p-toluenesulfonic acid monohydrate concentration effect on the cyclohexene methoxycarbonylation reaction

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Abstract

Taking into account the data on water binding to stable acetic acid hydrates, an interpretation of the dependence of the rate of the cyclohexene methoxycarbonylation reaction catalyzed by the system Pd(OAc)2 – PPh3 – p-toluenesulfonic acid monohydrate, depending on the last component concentration is proposed. This reaction mechanism scheme is supplemented by the reaction of formation of stable acetic acid hydrates AcOH×(H2O)n, where n =1–10. The effective rate constant of cyclohexene methoxycarbonylation has been estimated. It is con-cluded that the stable acetic acid hydrates formation in the presence of small water amounts in toluene medium is possible.

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About the authors

N. T. Sevostyanova

Tula State Lev Tolstoy Pedagogical University

Author for correspondence.
Email: sevostyanova.nt@gmail.com
Russian Federation, Tula

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Supplementary files

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2. Scheme (1)

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3. Fig. 1. Effect of TsOH H2O concentration on the initial rate of cyclohexene methoxycarbonylation catalyzed by the Pd(OAc)2 – PPh3 – TsOH H2O system at T = 378 K, PCO = 2.10 106 Pa; concentrations, mol/l: C0(C6H10) = 0.100, C0(CH3OH) = 0.450, C0(Pd(OAc)2) = 1.00 ∙ 10-3, C0(PPh3) = 8.00 ∙ 10-3. Points are experimental data; lines are data calculated using equation (19): 1 is the result of calculation using equation (19) for n = 1; 2 is the result of calculation using equation (19) for n = 6.

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4. Scheme 1

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5. Fig. 2. Effect of free H2O concentration on the initial rate of cyclohexene methoxycarbonylation catalyzed by the Pd(OAc)2 – PPh3 – TsOH H2O system at T = 378 K, PCO = 2.10 106 Pa; concentrations, mol/l: C0(C6H10) = 0.100, C0(CH3OH) = 0.450, C0(Pd(OAc)2) = 1.00 10-3, C0(PPh3) = 8.00 ∙ 10-3, C0(TsOH H2O) = 2.40 10-2.

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