2-Spiroanellated 1,3-Benzodioxoles from the Reaction of 2,3-Dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrol-3-ones with Tetrachloro-1,2-benzoquinone

Summary. Novel spiro[1,3-benzodioxole-2,2-(2,3-dihydro-1H-pyrrol-3-ones)] were obtained from 2-aminomethylene-2,3-dihydropyrrol-3(1H)-ones and tetrachloro-1,2-benzoquinone in ethanol at room temperature. However, in addition, 3,4-dichloro-7-methoxy-5-(4-methoxyphenyl)-5,10-dihydrophenazine-1,2-dione was formed in the reaction of 1-(4-methoxyphenyl)-2-(4-methoxyphenylaminomethylene)-4,5-diphenyl-1,2-dihydropyrrol-3-one with tetrachloro-1,2-benzoquinone.     

Synthesis of 3-(3′-Acetyl-5′-aroyl-1′,3′,4′-oxadiazolyl-2′)-chromones

A general method has been proposed for synthesizing 3-(3-acetyl-5-aroyl-1,3,4-oxadiazolyl-2)-chromones that has been based on conversion of 3-formylchromones to acylhydrazones and of theacylhydrazones into the heterocyclic chromones.     

Synthesis of derivatives of the new heterocyclic system pyrimido[4′,5′:4,5]pyrimido[1,2-a]benzimidazole

3-Phenyl-5-methyl(phenyl)-1H,3H-pyrimido[4,5:4,5]pyrimido[1,2-a]benzimi-dazole-2,4-diones were obtained by the cyclization of N-phenyl-N-[3-ethoxycar-bonyl-4-methyl(phenyl)pyrimido [1,2-a]benzimidazol-2-yl]ureas by the action of potassium carbonate. 2-Methyl-5-phenyl-1H-pyrimido[4,5:4,5]pyrimido[1,2-a]benzimidazol-4-one was obtained by the reaction of N-3-ethoxycarbonyl-4-phenylpyrimido[1,2-a]benzimidazol-2-yl]-N,N-dimethylacetamidine with ammonium acetate in ethanol. The synthesized compounds are members of a new heterocyclic system. The molecular and crystal structure of the solvate of 3-phenyl-5-methyl-1H,3H-pyrimido[4,5:4,5] pyrimido[1,2-a]benzimidazole-2,4-dione with two molecules of DMF was studied by x-ray crystallographic analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2587–2592, November, 1991.     

Investigations of 2,3′-biquinolyl. 9. Reaction of 1′,4′-dihydro-2,3′-biquinolyl with organolithium compounds

The 1,4-dihydro-2,3-biquinolyl reacts with organolithium compounds to form the mixture of 4-R-1,4-dihydro-2,3-biquinolyls and 2-R-1,2-dihydro-2,3-biquinolyls in the ratio analogous to the conversion in the series of 2,3-biquinolyl. The utilization of the complex, the organolithium compound-TMEDA, in this process leads, after treatment of the reaction mixture with water, exclusively to 2-R-1,2-dihydro-2,3-biquinolyls. Treatment with methyl iodide leads to 1-methyl-2-R-1,2-dihydro-2,3-biquinolyls.     

Transformation of batridene

Transformations of 1,1,6,6,7,7-hexahydroxy-3,3-dimethyl-5,5-diisopropyl-2,2-dinaphthylidene-8,8-dibarbituric acid (batridene) in DMSO are studied.     

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].     

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.     

1-Aryl-6-azauracile, 4. Mitt.: Die Synthese des 1-Phenyl-5-[5′-methyl-1′,2′,4′-oxdiazolyl-(3′)]-6-azauracils und einiger seiner Derivate

Zusammenfassung Arylhydrazon-cyanacetylcarbamidsäureäthylester (I) wurde durch Einwirkung einer Na₂CO₃-Lösung auf 1-Aryl-5-cyan-6-azauracile (II)^1,2 cyclisiert. Nitrile (II) wurden durch Addition von Hydroxylamin in entsprechende Amidoxime (III) übergeführt, welche durch Kochen mit Acetanhydrid die zugehörigen 1-Aryl-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracile (IV) lieferten.

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Aryl hydrazone-cyanoacetylcarbamic acid ethyl esters (I) have been cyclized in Na₂CO₃ soln. yielding 1-aryl-5-cyano-6-azauraciles (II)^1,2. Addition of NH₂OH to the nitriles (II) gave the corresponding amidoximes (III), which by refluxing with Ac₂O were converted to the corresponding 1-aryl-5-[5-methyl-1, 2, 4-oxdiazolyl(3)]-6-azauraciles (IV).

     

Investigations in the field of oxygen-containing heterocycles

2-(4-Chloro-2-methyl-2-butenyl)tetrahydropyran and 2-(4-chloro2, 3-dimethyl-2-butenyl)tetrahydropyran react with organomagnesium compounds and also with sodium amalgam with the formation of mixtures of the 2-(2-alkenyl)tetrahydropyrans corresponding to the initial chlorides and the 2-(3-alkenyl)tetrahydropyrans corresponding to the allyl isomers of the initial chlorides. The structure and composition of the products have been established by IR and NMR spectroscopy and by gas-liquid chromatography.For part V, see [1].     

Bisindoles. 10. Synthesis of 1,2-(5,5′-diindolyl)ethane

A 2,2-diethoxycarbonyl derivative of a new bisindole system, viz., 1,2-(5,5-diindolyl)ethane, was obtained by cyclization of ethyl pyruvate sym-4,4-diphenyleneethanedihydrazone. 5-(-Phenylethyl)-2-ethoxycarbonylindole was also isolated in very low yield from the reaction products. Saponification of the 2,2-diethoxycarbonyl derivative gave the corresponding dicarboxylic acid, the thermal decarboxylation of which leads to the formation of 1,2-(5,5-diindolyl) ethane. The syn,syn and anti,anti forms of ethyl pyruvate sym-4,4-diphenyleneethane-dihydrazone were also obtained and characterized.See [1, 2] for Communications 8 and 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 348–351, March, 1982.     

Diazabicycloalkanes with nitrogen atoms in bridgehead positions. 16. Synthesis and properties of benzo[b]-1,4-diazabicyclo[2.2.2]octene and dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene,containing primary aromatic amino acids

4-Aminobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-aminodibenzo[1,2-b, e]-1,4-diazabicyclo[2.2.2]octadiene have been prepared by cyclization reactions of N--chloroethyl derivatives of 1,2,4-triaminobenzene and aminophenazine, and subsequent catalytic hydrogenation of the corresponding 4-nitrobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-benzylaminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]-octadiene. Using the conversion of these compounds to azides as an example, we have demonstrated the feasibility of applying these primary aromatic amines for the synthesis of derivatives of these heterocycles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 831–837, June, 1988.     

Coumarin composition of Seseli grandivittatum

Summary From the roots ofSeseli grandivittatum, together with -sitosterol and (–)-3R-decursinol, found in nature for the first time, and its angelate, we have isolated two new compounds which we have called grandivittin and grandivittinol.On the basis of IR, PMR, and mass spectra and chemical transformations, the structure of 3-senecioyloxy-3,4-dihydro-3R-xanthyletin is proposed for grandivittin, and 7-hydroxy-6-(3-hydroxy-2-senecioyloxyisopentyl) coumarin for grandivittinol.Leningrad Sanitary-Hygienic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 640–646, September–October, 1977.     

Synthesis of benzotristriazole. 4-nitrobenzo[1,2-d:3,4-d′] bistriazole and 4,4′-dicarboxy-5,5′-1H-1,2,3-triazole

The treatment of 2,5,8-tri(2,4-dinitrophenyl)benzotristriazole, 2,7-di(2,4-dinitrophenyl)-4-nitrobenzo[1,2-d3,4-d]bistriazole, and 4,4-dicarboxy-5,5-bis[2- (2,4-dinitrophenyl)-2H-1,2,3-triazole with sodium methylate leads to loss of the 2,4-dinitrophenyl group as 2,4-dinitroanisole and formation of benzotristriazole, 4-nitrobenzo[1,2-d3,4-d]bistriazole, and 4,4-dicarboxy-5,5-bis-1H-1,2,3-triazole, respectively, in good yields.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1364–1367, October, 1993.     

Investigations of 2,3′-biquinolyl. 7. Thiolation of 1-alkyl-3-(2-quinolyl)quinolinium halides

Thiolation of 1-alkyl-3-(2-quinolyl)quinolinium halides by a mixture of sulfur with KOH in DMF leads to formation of 1-alkyl-1,4-dihydro-2,3-biquinolyl-4-thiones, rearrangement of which in boiling ethylene glycol makes it possible to obtain 4-alkylthio-2,3-biquinolyls.     

Polarographic behavior of 2,2′-bifuryl and 2,2′-furoin

In aqueous and aqueous-ethanolic buffer solutions at pH<9, 2, 2-bifuryl and 2, 2-furoin give two-electron polarographic electroreduction waves, the half-wave potentials of which depend on the pH. The primary product of the electroreduction of 2, 2-bifuryl is trans-1,2-dihydroxy-1,2-bis(, -furyl)ethylene, which then rearranges into 2, 2-furoin. The anode-cathode wave of 2,2-bifuryl has been studied by means of a Kalousek commutator. It has been shown that the polarographic behavior of 2,2-bifuryl and 2, 2-furoin is similar to that of benzil and benzoin, but differs from the behavior of analogs of the pyridine series.     

Cobalt(II) and nickel(II) chloride complexes with some 2-(4′-Methyl-2′-pyridyl and 2′- or 8′-quinolyl)benz-X-azoles

Summary Complexes of general formula ML_mCl₂ · nH₂O, where M=cobalt(II) or nickel(II); 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), or 2-(4-methyl, 8-quinolyl)benzoxazole (mqbo); m=1,2; n=0–3, were prepared and characterized by t.g.a., conductance and magnetic measurements, i.r. and diffuse-reflectance electronic spectra.All the ligands behave as bidentate and coordinate through the pyridine- and isoxazole-nitrogen atoms.The nickel complexes have distorted octahedral or fivecoordinate structures. The cobalt complexes arepseudo-tet- rahedral except Co(mpbo)₂Cl₂·2H₂O where the metal is six-coordinate.     

Über Tetrahydrospiro [cyclohexan-1,4′(1′H)-chinazolin]-2′(3′H)-one

Zusammenfassung Cyclohexanon bzw. Cyclopentanon sowie ihre durch Aldolreaktion entstehenden Dimeren reagieren mit Harnstoff im sauren Medium zu 5,6,7,8-Tetrahydrospiro[cyclohexan-1,4(1H)-chinazolin]-3(2H)-onen (2) bzw. zum Dihydrospiro-(cyclopentan-1,4(1H)-5H-cyclopenta[d]pyrimidin)-2(3H)-on (10). Substituierte Harnsotoffe geben Gemische der isomeren 5,6,7,8-Tetrahydro- und 4a,5,6,7-Tetrahydroverbindungen (2, 3) bzw. 6,7-Dihydro-tH- und 5,6-Dihydro-4aH-verbindungen (10, 11). Charakteristisch für2 (3),10 (11) ist die Reaktivität der Kernstellen 8 bzw. 7 gegenüber elektrophilen Agentien (2f-v, 3f-j, 9 a-i, 10 d-f). Äthylmalonsäurebis-trichlorphenylester bzw. Formaldehyd und prim. Amine führen2 in ein partiell hydriertes 1H-Pyrido[3,2,1-ij]chinazolintrion (6) bzw. 1H-Pyrimido[5,6,1-ij]chinazolinon (7) über. Die 1-Alkylverbindungen (2) geben mit Formaldehyd und primären Aminen Hexahydro-8a-hydroxy-4a,8-propanospiro-(cyclohexan-1,4(1H)-pyrido[4,3-d]pyrimidin)-2(3H)-one (8).

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Heterocycles, XXV: tetrahydrospiro [cyclohexane-1,4(1H)-quinazoline]-2(3H)-ones

Cyclohexanone and cyclopentanone, resp., as well as their dimers (formed by aldol reaction) react with urea in the presence of acids to 5,6,7,8-tetrahydrospiro[cyclohexane-1,4-(1H)-quinazoline]-3(2H)-ones (2) and to the dihydrospiro-(cyclopentane-1,4(2H)-5H-cyclopenta[d]pyrimidine)-2(3H)-one (10), resp. Substituted ureas give the isomeric 5,6,7,8-tetrahydro- and 4a,5,6,7-tetrahydro compounds (2, 3), and 6,7-dihydro-5H- and 5,6-dihydro-4aH-compounds (10, 11), resp. Characteristic for2 (3),10 (11) is the reactivity of the nuclear places 8 and 7 with electrophilic agents (2f-v, 3f-j, 9a-i, 10d-f). Ethylmalonic acid bistrichlorophenylester resp. formaldehyde and primary amines react with2 to the partially-hydrogenated 1H-pyrido[3,2,1-ij]-quinazolinetrione (6) and 1H-pyrimido[5,6,1-ij]-quinazolinone (7), resp. The 1-alkyl compounds (2) give with formaldehyde and primary amines hexahydro-8a-hydroxy-4a, 8-propanospiro(cyclohexane-1,4-(1H)-pyrido[4,3-d]pyrimidine)-2(3H)-ones (8).

     

New chiral acyclic analogs of 2′-deoxynucleosides

Convenient methods for the synthesis of chiral 2,3-seco-2-deoxynucleosides were developed. An isopropylidene protective group was used to block the 3,5-hydroxy groups in 2,3-seco-uridine. Conversion of the hydroxymethyl group to a methyl group was accomplished by chlorination with a mixture of CCl₄ and Ph₃P with subsequent reduction with n-Bu₃SnH. 2,3-seco-2-Deoxyuridine was obtained after deacetonation. The (S) enantiomer was similarly synthesized starting from 1-(-D-arabinofuranosyl)uracil. 3-O-tert-Butyldimethylsilyl-5-O-(p-monomethoxytrityl)-2,3-seco-2-deoxyuridine, which has optically active centers at C₍₁₎ and C₍₄₎, was also synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–826, June, 1988.The authors thank Professor M. Ya. Karpeiskii for his constant interest in this research.     

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.