含窒素複素環化合物のアンモ酸化に関する研究(第6報)ピコリン類およびメチルジアジン類の気相アンモ酸化

概要

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Vapor-phase ammoxidation of 2-picoline, 3-picoline, 4-picoline, methylpyrazine, 2-methylpyrimidine, and 5-methylpyrimidine was studied over 1% Cr_2O_3-10% V_2O_5-pumice stone catalyst. Experiments were carried out in a flow reactor system at atmospheric pressure. By these reactions, nitriles were formed selectively and by-product formation was negligible. From kinetic analysis, experimental rate data were found to be well interpreted by the Langmuir-Hinshelwood mechanism, where the rate-determining step was the surface reaction between adsorbed picoline or methyldiazine and dissociatively adsorbed oxygen. The rate constants and apparent activation energies of these compounds were compared with π-electron density on ring carbon atoms bonded to the methyl groups, and with carbon-13 chemical shifts of methyl carbons. From these results, it was found that the reactivity of these compounds under ammoxidation conditions decreased with increasing electron density on the methyl carbon atoms.
社団法人日本薬学会の論文
1978-11-25