^‡ These authors contributed equally to this work.

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.

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.

中文翻译：

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改善对1,8-二氯-10-（乙炔基）蒽的获取：(半）刚性有机框架的有用构建基块

^‡这些作者对这项工作做出了同等的贡献。

抽象的

据报道，很容易获得1,8-二氯-10-（乙炔基）蒽，它广泛适用于在两个1,8-二氯蒽单元之间建立刚性连接基。为此，在CeCl ₃存在下，使1,8-二氯蒽-10（9 H）-1与乙炔基溴化镁反应; 产率为65％。该结构单元用作（交叉）偶联反应和（例如）1,8-双[（1,8-dichloroanthracen-10-yl）-合成乙炔基萘或1,2-双[（1,8-二氯蒽-10-基）乙炔基]-苯）的产率中等至中等。还使用10-溴-1,8-二氯蒽和双乙炔基取代的底物通过交叉偶联反应合成了连接的1,8-二氯蒽-10-基团衍生物。1,8-二氯蒽单元之间的连接基为：丁二炔二基，二甲基甲硅烷基二乙炔基，辛基1,8,7-二炔-1,8-二基，丙烷-1,3-二基双（二甲基甲硅烷基）二乙炔基，苯1,2-二乙炔基，萘-1，8-二基二乙炔基和蒽-1，8-二基二乙炔基。通过NMR光谱，高分辨率质谱对新型蒽化合物进行了表征，并且

据报道，很容易获得1,8-二氯-10-（乙炔基）蒽，它广泛适用于在两个1,8-二氯蒽单元之间建立刚性连接基。为此，在CeCl ₃存在下，使1,8-二氯蒽-10（9 H）-1与乙炔基溴化镁反应; 产率为65％。该结构单元用作（交叉）偶联反应和（例如）1,8-双[（1,8-dichloroanthracen-10-yl）-合成乙炔基萘或1,2-双[（1,8-二氯蒽-10-基）乙炔基]-苯）的产率中等至中等。还使用10-溴-1,8-二氯蒽和双乙炔基取代的底物通过交叉偶联反应合成了连接的1,8-二氯蒽-10-基团衍生物。1,8-二氯蒽单元之间的连接基为：丁二炔二基，二甲基甲硅烷基二乙炔基，辛基1,8,7-二炔-1,8-二基，丙烷-1,3-二基双（二甲基甲硅烷基）二乙炔基，苯1,2-二乙炔基，萘-1，8-二基二乙炔基和蒽-1，8-二基二乙炔基。通过NMR光谱，高分辨率质谱对新型蒽化合物进行了表征，并且