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2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties

A series of derivatives of 2-hetaryl-1,3-tropolone (β-tropolone) was prepared by the acid-catalyzed reaction of 2-methylbenzoxazoles, 2-methylbenzothiazoles and 2,3,3-trimethylindoline with 3,4,5,6-tetrachloro-1,2-benzoquinone. The molecular structures of the three representative compounds were dete...

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Autores principales: Sayapin, Yury A, Tupaeva, Inna O, Kolodina, Alexandra A, Gusakov, Eugeny A, Komissarov, Vitaly N, Dorogan, Igor V, Makarova, Nadezhda I, Metelitsa, Anatoly V, Tkachev, Valery V, Aldoshin, Sergey M, Minkin, Vladimir I
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4661002/
https://www.ncbi.nlm.nih.gov/pubmed/26664640
http://dx.doi.org/10.3762/bjoc.11.236
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author Sayapin, Yury A
Tupaeva, Inna O
Kolodina, Alexandra A
Gusakov, Eugeny A
Komissarov, Vitaly N
Dorogan, Igor V
Makarova, Nadezhda I
Metelitsa, Anatoly V
Tkachev, Valery V
Aldoshin, Sergey M
Minkin, Vladimir I
author_facet Sayapin, Yury A
Tupaeva, Inna O
Kolodina, Alexandra A
Gusakov, Eugeny A
Komissarov, Vitaly N
Dorogan, Igor V
Makarova, Nadezhda I
Metelitsa, Anatoly V
Tkachev, Valery V
Aldoshin, Sergey M
Minkin, Vladimir I
author_sort Sayapin, Yury A
collection PubMed
description A series of derivatives of 2-hetaryl-1,3-tropolone (β-tropolone) was prepared by the acid-catalyzed reaction of 2-methylbenzoxazoles, 2-methylbenzothiazoles and 2,3,3-trimethylindoline with 3,4,5,6-tetrachloro-1,2-benzoquinone. The molecular structures of the three representative compounds were determined by X-ray crystallography. In crystal and (as shown by the DFT PBE0/6-311+G** calculations) in solution, 2-hetaryl-4,5,6,7-tetrachloro- and 2-hetaryl-5,6,7-trichloro-1,3-tropolones exist in the NH-tautomeric form with a strong resonance-assisted intramolecular N–H···O hydrogen bond. The mechanism of the formation of 1,3-tropolones in the reaction of methylene-active five-membered heterocycles with o-chloranil in acetic acid solution has been studied using density functional theory (DFT) methods. The reaction of 2-(2-benzoxa(thia)zolyl)-5,6,7-trichloro(4,5,6,7-tetrachloro)-1,3-tropolones with alcohols leads to the contraction of the seven-membered tropone ring with the formation of 2-(2-benzoxa(thia)zolyl)-6-alkoxycarbonylphenols. The molecular structure of 2-(2-ethoxycarbonyl-6-hydroxy-3,4,5-trichlorophenyl)benzoxazole has been determined by X-ray diffraction. 2-(2-Benzoxa(thia)zolyl)-6-alkoxycarbonylphenols display intense green fluorescence with anomalous Stokes shifts caused by the excited state intramolecular proton transfer (ESIPT) effects.
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spelling pubmed-46610022015-12-09 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties Sayapin, Yury A Tupaeva, Inna O Kolodina, Alexandra A Gusakov, Eugeny A Komissarov, Vitaly N Dorogan, Igor V Makarova, Nadezhda I Metelitsa, Anatoly V Tkachev, Valery V Aldoshin, Sergey M Minkin, Vladimir I Beilstein J Org Chem Full Research Paper A series of derivatives of 2-hetaryl-1,3-tropolone (β-tropolone) was prepared by the acid-catalyzed reaction of 2-methylbenzoxazoles, 2-methylbenzothiazoles and 2,3,3-trimethylindoline with 3,4,5,6-tetrachloro-1,2-benzoquinone. The molecular structures of the three representative compounds were determined by X-ray crystallography. In crystal and (as shown by the DFT PBE0/6-311+G** calculations) in solution, 2-hetaryl-4,5,6,7-tetrachloro- and 2-hetaryl-5,6,7-trichloro-1,3-tropolones exist in the NH-tautomeric form with a strong resonance-assisted intramolecular N–H···O hydrogen bond. The mechanism of the formation of 1,3-tropolones in the reaction of methylene-active five-membered heterocycles with o-chloranil in acetic acid solution has been studied using density functional theory (DFT) methods. The reaction of 2-(2-benzoxa(thia)zolyl)-5,6,7-trichloro(4,5,6,7-tetrachloro)-1,3-tropolones with alcohols leads to the contraction of the seven-membered tropone ring with the formation of 2-(2-benzoxa(thia)zolyl)-6-alkoxycarbonylphenols. The molecular structure of 2-(2-ethoxycarbonyl-6-hydroxy-3,4,5-trichlorophenyl)benzoxazole has been determined by X-ray diffraction. 2-(2-Benzoxa(thia)zolyl)-6-alkoxycarbonylphenols display intense green fluorescence with anomalous Stokes shifts caused by the excited state intramolecular proton transfer (ESIPT) effects. Beilstein-Institut 2015-11-12 /pmc/articles/PMC4661002/ /pubmed/26664640 http://dx.doi.org/10.3762/bjoc.11.236 Text en Copyright © 2015, Sayapin et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Sayapin, Yury A
Tupaeva, Inna O
Kolodina, Alexandra A
Gusakov, Eugeny A
Komissarov, Vitaly N
Dorogan, Igor V
Makarova, Nadezhda I
Metelitsa, Anatoly V
Tkachev, Valery V
Aldoshin, Sergey M
Minkin, Vladimir I
2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties
title 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties
title_full 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties
title_fullStr 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties
title_full_unstemmed 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties
title_short 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties
title_sort 2-hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4661002/
https://www.ncbi.nlm.nih.gov/pubmed/26664640
http://dx.doi.org/10.3762/bjoc.11.236
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