Regioisomerically Pure 1,7-Dibromo-Substituted Perylene Bisimide Dyes: Efficient Synthesis, Separation, and Characterization

• Published in: European journal of organic chemistry Vol. 2015; no. 15; pp. 3296 - 3302
• Main Authors: Ma, Jiajun, Yin, Leicheng, Zou, Gang, Zhang, Qijin
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.05.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Chemistry; Chemistry, Organic; Dyes/Pigments; Physical Sciences; Regioselectivity; Science & Technology; Separation methods; Spectrum analysis; UV/Vis spectroscopy; ENERGY; Regioselectivity; 1,6-REGIOISOMERS; DIIMIDES; Separation methods; UV/Vis spectroscopy; Dyes/Pigments
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201500206

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. 1,7‐Dibromo‐substituted perylene bisimides have been isolated from regioisomeric mixtures by column chromatography in yields of at least 60 %. The 1,7‐disubstituted intermediates can provide a convenient and efficient approach to novel perylene bisimide derivatives.