RAC-2005

P. B20

5-9 September 2005

Influence of p-Benzoquinone on Methanol Oxidative Carbonylation Process to Dimethyloxalate

O. N. Temkin, S. N. Gorodsky*, O. N. Kozakova, Wu Hong Shon, L.G. Bruk, Lomonosov State Academy of Fine Chemical Technology 86, prospect Vernadskogo, 119571, Moscow, Russian Federation
Introduction The problem of electrons transfer mechanism to an oxidant in homogeneous catalysis by palladium complexes is an all-important question in the theory and practice of homogeneous oxidation processes. Special interest in this area cause reactions with quinones participation as oxidants due to variety of quinone functions in these processes 1. Except for an oxidant role, quinones can act as ligands and catalysts, changing a direction of catalytic reaction. Results and Discussion Earlier it was be showed 2, 3, that in solutions of Pd (II) and Pd (I) complexes at presence of p-benzoquinones (Q) as oxidant the direction of methanol oxidative carbonylation changed - instead of dimetylcarbonate (DMC) it is formed dimetyloxalate (DMO). For the verification of the proposed mechanism of reaction (Figure 1.) we studied dependences of DMO synthesis reaction rate from [Q] in the system PdCl2 - LiCl - PhCOONa - PhCOOH Q - MeOH at 200 in the closed reactor 1, 2.

2CO + 2MeOH + Q (COOMe)2 + QH2

ClPd(COOMe) Q

MeOH

HPdCl (MeO)2CO

Q,H

Pd(II) + QH2

QClPd(COOMe) CO, MeOH

QPd(COOMe)2

2H+

Pd(II) + QH2 + (COOMe)2

Figure 1. The mechanism of methanol oxidative carbonylation reaction

During process an electric potentials difference (EPt), acidity of solution (pH) and volume of the consumed gas were measured. In the course of experiments the composition of liquid and gas phases - concentration Q, dimetyloxalate (DMO), CO, and 2 were determined. It has been shown, that reaction has the first order both on the catalyst, and on an oxidant. Influence of initial concentration components ratio in buffer solution (sodium benzoate benzoic acid) at their constant sum on process rate has been investigated. It was shown, that the maximal DMO formation speed (0,7 mmol/l*min) is reached at concentration sodium benzoate and benzoic acid equal 0,05 mol/l. At simultaneous concentration increase of both components DMO formation rate grows up to the concentration equal 0, 05 mol/l, and then stop to grow, remaining a constant. Base on the literary data and experimental dependences the DMO formation mechanism in investigated process is offered:
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RAC-2005
Pd(II) + CO + MeOH X1 + Q K2 X1Q k3 k4 QPd(COOMe)2 + H+ K1 X1 + H +

5-9 September 2005

(1) (2) (3) (4)

X1Q + CO + MeOH QPd(COOMe)2 + 2H+

QH2 + Pd(II)+ (COOMe)2

where X1 = ClPd (COOMe), and the stage (3) is rate limiting. The final equation of DMO formation rate looks like: K [Q] * [Pd] rDMO = [H+ ] + K1 * PCO* [MeOH] This equation satisfactory describes experimental data.

Conclusions In result it has been shown, that p-benzoquinone participates in intermediates transformation stages before the rate limiting stage. It changes the process direction, so instead of dimetylcarbonate dimetyloxalate with selectivity 82 - 85 % is formed. Acknowledgments Work is executed at financial support of the Russian Foundation for Basic Research (Projects 03-03-32489, 05-03-33151) and YUKOS Research and Development Centre. References: 1. O. N. Temkin, L. G. Bruk, Kinetic and Catalysis, 44, 2003 601. 2. L. N. Zir-Lebed, O. N. Temkin, et al., Kinetic and Catalysis, 25, 2, 1984 316. 3. L. N. Zir-Lebed, O. N. Temkin, et al., Kinetic and Catalysis, 25, 2, 1984 325.

* : Gorodsky@yandex.ru

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