C 73 Combination of the Suzuki–Miyaura cross-coupling and nucleophilic aromatic substitution of hydrogen (HSN) reactions as a versatile route to pyrimidines bearing thiophene fragments / E. V. Verbitskiy, E. M. Cherprakova, P. A. Slepukhin, M. I. Kodess, M. A. Ezhikova, M. G. Pervova, G. L. Rusinov, O. N. Chupakhin, V. N. Charushin // Tetrahedron. - 2012. - Vol.68, №27-28. - С. 5445-5452 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): SUZUKI–MIYAURA -- CROSS-COUPLING -- PYRIMIDINES Аннотация: It has been shown that combination of the Suzuki–Miyaura cross-coupling and nucleophilic aromatic substitution of hydrogen is a versatile method for the synthesis of 4-(thiophen-2-yl)-, 5-(thiophen-2-yl)-, and 4,5-di(thiophen-2-yl) substituted pyrimidines from the commercially available 5-bromopyrimidine. The HSN (AE)- and HSN (AO)-reactions of 5-bromopyrimidine with thiophene and 2-bromothiophene have been studied by gas–liquid chromatography/mass-spectrometry. The structures of intermediate σH-adducts, as well as thiophene-(thiophenyl)pyrimidine and bithiophene-(thiophenyl)pyrimidine dyads have first been established by X-ray crystallography analysis \\\\Expert2\\nbo\\Tetrahedron\\2012, v. 68, p. 5445.pdf |
S 98 Synthesis, photophysical and electrochemical properties of novel 6,12-di(thiophen-2-yl) substituted indolo[3,2-b]carbazoles [Electronic resource] / R. A. Irgashev, A. Yu. Teslenko, E. F. Zhilina, A. V. Schepochkin, O. S. Eltsov, G. L. Rusinov, V. N. Charushin // Tetrahedron. - 2014. - Vol.70, №31. - С. 4685-4696 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): INDOLO[3,2-B]CARBAZOLE -- INDOLE -- THIOPHENE Аннотация: Novel 5,11-dialkyl-6,12-di(thiophen-2-yl) substituted 5,11-dihydroindolo[3,2-b]carbazoles have been obtained and plausible ways for their further modifications via the Friedel–Crafts reaction are presented. The formylation of these indolo[3,2-b]carbazoles with dichloromethyl alkyl esters catalysed by Lewis acids leads to the formation of the corresponding 2,8-diformyl derivatives. Applicability of this formylation method for modification of indolo[3,2-b]carbazoles bearing electron-rich aromatic substituents at C-6 and C-12 has also been demonstrated. The Knoevenagel condensation of 2,8-dialdehydes with active methylene nitriles has been studied. The measurements of optical and redox properties for a number of new indolo[3,2-b]carbazoles have been performed \\\\expert2\\nbo\\Tetrahedron\\2014, v. 70 , p. 4685-4696.pdf |
A 10 A facile and convenient synthesis and photovoltaic characterization of novel thieno[2,3-b]indole dyes for dye-sensitized solar cells [Electronic resource] / R. A. Irgashev, A. A. Karmatsky, S. Kozyukhin, V. K. Ivanov, A. Sadovnikov, V. V. Kozik // Synthetic Metals. - 2015. - Vol. 199. - С. 152-158. - Bibliogr. : p. 158 (28 ref/) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): THIENO[2,3-b]INDOLE -- DYES -- THIOPHENE Аннотация: Two novel dyes IK-1,2 bearing the 8-alkyl-8H-thieno[2,3-b]indole unit as an electron-donating part of the push-pull system have been designed and prepared, as promising sensitizers for solar cells. The key steps of the synthesis involve the crotonic condensation of 1-alkylisatins with 2-acetylthiophene, followed by reduction of the C=C double bond and further cyclization through the Paal-Knorr reaction with the Lawesson reagent, thus leading to the formation of 2-(thien-2-yl) substituted thieno[2,3-b] indole derivatives. The optical and electrochemical properties of these dye's have been investigated by using spectrophotometry and cyclic voltammetry respectively, while their photovoltaic performance was evaluated by a device fabricatien study. The DSSCs based on IK-1 and IK-2 have demonstrated an efficiency of eta = 0.37% (FF = 73%) and eta = 0.7g% (FF = 69%) under 100 mW cm(-2) simulated AM 1.5G solar irradiation, respectively. \\\\expert2\\nbo\\Synthetic Mеtals\\2015, V.199, p. 152-158.pdf |
D 47 Detection of nitroaromatic explosives by new D-π-A sensing fluorophores on the basis of the pyrimidine scaffold [Electronic resource] / E. V. Verbitskiy, A. A. Baranova, K. I. Ludovik, M. Z. Shafikov, K. O. Khokhlov, E. M. Cheprakova, G. L. Rusinov, O. N. Chupakhin, V. N. Charushin // Analytical and Bioanalytical Chemistry. - 2016. - Ahead of Print Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): NITROAROMATIC EXPLOSIVES -- PYRIMIDINE SCAFFOLD Аннотация: A series of D-π-A- type dyes based on pyrimidines, bearing various thiophene linkers, have been studied as sensing fluorophores. Fluorescence studies have demonstrated that the emission of all derivs. is sensitive to the presence of nitroarom. explosives, such as 2,4,6-trinitrophenol (PA), 2,4,6-trinitrotoluene (TNT), and 2,4-dinitrotoluene (DNT), in their acetonitrile solns. The detection limits of fluorophores to PA, TNT, and DNT proved to be in the range from 5.83 × 10-6 to 2.38 × 10-7 mol/L, 1.70 × 10-4 to 8.40 × 10-6 mol/L, and 8.39 × 10-5 to 6.87 × 10-6 mol/L, resp. The theor. investigation into the quenching mechanism in the presence of fluorophore has been performed. All compds. have shown a good efficiency as sensor materials when tested as elements of the original device < \\\\expert2\\nbo\\Analytical and Bioanalytical Chemistry\\2016, Ahead Print.pdf |
C 75 Construction of Heteroacenes with Fused Thiophene and Pyrrole Rings via the Fischer Indolization Reaction [Electronic resource] / R. A. Irgashev, A. A. Karmatsky, G. L. Rusinov, V. N. Charushin // Organic Letters. - 2016. - Vol. 18, № 4. - С. 804-807 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): FUSED THIOPHENE -- PYRROLE RINGS -- FISCHER INDOLIZATION REACTION Аннотация: A convenient approach to ladder-type 6H-benzo[4',5']thieno[2',3':4,5]thieno[3,2-b]indoles, e.g., I (X-rays single crystal structure shown), bearing various substituents in both terminal benzene rings has been developed. The protocol suggested for prepg. these N,S-heteroacenes is based on using easily available reagents, such as cinnamic acids and arylhydrazines, which can be involved in the Fischer indole synthesis, as the key step. A similar condensed system of 12H-benzo[4'',5'']thieno[2'',3'':4',5']thieno[2',3':4,5]thieno[3,2-b]indole, bearing six rings, has also been obtained. \\\\expert2\\nbo\\Organic Letters\\2016, v.18, N 4, p.804-807,pdf.pdf |
C 10 C-H functionalization of triazolo[a]-annulated 8-azapurines [Electronic resource] / E. B. Gorbunov, G. L. Rusinov, E. N. Ulomskii, V. L. Rusinov, V. N. Charushin, O. N. Chupakhin // Tetrahedron Letters. - 2016. - Vol. 57, № 21. - С. 2303-2305 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): FUSED PYRIMIDINES -- C-H FUNCTIONALIZATION -- 8-AZAPURINES Аннотация: Direct C-H functionalization of triazolo[a]-annulated 8-azapurines with phenol ethers or thiophene has been performed using the oxidative nucleophilic displacement of a hydrogen on the pyrimidine ring, proceeding through the intermediacy of the corresponding sigma(H)-adducts. \\\\expert2\\NBO\\Tetrahedron Letters\\2016, v. 57, p. 2303.pdf |
N 52 New 4,5-di(hetero)arylpyrimidines as sensing elements for detection of nitroaromatic explosives in vapor phase / E. V. Verbitskiy, A. A. Baranova, K. I. Lugovik, K. O. Khokhlov, E. M. Cheprakova, M. Z. Shafikov, G. L. Rusinov, O. N. Chupakhin, V. N. Charushin // Dyes and Pigments. - 2016. - Vol. 137. - С. 360-371. - Bibliogr. : p. 370-371 (50 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): 4,5-DI(HETERO)ARYLPYRIMIDINES -- NITROAROMATIC EXPLOSIVES -- VAPOR PHASE Аннотация: A series of D–π–A–π–D type dyes based on pyrimidines, bearing thiophene linkers, have been studied as sensing fluorophores. Fluorescence studies have demonstrated that the emission of all derivatives is sensitive to the presence of 2,4,6-trinitrotoluene (TNT) and other nitroaromatic compounds (NACs), in their acetonitrile solutions. The detection limits of fluorophores to NACs proved to be in the range from 10−4 to 10−6 mol/L. The time-resolved fluorescence measurements and theoretical investigation into the quenching mechanism in the presence of fluorophore has been performed. The two types of sensor prototypes for handheld sniffer «Nitroscan» (Plant «Promautomatika», Ekaterinburg, Russia) on the basis of non-woven dry wipe and spunlace non-woven fabric with various quantities of the most sensitive fluorophore have been fabricated. The reusable, reversible and sensitive response of the designed prototypes to NACs enables one to qualify these compounds as promising fluorescent sensory materials for detection of NACs. \\\\expert2\\nbo\\Dyes and Pigments\\2016, v. 137, p.360-371.pdf |
N 52 New 4,5-di(hetero)arylpyrimidines as sensing elements for detection of nitroaromatic explosives in vapor phase / E. V. Verbitskiy, A. A. Baranova, K. I. Lugovik, K. O. Khokhlov, E. M. Cheprakova, M. Z. Shafikov, G. L. Rusinov, O. N. Chupakhin, V. N. Charushin // Dyes and Pigments. - 2017. - Vol. 137. - P360-371 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): FLUORESCENCE QUENCHING -- NITROAROMATIC EXPLOSIVES -- TRIPHENYLAMINES -- CARBAZOLES -- PYRIMIDINES Аннотация: A series of D–π–A–π–D type dyes based on pyrimidines, bearing thiophene linkers, have been studied as sensing fluorophores. Fluorescence studies have demonstrated that the emission of all derivatives is sensitive to the presence of 2,4,6-trinitrotoluene (TNT) and other nitroaromatic compounds (NACs), in their acetonitrile solutions. The detection limits of fluorophores to NACs proved to be in the range from 10−4 to 10−6 mol/L. The time-resolved fluorescence measurements and theoretical investigation into the quenching mechanism in the presence of fluorophore has been performed. The two types of sensor prototypes for handheld sniffer «Nitroscan» (Plant «Promautomatika», Ekaterinburg, Russia) on the basis of non-woven dry wipe and spunlace non-woven fabric with various quantities of the most sensitive fluorophore have been fabricated. The reusable, reversible and sensitive response of the designed prototypes to NACs enables one to qualify these compounds as promising fluorescent sensory materials for detection of NACs. |
A 10 A convenient synthesis of new 5,11-dihydroindolo[3,2-b]carbazoles bearing thiophene, 2,2′-bithiophene or 2,2′:5′,2″-terthiophene units at C-2 and C-8 positions / R. A. Irgashev, N. A. Kazin, G. L. Rusinov, V. N. Charushin // Tetrahedron Letters. - 2017. - Vol. 58, № 32. - P3139-3142 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): 5,11-DIHYDROINDOLO[3,2-B]CARBAZOLE -- THIOPHENE -- 3-CHLOROACRYLALDEHYDE -- THE VILSMEIER–HAACK FORMYLATION -- THE FIESSELMANN REACTION Аннотация: A series of new 5,11-dihydroindolo[3,2-b]carbazole derivatives, containing functional thiophene, 2,2′-bithiophene or 2,2′:5′,2″-terthiophene moieties at both C-2 and C-8 positions of their fused scaffolds, have been obtained from 2,8-diacetyl-substituted 5,11-dihydroindolo[3,2-b]carbazole compounds through the effective strategy, which is based on the sequence of two reactions, namely the Vilsmeier–Haack formylation and the Fiesselmann thiophene synthesis. The starting acetyl substituted materials have been transformed into the corresponding 3-chlorocrylaldehyde-containing compounds by treatment with POCl3-DMF complex, followed by the reaction with alkyl thioglycolates or α-mercaptoacetone in the presence of triethylamine to afford 2-carboalkoxythiophene- or 2-acetylthiophene-linked derivatives. 2-Acetylthiophene derivatives have further been involved into the same sequence of reactions to obtain 2,2′-bithiophene-, and 2,2′:5′,2″-terthiophene-linked 5,11-dihydroindolo[3,2-b]carbazole compounds. \\\\Expert2\\NBO\\Tetrahedron Letters\\2017 v.58 p.3139-3142.pdf |
N 89 Novel push-pull thieno[2,3-b]indole-based dyes for efficient dye-sensitized solar cells (DSSCs) / R. A. Irgashev, A. A. Karmatsky, G. A. Kim, G. L. Rusinov, V. N. Charushin, A. A. Sadovnikov, V. K. Ivanov, S. A. Kozyukhin, V. V. Emets, V. A. Grinberg // Arkivoc. - 2017. - Vol. 4. - P34-50 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): DYE-SENSITIZED SOLAR CELLS -- ELECTRON-RICH HETEROCYCLES -- METAL-FREE DYES -- PHOTOVOLTAIC PROPERTIES -- PUSH-PULL STRUCTURE -- THIENO[2,3-B]INDOLE Аннотация: New metal-free sensitizers (IK 3-6), based on the thieno[2,3-b]indole ring system, bearing various aliphatic substituents at the nitrogen atom (electron-donating part), several thiophene units (π-bridge linker) and 2-cyanoacrylic acid (the electron-accepting and anchoring group) have been synthesized for application in dye-sensitized solar cells (DSSCs). The relationship between the IK dye structure and efficiency of the corresponding DSSC has been elucidated. Power conversion efficiency (PCE) up to 6.3% (short-circuit photocurrent density (JSC) 19.0 mA cm-2, open-circuit voltage (VOC) 0.59 V, and fill factor (FF) 56.4%) were obtained for the DSSC, based on 2-cyano-3-{5-[8-(2-ethylhexyl)-8H-thieno[2,3-b]indol-2-yl]thiophen-2-yl}acrylic acid (IK 3), which proved to be a highly synthetic available compound, under simulated AM 1.5 G irradiation (100 mW cm-2), thus indicating that thieno[2,3-b]indole-based organic dyes are perspective candidates for DSSCs. \\\\Expert2\\NBO\\ARKIVOC\\2017 v.4 p.34-50.pdf |
Features of a multicomponent biginelli reaction involving 3-oxobutanoyl-containing podands, aromatic aldehydes, and 1,2,4-triazol-3-amine / E. S. Filatova, O. V. Fedorova, K. A. Chistyakov [et al.] // Chemistry of heterocyclic compounds. - 2020. - Vol. 56, № 1. - P88-91 Кл.слова (ненормированные): DIHYDROPYRIMIDINE -- MONOSUBSTITUTED PODAND -- PODAND -- TRIAZOLO[1,5-А]PYRIMIDINE -- TRIAZOLO[4,3-А]PYRIMIDINE -- TUBERCULOSTATIC ACTIVITY Аннотация: [Figure not available: see fulltext.] A reaction of 3-oxobutanoyl-containing podands with thiophene-2-carbaldehyde (or benzaldehyde) and 3-amino-1,2,4-triazole gave podands featuring a 4,7-dihydro[1,2,4]triazolo[1,5-а]pyrimidine motif. It was established that the process was accompanied by the formation of [4,3-а]-isomers, which occurred in a slight excess during the synthesis of a podand containing a phenyl group at position 7 and, on the other hand, were observed as the minor products during the synthesis of podands bearing a thiophen-2-yl substituent. Trace amounts of monosubstituted podands were also detected, containing a free hydroxy group along with the triazolodihydropyrimidine pharmacophore. |
Benzo[ b]selenophene/thieno[3,2-b]indole-based n,s,se-heteroacenes for hole-transporting layers / M. S. Demina, N. A. Rasputin, R. A. Irgashev [и др.] // ACS omega. - 2020. - № 5. - С. 9377-9383 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Two series of new N,S,Se-heteroacenes, namely, 6H-benzo[4′,5′]selenopheno[2′,3′:4,5]thieno[3,2-b]indoles and 12H-benzo[4″,5″]selenopheno[2″,3″:4′,5′]thieno[2′,3′4,5]thieno[3,2-b]indoles, were successfully obtained using an effective strategy based on Fiesselmann thiophene and Fischer indole synthesis. The new molecules exhibit a large optical band gap (2.82 eV Egopt 3.23 eV) and their highest occupied molecular orbital (HOMO) energy formed by the plane Ï-core ranges between-5.2 and-5.6 eV, with the narrower optical band gap and lower HOMO level corresponding to selenated heteroacenes. In thin solid films of the heteroacenes, hole mobility measured using the conventional CELIV technique ranges between 10-5 and 10-4 cm2·V-1·s-1. All these make the proposed condensed-ring compounds a promising platform for the development of hole-transporting materials applicable in organic electronics. |