S 98 Synthesis of fluorine-containing analogs of ellipticine and other heterocycles from 2-Nitro-and 2-amino-4,5-difluoroanilines [Electronic resource] / V. N. Yarovenko, A. V. Polushina, K. S. Levchenko, I. V. Zavarzin, M. M. Krayushkin, S. K. Kotovskaya, V. N. Charushin // Russian Journal of Organic Chemistry (Translation of Zhurnal Organicheskoi Khimii). - 2007. - Vol. 43, № 9. - P1387-1392 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: 2-Nitro- and 2-amino-4,5-difluoroanilines were used as starting materials to synthesize fluorine-containing imidazole, oxazole, and indoloquinoxaline derivatives. The latter may be regarded as ellipticine analogs \\\\Expert2\\nbo\\Russian Journal of Organic Chemistry\\2007, 43 (9), 1387.pdf |
H 62 Heterospin complexes based on dinuclear CuII triketonate and nitroxides [Electronic resource] / V. Ovcharenko, S. V. Fokin, G. V. Romanenko, V. Ikorskii, R. S. Sagdeev, D. S. Yachevskii, D. L. Chizhov, V. N. Charushin // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2006. - Vol. 55, № 11. - P1904-1908 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Heterospin complexes of bis(?2-1,1,2,2,8,8,9,9-octafluorononane-3,5,7-trionato)dicopper(II) ([Cu2L2]) with nitronyl nitroxides 2-(1-methyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl 3-oxide (2) and 4,4,5,5-tetramethyl-2-(3-pyridinyl)-4,5-dihydro-1H-imidazole-1-oxyl 3-oxide (1) were synthesized and structurally characterized. Crystals of the complexes are formed by the discrete bis[1-methyl-4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)-1H-pyrazole]-bis (?2-1,1,2,2,8,8,9,9-octafluorononane-3,5,7-trionato)dicopper(II) etherate (3) and bis[3-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyridine]-bis (?2-1,1,2,2,8,8,9,9-octafluorononane-3,5,7-trionato)dicopper(II) (4) molecules. Each Cu atom of the dinuclear chelate fragment coordinates one paramagnetic ligand through the N atom of the pyrazole or pyridine fragment, respectively. In complex 3, the paramagnetic ligands are located on one side of the plane of the chelate fragment, whereas the ligands in complex 4 are located above and below the plane of the chelate fragment. The magnetic properties of complexes 3 and 4 are determined by dominant antiferromagnetic exchange interactions between the unpaired electrons of the CuII atoms in the dinuclear Cu2L2 moiety \\\\Expert2\\nbo\\Russian Chemical Bulletin\\2006, 55 (11), 1904.pdf |
S 98 Synthesis and reactivity of monothiooxamides of the aminonitroarene series [Electronic resource] / V. N. Yarovenko, A. V. Polushina, K. S. Levchenko, I. V. Zavarzin, M. M. Krayushkin, S. K. Kotovskaya, V. N. Charushin // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2009. - Vol. 58, № 6. - P1276-1280 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Monothiooxamides containing aminonitrobenzene and aminonitropyridine fragments have been synthesized. A possibility to synthesize thioesters and fused imidazole and diazepine derivatives on their basis has been demonstrated \\\\Expert2\\nbo\\Russian Chemical Bulletin\\2009, 58 (6), 1276-1280.pdf |
H 62 Heterospin complexes of fluorinated dinuclear Cu(II) and Mn(II) triketonates with nitroxides [Electronic resource] / V. Ovcharenko, S. V. Fokin, G. V. Romanenko, A. S. Bogomyakov, D. S. Yachevskii, D. L. Chizhov, V. N. Charushin, O. N. Chupakhin // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2010. - Vol. 59, № 6. - P1162-1174 : il. - Bibliogr. : p. 1174 (21 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): COPPER(II) -- MANGANESE(II) -- METAL TRIKETONATES -- NITROXIDES -- x-RAY DIFFRACTION STUDY -- MAGNETIC PROPERTIES Аннотация: Dinuclear heterospin complexes of CuII and MnII 1,1,1,7,7,7-hexafluoroheptane-2,4,6-trionates ([Cu2L2] and [Mn2L2], respectively) with nitronyl nitroxides 2-R-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide 1-oxyls (NIT-R, R = H, Me, Et, m-C5H4N, m-NCC6H4, p-NCC6H4, PzMe) and the diradical NIT-Pz-(CH2)4-Pz-NIT (Pz is 1,4-pyrazolylene) were synthesized and structurally characterized. In the complexes under study, the CuII atom tends to have the square-pyramidal coordination environment, and the MnII atom is in an octahedral environment. The magnetochemical investigation of the compounds in the temperature range of 2–300 K showed that the antiferromagnetic exchange coupling dominates in the [Cu2L2] molecules, whereas this coupling in [Mn2L2] is manifested in the experimental plot µeff(T) at T < 100 K. The magnetic properties of the heterospin complexes of [Cu2L2] with NIT-R are also determined by the intramatrix antiferromagnetic exchange coupling. For the complexes of [Mn2L2] with NIT-R, the coordination mode of the nitroxide plays a decisive role. \\\\Expert2\\nbo\\Russian Chemical Bulletin\\2010, 59 (6), 1162-1174.pdf |
P 17 Palladium(II)-Catalyzed Oxidative C–H/C–H Coupling and Eliminative SNH Reactions in Direct Functionalization of Imidazole Oxides with Indoles / M. V. Varaksin, I. A. Utepova, O. N. Chupakhin, V. N. Charushin // Journal of Organic Chemistry. - 2012. - Vol.77, №20. - С. 9087-9093 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): IMIDAZOLE OXIDES -- INDOLES Аннотация: Two novel synthetic approaches to realize the direct C(sp2)–H bond functionalization in cyclic nitrones are reported. Palladium(II)-catalyzed oxidative C–C coupling of 2,2-dialkyl-4-phenyl-2H-imidazole 1-oxides with indoles was shown to result in the formation of 5-indolyl-3-yl derivatives, while nucleophilic substitution of hydrogen (SNH) at C(5) of the same imidazole system was found to afford the corresponding deoxygenated compounds \\\\Expert2\\nbo\\Journal of Organic Chemistry\\2010, v.77, p.9087.pdf |
B 62 Bis(1,1,1,3,5,5,5-heptafluoro-4-iminopent-2-ene-2-aminato)copper(ii) — a new metal-containing matrix in the design of heterospin systems [Electronic resource] / S. V. Fokin, V. Ovcharenko, G. V. Romanenko, E. V. Tretyakov, A. S. Bogomyakov, V. I. Saloutin, T. I. Filyakova, L. V. Saloutina, V. N. Charushin, O. N. Chupakhin // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2011. - Vol.60, №5. - С. 816-823. - Bibliogr. : p. 823 (11 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): COPPER(II) -- BISCHELATES -- NITROXIDES Аннотация: The first heterospin compounds based on bis(1,1,1,3,5,5,5 heptafluoro 4 iminopent 2 ene 2 aminato)copper(II) (CuL2) and nitronyl nitroxide radicals, 2 R 4,4,5,5 tetramethyl 4,5 dihydro 1H imidazole 3 oxide 1 oxyls (NIT R, where R = H, Me, Ph, and 1 methyl pyrazol 4 yl), were synthesized and structurally characterized. An important peculiarity of the structure of synthesized solid phases is the formation of a supramolecular structure due to hydrogen bonds between the oxygen atoms of the nitronyl nitroxide fragments of NIT R and the hydrogen atoms of the NH groups of CuL2 \\\\expert2\\NBO\\Russian Chemical Bulletin\\2011, 60 (5), 816-823.pdf |
C 98 Cyclization of N-alkylazinium cations with binucleophiles. 8. Annellation of the imidazole ring with pyrazines and quinoxalines [Electronic resource] / V. N. Charushin, V. G. Baklykov, O. N. Chupakhin, N. N. Vereshchagina, L. M. Naumova, N. N. Sorokin // Chemistry of Heterocyclic Compounds. - 1983. - Vol. 19, № 12. - P1333-1338. - Bibliogr. : p. 1337-1338 (15 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): PYRAZINIUM ION -- QUINOXALINIUM ION Аннотация: Monosubstituted and N,N′-disubstituted thioureas enter into cyclization with pyrazinium and quinoxalinium ion to form imidazo[4,5-b]-annellated pyrazines and quinoxalines \\\\expert2\\nbo\\Chemistry of Heterocyclic Compounds\\1983, v.19, N 12, p. 1333.pdf |
C 98 Cyclization of N-alkylammonium cations with bifunctional nucleophiles. 17. Annelation of imidazole and 1,2,4-triazine rings with pyrazines via the reactions of thiosemicarbazides with pyrazinium salts [Electronic resource] / V. G. Baklykov, V. N. Charushin, O. N. Chupakhin, N. N. Sorokin // Chemistry of Heterocyclic Compounds. - 1985. - Vol. 21, № 7. - С. 798-804. - Bibliogr. : p. Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): 1,4-DISUBSTITUTED THIOSEMICARBAZIES -- CYCLIZATION REACTIONS -- THIOSEMICARBAZIDES Аннотация: 1- and 4-mono- as well as 1,4-disubstituted thiosemicarbazies undergo cyclization reactions upon treatment with N-alkylpyrazinium and quinoxalinium salts to give N-aminosubstituted imidazo[4,5-b]pyrazines and imidazo[4,5-b]quinoxalines, respectively. Thiosemicarbazides containing substituents in the 2-position react with N-alkylquinoxaline salts to give 1,2,4-triazino[5,6-b]quinoxalines after cyclization. \\\\expert2\\nbo\\Chemistry of Heterocyclic Compounds\\1985, v.21, N 7, p. 798.pdf |
A 67 Application of 1H and 13C NMR to the structural elucidation of tetrahydroquinoxalines condensed with five-membered heterocycles [Electronic resource] / V. N. Charushin, A. I. Chernyshev, N. N. Sorokin, O. N. Chupakhin // Organic Magnetic Resonance. - 1984. - Vol. 22, № 12. - P775-778. - Bibliogr. : p. 778 (22 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): N-METHYLTETRAHYDROQUINOXALINES -- PYRROLE -- IMIDAZOLE Аннотация: 1H and 13C NMR spectral data for 21 N-methyltetrahydroquinoxalines annelated with furan, pyrrole, imidazole or thiazole rings are reported. Unambiguous assignments of the ring junction 13C resonances were made on the basis of selective decoupling experiments and with the aid of one-bond and long-range 13C–1H coupling constants. The effects of five-membered heterocycles on the 1H and 13C chemical shifts of the ring junction hydrogen and carbon atoms are considered. Values of one-bond 1J(CH) and vicinal 3J(HH) coupling constants between the ring junction protons are also discussed as a diagnostic means for structural elucidation of tetrahydroquinoxalines condensed with five-membered heterocycles. \\\\expert2\\nbo\\Organic Magnetic Resonance\\1984. V. 22, N 12. P. 775.pdf |
C 47 Charushin, V. N. The Reactions of Azines on Treatment with 1,3-Bifunctional Nucleophiles [Electronic resource] / V. N. Charushin, O. N. Chupakhin // Russian Chemical Reviews. - 1984. - Vol. 53, № 10. - P956-970. - Bibliogr. : p. 969-970 (152 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): AZINES -- 1,3-BIFUNCTIONAL NUCLEOPHILES -- FURAN -- PYRROLE -- IMIDAZOLE Аннотация: The literature data on the o-cyclisation reactions of azines with 1,3-bifunctional nucleophiles, which make it possible to annelate furan, pyrrole, imidazole, and other five-membered rings to an aromatic aza-ring are surveyed and described systematically. The cyclisation reactions leading to m-linked cyclic adducts or products of the transformation of azines via the intermediate formation of cyclic m- and p-adducts are also examined. \\\\expert2\\nbo\\Russian Chemical Reviews\\1984, V.53, N10, p. 956-970.pdf |
S 98 Synthesis and properties of new π-conjugated imidazole/carbazole structures / R. A. Irgashev, N. A. Kazin, N. I. Makarova, I. V. Dorogan, V. V. Malov, A. R. Tameev, G. L. Rusinov, A. V. Metelitsa, V. I. Minkin, V. N. Charushin // Dyes and Pigments. - 2017. - Vol. 141. - P512-520 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): IMIDAZOLES -- CARBAZOLES -- ABSORPTION SPECTRA -- PHOTOLUMINESCENCE -- TDDFT CALCULATIONS -- CHARGE MOBILITY Аннотация: New 3-(1H-imidazol-2-yl)-9H-carbazoles and 6,6′-di(1H-imidazol-2-yl)-9H,9′H-3,3′-bicarbazoles have been prepared, starting from 9-ethyl-9H-carbazole-3-carbaldehyde or 9,9′-diethyl-9H,9′H-[3,3′-bicarbazole]-6,6′-dicarbaldehyde through their reactions with 4-methoxyaniline or 4-fluoroaniline, benzil or 2,2′-thenil [1,2-di(thien-2,2′-yl) glyoxal] and ammonium acetate on reflux in glacial acetic acid. The obtained compounds have been shown to demonstrate an effective fluorescence in the blue spectral region, exhibiting quantum yields in the range of 0.08–0.51, depending on their molecular structure and solvent polarity. The nature of the observed absorption spectra has been elucidated by the TDDFT calculations. |
V 29 Varaksin, M. V. Strategy of direct C(SP2)-H functionalization in non-aromatic azaheterocycles as an efficient approach towards novel 2H-imidazole derivatives / M. V. Varaksin, A. A. Akulov, T. D. Moseev, O. N. Chupakhin, V. N. Charushin // Современные синтетические методологии для создания лекарственных препаратов и функциональных материалов (MOSM2018): вторая международная научно-практическая конференция : материалы и доклады. - Екатеринбург, 2019. - С. 139-140 Рубрики: ХИМИЧЕСКИЕ НАУКИ |
B 68 Blue-light-promoted radical c-h azolation of cyclic nitrones enabled by selectfluor® / A. A. Akulov, M. V. Varaksin, A. N. Tsmokalyuk [et al.] // Green Chemistry. - 2021. - Vol. 23, № 5. - P2049-2057 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: An original approach to achieve the C(sp2)–H azolation of cyclic aldonitrones mediated by Selectfluor® has first been employed. By exploiting a metal-free, visible-light-promoted cross-dehydrogenative C–N coupling reaction between model aldonitrones, 2H-imidazole 1-oxides, and NH-containing azoles, a series of novel azaheterocyclic derivatives have been obtained in yields up to 94%. The elaborated protocol has proved to be appropriate for gram-scale processes and displayed potential for utilization in the synthesis of novel structural analogues of lanabecestat. Besides, mechanistic studies have revealed that this coupling reaction is likely to proceed via a nitroxide-involving radical pathway, encompassing a chain of electron transfer events, such as hydrogen atom transfer (HAT) and single electron transfer (SET). |
D 46 Design and antioxidant properties of bifunctional 2H-imidazole-derived phenolic compounds-a new family of effective inhibitors for oxidative stress-associated destructive processes / E. L. Gerasimova, E. R. Gazizullina, M. V. Borisova [et al.] // Molecules. - 2021. - Vol. 26, № 21. - Ст. 6534 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): 2H-IMIDAZOLE -- POLYPHENOLS -- ANTIOXIDANT CAPACITY -- ANTIRADICAL CAPACITY Аннотация: The synthesis of inhibitors for oxidative stress-associated destructive processes based on 2H-imidazole-derived phenolic compounds affording the bifunctional 2H-imidazole-derived phenolic compounds in good-to-excellent yields was reported. In particular, a series of bifunctional organic molecules of the 5-aryl-2H-imidazole family of various architectures bearing both electron-donating and electron-withdrawing substituents in the aryl fragment along with the different arrangements of the hydroxy groups in the polyphenol moiety, namely derivatives of phloroglucinol, pyrogallol, hydroxyquinol, including previously unknown water-soluble molecules, were studied. The structural and antioxidant properties of these bifunctional 5-aryl-2H-imidazoles were comprehensively studied. The redox transformations of the synthesized compounds were carried out. The integrated approach based on single and mixed mechanisms of antioxidant action, namely the AOC, ARC, Folin, and DPPH assays, were applied to estimate antioxidant activities. The relationship “structure-antioxidant properties” was established for each of the antioxidant action mechanisms. The conjugation effect was shown to result in a decrease in the mobility of the hydrogen atom, thus complicating the process of electron transfer in nearly all cases. On the contrary, the conjugation in imidazolyl substituted phloroglucinols was found to enhance their activity through the hydrogen transfer mechanism. Imidazole-derived polyphenolic compounds bearing the most electron-withdrawing functionality, namely the nitro group, were established to possess the higher values for both antioxidant and antiradical capacities. It was demonstrated that in the case of phloroglucinol derivatives, the conjugation effect resulted in a significant increase in the antiradical capacity (ARC) for a whole family of the considered 2H-imidazole-derived phenolic compounds in comparison with the corresponding unsubstituted phenols. Particularly, conjugation of the polyphenolic subunit with 2,2-dimethyl-5-(4-nitrophenyl)-2H-imidazol-4-yl fragment was shown to increase ARC from 2.26 to 5.16 (104 mol-eq/L). This means that the considered family of compounds is capable of exhibiting an antioxidant activity via transferring a hydrogen atom, exceeding the activity of known natural polyphenolic compounds. |
Metal-free C-H/C-H coupling of 2 H-imidazole 1-oxides with polyphenols toward imidazole-linked polyphenolic compounds / T. D. Moseev, E. A. Nikiforov, M. V. Varaksin [et al.] // Journal of Organic Chemistry. - 2021. - Vol. 86, № 19. - P13702–13710 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: The methodology of nucleophilic substitution of hydrogen (SNH) was successfully applied as a convenient synthetic tool to afford azaheterocyclic derivatives of phenols of various architectures. A series of 26 novel imidazole-linked polyphenolic compounds were first prepared in 72–95% yields through the direct metal-free C–H/C–H coupling of polyphenols with 2H-imidazole 1-oxides. Comprehensive studies on the reaction condition optimization, scope, and limitations enabled the development of a straightforward method toward novel bifunctional derivatives bearing both phenolic and imidazole scaffolds of particular interest in the design of challenging molecules for versatile applications in medicinal chemistry and materials science. |
Fluoroaromatic 2H-imidazole-based push-pull fluorophores: Synthesis, theoretical studies, and application opportunities as probes for sensing the pH in saliva / T. D. Moseev, M. V. Varaksin, E. A. Virlova [et al.] // Dyes and Pigments. - 2022. - Vol. 202. - Ст. 110251 Рубрики: ХИМИЧЕСКИЕ НАУКИ |
C-H/C-H coupling of 4h-imidazole-3 oxides with indoles in the synthesis of bifunctional azaheterocyclic derivatives / N. F. Vaskina, E. A. Nikiforov, T. D. Moseev [et al.] // Современные синтетические методологии для создания лекарственных препаратов и функциональных материалов : сборник тезисов VI Международной конференции. - Екатеринбург, 2022. - Ст. I-28. - P79 Рубрики: ХИМИЧЕСКИЕ НАУКИ |
Direct C-H/S-H coupling of 2н-imidazole-1-oxides and thiophenols in the synthesis of perspevtive azaheterocyclic compounds / N. F. Vaskina, E. A. Nikiforov, T. D. Moseev [et al.] // Современные синтетические методологии для создания лекарственных препаратов и функциональных материалов : сборник тезисов VI Международной конференции. - Екатеринбург, 2022. - Ст. I-30. - P81 Рубрики: ХИМИЧЕСКИЕ НАУКИ ЗДРАВООХРАНЕНИЕ. МЕДИЦИНСКИЕ НАУКИ |