【作者】 张英俊；

【导师】 安德烈；

【作者基本信息】 湖南大学 ， 有机化学， 2007， 博士

【摘要】 本文在对环芳化合物的大量的文献调研的基础上,综述了环芳化合物的合成以及它们在各个领域的应用研究。经过几十年的发展,环芳化学已经成为超分子化学、分子识别学、有机催化剂的构筑学、分子接受器的模板构筑学、冠醚化学、穴状配体的构筑学和富碳化学等领域的重要组成部分。本文还进一步阐述了本实验室以前的工作,在此基础上设计并合成了一系列新型的光学活性的环芳化合物及其衍生物。由于联萘在反应前后构型保持的稳定性,以及乙炔键在空间上良好的定向作用,本文选择了光学活性的2,2’-二乙炔基-1,1’-联萘作为合成模板来构筑目标分子。第二章主要讨论具有单一手性[(R)构型或(S)构型]的2,2’-二乙炔基-1,1’-联萘模板的合成。光学纯的(R)-或(S)-联萘二酚可以方便的购买,是一个理想的起始原料。通过酚羟基的酯化反应、磺酸酯与格氏试剂的Kumada反应、甲基的溴化反应、二溴甲基的水解反应和特殊的Wittig反应来制得2,2’-二乙炔基-1,1’-联萘。第三章主要讨论了新型手征性笼状化合物的设计与合成。从(R)和(S)-2,2’-二乙炔基-1,1’-联萘模板出发,通过保护基的控制导入,偶联反应,保护基脱去以及分子间偶合成环4个步骤成功地合成了光学活性分子方?—(R,R,R,R)-95和(S,S,S,S)-95。为了增加化合物的内穴的大小,本文又设计并合成了一组联萘炔单元之间的连接桥的长度不一的化合物(R,R,R,R)-96、(R,R,R,R)-97以及(R,R,R,R)-98,这组化合物结构中的联萘单元之间的连接桥为对位的苯环基团。同时以(R)和(S)-2,2’-二乙炔基-1,1’-联萘模板出发,以间位亚苯基为连接桥,通过Cu催化的Eglinton反应和Cu、Pd共催化的Sonogashira反应,分别设计合成了具有相同片断的含4、6、8个联萘单元的笼状化合物(R,R,R,R)-和(S,S,S,S)-99、(R,R,R,R,R,R)-100以及(R,R,R,R,R,R,R,R)-和(S,S,S,S,S,S,S,S)-101。在化合物(R,R,R,R)-95和(S,S,S,S)-95的合成中,通过Sonogashira反应条件下的炔的二聚反应,本文成功地解决了基团TMS在一般的Eglinton反应条件下会变质的问题。本文还测定这些化合物的CD、比旋光度、紫外等性能,异构体的CD谱呈现出良好的镜像对称关系,这表明了异构体为对映异构体。通过Chem3D的计算,本文给出了化合物结构的填充模型图,并且计算了目标化合物的空穴大小。目标化合物的空穴尺度的大小达到了1.0-2.3 nm,可以容纳下1-3个C60。对这些化合物的空穴尺度的大小的研究,对主客体化学有着重要的意义。第四章从(R)-2,2’-二乙炔基-1,1’-联萘模板出发,通过保护基的控制导入,连接桥的链接以及分子内的Sonogashira反应等步骤设计并合成了以间位和邻位亚苯基为连接桥的具有双螺旋结构的化合物(R,P)-102和(R,P)-103。对于最后一步分子内的Sonogashira反应,我们采用定时注射泵来控制反应物滴入的速率,从而达到控制反应物浓度的目的,以防止因为反应物浓度过高而造成的分子间的Sonogashira反应和两分子炔氢的偶联反应。通过此种方法,本文大大提高了最后一步的分子内关环反应的产率。第五章从(R)-2,2’-二乙炔基-1,1’-联萘出发,以具有双螺旋结构的环芳化合物为哑铃的球体,刚性的苯基炔化合物为连接桥,通过Sonogashira偶联反应成功地合成了几个光学活性的哑铃状化合物[(R,P),(R,P)]-104-106以及螺旋单元构筑的枝状化合物[(R,P),(R,P),(R,P)]-107。本章化合物的合成都需串行反应十五步左右,在合成上有很大的挑战性。通过长时间的努力,顺利地合成了化合物104-107,并且通过Chem3D的计算,给出了化合物结构的填充模型图。计算得出,化合物104-107的分子大小都达到了2-3纳米,可望在纳米材料方面得到应用。本文当中所有的中间体和目标化合物都经过MS、IR、1H NMR、13C NMR和DEPT组合测定得到确认。更多还原

【Abstract】 The synthesis of cyclophynes and their applications in various fields are reviewed in this paper based on a large number of references. After several decades’development, the chemistry of cyclophynes has become a major component of supramolecular chemistry, of molecular recognition, of the building blocks for organic catalysts, receptor models, crown ethers, cryptands and of carbon-rich chemistry. The previous work of our lab was described, and a series of new type of cyclophynes and their derivatives were designed and synthesized.Because of the stability of binaphthalene’s configuration in the reactions and the fine directional function of ethynyl in the space, enantiopure 2,2’-diethynyl-1,1’-binaphthyl was used as synthetic template for the synthesis of target molecules. In the second chapter in this paper, the synthesis of enantiopure [(R)- or (S)-form] 2,2’-diethynyl-1,1’-binaphthyl was described. Enantiopure (R)- or (S)-binapythol can be purchased conveniently and was a good material. 2,2’-Diethynyl-1,1’-binaphthyl was synthesized from binapythol by esterification of hydroxyl, Kumada reaction of sulfonic ester with Grignard reagent, bromination of methyl, hydrolyzation of dibromomethyl and especial Wittig reaction.In the third chapter, the design and synthesis of enantiopure compounds with cage structure were described. Enantiopure molecule square--(R,R,R,R)- and (S,S,S,S)-95 were synthesized from (R)- and (S)-2,2’-diethynyl-1,1’-binaphthyl templates by four steps including the introduction of protecting group, intermolecular coupling reaction, removal of protecting group, and intermolecular cross-coupling cyclization. In order to enhance the cavity sizes of compounds, a series of compounds with different length linkages of p-phenylene groups between 2,2’-diethynyl-1,1’-binaphthyl, including (R,R,R,R)-96, (R,R,R,R)-97 and (R,R,R,R)-98, were also designed and synthesized in this paper. In addition, via the linking of m-phenylene, compounds (R,R,R,R)- and (S,S,S,S)-99, (R,R,R,R,R,R)-100, (R,R,R,R,R,R,R,R)- and (S,S,S,S,S,S,S,S)-101 with cage structure were designed and synthesized from (R)- and (S)-2,2’-diethynyl-1,1’-binaphthyl templates. These compounds have the same building block and involve four, six and eight units of binaphthyl, respectively. In the synthesis of compounds (R,R,R,R)-95 and (S,S,S,S)-95, the decomposition of TMS group in common Eglinton reaction was successfully avoided by the homocoupling of alkyne under Sonogashira reaction condition. The circular dichroism (CD) spectra, specific rotations ([α]D25) and UV spectra of these compounds were characterized. Their CD spectra represented exactly mirror images of each other, which reflected unambiguously enantiomeric relation between two isomers. The space models of these compounds were obtained and the cavity sizes of these compounds were calculated using Chem3D. The cavity sizes of the target compounds were 1.0-2.3 nm, which are 1-3 times of the diameter of C60. Study on the cavity sizes of these compounds is of great significance to host-guest chemistry.In the fourth chapter, compounds (R,P)-102 and (R,P)-103 with double helical structure were designed and synthesized from (R)-2,2’-diethynyl-1,1’-binaphthyl by the introduction of protecting group, the connecting of linking bridges and intramolecular Sonogashira reaction. In the last intramolecular Sonogashira reaction, a syringe pump that can control the dropping rate of reactant solution was used in order to avoid the high concentration of reactant. The high concentration of reactant will produce intermolecular Sonogashira and Eglinton reaction. By using the syringe pump, the yields of the last step of intramolecular Sonogashira reaction were greatly improved.In the fifth chapter, several enantiopure Dumbbell-compounds [(R,P),(R,P)]-104-106 and dentritic compound [(R,P),(R,P),(R,P)]-107 with helical units were synthesized from (R)-2,2’-diethynyl-1,1’-binaphthyl by Sonogashira coupling reaction. In the structures of these compounds, cyclophyne bearing helical structure and rigid phenylethynyl were used as the ball of dumbbell and linking bridge, respectively. The synthesis of these compounds is a big challenge because abount 15 steps are required for each compound. Compounds 104-107 were successfully synthesized after great efforts, and their space models were given using Chem3D. The molecular sizes of compounds 104-107 are 2-3 nm, which makes these compounds have potential application as nanomaterials.All the intermediates and target compounds synthesized in this paper were characterized by MS, IR, 1H NMR, 13C NMR and DEPT.更多还原