title: 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties.
abstract: 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.
authors.affiliation: Southern Scientific Center of Russian Academy of Sciences, 141 Chekhov St., 344006 Rostov on Don, Russian Federation ; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Yury A
authors.initials: YA
authors.lastname: Sayapin
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Inna O
authors.initials: IO
authors.lastname: Tupaeva
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Alexandra A
authors.initials: AA
authors.lastname: Kolodina
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Eugeny A
authors.initials: EA
authors.lastname: Gusakov
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Vitaly N
authors.initials: VN
authors.lastname: Komissarov
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Igor V
authors.initials: IV
authors.lastname: Dorogan
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Nadezhda I
authors.initials: NI
authors.lastname: Makarova
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Anatoly V
authors.initials: AV
authors.lastname: Metelitsa
authors.affiliation: Institute of Problems of Chemical Physics of Russian Academy of Sciences, 1 Akad. Semjonov N.N. Ave., 142432 Chernogolovka, Moscow region, Russian Federation.
authors.forename: Valery V
authors.initials: VV
authors.lastname: Tkachev
authors.affiliation: Institute of Problems of Chemical Physics of Russian Academy of Sciences, 1 Akad. Semjonov N.N. Ave., 142432 Chernogolovka, Moscow region, Russian Federation.
authors.forename: Sergey M
authors.initials: SM
authors.lastname: Aldoshin
authors.affiliation: Southern Scientific Center of Russian Academy of Sciences, 141 Chekhov St., 344006 Rostov on Don, Russian Federation ; Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka St., 344090 Rostov on Don, Russian Federation.
authors.forename: Vladimir I
authors.initials: VI
authors.lastname: Minkin
keywords: X-ray analysis; fluorescence; intramolecular hydrogen bond; tautomerism; β-tropolones