- 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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- TRANSITION-METAL COMPLEX CATALYZED POLYFLUOROALKYLATION. I. FACILE ADDITION OF POLYFLUOROALKYL HALIDES TO CARBON-CARBON MULTIPLE BONDS
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Addition of polyfluoroalkyl halides to alkynes and alkenes bearing a variety of substituents is effected by the catalysis of iron, cobalt and ruthenium carbonyl complexes to give the corresponding adducts in good to excellent yields under mild conditions.
- Fuchikami, Takamasa,Ojima, Iwao
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Read Online
- Cap-and-tag solid phase oligosaccharide synthesis
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(Chemical Equation Presented) A new "cap-and-tag" strategy is applied to solid phase oligosaccharide synthesis. Acetyl-capping and fluorous-tagging allowed for the facile separation of the desired F-tagged oligosaccharide from the acetyl-capped deletion sequences using fluorous solid phase extraction. To illustrate this approach, a protected Glc-β-(1→6) -Man-α-(1→6)-Glc-β-1→pentenyl trisaccharide was synthesized.
- Carrel, Frederic R.,Seeberger, Peter H.
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p. 2058 - 2065
(2008/09/19)
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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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- Ionic transformations in extremely nonpolar fluorous media: Phase transfer catalysis of halide substitution reactions
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Fluorous solutions of alkyl halides R18(CH2) mX (m = 2, 3; X = Cl, Br, I) are inert toward solid or aqueous NaCl, NaBr, and Kl, but halide substitution occurs in the presence of fluorous phosphonium salts (10 mol %, 76-100 °C).
- Consorti, Crestina S.,Jurisch, Markus,Gladysz, John A.
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p. 2309 - 2312
(2008/02/05)
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- Copper salt-catalysed reaction of perfluoroalkyl halides with olefins
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Perfluoroalkyl halides react with olefins in the presence of copper acetate and hydrazine to give 1,2-addition products.
- Igumnov, Sergei M.,Don, Veronika L.,Vyazkov, Vladimir A.,Narinyan, Karen E.
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p. 189 - 190
(2007/10/03)
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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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- Metallic copper catalyst for polyfluoroalkylethyl iodide production and process for producing polyfluoroalkylethyl iodide
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The present invention provides a metallic copper catalyst for use in an ethylene addition reaction to polyfluoroalkyl iodides, a process for efficiently producing a polyfluoroalkylethyl iodide using such a metal copper catalyst in an ethylene addition reaction to a polyfluoroalkyl iodide, and a process for efficiently producing a polyfluoroalkylethyl iodide from a polyfluoroalkyl iodide using the same metallic copper catalyst in a telomerization reaction and a subsequent ethylene addition reaction.
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Page/Page column 4-5
(2008/06/13)
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- PROCESS FOR PRODUCING FLUOROALKYL IODIDE
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The present invention provides a process for producing a fluoroalkyl iodide represented by the general formula (II):Rf-CH2CH2I wherein Rf is a perfluoroalkyl or polyfluoroalkyl group comprising 1 to 20 carbons, the process comprising reacting hydrogen iodide gas with a fluoroalkene in the presence of a catalyst. The present invention also provides a process for producing a fluoroester by reacting the fluoroalkyl iodide with a carboxylate.
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Page column 8
(2008/06/13)
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- Coupling between a fluorinated olefin and a perfluorinated iodide: A model study on the reaction mechanism of perfluorinated polymer cross-linking
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In a model study, 1H, 19C, 13 C-1H and 1H-1H correlated NMR techniques confirm a Markovnikov type reaction intermediate for the major coupling products between a short, low MW perfluorinated iodide C2F5I (I) and a short, low MW fluorinated olefin CF3(CF2)7CH=CH2 (II). The reaction is peroxide induced (di-t-butyl peroxide, DTBP) and is conducted at 140 °C for a 3 h reaction time in a sealed glass ampoule. Side reaction products due to the reaction of DTBP with radical reaction intermediates were also observed and identified. The study aimed to mimic as closely as possible the peroxide-initiated coupling reaction between an iodine terminated fluoropolymer (model compound I) and its fluorinated di-olefin coupling agent (model compound II). A mono-olefin was chosen to simplify the model reaction.
- Wlassics, Ivan,Barchiesi,Sala
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p. 119 - 126
(2007/10/03)
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- Application of trimethylvinylsilane as a convenient synthetic precursor of (perfluoroalkyl)ethenes: An unusual fluoride-induced elimination-desilylation coupled reaction
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(equation presented) A convenient and effective method for the preparation of perfluoroalkylated ethenes is described. First, the free radical addition of perfluoroalkyl iodides to trimethylvinylsilane in the presence of AIBN gave iodoethylsilane intermediates (F(CF2)nCH2CHISiMe3, n = 4 (1), 6 (2),8 (3), 10 (4); 94-99%). Then an unusual dehydrohalogenation-desilylation reaction was effected by tetrabutylammonium fluoride, and finally the product isolation (F(CF2)nCH=CH2 (5-8), 62-87%) was facilitated using a fluorous phase separation technique. This novel approach can also be applied to adjust short C2 hydrocarbon units to functionalized fluorinated segments (e.g., HOCH2(CF2)8CH=CH2 (11), 71%). All structures were verified by state-of-the-art multinuclear one- and two-dimensional NMR experiments involving both homo-(19F-19F) and heteronuclear (1H-13C, 19F-13C) correlations based on the GMQFCOPS and inverse 1H and/or 19F detected GHSQC, GHMQC sequences with broad-band adiabatic 13C decoupling.
- Szlávik, Zoltán,Tárkányi, Gábor,G?m?ry, ágnes,Rábai, József
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p. 2347 - 2349
(2007/10/03)
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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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- Process for preparing polyfluoroalkyl-substituted compounds
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A process for preparing a perfluoroalkyl-substituted compound is disclosed. The process comprises reacting a halopolyfluoroalkane having 1 to 20 carbon atoms with a compound selected from the group consisting of (1) a substituted or unsubstituted ethylene, (2) a substituted or unsubstituted acetylene and (3) a substituted or unsubstituted allylsilane, in the presence of a metal-carbonyl complex of the metal of the Group VIII of the Periodic Table. Alternatively, the reaction between the halopolyfluoroalkane and the substituted or unsubstituted allylsilane is effected under radical generating condition.
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- Lysosometropic detergent therapeutic agents
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The present invention is concerned with the preparation of lysosomotropic detergent agents and pharmaceutical composition useful in the treatment of cancer. These compounds are amine derivatives having a pK of 3.5 of the general structure STR1 in which R1 is C8-30 alkyl, C8-30 -alkenyl, substituted C4-30 alkyl or substituted C4-30 -alkenyl; R2 is hydrogen or C1-4 alkyl and Y is an electron withdrawing group, to control the pK, selected from trifluoroethyl, and difluoroethyl.
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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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- Reaction of Perfluoroalkyl Iodides with Electron Donor Nucleophiles. Addition of Perfluoroalkyl Iodides to Olefins Initiated by Electron Transfer
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The radical chain addition of primary and secondary perfluoroalkyl iodides to olefins is initiated by sodium arene- and alkanesulfinates.The process occurs at room temperature and is favored by the use of dipolar aprotic solvents.The reaction of perfluorooctyl iodide with sodium p-toluenesulfinate in the absence of olefin requires higher temperatures and gives only 1-H-perfluorooctane; no anion-perfluoroalkyl radical coupling products were detected.Reaction of perfluorooctyl iodide with the sodium salt of diethyl methylmalonate also gives no coupling product; only 1-H-perfluorooctane and a dimer of the malonate anion are produced.These results are compared with the reaction of perfluoroalkyl iodides with nitronate and thiolate anions where formation of SRN1 substitution products was observed.
- Feiring, Andrew E.
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p. 3269 - 3274
(2007/10/02)
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- Lysosomotropic Agents. 4. Carbobenzoxyglycylphenylalanyl, a New Protease-Sensitive Masking Group for Introduction into Cells
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Bioactive primary and secondary amines, when acylated with the Z-Gly-Phe group, are transported into pinocytic cells, such as macrophages, P-815 mastocytoma, SV-40 3T3, and leukemia 1210, much faster than the parent compounds.Amines, such as lysosomotropic detergents and nitrogen mustard, which are deactivated by acylation, are unmasked by enzymic action intracellularly, probably in lysosomes because an acidic pH maximum in activity exists which acts only on the L isomer.The added polarity and molecular weight brought about by acylation prevents the amines' normally facile entry into cells by simple diffusion, restricting it to an active-transport mechanism.
- Firestone, Raymond A.,Pisano, Judith M.,Bailey, Philip J.,Sturm, Anita,Bonney, Robert J.,et al.
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p. 539 - 544
(2007/10/02)
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