Selective bromination of perylene diimides under mild conditions

被引：202

作者：

Rajasingh, Paramasivan ^{[1
]}

Cohen, Revital ^{[1
]}

Shirman, Elijah ^{[1
]}

Shimon, Linda J. W. ^{[1
]}

Rybtchinski, Boris ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, Chem Res Support Unit, IL-76100 Rehovot, Israel

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 72卷 / 16期

关键词：

D O I：

10.1021/jo070367n

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A novel method for the bromination of perylene diimides, PDI (1), under mild conditions is reported. Variation of the reaction conditions allows mono- and dibromination of PDIs to afford 2 and 3 (these can be separated through standard procedures) or exclusive dibromination to afford 3. Pure 1,7 regioisomers are obtained through repetitive crystallization. The structure of 1,7-3b was elucidated by a single-crystal X-ray analysis. The facility of the bromination reaction, which decreases in the order 1a > 1b > 1c, depends on PDI aggregation propensities. Monobrominated PDIs were utilized for the syntheses of novel unsymmetrical piperidinyl (4a and 4b) and trimethylsilylethynyl derivatives (5a and 5b). Computational studies (DFT) on imide substituent rotation in PDIs reveal that in the case of bulky groups there is a restricted rotation leading to isomers, in agreement with our experimental results. An aromatic core twist in PDIs bearing one and two bromine substituents was also investigated by DFT.

引用

页码：5973 / 5979

页数：7

共 49 条

[1] Synthesis of a bis(pyridyl)-substituted perylene diimide ligand and incorporation into a supramolecular rhomboid and rectangle via coordination driven self-assembly [J].