Regioisomerically Pure 1,7-Dibromo-Substituted Perylene Bisimide Dyes: Efficient Synthesis, Separation, and Characterization
Regioisomerically Pure 1,7-Dibromo-Substituted Perylene Bisimide Dyes: Efficient Synthesis, Separation, and Characterization
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区域异构纯 1,7-二溴取代苝双酰亚胺染料：高效合成、分离和表征
DOI：
10.1002/ejoc.201500206
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发表时间：
2015-05-01
影响因子：
2.8
通讯作者：
Zhang, Qijin
中科院分区：
文献类型：
--
作者：
Ma, Jiajun;Yin, Leicheng;Zhang, Qijin
用2-(二乙氨基)乙胺或2-(二甲氨基)乙胺处理常用的二溴-3，4，9，10-四羧酸二酸酐，然后用常规柱色谱从区域异构体混合物中分离出1，7-异构体，得到了产率至少为60%的区域异构化的1，7-二溴取代二亚胺。各区域异构体均经核磁共振氢谱和高分辨质谱学确证。利用位于芳香区和亚胺氮原子附近的质子的信号来确认异构体的化学结构。以2-二甲氨基乙胺为原料，方便、高效地合成了1，7-二溴异构体，并进一步通过皂化、酰胺化、海湾取代反应合成了1，7-二取代二苯二亚胺衍生物。这些化合物在光谱分析中表现出明显的红移和吸收和发射展宽。
1,7‐Dibromo‐substituted perylene bisimides have been obtained in yields of at least 60 % in regioisomerically pure form by treating the commonly used dibromoperylene‐3,4,9,10‐tetracarboxylic dianhydride with 2‐(diethylamino)ethylamine or 2‐(dimethylamino)ethylamine and then separating the 1,7‐isomer from the regioisomeric mixtures by conventional column chromatography and without recrystallization. The individual regioisomers were fully characterized by 1H NMR spectroscopy and HRMS. The signals of the protons located in the aromatic region and neighboring the imide nitrogen atom were utilized to confirm the chemical structures of the isomers. The 1,7‐dibromo isomer obtained with 2‐(dimethylamino)ethylamine in such a convenient and efficient way was further used to prepare 1,7‐disubstituted perylene bisimide derivatives by saponification, amidation, and then bay‐position substitution reactions. These compounds exhibited a significant redshift and broadening of their absorption and emission in optical spectroscopy analysis.