Synthesis of Regioisomerically Pure 1,7-Dibromoperylene-3,4,9,10-tetracarboxylic Acid Derivatives

• Published in: Journal of organic chemistry Vol. 79; no. 14; pp. 6655 - 6662
• Main Authors: Sengupta, Sanchita, Dubey, Rajeev K, Hoek, Rob W. M, van Eeden, Sjoerd P. P, Gunbaş, D. Deniz, Grozema, Ferdinand C, Sudhölter, Ernst J. R, Jager, Wolter F
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 18-07-2014
• Subjects: Butyrates - chemical synthesis; Butyrates - chemistry; Molecular Structure; Perylene - analogs & derivatives; Perylene - chemical synthesis; Perylene - chemistry; Stereoisomerism
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo501180a

The perylene derivative 1,7-dibromo­perylene-3,4,9,10-tetracarboxylic tetrabutylester has been obtained in regioisomerically pure form, by employing a highly efficient, scalable, and robust synthesis starting from commercially available perylene-3,4,9,10-tetra­carboxylic bisanhydride. Subsequently, this compound is utilized for the synthesis of extremely valuable and versatile regioisomerically pure intermediates, namely, 1,7-dibromo­perylene-3,4,9,10-tetra­carboxylic dibutylester monoanhydride, 1,7-dibromo­perylene-3,4,9,10-tetra­carboxylic bisanhydride, and 1,7-dibromo­perylene monoimid monoanhydride. These compounds possess at least one anhydride functionality in addition to the 1,7 bromo substituents and thus allow for a virtually limitless attachment of substituents both at the “peri” and the “bay” positions. The intermediate 1,7-dibromoperylene monoimide monoanhydride is of special interest as it provides access to unsymmetrically imide-substituted 1,7-dibromoperylene derivatives, which are not accessible by previously known procedures. Finally, substitution of the 1,7 bromine atoms in the bay area by phenoxy groups, which is a generally applied reaction for 1,7-dibromoperylene bisimides, was proven to be equally effective for a 1,7-dibromoperylene tetraester and a 1,7-dibromoperylene diester monoimid.