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Antoni Martinezandreu - One of the best experts on this subject based on the ideXlab platform.

  • isobaric vapor liquid equilibria for 1 propanol water 1 ethyl 3 methylimidazolium trifluoromethanesulfonate at 100 kpa
    Journal of Chemical & Engineering Data, 2008
    Co-Authors: Vicent A Orchilles, Ernesto Vercher, Antoni Martinezandreu
    Abstract:

    Isobaric vapor−liquid equilibria for the binary systems 1-propanol + water, 1-propanol + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][Triflate]), and water + [emim][Triflate] as well as the vapor−liquid equilibria for the 1-propanol + water + [emim][Triflate] ternary system have been obtained at 100 kPa using a recirculating still. Electrolyte NRTL fitting parameters for the 1-propanol + water and water + [emim][Triflate] systems were calculated. The measured ternary data were correlated using Mock’s electrolyte NRTL model which reproduces reasonably well the experimental values. The results show that the addition of [emim][Triflate] to 1-propanol + water produced an important salting-out effect, and the model predicts that at 100 kPa the azeotrope disappears when the mole fraction of ionic liquid in the liquid phase is greater than 0.34.

  • isobaric vapor liquid equilibria for ethyl acetate ethanol 1 ethyl 3 methylimidazolium trifluoromethanesulfonate at 100 kpa
    Journal of Chemical & Engineering Data, 2007
    Co-Authors: Vicent A Orchilles, Pablo J. Miguel, And Ernesto Vercher, Antoni Martinezandreu
    Abstract:

    Isobaric vapor−liquid equilibria for the binary systems ethyl acetate + ethanol, ethyl acetate + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][Triflate]), and ethanol + [emim][Triflate] as well as the vapor−liquid equilibria for the ethyl acetate + ethanol + [emim][Triflate] ternary system have been obtained at 100 kPa using a recirculating still. NRTL fitting parameters for the ethyl acetate + ethanol and ethanol + [emim][Triflate] systems were calculated. The measured ternary data were correlated using the Mock electrolyte NRTL model, which reproduces reasonably well the experimental values. The results suggest that the addition of [emim][Triflate] to the ethyl acetate + ethanol mixture produced an important salting-out effect, and the azeotrope disappears when the mole fraction of ionic liquid in the liquid phase is greater than 0.20.

Vicent A Orchilles - One of the best experts on this subject based on the ideXlab platform.

  • isobaric vapor liquid equilibria for 1 propanol water 1 ethyl 3 methylimidazolium trifluoromethanesulfonate at 100 kpa
    Journal of Chemical & Engineering Data, 2008
    Co-Authors: Vicent A Orchilles, Ernesto Vercher, Antoni Martinezandreu
    Abstract:

    Isobaric vapor−liquid equilibria for the binary systems 1-propanol + water, 1-propanol + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][Triflate]), and water + [emim][Triflate] as well as the vapor−liquid equilibria for the 1-propanol + water + [emim][Triflate] ternary system have been obtained at 100 kPa using a recirculating still. Electrolyte NRTL fitting parameters for the 1-propanol + water and water + [emim][Triflate] systems were calculated. The measured ternary data were correlated using Mock’s electrolyte NRTL model which reproduces reasonably well the experimental values. The results show that the addition of [emim][Triflate] to 1-propanol + water produced an important salting-out effect, and the model predicts that at 100 kPa the azeotrope disappears when the mole fraction of ionic liquid in the liquid phase is greater than 0.34.

  • isobaric vapor liquid equilibria for ethyl acetate ethanol 1 ethyl 3 methylimidazolium trifluoromethanesulfonate at 100 kpa
    Journal of Chemical & Engineering Data, 2007
    Co-Authors: Vicent A Orchilles, Pablo J. Miguel, And Ernesto Vercher, Antoni Martinezandreu
    Abstract:

    Isobaric vapor−liquid equilibria for the binary systems ethyl acetate + ethanol, ethyl acetate + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][Triflate]), and ethanol + [emim][Triflate] as well as the vapor−liquid equilibria for the ethyl acetate + ethanol + [emim][Triflate] ternary system have been obtained at 100 kPa using a recirculating still. NRTL fitting parameters for the ethyl acetate + ethanol and ethanol + [emim][Triflate] systems were calculated. The measured ternary data were correlated using the Mock electrolyte NRTL model, which reproduces reasonably well the experimental values. The results suggest that the addition of [emim][Triflate] to the ethyl acetate + ethanol mixture produced an important salting-out effect, and the azeotrope disappears when the mole fraction of ionic liquid in the liquid phase is greater than 0.20.

Keitaro Ishii - One of the best experts on this subject based on the ideXlab platform.

  • metal Triflate catalyzed cationic benzylation and allylation of 1 3 dicarbonyl compounds
    ChemInform, 2007
    Co-Authors: Masahiro Noji, Yosuke Konno, Keitaro Ishii
    Abstract:

    The rare earth metal and hafnium Triflate-catalyzed secondary benzylation and allylation of 1,3-diketones, ketoesters, and ketoamides are described. The procedure was carried out under non-anhydrous conditions. Various 1-phenylethyl cations were generated from substituted 1-phenylethanols using 0.5 mol % of the metal Triflates in CH3NO2. The cations reacted with 1,3-diketones and ketoesters to give benzylated products in high yields. Following the GC analysis, the reaction conditions were easily optimized by the selection of catalysts based on the Lewis acidity of the Triflates and reaction temperature. A tertiary-alkylated diketone and a corresponding ketoester were also benzylated to afford products with a quaternary carbon atom in 57-84% yield. The ketoamide reactions required stronger Lewis acids than those used in the diketone and ketoester reactions. The reactions of benzylic alcohols possessing various substituents on the aromatic ring and dibenzoylmethane (2b) as a diketone were examined in the presence of Hf(OTf)4. Electron-rich benzylic alcohols reacted with 2b in 86-96% yield, and electron-deficient alcohol gave the desired product in 79-65% yield. Despite possessing a strong electron-withdrawing group, the reaction of 1-(4-nitrophenyl)ethanol gave the corresponding product in 61% yield. It was also possible to use allylic alcohols directly for the allylation of diketone 2b. The catalyst can be recovered by water extraction and reused up to five times.

  • metal Triflate catalyzed cationic benzylation and allylation of 1 3 dicarbonyl compounds
    Journal of Organic Chemistry, 2007
    Co-Authors: Masahiro Noji, Yosuke Konno, Keitaro Ishii
    Abstract:

    The rare earth metal and hafnium Triflate-catalyzed secondary benzylation and allylation of 1,3-diketones, ketoesters, and ketoamides are described. The procedure was carried out under non-anhydrous conditions. Various 1-phenylethyl cations were generated from substituted 1-phenylethanols using 0.5 mol % of the metal Triflates in CH3NO2. The cations reacted with 1,3-diketones and ketoesters to give benzylated products in high yields. Following the GC analysis, the reaction conditions were easily optimized by the selection of catalysts based on the Lewis acidity of the Triflates and reaction temperature. A tertiary-alkylated diketone and a corresponding ketoester were also benzylated to afford products with a quaternary carbon atom in 57−84% yield. The ketoamide reactions required stronger Lewis acids than those used in the diketone and ketoester reactions. The reactions of benzylic alcohols possessing various substituents on the aromatic ring and dibenzoylmethane (2b) as a diketone were examined in the pr...

  • secondary benzylation using benzyl alcohols catalyzed by lanthanoid scandium and hafnium Triflate
    Journal of Organic Chemistry, 2003
    Co-Authors: Masahiro Noji, Tomoko Ohno, Koji Fuji, Noriko Futaba, H Tajima, Keitaro Ishii
    Abstract:

    The combination of a secondary benzyl alcohol and a metal Triflate (e.g., La, Yb, Sc, and Hf Triflate) in nitromethane was a highly effective secondary-benzylation system. Secondary benzylation of carbon (aromatic compounds, olefins, an enol acetate), nitrogen (amide derivatives), and oxygen (alcohols) nucleophiles was carried out with a secondary benzyl alcohol and 0.01−1 mol % of a metal Triflate in the presence of water. Secondary benzyl alcohols and nucleophiles bearing acid-sensitive functional groups (e.g., tert-butyldimethylsilyloxy and acetoxy groups and methyl and benzyl esters) could be used for alkylation. Hf(OTf)4 was the most active catalyst for this alkylation, and trifluoromethanesulfonic acid (triflic acid, TfOH) was also a good catalyst. The catalytic activity of metal Triflates and TfOH increased in the order La(OTf)3 < Yb(OTf)3 < TfOH < Sc(OTf)3 < Hf(OTf)4. A mechanistic study was also performed. The reaction of 1-phenylethanol (4a) in the presence of Sc(OTf)3 in nitromethane gave an eq...

Masahiro Noji - One of the best experts on this subject based on the ideXlab platform.

  • metal Triflate catalyzed cationic benzylation and allylation of 1 3 dicarbonyl compounds
    ChemInform, 2007
    Co-Authors: Masahiro Noji, Yosuke Konno, Keitaro Ishii
    Abstract:

    The rare earth metal and hafnium Triflate-catalyzed secondary benzylation and allylation of 1,3-diketones, ketoesters, and ketoamides are described. The procedure was carried out under non-anhydrous conditions. Various 1-phenylethyl cations were generated from substituted 1-phenylethanols using 0.5 mol % of the metal Triflates in CH3NO2. The cations reacted with 1,3-diketones and ketoesters to give benzylated products in high yields. Following the GC analysis, the reaction conditions were easily optimized by the selection of catalysts based on the Lewis acidity of the Triflates and reaction temperature. A tertiary-alkylated diketone and a corresponding ketoester were also benzylated to afford products with a quaternary carbon atom in 57-84% yield. The ketoamide reactions required stronger Lewis acids than those used in the diketone and ketoester reactions. The reactions of benzylic alcohols possessing various substituents on the aromatic ring and dibenzoylmethane (2b) as a diketone were examined in the presence of Hf(OTf)4. Electron-rich benzylic alcohols reacted with 2b in 86-96% yield, and electron-deficient alcohol gave the desired product in 79-65% yield. Despite possessing a strong electron-withdrawing group, the reaction of 1-(4-nitrophenyl)ethanol gave the corresponding product in 61% yield. It was also possible to use allylic alcohols directly for the allylation of diketone 2b. The catalyst can be recovered by water extraction and reused up to five times.

  • metal Triflate catalyzed cationic benzylation and allylation of 1 3 dicarbonyl compounds
    Journal of Organic Chemistry, 2007
    Co-Authors: Masahiro Noji, Yosuke Konno, Keitaro Ishii
    Abstract:

    The rare earth metal and hafnium Triflate-catalyzed secondary benzylation and allylation of 1,3-diketones, ketoesters, and ketoamides are described. The procedure was carried out under non-anhydrous conditions. Various 1-phenylethyl cations were generated from substituted 1-phenylethanols using 0.5 mol % of the metal Triflates in CH3NO2. The cations reacted with 1,3-diketones and ketoesters to give benzylated products in high yields. Following the GC analysis, the reaction conditions were easily optimized by the selection of catalysts based on the Lewis acidity of the Triflates and reaction temperature. A tertiary-alkylated diketone and a corresponding ketoester were also benzylated to afford products with a quaternary carbon atom in 57−84% yield. The ketoamide reactions required stronger Lewis acids than those used in the diketone and ketoester reactions. The reactions of benzylic alcohols possessing various substituents on the aromatic ring and dibenzoylmethane (2b) as a diketone were examined in the pr...

  • secondary benzylation using benzyl alcohols catalyzed by lanthanoid scandium and hafnium Triflate
    Journal of Organic Chemistry, 2003
    Co-Authors: Masahiro Noji, Tomoko Ohno, Koji Fuji, Noriko Futaba, H Tajima, Keitaro Ishii
    Abstract:

    The combination of a secondary benzyl alcohol and a metal Triflate (e.g., La, Yb, Sc, and Hf Triflate) in nitromethane was a highly effective secondary-benzylation system. Secondary benzylation of carbon (aromatic compounds, olefins, an enol acetate), nitrogen (amide derivatives), and oxygen (alcohols) nucleophiles was carried out with a secondary benzyl alcohol and 0.01−1 mol % of a metal Triflate in the presence of water. Secondary benzyl alcohols and nucleophiles bearing acid-sensitive functional groups (e.g., tert-butyldimethylsilyloxy and acetoxy groups and methyl and benzyl esters) could be used for alkylation. Hf(OTf)4 was the most active catalyst for this alkylation, and trifluoromethanesulfonic acid (triflic acid, TfOH) was also a good catalyst. The catalytic activity of metal Triflates and TfOH increased in the order La(OTf)3 < Yb(OTf)3 < TfOH < Sc(OTf)3 < Hf(OTf)4. A mechanistic study was also performed. The reaction of 1-phenylethanol (4a) in the presence of Sc(OTf)3 in nitromethane gave an eq...

Jacques Dubac - One of the best experts on this subject based on the ideXlab platform.

  • Bismuth(III) chloride and Triflate: Novel catalysts for acylation and sulfonylation reactions. Survey and mechanistic aspects
    Synlett, 2002
    Co-Authors: Christophe Roux, Jacques Dubac
    Abstract:

    Acylation and sulfonylation reactions catalyzed by bismuth(III) chloride or Triflate are reviewed. For Friedel-Crafts reactions the mechanistic study reveals the different behavior of Bi(OTf) 3 , depending on the electrophilic agent used; either that of Lewis acid (with acid anhydrides) or that of procatalyst, carrier of Triflate groups (with acid chlorides), leading to in situ generation of mixed anhydrides (RCOOTf or RSO 2 OTf) responsible for the aromatic electrophilic substitution. Among the metal Triflates tested in these reactions, only Ga(III) and In(III) exhibit high activity. Bi(OTf) 3 appears to be superior to other metal Triflates known to catalyze the acylation of alcohols using acid anhydrides as reagents. BiCl 3 , especially in the presence of a metal iodide, is the only known efficient catalyst for acyldesilylation reactions of allyl- and enoxysilanes. The low cost of bismuth compounds and their low (or absence of) toxicity are emphasized.

  • bismuth iii trifluoromethanesulfonate an efficient catalyst for the sulfonylation of arenes
    Journal of Organic Chemistry, 1999
    Co-Authors: Sigrid Repichet, Jacques Dubac, Christophe Roux, And Pierre Hernandez, Jeanroger Desmurs
    Abstract:

    Sulfonylation reactions are one of the most important groups of aromatic electrophilic substitutions.1 The sulfonyl group is a widely used synthon for synthetic organic chemists,2 and sulfones have many industrial applications.3 In Friedel-Crafts (FC) acylation and sulfonylation, a consequence of the complexation of the Lewis acid with the reaction product implies that a stoichiometric amount of the activator is often required. However, some metal halides such as iron(III) chloride,1 Bronsted acids, for example polyphosphoric acid4 or triflic acid,5 and zeolites6,7 have been reported to catalyze the sulfonylation of arenes. In recent years, rare earth trifluoromethanesulfonates (Triflates) have been reported for the catalysis of the FC acylation8 but not for the catalysis of the FC sulfonylation. Also, our laboratory reported that bismuth(III) chloride (1a) and particularly bismuth(III) Triflate (1b) were catalysts for acylation reactions,9 especially for FC acylation.10 In a stoichiometric process from arylsulfonyl bromides, silver Triflate gives trifluoromethanesulfonic arenesulfonic anhydrides (ArSO2OTf), which are strong sulfonylating reagents.11 We present here a study of the catalytic activity of 1a and 1b for the sulfonylation reaction of arenes (eq 1), for which 1b proved to be a metal Triflate capable of realizing an outstanding catalytic process.

  • bismuth iii trifluoromethanesulfonate a chameleon catalyst for the friedel crafts acylation
    European Journal of Organic Chemistry, 1998
    Co-Authors: Sigrid Repichet, Christophe Le Roux, Jacques Dubac, Jeanroger Desmurs
    Abstract:

    A mechanism for acylations catalyzed by bismuth(III) Triflate (1) is proposed in the case of the benzoylation of benzene, toluene, and chlorobenzene. With Bz2O as a reagent, 1 acts as a Lewis acid and allows the benzoylation of toluene. It is almost completely recovered after the reaction. With BzCl, 1 promotes an exchange reaction which generates BzOTf, which is the active species of the benzoylation. In this latter case, the reaction leads to the formation of TfOH which finally reacts with BiCl3 to partially regenerate 1. The power of the Bz2O/1 system is less than that of BzCl/1, which allows not only the benzoylation of toluene but also that of benzene and deactivated chlorobenzene. The activity of 1 is much higher than that of other metallic Triflates previously reported, and is comparable with that of TfOH, however it also has the advantage that the Triflate moieties are more easily recoverable.