Carbon dioxide: a renewable feedstock for the synthesis of fine and bulk chemicals

The syntheses of carbon dioxide (CO2) based industrially important chemicals have gained considerable interest in view of the sustainable chemistry and “green chemistry” concepts. In this review, recent developments in the chemical fixation of CO2 to valuable chemicals are discussed. The synthesis of five-member cyclic carbonates via, cycloaddition of CO2 to epoxides is one of the promising reactions replacing the existing poisonous phosgene-based synthetic route. This review focuses on the synthesis of cyclic carbonates, vinyl carbamates, and quinazoline-2,4(1H,3H)-diones via reaction of CO2 and epoxide, amines/phenyl acetylene, 2-aminobenzinitrile and other chemicals. Direct synthesis of dimethyl carbonate, 1,3-disubstituted urea and 2-oxazolidinones/2-imidazolidinones have limitations at present because of the reaction equilibrium and chemical inertness of CO2. The preferred alternatives for their synthesis like transesterification of ethylene carbonate with methanol, transamination of ethylene carbonate with primary amine and transamination reaction of ethylene carbonate with diamines/β-aminoalcohols are discussed. These methodologies offer marked improvements for greener chemical fixation of CO2 in to industrially important chemicals.

[1]  M Aresta,et al.  二酸化炭素の酵素的活用対化学的活用 1 カルボキシル化反応における金属中心の役割 , 1995 .

[2]  Feng Shi,et al.  Electrochemical activation of carbon dioxide in ionic liquid: synthesis of cyclic carbonates at mild reaction conditions. , 2002, Chemical communications.

[3]  Yutaka Ikushima,et al.  A rapid and effective synthesis of propylene carbonate using a supercritical CO2-ionic liquid system. , 2003, Chemical communications.

[4]  S. Patai,et al.  THE SYNTHESIS OF 2,4[1H,3H]QUINAZOLINEDIONE AND SOME OF ITS 3-ARYL SUBSTITUTED DERIVATIVES , 1978 .

[5]  M. Mori,et al.  Novel Catalytic CO2 Incorporation Reaction: Nickel-Catalyzed Regio- and Stereoselective Ring-Closing Carboxylation of Bis-1,3-dienes , 2002 .

[6]  M. Arai,et al.  Non-catalytic clean synthesis route using urea to cyclic urea and cyclic urethane compounds , 2004 .

[7]  Takakazu Yamamoto,et al.  Poly(pyridine-2,5-diyl)–CuCl2 catalyst for synthesis of dimethyl carbonate by oxidative carbonylation of methanol: catalytic activity and corrosion influence , 2000 .

[8]  J. Spivey,et al.  Direct catalytic formation of acetic acid from CO2 and methane , 2003 .

[9]  P. Jessop,et al.  HOMOGENEOUS CATALYSIS IN SUPERCRITICAL FLUIDS : HYDROGENATION OF SUPERCRITICAL CARBON DIOXIDE TO FORMIC ACID, ALKYL FORMATES, AND FORMAMIDES , 1996 .

[10]  P. Giannoccaro.  Palladium-catalysed N,N′-disubstituted urea synthesis by oxidative carbonylation of amines under CO and O2 at atmospheric pressure , 1987 .

[11]  Pierre Braunstein,et al.  Reactions of carbon dioxide with carbon-carbon bond formation catalyzed by transition-metal complexes , 1988 .

[12]  Kazuo Sato,et al.  Synthesis and Herbicidal Activities of 4-Substituted 3-Aryl-5-tert-butyl-4-oxazolin-2-ones , 1998 .

[13]  B. Bhanage,et al.  Synthesis of dimethyl carbonate via transesterification of ethylene carbonate with methanol using poly-4-vinyl pyridine as a novel base catalyst , 2008 .

[14]  D. Ager,et al.  1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis. , 1996, Chemical reviews.

[15]  K. Tomishige,et al.  Catalytic properties and structure of zirconia catalysts for direct synthesis of dimethyl carbonate from methanol and carbon dioxide , 2000 .

[16]  J. E. Lyons,et al.  Catalysis research of relevance to carbon management: progress, challenges, and opportunities. , 2001, Chemical reviews.

[17]  Christopher L. Marshall,et al.  Review of Dimethyl Carbonate (DMC) Manufacture and Its Characteristics as a Fuel Additive , 1997 .

[18]  Y. Ishino,et al.  The simple solvent-free synthesis of 1H-quinazoline-2,4-diones using supercritical carbon dioxide and catalytic amount of base , 2004 .

[19]  J. Grunwaldt,et al.  Behavior of homogeneous and immobilized zinc-based catalysts in cycloaddition of CO2 to propylene oxide , 2005 .

[20]  A. Bell,et al.  Effects of Catalyst Phase Structure on the Elementary Processes Involved in the Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide over Zirconia , 2002 .

[21]  T. Endo,et al.  Reaction of Various Oxiranes and Carbon Dioxide. Synthesis and Aminolysis of Five-Membered Cyclic Carbonates , 2000 .

[22]  Hoon Sik Kim,et al.  Well-defined highly active heterogeneous catalyst system for the coupling reactions of carbon dioxide and epoxides , 2002 .

[23]  B. Han,et al.  Solvent-free synthesis of substituted ureas from CO2 and amines with a functional ionic liquid as the catalyst , 2008 .

[24]  Alan S. Lindsey,et al.  The Kolbe-Schmitt Reaction , 1957 .

[25]  B. Bhanage,et al.  Synthesis of 2-oxazolidinones/2-imidazolidinones from CO2, different epoxides and amino alcohols/alkylene diamines using Br−Ph3+P-PEG600-P+Ph3Br− as homogenous recyclable catalyst , 2008 .

[26]  H. Kim,et al.  Imidazolium zinc tetrahalide-catalyzed coupling reaction of CO2 and ethylene oxide or propylene oxide , 2003 .

[27]  D. Darensbourg,et al.  Homogeneous catalysts for carbon dioxide/hydrogen activation. Alkyl formate production using anionic ruthenium carbonyl clusters as catalysts , 1983 .

[28]  Takatoshi Ito,et al.  Solvent-free synthesis of quinazoline -2,4 (1H,3H) -diones using carbon dioxide and a catalytic amount of DBU , 2007 .

[29]  K. Kondo,et al.  New synthesis of ureas. Reaction of ammonia or aliphatic amines with carbon monoxide in the presence of selenium , 1971 .

[30]  M. Okano,et al.  Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis. , 1998, The Journal of organic chemistry.

[31]  Xiujuan Feng,et al.  Tertiary amino group covalently bonded to MCM-41 silica as heterogeneous catalyst for the continuous synthesis of dimethyl carbonate from methanol and ethylene carbonate , 2004 .

[32]  M. Bruce,et al.  Vinylidene and Propadienylidene (Allenylidene) Metal Complexes , 1983 .

[33]  B. Bhanage,et al.  Palladium bis(2,2,6,6-tetramethyl-3,5-heptanedionate) catalyzed alkoxycarbonylation and aminocarbonylation reactions , 2009 .

[34]  B. Bhanage,et al.  Phosphane-Free Palladium-Catalyzed Carbonylative Suzuki Coupling Reaction of Aryl and Heteroaryl Iodides , 2009 .

[35]  T. Nishikubo,et al.  Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide , 1993 .

[36]  M. Larhed,et al.  Super fast cobalt carbonyl-mediated synthesis of ureas , 2005 .

[37]  A. Baba,et al.  Carbonate Formation from Oxiranes and Carbon Dioxide Catalyzed by Organotin Halide-Tetraalkylphosphonium Halide Complexes , 1987 .

[38]  J. F. Knifton,et al.  Ethylene glycol—dimethyl carbonate cogeneration , 1991 .

[39]  B. Bhanage,et al.  Synthesis of 1,3-Disubstituted Symmetrical/Unsymmetrical Ureas via Cs2CO3-Catalyzed Transamination of Ethylene Carbonate and Primary Amines , 2009 .

[40]  S. Fujita,et al.  Mechanisms of Methanol Synthesis from Carbon Dioxide and from Carbon Monoxide at Atmospheric Pressure over Cu/ZnO , 1995 .

[41]  A. Behr.  Carbon Dioxide as an Alternative C1 Synthetic Unit: Activation by Transition‐Metal Complexes , 1988 .

[42]  M. Aresta,et al.  Carbon Dioxide: A Substitute for Phosgene , 1997 .

[43]  M. Arai,et al.  Heterogeneous base catalyzed synthesis of 2-oxazolidinones/2-imidiazolidinones via transesterification of ethylene carbonate with β-aminoalcohols/1,2-diamines , 2008 .

[44]  J. Dean,et al.  Supercritical fluid extraction of analytes from environmental samples. A review , 1994 .

[45]  Yaqing Feng,et al.  Photocatalytic conversion of CH4 and CO2 to oxygenated compounds over Cu/CdS–TiO2/SiO2 catalyst , 2004 .

[46]  C. Xia,et al.  A method for the synthesis of 2-oxazolidinones and 2-imidazolidinones from five-membered cyclic carbonates and β-aminoalcohols or 1,2-diamines , 2007 .

[47]  F. Porta,et al.  Selective ruthenium carbonyl catalysed reductive carbonylation of aromatic nitro compounds to carbamates , 1984 .

[48]  Anthony B. Pinkerton,et al.  Bull. Soc. Chim. Fr. , 1957 .

[49]  M. Saito,et al.  Ruthenium complex catalysed hydrogenation of carbon dioxide to carbon monoxide, methanol and methane , 1993 .

[50]  C. Aymonier,et al.  Review on materials science and supercritical fluids , 2003 .

[51]  Mercedes Alvaro,et al.  Polymer-bound aluminium salen complex as reusable catalysts for CO2 insertion into epoxides , 2005 .

[52]  D. Brittelli,et al.  Antibacterials. Synthesis and structure-activity studies of 3-aryl-2-oxooxazolidines. 2. The "A" group. , 1989, Journal of medicinal chemistry.

[53]  Takatoshi Ito,et al.  Synthesis of 2,4-dihydroxyquinazolines using carbon dioxide in the presence of DBU under mild conditions , 2000 .

[54]  H. Koinuma,et al.  Copolymerization of carbon dioxide and epoxide with organometallic compounds , 1969 .

[55]  K. Nicholas,et al.  Rhodium-catalyzed hydrogenation of carbon dioxide to formic acid , 1992 .

[56]  Paul T. Anastas,et al.  Green Chemistry: Designing Chemistry for the Environment , 1996 .

[57]  B. Bhanage,et al.  Silica supported polyvinyl pyridine as a highly active heterogeneous base catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides , 2007 .

[58]  Y. Ishino,et al.  Highly efficient synthesis of 1H-quinazoline-2,4-diones using carbon dioxide in the presence of catalytic amount of DBU , 2002 .

[59]  Gabriele,et al.  Synthesis of 2-oxazolidinones by direct palladium-catalyzed oxidative carbonylation of 2-amino-1-alkanols , 2000, Organic letters.

[60]  C. Bruneau,et al.  Acetylene in Catalysis: a One-step Synthesis of Vinylcarbamates with [RuCl2(norbornadiene)]n , 1988 .

[61]  Liang‐Nian He,et al.  A poly(ethylene glycol)-supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO2 with epoxides under supercritical conditions , 2006 .

[62]  Hongzhou Yang,et al.  A novel ZrO2–SO42− supported palladium catalyst for syntheses of disubstituted ureas from amines by oxidative carbonylation , 2001 .

[63]  Masami Takeuchi,et al.  A 50 kg/day class test plant for methanol synthesis from CO2 and H2 , 1998 .

[64]  Yu-mei Shen,et al.  Recent progresses on the fixation of carbon dioxide , 2003 .

[65]  M. Shirai,et al.  Chemical Fixation of Carbon Dioxide to Propylene Carbonate Using Smectite Catalysts with High Activity and Selectivity , 2002 .

[66]  T. Tsuda,et al.  Nickel(0)-catalyzed alternating copolymerization of carbon dioxide with diynes to poly(2-pyrones) , 1992 .

[67]  H. Yoshida,et al.  Mg-Al mixed oxides as highly active acid-base catalysts for cycloaddition of carbon dioxide to epoxides , 1999 .

[68]  K. Fujimoto,et al.  Direct synthesis of dimethyl carbonate from carbon dioxide and methanol catalyzed by base , 1996 .

[69]  Masahiko Arai,et al.  Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides, and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity , 2001 .

[70]  Michele Aresta,et al.  Mechanism of formation of organic carbonates from aliphatic alcohols and carbon dioxide under mild conditions promoted by carbodiimides. DFT calculation and experimental study. , 2005, The Journal of organic chemistry.

[71]  S. J. Falcone,et al.  A Simple One-Pot Procedure for Preparing Symmetrical Diarylureas from Carbon Dioxide and Aromatic Amines , 1995 .

[72]  Hiroyuki Yasuda,et al.  Transformation of carbon dioxide. , 2007, Chemical reviews.

[73]  M. Benaglia,et al.  Gazz. Chim. Ital , 1995 .

[74]  P. Tundo.  New developments in dimethyl carbonate chemistry , 2001 .

[75]  T. Endo,et al.  One-pot non-isocyanate synthesis of polyurethanes from bisepoxide, carbon dioxide, and diamine , 2005 .

[76]  Takeshi Sako,et al.  Synthesis of dimethyl carbonate from carbon dioxide: catalysis and mechanism , 2000 .

[77]  Yi Pan,et al.  Carbon Dioxide as a Phosgene Replacement: Synthesis and Mechanistic Studies of Urethanes from Amines, CO2, and Alkyl Chlorides , 1995 .

[78]  T. Nishikubo,et al.  Soluble polymer‐supported catalysts containing pendant quaternary onium salts for the addition reaction of oxiranes with carbon dioxide , 1995 .

[79]  Hideomi Koinuma,et al.  Copolymerization of carbon dioxide and epoxide , 1969 .

[80]  J. Kizlink.  Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol in the Presence of Organotin Compounds , 1993 .

[81]  McCusker,et al.  W(CO)6-catalyzed oxidative carbonylation of primary amines to N,N'-disubstituted ureas in single or biphasic solvent systems. Optimization and functional group compatibility studies , 2000, The Journal of organic chemistry.

[82]  SonBinh T. Nguyen,et al.  Co(III) porphyrin/DMAP: an efficient catalyst system for the synthesis of cyclic carbonates from CO2 and epoxides , 2004 .

[83]  N. Puschin,et al.  Über die Verbindungen des Phosgens mit Hexamethylentetramin, m‐Toluidin und Äthylendiamin , 1937 .

[84]  D. H. Gibson.  Carbon dioxide coordination chemistry: metal complexes and surface-bound species. What relationships? , 1999 .

[85]  R. Nomura,et al.  Carbonylation of amines by carbon dioxide in the presence of an organoantimony catalyst , 1992 .

[86]  Changwen Hu,et al.  Synthesis of dimethyl carbonate from methanol and carbon dioxide in the presence of polyoxometalates under mild conditions , 2003 .

[87]  Fuwei Li,et al.  A novel and effective Ni complex catalyst system for the coupling reactions of carbon dioxide and epoxides. , 2003, Chemical communications.

[88]  J. Valle,et al.  Supercritical CO2 Extraction of Oilseeds: Review of Kinetic and Equilibrium Models , 2006, Critical reviews in food science and nutrition.

[89]  M. Arai,et al.  Synthesis of cyclic ureas and urethanes from alkylene diamines and amino alcohols with pressurized carbon dioxide in the absence of catalysts , 2003 .

[90]  K. Troev,et al.  Calcium chloride as co-catalyst of onium halides in the cycloaddition of carbon dioxide to oxiranes , 2003 .

[91]  P. Debenedetti.  Supercritical fluids : fundamentals and applications , 1994 .

[92]  N. Isaacs,et al.  High pressure routes to dimethyl carbonate from supercritical carbon dioxide , 1999 .

[93]  Yoshihisa Watanabe,et al.  Ruthenium catalyzed selective synthesis of enol carbamates by fixation of carbon dioxide , 1987 .

[94]  B. Bhanage,et al.  N-Arylation of aliphatic, aromatic and heteroaromatic amines catalyzed by copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate) , 2007 .

[95]  F. Rivetti,et al.  Dimethylcarbonate and Its Production Technology , 1996 .

[96]  C. Bruneau,et al.  Catalytic synthesis of vinyl carbamates from carbon dioxide and alkynes with ruthenium complexes , 1989 .

[97]  Y. Inoue,et al.  CATALYTIC FIXATION OF CARBON DIOXIDE TO FORMIC ACID BY TRANSITION-METAL COMPLEXES UNDER MILD CONDITIONS , 1976 .

[98]  M. Jacobs,et al.  Anti-anaerobic activity of AZD2563, a new oxazolidinone, compared with eight other agents. , 2002, The Journal of antimicrobial chemotherapy.

[99]  R. J. Kuhr,et al.  Carbamate insecticides: chemistry, biochemistry, and toxicology. , 1976 .

[100]  Robert J. Davis,et al.  Cycloaddition of CO2 to epoxides over solid base catalysts , 2001 .

[101]  Kazufumi Takahashi,et al.  Carboxylation of alkali metal phenoxide with carbon dioxide at terrestrial temperature , 2000 .

[102]  M. Tojo,et al.  A novel non-phosgene polycarbonate production process using by-product CO2 as starting materialPresented at The First International Conference on Green & Sustainable Chemistry, Tokyo, Japan, March 13?15, 2003. , 2003 .

[103]  M. Arai,et al.  Synthesis of N,N'-Disubstituted Urea from Ethylene Carbonate and Amine Using CaO , 2004 .

[104]  R. Srivastava,et al.  Synthesis of Polycarbonate Precursors over Titanosilicate Molecular Sieves , 2003 .

[105]  K. Nicholas,et al.  Palladium-Catalyzed Carboxylation of Allyl Stannanes , 1997 .

[106]  M. Arai,et al.  Synthesis of dimethyl carbonate from carbon dioxide and methanol in the presence of methyl iodide and base catalysts under mild conditions: effect of reaction conditions and reaction mechanism , 2001 .

[107]  Jiajian Peng,et al.  Alternatives to phosgene and carbon monoxide: synthesis of symmetric urea derivatives with carbon dioxide in ionic liquids. , 2003, Angewandte Chemie.

[108]  Noboru Yamazaki,et al.  Carbonylation of amines with carbon dioxide under atmospheric conditions , 1974 .

[109]  Jiajian Peng,et al.  Cycloaddition of carbon dioxide to propylene oxide catalyzed by ionic liquids , 2001 .

[110]  K. Tomishige,et al.  Promoting effect of phosphoric acid on zirconia catalysts in selective synthesis of dimethyl carbonate from methanol and carbon dioxide , 2000 .

[111]  Jacob A. Moulijn,et al.  Mitigation of CO2 by Chemical Conversion: Plausible Chemical Reactions and Promising Products , 1996 .

[112]  Dae-Won Park,et al.  Comparative studies on the performance of immobilized quaternary ammonium salt catalysts for the addition of carbon dioxide to glycidyl methacrylate , 2004 .

[113]  T. Sakakura,et al.  Cyclic carbonate synthesis from supercritical carbon dioxide and epoxide over lanthanide oxychloride , 2002 .

[114]  B. Bhanage,et al.  Synthesis of cyclic carbonates from carbon dioxide and epoxides using alkali metal halide supported liquid phase catalyst , 2006 .

[115]  H. Ringsdorf,et al.  Preparation and Polymerization of S-, O-, and N-Vinyl Derivatives of Carbonic Acid.1Unsaturated Carbonic Acid Derivatives. II , 1962 .

[116]  H. Kim,et al.  Isolation of a Pyridinium Alkoxy Ion Bridged Dimeric Zinc Complex for the Coupling Reactions of CO2 and Epoxides , 2000 .

[117]  R A Mueller,et al.  Discovery of a novel class of potent HIV-1 protease inhibitors containing the (R)-(hydroxyethyl)urea isostere. , 1993, Journal of medicinal chemistry.

[118]  Takatoshi Ito,et al.  Synthesis of quinazolines using carbon dioxide (or carbon monoxide with sulfur) under mild conditions , 2000 .

[119]  E. Beckman.  Making Polymers from Carbon Dioxide , 1999, Science.

[120]  R. He,et al.  Synthesis of ethylene carbonate from supercritical carbon dioxide/ethylene oxide mixture in the presence of bifunctional catalyst , 2002 .

[121]  Jacqueline Seyden-Penne,et al.  Chiral Auxiliaries and Ligands in Asymmetric Synthesis , 1995 .

[122]  A. Behr,et al.  Telomerization of Carbon Dioxide and 1,3‐Butadiene: Process Development in a Miniplant , 2000 .

[123]  K. Kunimori,et al.  Catalytic and direct synthesis of dimethyl carbonate starting from carbon dioxide using CeO2-ZrO2 solid solution heterogeneous catalyst: effect of H2O removal from the reaction system , 2002 .

[124]  R. Maggi,et al.  Cycloaddition of CO2 to epoxides over both homogeneous and silica-supported guanidine catalysts , 2003 .

[125]  P. Dixneuf,et al.  A novel catlytic synthesis of vinyl carboamtes from carbon dioxide, diethylamine, and alkynes in the presence of Ru3(CO)12 , 1986 .

[126]  M. Arai,et al.  One-pot synthesis of styrene carbonate from styrene in tetrabutylammonium bromide , 2004 .

[127]  S. Fujita,et al.  二酸化炭素の化学的固定化 : 二酸化炭素からのカーボネート, 環状ウレアおよび環状ウレタン化合物の合成 , 2005 .

[128]  H. Vorbrüggen,et al.  The introduction of nitrile-groups into heterocycles and conversion of carboxylic groups into their corresponding nitriles with chlorosulfonylisocyanate and triethylamine , 1994 .

[129]  Ryoji Noyori,et al.  Homogeneous Hydrogenation of Carbon Dioxide , 1995 .

[130]  P. Jessop,et al.  Homogeneous Catalysis in Supercritical Fluids , 1995, Science.

[131]  Qinghua Zhang,et al.  From CO oxidation to CO2 activation: an unexpected catalytic activity of polymer-supported nanogold. , 2005, Journal of the American Chemical Society.

[132]  T. Sakakura,et al.  Synergistic hybrid catalyst for cyclic carbonate synthesis: remarkable acceleration caused by immobilization of homogeneous catalyst on silica. , 2006, Chemical communications.

[133]  D. Darensbourg,et al.  Catalysts for the reactions of epoxides and carbon dioxide , 1996 .

[134]  B. Bhanage,et al.  Cesium carbonate catalyzed efficient synthesis of quinazoline-2,4(1H,3H)-diones using carbon dioxide and 2-aminobenzonitriles , 2008 .

[135]  P. Dixneuf,et al.  Ruthenium-catalyzed synthesis of vinyl carbamates from carbon dioxide, acetylene, and secondary amines , 1987 .

[136]  M. Arai,et al.  Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides and methanol using heterogeneous Mg containing smectite catalysts: effect of reaction variables on activity and selectivity performance , 2003 .

[137]  A. Bell,et al.  An in Situ Infrared Study of Dimethyl Carbonate Synthesis from Carbon Dioxide and Methanol over Zirconia , 2001 .

[138]  Yuhan Sun,et al.  Cycloaddition between propylene oxide and CO2 over metal oxide supported KI , 1999 .

[139]  M. Shirai,et al.  Concurrent Synthesis of Dimethyl Carbonate and Ethylene Glycol via Transesterification of Ethylene Carbonate and Methanol Using Smectite Catalysts Containing Mg and/or Ni , 2002 .

[140]  A. Lapidus,et al.  Conversion of Primary Amines to N,N′-Disubstituted Ureas Using Montmorillonitebipyridinepalladium(II)-acetate and Di-Tert Butyl Peroxide , 1991 .

[141]  M. Nakaiwa,et al.  Reaction Rate of the Production of Dimethyl Carbonate Directly from the Supercritical CO2 and Methanol , 2005 .

[142]  J. Bart,et al.  Copper-Zinc Oxide-Alumina Methanol Catalysts Revisited , 1987 .

[143]  S. Murahashi,et al.  Palladium-catalysed cross double carbonylation of amines and alcohols: synthesis of oxamates , 1987 .

[144]  T. Yano,et al.  Magnesium oxide-catalysed reaction of carbon dioxide with anepoxide with retention of stereochemistry , 1997 .

[145]  Y. Ikushima,et al.  Chemical fixation of carbon dioxide to styrene carbonate under supercritical conditions with DMF in the absence of any additional catalysts , 2000 .

[146]  T. Baba,et al.  Catalytic Methoxycarbonylation of Aromatic Diamines with Dimethyl Carbonate to Their Dicarbamates Using Zinc Acetate , 2002 .

[147]  Juraj Kizlink,et al.  Preparation of Dimethyl Carbonate from Methanol and Carbon Dioxide in the Presence of Sn(IV) and Ti(IV) Alkoxides and Metal Acetates , 1995 .

[148]  F. Bigi,et al.  Selected syntheses of ureas through phosgenesubstitutes , 2000 .

[149]  Youquan Deng,et al.  First gold(I) complex-catalyzed oxidative carbonylation of amines for the syntheses of carbamates , 2001 .

[150]  A. Baiker,et al.  Solvent-free ruthenium-catalysed vinylcarbamate synthesis from phenylacetylene and diethylamine in ‘supercritical’ carbon dioxide , 2001 .

[151]  Yue Fu,et al.  Carbonylation of o-Phenylenediamine and o-Aminophenol with Dimethyl Carbonate Using Lead Compounds as Catalysts , 2001 .

[152]  R. Schnur,et al.  Selective N-dealkylation of tertiary amines with vinyl chloroformate: An improved synthesis of naloxone , 1977 .

[153]  Yoshiki Ikeda,et al.  A novel method of direct synthesis of dimethyl carbonate from methanol and carbon dioxide catalyzed by zirconia , 1999 .

[154]  R. Srivastava,et al.  Synthesis of Cyclic Carbonates from Olefins and CO2 over Zeolite-Based Catalysts , 2003 .

[155]  Yu-mei Shen,et al.  Chemical fixation of carbon dioxide catalyzed by binaphthyldiamino Zn, Cu, and Co salen-type complexes. , 2003, The Journal of organic chemistry.

[156]  X. Wang,et al.  A phosgene-free process for the synthesis of methyl N-phenyl carbamate by the reaction of aniline with methyl carbamate , 2004 .

[157]  C. Bruneau,et al.  RUTHENIUM-CATALYZED SYNTHESIS OF SYMMETRICAL N,N'-DIALKYLUREAS DIRECTLY FROM CARBON DIOXIDE AND AMINES , 1991 .

[158]  S. Boileau,et al.  Chemical modification of poly(vinyl chloroformate) and of its copolymers using phase transfer catalysis , 1983 .

[159]  B. Bhanage,et al.  Ruthenium tris(2,2,6,6-tetramethyl-3,5-heptanedionate) catalyzed synthesis of vinyl carbamates using carbon dioxide, amines and alkynes , 2008 .

[160]  T. Endo,et al.  Catalytic activity of various salts in the reaction of 2,3-epoxypropyl phenyl ether and carbon dioxide under atmospheric pressure , 1993 .

[161]  R. Nomura,et al.  Synthesis of cyclic carbonates from carbon dioxide and epoxides in the presence of organoantimony compounds as novel catalysts , 1980 .

[162]  N. Nagaraju,et al.  A new catalyst for the synthesis of N,N-biphenylurea from aniline and dimethyl carbonate , 2002 .

[163]  Liang‐Nian He,et al.  Organic solvent-free process for the synthesis of propylene carbonate from supercritical carbon dioxide and propylene oxide catalyzed by insoluble ion exchange resins , 2005 .

[164]  Peng Li,et al.  Highly Efficient Synthesis of Sterically Hindered Peptides Containing N-Methylated Amino Acid Residues using a Novel 1H-Benzimidazolium Salt , 2000 .

[165]  R. He,et al.  Syntheses of cyclic carbonates from carbon dioxide and epoxides with metal phthalocyanines as catalyst , 2000 .

[166]  Takanori Kobayashi,et al.  A Convenient Direct Synthesis of Ureas from Carbon Dioxide and Amines , 1978 .

[167]  B. Gabriele,et al.  Efficient synthesis of ureas by direct palladium-catalyzed oxidative carbonylation of amines. , 2004, The Journal of organic chemistry.

[168]  T. Tatsumi,et al.  Synthesis of dimethyl carbonate from ethylene carbonate and methanol using TS-1 as solid base catalyst , 1996 .

[169]  D. Vos,et al.  Synthesis of symmetrical or asymmetrical urea compounds from CO2via base catalysis , 2007 .

[170]  F. Molnár,et al.  On the formation of aliphatic polycarbonates from epoxides with chromium(III) and aluminum(III) metal-salen complexes. , 2005, Chemistry.

[171]  A. Nacci,et al.  Cyclic carbonate formation from carbon dioxide and oxiranes in tetrabutylammonium halides as solvents and catalysts. , 2002, Organic letters.

[172]  Fuwei Li,et al.  An easily recoverable and efficient natural biopolymer-supported zinc chloride catalyst system for the chemical fixation of carbon dioxide to cyclic carbonate , 2005 .

[173]  P. Seneci,et al.  Synthesis and antimicrobial activity of oxazolidin-2-ones and related heterocycles , 1994 .

[174]  W. Leitner,et al.  Hydrogenation of carbon dioxide to formic acid using water-soluble rhodium catalyststs , 1993 .

[175]  J. Kizlink,et al.  Preparation of Dimethyl Carbonate from Methanol and Carbon Dioxide in the Presence of Organotin Compounds , 1994 .

[176]  Martin Palmer,et al.  Applications for supercritical fluid technology in food processing , 1995 .

[177]  D. O'Hagan,et al.  A short synthesis of (S)-α-(diphenylmethyl)alkyl amines from amino acids , 1999 .

[178]  Hong Zhu,et al.  Synthesis of propylene carbonate and some dialkyl carbonates in the presence of bifunctional catalyst compositions , 1996 .

[179]  Eric J. Doskocil,et al.  UV−Vis Spectroscopy of Iodine Adsorbed on Alkali-Metal-Modified Zeolite Catalysts for Addition of Carbon Dioxide to Ethylene Oxide , 1999 .

[180]  C. Galli.  “CESIUM ION EFFECT” AND MACROCYCLIZATION. A CRITICAL REVIEW , 1992 .

[181]  Takatoshi Ito,et al.  Solvent-Free Synthesis of Urea Derivatives from Primary Amines and Sulfur under Carbon Monoxide and Oxygen at Atmospheric Pressure , 2007 .

[182]  Masahiko Arai,et al.  Synthesis of 1,3-dialkylurea from ethylene carbonate and amine using calcium oxide , 2005 .

[183]  A. Clifford.  Reactions in Supercritical Fluids , 1994 .

[184]  D. Chaturvedi,et al.  Versatile Use of Carbon Dioxide in the Synthesis of Carbamates , 2006 .

[185]  H. García,et al.  CO2 fixation using recoverable chromium salen catalysts: use of ionic liquids as cosolvent or high-surface-area silicates as supports , 2004 .

[186]  S. Nguyen,et al.  Chemical CO2 Fixation: Cr(III) Salen Complexes as Highly Efficient Catalysts for the Coupling of CO2 and Epoxides , 2001 .

[187]  T. Tatsumi,et al.  Hydrotalcite-type materials as catalysts for the synthesis of dimethyl carbonate from ethylene carbonate and methanol , 1998 .

[188]  J. C. Yarbrough,et al.  Mechanistic aspects of the copolymerization reaction of carbon dioxide and epoxides, using a chiral salen chromium chloride catalyst. , 2002, Journal of the American Chemical Society.

[189]  R. Srivastava,et al.  Transesterifications over titanosilicate molecular sieves , 2004 .