Abstract
A non-petroleum approach for the catalytic synthesis of methyl acrylate via methoxycarbonylation of acetylene with carbon monoxide and methanol as nucleophilic reagent has been studied under various conditions. Pd(OAc)2/2-PyPPh2/p-tsa was found to be a highly efficient catalytic system. The types of phosphorus ligands and their concentration was a determinative factor for catalytic activity. Mono-dentate phosphorus ligand such as triphenylphosphine has no activity while 2-(diphenylphosphino)pyridine with a mixed N-P bidentate structure has an excellent activity. Catalytic performance of acids depends on their acidic strength and coordinative property. Among all acidic promoters, p-toluenesulfonic acid displayed an excellent performance. Other parameters such as solvent polarity and initial pressure of carbon monoxide have also important influences on the hydroesterification of acetylene. It is beneficial for the reaction that the solvents have a high polarity. At low pressure of carbon monoxide, to high active palladium catalyst, the reaction easily proceeded. However, at high pressure of carbon monoxide, acetylene will transfer from solution to gas phase, resulting in lower conversion of acetylene. In addition, due to steric hindrance of alcohols, methanol has a highest activity in hydroesterification of acetylene in low carbon alcohols. Under the optimal reaction conditions, 99.5% of acetylene conversion and 99.7% of selectivity toward methyl acrylate as well as 2,502 h−1 TOF were achieved.
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G. Strohlein, Y. Assuncao, N. Dube, A. Bardow, M. Mazzotti and M. Morbidelli, Chem. Eng. Sci., 61, 5296 (2006).
A. Brennfuhrer, H. Neumann and M. Beller, Chemcatchem, 1, 28 (2009).
S. Doherty, J. G. Knight and M. Betham, Chem. Commun., 88 (2006).
T. Takahashi, C. J. Xi, Y. Ura and K. Nakajima, J. Am. Chem. Soc., 122, 3228 (2000).
S. Jayasree, A. Seayad, S. P. Gupte and R.V. Chaudhari, Catal. Lett., 58, 213 (1999).
G. Kiss, Chem. Rev., 101, 3435 (2001).
S. Kunichika, Y. Sakakibara and T. Nakamura, B. Chem. Soc. Jpn., 41, 390 (1968).
Y. Sakakibara, B. Chem. Soc. Jpn., 37, 1601 (1964).
S. K. Bhattacharyya and A. K. Sen, Ind. Eng. Chem. Process Des. Dev., 3, 169 (1964).
S. K. Bhattach and D. P. Bhattach, J. Appl. Chem., 16, 202 (1966).
S.K. Bhattacharyya and A. K. Sen, J. Appl. Chem., 13, 498 (1963).
Y. Z. An, J.M. Qiu, D. H. Yang, D. H. He and Z. S. Wang, Nat. Gas. Chem. Ind., 16 (1991).
X.G. Yang, J. Q. Zhang and Z. T. Liu, Appl. Catal. A-Gen., 173, 11 (1998).
C.M. Tang, Y. Zeng, P. Cao, X.G. Yang and G.Y. Wang, Catal. Lett., 129, 189 (2009).
S. B. Atla, A. A. Kelkar and R. V. Chaudhari, J. Mol. Catal. AChem., 307, 134 (2009).
J. Takaya and N. Iwasawa, J. Am. Chem. Soc., 130, 15254 (2008).
B. K. Munoz, C. Godard, A. Marinetti, A. Ruiz, J. Benet-Buchholz and C. Claver, Dalton T., 5524 (2007).
G. Keglevich, T. Kegl, I. L. Odinets, N.M. Vinogradova and L. Kollar, CR. Chem., 7, 779 (2004).
J. Girones, J. Duran, A. Polo and J. Real, J. Mol. Catal. A-Chem., 198, 77 (2003).
F. De Angelis, A. Sgamellotti and N. Re, Organometallics, 19, 4104 (2000).
A. Seayad, A.A. Kelkar, R.V. Chaudhari and L. Toniolo, Ind. Eng. Chem. Res., 37, 2180 (1998).
K. Nozaki, M. L. Kantam, T. Horiuchi and H. Takaya, J. Mol. Catal. A-Chem., 118, 247 (1997).
Y. Kushino, K. Itoh, M. Miura and M. Nomura, J. Mol. Catal., 89, 151 (1994).
D. Zargarian and H. Alper, Organometallics, 12, 712 (1993).
K. Itoh, M. Miura and M. Nomura, Tetrahedron Lett., 33, 5369 (1992).
E. Drent, P. Arnoldy and P. H.M. Budzelaar, J. Organomet. Chem., 475, 57 (1994).
E. Drent, P. Arnoldy and P. H.M. Budzelaar, J. Organomet. Chem., 455, 247 (1993).
C. M. Tang, Y. Zeng, X.G. Yang, Y. C. Lei and G.Y. Wang, J. Mol. Catal. A-Chem., 314, 15 (2009).
K. J. Knifton, US 3904672 (1975).
A. Seayad, A. A. Kelkar, L. Toniolo and R.V. Chaudhari, J. Mol. Catal. A-Chem., 151, 47 (2000).
J. Liu, C. Jacob, K. J. Sheridan, F. Al-Mosule, B. T. Heaton, J. A. Iggo, M. Matthews, J. Pelletier, R. Whyman, J. F. Bickley and A. Steiner, Dalton T., 39, 7921 (2010).
L. Yan, Y. J. Ding, H. J. Zhu, J. M. Xiong, T. Wang, Z. D. Pan and L.W. Lin, J. Mol. Catal. A-Chem., 234, 1 (2005).
H. J. Zhu, Y. J. Ding, L. Yan, D. P. He, T. Wang, W. M. Chen, Y. Lv and L.W. Lin, Chinese J. Catal., 25, 653 (2004).
C. Larpent and H. Patin, Tetrahedron, 44, 6107 (1988).
B. R. Sarkar and R.V. Chaudhari, Catal. Surv. Asia, 9, 193 (2005).
A. Scrivanti, V. Beghetto, M. Zanato and U. Matteoli, J. Mol. Catal. A-Chem., 160, 331 (2000).
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Tang, CM., Li, XL. & Wang, GY. A highly efficient catalyst for direct synthesis of methyl acrylate via methoxycarbonylation of acetylene. Korean J. Chem. Eng. 29, 1700–1707 (2012). https://doi.org/10.1007/s11814-012-0073-5
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DOI: https://doi.org/10.1007/s11814-012-0073-5