Improved Access to 1,8-Dichloro-10-(ethynyl)anthracene: A Useful Building Block for (Semi-)rigid Organic Frameworks
Improved Access to 1,8-Dichloro-10-(ethynyl)anthracene: A Useful Building Block for (Semi-)rigid Organic Frameworks
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改善 1,8-二氯-10-（乙炔基）蒽的获取：（半）刚性有机框架的有用构件
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发表时间：
2018
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通讯作者：
N. Mitzel
中科院分区：
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作者：
Jan;Philipp Niermeier;L. A. Körte;B. Neumann;H. Stammler;N. Mitzel
本文报道了1，8-二氯-10-(乙炔基)菲的一种易得方法，该方法广泛适用于在两个1，8-二氯菲单元之间建立刚性连接体。为此，在CeCl3存在下，1，8-二氯芳烃-10(9H)-酮与乙炔基溴化镁反应，产率为65%。这种构筑块被用作(交叉)偶联反应的底物，并以良好到中等的产率合成了一些连接的1，8-二氯菲-10-YL(例如，1，8-bis[(1，8-dichloroanthracen-10-yl)-ethynyl]naphthalene或1，2-bis[(1，8-dichloroanthracen-10-yl)ethynyl]-benzene))。以10-溴-1，8-二氯菲和双乙炔取代的底物为原料，通过交叉偶联反应合成了1，8-二氯菲-10-基衍生物。1，8-二氯菲单元之间的连接基是：丁二炔、二甲基硅二乙炔、八-1，7-二炔-1，8-二乙基、丙烷-1，3-二(二甲基硅基)二乙炔、苯-1，2-二乙炔、萘-1，8-二乙炔和菲-1，8-二乙炔。用核磁共振谱、高分辨质谱仪和部分X射线衍射仪对新的菲类化合物进行了表征。
Abstract An easy access to 1,8-dichloro-10-(ethynyl)anthracene is reported, which is widely applicable for building up rigid linkers between two 1,8-dichloroanthracene units. For this, 1,8-dichloroanthren-10(9H)-one was reacted with ethynylmagnesium bromide in the presence of CeCl3; the yield was 65%. This building block was used as a substrate in (cross-)coupling reactions and some examples of linked 1,8-dichloroanthracen-10-yls (e.g., 1,8-bis[(1,8-dichloroanthracen-10-yl)-ethynyl]naphthalene or 1,2-bis[(1,8-dichloroanthracen-10-yl)ethynyl]-benzene) were synthesized in good to moderate yields. Linked 1,8-dichloroanthracen-10-yl derivatives were also synthesized by cross-coupling reactions using 10-bromo-1,8-dichloroanthracene and doubly ethynyl-substituted substrates. Linkers between the 1,8-dichloroanthracene units were: butadiynediyl, dimethylsilyldiethynyl, octa-1,7-diyne-1,8-diyl, propane-1,3-diylbis(dimethylsilyl)diethynyl, benzene-1,2-diethynyl, naphthalene-1,8-diyldiethynyl, and anthracene-1,8-diyldiethynyl. The new anthracene compounds were characterized by NMR spectroscopy, high-resolution mass spectrometry, and, in part, by X-ray diffraction experiments.