Abstract
Carbon dioxide, one of the major man-made greenhouse gas, is a renewable resource of carbon which can be viewed as a C1 synthon to build valuable chemicals. The development of new applications is of major interest considering CO2 conversion and environmentally friendly reactions. As chemical catalysis offers interesting options, we are studying the molecular design of catalysts for the formation of dialkyl carbonates from alcohols and CO2. This paper reports results on the mechanistic approach for dialkyl carbonate formation with alkoxybutyl tin(IV) compounds. The insertion of CO2 into Sn-OR bonds (R = Me, 1Pr) occurs at atmospheric pressure and room temperature leading to alkylcarbonato tin fragments, Sn-OCO2R. For dialkoxy derivatives, only one Sn-OR bond reacts with CO2 due to a dimerization pathway. Preliminary DFT calculations confirm that the dimer is more stable than the corresponding monocarbonated and dicarbonated monomers. Under catalytic conditions, n-Bu2Sn(OMe)2 gives dimethyl carbonate (selectivity = 100%). Pressure and temperature effects as well as reaction time were studied. The best yield in dimethyl carbonate is obtained under supercritical CO2 conditions (200 bar, 145 °C). The carbonated distannoxane, (n-Bu2SnOMe)(n-Bu2Sn(OCO2Me)O, has ben identified as an intermediate. The relevance of this species for dimethyl carbonate synthesis is discussed.
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REFERENCES AND NOTES
Armor J.N. Appl Catal A: General 1999; 189:153-162.
Phosgene use is expanding for pharmaceutical intermediate production thanks to new selective cleaner processes: Senet J.-P. CR Acad Sci Paris, Série IIC, Chimie/ Chemistry 2000;3:505-516.
Romano U., Tesei R., Mauri M.M., Rebora P. Ind Eng Chem Prod Res Dev 1980; 19:396-403.
Rivetti F. CR Acad Sci Paris, Série IIC, Chimie/Chemistry 2000; 3:497-503.
Uchiumi S., Ataka K., Matsuzaki T. J Organomet Chem 1999; 576:279-89.
Atom utilization is expressed in % by dividing the molecular weight of the desired product by the sum of the molecular weights of all substances produced in the stoichiometric equation: Sheldon R.A. CHEMTECH 1994; 24:38-47.
Rivetti F., Romano U., Delledonne D. “In Green Chemistry” Anastas P.T. , Williamson T.C. Eds, ACS Symposium Series, 1996; 626:70-80.
Pacheco M. A., Marshall C. L. Energy & Fuels 1997; 11:2-29.
Knifton J.F., Duranleau R.G. J Mol Catal 1991; 67:389-99.
Suciu E.N., Kuhlmann B., Knudsen G.A., Michaelson R.C. J Organomet Chem 1998; 556:41-54.
Ryu J. Y. US Patent 5,902,894, 1999.
Chem. Abstr. 1999; 130:325482e.
Kizlink J., Pastucha I. Collect Czech Chem Commun 1994;59:2116-18.
Aresta M., Quaranta E. CHEMTECH 1997; 27:32-40.
Yamazaki N., Nakahama S. Ind Eng Chem Prod Res Dev 1979; 18:249-52.
Genz J., Heitz W. Ger DE 3 203 190, 1983; Chem. Abstr. 1983; 99:139320s.
Wagner A., Löffler W., Haas B. Ger DE 4,310,109, 1994; Chem Abstr 1995; 122:186964h.
Tomishige K., Sakaihori T., Ikeda Y., Fujimoto K. Catal Letters 1999; 58:225-29.
Zhong S.H., Wang J.H., Xiao X.F., Li H.S. Stud Surf Sci Catal 2000; 130:1565-70.
Ballivet-Tkatchenko D., Douteau O., Stutzmann, S. Organometallics, 2000; 19:4563-67.
Choi J-C, Sakakura T., Sako T. J Am Chem Soc 1999; 121:3793-94.
Davies A.G., Organotin Chemistry. VCH: Weinheim, 1997; p 145.
Primel O., Llauro M.-F., Pétiaud R., Micel A. J Organomet Chem 1998; 558:19-33.
Blunden S.J., Hill R., Ruddick J..R. J Organomet Chem 1984; 267:C5-C8.
Chermette H., Coord Chem Rev 1998; 699:178-80.
Chemical Synthesis Using Supercritical Fluids, Jessop P.G., Leitner W. Eds Wiley-VCH: Weinheim, 1999.
Davies A.G., Kleinschmidt D.C., Palan P.R., Vasishtha S.C. J Chem Soc (C) 1971; 3972-76.
Baerends E.J., Ellis, D.E., Ros P. Chem Phys 1973; 2:41-51.
te Velde G., Baerends E.J. J Comput Phys 1992; 99:84-98.26.
ADF 1999, Baerends E.J., Bérces A., Bo C., Boerrigter P.M., Cavallo L., Deng L., Dickson R.M., Ellis D.E., Fan L., Fischer T.H., Fonseca Guerra C., van Gisbergen S.J.A., Groeneveld J.A., Gritsenko O.V., Harris F.E., van den Hoek P., Jacobsen H., van Kessel G., Kootstra F., van Lenthe E., Osinga V.P., Philipsen P.H.T., Post D., Pye C.C., Ravenek W., Ros P., Schipper P.R.T., Schreckenbach G., Snijders J.G., Sola M., Swerhone D., te Velde G., Vernooijs P., Versluis L., Visser O., van Wezenbeek E., Wiesenekker G., Wolff S.K., Woo T.K., Ziegler T.
Perdew J. P. in Electronic Structure of Solids 91; Ziesche P., Eschrig H., Eds.; Academic Verlag: Berlin, 1991.
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Ballivet-Tkatchenko, D., Chermette, H., Jerphagnon, T. (2002). CO2 as a C1-Building Block for Dialkyl Carbonate Synthesis. In: Maroto-Valer, M.M., Song, C., Soong, Y. (eds) Environmental Challenges and Greenhouse Gas Control for Fossil Fuel Utilization in the 21st Century. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-0773-4_26
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DOI: https://doi.org/10.1007/978-1-4615-0773-4_26
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