Abstract
The synthesis of methyl acetoacetate (MAA) by methoxycarbonylation of acetone with dimethyl carbonate (DMC) was carried out in the presence of MgO and alkali-promoted MgO catalysts. From among Li, Na, K, and Cs, potassium was found to be the most effective promoter to improve the activity of MgO. The effect of K/MgO with variable content of K was also investigated, and the individual catalysts were characterised by the XRD, BET, SEM, CO2-TPD, and in situ CO2 IR techniques. The results showed that the addition of a small amount of K (1.97 mass %) could promote MAA formation, but a higher K loading caused a decrease in the yield of MAA, which might result from particle agglomeration and the presence of stable potassium carbonates. In situ FTIR experiments of co-adsorbed reactants indicated that the reaction probably proceeded via abstraction of Hα from acetone by base sites.
Similar content being viewed by others
References
Beutel, T. (1998). Spectroscopic and kinetic study of the alkylation of phenol with dimethyl carbonate over NaX zeolite. Journal of the Chemical Society, Faraday Transactions, 94, 985–993. DOI: 10.1039/a706356c.
Díez, V. K., Apesteguía, C. R., & Di Cosimo, J. I. (2006). Aldol condensation of citral with acetone on MgO and alkali-promoted MgO catalysts. Journal of Catalysis, 240, 235–244. DOI: 10.1016/j.jcat.2006.04.003.
Díez, V. K., Apesteguía, C. R., & Di Cosimo, J. I. (2000). Acid-base properties and active site requirements for elimination reactions on alkali-promoted MgO catalysts. Catalysis Today, 63, 53–62. DOI: 10.1016/S0920-5861(00)00445-4.
Di Cosimo, J. I., Díez, V. K., & Apesteguía, C. R. (1996). Base catalysis for the synthesis of α,β-unsaturated ketones from the vapor-phase aldol condensation of acetone. Applied Catalysis A: General, 137, 149–166. DOI: 10.1016/0926-860X(95)00289-8.
Fischer, R. (1995). Preparation of α,ω-dicarboxylic acid diesters. U.S. Patent No. 5453535. Washington, D.C., USA: U.S. Patent and Trademark Office.
Fu, Y., Baba, T., & Ono, Y. (1998). Vapor-phase reactions of catechol with dimethyl carbonate. Part I. O-Methylation of catechol over alumina. Applied Catalysis A: General, 166, 419–424. DOI: 10.1016/S0926-860X(97)00287-1.
Fuming, M., Zhi, P., & Guangxing, L. (2004). The transesterification of dimethyl carbonate with phenol over Mg-Al-hydrotalcite catalyst. Organic Process Research & Development, 8, 372–375. DOI: 10.1021/op0302098.
Jyothi, T. M., Raja, T., Talawar, M. B., & Rao, B. S. (2001). Selective O-methylation of catechol using dimethyl carbonate over calcined Mg-Al hydrotalcites. Applied Catalysis A: General, 211, 41–46. DOI: 10.1016/S0926-860X(00)00839-5.
Kanno, T., & Kobayashi, M. (1994) Evaluation of basicity of alkali metal-doped MgO in the scope of change of carbonate species. In H. Hattori, M. Misono, & Y. Ono (Eds.), Acid-base catalysis II: Proceedings of the international symposium on acid-base catalysis II, Sapporo, December 2–4, 1993 (pp. 207–216). Tokyo, Japan: Kodansha.
Koehler, G., & Metz, J. (1998). Process for preparing diesters of higher α,ω-dicarboxylic acids. U.S. Patent No. 5786502. Washington, D.C., USA: U.S. Patent and Trademark Office.
Köhler, G. (1995). Process for the preparation of pimelic esters. U.S. Patent No. 5436365. Washington, D.C., USA: U.S. Patent and Trademark Office.
Lapidus, A. L., Eliseev, O. L., Bondarenko, T. N., Sizan, O. E., & Ostapenko, A. G. (2001). Carbonylation of chloroacetone to methyl acetoacetate. Russian Chemical Bulletin, 50, 2239–2241. DOI: 10.1023/A:1015042510988.
Lide, D. R. (1990). Handbook of chemistry and physics (71st ed.). Boca Raton, FL, USA: CRC Press.
Marques, C. A., Selva, M., Tundo, P., & Montanari, F. (1993). Reaction of oximes with dimethyl carbonate: a new entry to 3-methyl-4,5-disubstituted-4-oxazolin-2-ones. Journal of Organic Chemistry, 58, 5765–5770. DOI: 10.1021/jo00073a041.
Pohl, F. J., & Schmidt, W. (1944). Process of preparing acetoacetic esters. U.S. Patent No. 2351366. Washington, D.C., USA: U.S. Patent and Trademark Office.
Ruest, L., Blouin, G., & Deslongchamps, P. A. (1976). Convenient synthesis of 2-carbomethoxycyclohexanone. Synthetic Communications, 6, 169–174. DOI: 10.1080/00397917608072627.
Selva, M., Marques, C. A., & Tundo, P. (1993). The addition reaction of dialkyl carbonates to ketones. Gazzetta Chimica Italiana, 123, 515–518.
Shieh, W.-C., Dell, S., Bach, A., Repi., O., & Blacklock, T. J. (2003). Dual nucleophilic catalysis with DABCO for the N-methylation of indoles. Journal of Organic Chemistry, 68, 1954–1957. DOI: 10.1021/jo0266644.
Shivarkar, A. B., Gupte, S. P., & Chaudhari, R. V. (2005). Selective synthesis of N,N-dimethyl aniline derivatives using dimethyl carbonate as a methylating agent and onium salt as a catalyst. Journal of Molecular Catalysis A: Chemical, 226, 49–56. DOI: 10.1016/j.molcata.2004.09.025.
Tundo, P., Moraglio, G., & Trotta, F. (1989). Gas-liquid phase-transfer catalysis: a new continuous-flow method in organic synthesis. Industrial & Engineering Chemistry Research, 28, 881–890. DOI: 10.1021/ie00091a001.
Tundo, P., & Selva, M. (2002). The chemistry of dimethyl carbonate. Accounts of Chemical Research, 35, 706–716. DOI: 10.1021/ar010076f.
Tundo, P., Trotta, F., Moraglio, G., & Ligorati, F. (1988). Continuous-flow processes under gas.liquid phase-transfer catalysis (GL-PTC) conditions: the reaction of dialkyl carbonates with phenols, alcohols, and mercaptans. Industrial & Engineering Chemistry Research, 27, 1565–1571. DOI: 10.1021/ie00081a002.
Vauthey, I., Valot, F., Gozzi, C., Fache, F., & Lemaire, M. (2000). An environmentally benign access to carbamates and ureas. Tetrahedron Letters, 41, 6347–6350. DOI: 10.1016/S0040-4039(00)01051-0.
Wu, D., Fu, X., Li, J., Zhao, N., Wei, W., & Sun, Y. (2008). A novel route for the synthesis of methyl acetoacetate from dimethyl carbonate and acetone over solid base. Catalysis Today, 131, 372–377. DOI: 10.1016/j.cattod.2007.10.047.
Yadav, G. D., & Lathi, P. S. (2004). Synergism between microwave and enzyme catalysis in intensification of reactions and selectivities: transesterification of methyl acetoacetate with alcohols. Journal of Molecular Catalalysis A: Chemical, 223, 51–56. DOI: 10.1016/j.molcata.2003.09.050.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wu, D., Chen, Z. Synthesis of methyl acetoacetate from acetone and dimethyl carbonate with alkali-promoted MgO catalysts. Chem. Pap. 64, 758–766 (2010). https://doi.org/10.2478/s11696-010-0068-9
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.2478/s11696-010-0068-9