Catalytic Oxidation of Ethylene in Solutions of Palladium(II) Cationic Complexes in Binary and Ternary Aqueous Organic Solvents1
I. V. Oshaninaa, *, A. V. Podtyaginab, U. V. Pestunovaa, I. N. Rusnaka, and O. N. Temkina
a Russian Technological University (Lomonosov Institute of Fine Chemical Technologies, MIREA), Moscow, 119571 Russia
b DNA-Technology, Moscow, 117587 Russia
Correspondence to: *e-mail: oshanina.irina@gmail.com
1Abbreviations and notation: CH, cyclohexene; DMF, dimethylformamide; AN, acetonitrile; NMP, N-methylpyrrolidone; DMSO, dimethyl sulfoxide; DMA, dimethyl acetamide; ADN, adipodinitrile; PhCH2CN, benzyl cyanide; AAc, acetic acid; t‑BuOH, tert-butanol; BQ, p-benzoquinone; CH-one, cyclohexanone; TSA, toluene sulfoacid: НХ, HClO4 or TSA; GLC, gas liquid chromatography; GAC, gas adsorption chromatography.
Received 14 May, 2021
Abstract—The effect of organic solvents on the rate of ethylene oxidation with p-benzoquinone to acetaldehyde in aqueous organic solutions of palladium cationic complexes has been studied. It was found that the reaction rate increased when the acceptor number of the solvent increased and the donor number decreased. The oxidation of ethylene and cyclohexene in binary (N-methylpyrrolidone–H2O) and ternary (acetonitrile–N-methylpyrrolidone–H2O) solvents was studied in more detail. In contrast to the acetonitrile–Н2О system, in the N-methylpyrrolidone–Н2О binary solvent hydrogen peroxide oxidizes ethylene to acetaldehyde in the presence of Pd(II) cationic complexes. The use of a solvent N-methylpyrrolidone acceptable for cyclohexene (CH) oxidation technology leads to a decrease in the rate and selectivity of cyclohexanone synthesis.
Keywords: ethylene, cyclohexene, oxidation, acetonitrile, N-methylpyrrolidone, p-benzoquinone, hydrogen peroxide, cationic palladium complexes
DOI: 10.1134/S0023158421060148