| Project/Area Number |
04555208
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | HIROSHIMA UNIVERSITY |
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Principal Investigator |
FUJIWARA Yuzo Hiroshima Univ.Fac.of Eng.(Professor), 工学部, 教授 (10029481)
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| Co-Investigator(Kenkyū-buntansha) |
JINTOKU Tetsuro Idemitsu Petrochem.Co., Ltd.(Research Manager), 化成品研究所, 室長
TANIGUCHI Yuki Hiroshima Univ.Fac.of Eng.(Assistant), 工学部, 助手 (50217139)
TAKAKI Ken Hiroshima Univ.Fac.of Eng.(Associate Professor), 工学部, 助教授 (80116615)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 1993: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1992: ¥2,900,000 (Direct Cost: ¥2,900,000)
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| Keywords | One-step Phenol Synthesis / Oxidation of Benzene / Pd(OAc)_2 / phen / CO Catalysts / Phenanthroline / C-H Bond Activation / Homogeneous Catalyst / Phenol from Benzene / Carbon Monoxide / パラジウム触媒 / フェナントロリン / CO / O_2混合ガス / O_2 / CO系によるベンゼンの酸化 / 酢酸パラジウム / ベンゼンの酸化 |
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| Research Abstract |
Our research on this project has developed the high possibility of industrialization of our new phenol synthetic process.
1. Palladium Catalysts
The Pd(OAc)_2/phen/O_2/CO system gives phenol in 1270% yield based on Pd with 91% selectivity. Pd(acac)_2, Pd-black, Pd-carbon are also good catalysts. Without CO, the phenol yield reaches to 50000% but the selectivity decreases to 56%.
2. Mechanism
By ^<18>O isotope experiments, it has been confirmed that the O atom of phenol comes from O_2, and that the another O atom of O_2 is accepted by CO to give CO_2.
3. Substitution of CO with Other Reductants
Although CO increases the phenol selectivity, four equivalents of CO_2 are formed per one mole of phenol. Thus, other reductants rather than CO were tested to find that addition of n-methylmorphorine to the Pd(OAc)_2/phen/O_2 system gives phenol in 4060% yield with 91% selectivity, and that the Pd(OAc)_2/O_2/hexafluoroacetylacetone or bipyrizylmethane systems give phenol selectively in 830 and 950% yields, respectively.
In summary, the Pd/phen/CO/O_2, Pd/phen/n-methylmorphorine/O_2 and Pd/O_2/hexafluoroacetylacetone or bipyrizylmethane systems are newly developed for direct phenol synthesis from benzene, which have high possibility of industrialization in near future.
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