J. Technology and Education, Vol.13, No.2, pp.53-62, 2006

研究論文

　

酸素分子の還元により生成するスーパーオキシドイオンと安息香酸無水物との

反応により発生させた活性酸素種による環状炭化水素の酸化

　

津田良弘^＊１、高橋光信^２

¹沼津工業高等専門学校　物質工学科（〒410-8501 沼津市大岡3600）

*tsuda@numazu-ct.ac.jp

^２金沢大学大学院自然科学研究科　物質科学専攻（〒920-1192 金沢市角間町）

　

Oxidation of cyclic hydrocarbon with an active oxygen species produced by reducing dioxygen in the presence of benzoic anhydride

　

Yoshihiro TSUDA^*1 and Kohshin TAKAHASHI²

¹Department of Chemistry and Biochemistry, Numazu National College of Technology

(3600 Ooka, Numazu 410-8501, Japan)

²Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University

(Kakumamachi, Kanazawa 920-1192, Japan)

　

(Received September 21, 2006; Accepted October 16, 2006)

　

Abstract

The oxidation of cyclohexane to cyclohexanone proceeded by adding hexylviologen as an electron mediator to an air-equilibrated acetonitrile suspension containing cyclohexane as a substrate, benzoic anhydride as a cleaving reagent of the dioxygen O=O bond, and insoluble zinc powder as a reductant.　When cyclohexene, rather than cyclohexane, was used as a substrate for this system, allylic oxidation products, such as 2-cyclohexene-1-one and 2-cyclohexene-1-ol, and a C=C bond oxidation product, such as cyclohexene oxide, were obtained.　The oxidation mechanism was investigated by adding 3,5-di-tert-butyl-p-hydroxyltoluene(BHT) as a radical inhibitor into this system and discussed in relation to the redox properties of the chemical species contained in this system.　The active oxygen species for the oxidation of cyclohexene to 2-cyclohexene-1-one and 2-cyclohexene-1-ol and that for the oxidation of cyclohexane to cyclohexanone and cyclohexene to cyclohexene oxide may be benzoylperoxyl radical(C₆H₅COOO^・) and benzoylperoxide ions (C₆H₅COOO^-), respectively.

Key words: active oxygen species, reducing dioxygen, benzoic anhydride, cyclic hydrocarbon