N 89 Novel 1-trifluoromethyl substituted 1,2-ethylenediamines and their use for the synthesis of fluoroquinolones [Text] / A. Y. Aizikovich, M. V. Nikonov, M. I. Kodess, V. Yu. Korotaev, V. N. Charushin, O. N. Chupakhin // Tetrahedron. - 2000. - Vol. 56, N 13. - P1923-1927 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: A common approach to the synthesis of 1-trifluoromethyl-1,2-ethylenediamines was deweloped. Based on these original building blocks the new derivatives of N-substituted fluoroquinolones bearing the trifluoromethyl group were obtined |
S 98 Synthesis of stereoisomers of 2,4-diaminoglutaric and 2,5-diaminoadipic acids [Electronic resource] / V. P. Krasnov, E. A. Zhdanova, M. A. Koroleva, I. M. Bukrina, M. I. Kodess, V. K. Kravtsov, V. N. Biyushkin // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 1997. - Vol. 46, N 2. - P319-323 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Stereoisomers of 2,4-diaminodlutaric and 2,5-diaminoadipic acids were synthesized from dlutamic and 2-aminoadipic acids, respectively. The stereochemistry of the products was established by IH NMR spectroscopy and X-ray analysis \\\\Expert2\\nbo\\Russian Chemical Bulletin\\1997, 46 (2), 319-323.pdf |
T 44 The structure of 4-phenyl-2,6-bis(trifluoroacetyl)cyclohexanone and its dilithium salt in the crystal state, solution and gas phase [Electronic resource] / D. V. Sevenard, O. Kazakova, E. Lork, T. Duelcks, D. L. Chizhov, G. -V. Roeschenthaler // Journal of Molecular Structure. - 2007. - Vol. 846, № 1-3. - P87-96 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: 4-Phenyl-2,6-bis(trifluoroacetyl)cyclohexanone and its dilithium salt were synthesized starting from the commercially available 4-phenylcyclohexanone. With X-ray structure analysis of these compounds, for the first time the solid state structure determination for a fluorinated 1,3,5-triketone and an alkaline salt of 1,3,5-triketone was achieved. The subsequent multinuclear NMR and MS investigations revealed that in solution and gas phase, analogously to the crystal, both compounds exist predominantly in a highly delocalized double U-enol(ate) form. The carbonyl O…O distances in the dilithium salt were established to be considerably longer than the distances between oxygens of the parent 1,3,5-triketone, bonded by strong (short) resonance assisted hydrogen bonds. Among the 1,3,5-tricarbonyl compounds with known crystal structure, the entitled 1,3,5-triketone shows comparatively weak delocalization over the conjugated bis-enolone backbone. \\\\Expert2\\nbo\\Journal of Molecular Structure\\2007, v.846, p.87.pdf |
A 18 Acidic hydrolysis of N-acyl-1-substituted 3-amino-1,2-dicarba-closo-dodecaboranes [Electronic resource] / G. L. Levit, A. M. Demin, M. I. Kodess, M. A. Ezhikova, L. Sh. Sadretdinova, V. A. Ol'shevskaya, V. N. Kalinin, V. P. Krasnov, V. N. Charushin // Journal of Organometallic Chemistry. - 2005. - Vol. 690, № 11. - P2783-2786 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Acidic hydrolysis of N-acyl 1-methyl- and 1-phenyl-3-amino-1,2-dicarba-closo-dodecaboranes has been studied. It has been shown that acidic hydrolysis of diastereomeric amides of 1-methyl-3-amino-1,2-dicarba-closo-dodecaborane results in the partial racemization of the target 3-amino-1-methylcarborane. Under the similar conditions, the hydrolysis of N-acyl-3-amino-1-phenyl-1,2-dicarba-closo-dodecaboranes resulted in amide bond cleavage accompanied by simultaneous deboronation with the removal of boron atom at position 6 of carborane cage and formation of 7,8-dicarba-nido-undecaborane derivative according to 11B and 1H NMR spectroscopy. \\\\Expert2\\nbo\\Journal of Organometallic Chemistry\\2005, v. 690, p.2783.pdf |
N 72 NMR determination of enantiomeric composition of 1-substituted 3-amino-1,2-dicarba-closo-dodecaboranes using Eu(hfc)3 [Electronic resource] / M. I. Kodess, M. A. Ezhikova, G. L. Levit, V. P. Krasnov, V. N. Charushin // Journal of Organometallic Chemistry. - 2005. - Vol. 690, № 11. - P2766-2768 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Experimental conditions for determination of enantiomeric composition of 1-substituted 3-aminocarboranes by 1H and 13C NMR spectroscopy using chiral shift reagent Eu(hfc)3 have been found. \\\\Expert2\\nbo\\Journal of Organometallic Chemistry\\2005, v. 690, p.2766.pdf |
S 98 Synthesis, structure and luminescence of ruthenium complexes with 6-cyano-2,2'-bipyridines [Electronic resource] / V. N. Kozhevnikov, D. N. Kozhevnikov, O. V. Shabunina, V. L. Rusinov, O. N. Chupakhin, M. Zabel, B. Koenig // Mendeleev Communications. - 2005. - Vol. 15, № 1. - P6-8 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: The crystallographic data, NMR and UV-VIS spectra and luminescence of the heteroleptic complexes [Ru(L)(bpy)2](PF6)2 (L = 5-aryl-6-cyano-2,2'-bipyridine) are described. \\\\Expert2\\nbo\\Mendeleev Communications\\2005, v.15,p.6.pdf |
S 89 Structure and properties of 4-amino derivatives of 5-oxoproline [Text] / V. P. Krasnov, I. A. Nizova, A. Yu. Vigorov, T. V. Matveeva, G. L. Levit, P. A. Slepukhin, M. A. Ezhikova, M. I. Kodess // European Journal of Organic Chemistry. - 2008. - № 10. - P1802-1810 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: On the basis of the results obtained from NMR spectroscopy, X-ray analysis and chemical transformations, it was established that acidic hydrolysis of (2S,4S)-4-arylaminoglutamates results in the formation of lactams in which ring closure occurs with the participation of the Y-amino and alfa-COOH groups; but isomeric lactams resulting from the participation of the alfa-amino and Y-COOH groups are not formed. Isomeric lactams, that is, (2S,4S)-4-arylamino-5-oxoprolines, can be easily converted in acidic medium into more stable 4-amino-1-aryl-5-oxoprolines. |
S 98 Synthesis and the reactions of trifluoromethylated 1,2,3-triketones 2-(het)arylhydrazones and 4,7-dihydroazolo[5,1-c]triazines [Electronic resource] / O. G. Khudina, E. V. Shchegol'kov, Ya. V. Burgart, M. I. Kodess, O. N. Kazheva, A. N. Chekhlov, G. V. Shilov, O. A. Dyachenko, V. I. Saloutin, O. N. Chupakhin // Journal of Fluorine Chemistry. - 2005. - Vol. 126, № 8. - P1230-1238 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: The coupling of trifluoromethylated 1,3-diketones with (het)aryldiazonium chlorides results mainly in the formation of 1,2,3-triketones 2-(het)arylhydrazones while using hetarylamine with a NH-group at the ?-position of the heterocycle as the diazonium component gives 4,7-dihydroazolo[5,1-c]triazines due to cyclization at the trifluoroacetyl fragment. Trifluoromethylated 1,2,3-triketones 2-(het)arylhydrazones and 7-hydroxy-4,7-dihydroazolo[5,1-c]triazines react regio-selectively with methyl hydrazine and phenyl hydrazine to form 3-CF3-pyrazoles. The long-range coupling constants (JF-H) of 1-methylpyrazoles and the chemical shifts of trifluoromethyl groups in the 19F NMR spectra can be used for the determination of regio-isomeric structures of mono(trifluoromethyl)-substituted pyrazoles. 2-(Het)arylhydrazones and 4,7-dihydroazolo[5,1-c]triazines with two trifluoromethyl substituents afford the mixtures of cis- and trans-azopyrazoles in the reactions with hydrazines. \\\\Expert2\\nbo\\Journal of Fluorine Chemistry\\2005, v.126, p.1230.pdf |
A 53 An Unusually easy oxidative dequaternization of N-alkyl-1,2,4-triazinium salts [Electronic resource] / O. N. Chupakhin, B. V. Rudakov, P. McDermott, S. G. Alexeev, V. N. Charushin, F. Hegarty // Mendeleev Communications. - 1995. - Vol. 5, № 3. - P104-105 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Unusually easy dequaternization has been found to occur on treatment of 1-alkyl-3-morpholino-5-phenyl-1,2,4-triazinium iodides with triethylamine in alcohol or acetone solutions at room temperature; a plausible reaction mechanism has been advanced on the basis of NMR and kinetic studies \\\\expert2\\nbo\\Mendeleev Communications\\1995, v.5, N 3. p.104.pdf |
5(6)-Fluoro-6(5)-R-benzofuroxans: synthesis and NMR 1H, 13C and 19F studies [Text] / S. K. Kotovskaya, S. A. Romanova, V. N. Charushin, M. I. Kodess, O. N. Chupakhin // Journal of Fluorine Chemistry. - 2004. - Vol. 125, № 3. - P421-428 : ил. - Библиогр.: с. 428 (14 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): 5,6-DIFLUOROBENZOFUROXAN -- NUCLEOPHILIC SUBSTITUTION -- X-RAY CRYSTALLOGRAPHY Аннотация: 5(6)-Fluoro-6(5)-substituted benzofuroxans were obtained by the reactions of 5,6-difluorobenzofuroxan with a number of nucleophiles, such as alkylamines, cycloalkylimines, sodium azide and sodium alkoxides. The features of tautomerism in the series of asymmetrical 5(6)-fluorobenzofuroxans in acetone solutions have been studied by 1H, 13C and 19F NMR.???? \\\\Expert2\\nbo\\Journal of Fluorine Chemistry\\2004, v.125, p.421.pdf |
S 98 Syntheses of novel 4-polyfluoroalkyl-substituted 5,6-oligomethylene pyrimidines [Text] / D. V. Sevenard, O. G. Khomutov, O. V. Koryakova, V. V. Sattarova, M. I. Kodess, J. Stelten, I. Loop, E. Lork, K. I. Pashkevich, G. -V. Roeschenthaler // Synthesis. - 2000. - № 12. - P1738-1748 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: 2-Acylcycloalkanones having polyfluoroalkyl groups react with guanidine, urea, thiourea, methylisothiourea, benzamidine, guanylthiourea, dicyanodiamide, and trifluoroacetylurea by Lewis-acid catalysis to form the corresponding 5,6-oligomethylene pyrimidines. A decrease in the yields along with increase of polyflyoroalkyl substituent length in the molecule of the starting 1,3-diketone was observed in the case of reagents with lower nucleophilicity (urea, thiourea, dicyanodiamide). The pyrimidines obtained from aromatic aldehydes showed E-configuration with respect to the arylidene double bond. Tautomeric structures as a function of the substituent in 2 position in the pyrimidine ring both in liquid and solid state were investigated by X-ray diffraction, IR and NMR spectroscopy. \\\\expert2\\nbo\\Synthesis\\2000, № 12. p.1738.pdf |
H 10 H-1 and C-13-NMR investigations on-adduct formation of 1,2,4-triazine 4-oxides and 3-chloro-6-phenyl-1,2,4-triazine with liquid ammonia and alkylamines [Text] / A. Rykowski, O. N. Chupakhin, D. N. Kozhevnikov, V. N. Kozhevnikov, V. L. Rusinov, der Plas H. C. Van // Heterocycles. - 2001. - Т. 55, № 1. - P127-133 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: 1H- and 13C-NMR spectra of the ?-adducts formed between 6-phenyl-1,2,4-triazine 4-oxide (1a), 3-ethyl-6-phenyl-1,2,4-triazine 4-oxide (1b) and liquid ammonia, methylamine or dimethylamine are described, together with 1H NMR spectra of 3-chloro-6-phenyl-1,2,4-triazine (7) in liquid ammonia. The results of the NMR study have shown that the carbon C-5 in 1a-b and 7 is the preferred site for nucleophilic attack by liquid ammonia and alkylamines at low temperatures (from -75° to -20°C). The ?-adduct (5e) formed between 1a and dimethylamine at -75°C on heating to -20°C irreversibly converts to open-chain product (3a), via intermediary C-3 ?-adduct (6). The amination of 7 into 3-amino-6-phenyl-1,2,4-triazine (10) occurs via SN(AE) mechanism involving the isomerisation of the C-5 ?-adduct (8) into the C-3 ?-adduct (9) as confirmed by a 15N study with labeled liquid ammonia. |
N 10 N-(2-Carboxyethyl)chitosans: Regioselective synthesis, characterisation and protolytic equilibria [Text] / Yu. A. Skorik, C. A. R. Gomes, M. T.S.D. Vasconcelos, Yu. G. Yatluk // Carbohydrate Research. - 2003. - Vol. 338, № 3. - P271-276 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): CARBOXYETHYLATION POLYSACCHARIDES -- N-(2-CARBOXYETHYL)CHITOSAN -- POLYAMPHOLYTE Аннотация: N-(2-Carboxyethyl)chitosans were obtained by reaction of low molecular weight chitosan with a low degree of acetylation and 3-halopropionic acids under mild alkaline media (pH 8-9, NaHCO3) at 60°C. The chemical structure of the derivatives obtained was determined by 1H and 13C NMR spectroscopies. It was found that alkylation of chitosan by 3-halopropionic acids proceeds exclusively at the amino groups. The products obtained are described in terms of their degrees of carboxyethylation and ratio of mono-, di-substitution and free amine content. The protonation constants of amino and carboxylate groups of a series of N-(2-carboxyethyl)chitosans were determined by pH-titration at ionic strength 0.1 M KNO3 and 25°C. © 2002 Elsevier Science Ltd. All rights reserved. |
R 30 Reaction of 5-halo-1,2,3-thiadiazoles with aliphatic diamines. Synthesis and intramolecular cyclization of bis(1,2,3-triazolyl-1,2,3-thiadiazolyl)sulfides [Text] / N. N. Volkova, E. V. Tarasov, M. I. Kodess, L. Van Meerlent, W. Dehaen, V. A. Bakulev // Organic and Biomolecular Chemistry. - 2003. - Vol. 1, № 22. - P4030-4038 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Bis[1,2,3]triazolo[1,5-f:5?,1?-b][1,3,6]thiadiazepine and [1,5-g:5?,1?-b][1,3,7]thiadiazocine ring systems have been synthesized from 5-halo-1,2,3-thiadiazoles and aliphatic diamines. We have found that the last step of the process is the cyclization of initially formed bis(1,2,3-triazolyl-1,2,3-thiadiazolyl)sulfides. The structures of the intermediates and products were supported by different NMR spectroscopic methods (1H coupled 13C NMR, 2D HETCOR, HMBC and 1D INADEQUATE experiments) and mass spectrometry. Differences in the reaction pathway for aliphatic and less nucleophilic aromatic diamines were determined. |
F 98 Fused fluoroquinolones: synthesis and 1H and 19F NMR studies [Text] / V. N. Charushin, E. V. Nosova, G. N. Lipunova, M. I. Kodess // Journal of Fluorine Chemistry. - 2001. - Vol. 110, № 1. - P25-30. - Bibliogr. : p. 30 (19 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: New derivatives of fused fluoroquinolones bearing five aromatic rings have been obtained. The 19F NMR spectra of these pentacyclic fluoroquinolones demonstrate unusual through space 1H–19F and 19F–19F spin–spin interactions with coupling constants 6J(F, H)=2.0–3.0 Hz, 7J(F, F)=3.5–4.0 Hz and 9J(F, H)=3.0–3.5 Hz. Relative reactivities of fluorine atoms in pentacyclic fluoroquinolones in the amino-defluorination reactions are also different relative to bi- and tricyclic fluoroquinolones???? \\\\Expert2\\nbo\\Journal of Fluorine Chemistry\\2001.v.110. p. 25.pdf |
S 98 Synthesis and Tautomeric Equilibrium of Polyfluoroacyl-Containing 1,5-Benzodiazepines [Text] / D. S. Yachevskii, D. L. Chizhov, M. I. Kodess, K. I. Pashkevich // Monatshefte fur Chemie . - 2004. - Vol. 135, № 1. - P23-30 : ил. - Библиогр.: с. 30 (8 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): NMR -- TAUTOMERISM -- SYNTHESIS Аннотация: The reaction of bis(polyfluoroalkyl)-containing 1,3,5-triketones with o-phenylenediamine yielded 2-polyfluoroacylmethylene-4-polyfluoroalkyl-1,3- or 1,5-dihydro-1,5-benzodiazepines. The tautomeric equilibrium of the obtained benzodiazepines in CDCl3, CD3CN, DMSO, and DMF solution was studied.?? |
R 30 Reactions of radicals generated from 1-ethyl-1,4-diazinium salts: Addition to the C-C triple bond versus dimerization [Text] / G. L. Rusinov, E. V. Verbitskiy, P. A. Slepukhin, O. N. Zabelina, M. I. Kodess, M. A. Ezhikova, V. N. Charushin, O. N. Chupakhin // Heterocycles. - 2009. - Vol. 78, № 9. - P2315-2324 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Radical species generated from 5-aryl-substituted 1-ethyl-2,3-dicyano-1,4-diazinium salts by action of sodium iodide undergo dimerization into [2,2?]bipyrazinyl derivatives, as evidenced by NMR and X-ray crystallography data. The pyrazinyl radicals can also be involved into the addition reaction on the C-C triple bond, thus demonstrating a new synthetic route to modify the structure of pyrazines. The structures of E- and Z-isomers of 1-(1?,2?-dihydropyrazinyl-2?)-2-iodoethenes have been proved by 1H and 13C NMR spectroscopy and X-ray analysis |
1H NMR evidence for 5(4H)-oxazolones formation and racemization [Text] : доклад, тезисы доклада / O. N. Chupakhin, V. P. Krasnov, A. M. Demin, G. L. Levit, M. I. Kodess // XXth European Colloquium on Heterocyclic Chemistry, Stockholm,Sweden, 18-21 Aug. 2002 г. - Stockholm, 2002. - C:2 Рубрики: ХИМИЧЕСКИЕ НАУКИ |
D 98 Dynamic kinetic resolution via 5(4H)-oxazolone formation [Text] : доклад, тезисы доклада / O. N. Chupakhin, V. P. Krasnov, N. Z. Solieva, E. A. Zhdanova, I. M. Bukrina, L. Sh. Sadretdinova, G. L. Levit, M. I. Kodess // XXth European Colloquium on Heterocyclic Chemistry, Stockholm,Sweden, 18-21 Aug. 2002 г. - Stockholm, 2002. - C:3 Рубрики: ХИМИЧЕСКИЕ НАУКИ |
G 37 Geometric isomerism in the series of fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones [Electronic resource] / O. G. Khudina, E. V. Shchegol'kov, M. I. Kodess, Ya. V. Burgart, V. I. Saloutin, O. N. Chupakhin // Russian Journal of Organic Chemistry (Translation of Zhurnal Organicheskoi Khimii). - 2007. - Vol. 43, № 3. - P380-387 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): 2-ARYLHYDRAZONES -- X-RAY DIFFRACTION Аннотация: According to the 1H, 13C, and 19F NMR data, fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones in CDCl3 exist exclusively, while in (CD3)2CO preferentially, as isomers in which the acyl or aroyl group is involved in intramolecular hydrogen bond. The isomer structure was assigned on the basis of the chemical shifts of the carbonyl carbon atoms and fluorine atoms and carbon-fluorine spin-spin coupling constants J C-F. X-Ray diffraction data showed that 1,2,3-trione 2-arylhydrazones in crystal have the same structure as in CDCl3 solution. Quantum-chemical calculations were performed to rationalize predominant formation of 1,2,3-trione 2-arylhydrazone isomers with a free polyfluoroacyl group \\\\Expert2\\nbo\\Russian Journal of Organic Chemistry\\2007, 43 (3), 380-387.pdf |