80233-96-1Relevant articles and documents
SOME APPROACHES TO THE SYNTHESIS OF FLUORINATED ALCOHOLS AND ESTERS. II. USE OF F-ALKYL IODIDES FOR THE SYNTHESIS OF F-ALKYL ALKANOLS
Brace, Neal O.
, p. 313 - 328 (1982)
Free radical addition of an F-alkyl iodide (RFI) to an alkenol or ester, followed by appropriate reduction is an efficient method for preparating the corresponding F-alkyl-alkanols of the homologous series, RF(CH2)nOH.When n=2, 4 or higher, the two steps take place smoothly.The 1,2,3-substituted systems RFCH2CHYCH2Z, however, are susceptible to surprising difficulties.Reduction of RFCH2CHICH2OH to RF(CH2)3OH by hydrogen and catalyst (strong base acid acceptor), can be done either in one step or via RFCH=CHCH2OH; however, dehydrohalogenation may also give the epoxide, and reduction in this case leads to the secondary alcohol, RFCH2CH(CH3)OH.By contrast, reduction of RFCH2CHICH2OAc by tributyltin hydride or with hydrogen over palladium (diethylamine acid acceptor) goes smoothly.Zinc and acid reduction of RFCH2CHICH2OAc gives elimination to RFCH2CH=CH2; even RFCH=CICH2OH gives RFCH=C=CH2 besides RFCH=CHCH2OH.RFCH=CICH2CH2OH, however, with zinc and acid is reduced cleanly to RFCH=CHCH2CH2OH.
Preparation of novel side-chain fluoroalkyl polyether oligomers with terminal acrylate for emulsion copolymerization and application on cotton fabric finishing
Zong, Yakun,Wang, Lei,Sun, Yi,Li, Zhanxiong
, p. 2563 - 2574 (2019)
Three novel side-chain fluoroalkyl polyether oligomers with different molecular weight were synthesized base on the ring-opening polymerization of 3-perfluoro-n-butyl-1,2-epoxypropane, followed by terminal esterification using acryloyl chloride. The oligomer intermediates were used as functional monomers for emulsion copolymerization with methyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate. The produced latexes were used for hydrophobic and oil-phobic finishing on cotton fabric surface and the treated cotton fabrics were tested by scanning electron microscopy and energy-dispersive spectroscopy, combined with chemical composition analysis by X-ray photoelectron spectroscopy. The result showed that fluorinated copolymers were successfully coated on the cotton fibers’ surface. Water contact angles was used to evaluate the wettability and the results showed that treated cotton fabrics possessed good hydrophobicity with the contact angle of 139.1 ± 1°, and the heat resistance of treated cotton fabrics was identified improved through the thermogravimetric analyses (TGA).
Light-induced iodoperfluoroalkylation reactions of carbon-carbon multiple bonds in water
Slodowicz,Barata-Vallejo,Vázquez,Nudelman, N. Sbarbati,Postigo
, p. 137 - 143 (2012)
In this work we have undertaken the radical-induced addition of 1-iodo-n-perfluorobutane onto electron-rich alkenes, alkenes with electron withdrawing groups, and alkynes in water, initiated photochemically. The lack of hydrogen donor (i.e.: (Me3Si)3SiH) in our reaction medium facilitates a Halogen Atom-transfer reaction (HAT), affording the respective perfluorobutylated alkyl and alkenyl halides (iodides) in good yields in water. We have also found that water exerts a relevant solvent effect on the rates of perfluoroalkyl radical additions onto double and triple bonds. The stereoselectivity of the radical addition reaction of alkynes is studied. The novelty of this work relies on the photochemical generation of fluorinated radicals in water, and the Halogen Atom-transfer addition reactions of iodoperfluoroalkanes onto carbon-carbon unsaturated bonds in water induced by light.
End-Blocked Silanization of Side-Chain Fluoroalkyl Oligoether and its Surface Properties
Wang, Lei,Chen, Lei,Li, Zhanxiong
, p. 855 - 862 (2018/10/31)
In this study, three novel side-chain fluoroalkyl oligoethers with different molecular weights were synthesised via a ring-opening reaction of 2,2,3,3,4,4,5,5,5-nonafluoropentyloxirane. The fluorooligoethers were then silanized and characterised by FT-IR,1H, and 19F NMR spectroscopies. These silanlized fluorooligoethers were used to fabricate hydrophobic coatings on silicon substrates, which were pre-treated with O2 plasma, by the method of liquid phase deposition. The chemical compositions and structures of the film surfaces were analysed by X-ray photoelectron spectroscopy and the results showed that silanized fluorooligoethers formed self-assembled films on the silicon wafer. The surface wettability of the coatings was measured by water contact angles. It is noted that the annealing process can improve the hydrophobicity with the highest water contact angle being 115.2 ± 1° and hexadecane contact angle being 67.2 ± 1°. The surface morphologies and roughness of the self-assembled films were measured by atomic force microscopy (AFM), as a result, the surface was found to be rougher with the increment of the molecular weight of the fluorooligoethers.
Benzophenone vs. Copper/Benzophenone in Light-Promoted Atom Transfer Radical Additions (ATRAs): Highly Effective Iodoperfluoroalkylation of Alkenes/Alkynes and Mechanistic Studies
Beniazza, Redouane,Atkinson, Rachel,Absalon, Christelle,Castet, Frédéric,Denisov, Sergey A.,McClenaghan, Nathan D.,Lastécouères, Dominique,Vincent, Jean-Marc
, p. 2949 - 2961 (2016/09/16)
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.).
Liquid crystalline and charge transport properties of novel non-peripherally octasubstituted perfluoroalkylated phthalocyanines
Sosa-Vargas, Lydia,Nekelson, Fabien,Okuda, Daiju,Takahashi, Minokazu,Matsuda, Yukimasa,Dao, Quang-Duy,Hiroyuki, Yoshida,Fujii, Akihiko,Ozaki, Masanori,Shimizu, Yo
, p. 1757 - 1765 (2015/10/20)
Two new perfluoroalkylated phthalocyanine derivatives were synthesised and characterised in order to investigate the effects of the fluorophobic/fluorophilic interactions on their mesophase and electronic properties. Both compounds exhibit columnar mesomo
Syntheses of fluorous propenes from 3-perfluoroalkyl-2-iodo-1-propanols
Szíjjártó, Csongor,Ivanko, Peter,Takács, Ferenc T.,Szabó, Dénes,Rábai, József
, p. 386 - 389 (2008/12/21)
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.
3-(Perfluoroalkyl)propanols: Valuable building blocks for fluorous chemistry
Rabai, Jozsef,Szijjarto, Csongor,Ivanko, Peter,Szabo, Denes
, p. 2581 - 2584 (2008/03/13)
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.
Fluorous dimethylthiocarbamate (FDMTC) protecting groups for alcohols
Kojima, Masaru,Nakamura, Yutaka,Ishikawa, Takuma,Takeuchi, Seiji
, p. 6309 - 6314 (2007/10/03)
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.
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
Laurent, Philippe,Blancou, Hubert,Commeyras, Auguste
, p. 125 - 128 (2007/10/02)
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.
