杯芳烃衍生物的合成研究
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摘要
杯芳烃是由苯酚单元与甲醛缩合而成的大环化合物,具有空腔可调节、构象可变化、结构易修饰和合成较方便等优点,被认为是继冠醚、环糊精之后的第三代主体化合物。
杯芳烃与树枝状大分子是超分子化学中两类极为重要的主体分子,将这两种主体分子结合在一起所得到的含有杯芳烃的树枝状大分子,不仅能够将两者的优点集中到一个分子之中,同时还有可能产生一些新颖的性能,成为新型的智能材料、分子器件或是纳米材料。
十年前,一种新型的由硫原子取代杯芳烃中桥联亚甲基的硫杂杯[4]芳烃作为新型杯芳烃主体分子,成为超分子化学研究新热点受到广泛关注,与传统杯芳烃相比,桥联硫原子的存在使硫杂杯芳烃具有一些优异的特征,例如更好的络合能力,易于化学修饰,不同的空腔结构和立体构型等。在近十年中硫杂杯芳烃的化学研究取得了非常丰富的研究成果。
本论文开展了以亚甲基杯芳烃为重复单元合成树枝状分子和以硫杂杯芳烃的为主体进行化学结构修饰合成含有硫醚功能基的分子的研究。以期在分子识别、多重识别以及自组装方面有有特异的性质,本文主要成果如下:
1.通过Williamson成醚反应对叔丁基亚甲基杯芳烃的下沿结构进行了修饰;通过Sonogashira偶联合成“Y”、“X”型芳炔内核,并通过Sonogashira偶联反应高产率的合成了“Y”、“X”型树枝状目标分子。并对合成过程的一些重要反应进行研究。
2.通过一步法合成了对叔丁基硫杂杯芳烃,随后以硫杂杯芳烃母体进行结构修饰,先后通过Friedel-crafts的逆反应、NBS溴化、Williamson成醚反应以及Sonogashira偶联反应成功的合成出了具有硫醚功能基的硫杂杯芳烃衍生物。
一些中间化合物和所有的目标分子的结构经过~1H NMR、~(13)C NMR、及MS表征得到了确认。
Calixarene is one kind of macrocyclic compounds derived from the condensation of phenol with aldehyde. With ease of sythesis, much more functionality, persistent shape and size as well as easily chemical modification calixarenes are named as the third generation superamolecular hosters and have been used as the platforms for so many types of chemical researches.
Calixarenes and dendrimers are two types of the most important host molecules in supramolecular chemistry. The link between calixarene and dendrimer has long been regarded as one of the most ambitious targets in this field. Calixarene-based dendrimers have some promising advantages and novel properties due to their unique structures consisting of both calixarene and dendrimer. They can be potentially applied to many fascinating areas such as smart materials, molecular devices and nano materials.
Form 1997 thiacalixarene in which methylene bridge replaced by sulfur bond has been recongnized and quickly become new important class of synthetic host molecules and have versatile applications in supramolecular chemistry such as complex extraction, molecular devices, molecular recongnition, self-assembly and nanomaterials. The presence of sulfur atoms in place of the usual CH2 bridges makes thiacalix[4]arenas very interesting molecules, with many features that are not present in the chemistry of classical calixarenes. It is now obvious that these compounds posses some very uncommon features, different conformational preferences, and special complexation properties, and thus have many potential applications.
In this paper we studied the synthesis of calixarene-based dendrimers and used thiacalix[4]arene as the platform for the synthesis of arylthioether. We hoped it could have some novel properties in molecular recognition、multiple recognition and self-assembly. The synthesis result of this paper as follows:
1.We used the Williamson reaction to change the lower rim of the calixarene, then used the Sonogashira reaction to synthesis the shape of“Y”、“X”arylacetylene core. At last we got the dendrimers molecular used sonogashira reaction in high yield. We had also studied the process of some important reactions in the synthesis.
2. We used one step reaction to synthesis of thiacalixarene, then used it as the platform for the synthesis of arylthioether compound. For the synthesis of the title compound we had been used Friedel-crafts reaction、NBS bromide、Williamson and Sonogashira coupling reaction.
The structure of some intermediates and all target compounds synthesized in this paper were characterized by ~1H NMR, ~(13)C NMR, and MS.
杯芳烃与树枝状大分子是超分子化学中两类极为重要的主体分子,将这两种主体分子结合在一起所得到的含有杯芳烃的树枝状大分子,不仅能够将两者的优点集中到一个分子之中,同时还有可能产生一些新颖的性能,成为新型的智能材料、分子器件或是纳米材料。
十年前,一种新型的由硫原子取代杯芳烃中桥联亚甲基的硫杂杯[4]芳烃作为新型杯芳烃主体分子,成为超分子化学研究新热点受到广泛关注,与传统杯芳烃相比,桥联硫原子的存在使硫杂杯芳烃具有一些优异的特征,例如更好的络合能力,易于化学修饰,不同的空腔结构和立体构型等。在近十年中硫杂杯芳烃的化学研究取得了非常丰富的研究成果。
本论文开展了以亚甲基杯芳烃为重复单元合成树枝状分子和以硫杂杯芳烃的为主体进行化学结构修饰合成含有硫醚功能基的分子的研究。以期在分子识别、多重识别以及自组装方面有有特异的性质,本文主要成果如下:
1.通过Williamson成醚反应对叔丁基亚甲基杯芳烃的下沿结构进行了修饰;通过Sonogashira偶联合成“Y”、“X”型芳炔内核,并通过Sonogashira偶联反应高产率的合成了“Y”、“X”型树枝状目标分子。并对合成过程的一些重要反应进行研究。
2.通过一步法合成了对叔丁基硫杂杯芳烃,随后以硫杂杯芳烃母体进行结构修饰,先后通过Friedel-crafts的逆反应、NBS溴化、Williamson成醚反应以及Sonogashira偶联反应成功的合成出了具有硫醚功能基的硫杂杯芳烃衍生物。
一些中间化合物和所有的目标分子的结构经过~1H NMR、~(13)C NMR、及MS表征得到了确认。
Calixarene is one kind of macrocyclic compounds derived from the condensation of phenol with aldehyde. With ease of sythesis, much more functionality, persistent shape and size as well as easily chemical modification calixarenes are named as the third generation superamolecular hosters and have been used as the platforms for so many types of chemical researches.
Calixarenes and dendrimers are two types of the most important host molecules in supramolecular chemistry. The link between calixarene and dendrimer has long been regarded as one of the most ambitious targets in this field. Calixarene-based dendrimers have some promising advantages and novel properties due to their unique structures consisting of both calixarene and dendrimer. They can be potentially applied to many fascinating areas such as smart materials, molecular devices and nano materials.
Form 1997 thiacalixarene in which methylene bridge replaced by sulfur bond has been recongnized and quickly become new important class of synthetic host molecules and have versatile applications in supramolecular chemistry such as complex extraction, molecular devices, molecular recongnition, self-assembly and nanomaterials. The presence of sulfur atoms in place of the usual CH2 bridges makes thiacalix[4]arenas very interesting molecules, with many features that are not present in the chemistry of classical calixarenes. It is now obvious that these compounds posses some very uncommon features, different conformational preferences, and special complexation properties, and thus have many potential applications.
In this paper we studied the synthesis of calixarene-based dendrimers and used thiacalix[4]arene as the platform for the synthesis of arylthioether. We hoped it could have some novel properties in molecular recognition、multiple recognition and self-assembly. The synthesis result of this paper as follows:
1.We used the Williamson reaction to change the lower rim of the calixarene, then used the Sonogashira reaction to synthesis the shape of“Y”、“X”arylacetylene core. At last we got the dendrimers molecular used sonogashira reaction in high yield. We had also studied the process of some important reactions in the synthesis.
2. We used one step reaction to synthesis of thiacalixarene, then used it as the platform for the synthesis of arylthioether compound. For the synthesis of the title compound we had been used Friedel-crafts reaction、NBS bromide、Williamson and Sonogashira coupling reaction.
The structure of some intermediates and all target compounds synthesized in this paper were characterized by ~1H NMR, ~(13)C NMR, and MS.
引文
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[2] Gutsehe C D, Ramurthi M. Calixarene analysis of the product mixtures produced by the based-catalyzed condensation of formaldehyde with para-substituted phenols. J. Org. Chem., 1978, 43(25): 4905-4906
[3] Tabakci M, Memon S, Yilmaz M, et al. Synthesis and evaluation of extraction ability of calix[4]-cown-6 cone conformer and its oligomeric analogue. Reactive and Functional Polymers., 2004, 58(l): 27-34
[4] Narumi F, Hattori T, Matsumura N, et al. Synthesis of an inherently chiral O,Oˊ-bridged thiacalix[4]crowncarboxylic acid and its application to a chiral solvating agent. Tetrahedron., 2004, 60(36): 7827-7833
[5] Bohmer V. Calixarenes, macrocycles with (almost) unlimited possibilities. Angew. Chem., Ed. Engl.,1995,34(7): 713-745
[6] Casnati A,Sansone F,Ungaro R. Peptido-and glycocalixarenes: playing with hydrogen bonds around hydrophobic cavity. Acc. Chem. Res., 2003,36(4): 246-254
[7]吴萍,韩军,戈云.超分子砌块间苯二酚杯芳烃的研究进展.有机化学.,2006, 26(4): 431-441
[8]王腾凤,杨石柱.杯芳烃催化剂在有机反应中的应用.化学试剂.,2000,22(5): 274-278
[9] Gutsche C D, Nam K C. Synthesis Properties and metal complexation of aminocalixarenes. J. Am. Chem. Soc., 1988, 110(18): 6153-6162
[10] Shinkai S, Mori S, Tsubrki T, et al. New water-soluble host molecules derived from calix[6]arene. Tetrahedron Lett., 1984, 25(46): 5315-5318
[11] See K A, Fronczek F R, Gutsche C D, et al. Selective esterification and selective ester cleavage of calix[4]arenes. J. Org. Chem., 1991, 56(26): 7256-7268
[12] Sharma S K, Gutsehe C D. Synthesis and Reactions of Calix[4]arene Bisanhydrides. J. Org. Chem., 1999, 64(10): 3507-3512.
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