW olff-Kishner reduction by having an anionic intermediat...

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Generation and thermal polymerization of 1-fluoro-2-phenylacetylene

Cited by 31 publications

References 16 publications

Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

Synthesis of poly(p‐methoxyphenylacetylene) with the vanadium acetylacetonate‐aluminum triethyl Ziegler–Natta catalyst system: Cyclotrimers/polymer ratio analysis

Denitrogenative Hydrotrifluoromethylation of Benzaldehyde Hydrazones: Synthesis of (2,2,2‐Trifluoroethyl)arenes

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