Oxidation of Quinoline to Quinolinic Acid by High-Valenced Ruthenium Catalyst

高价钌催化剂氧化喹啉制备喹啉酸

• 批准号: 61550614
• 负责人: HARA Takao
• 金额: $ 1.22万
• 依托单位: Yokohama National University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-61550614/
• 关键词: 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

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 … More 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

吡啶-2,3-二羧酸（喹啉酸）是生产农药、药品和专用表面涂料的重要中间体。四氧化钌被认为是一种强氧化剂，可以在环境温度下裂解芳环。在CCl_4-H_2O两相体系中，采用ClO与催化量为RuO_2或RuCl_3的组合，将萘氧化裂解为酞酸。在本研究中，喹啉在常温碱性水溶液中，在钌催化剂（Qu/Ru=200-4000）的存在下，被ClO定量氧化为喹啉酸。用光谱法讨论了钌在水溶液中的活性组分。并考察了取代基对异喹啉氧化反应的影响。在水溶液中，只有当溶液中OH^-的浓度达到一定的浓度时，钌催化剂才能将喹啉快速、定量地氧化为喹啉酸（喹啉酸的分离收率为84%）。一分子喹啉反应的ClO消耗接近于8，这对应于一个化学计量值。随着反应的进行，OH的浓度随着喹啉酸的生成而降低。当OH浓度达到0.20 ~ 0.24 M时，喹啉的大量消耗伴随着在较高OH浓度下定量形成的喹啉酸的分解。分光光度法研究表明，喹啉选择性氧化生成喹啉酸的活性物质可能是（Ru(VII)O_4）（吸收最大值为385nm）。在OH浓度为0.20 ~ 0.24 M时，吸附消失，在较高的OH浓度为3.3 ~ 4.5 M时，主要生成草酸。以喹啉为原料，分离得到的草酸收率可达168%。发现选择性生成草酸的活性物质为(Ru(VI)_4^<—> Less

项目成果

原孝夫: 化学工業. 37. 390-396 (1986)

原高雄：化学工业。37. 390-396 (1986)

T.Hara: "Long-Term Storage Stabilities of Liquid Fuels" Southwest Research Institute, 926 (1986)

T.Hara：“液体燃料的长期储存稳定性”西南研究院，926（1986）

原孝夫: 第23回石炭科学会議発表論文集. 1986. 359-361 (1986)

Takao Hara：第 23 届煤炭科学会议论文集，1986 年。359-361 (1986)。

M.Yudasaka: "Synthetic Metals" Elsevier Sequoia S.A., (1987)

M.Yudasaka：“合成金属”Elsevier Sequoia S.A.，（1987）

T.Hara: Studies in Organic Chemistry 33,"Role of Oxygen in Chemistry and Biochemistry". 33. 347-350 (1988)

T.Hara：有机化学研究 33，“氧在化学和生物化学中的作用”。