含酚Mannich碱双核铜配合物的合成、结构及磁性研究
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摘要
Mannich反应是一类重要的有机合成反应,在医药和生物碱的合成中有广泛的应用价值。所得到的产物Mannich碱还可以作为中间体,通过消除、取代、还原加成、环化等反应制备一般方法难以合成的化合物。Mannich碱及其衍生物最初是作为药物而得到应用的,在医药方面可以做镇静止痛药、杀菌剂、水肿抑制药、抗肿瘤药、保肝药、抗凝血药。但随着时间的推移,Mannich反应的应用已经远远超出了它最初的研究范围,可以做炸药及推进剂、高分子絮凝剂、防腐剂、硫化促进剂等。
以酚为酸组分的Mannich碱及其与过渡金属Cu配合物的合成与磁性研究,是本文的主要研究内容。本文设计合成了国内外尚未报道的29种新型含酚Mannich碱及其与铜的配合物,对配合物做了磁性研究,并研究了配合物结构与磁性的关系。具体内容分为三部分:
1.以对取代酚作为酸组分,与伯胺和甲醛缩合,分别在室温和加热回流的条件下合成了29种新型Mannich碱。目标化合物的结构经过IR、~1HNMR和MS进行了确证。对一些目标化合物进行了X-射线晶体衍射。
2.以Mannich碱为配体,乙酸铜为阳离子的供体,以绝对甲醇和绝对乙醇做溶剂,加入少量三乙胺使整个溶剂显弱碱性,在室温和加热回流的条件使其配位。所得配合物经晶体结构表明都是双核配合物。未Nx-射线晶体衍射结构测定的目标产物通过IR、~1HNMR、和热重分析进行了表征。
3.分子基磁性材料越来越成为物理学家和化学家研究的热点。金属配合物的单晶结构有利于对分子基磁性中磁性来源和磁性作用机理的研究。本文用上述合成的双核配合物进行了磁性测定,并研究了结构与磁性之间的关系。
Mannich reaction is an important organic synthesis reaction. It has an abroad application in the synthesis of medicine and alkaloid. As intermediates, Mannich bases can be converted to compounds difficultly available by elimination reaction, substitution, reduction reaction and cyclization. Mannich base and its derivatives firstly are used for drug application, such as sedation analgesia drugs, microbicides, edema inhibitors, antineoplastic agents, detonator and anticoagulants. As time goes on, Mannich reaction has been applied far beyond its original scope of study can be done in explosives and propellants, polymer flocculants, preservatives, for vulcanization accelerator and so on.
Our study focus on the synthesis of Mannich bases, their copper complexes and magnetic properties of the copper complexes. In this thesis, 29 kinds of new Mannich bases and their copper complexes were designed and synthesized. Furthermore, their magnetism and structure-activity relationships were studied. This thesis is divided into three parts as follows:
4-Substituted phenol, as the acid component, was condensed with primary amines and formaldehyde at room temperature or in the presence of heat to yielded 29 kinds of new Mannich bases. The structures of the target molecules were identified by IR, ~1HNMR and MS analysis, some of them were determined by X-ray crystal diffraction.
Mannich bases as ligands were coordinated with copper acetate in absolute ethanol or methanol in the presence of a small amount of triethylamine at room temperature or heating conditions to give the copper complexes. The crystal structures of the complexes show that they are binuclear copper complexes. Structures of the objectives with no X-ray crystal structural determination were confirmed by IR, ~1HNMR and thermal analysis.
Molecular-magnetic material is increasingly becoming the research hotspots of physics and chemistry. Metal complexes crystal structure is conducive to the theory of molecular-magnetic in the magnetic source and mechanism of magnetic research. in this thesis, magnetic of the binuclear complexes were measured, and the relationship between the structure and magnetic properties was studied.
以酚为酸组分的Mannich碱及其与过渡金属Cu配合物的合成与磁性研究,是本文的主要研究内容。本文设计合成了国内外尚未报道的29种新型含酚Mannich碱及其与铜的配合物,对配合物做了磁性研究,并研究了配合物结构与磁性的关系。具体内容分为三部分:
1.以对取代酚作为酸组分,与伯胺和甲醛缩合,分别在室温和加热回流的条件下合成了29种新型Mannich碱。目标化合物的结构经过IR、~1HNMR和MS进行了确证。对一些目标化合物进行了X-射线晶体衍射。
2.以Mannich碱为配体,乙酸铜为阳离子的供体,以绝对甲醇和绝对乙醇做溶剂,加入少量三乙胺使整个溶剂显弱碱性,在室温和加热回流的条件使其配位。所得配合物经晶体结构表明都是双核配合物。未Nx-射线晶体衍射结构测定的目标产物通过IR、~1HNMR、和热重分析进行了表征。
3.分子基磁性材料越来越成为物理学家和化学家研究的热点。金属配合物的单晶结构有利于对分子基磁性中磁性来源和磁性作用机理的研究。本文用上述合成的双核配合物进行了磁性测定,并研究了结构与磁性之间的关系。
Mannich reaction is an important organic synthesis reaction. It has an abroad application in the synthesis of medicine and alkaloid. As intermediates, Mannich bases can be converted to compounds difficultly available by elimination reaction, substitution, reduction reaction and cyclization. Mannich base and its derivatives firstly are used for drug application, such as sedation analgesia drugs, microbicides, edema inhibitors, antineoplastic agents, detonator and anticoagulants. As time goes on, Mannich reaction has been applied far beyond its original scope of study can be done in explosives and propellants, polymer flocculants, preservatives, for vulcanization accelerator and so on.
Our study focus on the synthesis of Mannich bases, their copper complexes and magnetic properties of the copper complexes. In this thesis, 29 kinds of new Mannich bases and their copper complexes were designed and synthesized. Furthermore, their magnetism and structure-activity relationships were studied. This thesis is divided into three parts as follows:
4-Substituted phenol, as the acid component, was condensed with primary amines and formaldehyde at room temperature or in the presence of heat to yielded 29 kinds of new Mannich bases. The structures of the target molecules were identified by IR, ~1HNMR and MS analysis, some of them were determined by X-ray crystal diffraction.
Mannich bases as ligands were coordinated with copper acetate in absolute ethanol or methanol in the presence of a small amount of triethylamine at room temperature or heating conditions to give the copper complexes. The crystal structures of the complexes show that they are binuclear copper complexes. Structures of the objectives with no X-ray crystal structural determination were confirmed by IR, ~1HNMR and thermal analysis.
Molecular-magnetic material is increasingly becoming the research hotspots of physics and chemistry. Metal complexes crystal structure is conducive to the theory of molecular-magnetic in the magnetic source and mechanism of magnetic research. in this thesis, magnetic of the binuclear complexes were measured, and the relationship between the structure and magnetic properties was studied.
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