- Heterogeneous photoinduced homolytic aromatic substitution of electron-rich arenes with perfluoroalkyl groups in water and aqueous media - A radical-ion reaction
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The photoinduced electron transfer (PET) substitution reaction of electron-rich aromatic nuclei with perfluoroalkyl Rf groups was carried out in water or aqueous mixtures to render substitution products resulting from replacement of aromatic H atoms with the Rf moiety in good yields (57-88 %). Some mechanistic aspects are discussed, supporting the notion of a PET reaction leading to a classical radical homolytic aromatic substitution (HAS) followed by an electron transfer (ET) and then a proton transfer (PT) sequence. A radical mechanism superimposed on a redox process is proposed to account for product formation. Evidence for the radical cation species (as an initiation event) generated from electron-rich arenes in the presence of perfluoroalkyl halides is provided by the UV/Vis transient spectra obtained by Nanosecond Laser Flash Photolysis techniques. Copyright
- Barata-Vallejo, Sebastian,Flesia, Marina Martin,Lantano, Beatriz,Argueello, Juan E.,Penenory, Alicia B.,Postigo, Al
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p. 998 - 1008
(2013/03/14)
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- Nickel(0)-catalyzed fluoroalkylation of alkenes, alkynes, and aromatics with perfluoroalkyl chlorides
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Treatment of perfluoroalkyl chlorides (RFCl) with alkenes, alkynes, or aromatics in the presence of 0.1 equiv of nickel dichloride, 1.5 equiv of zinc powder, and 0.4 equiv of triphenylphosphine in DMF at 95-100 °C for 6-8 h give the correspondi
- Huang,Chen
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p. 4651 - 4656
(2007/10/03)
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- Complexation and Photoinduced Electron-transfer Reaction between Perfluoroalkyl Iodides and N,N,N',N'-Tetramethylphenylene-1,4-diamine, Anilines and Piperazines
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Treatment of tetrafluoro-1,2-diiodoethane 1a or dodecafluoro-1,6-diiodohexane 1b with N,N,N',N'-tetramethylphenylene-1,4-diamine 2 gave 1 + 1 solid complexes 3a or 3b in high yields.Complex 3a decomposed to give tetrafluoroethylene, iodine and 2 when irradiated with UV or heated.Complex 3b was converted into 6H-dodecafluorohexyl-N,N,N',N'-tetramethylphenylene-1,4-diamine 4 when irradiated with UV.On treatment of 1a and 1b with piperazine 6a and N,N'-dimethylpiperazine 6b, 1 + 1 solid complexes 7 were similarly obtained.However, heating or irradiating 7 gave no perfluoroalkylated products.Irradiating a mixture of 2 or anilines 13 and perfluoroalkyl iodides 10 in dimethylformamide also gave perfluoroalkylated products.The photoinduced electron transfer reaction involved radical cation 2*+ as a reactive intermediate which was detected by EPR techniques.
- Chen, Qing-Yun,Li, Zhan-Ting,Zhou, Cheng-Min
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p. 2457 - 2462
(2007/10/02)
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- DIRECT PERFLUOROALKYLATION OF FUNCTIONALIZED BENZENES WITH PERFLUOROALKYL HALIDES AND COPPER BRONZE
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Perfluoroalkyl halides were found to react with functionalized benzenes in the presence of copper bronze to give the corresponding perfluoroalkylated products directly in moderate to good yields.The reaction may involve' active species' other than perfluoroalkylcopper species.Synthetic utility and possible mechanisms of the present one-step reaction are discussed.
- Fuchikami, Takamasa,Ojima, Iwao
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p. 541 - 556
(2007/10/02)
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- PERFLUOROALKYLATION OF AROMATIC COMPOUNDS WITH RfI(Ph)OSO2CF3
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Perfluoroalkylation of various aromatic compounds with perfluoroalkylphenyliodonium trifluoromethanesulfonate (FITS) under mild conditions was described.The reactivity of other perfluoroalkyliodonium salts was also examined.
- Umemoto, Teruo,Kuriu, Yuriko,Shuyama, Hideo
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p. 1663 - 1666
(2007/10/02)
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