Synthesis of 9-diazo-4-azafluorenes

Stable diazo compounds of the azafluorene series, viz., 9-diazo-4-azafluorenone and 1,3-diphenyl-4-azafluorene, were obtained from 4-azafluorenone and 1,3-diphenyl-4-azafluorene tosylhydrazones. 1,2-Dicarbomethoxyspiro(4-azafluorene-9,3-cyclopropane) was obtained from 4-azafluorenone tosylhydrazone, and 4,5-dicarbomethoxyspiro(4-azafluorene-9,3-pyrazolenine) was obtained from 9-diazo-4-azafluorene. It is assumed that the product in the latter case is obtained as a result of reaction of a carbene, viz., 4-azafluorenylidene carbene, which is formed from 9-diazo-4-fluorene, with dimethyl acetylenedicarboxylate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 951–953, July, 1979.     

Condensation of 4-azafluorenone and 9-phenacylidene-4-azafluorene with acetophenone. Synthesis of 3′-oxo-spiro-[4-azafluorene-9,1′-indane]

Condensation of 4-azafluorenone and 9-phenacylidene-4-azafluorene with acetophenone leads to the formation of 9,9-diphenacyl-4-azafluorene and 9-(1,2-dibenzoylethylidene)-4-azafluorene. The structures of these products were confirmed based on their spectral and chemical data. The conversion of 9,9-diphenacyl-4-azafluorene to 3-oxo-spiro-[4-azafluorene-9,1-indane] represents a novel method for the preparation of this heterocycle.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1242, September, 1988.     

Cyanoethylation of 3-methyl-2-azafluorene

3-Methyl-9,9-di(-cyanoethyl)-2-azafluorene was obtained from 3-methyl-2-azafluorene via the Michael reaction and was converted to the dibasic acid and its diester. Dieckmann condensation of the latter and subsequent hydrolysis gave 3-methyl-4-oxospiro(2-azafluorene-9,1-cyclohexane).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1668–1670, December, 1972.     

(9-(Pyridazinyl-4)-4-azafluorenes and spiro compounds with 4-azafluorene and indeno[1,2-c]pyridazine (4h-5,6-dihydro-1,2-diazepine) fragments

9-(3,6-Diphenylpyridazinyl-4)-4-azafluorene has been synthesized, and its conversions at the C⁹ position have been studied. From its C⁹-hydroxy derivative, 3-phenylspiro-[4-azafluorene-9,5-indeno[1,2-c]pyridazine] has been obtained. From 9-(1,2-dibenzoylethylidene-4-azafluorene, 3,7-diphenylspiro-[4H-5,6-dihydro-1,2-diazepine-5,9-4-azafluorene] has been synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1357–1360, October, 1992.     

Synthesis of spiro[9,10-dihydro-10-sila-2-azaanthracene-9,1′-cyclopropanes

The Z- and E-isomers of 9,14dihydro-10,10-&-methyl-2-trimethylsilyl(2phenyl-3 fornryl)spiro[IO-sila-2-azaanthracene-9,1 -cyclopropane] have been obtained by heating 9-diazo-9,10-dihydro-10,10-dimethyl-10-sila-2azaanthracene with trimethylvinylsilane and with cinnanuaidehyde.     

Formation of a spiran structure in the condensation of 2-azafluorene with esters of α, ß-unsaturated acids

4-Hydroxy-3-methyl-2,6-diphenyl-3ethoxycarbonylspiro(2-azafluorene-9, 1-cyclohex-3-ene) was obtained by condensation of 3-methyl-2-azafluorene with ethyl cinnamate in the presence of potassium. The chemical mechanism of its formation and its three-dimensional structure are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1231–1234, September, 1976.     

Reaction of 9-amino(phenylamino)methylene- and 9-α-aminobenzylidene-4-azafluorenes with some electrophilic reagents

It was shown that initial protonation of 9-aminomethylene-4-azafluorene takes place at the pyridine nitrogen atom. In nitrosation of this azafluorene, 4-azafluorenone oxime is formed, and in reaction with dichlorocarbene, 1-amino-2, 2'-dichlorospiro[4-azafluorene-9,3-cyclopropane] is formed. Acylation yields mono- or diacyl derivatives as a function of the acylating agent and reaction conditions.Russian University of National Friendship, Moscow 117923. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 527–533, April, 1995. March 14, 1995.     

Spiro[4-azafluorenepyrazolenines] and their thermal rearrangement to pyrazoloazaphenanthrenes

Reaction of 9-diazo-4-azafluorene with phenylacetylene gives spiro[4-azafluorene-9,3-pyrazolenines], isomeric according to the position of the substituent in the pyrazolenine ring. Their thermal rearrangement to pyrazolo-4-azaphenanthrenes that are isomeric according to ring linkage and position of the substituent in the pyrazole ring has been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1522–1525. November, 1988.     

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.     

Synthesis of isomeric spiro[azafluoreneoxiranes] from 3-methyl-2-azafluorene and 4-azafluorene

Compounds that belong to the class of new spiran heterocyclic systems that contain azafluorene and oxirane fragments were obtained from the corresponding azafluorenes and benzaldehyde under interphase-catalysis conditions. The Z and E isomers of 3-methyl-3-phenylspiro(2-azafluorene-9,2-oxirane) and 3-phenylspiro(4-azafluorene-9,2-oxirane) were isolated, and their configurations were established by NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1393–1395, October, 1982.     

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.

     

Spiro compounds with fragments of 4-azafluorene-[indeno)2,3-e)-1,2-dihydropyridine] and pyrazoline

9-Phenacylidene-4-azaf luorene and 9-bromo-9-(-bromophenacyl)-4-azafluorene have been used in the synthesis of spiro compounds with fragments of substituted pyrazolines. 1-Methyl-2-oxo-5 phenacylidene-indeno[2, 3-e]-1,2-dihydropyridine and hydrazine gave 1-methyl-2-oxo-3 phenylspiro[indeno(2, 3-e)-1,2-dihydropyridine-5,5-pyrazoline-2].     

Studies in the area of 2,3′-biquinolyl. 1. Arylation and hetarylation of 2,3′-biquinolyl dianion

The 2,3-biquinolyl dianion, when reacting with aryl- and hetaryl halides, forms arylation products at the 4 position, and treatment of these products with alkyl halides or water yields 1-alkyl-4-aryl-1,4-dihydro-2,3-biquinolyls or 4-aryl-1,4-dihydro-2,3-biquinolyls, respectively. Oxidation of the latter yields 4-aryl-2,3-biquinolyls. The cation dependence of the arylation reaction is demonstrated.Stavropol' State University, Stavropol' 355009. Russian Chemical Engineering University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1094–1099, August, 1997.     

Investigations in the region of 2,3′-biquinolyl 4. Alkylation of the dianion of 2,3′-biquinolyl

With alkyl chlorides and alkyl phenyl ethers the dianion of 2,3-biquinolyl forms the products from alkylation at position 4. Their treatment with alkyl halides or water gives 1, 4-dialkyl-1, 4-dihydro-2,3-biquinolyls or 4-alkyl-1,4-dihydro-2,3-biquinolyls respectively.For communication 3, see [1].Stavropol State University, Stavropol, Russia 355009. Russian Chemical Technology University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1214–1217, September, 1998.     

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.     

1,2-bis(2',6'-dimethyl-i',3'-dioxa-6'-aza-2'-silacyclooctyl-2')ethane and the corresponding ethylene and acetylene derivatives

Conclusions The reaction of 1,2-bis(methyldimethoxysilyl)ethane and the corresponding ethylene and acetylene derivatives with bis(2-hydroxyethyl)methylamine gives 1,2-bis(2,6-dimethyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)ethane and the corresponding ethylene and acetylene derivatives. Analogously, 1,2-bis(vinyldimethoxysilyl)acetylene gave 1,2-bis(2-vinyl-6-methyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)acetylene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1420–1421, June, 1988.     

Synthesis of heterocycles from 1,5-diketones. 3. Alicyclic 1,5-diketones in reaction with phenylhydrazine

8-R-7aH-5,6,7,8,9,10,11,12-Octahydroindolo[3.2.1-d,e]acridines, 1,2,3,4-tetra-hydrocarbazole, 9-R-sym-octahydroacridines, and 9-R,10-phenyl-sym-octahydroacridinium salts are formed by the action of phenyl-hydrazine on alkylidene-2,2-dicyclohexanone or the corresponding 8-R-tricyclo(7.3.1.0^2,7)tridecan-2-ol-13-ones in an acid medium. Postulations were made for the paths of formation of these compounds.2,2-Dimethyl-3-oxa-4a-(2,2-dimethyltetrahydropyran-4-on-5yl-methyl)-4aH-1, 2,3,4-tetrahydrocarbazole, 3,3,14,14-tetramethyl-2-oxa-5a,10b-(methanoxyisobutane)-1,2,3,4,5a,10b,11,11a-octahydroquinindoline, 2,2-dimethyl-3-oxa-1,2,3,4-tetrahydrocarbazole and 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydroacridine were obtained by the reaction of methylene-3,3-di(6,6-dimethyltetrahydropyran-4-one) with phenylhydrazine in acetic acid. The quinindoline structure was confirmed by the synthesis of this compound from 2,2-dimethyl-3-oxa-4a-(2,2-dimethyl-tetrahydropyran-4-on-5-ylmethyl)-4aH-1,2,3,4-tetrahydrocarbazole by the action of ammonia.For article 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 46–52, January, 1986.     

Derivatives of condensed thienopyrimidines. 11. Synthesis of 2,4-dithioxopyrano(thiopyrano)-[4′,3′∶4,5]thieno[2,3-d]pyrimidines

Methods for the synthesis of 2,4-dithioxo-6,6-dimethyl-5,6-dihydro-8H-pyrano(thiopyrano)[4,34,5]thieno[2,3-d]pyrimidines have been developed.For Communication 10 see [1].A. L. Mndzhoyan Institute of Technical Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 803–804, June, 1998.     

Unexpected variations of the rate of catalytic ethylene hydrogenation on nickel versus the flow-rate of the reacting mixture

Different shapes of the plot rate vs. flow-rate can be obtained for ethylene hydrogenation on nickel. They relate to the presence of oxygen traces and the way they are introduced into the reacting mixture. A previous statement according to which active centers are produced by the conversion of oxygen into water is thus confirmed.

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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