四氮杂环蕃CP_（44）的修饰、分子识别和含氮杂环二茂铁磺酰胺的合成研究
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摘要
四氮杂环蕃是环蕃中一类重要的化合物，也是主-客体化学中可以充当主体的一类化合物。作为人工模拟酶，利用它本身所具有疏水性空腔，根据环的形状、大小以及静电作用等的不同俘获不同种类的有机分子，形成主-客体包结络合物。氮杂环蕃化合物在一些有机反应体系中可以模拟酶，对其底物进行络合和催化，从而可有选择性地控制反应提高反应速率。通过改变氮杂环蕃化合物的形状以及引入活性基团，构成不同的具有协同包结和多重识别功能的活性中心，形成不同包结性能的主体，与客体形成超分子体系，实现酶功能模拟和分子识别。本文第一部分对1，6，20，25-四氮杂[6．1．6．1]对环蕃(CP_(44))进行了修饰，合成了四种含有生物活性基团的1，6，20，25-四氮杂[6．1．6．1]对环蕃衍生物。通过MS、IR对1，6，20，25-四氮杂[6．1．6．1]对环蕃与含氮杂环的分子识别进行了研究。
二茂铁及其衍生物在各个领域的作用愈来愈受到人们的重视，尤其是在医药、生化、燃料、催化剂等领域已有广泛的应用。本文第二部分选择了氮杂环化合物吲哚、吗啉、咪唑、苯并三唑、苯并咪唑衍生物分别与具有较强生物活性的二茂铁磺酰氯反应，制得了九种未见文献报道的氮杂环取代的二茂铁磺酰胺衍生物，并用IR，~1H NMR进行了表征。
微波促进下，反应具有加热时间短，产率高，产生的废弃物少、产品容易纯化、对环境污染小等优点，受到人们的广泛关注。微波在有机合成中得到了广泛的应用并迅速发展，到目前为止，微波促进的有机反应类型已经扩展到许多方面，本文第三部分对微波促进的芳香胺磺化重排反应进行了研究，提出了一种合成含磺酸基的芳香胺的有效方法。在微波促进下，三个芳香胺的硫酸盐重排得到了它们的磺化产物。
Tetraazaparacyclophane is a kind of important compound in cyclophane, and a kind of compound which can act as host in host-guest chemistry. As artificial enzymes, using hydrophobic cavities, they can capture different organic molecule to form the host-guest system, based the difference of the ring site , size and interaction. Azaparacyclophane play a significant role in the simulation of enzyme function in some organic reaction system to mimic the binding of substrates and catalyze the reaction, consequently control the reaction specially and increase the reaction velocity. By changing the ring site and size or modifying the cyclophane with the active unit, we can design the novel active center with coordinated inclusion and multirecognition to get the special host, which would form the supramolecular system with the guest and actualize the molecular recognition and the simulation of enzyme function. In the Part 1, the two bioactive units were introduced into l,6,20,25-tetraaza[6.1.6.1] paracyclophane(CP44)
to get the four tetraazaparacyclophane derivatives with the bioactive units. The molecular recognition between the CP44 and the nitrogen heterocyclic compounds were researched through the MS and IR.
The application of ferrocene and the derivatives have been attached the importance in many domains, especially in the field of medicine, biochemistry, fuel, catalyzer, In the Part 2, nine new nitrogen heterocyclic ferrocenesulfonyl amines were synthesized from ferrocenesulfonyl chloride and the nitrogen heterocycles (Indole, Morpholine, Imidazole, 1,2,3-Benzotriazole and Benzimidazole derivatives), which were confirmed by 1H NMR, IR and Elemental analysis.
Under the microwave irradiation, there are many benefits for organic reaction, such as short reaction time, high yield, less waste residue, easy purification, less pollution, which have won wide attention. The Microwave Induced Organic Reaction Enhancement Chemistry is now found wide application and develops quickly. Now the microwave-induced organic reaction has been extended to more fields. In the Part 3, the rearrangement of aromatic amine sulfate was researched.
Under the microwave irradiation, the three sulfonation products were obtained.
二茂铁及其衍生物在各个领域的作用愈来愈受到人们的重视，尤其是在医药、生化、燃料、催化剂等领域已有广泛的应用。本文第二部分选择了氮杂环化合物吲哚、吗啉、咪唑、苯并三唑、苯并咪唑衍生物分别与具有较强生物活性的二茂铁磺酰氯反应，制得了九种未见文献报道的氮杂环取代的二茂铁磺酰胺衍生物，并用IR，~1H NMR进行了表征。
微波促进下，反应具有加热时间短，产率高，产生的废弃物少、产品容易纯化、对环境污染小等优点，受到人们的广泛关注。微波在有机合成中得到了广泛的应用并迅速发展，到目前为止，微波促进的有机反应类型已经扩展到许多方面，本文第三部分对微波促进的芳香胺磺化重排反应进行了研究，提出了一种合成含磺酸基的芳香胺的有效方法。在微波促进下，三个芳香胺的硫酸盐重排得到了它们的磺化产物。
Tetraazaparacyclophane is a kind of important compound in cyclophane, and a kind of compound which can act as host in host-guest chemistry. As artificial enzymes, using hydrophobic cavities, they can capture different organic molecule to form the host-guest system, based the difference of the ring site , size and interaction. Azaparacyclophane play a significant role in the simulation of enzyme function in some organic reaction system to mimic the binding of substrates and catalyze the reaction, consequently control the reaction specially and increase the reaction velocity. By changing the ring site and size or modifying the cyclophane with the active unit, we can design the novel active center with coordinated inclusion and multirecognition to get the special host, which would form the supramolecular system with the guest and actualize the molecular recognition and the simulation of enzyme function. In the Part 1, the two bioactive units were introduced into l,6,20,25-tetraaza[6.1.6.1] paracyclophane(CP44)
to get the four tetraazaparacyclophane derivatives with the bioactive units. The molecular recognition between the CP44 and the nitrogen heterocyclic compounds were researched through the MS and IR.
The application of ferrocene and the derivatives have been attached the importance in many domains, especially in the field of medicine, biochemistry, fuel, catalyzer, In the Part 2, nine new nitrogen heterocyclic ferrocenesulfonyl amines were synthesized from ferrocenesulfonyl chloride and the nitrogen heterocycles (Indole, Morpholine, Imidazole, 1,2,3-Benzotriazole and Benzimidazole derivatives), which were confirmed by 1H NMR, IR and Elemental analysis.
Under the microwave irradiation, there are many benefits for organic reaction, such as short reaction time, high yield, less waste residue, easy purification, less pollution, which have won wide attention. The Microwave Induced Organic Reaction Enhancement Chemistry is now found wide application and develops quickly. Now the microwave-induced organic reaction has been extended to more fields. In the Part 3, the rearrangement of aromatic amine sulfate was researched.
Under the microwave irradiation, the three sulfonation products were obtained.
引文
1．刘育，尤长城，张衡益，《超分子化学—合成受体的分子识别与组装》，南开大学出版社。
2. Diederich,F., "Cyclophane", Stoddart, J. F., Ed., Monographs in Suprarnolecular Chemistry, The Royal Society of Chemistry, Cambridge, 1991.
3. Schneider, H.J., Machanisms of molecular recognition. Angew Chem Int Ed Engl, 1991, 30: 1417-1436.
4. Cram, D. J.; Trueblood, K. N. Topic in the Current Chemistry. 1981.
5．史真，《现代杂环化学选论》，陕西科学技术出版社，1996．
6. Setter, H., Roos, E. E. Chem.Ber. 1955, 88, 1390.
7. Hilggenfeld, R.; Saenger, W., Angew. Chem.,Int. Ed. Engl, 1982, 21, 787-788
8. a) K. Odashima, Y. Iitaka, K. Koga, J. Am. Chem. Soc. 1980, 102, 2504. b) K. Odashima, A. Itai, Y. Iitaka, K. Koga, J. Org. Chem. 1985, 50, 4478-4484.
9．白银娟；史真，《大环化学和超分子化学研究进展论文选集》，西北大学出版社，1994．
10. K. Odamshima, A. Itai, Y. Iitaka, Y. Arata, and K. Koga, Tetrahedron Lett., 1980, 21, 4347.
11. Dickert, F.; Haunschild, A.; Reif, M.; Bulst, W-E. Adv.Mater. 1993, 5, 277-279.
12. K. Mori, K. Odashima, A. Itai, Y. Iitaka, and K. Koga, Heterocycles, 1984, 21, 388.
13. K. Odashima, K. Koga, Heterocycles. 1981, 15(2), 1151-4.
14. Chung-Fang Lai, K. Odashima, K. Koga, Tetrahedron Lett. 1985, 26(42), 5179-5182.
15. Y. Murakami, T. Ohno, O. Hayashida, Y. Hisaeda, J. CHEM. SOC., CHEM. COMMUN., 1991,950-952.
16. T. Shino. et. al., Separation of Aromatic Isomers on Cyclophane-bonded Stationary Phases; J. Chromatory. A, 2000, 877:61-69.
17. J. -Ichi Kikuchi, Steroid Cyclophane as a Versatile Artificial Receptor. Molecular Recognition in Water, at Air-Water Interface, and in Lipid Bilayer Membrane. J Supram Chem. 2001, 1, 275-281.
18. Webb T. H., Wilcox C. S.. Chem. Soc. Rev., 1993, 22(6): 383-395
19. Lehn J. M..Angew. Chem. Int Ed. Engl., 1988, 27(1): 89-112
20．WANG Chuan-Zhang(王传忠)，ZHU Zhi-ang(朱志昂)，LI Ying(李瑛) et al., Chem. J.
Chinese Universities(高等学校化学学报), 2001, 22(2): 262-264
21．LIU Yu(刘育)，YOU Chang-Cheng(尤长城). Chem. J. Chinese Universities(高等学校化学学报)，2001，22(4)：591-597
22. Schneideer H. J. Angew. Chem. Int Ed. Engl., 1991, 30: 1417-1436
23. Francis, E. R.; Louis, S., Org. Chem., 1950, 15, 1037-1042
2. Diederich,F., "Cyclophane", Stoddart, J. F., Ed., Monographs in Suprarnolecular Chemistry, The Royal Society of Chemistry, Cambridge, 1991.
3. Schneider, H.J., Machanisms of molecular recognition. Angew Chem Int Ed Engl, 1991, 30: 1417-1436.
4. Cram, D. J.; Trueblood, K. N. Topic in the Current Chemistry. 1981.
5．史真，《现代杂环化学选论》，陕西科学技术出版社，1996．
6. Setter, H., Roos, E. E. Chem.Ber. 1955, 88, 1390.
7. Hilggenfeld, R.; Saenger, W., Angew. Chem.,Int. Ed. Engl, 1982, 21, 787-788
8. a) K. Odashima, Y. Iitaka, K. Koga, J. Am. Chem. Soc. 1980, 102, 2504. b) K. Odashima, A. Itai, Y. Iitaka, K. Koga, J. Org. Chem. 1985, 50, 4478-4484.
9．白银娟；史真，《大环化学和超分子化学研究进展论文选集》，西北大学出版社，1994．
10. K. Odamshima, A. Itai, Y. Iitaka, Y. Arata, and K. Koga, Tetrahedron Lett., 1980, 21, 4347.
11. Dickert, F.; Haunschild, A.; Reif, M.; Bulst, W-E. Adv.Mater. 1993, 5, 277-279.
12. K. Mori, K. Odashima, A. Itai, Y. Iitaka, and K. Koga, Heterocycles, 1984, 21, 388.
13. K. Odashima, K. Koga, Heterocycles. 1981, 15(2), 1151-4.
14. Chung-Fang Lai, K. Odashima, K. Koga, Tetrahedron Lett. 1985, 26(42), 5179-5182.
15. Y. Murakami, T. Ohno, O. Hayashida, Y. Hisaeda, J. CHEM. SOC., CHEM. COMMUN., 1991,950-952.
16. T. Shino. et. al., Separation of Aromatic Isomers on Cyclophane-bonded Stationary Phases; J. Chromatory. A, 2000, 877:61-69.
17. J. -Ichi Kikuchi, Steroid Cyclophane as a Versatile Artificial Receptor. Molecular Recognition in Water, at Air-Water Interface, and in Lipid Bilayer Membrane. J Supram Chem. 2001, 1, 275-281.
18. Webb T. H., Wilcox C. S.. Chem. Soc. Rev., 1993, 22(6): 383-395
19. Lehn J. M..Angew. Chem. Int Ed. Engl., 1988, 27(1): 89-112
20．WANG Chuan-Zhang(王传忠)，ZHU Zhi-ang(朱志昂)，LI Ying(李瑛) et al., Chem. J.
Chinese Universities(高等学校化学学报), 2001, 22(2): 262-264
21．LIU Yu(刘育)，YOU Chang-Cheng(尤长城). Chem. J. Chinese Universities(高等学校化学学报)，2001，22(4)：591-597
22. Schneideer H. J. Angew. Chem. Int Ed. Engl., 1991, 30: 1417-1436
23. Francis, E. R.; Louis, S., Org. Chem., 1950, 15, 1037-1042