Triptycene-based expanded oxacalixarenes: synthesis, structure, and tubular assemblies in the solid state.
Triptycene-based expanded oxacalixarenes: synthesis, structure, and tubular assemblies in the solid state.
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DOI：
10.1021/jo0702490
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发表时间：
2007-04
期刊：
影响因子：
--
通讯作者：
Chun Zhang;Chuanning Chen
中科院分区：
文献类型：
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作者：
Chun Zhang;Chuanning Chen
利用三蝶烯独特的三维刚性结构，在碳酸铯存在下，通过2，7-二羟基三蝶烯与2，3，5，6-四氯吡啶的SNAr反应，一步合成了两种新型的膨胀氧杂杯芳烃5a和5 b。同样地，通过2，7-二羟基三蝶烯分别与1，5-二氟-2，4-二硝基苯和三聚氯氰的SNAr反应，也可以得到另外两对基于三蝶烯的扩展oxaxalixaenes 7a，7 b和9a，9 b.通过核磁共振、质谱和X-射线晶体结构分析研究了扩链氧杂杯芳烃的结构。结果表明，氧杂杯芳烃9 b在船式构象和椅式构象之间发生了动态的相互转化。此外，我们还发现，膨胀的氧杂杯芳烃5a，5 b和9a都可以组装成有机管状结构和进一步的多孔结构在固态下，其中的氯键，如C-Cl…Cl，C-Cl. O和C-Clπ的相互作用，发挥了重要作用。
Owing to the unique 3D rigid structure of triptycene, two novel expanded oxacalixarenes 5a and 5b as a pair of diastereomers were efficiently synthesized in a single step by the SNAr reaction of 2,7-dihydroxytriptycene with 2,3,5,6-tetrachloropyridine in the presence of cesium carbonate. Similarly, two pairs of other triptycene-based expanded oxaxalixaenes 7a,7b and 9a,9b could also be obtained by the SNAr reactions of 2,7-dihydroxytriptycene with 1,5-difluoro-2,4-dinitrobenzene and cyanuric chloride, respectively. The structures of the expanded oxacalixarenes were studied by NMR, MS spectra, and X-ray crystal structure analyses. It was found that the expanded oxacalixarene 9b showed a dynamic interconversion between boat and chair conformations. Moreover, we also found that the expanded oxacalixarenes 5a, 5b, and 9a could all assemble into organic tubular structures and further porous architectures in the solid state, in which chlorine bonding, such as C-Cl...Cl, C-Cl...O, and C-Cl...pi interactions, played an important role.