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581.
I. O. Tupaeva Yu. A. Sayapin Zyong Ngia Bang V. N. Komissarov V. V. Tkachev G. V. Shilov S. M. Aldoshin V. I. Minkin 《Russian Chemical Bulletin》2013,62(2):492-496
An acid-catalyzed reaction of 2-methylbenzoxazole with 3,4,5,6-tetrachloro-1,2-benzoquinone leads to 2-(benzoxazol-2-yl)-5,6,7-trichloro-1,3-tropolone and 2-(benzoxazol-2-yl)-4,5,6,7-tetrachloro-1,3-tropolone. 1,3-Tropolones upon reflux in ethyl alcohol undergo the rearrangement resulted in the seven-membered ring contraction to form ethyl 2-(benzoxazol-2-yl)-5,6-dichloro-3-hydroxybenzoate and ethyl 2-(benzoxazol-2-yl)-4,5,6-trichloro-3-hydroxybenzoate. The molecular structure of the latter was established by X-ray diffraction analysis. 相似文献
582.
Yu. A. Sayapin E. A. Gusakov Zyong Ngia Bang I. O. Tupaeva V. N. Komissarov I. V. Dorogan V. V. Tkachev S. M. Aldoshin V. I. Minkin 《Russian Chemical Bulletin》2013,62(2):480-491
A reaction of substituted 2-(quinolin-2-yl)-1,3-tropolones with POCl3 leads to the new3-chloro-2-(quinolin-2-yl)tropone derivatives. New 2-(4-arylaminoquinolin-2-yl)-3-aryl-aminocyclohepta-2,4,6-trien-1-ones and 2-[4-morpholino(piperidino)quinolin-2-yl]-3-aryl-aminocyclohepta-2,4,6-trien-1-ones were obtained by nucleophilic substitution reaction of the halogen atom in 2-(4-chloroquinolin-2-yl)-3-chlorotropones and 3-chloro-2-[4-morpholino-(piperidino)quinolin-2-yl]tropones. Molecular structures of 3-chloro-2-(quinolin-2-yl)tropone and 3-arylamino-2-(quinolin-2-yl)tropone were established by X-ray diffraction analysis. Energy and structural characteristics of isomers of 3-arylamino-2-(quinolin-2-yl)tropones in the gas phase and in solution were calculated by the density functional theory method (PBE0/6-31G**). 相似文献
583.
M. Yu. Antipin E. P. Ivakhnenko Yu. V. Koshchienko P. A. Knyazev M. S. Korobov A. V. Chernyshev K. A. Lyssenko A. G. Starikov V. I. Minkin 《Russian Chemical Bulletin》2013,62(8):1744-1751
Adducts of cobalt(II) bis(salicylaldiminates) and 2,4,6,8-tetra-tert-butylphenoxazin-1-one were synthesized and their molecular and crystal structures were determined. According to the ESR and magnetochemical data, the metal atom is in the low-spin trivalent state (CoIII) due to the intramolecular electron transfer to the redox-active ligand. In the solid state, the mixedligand complexes are stable in air for several months, but in solution at elevated temperatures they dissociate to the starting components. Such a behavior detected by the temperature dependence of the effective magnetic moment is explained by the quantum chemical DFT calculations of the energy barriers of possible valence tautomeric dynamics, whose values were found to be higher than the enthalpy of dissociation. 相似文献
584.
Steglenko DV Kletsky ME Kurbatov SV Tatarov AV Minkin VI Goumont R Terrier F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(27):7592-7604
The Diels–Alder reaction of 4‐nitrobenzodifuroxan (NBDF) with 1‐methoxy‐3‐trimethylsilyloxy‐1,3‐butadiene has been investigated experimentally and theoretically. Treatment of NBDF with excess diene in chloroform at room temperature was found to afford a single product that contained a carbonyl functionality. Based on an X‐ray structure and NMR spectroscopic data, the product appeared to be a result of the hydrolysis of the OSiMe3 moiety of the thermodynamically more stable endo [2+4] cycloadduct, characterized by a cis arrangement of the MeO and NO2 functionalities. In situ NMR investigations of the interaction were carried out at room temperature in CDCl3 and at ?40 °C in deuterated acetonitrile. Calculations at the B3LYP/6‐31G* level in the gas phase and in acetonitrile were carried out under the assumption that the most stable cis conformation of the diene is also the most reactive in the interaction. The analysis revealed the NBDF/cis diene interaction involves the formation of a zwitterionic intermediate. Importantly, this intermediate is formed in two preferred conformations, which correspond to the endo and exo modes of approach of the reagents. Cyclization of these two identified conformations afforded the experimentally characterized endo and exo [2+4] cycloadducts. According to the calculations, the interconversion of the two conformers can either take place through a return to the pre‐reaction complexes or it can occur by rotation through an intermediate conformation of lesser stability. In view of the stepwise character of the interaction, the possibility that the intermediate zwitterion is the result of the interaction between NBDF and the trans diene could not be excluded. Calculations carried out with the most stable and more populated s‐trans conformer confirmed this idea and supported the role of the zwitterion in the overall interaction. 相似文献