醌类化合物催化氧化性能的研究
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摘要
醌类化合物广泛存在于自然界中,是生物体内重要的电子转移和递氢体,广泛参与脱氢氧化反应,研究其催化氧化性能具有重要的理论价值和应用前景。本论文旨在通过对醌类化合物催化性能的研究,开发温和条件下,以分子氧为氧化剂的催化氧化有机催化体系。
论文首先研究了醌类化合物和N-羟基邻苯二甲酰亚胺(NHPI)组成的催化体系催化烃类化合物加氧化反应的性能。结果表明,具有缺电子取代基的2,3-二氯-5,6-二氰基对苯醌(DDQ)和NHPI组成的催化体系,在乙苯氧化反应中表现出了较好的催化活性。在80℃和0.3 MPa氧气压力下,反应10小时后,乙苯转化率达到72.2%,苯乙酮选择性达92.3%。采用紫外可见光谱技术,证实了醌类化合物和NHPI之间确实存在一定的作用力,DDQ促进了NHPI向PINO的转化,从而促进了反应的进行。并将该催化体系用于烯烃、芳烃侧链等化合物的氧化,同样表现出较好的活性,表明该催化体系具有较好的底物普适性。
通过考察取代基位阻效应的影响,发现醌环上引入位阻大的取代基之后,可以阻止自由基与醌环上C=C双键的反应,有利于其催化性能的发挥。然而,数目过多、体积过大的取代基又阻碍了醌环上反应中心与底物的接触,降低了其催化性能。
本论文还研究了醌催化分子氧氧化醛生成羧酸、维生素C生成脱氢抗坏血酸的反应,证明了醌类化合物也可以高效催化这些过程。
Quinones are ubiquitous in nature, which play an important role in transfer of electron and hydrogen atom in biochemical dehydrogenation redox process. Therefore, study of the catalytic performance of quinones is very necessary from the views of academic and application. This thesis is dedicated to develop a new organocatalyst system for hydrocarbon oxidation using molecular oxygen as oxidant under mild conditions through the study of the catalytic properties of quinones.
Firstly, the catalytic property of quinones was investigated in the oxidation of hydrocarbons using quinones combined with N-hydroxyphthalimide (NHPI) as catalyst.72.2% conversion with 92.3% selectivity for acetophenone was obtained in ethylbenzene oxygenation catalyzed by NHPI and 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) under 0.3 MPa of molecular oxygen at 80℃for 10 h. UV/Vis spectroscopy of the catalytic system indicated that there was interaction between quinones and NHPI, and DDQ accelerated the generation of free radical phthalimido-N-oxyl (PINO) by abstracting a hydrogen atom from NHPI. In addition, the catalytic system DDQ/NHPI also exhibited excellent catalytic activity in the selective oxidation of alkene and the alkyl of aromatic hydrocarbon.
The study on the steric effects of substituents of quinones showed that sterically-hindered substituents reduced the chance of elimination of radicals by C=C double bonds in the quinone ring, which is related to the catalytic performance of quinones. On the other hand, too many substituents hindered the contact between the reaction center of quinone (C=O) and the reactant, which led to the decrease of the catalytic activity.
In addition, the oxidation of aldehyde to carboxylic acid and of ascorbate to dehydroascorbic acid catalyzed by quinone also was researched. Quinone showed high efficiency in these oxidation reactions.
论文首先研究了醌类化合物和N-羟基邻苯二甲酰亚胺(NHPI)组成的催化体系催化烃类化合物加氧化反应的性能。结果表明,具有缺电子取代基的2,3-二氯-5,6-二氰基对苯醌(DDQ)和NHPI组成的催化体系,在乙苯氧化反应中表现出了较好的催化活性。在80℃和0.3 MPa氧气压力下,反应10小时后,乙苯转化率达到72.2%,苯乙酮选择性达92.3%。采用紫外可见光谱技术,证实了醌类化合物和NHPI之间确实存在一定的作用力,DDQ促进了NHPI向PINO的转化,从而促进了反应的进行。并将该催化体系用于烯烃、芳烃侧链等化合物的氧化,同样表现出较好的活性,表明该催化体系具有较好的底物普适性。
通过考察取代基位阻效应的影响,发现醌环上引入位阻大的取代基之后,可以阻止自由基与醌环上C=C双键的反应,有利于其催化性能的发挥。然而,数目过多、体积过大的取代基又阻碍了醌环上反应中心与底物的接触,降低了其催化性能。
本论文还研究了醌催化分子氧氧化醛生成羧酸、维生素C生成脱氢抗坏血酸的反应,证明了醌类化合物也可以高效催化这些过程。
Quinones are ubiquitous in nature, which play an important role in transfer of electron and hydrogen atom in biochemical dehydrogenation redox process. Therefore, study of the catalytic performance of quinones is very necessary from the views of academic and application. This thesis is dedicated to develop a new organocatalyst system for hydrocarbon oxidation using molecular oxygen as oxidant under mild conditions through the study of the catalytic properties of quinones.
Firstly, the catalytic property of quinones was investigated in the oxidation of hydrocarbons using quinones combined with N-hydroxyphthalimide (NHPI) as catalyst.72.2% conversion with 92.3% selectivity for acetophenone was obtained in ethylbenzene oxygenation catalyzed by NHPI and 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) under 0.3 MPa of molecular oxygen at 80℃for 10 h. UV/Vis spectroscopy of the catalytic system indicated that there was interaction between quinones and NHPI, and DDQ accelerated the generation of free radical phthalimido-N-oxyl (PINO) by abstracting a hydrogen atom from NHPI. In addition, the catalytic system DDQ/NHPI also exhibited excellent catalytic activity in the selective oxidation of alkene and the alkyl of aromatic hydrocarbon.
The study on the steric effects of substituents of quinones showed that sterically-hindered substituents reduced the chance of elimination of radicals by C=C double bonds in the quinone ring, which is related to the catalytic performance of quinones. On the other hand, too many substituents hindered the contact between the reaction center of quinone (C=O) and the reactant, which led to the decrease of the catalytic activity.
In addition, the oxidation of aldehyde to carboxylic acid and of ascorbate to dehydroascorbic acid catalyzed by quinone also was researched. Quinone showed high efficiency in these oxidation reactions.
引文
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