Oxidation and epoxidation of hydrocarbons with O2 catalysed by EuCl3

✍ Scribed by Ichiro Yamanaka; Takashi Akimoto; Katsumi Nakagaki; Kiyoshi Otsuka

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 922 KB
• Volume: 110
• Category: Article
• ISSN: 1381-1169
• DOI: 10.1016/1381-1169(96)00066-0

✦ Synopsis

Oxidation of cyclohexane and epoxidation of I-hexene with 0, by EuCl, catalytic systems (EuCl,, Zn powder, carboxylic acid, and solvent) were studied in detail. Combination of proton donors and solvents strongly affected the turnover number (TON) and the selectivity of the monooxygenation. The maximum TON of 11.7 in 1 h for oxidation of cyclohexane to cyclohexanol and cyclohexanone (= 100% total selectivity) was obtained using acetic acid and dichloromethane at P(0,) = 101 kPa and T = 40°C. The selectivity to cyclohexanone increased with increasing the yield for sum of the products. A successive reaction of cyclohexanol to cyclohexanone became obvious at higher yields in oxidation of cyclohexane. In the case of epoxidation, the maximum TON of the epoxide (81.4% selectivity) of 14.2 in 1 h was obtained using 1,2-dichloroethane and propionic acid at P(O,) = 101 kPa and T = 40°C. The selectivity to the epoxide did not change with the total yield. A successive reaction of 1,Zepoxyhexane to by-products was not observed in the oxidation of 1-hexene. A small amount of CO, was produced from carboxylic acid, but none from the reactant. The efficiency of Zn powder used to the monooxygenations was not more than 5%.