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The influence of composition of binary solvent CH3CN-H2O on the kinetics of oxidation of cyclohexene by p-BENZOQUINONES in solutions of cationic palladium(II) complexes

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Abstract

During the study of cyclohexene oxidation by p-benzoquinones into cyclohexanone in water-organic solutions of cationic complexes of palladium(II) it was demonstrated that the initial reaction rate R0 depends complicatedly on water molar fraction for three studied solvents: acetonitrile (AN), dimethylformamide, and dimethylsulfoxide. In order to explain the obtained bimodal dependence for the example of AN-water system, modeling of phase equilibrium in the studied system was performed. The existence of two- and three-phase immiscibility areas as well as a three-component heteroazeotrope was found. By UV spectroscopy it was stated that varying of water molar fraction in the binary solvent substantially changes the state of starting cationic complexes [Pd(АН)x(H2O)4-x]2+. For mathematical description of medium effect on R0 value three models were proposed taking into account different factors, such as: a) physico-chemical properties of binary solvent; b) composition of possible associates AN-water; c) composition of starting [Pd(АН)x(H2O)4-x]2+ complexes. The adequate description of bimodal dependency was obtained in the model considering the changes of [Pd(АН)x(H2O)4-x]2+ complexes composition with simultaneous presence of an associate of (АН)2(H2O) composition.

About the Authors

D. S. Zakharova
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


A. N. Semenyako
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


O. A. Chertkova
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


A. V. Frolkova
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


E. A. Katsman
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


L. G. Bruk
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


O. N. Temkin
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


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For citation:


Zakharova D.S., Semenyako A.N., Chertkova O.A., Frolkova A.V., Katsman E.A., Bruk L.G., Temkin O.N. The influence of composition of binary solvent CH3CN-H2O on the kinetics of oxidation of cyclohexene by p-BENZOQUINONES in solutions of cationic palladium(II) complexes. Fine Chemical Technologies. 2015;10(3):77-84. (In Russ.)

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