| Project/Area Number |
63430017
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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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 |
TOMINAGA Hiro-o University of Tokyo, Faculty of Engineering, Professor, 工学部, 教授 (00010760)
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| Co-Investigator(Kenkyū-buntansha) |
KODA Seiichiro University of Tokyo, Faculty of Engineering, Professor, 工学部, 助教授 (10011107)
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| Project Period (FY) |
1988 – 1990
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| Project Status |
Completed (Fiscal Year 1990)
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| Budget Amount *help |
¥14,600,000 (Direct Cost: ¥14,600,000)
Fiscal Year 1990: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1989: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1988: ¥10,000,000 (Direct Cost: ¥10,000,000)
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| Keywords | Excimer Laser / Aliphatics / Partial Oxidation / Photochemical Reaction / Oxygen-Containing Compounds / Radical Recombination / Singlet Oxygen Atom / Triplet Oxygen Atom / エキシマーレーザー / 炭化水素 / 亜酸化窒素 / オゾン / 気相酸素 / 酸素同位体 |
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| Research Abstract |
Study of partial oxidation of hydrocarbons, such as ethane, propane, cyclohexane and benzene, initiated by irradiation of ArF or KrF excimer laser on various initiators, has led to the conclusions as follows ;
(1) Partial oxidation of paraffins initiated by N_2O or O_3 photolysis
Reaction is initiated by photochemical decomposition of either N_2O or O_3 by excimer laser light. The singlet oxygen produced by the photolysis of N_2O reacted with hydrocarbons by insertion into C-H bond to produce "hot" alcohols. The product distribution of the reaction in which O_3 is introduced as an initiator shows that use of KrF laser light to generate O(^1D) from ozone was found to have the advantage, over ArF laser and N_2O, of better selectivity for cyclohexanol and cyclohexanone. The advantage essentially results from the fact that KrF laser light does not promote the decarbonylation of cyclohexanone to cyclopentane and carbon monoxide, while ArF laser light does.
(2) Partial oxidation of cyclohexane in liquid phase
In the liquid phase oxidation, selectivity for oxygen-containing compounds is over 85%, and quantum yield is more than 10^3 times larger than that in gas phase reaction, which may be due to higher concentration of cyclohexane. The formation of compounds formed by radical recombination, which was not observed in gas phase reaction at all, can be explained by the cage effect in the liquid phase oxidation.
(3) Reactions of aromatics by irradiation of excimer laser
In the photoreactions of aromatics (benzene and toluene), decomposition into C_2 - C_4 olefins occurs and no oxygen-containing compounds are observed, due to the photolysis of the reactant itself by absorbing of either ArF or KrF excimer laser light.
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