苯并噻唑衍生物的合成及其金属配合物催化羰基化反应研究

【作者】 张斌；

【导师】 史真；

【作者基本信息】 西北大学 ， 有机化学， 2009， 博士

【摘要】 羰基化反应是在有机化合物分子内引入羰基、羧基、酯基、酰胺基等官能团成为含氧化合物的一类反应。羰基化反应已成为合成醛、酮、羧酸、酯、内酯、酰胺等有机化合物的重要方法之一。羰基化反应催化工艺的研究已成为有机合成化学中非常活跃的研究领域。本论文研究了苯并噻唑衍生物及其钴、铑金属配合物的合成,并研究了两类金属配合物的羰基化催化性能,提供了合成苯并噻唑衍生物的可行路线,拓宽了苯并噻唑金属配合物的应用范围,催化羰基化合成苯乙酸的研究具有重要的实用价值。全文分为四章,主要内容如下:1.以2-氨基苯并噻唑为原料,合成了苯并噻唑-2-羧酸衍生物、2-(4,5-二氢-2-噻唑基)苯并噻唑衍生物和2-(2-苯并噻唑基)-4,5-二氢-4-噻唑羧酸衍生物三类、共11个苯并噻唑衍生物,其中3个化合物未见文献报道。2.对2-氰基苯并噻唑衍生物4个重要的中间体优化了合成条件,简化了合成步骤。对苯并噻唑-2-羧酸衍生物采用2-氰基苯并噻唑衍生物水解,在碱性条件下获得较好的产率,为苯并噻唑-2-羧酸衍生物提供了一条新的合成路线。3.2-(4,5-二氢-2-噻唑基)苯并噻唑衍生物采用碱性条件下与巯基乙胺盐酸盐反应制备,获得了两个衍生物的单晶,并通过X-单晶衍射分析其超分子结构。4.以苯并噻唑-2-羧酸、2-(4,5-二氢-2-噻唑基)苯并噻唑、2-(2-苯并噻唑基)-4,5-二氢-4-噻唑羧酸三类苯并噻唑衍生物为配体,合成了18个未见文献报道的钴、铑配合物,并对其结构进行了表征和分析。结果表明,配合物结构为不饱和配位或有易离去配位体,适合用于配位催化。5.合成得到6-甲氧基苯并噻唑-2-羧酸钴和2-(4,5-二氢-2-噻唑基)-6-甲氧基苯并噻唑氯化钴的单晶,通过X-单晶衍射说明:6-甲氧基苯并噻唑-2-羧酸钴的空间结构为六配位的单核结构、畸变的八面体几何构型;2-(4,5-二氢-2-噻唑基)-6-甲氧基苯并噻唑氯化钴为五配位的双核结构、畸变的四角锥几何构型。6.对钴配合物催化苄氯羰基化合成苯乙酸工艺进行了研究,分别对相转移催化剂、溶剂、温度、碱的种类和浓度进行了优化,并对氮肥厂废气CO利用和催化剂的回收进行了研究。该工艺的苯乙酸产率略高于同类催化剂,是一条具有工业化前景的羰基化合成苯乙酸新工艺,该技术已申请国家发明专利。7.对铑配合物催化苄氯羰基化合成苯乙酸进行了尝试,苯乙酸产率超过90%,产品纯度达99%。更多还原

【Abstract】 Carbonylation is a transition metal-catalyzed reaction using carbon monoxide as a carbonyl source of aldehydes,ketones,carboxylic acids and their derivatives.Carbonylation has been widely used in organic synthetic chemistry.The catalytic process of carbonylation has become an attractive subject in organic chemistry and coordination chemistry.In this thesis,benzothiazole derivatives have been synthesized,and the complexes of cobalt and rhodium have also been prepared as catalysts for carbonylation.The capabilities in carbonylation have been investigated.The studies are significant to propose the synthetic methodology of benzothiazole derivatives,broaden the application of the metal complexes of benzothiazoles.It is practical value of the research in preparation of phenylacetic acid from metal-catalyized carbonylation.The thesis consists of four chapters.The main contributions are listed as follows.1.Eleven benzothiazole derivatives were synthesized using 2-aminobenzothiazole as raw material,which are the derivatives of benzothiazole-2-carboxylic acid,2-(4,5-dihydro-2-thiazolyl)benzothiazole and 2-(2-benzothiazolyl)-4,5-dihydro-(4S)-4-thiazolecarboxylic acid.2.The synthesis conditions of four derivatives of 2-cyanobenzothiazole were studied and optimized.Benzothiazole-2-carboxylic acids were synthesized in a good yield with hydrolyzation of 2-cyanobenzothiazoles in alkalic conditions.A novel method of synthesis of benzothiazole-2-carboxylic acids was proposed.3.The derivatives of 2-(4,5-dihydro-2-thiazolyl)benzothiazole were synthesized in alkalic conditions.Two single crystals were obtained,and the supramolecular structures were determined by X-ray diffraction.4.Eighteen novel cobalt and rhodium complexes of the ligands of benzothiazole-2-carboxylic acids,2-(4,5-dihydro-2-thiazolyl)benzothiazoles and 2-(2-benzothiazolyl)-4,5-dihydro-(4S)-4-thiazolecarboxylic acids were synthesized and characterized.5.The single-crystal structures of complexes bis(N,N-Dimethylformamide)bis(6-methoxyl benzothiazole-2-carboxylato)cobalt(Ⅱ) and bis[2-(4,5-dihydro-2-thiazolyl)-6-methoxyl- benzothiazole]dichlorocobalt(Ⅱ) were determined by X-ray diffraction.The single-crystal structural analysis revealed that the complex of bis(N,N-Dimethylformamide)bis-(6-methoxylbenzothiazole-2-carboxylato)cobalt(Ⅱ)was a distorted octahedron conformation, and the complex of bis[2-(4,5-dihydro-2-thiazolyl)-6-methoxylbenzothiazole]-dichlorocobalt (Ⅱ) was distorted pyramid conformation.6.The synthesis of phenylacetic acid from the carbonylation of benzyl chlorine catalyzed by cobalt complexes was studied.The effects of phase transfer catalysts,solvents,reaction temperature and the concentration of alkali on the reactions were investigated.The use of abandoned carbon monoxide from Nitrogenous Fertilizer Plant and the recycling of the catalysts were studied.The research indicated that the yield of phenylacetic acid in this catalytic system was slightly higher than in a similar one.The technology has been applied for national invention patent.7.The synthesis of phenylacetic acid from the carbonylation of benzyl chlorine catalyzed by rhodium complexes was studied.The yield of phenylacetic acid was more than 90%.The purity was 99%.更多还原