Separation and Catalysis of Carboxylates: Byproduct Reduction during the Alkylation with Dimethyl Carbonate

Quaternary ammonium carboxylates (both ionic liquids and resins) can be used for formation of methyl carboxylate esters in an alkylation reaction with dimethyl carbonate (DMC). This reaction is pursued in the context of a low-waste process for recovery and upgrading of fermentative carboxylates. Byproducts, such as methanol, are produced during the alkylation reaction with DMC. A molar yield of methyl acetate on acetate of 0.84 and modest selectivity (0.54–0.95 mol of methyl acetate/mol of methanol) are obtained with an anion exchanger fully in the acetate form. Water and DMC concentrations have a strong effect on the yield and selectivity of the reaction. Model calculations indicate that an excess of 50 mol of DMCin/mol of acetatein in DMC is needed to achieve yields above 0.98 mol of methyl acetate/mol of acetatein, and water concentrations in the resin below 0.04 g of water/g of resin to achieve a selectivity above 1.1 mol of methyl acetate/mol of methanol. The explanation for the modest selectivity is...

[1]  M. Fraaije,et al.  Synthesis of methyl propanoate by Baeyer-Villiger monooxygenases. , 2014, Chemical communications.

[2]  Adrie J J Straathof,et al.  Recovery of carboxylic acids produced by fermentation. , 2014, Biotechnology advances.

[3]  A. Perosa,et al.  Carbonate phosphonium salts as catalysts for the transesterification of dialkyl carbonates with diols. The competition between cyclic carbonates and linear dicarbonate products. , 2014, Organic & biomolecular chemistry.

[4]  S. Atsumi,et al.  Expanding ester biosynthesis in Escherichia coli. , 2014, Nature chemical biology.

[5]  Adrie J J Straathof,et al.  Transformation of biomass into commodity chemicals using enzymes or cells. , 2014, Chemical reviews.

[6]  Adrie J. J. Straathof,et al.  Green upgrading of succinate using dimethyl carbonate for a better integration with fermentative production , 2014 .

[7]  David J Gorin,et al.  Catalytic methyl transfer from dimethylcarbonate to carboxylic acids. , 2013, The Journal of organic chemistry.

[8]  A. Perosa,et al.  Upgrading of Levulinic Acid with Dimethylcarbonate as Solvent/Reagent , 2013 .

[9]  F. Duus,et al.  Methyl esterification of carboxylic acids with dimethyl carbonate promoted by K2CO3/tetrabutylammonium chloride , 2013 .

[10]  Marcel Ottens,et al.  Direct downstream catalysis: From succinate to its diethyl ester without intermediate acidification , 2012 .

[11]  Gary W. Earl,et al.  Investigation of the Stability of Quaternary Ammonium Methyl Carbonates , 2012 .

[12]  A. Perosa,et al.  Methylcarbonate and bicarbonate phosphonium salts as catalysts for the nitroaldol (Henry) reaction. , 2012, The Journal of organic chemistry.

[13]  A. Górak,et al.  Transesterification of Dimethyl Carbonate with Ethanol To Form Ethyl Methyl Carbonate and Diethyl Carbonate: A Comprehensive Study on Chemical Equilibrium and Reaction Kinetics , 2011 .

[14]  Martyn Poliakoff,et al.  Continuous Acid-Catalyzed Methylations in Supercritical Carbon Dioxide: Comparison of Methanol, Dimethyl Ether and Dimethyl Carbonate as Methylating Agents , 2010 .

[15]  V. Lucchini,et al.  Ionic liquids made with dimethyl carbonate: solvents as well as boosted basic catalysts for the michael reaction. , 2009, Chemistry.

[16]  B. Lu,et al.  Studies on synthesis of dimethyl carbonate from methanol and carbon dioxide , 2009 .

[17]  A. Perosa,et al.  Green chemistry metrics: a comparative evaluation of dimethyl carbonate, methyl iodide, dimethyl sulfate and methanol as methylating agents , 2008 .

[18]  Armando Carlone,et al.  Reaction of dicarbonates with carboxylic acids catalyzed by weak Lewis acids: General method for the synthesis of anhydrides and esters , 2007 .

[19]  M. Aresta,et al.  On the existence of the elusive monomethyl ester of carbonic acid [CH3OC(O)OH] at 300 K : 1H- and 13C NMR measurements and DFT calculations , 2006 .

[20]  Murray J. Thomson,et al.  Chemical Kinetic Modeling of Dimethyl Carbonate in an Opposed-Flow Diffusion Flame , 2005 .

[21]  A. Döhring,et al.  A convenient protocol for the esterification of carboxylic acids with alcohols in the presence of di-t-butyl dicarbonate , 2004 .

[22]  J. Canosa,et al.  Vapour–liquid equilibria of dimethyl carbonate with linear alcohols and estimation of interaction parameters for the UNIFAC and ASOG method , 2002 .

[23]  Pietro Tundo,et al.  The chemistry of dimethyl carbonate. , 2002, Accounts of chemical research.

[24]  Rafiqul Gani,et al.  Estimation of mixture properties from first- and second-order group contributions with the UNIFAC model , 2002 .

[25]  Oljan Repic,et al.  Nucleophilic catalysis with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) for the esterification of carboxylic acids with dimethyl carbonate. , 2002, The Journal of organic chemistry.

[26]  Jürgen Gmehling,et al.  Reaction Kinetics and Chemical Equilibrium of Homogeneously and Heterogeneously Catalyzed Acetic Acid Esterification with Methanol and Methyl Acetate Hydrolysis , 2000 .

[27]  C. Fité,et al.  Drying of Acidic Macroporous Styrene−Divinylbenzene Resins with 12−20 Cross-Linking Degree , 2000 .

[28]  Yuhan Sun,et al.  Novel reaction route for dimethyl carbonate synthesis from CO2 and methanol , 2000 .

[29]  Yoshio Ono,et al.  Catalysis in the Production and Reactions of Dimethyl Carbonate, an Environmentally Benign Building-Block , 1997 .

[30]  Y. Ono,et al.  Synthesis of methyl N-phenyl carbamate by methoxycarbonylation of aniline with dimethyl carbonate using Pb compounds as catalysts , 1994 .

[31]  C. Fité,et al.  Drying of acidic macroporous styrene-divinylbenzene resins , 1993 .

[32]  U. Romano,et al.  SYNTHESIS OF DIMETHYL CARBONATE FROM METHANOL, CARBON MONOXIDE, AND OXYGEN CATALYZED BY COPPER COMPOUNDS , 1981 .

[33]  G. Cainelli,et al.  The Use of Anion-Exchange Resins in the Synthesis of Esters from Carboxylic Acids and Alkylating Agents , 1975 .

[34]  E. W. Robb,et al.  Preparation of Methyl Esters for Gas Liquid Chromatography of Acids by Pyrolysis of Tetramethylammonium salts. , 1963 .