Cyclization of a 1,8‐Diphenylanthracene by Scholl Reactions to Form Five‐ and Seven‐Membered Ring Embedded Polycyclic Aromatic Hydrocarbons
- 1Department of Chemistry School of Science Institute of Science Tokyo Tokyo Japan
Abstract
Scholl reactions of 10‐mesityl‐1,8‐diphenylanthracene with DDQ (or chloranil) in TfOH/CH2Cl2 yielded three cyclized products depending on the equivalent of the oxidant. The singly cyclized product was a benzo[a]fluoranthene derivative, which further cyclized to the doubly cyclized product by formation of a seven‐membered ring. Reactions with a large amount of DDQ yielded a deep red product, which was identified as an unexpected triply cyclized product with a rubicene framework formed via the migration of a methyl group in the mesityl group. The molecular structures and aromaticity of these five‐ and seven‐membered ring products were investigated by X‐ray analysis and DFT calculations. The optical and electrochemical properties depend on the HOMO–LUMO gap, which decreases as the cyclization proceeds. The rubicene formation is proposed to proceed via an arenium ion intermediate and a 1,2‐methyl shift step.
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BibTeX
@article{sasaki2026cyclization,
title = {{Cyclization of a 1,8‐Diphenylanthracene by Scholl Reactions to Form Five‐ and Seven‐Membered Ring Embedded Polycyclic Aromatic Hydrocarbons}},
author = {Tatsuhiro Sasaki and Eiji Tsurumaki and Shinji Toyota},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = jul,
doi = {10.1002/chem.71449},
url = {https://doi.org/10.1002/chem.71449},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Cyclization of a 1,8‐Diphenylanthracene by Scholl Reactions to Form Five‐ and Seven‐Membered Ring Embedded Polycyclic Aromatic Hydrocarbons
AU - Tatsuhiro Sasaki
AU - Eiji Tsurumaki
AU - Shinji Toyota
PY - 2026
DA - 2026/07/20
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71449
UR - https://doi.org/10.1002/chem.71449
AB - Scholl reactions of 10‐mesityl‐1,8‐diphenylanthracene with DDQ (or chloranil) in TfOH/CH2Cl2 yielded three cyclized products depending on the equivalent of the oxidant. The singly cyclized product was a benzo[a]fluoranthene derivative, which further cyclized to the doubly cyclized product by formation of a seven‐membered ring. Reactions with a large amount of DDQ yielded a deep red product, which was identified as an unexpected triply cyclized product with a rubicene framework formed via the migration of a methyl group in the mesityl group. The molecular structures and aromaticity of these five‐ and seven‐membered ring products were investigated by X‐ray analysis and DFT calculations. The optical and electrochemical properties depend on the HOMO–LUMO gap, which decreases as the cyclization proceeds. The rubicene formation is proposed to proceed via an arenium ion intermediate and a 1,2‐methyl shift step.
SN - 0947-6539
SN - 1521-3765
ER -