- Synthesis and characterization of a new class of polyfluorinated alkanes: Tetrakis(perfluoroalkyl)alkane
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The synthesis and physico-chemical characterization of 1,1,2,2-tetrakis(perfluoroalkyl-methylene)ethane {[F(CF2)nCH2]2CH}2 (n=6, TK6;n=8, TK8 ) are reported. The synthesis consists of four steps: (1) addition of allyl alcohol to a perfluoroalkyl iodide, F(CF2)nI(n=6,8) to give the corresponding iodo-adduct; (2) dehalogenation of the adduct by treatment with zinc in aqueous acetic acid, yielding 3-perfluoro-n-alkyl-1-propene; (3) addition of 3-perfluoro-n-alkyl-l-propene to perfluoroalkyl iodide, F(CF2)nI (n=6,8) to give 1,3-perfluoro-n-alkyl-2-iodo-propane; (4) coupling of 1,3-perfluoro-n-alkyl-2-iodo-propane by zinc in acetic anhydride giving the final products. TK6 and TK8 are characterized by very low surface tension values and exhibit very good properties as potential ski-waxes.
- Gambaretto,Conte,Fornasieri,Zarantonello,Tonei,Sassi,Bertani, Roberta
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- Addition of RFI (CnF2n+1I; n = 4, 6, 8) to allyl alcohol catalyzed by zinc in different solvents: application to the synthesis of F-alkyl epoxypropanes
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The addition of RFI to allyl alcohol catalyzed by zinc in different solvents has been studied.The adduct RFCH2CHICH2OH readily gives the corresponding F-alkyl epoxypropane.
- Laurent, Philippe,Blancou, Hubert,Commeyras, Auguste
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- Regioselective ring opening of [(perfluoroalkyl)methyl] oxiranes with N-nucleophiles
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The reactions of C8F17CH2CHCH2O with some primary and secondary aliphatic amines affording selective ring opening at Cβ are reported. The reactions with secondary amines HNR1R2 (R1 = R2 = Et; R1 = But, R2 = CH2CH2O(CO)C(CH 3)CH2; R1 = Et, R2 = CH 2CH2OH; R1 = R2 = CH 2CH2OH) gave the corresponding C8F 17CH2CH(OH)CH2NR1R2 derivatives. For R1 = Et, R2 = CH2CH 2OH; R1 = R2 = CH2CH2OH, the reactions proceed through the selective nucleophilic attack of the NH moiety with no evidence of reactivity of the OH group. The reactions with the primary amines, allylamine and n-hexamethylenediamine, gave different products depending on reaction conditions.
- Conte,Maniero,Zaggia,Bertani,Gambaretto,Berton,Seraglia
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- The Different Faces of Photoredox Catalysts: Visible-Light-Mediated Atom Transfer Radical Addition (ATRA) Reactions of Perfluoroalkyl Iodides with Styrenes and Phenylacetylenes
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A photoredox-catalyzed procedure for the iodoperfluoroalkylation of styrenes and phenylacetylenes using readily available copper phenanthroline catalyst is reported. In contrast to commonly employed [Ru(bpy)3]Cl2, [Ru(phen)3/su
- Rawner, Thomas,Lutsker, Eugen,Kaiser, Christian A.,Reiser, Oliver
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p. 3950 - 3956
(2018/05/22)
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- Benzophenone vs. Copper/Benzophenone in Light-Promoted Atom Transfer Radical Additions (ATRAs): Highly Effective Iodoperfluoroalkylation of Alkenes/Alkynes and Mechanistic Studies
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Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo-promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1. In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low-pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (3BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular.CH2OH, play a key role in the initiation step forming Rf.by reacting with RfI, Rf.then entering a radical chain cycle.1H NMR studies provided evidence that a substantial amount (~7% NMR yield) of the hemiacetal CH3OCH2OH is formed, i.e., the possible by-product of the reaction between.CH2OH and RfI. Finally, DFT calculations indicate that a triplet-triplet energy transfer (TTET) process from3BP* to perfluorooctyl iodide (C8F17I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies. (Figure presented.).
- Beniazza, Redouane,Atkinson, Rachel,Absalon, Christelle,Castet, Frédéric,Denisov, Sergey A.,McClenaghan, Nathan D.,Lastécouères, Dominique,Vincent, Jean-Marc
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p. 2949 - 2961
(2016/09/16)
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- Self-assembled monolayers on gold generated from terminally perfluorinated alkanethiols bearing propyl vs. ethyl hydrocarbon spacers
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This paper examines the structural and interfacial properties of terminally perfluorinated self-assembled monolayers (FSAMs) on gold generated from the adsorption of a new series of terminally perfluorinated propanethiols F(CF2)n(CH2)3SH, where n = 8, 10, and 12. Analysis of these FSAMs by ellipsometry and X-ray photoelectron spectroscopy (XPS) confirmed the formation of the monolayer films. The contact angles of water and n-hexadecane on these FSAMs indicated a high degree of hydrophobicity and oleophobicity. Polarization modulation infrared reflection-adsorption spectroscopy (PM-IRRAS) analysis of the films revealed that the fluorinated chains are oriented largely perpendicular to the gold surface. In addition, the FSAMs formed from the new adsorbates were compared to known FSAMs derived from F(CF2)n(CH2)2SH, where n = 8, 10, and 12, to examine the influence of the number of CH2 groups in the short alkyl spacer upon the conformational order and packing structure of the films. Analysis of the XPS spectra for the normalized peak intensity of the F 1s and S 2p binding energies for both types of films suggest a slight increase in packing density for the chains having the propyl vs. the ethyl hydrocarbon spacer. This conclusion is consistent with the observed decrease in the wetting behavior of hexadecane on the FSAMs formed from the new adsorbates. However, the preponderance of the data indicates that these two series of partially fluorinated alkanethiols form films with highly similar structure/packing characteristics with no discernible "odd-even" effect between the two series.
- Zenasni, Oussama,Jamison, Andrew C.,Marquez, Maria D.,Lee, T. Randall
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p. 128 - 136
(2015/03/05)
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- Mesophase structure of low-wetting liquid crystalline polyacrylates with new perfluoroalkyl benzoate side groups
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The synthesis, thermal behavior, bulk microstructure, and wettability of new polyacrylates carrying spaced 4-perfluorohexylpropyl benzoate and 4-perfluorooctylpropyl benzoate units in the side groups were Investigated. X-ray diffraction analysis proved the formation of different smectic mesophases (SmI2, SmF2, and SmC2) and the evolution of their structures and lattice parameters with temperature. The mesophase polymorphic behavior depended on the length of the perfluorinated chain segment in the repeat unit. The electron density profiles along the smectic layer normal were drawn and provided a deeper insight into the packing of the side chains in a tilted, double layer structure. Thin polymer films were cast from solution, and their low wettability was established by measurements of contact angles with different probing liquids. We suggest that the hydrophobicity and lipophobicity of the films are enhanced by the mesophase surface structure which is mediated by the high-order, mesophase bulk structure.
- Martinelli, Elisa,Paoli, Francesca,Gallot, Bernard,Galli, Giancarlo
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experimental part
p. 4128 - 4139
(2011/10/30)
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- Br?nsted acidic imidazolium salts containing perfluoroalkyl tails catalyzed one-pot synthesis of 1,8-dioxo-decahydroacridines in water
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One-pot three-component synthesis of 1,8-dioxo-9,10-diaryl-decahydroacridines in water was efficiently realized in the presence of the Br?nsted acidic imidazolium salts containing perfluoroalkyl tails in good yields. The method provided several advantages such as low catalyst loading; recycle of the catalyst and simple work procedure.
- Shen, Wei,Wang, Li-Min,Tian, He,Tang, Jun,Yu, Jian-jun
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body text
p. 522 - 527
(2009/11/30)
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- Syntheses of fluorous propenes from 3-perfluoroalkyl-2-iodo-1-propanols
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3-(Perfluoroalkyl)-1-propenes are obtained in excellent yields up to 100-g quantities by deiodination-dehydroxylation reactions of the easily accessible 2-iodo-3-(perfluoroalkyl)-propanols with red phosphorus and catalytic amounts of iodine or with an SnCl2/POCl3 reagent pair in pyridine (fluorous Cornforth reaction). Both methods afford fluorous propenes in high GC purity, the former one has high atom-economy and proceeds safely if the fluorous iodohydrin precursors are added in increments; for the solid ones using a 'hot-melt' dropping funnel. The title fluorous propenes are effectively isolated by co-distillation with pyridine.
- Szíjjártó, Csongor,Ivanko, Peter,Takács, Ferenc T.,Szabó, Dénes,Rábai, József
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p. 386 - 389
(2008/12/21)
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- 3-(Perfluoroalkyl)propanols: Valuable building blocks for fluorous chemistry
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2-Iodo-3-(perfluoroalkyl)propanols are obtained in excellent yields and several-hundred-gram quantities by the controlled radical addition of commercially available n-perfluoroalkyl and perfluoroisoalkyl iodides to allyl alcohol. Their consecutive reduction with hydrazine hydrate and Raney nickel catalyst in methanol afforded the corresponding 3-(perfluoroalkyl)propanols in high yields and purity. Georg Thieme Verlag Stuttgart.
- Rabai, Jozsef,Szijjarto, Csongor,Ivanko, Peter,Szabo, Denes
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p. 2581 - 2584
(2008/03/13)
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- Fluorous dimethylthiocarbamate (FDMTC) protecting groups for alcohols
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N,N-Bis(perfluoroalkyl)thiocarbamoyl chlorides (FDMTC-Cls) were synthesized as reagent for the protection of alcohols. Using the crystalline FDMTC-Cls, the FDMTC groups were introduced into the alcohol molecules in excellent yields in the presence of sodium hydride in THF at room temperature. The products were separated from the excess alcohols by solid-phase extraction with a fluorous reverse-phase silica gel column (Fluorous Solid Phase Extraction; FSPE). The FDMTC groups were readily removed by oxidation with m-chloroperbenzoic acid (m-CPBA) and subsequent hydrolysis with KHCO3.
- Kojima, Masaru,Nakamura, Yutaka,Ishikawa, Takuma,Takeuchi, Seiji
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p. 6309 - 6314
(2007/10/03)
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- Synthesis and surface antimicrobial activity of a novel perfluorooctylated quaternary ammonium silane coupling agent
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A novel perfluorooctyl-containing quaternary ammonium salt was designed and synthesized, which was applied as a surface modification agent to provide the treated cotton fabrics with antimicrobial activity and low critical surface energy.
- Shao, Hui,Meng, Wei-Dong,Qing, Feng-Ling
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p. 721 - 724
(2007/10/03)
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- Synthesis and antimicrobial activity of a perfluoroalkyl-containing quaternary ammonium salt
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A novel perfluoroalkyl-containing quaternary ammonium salt 5 was designed and synthesized. Consequently, the antimicrobial activities of compound 5 were measured with Escherichia coli 8099 as a Gram-negative strain and Staphylococcus aureus ATCC 6538 as a
- Shao, Hui,Jiang, Li,Meng, Wei-Dong,Qing, Feng-Ling
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- Fluorous biphasic catalysis. 2. Synthesis of fluoroponytailed amine ligands along with fluoroponytailed carboxylate synthons, [M(C8F17(CH2)2CO2) 2] (M = Mn2+ or Co2+)
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Fluorous biphasic catalysis (FBC) is a relatively new concept for homogeneous catalysis where the fluorocarbon soluble catalyst resides in a separate phase from the substrate and products. Therefore, separation of the catalyst and the products occurs by a
- Vincent,Rabion,Yachandra,Fish
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p. 888 - 895
(2007/10/03)
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- Syntheses with perfluoroalkyl radicals from perfluoroalkyl iodides. A rapid survey of synthetic possibilities with emphasis on practical applications. Part one: Alkenes, alkynes and allylic compounds
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This review concerns the free radical chemistry of perfluoroalkyl iodides (RFI) in the synthesis of organic substances of a large variety of structures. Radical chain reactions of RFI are readily initiated by azonitrile initiators an
- Brace, Neal O.
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- Fluorous Biphasic Catalysis: Complexation of 1,4,7-3-1,4,7-Triazacyclononane with (M = Mn, Co) To Provide Perfluoroheptane-Soluble Catalysts for Alkane and Alkene Functionalization in the Presence of t-BuOOH and O2
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Keywords: biphasic catalysis; cobalt; fluorohydrocarbons; manganese; oxidations
- Vincent, Jean-Marc,Rabion, Alain,Yachandra, Vittal K.,Fish, Richard H.
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p. 2346 - 2349
(2007/10/03)
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- Electron transfer initiated free radical additions of perfluoroalkyl iodides and diiodides to alkenes
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Perfluoroalkyl iodides were added in very good yields to 1,2-dialkyl substituted double bonds of e.g. petroselinic acid initiated by lead/copper(II) acetate in methanol and by copper without solvent, respectively. Using the new initiator system lead/copper(II) acetate, we also obtained good yields in the additions of perfluoroalkyl iodides to allyl alcohol and co-unsaturated alcohols and of perfluoroalkyl 1,ω-diiodides to methyl 10-undecenoate. VCH Verlagsgesellschaft mbH, 1996.
- Metzger, Juergen O.,Mahler, Ralf,Schmidt, Andreas
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p. 693 - 696
(2007/10/03)
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- Transition-Metal Complex Catalyzed Polyfluoroalkylation. A Facile Synthesis of Fluorine-Containing Oxiranes and Enynes
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Palladium-catalyzed reaction of polyfluoroalkyl halides with allylic alcohols in the presence of potassium carbonate gives polyfluoroalkylmethyl-substituted oxiranes directly.Perfluoroalkyl-substituted enynes can be also prepared from perfluoroalkyl iodides and terminal alkynes under similar conditions.
- Fuchikami, Takamasa,Shibata, Yoshiko,Urata, Hisao
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p. 521 - 524
(2007/10/02)
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