Abstract

Sixfold electrophilic bromination and iodination of the molecular periphery of the bridgehead-tetramethylated tribenzotriquinac­ene (TBTQ) with N-bromosuccinimide (NBS) and N-iodosuccinimide (NIS), respectively, under various conditions was studied to develop an alternative preparative approach to the classical Lewis acid catalyzed bromination. Running these reactions in trifluoroacetic acid either in pure form or with chloroform as a co-solvent at elevated temperatures, or under sonication or microwave irradiation was found to give increasingly fast and efficient conversion of TBTQ to the target hexahalogenated TBTQ derivatives in excellent yields. NIS was found to be markedly more reactive than NBS, whereas N-chlorosuccimide reacted hardly. The new method was applied to the sixfold functionalization of the 4b,8b,12b-tripropyl-12d-methyl-TBTQ analogue to give the corresponding hexabromo and hexaiodo derivatives. Some sixfold C–C cross-coupling reactions of hexahalo derivatives of TBTQ were carried out in excellent yields to enlarge the three spatially orthogonal indane wings of the TBTQ core.

Sixfold electrophilic bromination and iodination of the molecular periphery of the bridgehead-tetramethylated tribenzotriquinac­ene (TBTQ) with N-bromosuccinimide (NBS) and N-iodosuccinimide (NIS), respectively, under various conditions was studied to develop an alternative preparative approach to the classical Lewis acid catalyzed bromination. Running these reactions in trifluoroacetic acid either in pure form or with chloroform as a co-solvent at elevated temperatures, or under sonication or microwave irradiation was found to give increasingly fast and efficient conversion of TBTQ to the target hexahalogenated TBTQ derivatives in excellent yields. NIS was found to be markedly more reactive than NBS, whereas N-chlorosuccimide reacted hardly. The new method was applied to the sixfold functionalization of the 4b,8b,12b-tripropyl-12d-methyl-TBTQ analogue to give the corresponding hexabromo and hexaiodo derivatives. Some sixfold C–C cross-coupling reactions of hexahalo derivatives of TBTQ were carried out in excellent yields to enlarge the three spatially orthogonal indane wings of the TBTQ core.

中文翻译：

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三苯并三喹乙炔的六倍周边卤化：有用的TBTQ构件的替代途径

摘要

研究了桥头四甲基化三苯并三喹并二烯（TBTQ）与N-溴代琥珀酰亚胺（NBS）和N-碘代琥珀酰亚胺（NIS）分别在不同条件下的六倍亲电溴化和碘化反应，以开发出经典Lewis的另一种制备方法酸催化溴化。发现这些反应在纯氟形式或与氯仿作为助溶剂的三氟乙酸中在升高的温度下，或在超声或微波辐射下进行，能够以优异的收率越来越快速有效地将TBTQ转化为目标六卤代TBTQ衍生物。发现NIS的反应活性明显高于NBS，而N-氯琥珀酰亚胺几乎不反应。将该新方法应用于4b，8b，12b-三丙基-12d-甲基-TBTQ类似物的六重官能化，得到相应的六溴和六碘代衍生物。TBTQ六卤代衍生物的六倍C–C交叉偶联反应以优异的产率进行，从而扩大了TBTQ核的三个空间正交的茚满双翼。

研究了桥头四甲基化三苯并三喹并二烯（TBTQ）与N-溴代琥珀酰亚胺（NBS）和N-碘代琥珀酰亚胺（NIS）分别在不同条件下的六倍亲电溴化和碘化反应，以开发出经典Lewis的另一种制备方法酸催化溴化。发现这些反应在纯氟形式或与氯仿作为助溶剂的三氟乙酸中在升高的温度下，或在超声或微波辐射下进行，能够以优异的收率越来越快速有效地将TBTQ转化为目标六卤代TBTQ衍生物。发现NIS的反应活性明显高于NBS，而N-氯琥珀酰亚胺几乎不反应。将该新方法应用于4b，8b，12b-三丙基-12d-甲基-TBTQ类似物的六重官能化，得到相应的六溴和六碘代衍生物。TBTQ六卤代衍生物的六倍C–C交叉偶联反应以优异的产率进行，从而扩大了TBTQ核的三个空间正交的茚满双翼。