【作者】 韩磊；

【导师】 颜朝国；

【作者基本信息】 扬州大学 ， 有机化学， 2007， 硕士

【摘要】 酰腙、酰基脲及酰基硫脲类作为一种特殊的Schiff碱，具有很强的配位能力和多样的配位方式，可以和过渡金属、稀土金属形成多种多样的的酰腙类金属配合物，并且表现出一些特殊的性能，使其成为很有潜力的治疗药物和功能材料，是现代配位化学的重要课题之一。本论文开展了芳基桥联的双齿和多齿酰腙、酰基脲及酰基硫脲配体的合成，过渡金属、稀土金属多核络合物的制备和分子结构的研究，初步取得了一些有意义的实验结果。以间二甲苯、对二甲苯、2，6-二甲基吡啶为起始原料，经氧化、甲酯化和肼解反应生成了芳亚甲基桥联的双酰肼衍生物，再分别与水杨醛、2-吡啶甲醛进行缩合反应生成6种双酰腙类桥联配体。研究了这些配体和过渡金属、稀土金属的配位反应。单晶结构分析表明铅配合物具有少见的扭曲四配位方式。用间苯二酚、异丙基间苯二酚和间硝基苯基间苯二酚杯芳烃为起始原料，通过烃基化和酰肼化以及与水杨醛、2-吡啶甲醛缩合反应生成两种双酰腙，两种四酰腙和两种八酰腙的多齿配体。研究了这些配体和过渡金属、稀土金属的配位反应。通过红外光谱、核磁共振氢谱、x-单晶衍射等方法对所合成的化合物进行了初步表征。采用研磨法，非常方便的将上述酰肼化合物分别与正丁基异氰酸酯、异硫氰酸苯酯进行缩合反应，合成了多种酰基脲和酰基硫脲类配体。研究了这些配体和过渡金属的配位反应。本论文还研究了对叔丁基杯[n]芳烃(n=4，6，8)与1-溴3-氯丙烷、1，2-二溴乙烷的烃基化反应，合成了6个对叔丁基杯[n]芳烃醚类衍生物。两个化合物的x-单晶衍射表明烃基化反应具有比较复杂的反应方式。更多还原

【Abstract】 Acylhydrazone, acylurea and acylthiourea are a special group of Schiff bases and have stronger coordination ability and versatile complexing style. They have been used to coordinate transition metal, rear earth metal ions to form a lot of complexes and these complexes show some unusual properties which make them to be potential drugs and functional materials. The study of metal complexes of acylhydrazone, acylurea and acylthiourea has become a very hot research field of modem coordination chemistry. In this thesis we initiated the study of synthesis, multinuclear complexes and crystal structures of some phenylene bridging acylhydrazone, acylurea and acylthiourea. The main experimental results are as fellows:m-Xylene, p-xylene and 2,6-dimethylpyridine were oxidized with KMnO₄, esterified with methanol and aminolysized with hydrazine to give double acylhydrazine derivatives, which in turn reacted with salicylaldehyde and 2-pyridinecarboaldehyde to give the six m-phenylene, p-phenylene and 2,6-pyridinyl bridged double acylhydrazone ligands. These didentate ligands can form transition metal and rear earth metal complexes. As shown by X-ray crystal analysis of lead complex each lead ion show an unusually N₂O₂ distorted planar square coordination geometry. Resorcinol, isopropyl biresorcinol and m-nitrophenylresorcinarene were alkylated with ethyl chloroacetate, aminolysized with hydrazine and condensated with salicylaldehyde and 2-pyridinecarboaldehyde to give polydentate lignads with two, four, and eight acylhydrazones, which can be coordinated with transition metal ions to form multinuclear complexes. The structures of all new products were prelimarily characterized with IR, H NMR and X-ray single crystal analysis.A series of acylurea and acylthiourea have been efficiently synthesized by grinding the above mentioned acylhydrazines with butylisoyanate and phenylthioisocyanate in high yields. Their complexing reactions with transition metal ions have also conducted and the structure of the complexes needs further determination.In this thesis alkylation reactions of calix[n]arenes （n = 4, 6, 8） with 1-bromo-3-chloropropane and 1,2-dibromoethane were investigated and several new compounds have been isolated. The X-ray single crystal analysis of two representative compounds showed that the alkylation reaction of calixarene is very interesting and variable alkylated products could be produced according to reaction conditions.更多还原