采用分子间Glaser 半环闭环法合成了带内取向柔性多醚链的苯炔大环. 用1H NMR, 13C NMR, HRMS, UV 及PL(photduminescence)确证了目标大环结构, 凝胶色谱测定了目标大环纯度. 经偏光显微镜(POM)和差热分析仪(DSC)测试表明大环没有呈现预期的液晶性质, 可能是由于环内柔性链过于拥挤, 不能形成与环平面共面结构, 以至于难于进行有序堆积的缘故.
Shape-persistent phenyl ethynylene macrocycles with intraanular flexible oligooxylethylene chains were synthesized by intramolecular Glaser coupling reaction of half rings. The structures of target phenyl ethynylene macrocycles were identified by 1H NMR, 13C NMR, HRMS, UV and PL (photduminescence), The purity of the target macrocycles was determined by GPC. All the macrocycles are nomesogens as indicated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC), the reason is analyzed as the streric hindrance of the intrannular flexible chains which led to the anordered aggregation of the macrocycles.
[1] Cheng, X. H.;Ju, X. P.; H?ger,S. Chin. J.Org.Chem.2006, 26(5),733 (in Chinese)
（程晓红，鞠秀萍，Hoeger,Sigurd，有机化学，2006，26(5)，733）
[2] Rosselli, S.; Ramminger, A. D.; Wagner, T.; Silier, B.; Wiegand, S.; H?u?ler,W; Lieser, G.; Scheumann, V.; H?ger, S. Angew. Chem. 2001, 113,3233.
[3] Rosselli, S.; Ramminger, A. D.; Wagner, T.; Lieser, G.; H?ger, S. Chem. Eur. J. 2003, 9, 3481.
[4] H?ger, S.; Morrison, D. L.; Enkelmann,V. J. Am. Chem. Soc. 2002, 124(23), 6734.
[5] Zhang, J. S.; Moore, J. S. J. Am. Chem. Soc. 1994,116,2655.
[6] Fischer, M.; Lieser,G.; Rapp, A.; Schnell, I.; Mamdouh, W.; Feyter, S. D.; Schryver, F. C. D.; H?ger,S. J. Am. Chem. Soc. 2004, 126, 214.
[7] Kawase ,T.; Seirai, Y.; Darabi, H. R.; Oda, M.; Sarakai,Y.; Tashiro, K. Angew Chem. 2003,115(14), 1662.
[8] Kawase,T.; Nishiyama,Y.; Nakamura,T.; Ebi,T.; Matsumoto,K.; Kurata, H.; Oda. M. Angew Chem. 2007,119(7),1104.
[9] Xie, Z.; Zhang, W.; Huang, P. C. Chin. J.Org.Chem. 2002,22(8),543.
（谢政,张炜,黄鹏程,有机化学,2002,22(8),543．）
[10] Moore, J. S. Acc. Chem. Res. 1997, 30, 402.
[11] H?ger,S. J. Poly. Sci.: Part A: Poly. Chem. 1999,37, 2685.
[12] H?ger,S. Chem. Eur. J. 2004, 10, 1320.
[13] Cheng, X. H.; H?ger,S. Chem. J. Chin. Uni.2007,28(1),65.
（程晓红，Sigurd H?ger，高等学校化学学报，2007，28（1），65．）
[14] Liu, W. J. ; Zhou,Y.; Zhou, Q. F.; Ma,Y. G.; Pei, J. Org. Lett.,2008, 10(11),2123.
[15] Staab, H. A.; Neunhoeffer, K. Synthesis 1974,424.
[16] H?ger, S.; Enkelmann,V.; Bonrad, K.; Tschiers,C. Angew. Chem., Int. Ed,2000, 39, 2267.
[17] H?ger, S.; Cheng, X. H.; Ramminger, A. D.; Enkelmann,V.; Rapp, A.; Mondeshki; M.; Schnell,I. Angew. Chem. Int. Ed. 2005, 44, 2801.
[18] H?ger, S.; Weber, J.; Leppert, A.; Enkelmann,V. Beilstein J. Org. chem., 2008, 4, 1.
