- Highly Site-Selective Formation of Perfluoroalkylated Anilids via a Protecting Strategy by Molybdenum Hexacarbonyl Catalyst
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Introducing a perfluoroalkyl group on the aromatic ring with high site selectivity remains a challenging area in organofluorine chemistry. We herein report a highly para-selective C-H perfluoroalkylation of aniline substrates using the molybdenum hexacarbonyl catalyst. Various substituted anilids derived from anilids were well-tolerated, affording the corresponding products in moderate to good yields. Preliminary mechanism studies and density functional theory calculations revealed the coordination of Mo catalyst with amides as the key factor to realize para selectivity.
- Yuan, Chunchen,Dai, Ping,Bao, Xiaoguang,Zhao, Yingsheng
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supporting information
p. 6481 - 6484
(2019/08/20)
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- A fast response photo isomerous 4-Fluoalkyl azo-phenyl propylene ether and its preparation method
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The invention discloses rapid-response photoisomerization 4-perfluoroalkyl azobenzene allyl ether and a preparation method thereof. The general structural formula of 4-perfluoroalkyl azobenzene allyl ether is shown in the Specification. The preparation method includes the following steps: dissolving the starting compounds, 4-iodoaniline and fluorine-containing alkyl iodide, into a high boiling point solvent, and under the protection of nitrogen, heating, and catalyzing the solvent by copper powder to obtain fluoroalkyl aniline; after diazotizing fluoroalkyl aniline using hydrochloric acid/nitrite system at a temperature of 0-5 DEG C, enabling the diazotized solution to react with the phenol alkaline solution to obtain perfluoroalkyl azo phenol; under the protection of nitrogen, heating perfluoroalkyl azo phenol and 3-bromopropylene in an anhydrous and oxygen-free polar solvent under a weak base condition to obtain 4-fluoroalkyl azobenzene propenyl ether. The fluorine-containing azobenzene compound photoisomerization provided by the invention can response rapidly, has an active functional group propenyl, is capable of participating in addition reactions or polymerization reactions, and can be applied widely.
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Paragraph 0031; 0032; 0033
(2019/12/25)
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- Facile fabrication of multifunctional perfluoroalkyl functionalized graphene hydrogel via a synchronous reduction and grafting strategy
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Fluorine-containing groups represent very promising functionalities because fluorine not only changes the physico-chemical properties of the graphene surface, it may also alter its electronic and magnetic properties. Herein, we describe, for the first tim
- Li, Ting,Ding, Yunqiao,Liu, Libin,Liu, Jian,Fang, Wenyuan,Xiang, Yu,Li, Tianduo
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p. 21744 - 21753
(2015/11/10)
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- Benign Perfluoroalkylation of Aniline Derivatives through Photoredox Organocatalysis under Visible-Light Irradiation
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In this work, we present a room- or solar-light-initiated transition-metal-free radical homolytic aromatic substitution (HAS) reaction of aniline derivatives with perfluoroalkyl moieties employing perfluoroalkyl halides as readily available perfluoroalkyl
- Barata-Vallejo, Sebastián,Yerien, Damian E.,Postigo, Al
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supporting information
p. 7869 - 7875
(2015/12/24)
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- Synthesis and characterization of photoresponsive POSS-based polymers and their switchable water and oil wettability on cotton fabric
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Fast photoresponsive polymers containing polyhedral oligomeric silsesquioxane (POSS) and fluorinated azobenzene groups were successfully prepared via radical polymerization and characterized by NMR, FTIR, XRD, GPC, TGA, etc. The photoresponsive properties of the polymers were investigated through ultraviolet-visible absorption spectra. The trans-cis photoisomerization of the polymers in solution conformed to a first-order reaction kinetics equation. Superhydrophobicity and high oleophobicity of the cotton fabric coated with the polymer was observed when the POSS mole ratio was 3.0%. More importantly, the surface wettability of both water and oil on the coated fabrics could be intelligently controlled by applying UV irradiation in a short time.
- Huang, Jianbao,Huang, Yangen,He, Chuanglong,Gao, Yu
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p. 100339 - 100346
(2015/12/04)
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- Synthesis and catalytic activity of fluorous chiral primary amine-thioureas
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Three enantiopure fluorous thioureas featuring a free -NH2 group were synthesized by direct addition of aromatic isothiocyanates bearing a single n-C8F17 substituent in the ortho, meta and para position, respectively, to e
- Orlandi, Simonetta,Pozzi, Gianluca,Ghisetti, Mauro,Benaglia, Maurizio
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p. 4140 - 4147
(2013/12/04)
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- Design, synthesis, application and recovery of a minimally fluorous diaryl diselenide for the catalysis of stannane-mediated radical chain reactions
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The synthesis of a minimally fluorous (52% F) diaryl diselenide is described. On reduction in situ with tributylstannane this diselenide provides a fluorous selenol which is effective in inhibiting a range of stannane-mediated radical rearrangements, including a cyclopropylcarbinyl ring opening. A method for the recovery of the fluorous diselenide involving continuous extraction in a modified, cooled continuous extractor is described.
- Crich, David,Xiaolin, Hao,Lucas, Mathew
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p. 14261 - 14268
(2007/10/03)
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- Inhibition of stannane-mediated radical rearrangements by a recoverable, minimally fluorous selenol
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(equation presented) The preparation of a minimally fluorous diaryl diselenide is described. It is demonstrated that this diselenide, reduced in situ to the corresponding selenol, may be used in conjunction with stannanes to prevent a number of radical rearrangements. A 1 M solution of this selenol used in admixture with Breslow's water-soluble stannane can be used to significantly inhibit a cyclopropylcarbinyl ring opening. The combination of the fluorous selenol and the polar stannane permits recovery of the selenol by continuous fluorous extraction and isolation of a stannane-free hydrocarbon product.
- Crich, David,Hao, Xiaolin,Lucas, Mathew A.
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p. 269 - 271
(2008/02/13)
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- Syntheses of Azobenzene Derivatives Having Fluoroalkyl Chain and Their Monomolecular Film Formation at the Air/Water Interface
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The compounds, 4-(nonafluorobutyl)aniline, 4-(tridecafluorohexyl)aniline, and 4-(heptadecafluorooctyl)aniline were prepared by the reaction of corresponding perfluoroalkyl iodide with 4-iodoaniline in the presence of copper bronze.Six azobenzene derivatives (4-(4-fluorophenylazo)phenol, F(C6H4)N=N(C6H4)OH (1) (C6H4=p-phenylene), 4-(trifluoromethylphenylazo)phenol, CF3(C6H4)N=N(C6H4)OH (2), 4-(4-heptafluoropropylphenylazo)phenol, C3F7(C6H4)N=N(C6H4)OH (3), 4-(4-nonafluorobutylphenylazo)phenol, C4F9(C6H4)N=N(C6H4)OH (4), 4-(4-tridecafluorohexylphenylazo)phenol, C6F13(C6H4)N=N(C6H4)OH (5), and 4-(4-heptadecafluorooctylphenylazo)phenol, C8F17(C6H4)N=N(C6H4)OH (6)) were prepared by the usual diazo coupling reactions using 4-(perfluoroalkyl)aniline and phenol.The monomolecular film formations of the azobenzene derivatives at the air/water interface were investigated by surface pressure measurements to be dependent on the fluoroalkyl chain length (n).The compounds 5 (n=6) and 6 (n=8) formed stable monomolecular films at the air/water interface.
- Yoshino, Norio,Kitamura, Mitsuharu,Seto, Tsuyoshi,Shibata, Yasuhiro,Abe, Masahiko,Ogino, Keizo
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p. 2141 - 2144
(2007/10/02)
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- Reactions of Trifluoromethyl Bromide and Related Halides: Part 10. Perfluoroalkylation of Aromatic Compounds induced by Sulphur Dioxide Radical Anion Precursors
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Perfluoroalkylation of electron-rich aromatic compounds with trifluoromethyl bromide, or long-chain perfluoroalkyl iodides, was performed in the presence of sodium dithionite or zinc-sulphur dioxide.This alkylation occurred at the ortho and para positions relative to the amino or hydroxy substitutent.Pyrroles were perfluoroalkylated regioselectively at the 2-position.This alkylation was interpreted as a radical aromatic substitution; the formation of the perfluoroalkyl radical can be induced by a single-electron transfer from sulphur dioxide radical anion to the perfluoroalkyl halide.
- Tordeux, Marc,Langlois, Bernard,Wakselman, Claude
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p. 2293 - 2299
(2007/10/02)
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- LANGMUIR-BLODGETT FILMS OF POLYALLYLAMINE MODIFIED WITH (PERFLUOROALKYL)PHENYL GROUPS
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(Perfluoroalkyl)phenyl groups were introduced to polyallylamine by thiourea bonds.Langmuir-Blodgett (LB) films of the polymers were successfully prepared.Characterization of the films indicated that structural isomerism of substituted benzene has an effect upon the molecular ordering in the LB film and that the limiting area and critical surface tension of the LB films become smaller in the order, ortho, meta, and para isomers.
- Tamura, Masanori,Sekiya, Akira
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p. 231 - 234
(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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