Synthesis and structure of o-bis(2-fluoro-2,2-dinitroethyl)-nitromethyl ester of 2′-fluoro-2′, 2′-dinitroethyl-2″-fluoro-2″-nitroethylenecarboxime

Conclusions The product of conversion of O-bis(2-fluoro-2,2-dinitroethyl)nitromethylbis(2-fluoro-2,2-dinitroethyl)carboxime in methanol or ether is O-bis(2-fluoro-2,2-dinitroethyl)nitromethyl-2-fluoro-2,2-dinitroethyl-2'-fluoro-2-nitroethylenecarboxinie, the structure of which has been established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2019–2021, September, 1987.     

Synthesis and thermochemical properties of some fluorine-containing formals

Fluorination of bis(2-fluoro-2,2-dinitroethyl) and bis(2,2,2-trinitroethyl) thionocarbonates by elemental fluorine gave bis(2-fluoro-2,2-dinitroethyl) and bis(2,2,2-trinitroethyl) difluoroformals. The reaction of 2,2,2-trinitroethyl nitrate with 2-fluoro-2,2-dinitroethyl chloromethyl ether gave 2-fluoro-2,2-dinitroethyl 2,2,2-trinitroethyl formal. The standard heats of combustion and formation of the synthesized formals were determined by combustion in a calorimetric bomb. Increments of substitution of the trinitromethyl group by the fluorodinitromethyl group and of the H atom by F in the methylene group for formals were calculated and recommended for rough calculations. It was shown that it is possible to evaluate Hf⁰ of the formals by the method of increments and group contributions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2513–2517, November, 1991.     

New terpenoid coumarins from Ferula tadshikorum

Summary Two new terpenoid coumarins — tadzhiferin (I) and tadzhikorin (II) — have been isolated from the fruit ofFerula tadshikorum M. Pimen.On the basis of physicochemical and spectral investigations, the structure of 7-(9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin is proposed for (I) and that of 7-(4-acetoxy-9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin for (II).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 593–599, September–October, 1976.     

Bisindoles. 28. Synthesis of 7,7′-dimethyl-5,5′-bis-1H-indole

Cyclization of the 3,3-dimethyl-4,4-diphenylendihydrazone of ethyl pyruvate in polyphosphoric ester gave 7,7-dimethyl-2,2-dicarbethoxy-5,5-bis-1H-indole which was hydrolyzed and decarboxylated to give 7,7-dimethyl-5,5-bis-1H-indole.For Communication 27 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–345, March, 1990.     

9-(2′,5′-Dimethyl-4′-pyridyl)fluorene in syntheses of fluorospirodihydrofuropyridine and pyridofluoranthene

1,2,5-Trimethyl-4-(9-fluorenylidene)piperidine, which is formed by condensation of fluorene with 1,2,5-trimethyl-4-piperidone, is converted catalytically to 9(2,5-dimethyl-4-pyridyl)fluorene, from which 2-methylpyrido[4,5-a]fluoranthene and its demethylated analog were obtained by catalytic dehydrocyclization. Oxidation of 9-(2,5-dimethy1-4-pyridyl)fluorene gave 9-(2,5-dimethyl-4-pyridyl)9-fluorenol and fluorene-9-spiro-4-(6-oxo-2-carboxypyrido[4,5-c]-4-6-dihydrofuran). 6-Methyl-2-phenyl-7-(9-fluorenyl)indolizine was synthesized by the Chichibabin method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1090, August, 1978.     

Changes undergone by 2-amino-N-(pyridyl-3′) anilinesunder pschorr reaction conditions

Reaction of 2 -nitroaniline with 3 -brornopyridine, 3 -iodo-5 -methylpyridine, and 3-iodo-6-methylpyridine gives 54–73% yield of the hitherto unknown 2-nitro-N-(pyridyl-3) aniline, 2-nitro-N-(5 -methylpyridyl3) aniline, and 2-nitro-N-(6-methylpyridyl-3) aniline. The nitro compounds prepared can easily be reduced to the corresponding amino-N-pyridylanilines. The amino compounds do not form carbolines under Pschorr reaction conditions, but are converted to triazoles or N -(pyridyl-3)-aniline.     

Electronic structure and models of receptor of monooxygenase inductors from a number of polychlorinated polycyclic compounds. IV. MNDO calculations of halogen-substituted azobenzenes

The electron and geometric structures of the cis and trans isomers of 3,3,4,4-tetrachloroazobenzene (3,3,4,4-TCAB) and the trans isomers of 3,3,5,5-TCAB and 3,3-dichloro-4,4-difluoroazobenzene were calculated by the MNDO method. It was established that the trans isomer, which has a planar structure, is most stable for 3,3,4,4-TCAB. Change in the position of the Cl atoms in the azobenzene, i.e., the transition from 3,3,4,4-TCAB to 3,3,5,5-TCAB, does not lead to appreciable change in the formation energy, the position of the electronic levels, the nature of the frontier orbitals, or the charge distribution in the molecules. This gives reason to suggest that the biological activity of 3,3,4,4-TCAB is due to the metabolism products and not to the action of the substrates themselves.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1797–1801, August, 1990.     

1,1′,2,2′,6,6′-Hexaphenyl-4,4′-bipyridinium cation radical

Aniline reacts with 2,2,6,6-tetraphenyl-4,4-bipyrilium perchlorate to form 1,1,2,2,6,6-hexaphenyl-4,4-bipyridine perchlorate. A relatively stable cation radical is formed in the first stage of electrochemical reduction of this compound, which has been examined by ESR, where there are splittings from two nitrogen nuclei and the four protons in the 3,3,5,5 positions: a_N=0.38; a_H=0.14 mT.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 1, pp. 61–64, January–February 1992.     

Synthesis,structure, and spectral properties of some bioxazoles

Syntheses of systems containing two oxazole rings [2-phenyl-, 2-(2-furyl)-, and 2-(2-thienyl)-2,5-bioxazoles, and 2,2-(2,5-furylene)bisoxazole] from aldehydes obtained by formylating 2-phenyl-, 2-(2-furyl)-, and 2-(2-thienyl)oxazole have been developed. Terephthalate and thiophen-2,5-dicarboxylate esters have been used to obtain 2,2-(1,4-phenylene)- and 2,2-(2,5-thienylene)bisoxazoles. The PMR, UV, and luminescence spectra of these systems have been examined, and quantum chemical calculations carried out in the PPP approximation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 826–836, June, 1986.     

Thiazolobenzo-1, 2, 3-thiadiazoles and derived cyanine dyes

The following tricyclic heterocyclic compounds are synthesized: 2-methylthiazolov (5, 4-e) benzo-1, 2, 3thiadiazole, 2-methylthiazolo (4, 5-e) benzo-1, 2, 3-thiadiazole, 2-methylthiazolo (4, 5-g) benzo-1, 2, 3-thiadiazole, and 2-methylthiazolo (5, 4-g) benzo-1, 2, 3-thiadiazole. The quaternary salts of these bases are used to prepare symmetrical and unsymmetrical trimethinecyanines and dimethinemercocyanines containing N-ethylrhodanine residues. The absorption maxima of these dyes are shifted toward the long-wave region as compared with the corresponding thiacyanines.     

Coumarins of Smyrniopsis aucheri

Chemical transformations and spectral characteristics have enabled us to establish the structure and configurations of three coumarins: (+)-2,2-dimethyl-3-hydroxy-3,4-dihydropyrano(5,6:6,7)coumarin (I); (+)-4-hydroxy-5-(1-hydroxy-1-methylethyl)-4,5-dihydrofuro(2,3:6,7)coumarin (II); and (+)-4-hydroxy-5-(1-glucopyranosyloxy-1-methylethyl)-4,5-dihydrofuro(2,3:6,7)-coumarin (III) isolated from the roots ofSmyrnopsis aucheri Karjag. This is the first time that these compounds, which have been called smyrinol, smyrindiol, and smyrindioloside, have been detected in nature.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Azerbaidzhan State University, Baku. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 36–40, January–February, 1992.     

Untersuchung des Zerfalls verschiedener Azoinitiatoren in Lösung

The decomposition of various symmetric and unsymmetric azo-initiators (1,1-dichloro-1,1-diphenyl-1,1-azoethane, 2,2-dichloro-2,2-azopropane, 1,1-dichloro-1,1-azocyclohexane, 2,2-diacetoxy-2,2-azopropane, 1,1-diacetoxy-1,1-diphenyl-1,1-azoethane, 1,1-diacetoxy-1,1-azocyclohexane, 2,2-dipropionoxy-2,2-azopropane, 2,2-dicapronoxy-2,2-azopropane, 4,4-dimethyl-1,4-azobutyrolactone, azoisobutyronitrile, 2-t-butylazo-2-cyanobutan, 2-t-bytylazo-1-cyanocyclohexan) in solution was studied in dependence of temperature. Volumetry and differential-scanning-calorimetry (DSC) were used to determine decomposition rates; first order kinetics was found in all cases.

     

Soluble polysaccharides of Rhodotorula flava

Conclusions 1. Xanthalin has been shown to have the structure of 2, 2-dimethyl-3, 4,-diangeloyloxy-3, 4-dihydropyrano-5, 6:6, 7-coumarin on the basis of the preparation of a number of derivatives and cleavage products.2. The following products of the alkaline hydrolysis of xanthalin have been isolated and characterized for the first time: (±)-3, 4-dihydroxy-3, 4-dihydroxanthyletin (isokhellactone), C₁₄H₁₄O₅, with mp 213–215° C and (–)-trans-3-hydroxy-4-methoxy-3, 4-dihydroxanthyletin (isomethylkhellactone, C₁₅H₁₆O₅, with mp 136.5–138° C and [] _D ²⁰ –47.7 (ethanol).Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 14–19, 1970     

Synthesis of thymidine 5′-(β-l-mannopyranosyl) and (4,6-dideoxy-l-lyxo-hexopyranosyl) pyrophosphates

Conclusions We have prepared thymidine 5-(-L-mannopyranosyl pyrophosphate), thymidine 5-(4,6-dideoxy--L-lyxohexopyranosyl pyrophosphate), and thymidine 5-(4,6-dideoxy--L-lyxo-hexopyranosyl pyrophosphate), all analogs of thymidine 5-(-L-rhamnopyranosyl pyrophosphate), which is involved in the biosynthesis of the O-specific chains ofSalmonella lipopolysaccharides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2588–2591, November, 1976.     

New cardenolides from the leaves ofGomphocarpus fruticosus

Two new glycosides, gomphotin (1) and gomphotoxin (13), and also the known gomphoside (9) have been isolated from the leaves ofGomophocarpus fruticosus. Compounds (1) and (9) contain a 4,6-dideoxyhexosulose residue as the sugar component, and (13) a 6-deoxyhexosulose, which are attached to glycolic OH groups of the aglycons by 3-O-1,2-O-2 (9, 13) and 3-O-1,4-O-2 (1) acetal-ketal bonds. The structures of the new compounds are represented by the names (3-O-1,4-O-2)-(2,3-dihydroxy-4, 6dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (1) and (3-O-1,2-O-2)-(2,3,4-trihydroxy-6-deoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (13).State Scientific Center for Drugs of the Ministry of Health and the National Academy of Sciences of the Ukraine, Kharkov, fax 441118. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 824–832, November–December, 1995. Original article submitted May 22, 1995.     

Copper(II) chloride complexes of 2-(4′-Methyl-2′-pyridyl)-benzoxazole,their sulphur and nitrogen analogues and 2-(4′-Methyl-2′ {or8′} -quinolyl)benzoxazoles

Summary Copper(II) complexes CuLCl₂, where L=2-(4-methyl-2-pyridyl)benzimidazole(mpbi); 2-(4-methyl-2-pyridyl)benzothiazole(mpbt); 2-(4-methyl-2-pyridyl)benzoxazole (mpbo); 2-(4-methyl-2-quinolyl)benzoxazole (mqbo); 2-(4-methyl8-quinolyl)benzoxazole (mqbo), and Cu(mpbi)₂Cl₂(H₂O) have been synthesized and characterized by conductivity and magnetic measurements as well as by i.r., electronic and e.s.r. spectra. The ligands are bidentate donors through the pyridine and isoxazole nitrogen atoms. The CuLCl₂ complexes exhibit spectral properties consistent with CuN₂Cl₂ chromophores differing in the degree of tetrahedral distortion, which is found to parallel the steric hindrance near the donor sites. Cu(mpbi)₂ Cl₂(H₂O) is five-coordinate.     

The Mannich reaction with 2-methyl-5-vinylpyridine

1,3-Bis(dimethylamino)-2-(5-vinyl-2-pyridyl)propane and 2-(-dimethylaminoethyl)-5-vinylpyridine were prepared by the aminomethylation of 2-methyl-5-vinylpyridine. These Mannich bases have been transformed into 1-dimethylamino-2-(5-vinyl-2-pyridyl)-1-propene and 2,5-divinylpyridine by the decomposition of their quaternary salts.     

Structure of some components of the roots of Prangos ferulacea

Summary From a methanolic extract of the roots ofPrangos ferulacea (L) Lindl., growing in the Nakhichevan ASSR, in addition to the compounds found previously, another six substances (I–VI) have been isolated, of which (I) and (VI) have been identified as, respectively, meransin hydrate monoacetate, found for the first time in nature, and umbelliferone: and in the study of a crystalline mixture obtained from the resin of the roots of the plant under investigation collected in Armenia, two coumarins — (VII) and (VIII) — have been isolated.On the basis of a study of IR, NMR, and mass spectra and chemical properties, the structures of the six new cumarin derivatives (II–V, VII, and VIII) have been established. Compound (II) has the structure of 8-(3-methylbutenyloxy)furo-2,3:7,6-coumarin and has been called feruliden; (III) is 7-hydroxy-8-(3-hydroxy-2-senecioyloxyisopentyl) coumarin and has been called ferudiol; (IV) is 7-hydroxy-8-(3-methoxy-2-senecioyloxyisopentyl) coumarin; (V) is 5-[1-(2,3-dihydroxy-3-methylbutyroyloxy)-1-methylethyl]-4,5-dihydrofuro-2,3:7,6-coumarin and has been called lindiol; (VII) is 8-(2-hydroxy-3-methylbut-3-enyloxy)-7-methoxycoumarin and has been called ferudenol; (VIII) is 7-methoxy-8-(3-methyl-2-oxobut-3-enyl)coumarin and has been called prangone.Leningrad Sanitary-Hygenic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 568–574, September–October, 1974.     

Nitration,amination, and halogenation of Di-O-methylphloracetophenone

Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.

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Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon

Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.