Quantum Chemical Investigation of the Dimroth Rearrangement of 1‐(5‐Imino‐4,5‐dihydro‐1H‐1,2,3‐triazol‐1‐yl)anthracene‐9,10‐dione
- 1Department of Chemistry, Pharmaceutical Analysis and Postgraduate Education Ivano‐Frankivsk National Medical University Ivano‐Frankivsk Ukraine
- 2Department of Environmental Chemistry and Chemistry Education Vasyl Stefanyk Carpathian National University Ivano‐Frankivsk Ukraine
- 3Department of Applied Physics and Materials Science Vasyl Stefanyk Carpathian National University Ivano‐Frankivsk Ukraine
Abstract
This work is devoted to quantum chemical and experimental studies of the Dimroth rearrangement mechanism of 1‐(5‐imino‐4,5‐dihydro‐1H‐1,2,3‐triazol‐1‐yl)anthracene‐9,10‐dione. The study addresses how the bulky N‐ anthraquinonyl substituent affects the individual steps of the Dimroth rearrangement. The energy profile of the Dimroth rearrangement was calculated using density functional theory with the B3LYP approximation and the 6‐311++G(d,p) basis set. It was found that proton solvents (in particular, ethanol) play a critical role in hydrogen transfer via the hydrogen‐bond network, thereby ensuring the conversion of the initial triazene into a more stable cyclic 5‐aminotriazole. Further transformations involving ring opening and rotation do not have significant energy barriers. The final product is energetically most favorable, so the reaction proceeds easily in ethanol solution. The work demonstrates the convenience and efficiency of using the Dimroth rearrangement for the synthesis of new anthracenedione‐containing heterocycles. It provides an explanation of the mechanism of this rearrangement based on quantum‐chemical calculations for anthracene‐9,10‐dione derivatives.
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BibTeX
@article{melnyk2026quantum,
title = {{Quantum Chemical Investigation of the Dimroth Rearrangement of 1‐(5‐Imino‐4,5‐dihydro‐1H‐1,2,3‐triazol‐1‐yl)anthracene‐9,10‐dione}},
author = {Dmytro Melnyk and Vasyl Shupeniuk and Tetyana Taras and Volodymyr Kotsyubynsky},
journal = {ChemistryOpen},
year = {2026},
month = oct,
doi = {10.1002/open.70330},
url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.70330},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Quantum Chemical Investigation of the Dimroth Rearrangement of 1‐(5‐Imino‐4,5‐dihydro‐1H‐1,2,3‐triazol‐1‐yl)anthracene‐9,10‐dione
AU - Dmytro Melnyk
AU - Vasyl Shupeniuk
AU - Tetyana Taras
AU - Volodymyr Kotsyubynsky
PY - 2026
DA - 2026/10/28
JO - ChemistryOpen
DO - 10.1002/open.70330
UR - https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.70330
AB - This work is devoted to quantum chemical and experimental studies of the Dimroth rearrangement mechanism of 1‐(5‐imino‐4,5‐dihydro‐1H‐1,2,3‐triazol‐1‐yl)anthracene‐9,10‐dione. The study addresses how the bulky N‐ anthraquinonyl substituent affects the individual steps of the Dimroth rearrangement. The energy profile of the Dimroth rearrangement was calculated using density functional theory with the B3LYP approximation and the 6‐311++G(d,p) basis set. It was found that proton solvents (in particular, ethanol) play a critical role in hydrogen transfer via the hydrogen‐bond network, thereby ensuring the conversion of the initial triazene into a more stable cyclic 5‐aminotriazole. Further transformations involving ring opening and rotation do not have significant energy barriers. The final product is energetically most favorable, so the reaction proceeds easily in ethanol solution. The work demonstrates the convenience and efficiency of using the Dimroth rearrangement for the synthesis of new anthracenedione‐containing heterocycles. It provides an explanation of the mechanism of this rearrangement based on quantum‐chemical calculations for anthracene‐9,10‐dione derivatives.
SN - 2191-1363
SN - 2191-1363
ER -