Abstract
DMC is a versatile compound which represents an attractive ecofriendly alternative to both methyl halides (or dimethyl sulfate) and phosgene for methylation and carbonylation processes, respectively. DMC, produced nowadays by a clean process, possesses properties of no toxicity and biodegradability which makes it a true green reagent to be used in syntheses that prevent pollution at the source. The reactivity of DMC is tunable: at T ≤ 90°C, methoxycarbonylations take place, while at higher reaction temperatures, methylation reactions are observed with a variety of nucleophiles. Besides, DMC-mediated methylations are catalytic reactions which use safe solids (alkaline carbonates) avoiding the formation of undesirable inorganic salts as by-products. The high selectivity in methylation reactions is due to the ambident electrophilic character of DMC which reacts on its hard centre (the carbonyl group) with harder nucleophiles and on its soft one (the methyl group) with softer nucleophiles, according to the Hard-Soft Acid and Base (HSAB) theory.
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References
(a) P. Tundo, P. Anastas, D. StC. Black, J. Breen, T. Collins, S. Memoli, J. Miyamoto, M. Poliakoff, W. Tumas. Pure Appl. Chem. 72, 1207 (2000); (b) P. Tundo, A. Perosa, F. Zecchini in Methods and Reagents for Green Chemistry: An Introduction Wiley (2007).
R. A. Sheldon. Pure Appl. Chem. 72, 1233 (2000).
B. M. Trost. Science. 254, 1471 (1991).
P. T. Anastas and T. Williamson. In Green Chemistry: Designing Chemistry for the Environment, ACS Symposium Series 626, P. T. Anastas and T. Williamson (Eds.), pp. 1-17, American Chemical Society, Washington, DC (1996).
(a) U. Romano, F. Rivetti, N. Di Muzio. U.S. Patent 4,318,862,1981, C.A. 80141 (1979); (b) D. Delledonne, F. Rivetti, U. Romano. J. Organomet. Chem. 448, C15 (1995); (c) F. Rivetti, U. Romano, D. Delledonne. “Dimethylcarbonate and its production technology”, in Green Chemistry: Designing Chemistry for the Environment, ACS Symposium Series 626, P. T. Anastas and T. C. Williamson (Eds.), pp. 70-80, American Chemical Society, Washington, DC (1996).
Nisihra, K., Mizutare, K., Tanaka, S. Process for Preparing Diester of Carbonic Acid. EP Patent Appl. 425 197, (UBE Industries, Japan).
“The Merck Index,” 11th Ed., S. Budavari, Ed. (1989).
(a) P. Anastas, J. C. Warner, Green Chemistry: Theory and Practice; Oxford University Press: New York, p. 30 (1998).
(a) F. Rivetti, In Green Chemistry: Challenging Perspectives, P. Tundo, P. Anastas, Eds.; Oxford University Press: Oxford, p 201 (2000). (b) D. Delledonne, F. Rivetti, U. J. Romano, Organomet. Chem. 448, C15-C19 (1995). (c) U. Romano, F. Rivetti, N. Di Muzio, U.S. Patent 4,318,862 (1979). (d) P. Tundo, Continuous Flow Methods in Organic Synthesis, E. Horwood: Chichester, UK, p. 190 (1991).
Mizia, F.; Rivetti, F.; Romano, U. EP 0570071, 1993.
(a) P. Tundo, M. Selva, A. Bomben, Org. Synth. 76, 169 (1999); (b) P. Tundo, M. Selva, Acc. Chem. Res. 35, 706 (2002).
(a) P. Tundo, J. Org. Chem. 44, 2048 (1979); (b) P. Tundo, M. Selva, CHEMTECH 25, 31 (1995).
A. Bomben, M. Selva, P. Tundo, L. Valli, Ind. Eng. Chem. Res. 38, 2075 (1999).
P. Tundo, M. Selva, A. Perosa, S. Memoli, J. Org. Chem. 67, 1071 (2002).
R. G. Pearson, J. Am. Chem. Soc. 85, 3533 (1963).
R. G. Pearson, J. Songstad, J. Am. Chem. Soc. 89, 1827 (1967).
J. L. Gazquez, F. J. Mèndez, J. Phys. Chem. 98, 4049 (1994).
G. Klopman in Chemical Reactivity and Reaction Paths; Ed.; Wiley: New York, (1974).
G. Klopman, J. Am. Chem. Soc. 90, 223 (1968).
H. Tse-Lok, Chem. Rev. 75, 1, (1975).
(a) T. L. Gresham, J. E. Jansen, F. W. Shaver, J. T. Gregory, W. L. Beears, J. Am. Chem. Soc., 70, 1004 (1948); (b) T. L. Gresham, J. E. Jansen, F. W. Shaver, M. R. Frederick, F. T. Fiedorek, R. A. Bankert, J. T. Gregory, W. L. Beears, J. Am. Chem. Soc., 74, 1323 (1952); (c) T. L. Gresham, J. E. Jansen, F. W. Shaver, J. T. Gregory, J. Am. Chem. Soc., 70, 999 (1948); (d) T. L. Gresham, J. E. Jansen, F. W. Shaver, R. A. Bankert, J. Am. Chem. Soc., 71, 661 (1949).
R. S. Davidson, W. H. H. Gunther, S. M. Waddington-Feather, B. Lythgoe, J. Chem. Soc. 4907 (1964).
D. E. L. Carrington, K. Clarke, R. M. Scrowston, J. Chem. Soc. C, 3262 (1971).
A. C. Pierce, M. M. Joulliè, J. Org. Chem. 27, 3968 (1962).
(a) F. G. Bordwell, Organic Chemistry; Macmillan: New York, p. 218 (1963); (b) A. J. Parke, Adv. Phys. Org. Chem., 5, 173 (1967).
R. F. Hudson, G. Klopman, J. Chem. Soc., 5 (1964).
(a) M. Selva, C. A. Marques, P. Tundo, J. Chem. Soc., Perkin Trans. 1, 1323 (1994); (b) P. Loosen, P. Tundo, M. Selva, U.S. Patent 5, 278,533 (1994); (c) A. Bomben, C. A. Marques, M. Selva, P. Tundo, Tetrahedron, 51, 11573 (1995); (d) A. Bomben, M. Selva, P. Tundo, J. Chem. Res., Synop., 448 (1997); (e) P. Tundo, F. Trotta, G. Moraglio, Italian Pat. 20159A/90C, (1990).
J. F. Bunnett, G. T. Davis, J. Am. Chem. Soc., 82, 665 (1960).
W. P. Jencks, J. Carriuolo, J. Am. Chem. Soc., 82, 675 (1960).
(a) P. Anastas, D. Black, J. Breen, T. Collins, S. Memoli, J. Miyamoto, M. Polyakoff, W. Tumas, Pure Appl. Chem., 72 (7), 1207 (2000); (b) P. Tundo, L. Rossi, A. Loris, J. Org. Chem., 70(6), 2219 (2005); (c) P. Tundo, S. Bressanello, A. Loris, G. Sathicq, Pure Appl. Chem.,77 (10), 1719 (2005); (d) F. Trotta, P. Tundo, G. Moraglio, J. Org. Chem., 52 (7) 1300 (1987).
H. Buysch, H. Krimm, W. Richter, EP 483171 B1 (1981), to Bayer.
A. E.Gurgiolo, US 4,268,683, to DOW.
A. E.Gurgiolo, US 4,268,684, to DOW.
A. Bosetti, P. Cesti, F. Calderazzo US 5,698,731 (1997).
A. Bosetti, E. Cauchi, V. Carletti, P. Cesti, EP0881213 (1998).
P. Cesti, A. Bosetti,F. Mizia, M. Notari, M. Ricci, F. Rivetti, U. Romano, US 6,992,214 B2 (2006), to DOW.
P. Tundo, F. Trotta, G. Moraglio, F. Logorati, Ind. Eng. Chem. Res., 27, 1565 (1988).
1-Octanol (9.3 mmol) was reacted in an autoclave with 40 mL of DMC (solvent and reactant) in the presence of 11 mmol of K2CO3, at 200°C.
J. N. Greenshields, U. S. Patent 4,770,871, (1988).
S. Rahmathullah, J. E. Hall, B. C. Bender, D. R. McCurdy, R. R. Tidwell, D. W. Boykin, J. Med. Chem., 42, 3994 (1999).
(a) J. Bergman, L. Venemalm, J. Org. Chem. 57, 2495-2497 (1992); (b) H. Heaney, S. V. Ley, Organic Syntheses, 54, 58 (1974).
W.-C. Shieh, S. Dell, A. Bach, O. Repic, T. J. Blacklock, J. Org. Chem., 68, 1954 (2003).
M. Selva, C. A. Marques, P. Tundo, Gazz. Chim. It., 123, 515 (1993).
A. E. Rosamilia, F. Arico, P. Tundo, J. Org. Chem., In Press (2008).
(a) W. N. Olmstead, Z. Margolin, F. G. Bordwell, J. Org. Chem., 45, 3295 (1980); Y. Zhao, F. G. Bordwell, J.-P. Cheng, D. Wang, J. Am. Chem. Soc., 119, 9125 (1997).
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Tundo, P., Aricò, F., Rosamilia, A.E., Grego, S., Rossi, L. (2008). Dimethyl Carbonate: Green Solvent and Ambident Reagent. In: Tundo, P., Esposito, V. (eds) Green Chemical Reactions. NATO Science for Peace and Security Series. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8457-7_10
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DOI: https://doi.org/10.1007/978-1-4020-8457-7_10
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