- Novel fluorinated amphiphilic cyclodextrin derivatives: Synthesis of mono-, di- and heptakis-(6-deoxy-6-perfluoroalkylthio)-β-cyclodextrins
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A new series of fluorinated amphiphilic β-cyclodextrin derivatives has been synthesized. The strategy is based on the modification of the C-6 position of the mono-6-deoxy-6A-para-tolylsulfonyl, di-6A, 6D-deoxy-6A, 6D-(para-tolylsulfonyl) and heptakis-(6-deoxy-6-iodo)-β-cyclodextrin precursors. The synthesis lead to mono-perfluoroalkylthio-, di-perfluoroalkylthio- and heptakis-perfluoroalkylthio-β-cyclodextrin in excellent yields (90-99%).
- Peroche, Sandrine,Parrot-Lopez, Hélène
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- Synthesis and surface properties of a series of surfactants based on O-alkyl and O-perfluoro-N,N′-diisopropylisoureas
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O-Dodecyl-N,N′-diisopropylisourea and O-tridecafluorooctyl-N, N′-diisopropylisourea were synthesized by reaction of hydrogenated or fluorinated alcohols onto diisopropylcarbodiimide in quasi-quantitative yields. Adding various hydrogen halides (HCl, HBr, or HI) onto these isoureas enabled one to obtain isoureas hydrohalides with tensioactive properties. The surface properties of both series of hydrogenated and fluorinated surfactants were studied and compared. The influence of the counter-ions onto the surface properties showed that the tensioactive properties were improved in the following increasing order: I Cl Br. Fluorinated isourea hydrohalides exhibited better surfactant properties than their hydrogenated homologues.
- Badache, Leila,Boschet, Frédéric,Lehanine, Zineb,Boutevin, Bernard,Ameduri, Bruno
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- Synthesis of perfluoroalkyl-containing multifunctional groups compounds for textile finishing
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A new kind of perfluoroalkyl-containing multifunctional groups compound was designed. Treatment of 1H.1H.2H.2H-perfluorooctyltri- chlorosilane (4) with allylmagnesium bromide provided key intermediate 1H,1H,2H,2H-perfluorooctyltriallylsilane (2). Hydroboration followed by oxidation, epoxidation and dihydroxylation of 2 gave perfluoroalkyl-containing multifunctional groups compound 1a, 1b and 1c, respectively.
- Qing, Feng-Ling,Ji, Min,Lu, Ronghua,Yan, Kelu,Mao, Zhiping
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- Copper-Catalyzed Difluoromethylation of Alkyl Iodides Enabled by Aryl Radical Activation of Carbon–Iodine Bonds
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The engagement of unactivated alkyl halides in copper-catalyzed cross-coupling reactions has been historically challenging, due to their low reduction potential and the slow oxidative addition of copper(I) catalysts. In this work, we report a novel strategy that leverages the halogen abstraction ability of aryl radicals, thereby engaging a diverse range of alkyl iodides in copper-catalyzed Negishi-type cross-coupling reactions at room temperature. Specifically, aryl radicals generated via copper catalysis efficiently initiate the cleavage of the carbon–iodide bonds of alkyl iodides. The alkyl radicals thus generated enter the copper catalytic cycles to couple with a difluoromethyl zinc reagent, thus furnishing the alkyl difluoromethane products. This unprecedented Negishi-type difluoromethylation approach has been applied to the late-stage modification of densely functionalized pharmaceutical agents and natural products.
- Cai, Aijie,Liu, Wei,Wang, Chao,Yan, Wenhao
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supporting information
p. 27070 - 27077
(2021/11/18)
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- Environmentally friendly preparation method of fluorine-containing acrylate
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The invention relates to the technical field of preparation of new fluorine-containing materials, particularly to an environmentally friendly preparation method of fluorine-containing acrylate. The environmentally friendly preparation method comprises: carrying out a reaction on short-chain perfluoroiodoalkane and ethylene, separating, and purifying to obtain perfluoroalkylethyl iodide; carrying out hydrolysis on the perfluoroalkylethyl iodide, separating, and purifying to obtain perfluoroalkylethanol; and carrying out a reaction on the perfluoroalkylethanol and acrylic acid, separating, and purifying to obtain the product. According to the present invention, the perfluorooctyl-free product is synthesized, the potential risk of PFOA production cannot exist, and the obtained product is theenvironmentally friendly product, and meets the national industrial policy; the preparation method is simple, and is suitable for industrial production; and the reaction conversion rate is high, and the purity of the intermediate product is high, such that the subsequent reaction is easily performed, the yield is easily increased, and the cost is reduced.
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Paragraph 0023; 0026
(2019/01/06)
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- Fluorinated pyridinium and ammonium cationic surfactants
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New classes of partially fluorinated cationic surfactants, including pyridinium sulfonates and ammonium hydrochlorides have been prepared in which a fluoroalkyl chain is interrupted either by ether oxygen (-O-), or by methylene (-CH2-) units. These surfactants are obtained from multi-step syntheses via intermediate fluoroalkyl ethylene iodides (RfO(CF2CF2)nCH2CH2I, Rf = C3F7, C2F5, n = 1-3 or Rf(CH2CF2)m(CH2CH2)n, Rf = C4F9, C6F13m = 0-2, n = 1-2) or fluoroalkyl iodides (RfI, Rf = C3F7O(CF2CF2)3I, C6F13). The surface activities of these fluorinated cationic surfactants were examined and compared to commercially available fluorinated cationic surfactants used as additives in oil field applications. Some examples demonstrated good performance relative to controls yet are more fluorine efficient because they have lower fluorine content than their perfluoroalkyl analogues. For the ammonium hydrochlorides, the effect of different spacer groups between the cation and the fluorinated chain including ethylene, butylene and isopropylidene on surface activity was also examined.
- Yake, Allison,Corder, Tanya,Moloy, Kenneth,Coope, Tim,Taylor, Charles,Hung, Ming,Peng, Sheng
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- Crosslinking of fluoroelastomers by "click" azide-nitrile cycloaddition
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A fluoroelastomer that bears pendant nitrile groups is crosslinked with a telechelic bis-azido fluorinated curing agent by "click" azide-nitrile cycloaddition. Thermogravimetric analyses of the resulting press cured films reveal an improvement by 20 C of the thermal degradation profile under air, compared to that of the corresponding uncured fluoroelastomer.
- Tillet, Guillaume,Lopez, Gérald,Hung, Ming-Hong,Améduri, Bruno
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p. 1171 - 1173
(2015/04/14)
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- PROCESS FOR PRODUCING FLUORINATED ACRYLIC ESTER
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A mixture of fluorine-containing acrylic esters represented by CF3(CF2)nCH2CH2OCOCR1=CH2 wherein R1 is a hydrogen atom, a methyl group or a halogen atom and "n" is an integer of at least zero is subjected to distillation under such conditions that the esters are not polymerized, so as to give a mixture of the esters with a less content of impurities (that is, olefins represented by CF3(CF2)nCH=CH2 and alcohols represented by CF3(CF2)nCH2CH2OH) at a high yield.
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Page/Page column 6-7
(2008/06/13)
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- Purification of fluorinated alcohols
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A process for reducing the level of perfluoroalkanoic acids, perfluoroalkanoic esters, and perfluoroalkyliodides in fluorinated alcohols comprising heating a fluorinated alcohol, or mixtures thereof, containing said acids, esters, or iodides to a temperature of at least 175° C. in the presence of water and a base additive is disclosed.
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Page/Page column 4
(2008/06/13)
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- Synthesis of telechelic dienes from fluorinated α,ω-diiodoalkanes. Part I. Divinyl and diallyl derivatives from model I(C2F4)nI compounds
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The synthesis of five fluorinated non-conjugated dienes from commercially available α,ω-diiodoperfluoroalkanes is described.Preparation of the fluorinated divinyl derivatives H2C=CH(CF2)nCH=CH2 (n = 2, 4, 6) (2,2, 2,4 and 2,6) was effected by ethylenation of these diiodinated compounds in various ways followed by dehydroiodination in ethanolic potassium hydroxide.Allyl diolefines, H2C=CHCH2(CF2)nCH2CH=CH2 (4,4 and 4,6) were produced by the α,ω-bis-telomerization of allyl acetate followed by deiodoacetoxylation in the presence of zinc.The diacetate precursors 3,4 and 3,6 of the respective diallyls 4,4 and 4,6 were obtained rather than diacetate 3,2 because of the eventual decomposition of α,ω-diiodoperfluoroethane by β-scission.These five fluorinated non-conjugated dienes have been characterized by 1H, 13C and 19F NMR spectroscopy. - Keywords:Telechelic dienes; Fluorinated vinyl dienes; Fluorinated allyl dienes; α,ω-Diiodoperfluoroalkanes; NMR spectroscopy
- Manseri, A.,Ameduri, B.,Boutevin, B.,Kotora, M.,Hajek, M.,Caporiccio, G.
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p. 151 - 158
(2007/10/02)
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- Free-radical addition of 2-(perfluoroalkyl)ethanethiols to alkenes, alkadienes, cycloalkenes, alkynes and vinyl monomers
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The free-radical addition of 2-(perfluoroalkyl)ethanethiols (RFCH2CH2SH) to alkenes, cycloalkenes, alkadienes and alkynes has been studied to determine: (1) the mode of reaction, i.e. the stereochemistry, regiochemistry and any skeletal changes: (2) the relative reactivity towards unsaturates of differing structures and classes as affected by the presence of the RF group; and (3) the influence of the reaction conditions on the rate of addition or selectivity for different products.Adducts from 2-(F-hexyl)ethanethiol (1) and alkenes have been obtained in high yield,but containing small amounts of regio isomers.For example compound 1 with 1-heptene gave 1-heptane (3, 96percent yield) as well as 2-heptane (4, O.61percent) and 3-heptane (5, 2.22percent). 1,6-Hexadiene and 1,7-octadiene gave chiefly linear adducts, i.e.RFCH2CH2S(CH2)nCH=CH2 (7, n=4; or 12, n=6, respectively) and RFCH2CH2S(CH2)nSCH2CH2RF (8, n=6; or 14, n=8, respectively).A small amount (2-3percent) of cis- and trans-1-methyl-cyclohexane (13) isomers were present in 12.Compound 1 with 1,6-heptadiene gave 7--1-heptene (9), the bis adduct, 1,7-bis-heptane (11) and the cyclic adducts, cis- and trans-1-methal-2-methylcyclopentane (10).The relative amounts of cyclic isomers depended on the reactant ratio.Compound 1 added readily with free-radical initiation to vinyl monomers such as styrene and vinyl acetate, and to phenyl acetylene, propargyl acetate and ethyl propynoate.These new addition products are useful as models for further study.
- Brace, Neal O.
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p. 217 - 241
(2007/10/02)
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- SYNTHESIS OF FLUORINE-CONTAINING NITRO COMPOUNDS
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Fluoronitro alkanes (5a and 5b), possesing the structure -CF2CH2CH(NO2)2, were synthesized from 1-iodo-1H,1H,2H,2H-perfluoroalkanes by displacing the iodide with sodium nitrite and then oxidatively nitrating the 1-nitro-1H,1H,2H,2H-perfluoroalkanes with tetranitromathane.Reaction with formaldehyde gave the dinitroalcohols, 6a and 6b. α,ο-diiodoperfluoroalkames (1c and 1d) were similarly converted to tetranitrofluoroalkanes (5c and 5d), characterized as tetranitrodiols 6c and 6d, and Michael adducts with methyl acrylate, 7c and 7d.
- Malik, A. A.,Archibald, T. G.,Tzeng, L. C.,Garver, L. C.,Baum, K.
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p. 291 - 300
(2007/10/02)
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- Process for preparation of carboxylic acid ester containing fluorine
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Process for the preparation of carboxylic acid ester containing fluorine comprises the reaction of the reaction mixture obtained by the reaction of an organic halogen compound containing fluorine expressed by a general formula, , X - Rf- X′, , (in which, X and X′ independently stand for halogen atoms and Rfis an optionally fluorinated hydrocarbon) with carbon dioxide in the presence of zinc, with a halogenated hydrocarbon expressed by a general formula,, RY, , (in which R is an optionally fluorinated hydrocarbon and Y is a chlorine, bromine or iodine atom).
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- Reactions of perfluoroalkyl iodides with CC-multiple bonds induced by transition metal centers
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Additions of perfluoroalkyl iodides RFI to 1-alkenes can be catalyzed by transition metals, especially by noble metals such as ruthenium or platinum.Complexes of group VI-VIII metals in low oxidation states are even more effective and may also be employed for the addition of RFI to alkynes.Heterogeneous metal catalysts facilitate the transfer of the perfluoroalkyl group from RFI to aromatic ring systems.Iodo-perfluoroalkanes 1 belong to the most important intermediates in organofluorine chemistry.The addition of 1 to alkenes according to is known to be a radical process which can be initiated by means of heat, UV- or γ-radiation, electrocatalysis or by organic azo or peroxo compounds.We found that this type of reactions can generally be carried out using two kinds of transition metal catalysts.
- Werner, Konrad Von
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p. 229 - 234
(2007/10/02)
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- REACTIVITE DES PERFLUOROHALOGENOALCANES EN PRESENCE DE COUPLES METALLIQUES. REACTIVITE DE PERFLUOROIODOALCANES SUR DES DERIVES HALOGENES DANS DES SOLVANTS APROTIQUES DISSOCIANTS (DMSO, DMF).
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Perfluoroalkyl iodides (RFI) reacts with organic halide in dissociants solvents (DMF, DMSO) in the presence of zinc-copper couple through an organometallic route; in this way C6F13Cl, C6F13CH2CH2I, (C6F13)2Zn have been prepared.
- Blancou, H.,Commeyras, A.
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p. 255 - 266
(2007/10/02)
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