Oxidation of Quinoline to Quinolinic Acid by High-Valenced Ruthenium Catalyst
| Project/Area Number |
61550614
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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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 | Yokohama National University |
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Principal Investigator |
HARA Takao Faculty of Engineering, Yokohama National University, 工学部, 助教授 (10017999)
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| Project Period (FY) |
1986 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1987: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1986: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Keywords | Quinoline / Oxidation / Quinolinic acid / Ruthenium catalyst / Selectivity / Oxidizing reagent / Hypochlorite ion / 次亜塩素酸イオン / シンコメロン酸 / 高原子価ルテニウム触媒 / キノリンの酸化開裂反応 |
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| Research Abstract |
Pyridine-2,3-dicarboxylic acid (quinolinic acid) is an important intermediate reagent for making agrochemicals, pharmaseuticals and specialized surface coatings. Ruthenium tetraoxide is known as a strong oxidant to cleave aromatic rings at ambient temperatures. The combination of ClO with a catalytic ampunt of RuO_2 or RuCl_3 has been used for the oxidative cleavage of naphthalene to phtalic acid in two-phase system of CCl_4-H_2O. In the present study, quinoline is oxidized to quinolinic acid quantitatively by ClO in the presence of ruthenium catalyst (Qu/Ru=200-4000) at ambient temperatures in alkaline aqueous solution. The active species of ruthenium involved in aqueous solution is discussed by spectrometry. The effect of substituents as well as the oxidation of isoquinoline is also examined.
Quinoline was oxidized to quinolinic acid rapidly and quantitatively by ruthenium catalyst in conjunction with ClO in aqueous solution only in the case that appropriate concentration of OH^- was
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involved in the solution (isolated yield of quinolinic acid: 84%). The consumption of ClO over a molecule of quinoline reacted was close to 8, which corresponds to a stoichiometric value. As the reaction proceeded, the concentration of OH decreased along with the formation of quinolinic acid. When the concentration of OH reached to 0.20-0.24 M, drastic consumption of quinoline was observed, accompanied with the decomposition of quinolinic acid which had been formed quantitatively in the higher OH concentration. The spectrophotometric study indicates that the active species for selective oxidation of quinoline to quinolinic acid may be (Ru(VII)O_4) (absorption maximum:385nm). The absorption was found to be disappeared below OH_- concentration of 0.20-0.24 M. In the higher OH concentration of 3.3-4.5 M, oxalic acid was formed as a major reaction product. The isolated yield of oxalic acid reached to 168% based on quinoline reacted. The active species for the selective formation to oxalic acid is found to be (Ru(VI)_4^<--> Less
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Report
(2 results)
Research Products
(6 results)
