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.
[1] 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. http://dx.doi.org/10.1039/a706356c10.1039/a706356cSuche in Google Scholar
[2] 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. http://dx.doi.org/10.1016/j.jcat.2006.04.00310.1016/j.jcat.2006.04.003Suche in Google Scholar
[3] 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. http://dx.doi.org/10.1016/S0920-5861(00)00445-410.1016/S0920-5861(00)00445-4Suche in Google Scholar
[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. http://dx.doi.org/10.1016/0926-860X(95)00289-810.1016/0926-860X(95)00289-8Suche in Google Scholar
[5] 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. Suche in Google Scholar
[6] 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. http://dx.doi.org/10.1016/S0926-860X(97)00287-110.1016/S0926-860X(97)00287-1Suche in Google Scholar
[7] 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. http://dx.doi.org/10.1021/op030209810.1021/op0302098Suche in Google Scholar
[8] 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. http://dx.doi.org/10.1016/S0926-860X(00)00839-510.1016/S0926-860X(00)00839-5Suche in Google Scholar
[9] 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. http://dx.doi.org/10.1016/S0167-2991(08)61821-210.1016/S0167-2991(08)61821-2Suche in Google Scholar
[10] 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. Suche in Google Scholar
[11] 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. Suche in Google Scholar
[12] 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. http://dx.doi.org/10.1023/A:101504251098810.1023/A:1015042510988Suche in Google Scholar
[13] Lide, D. R. (1990). Handbook of chemistry and physics (71st ed.). Boca Raton, FL, USA: CRC Press. Suche in Google Scholar
[14] 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. http://dx.doi.org/10.1021/jo00073a04110.1021/jo00073a041Suche in Google Scholar
[15] 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. Suche in Google Scholar
[16] Ruest, L., Blouin, G., & Deslongchamps, P. A. (1976). Convenient synthesis of 2-carbomethoxycyclohexanone. Synthetic Communications, 6, 169–174. DOI: 10.1080/00397917608072627. http://dx.doi.org/10.1080/0039791760807262710.1080/00397917608072627Suche in Google Scholar
[17] Selva, M., Marques, C. A., & Tundo, P. (1993). The addition reaction of dialkyl carbonates to ketones. Gazzetta Chimica Italiana, 123, 515–518. Suche in Google Scholar
[18] 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. http://dx.doi.org/10.1021/jo026664410.1021/jo0266644Suche in Google Scholar
[19] 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. http://dx.doi.org/10.1016/j.molcata.2004.09.02510.1016/j.molcata.2004.09.025Suche in Google Scholar
[20] 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. http://dx.doi.org/10.1021/ie00091a00110.1021/ie00091a001Suche in Google Scholar
[21] Tundo, P., & Selva, M. (2002). The chemistry of dimethyl carbonate. Accounts of Chemical Research, 35, 706–716. DOI: 10.1021/ar010076f. http://dx.doi.org/10.1021/ar010076f10.1021/ar010076fSuche in Google Scholar
[22] 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. http://dx.doi.org/10.1021/ie00081a00210.1021/ie00081a002Suche in Google Scholar
[23] 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. http://dx.doi.org/10.1016/S0040-4039(00)01051-010.1016/S0040-4039(00)01051-0Suche in Google Scholar
[24] 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. http://dx.doi.org/10.1016/j.cattod.2007.10.04710.1016/j.cattod.2007.10.047Suche in Google Scholar
[25] 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. http://dx.doi.org/10.1016/j.molcata.2003.09.05010.1016/j.molcata.2003.09.050Suche in Google Scholar
© 2010 Institute of Chemistry, Slovak Academy of Sciences
Artikel in diesem Heft
- Chemical conjugation of biomacromolecules: A mini-review
- Talaromyces flavus and its metabolites
- Application of non-steroidal anti-inflammatory drugs for palladium determination
- A naked-eye, selective and sensitive chemosensor for fluoride ion
- Determination of catechin and epicatechin in the peel of apple varieties resistant and non-resistant to apple scab
- The use of sulfated tin oxide as solid superacid catalyst for heterogeneous transesterification of Jatropha curcas oil
- Effect of pH and washing on calcium and magnesium distribution between pulp and filtrate
- Influence of lead dioxide electrodes morphology on kinetics and current efficiency of oxygen-ozone evolution reactions
- Synthesis of methyl acetoacetate from acetone and dimethyl carbonate with alkali-promoted MgO catalysts
- Synthesis, crystal structure, and 1H NMR spectra of a chloride-bridged chain complex of dinuclear ruthenium(II,III) 3,4,5-tri(ethoxy-d 5)benzoate
- Modification of poly(vinyl alcohol) membrane via blending with poly(γ-benzyl l-glutamate)-block-poly(ethylene glycol) copolymer
- Oxidative polymerization of anilinium 5-sulfosalicylate with peroxydisulfate in water
- Morphological patterns of poly(N-isopropylacrylamide) derivatives synthesized with EGDMA, DEGDMA, and TEGDMA crosslinkers for application as thermosensitive drug carriers
- Influence of a Fe/activated carbon catalyst and reaction parameters on methane decomposition during the synthesis of carbon nanotubes
- Microwave assisted one pot synthesis of 7-substituted 2-(2-oxo-2H-chromen-3-yl)acetic acids as precursors of new anti-tumour compounds
- ZnO nanoparticles in the synthesis of AB ring core of camptothecin
- Novel benzopyranopyridine derivatives of 2-amino-3-formylchromone
- Polyethylene glycol-mediated synthesis of decahydroacridine-1,8-diones catalyzed by ceric ammonium nitrate
Artikel in diesem Heft
- Chemical conjugation of biomacromolecules: A mini-review
- Talaromyces flavus and its metabolites
- Application of non-steroidal anti-inflammatory drugs for palladium determination
- A naked-eye, selective and sensitive chemosensor for fluoride ion
- Determination of catechin and epicatechin in the peel of apple varieties resistant and non-resistant to apple scab
- The use of sulfated tin oxide as solid superacid catalyst for heterogeneous transesterification of Jatropha curcas oil
- Effect of pH and washing on calcium and magnesium distribution between pulp and filtrate
- Influence of lead dioxide electrodes morphology on kinetics and current efficiency of oxygen-ozone evolution reactions
- Synthesis of methyl acetoacetate from acetone and dimethyl carbonate with alkali-promoted MgO catalysts
- Synthesis, crystal structure, and 1H NMR spectra of a chloride-bridged chain complex of dinuclear ruthenium(II,III) 3,4,5-tri(ethoxy-d 5)benzoate
- Modification of poly(vinyl alcohol) membrane via blending with poly(γ-benzyl l-glutamate)-block-poly(ethylene glycol) copolymer
- Oxidative polymerization of anilinium 5-sulfosalicylate with peroxydisulfate in water
- Morphological patterns of poly(N-isopropylacrylamide) derivatives synthesized with EGDMA, DEGDMA, and TEGDMA crosslinkers for application as thermosensitive drug carriers
- Influence of a Fe/activated carbon catalyst and reaction parameters on methane decomposition during the synthesis of carbon nanotubes
- Microwave assisted one pot synthesis of 7-substituted 2-(2-oxo-2H-chromen-3-yl)acetic acids as precursors of new anti-tumour compounds
- ZnO nanoparticles in the synthesis of AB ring core of camptothecin
- Novel benzopyranopyridine derivatives of 2-amino-3-formylchromone
- Polyethylene glycol-mediated synthesis of decahydroacridine-1,8-diones catalyzed by ceric ammonium nitrate