A series of dialkyl and methyl alkyl carbonates has been synthesized and their reactivity investigated. The behavior of preferential leaving and entering groups for the newly synthesized carbonates has been accurately investigated. Both experimental and computational studies agreed that the scale of leaving groups follows the trend: PhCH2O–, MeO– ≥ EtO–, CH3(CH2)2O–, CH3(CH2)7O– > (CH3)2CHO– > (CH3)3CO–. Accordingly, the scale of the entering group has the same trend, with t-butoxide being the worst entering group. A preliminary attempt to rationalize the nucleofugality trends, limited to the (CH3)3CO– and CH3O– groups, has indicated that a likely origin of the observed trends lies in the different entropic contributions and solvation effects.
Conference
International Conference on Green Chemistry (ICGC-2), IUPAC International Conference on Green Chemistry, ICGC, Green Chemistry , 2nd, Moscow, Russia, 2008-09-14–2008-09-20
References
1 U. Romano, F. Rivetti, N. Di Muzio. U.S. patent 4318862, issued 9 March 1982, Anic SpA.Search in Google Scholar
2 Some industrial patents which involve the use of DMC are.Search in Google Scholar
2a X. Wu, Y. J. Park, K. S. Ryu, S. H. Chang, Y. Hong. U.S. Patent 20040105809, filed 25 August 2003, issued 3 June 2004.Search in Google Scholar
2b J. T. Carey, J. Thomas, H. Oumar-mahamat. U.S. Patent 5962379, filed 5 Oct. 1998, issued 5 Oct. 1999.Search in Google Scholar
2c R. H. Schlosberg, T. Larson, A. I. Yezrielev, Albert Ilya, G. Knudsen. U.S. Patent 6818049, publication filed 16 Nov. 2004, issued 10 Nov. 2000.Search in Google Scholar
2d L. Goldberg, M. Le Flohic, Marc. U.S. Patent 5346615, filed 12 Dec. 2000, issued 5 August 2003.Search in Google Scholar
3a 10.1021/cr950067i, A.-A. G. Shaik, S. Sivaram. Chem. Rev.96, 951 (1996).Search in Google Scholar
3b 10.1021/ar010076f, P. Tundo, M. Selva. Acc. Chem. Res.35, 706 (2002).Search in Google Scholar
3c 10.1021/jo701818d, A. E. Rosamilia, F. Arico, P. Tundo. J. Org. Chem.73, 1559 (2008).Search in Google Scholar
3d 10.1021/jp804814e, A. E. Rosamilia, F. Arico?, P. Tundo. J. Phys. Chem. B112, 14525 (2008).Search in Google Scholar
4 K. Nisihra, K. Mizutare, S. Tanaka. Process for Preparing Diester of Carbonic Acid, EP Patent appl. 425 197 (UBE Industries, Japan).Search in Google Scholar
5 F. Rivetti, U. Romano, D. Delledonne. “Dimethylcarbonate and its production technology”, in Green Chemistry: Designing Chemistry for the Environment, ACS Symposium Series No. 626, P. T. Anastas, T. C. Williamson (Eds.), pp. 70–80, American Chemical Society, Washington, DC (1996).Search in Google Scholar
6a P. Tundo. In Continuous Flow Methods in Organic Synthesis, Horwood, Chichester (1991).Search in Google Scholar
6b P. Tundo, A. Perosa, F. Zecchini. In Methods and Reagents for Green Chemistry: An Introduction, pp. 77–103, Wiley-Interscience, New York (2007).Search in Google Scholar
7a 10.1021/jo026057g, M. Selva, P. Tundo, A. Perosa, S. Memoli. J. Org. Chem.67, 1071 (2002).Search in Google Scholar
7b 10.1351/pac200779111855, M. Selva. Pure Appl. Chem.79, 1855 (2007).Search in Google Scholar
8a 10.1021/je034134e, M. S. Ding. J. Chem. Eng. Data49, 276 (2004).Search in Google Scholar
8b J. E. Plichta, M. S. Sleve. U.S. Patent 4292312, filed 6 July 1988, issued 2 Jan. 1990.Search in Google Scholar
8c 10.1039/b400175c, D. Rousse, C. George. Phys Chem. Chem. Phys.6, 3408 (2004).Search in Google Scholar
9a S. Kuze, Shigeki, R. Okumura, Y. Suwabe. U.S. Patent 5349042, filed 16 March 1993, issued 20 Sept. 1994, Idemitsu Petrochemical Co., Ltd. (Tokyo, JP).Search in Google Scholar
9b 10.1016/0040-4020(95)00424-7, M. Aresta, C. Berloco, E. Quaranta. Tetrahedron51, 8073 (1995).Search in Google Scholar
9c 10.1021/ma00020a030, A. I. Schneider, J. Blackwell, H. Pielartzik, A. Karbach. Macromolecules24, 5676 (1991).Search in Google Scholar
9d 10.1021/ie0702882, C. M. Comisar, S. E. Hunter, A. Walton, P. E. Savage. Ind. Eng. Chem. Res.47, 577 (2008).Search in Google Scholar
9e 10.1021/ma00080a033, H. Shah, I. B. Rufus, C. E. Hoyle. Macromolecules27, 553 (1994).Search in Google Scholar
9f 10.1021/jo00037a050, J. Stratton, B. Gatlin, K. S. Venkatasubban. J. Org. Chem.57, 3237 (1992).Search in Google Scholar
10a 10.1002/asia.200600199, M. Matsuzawa, H. Kakeya, J. Yamaguchi, M. Shoji, R. Onose, H. Osada, Y. Hayashi. Chem. Asian J.1, 845 (2006).Search in Google Scholar PubMed
10b A. Greco, G. Bertolini. U.S. Patent 4518766, filed 2 March 1984, issued 21 May 1985, Enichimica Secondaria, S.p.A.Search in Google Scholar
10c A. Greco. U.S. Patent 5219979, filed 10 Feb 1992, issued 15 June 1993, Enichimica Secondaria, S.p.A.Search in Google Scholar
11a 10.1021/ja00763a033, M. S. Newman, R. A. Markle. J. Am. Chem. Soc.94, 2733 (1972).Search in Google Scholar
11b 10.1021/je00028a012, C. S. Hong, R. Wakslak, H. Finston, V. Fried. J. Chem. Eng. Data27, 146 (1982).Search in Google Scholar
11c 10.1021/ma00046a040, R. F. Storey, D. C. Hoffman. Macromolecules25, 5369 (1992).Search in Google Scholar
11d K. Mieczysław, K. Dorota. J. Appl. Polym. Sci.80, 1776 (2001).Search in Google Scholar
11e 10.1295/polymj.32.280, H. Shirahama, A. Kanetani, H. Yasudah. Polym. J.32, 280 (2000).Search in Google Scholar
11f H. K. Chung. U.S. Patent 6686096, filed 4 August 2000, issued 3 Feb. 2004, New Billion Investments Limited (HK).Search in Google Scholar
12a 10.1103/PhysRevA.38.3098, A. D. Becke. Phys. Rev. A38, 3098 (1988).Search in Google Scholar
12b A. D. Becke. The Challenge of d- and f-Electrons: Theory and Computation, ACS Symposium Series No. 394, p. 165, American Chemical Society, Washington, DC (1989).Search in Google Scholar
12c 10.1063/1.464913, A. D. Becke. J. Chem. Phys.98, 5648 (1993).Search in Google Scholar
12d 10.1103/PhysRevB.37.785, C. Lee, W. Yang, R. G. Parr. Phys. Rev. B37, 785 (1988).Search in Google Scholar
13a 10.1063/1.1677527, W. J. Hehre, R. Ditchfield, J. A. Pople. J. Chem. Phys.56, 2257 (1972).Search in Google Scholar
13b 10.1007/BF00533485, P. C. Hariharan, J. A. Pople. Theor. Chim. Acta28, 213 (1973).Search in Google Scholar
13c 10.1002/jcc.540040303, T. Clark, J. Chandrasekhar, P. v. R. Schleyer. J. Comput. Chem.4, 294 (1983).Search in Google Scholar
13d 10.1063/1.447079, M. J. Frisch, J. A. Pople, J. S. Binkley. J. Chem. Phys.80, 3265 (1984).Search in Google Scholar
14a 10.1063/1.474659, M. T. Cancès, B. Mennucci, J. Tomasi. J. Chem. Phys.107, 3032 (1997).Search in Google Scholar
14b 10.1016/S0009-2614(98)00106-7, M. Cossi, V. Barone, B. Mennucci, J. Tomasi. Chem. Phys. Lett.286, 253 (1998).Search in Google Scholar
14c 10.1063/1.473558, B. Mennucci, J. Tomasi. J. Chem. Phys.106, 5151 (1997).Search in Google Scholar
14d 10.1021/jp971959k, B. Mennucci, E. Cancès, J. Tomasi. J. Phys. Chem. B101, 10506 (1997).Search in Google Scholar
14e 10.1016/S0166-1280(98)00553-3, J. Tomasi, B. Mennucci, E. Cancès. J. Mol. Struct. (Theochem)464, 211 (1999).Search in Google Scholar
15a 10.1016/0166-1280(88)80248-3, J. E. Carpenter, F. Weinhold. J. Mol. Struct. (Theochem)169, 41 (1988).Search in Google Scholar
15b 10.1021/cr00088a005, A. E. Reed, L. A. Curtiss, F. Weinhold. Chem. Rev.88, 899 (1988).Search in Google Scholar
16 Gaussian 03, Revision B.05, M. J. Frisch, G. W. Trucks et al., Gaussian, Inc., Wallingford, CT (2004).Search in Google Scholar
17 10.1021/ar50138a002, C. J. M. Stirling. Acc. Chem. Res.12, 198 (1979).Search in Google Scholar
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