邻—氧桥杂环杯芳烃的合成、结构及修饰
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摘要
主体分子的设计与合成一直是超分子化学研究的重要领域和创新源泉,长期以来,寻求方便易得、结构独特、并具有分子识别和自组装功能的主体分子一直是该领域的研究热点,新型主体分子的出现不仅会促进超分子化学研究的快速发展,而且将会进一步推动该领域与生物、物理、材料、环境以及信息等学科的交叉发展,从而产生可以改善人类生活的新材料、新产品。
随着杯芳烃和resorcin[4]arene在超分子化学研究领域的快速发展,近年来,杂原子桥连杯芳烃大环化合物(杯芳烃的结构衍生物)在超分子化学研究中也引起了人们极大的兴趣。通过对芳香环的结构以及桥联碳原子的改变(如-S、-N、-O等杂原子)来实现杯芳烃类化合物空间结构的多样化,从而达到改变分子空腔形状、大小以及捕获不同客体小分子的目的。本文主要研究了几类O-桥杂环不对称“杯芳烃”设计、合成与结构确定,并对其衍生物的合成开展了一些简单的探索工作。
1.以邻苯二酚和二氯代的氮杂芳香环或三嗪氯为原料,合成了4个不对称杯芳烃目标化合物。并用1H-NMR、13C-NMR、高分辨质谱以及X-Ray单晶衍射对其结构进行了确认。发现一些结构类似的化合物在固态下却采取了完全不同的立体构象,例如,邻-氧桥苯[3]嘧啶[3]杯芳烃(3.19)采取了中心构象结构,而邻-氧桥苯[3]吡嗪[3]杯芳烃(3.16)却采取了1,3,5-交替构象。
2.通过对已知杂原子桥连“杯芳烃”结构的分析,我们以邻／间苯二酚和三嗪氯为原料合成了2个不对称O-桥杂环“杯芳烃”化合物,并对其进行修饰,得到了2个咪唑取代衍生物。
The design and synthesis of host molecules is an important area of research and innovation source of supramolecular chemistry. For a long time, the main research focus on this area is to find host molecules that are convenient to synthesize, have unique structures and abilities to recognize‘guest molecules’, or have self-assembly properties. The emergence of any new‘host molecules’will not only accelerate the development of supramolecular chemistry, but also promote the crossing development between this field and other subjects. Such as, biological, physical, material, environmental and information sciences, which could eventually produce new materials and new products.
With the rapid development of Calixarenes and resorcin[4]arene in the field of supramolecular chemistry, the study of hetero-atom bridged calixarene macrocycles (derivatives of the structure of calixarene) in supramolecular chemistry has aroused great interest in recent years. Through the changes of aromatic ring structures and the bridging atoms (such as, S, N, O), the diversification of spatial structures of calixarene structures could be realized, and the objective of modulating the size and the shape of the cavity, and thus the binding abilities towards different guest molecules could also be achieved. In this paper, we present the design and synthesis of several new O-bridged asymmetric'calixarene’, and their modification have been explored.
1. By employing diphenols and chloro-substituted aza-aromatic ring (or triazine) as precursor, we have synthesized four asymmetric nitrogen containing oxocalixarenes. Their structures have been confirmed by1-NMR,13C-NMR, HRMS and single crystal X-RAY analysis. Structure analysis revealed that some of the structural isomers adopted completely different conformations in the solid state. For example, ortho-bridged oxocalix[3]arene[3]pyrimidine adopts a core conformation with C3 symmetry, while ortho-bridged oxocalix[3]arene[3]pyrazine adopts an 1,3,5-alternate conformation.
2. By the analysis structural conformation of the known hetero-atom bridged oxacalixerenes, we designed several new O-bridged asymmetric'calixarene' analogues and modified their structures, two other new derivatives were thus obtained.
随着杯芳烃和resorcin[4]arene在超分子化学研究领域的快速发展,近年来,杂原子桥连杯芳烃大环化合物(杯芳烃的结构衍生物)在超分子化学研究中也引起了人们极大的兴趣。通过对芳香环的结构以及桥联碳原子的改变(如-S、-N、-O等杂原子)来实现杯芳烃类化合物空间结构的多样化,从而达到改变分子空腔形状、大小以及捕获不同客体小分子的目的。本文主要研究了几类O-桥杂环不对称“杯芳烃”设计、合成与结构确定,并对其衍生物的合成开展了一些简单的探索工作。
1.以邻苯二酚和二氯代的氮杂芳香环或三嗪氯为原料,合成了4个不对称杯芳烃目标化合物。并用1H-NMR、13C-NMR、高分辨质谱以及X-Ray单晶衍射对其结构进行了确认。发现一些结构类似的化合物在固态下却采取了完全不同的立体构象,例如,邻-氧桥苯[3]嘧啶[3]杯芳烃(3.19)采取了中心构象结构,而邻-氧桥苯[3]吡嗪[3]杯芳烃(3.16)却采取了1,3,5-交替构象。
2.通过对已知杂原子桥连“杯芳烃”结构的分析,我们以邻／间苯二酚和三嗪氯为原料合成了2个不对称O-桥杂环“杯芳烃”化合物,并对其进行修饰,得到了2个咪唑取代衍生物。
The design and synthesis of host molecules is an important area of research and innovation source of supramolecular chemistry. For a long time, the main research focus on this area is to find host molecules that are convenient to synthesize, have unique structures and abilities to recognize‘guest molecules’, or have self-assembly properties. The emergence of any new‘host molecules’will not only accelerate the development of supramolecular chemistry, but also promote the crossing development between this field and other subjects. Such as, biological, physical, material, environmental and information sciences, which could eventually produce new materials and new products.
With the rapid development of Calixarenes and resorcin[4]arene in the field of supramolecular chemistry, the study of hetero-atom bridged calixarene macrocycles (derivatives of the structure of calixarene) in supramolecular chemistry has aroused great interest in recent years. Through the changes of aromatic ring structures and the bridging atoms (such as, S, N, O), the diversification of spatial structures of calixarene structures could be realized, and the objective of modulating the size and the shape of the cavity, and thus the binding abilities towards different guest molecules could also be achieved. In this paper, we present the design and synthesis of several new O-bridged asymmetric'calixarene’, and their modification have been explored.
1. By employing diphenols and chloro-substituted aza-aromatic ring (or triazine) as precursor, we have synthesized four asymmetric nitrogen containing oxocalixarenes. Their structures have been confirmed by1-NMR,13C-NMR, HRMS and single crystal X-RAY analysis. Structure analysis revealed that some of the structural isomers adopted completely different conformations in the solid state. For example, ortho-bridged oxocalix[3]arene[3]pyrimidine adopts a core conformation with C3 symmetry, while ortho-bridged oxocalix[3]arene[3]pyrazine adopts an 1,3,5-alternate conformation.
2. By the analysis structural conformation of the known hetero-atom bridged oxacalixerenes, we designed several new O-bridged asymmetric'calixarene' analogues and modified their structures, two other new derivatives were thus obtained.
引文
[1](法)莱恩(Lehn, J-M)著,沈兴海等译,超分子化学-概念和展望,北京大学出版社,2006。
[2]Baekeland, L.H. Eng. Chem. (Industry),1913,5(6):506.
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[8]余晓冬,吴采樱.杯芳烃构象的分子力学研究[J].高等学校化学学报,1998,19：1492.
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[13]Boehmer Volker, Chhim Phabet, Kaemmerer Hermann. Makromolekulare Chemie,1979,180 (10):2503.
[14]Boehmer Volker, Marschollek Frank, Zetta, Lucia. J. Org. Chem.,1987,52(15): 3200.
[15]Boehmer Volker, Zetta Lucia, Artur Wolff, Walter Vogt and Karl-Ludwig Platt. Tetrahedron,1991(47):1911.
[16]Harvey, P.D., Coordination Chemistry Reviews,233-234(2002):289.
[17]吕鉴泉.杯芳烃的功能化修饰及其在分子识别中的应用[J].化学进展,2001,13：209.
[18]Yutaka Morita, Toshio Agawa, Eisaku Nomura, Hisaji Taniguchi. J. Org. Chem., 1992,57:3658.
[19]Koji Iwamoto, Koji Araki, Seiji Shinkai. Tetrahedron,1991,47(25):4325.
[20]黄璜.含氮杯[4]芳烃及其聚合物的研究[D].武汉大学硕士学位论,1999：45-46.
[21]胡旭波.杯芳冠醚研究进展,化学通报,1997,4：18.
[22]Jeffrey L. Katz, Bram J. Geller, Peter D. Foster. Chem. Commun.,2007:1026.
[23]Gale, P. A., Sessler, J. L., Kra'l, V. Chem. Commun.,1998,1.
[24]Paris E. Georghiou, Muhammad Ashram, Howard J. Clase, and John N. Bridson. J.Org.Chem.,1998,63:1819.
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[26]Paris E. Georghiou, Shehadeh Mizyed, Sultan Chowdhury. Tetrahedron Lett., 1999,40:611.
[27]黄志镗.杯芳烃的研究进展[A].全国第七届大环化合物学术讨论会论文集[C],中国化学会,济南.1994,8.
[28]Mei-Xiang Wang and Hai-Bo Yang, J. Am. Chem. Soc.2004,126:15412.
[29]Iwamoto K, Araki K, Shinkai S., J.Org.Chem.,1991,56:4956.
[30]Stefaan Depraetere, Mario Smet, Wim Dehaen. Angew. Chem., Int. Ed.1999, 38(22):3359.
[31]Turner, B., Shterenberg, A., Kapon, M., Suwinska, K., Eichen,Y., Chem. Commun.,2001,13.
[32]Bucher, C., Zimmerman, R.S., Lynch, V., Kral, V., Sessler, J.L. J. Am. Chem. Soc (Communication).,2001,123(9):2099.
[33]Cafeo,G., Kohnke, F.H., La Torre, G.L., Parisi, M.F., Nascone, R.P., White, A.J.P., Williams, D.J. Chem-Eur. J.,2002,8:3148.
[34]Floriani, C. Chem. Commun.,1996,1257.
[35]Qi-Qiang Wang, De-Xian Wang, Qi-Yu Zheng, and Mei-Xiang Wang*. Org. Lett., 2007,9(15):2847.
[36]Jeffrey, L., Katz, Michael B., Feldman, and Rebecca R. Conry. Org. Lett.,2005, 7(1):91.
[2]Baekeland, L.H. Eng. Chem. (Industry),1913,5(6):506.
[3]Zinke, A., Ziegler, E. Chem. Ber.,1944,77:264.
[4]Gutsche, C.D., Ramamurthi, M. J. Org. Chem.,1978,43:4905.
[5]Gutsche, C.D. The Royal Society of Chemistry:Cambridge,1989,2:387.
[6]Shinkai, S. Tetrahedron,1993,49:8933.
[7]Qian Wang, Shi Yan Fan, Henry N. C. Wong, Zhong Li and Bing M. Fung, Robert J. Twieg, Huu Tinh Nguyen. Tetrahedron,1993,49:609.
[8]余晓冬,吴采樱.杯芳烃构象的分子力学研究[J].高等学校化学学报,1998,19：1492.
[9]李勇,郑衍昭等.杯[4]芳烃的构象间转换机理的CNDO/2法研究[J].物理化学学报,1995,11(7)：627.
[10]Vicens, J., Bohmer, V. Calixarenes:a versatile class of macrocyclic compounds[M]. Dordrecht; Boston:Kluwer Academic Publishers,1991.
[11]Gutsche, C.D., Balram Dhawan, Kwang Hyun No, Ramamurthi, M. J. Am. Chem. Soc.,1981,103:3782.
[12]John, P.M., van Duynhoven, Rob G. Janssen, Willem Verboom, Sybille M. Franken, Alessandro Casnati, Andrea Pochini, Rocco Ungaro, Javier de Mendoza, Pedro M. Nieto, J. Am. Chem. Soc.,1994,116:5814.
[13]Boehmer Volker, Chhim Phabet, Kaemmerer Hermann. Makromolekulare Chemie,1979,180 (10):2503.
[14]Boehmer Volker, Marschollek Frank, Zetta, Lucia. J. Org. Chem.,1987,52(15): 3200.
[15]Boehmer Volker, Zetta Lucia, Artur Wolff, Walter Vogt and Karl-Ludwig Platt. Tetrahedron,1991(47):1911.
[16]Harvey, P.D., Coordination Chemistry Reviews,233-234(2002):289.
[17]吕鉴泉.杯芳烃的功能化修饰及其在分子识别中的应用[J].化学进展,2001,13：209.
[18]Yutaka Morita, Toshio Agawa, Eisaku Nomura, Hisaji Taniguchi. J. Org. Chem., 1992,57:3658.
[19]Koji Iwamoto, Koji Araki, Seiji Shinkai. Tetrahedron,1991,47(25):4325.
[20]黄璜.含氮杯[4]芳烃及其聚合物的研究[D].武汉大学硕士学位论,1999：45-46.
[21]胡旭波.杯芳冠醚研究进展,化学通报,1997,4：18.
[22]Jeffrey L. Katz, Bram J. Geller, Peter D. Foster. Chem. Commun.,2007:1026.
[23]Gale, P. A., Sessler, J. L., Kra'l, V. Chem. Commun.,1998,1.
[24]Paris E. Georghiou, Muhammad Ashram, Howard J. Clase, and John N. Bridson. J.Org.Chem.,1998,63:1819.
[25]Paris E. Georghiou, Muhammad Ashram, Zhaopeng Li, Steven G. Chaulk. J.Org.Chem.,1995,60:7284.
[26]Paris E. Georghiou, Shehadeh Mizyed, Sultan Chowdhury. Tetrahedron Lett., 1999,40:611.
[27]黄志镗.杯芳烃的研究进展[A].全国第七届大环化合物学术讨论会论文集[C],中国化学会,济南.1994,8.
[28]Mei-Xiang Wang and Hai-Bo Yang, J. Am. Chem. Soc.2004,126:15412.
[29]Iwamoto K, Araki K, Shinkai S., J.Org.Chem.,1991,56:4956.
[30]Stefaan Depraetere, Mario Smet, Wim Dehaen. Angew. Chem., Int. Ed.1999, 38(22):3359.
[31]Turner, B., Shterenberg, A., Kapon, M., Suwinska, K., Eichen,Y., Chem. Commun.,2001,13.
[32]Bucher, C., Zimmerman, R.S., Lynch, V., Kral, V., Sessler, J.L. J. Am. Chem. Soc (Communication).,2001,123(9):2099.
[33]Cafeo,G., Kohnke, F.H., La Torre, G.L., Parisi, M.F., Nascone, R.P., White, A.J.P., Williams, D.J. Chem-Eur. J.,2002,8:3148.
[34]Floriani, C. Chem. Commun.,1996,1257.
[35]Qi-Qiang Wang, De-Xian Wang, Qi-Yu Zheng, and Mei-Xiang Wang*. Org. Lett., 2007,9(15):2847.
[36]Jeffrey, L., Katz, Michael B., Feldman, and Rebecca R. Conry. Org. Lett.,2005, 7(1):91.