Abstract
(Chemical Equation Presented) 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.
| Original language | English |
|---|---|
| Pages (from-to) | 5973-5979 |
| Number of pages | 7 |
| Journal | Journal of Organic Chemistry |
| Volume | 72 |
| Issue number | 16 |
| DOIs | |
| Publication status | Published - Aug 2007 |
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ASJC Scopus subject areas
- Organic Chemistry
Cite this
Selective bromination of perylene diimides under mild conditions. / Rajasingh, Paramasivan; Cohen, Revital; Shirman, Elijah; Shimon, Linda J W; Rybtchinski, Boris.
In: Journal of Organic Chemistry, Vol. 72, No. 16, 08.2007, p. 5973-5979.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Selective bromination of perylene diimides under mild conditions
AU - Rajasingh, Paramasivan
AU - Cohen, Revital
AU - Shirman, Elijah
AU - Shimon, Linda J W
AU - Rybtchinski, Boris
PY - 2007/8
Y1 - 2007/8
N2 - (Chemical Equation Presented) 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.
AB - (Chemical Equation Presented) 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.
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U2 - 10.1021/jo070367n
DO - 10.1021/jo070367n
M3 - Article
VL - 72
SP - 5973
EP - 5979
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 16
ER -