J. Technology and Education, Vol.23, No.1, pp.1-6 (2016)

研究論文

酸素分子の還元活性化により発生させた活性酸素種による

シクロヘキセンの酸化に対する溶媒効果

 

津田 良弘^*、廣野 秀明

福井工業高等専門学校　物質工学科（〒916-8507 鯖江市下司町）

*tsuda@fukui-nct.ac.jp

 

Solvent effect for the oxidation of cyclohexene with an active oxygen species

 produced by reducing dioxygen

 

Yoshihiro TSUDA* and Hideaki HIRONO

Department of Chemistry and Biology, National Institute of Technology, Fukui College

　(Geshi-cho, Sabae-shi, Fukui 916-8507, Japan）

 

(Received December 2, 2015; Accepted December 24, 2015)

 

Abstract

More oxidation products of cyclohexene (cyclohexene oxide (epoxide), 2-cyclohexene-1-one (1-one), and 2-cyclohexene-1-ol (1-ol)) were obtained by adding a Br^- ion to an air-equilibrated dichloromethane suspension containing soluble cyclohexene as a substrate, soluble benzoic anhydride as an activating reagent, and insoluble zinc powder as a reductant when soluble hexyl viologen was used as a mediator for electron transfer from zinc powder to dioxygen. Increasing the concentration of Br^- ions increased the amount of epoxide produced; however, the amount of 1-one and 1-ol produced had a maximum value that was the same as when acetonitrile, which has a larger dielectric constant and donor number as compared with dichloromethane, was used as a solvent. The result implies that the active oxygen species for producing epoxide and that for producing 1-one and 1-ol may be a hypobromous anion (BrO^-) and a hypobromous radical (BrO^.) in dichloromethane, respectively.

Key words: active oxygen species, Br^- ions, solvent effect, donor number