1989 Fiscal Year Final Research Report Summary
SYNTHESIS OF RAW MATERIALS FOR FINE CHEMICALS BY LIQUID PHASE OXYGENATION OF AROMATIC COMPOUNDS
| Project/Area Number |
63470069
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | THE UNIVERSITY OF TOKYO |
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Principal Investigator |
KAMIYA Yoshio THE UNIVERSITY OF TOKYO, FACULTY OF ENGINEERING, PROFESSOR, 工学部, 教授 (40010764)
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| Co-Investigator(Kenkyū-buntansha) |
FUTAMURA Shigeru THE UNIVERSITY OF TOKYO, FACULTY OF ENGINEERING, RESEARCH ASSISTANT, 工学部, 助手 (60165446)
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| Project Period (FY) |
1988 – 1989
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| Keywords | Base-catalyst / Oxygenation / Aromatic compounds / Oxidation rate / Products / Solvent effect / Additive effect |
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| Research Abstract |
The oxygenation of 9-methylanthracene with t-BuOK (0.2 M) in HMPA-t-BuOH afforded anthraquinone selectively. On the other hand, no anthraquinone was obtained from 2-methylanthracene or from anthracene. Reaction mechanism is of interest.
The oxygenation of p-cresol in the presence of NAOH and CoCl_2 in a polar solvent affords p-hydroxybenzaldehyde, which is an important synthetic intermediate. In the oxygenation of p-cresol in the presence of NAOH (4.5 M) and CoCl_2 (0.1 M) in MeOH-t-BuOH at 60ﾟC for 50 h, the p-cresol conversion was 90 % and p-hydroxybenzaldehyde was obtained in 66% selectivity. In aprotic polar solvents such as HMPA, the p-hydroxybenzaldehyde selectivity was as low as 10%, and the yield of p-hydroxybenzaldehyde was not greater than 38% in a single solvent such as methanol, ethanol, and t-butanol. Among the transition metal chlorides, CoCl_2 was the most effective additive, compared with the chlorides of Ni, Fe, and Mn. As for the Co catalysts, satisfactory results were obtained except for Co_3O_4.
In this research, the effects of base catalysts, solvent, and transition metal salt additives on the oxidation rate and the product distribution were investigated in the base-catalyzed oxygenation of aromatic compounds in order to effectively convert methylaromatics to aldehydes and carboxylic acids, and important results were obtained.
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Research Products
(5 results)
