Hydroacridines and related compounds. 23. Caprolactam derivatives and hydrocoumarins from 4a,10a-epidioxyperhydroacridines

The thermolysis of 10-R,9-R¹,9-R²-4a,10a-epidioxyperhydroacridines has given 1-R-3-[-(2-oxocyclohexyl)alkyl]hexahydroazepin-2-ones which have been reduced to the corresponding 2-hydroxycyclohexyl derivatives. Hydrolysis of the compounds obtained led to 3-[-(R-amino)butyl]hydrocoumarins.For communication 22, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 650–656 May, 1985.     

4-Hydroxy-2-quinolones. 44. Synthesis of 2-R-3-oxomorpholino[5,6-c]-6-R'-Quinolin-5-ones

Treatment of 1-R-2-oxo-4-hydroxyquinolin-3-ylamides of -halogen-substituted carboxylic acids with sodium methoxide leads to the formation of 2-R-3-oxomorpholino-[5,6-c]-6-R-quinolin-5-ones. The antituberculosis activity of the compounds synthesized was studied.For Communication 43, see [1].National Pharmaceutical Academy of Ukraine, Kharkov 310002; e-mail: igor@uiv.kharkov.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1080–1083, August, 2000.     

Pyrido[2,3-d]dipyrimidines 8. Synthesis of pyrrolo(2′,3′∶4,5)pyrido[2,3-d]pyrimidines

The reaction of 1,3-dimethyl-5-chloro-6-nitropyrido[2,3-d]pyrimidine-2,4-dione with CH-acids yielded 5-substituted pyridol[2,3-d]pyrimidines which were used in the synthesis of pyrrolo(2,34,5)pyrido[2,3-d]pyrimidines.For Communication 7, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 800–803, June, 1993.     

Transformed steroids. 160. Reaction of 20,20-dimethoxy-16α,17α-epoxypregn-5-ene-3β, 21-diol-20-one with pyridine thiocyanate and carbethoxyhydrazine

Conclusion The reaction of 20,20-dimethoxy-16,17-epoxypregn-5-ene-3,21-diol-20-one with pyridine thiocyanate in the presence of carbethoxyhydrazine proceeds by two competing paths: cisopening of the oxide ring by a -SCN ion at the C¹⁷ atom, and substitution of one of the methoxyl groups by -NCS ion. As a result 2,20-dicarbethoxyhydrazones of pregn-5-ene-3,21-diol-20-one-[17,16-d]-1,3-oxathiolan-2-one and 20-methoxy-16,17-epoxypregn-5-ene-3-ol-[20,21-d]-1,3-oxazolidine-2-thione are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 911–914, April, 1987.     

Derivatives of Condensed Thienopyrimidines. 22. Synthesis of 2-Substituted 4-Thioxopyrano[4′,3′:4,5]thieno[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidines

A method has been developed for the synthesis of 4-thioxopyrano[4,3: 4,5]thieno[2,3-d]pyrimidines from the corresponding acyl derivatives of 2-amino-3-cyanothieno[2,3-c]pyran.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 267–269, February, 2005.     

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).

     

Acetals of lactams and acid amides. 35. Synthesis of condensed two- and three-ring pyridine systems on the basis of enamino amides

The synthesis of 2,3,5,6-tetrahydropyrrolo[3,2-c]pyrid-6-one was accomplished by rearrangement of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1, 2-c]pyrimidine. Pyrrolo[3,2-c]pyrimidine, 1,6-naphthyridine, and pyrimido[4,3-b]-azepine derivatives were synthesized on the basis of enamino dinitriles. The hydrolysis of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1,2-c]-pyrimidine in 50% CH₃COOH leads to a pyrrolo[1,2-c]pyrido[4,3-d]pyrimidine derivative. A similar dipyrido[4,3-d-1,2-c]pyrimidine derivative was obtained from 1-cyano-9-dimethylaminomethylene-2,5,6,7,8,9-hexahydropyrido[1,2-c]pyrimidine under these conditions, and 3,4-dioxo-3,4,7,8,9,10-hexahydropyrido[1,2-c]pyrano[4,3-d]-pyrimidine was synthesized bytreatment with a 1 N solution of HCl.See [1] for Communication 34.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 518–522, April, 1982.     

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.     

Application of the Arbuzov reaction to establish the structure of D-mannitol tricyclic triethyl triphosphite

Conclusions The previously expressed theory that the tricyclic triethyl triphosphite of D-mannitol is 2-ethoxy-4, 5-bis-(2-ethoxy-1, 3, 2-dioxaphospholan-4-yl)-l,3,2-dioxa-4-phospholane was corroborated on the basis of the differential-thermal analysis and³¹P NMR data.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1390–1395, June, 1972.     

Selektive Synthesen zu 1′-aryl-, 1′-hetaryl-und 1′-alkylsubstituierten 3-Vinylindolen

Selective methods for deriving 1-aryl-, 1-indolyl-, 1-pyrrolyl- and 1-methyl-substituted 3-vinylindoles2 are described. In all cases the precursors were 3-acylindoles. The new compounds are synthetically useful synthons for annelation of the indole skeleton.

     

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.     

Die Chlorierung von Methylborazinderivaten

Zusammenfassung Bei der Chlorierung von 2,4,6-Trimethylborazin konnten unter anderen Reaktionsprodukten 2,4,6-Tris(dichlormethyl)-und 2,4,6-Tris(trichlormethyl)borazin erhalten werden. Weitergehende Chlorierung führt zum 2,4,6-Trichlorborazin. Bei der Chlorierung von 2,4,4,6,6-Pentamethyl-biborazinyl-(1,2) verläuft der Abbau der Verbindung rasch bis zum 2,4,6-Trichlorborazin. Bei der Chlorierung von 1,3,5-Trimethyl-2,4,6-trichlorborazin konnte eines der Reaktionsprodukte als 1,3-Bis(dichlorcarbo)-2,4-bis(dichlor)cyclodiborazan charakterisiert werden.

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Chlorination of 2,4,6-trimethylborazine leads to 2,4,6-tris-(dichloromethyl)-and 2,4,6-tris(trichloromethyl)borazine and finally to 2,4,6-trichloroborazine. Several other intermediates have been identified by mass spectrometry. Chlorination of 2,4,4,6,6-pentamethyl-biborazinyl-1,2 readily yields 2,4,6-trichloroborazine. Amongst the chlorination products of 1,3,5-trimethyl-2,4,6-trichloroborazine 1,3-bis(dichlorcarbo)-2,4-bis (dichlor)cyclodiborazane has been identified.

     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Investigation of naphthyridines

2-Acetyl-10-aryl-1,2,3,4-tetrahydrobenzo[b]-1,6-naphthyridines were obtained by reaction of 4-(2)-R-2-aminobenzophenones with 1-acetyl-4-piperidone, and their pK_a values were determined. It was found that they are oxidized by hydrogen peroxide to give the corresponding N-oxides in good yields. The N-oxides are converted to the 4-acetoxy derivatives by the action of acetic anhydride.See [1] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1383–1385, October, 1976.     

1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

Polynuclear heterocyclic compounds based on the adduct of o-cinnamoylbenzoic acid and cyclohexanone

The product of addition of cyclohexanone to o-cinnamoylbenzoic acid, which has the 4-phenyl-8a-hydroxyperhydrochroman-2-spiro-3-phthalide structure, reacts with nitrogen-containing nucleophiles to give hydrogenated derivatives of oxa-(aza, thia)indolizinespirophthalide and pyrido[1,21,2]imidazo[2,3-a]-isoin-dole, as well as 4-R-1-phthalazones. An isoindolo[1,2-a]quinoline derivative and a compound with a 7,8-diaza-D-homosteroid skeleton were obtained from the latter.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1280–1285, September, 1986.     

Bis(2,2′-bipyridine)(4,4′-diuntriacontanyl-2,2′-bipyridine)-ruthenium(II) chloride and related hydrophobic complexes

Summary New synthetic routes to 1-triacontanol and 1-bromotriacontane, and the novel ligands 4,4-diuntriacontanyl-2,2-bipy-ridine, 4-untriacontanyl-4'-methyl-2,2'-bipyridine and 4,4-ditricosyl-2,2-bipyridine are reported, as well as the preparation of the novel ruthenium(II) salts, [Ru(bipy)₂(bipy-4-R-4-R)]Cl₂ (bipy = 2,2'-bipyridine; R = R' = C₃₁H₆₃ or C₂₃H₄₇; R = C₃₁H₆₃, R' = Me).     

Pyrimidines

It is shown that the reaction of benzalbisurea with 3-amino-5-hydroxy-1-R-pyrazoles gives 1-R-dipyrazolo[3,4-b:4,3-e]pyridine (R=CH₃) or a spiro(pyrazole-4,5-pyrimidine) derivative (R=C₆H₅). Similar reactions of benzalbisurea with 3-hydroxy-5-amino-1-methylpyrazole give 2-methyldipyrazole[3,4-b:4,3-e]pyridine or substituted tetrahydropyrazolo[3,4-d] pyrimidine. Only the corresponding dipyrazolo[3,4-b:4,3-e]pyridines are formed in the reaction of 1-methylhydroxyaminopyrazoles with methylenebisurea.See [1] for communication XXXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 823–827, June, 1974.     

Die innere Wasserstoffbrücke als richtungsbestimmender Faktor bei einer chemischen Reaktion

Zusammenfassung Bei Umsetzungen zwischen aromatischen o-Hydroxyaldehyden mit innerer Wasserstoffbrücke und 2,4,6-Trinitrotoluol—durchgeführt in Gegenwart von Piperidin oder Morpholin—wird nicht das Stilbenskelett, sondern unter Verlust einer Nitrogruppe das Dibenz[b,f]oxepin-system gebildet. Beispielsweise liefert Salicylaldehyd dabei das 1,3-Dinitro-dibenz[b,f]oxepin. Mit dem wasser-stoffbrückenfreien Salicylaldehydmethoxymethyläther gibt 2,4,6-Trinitrotoluol jedoch in normaler Reaktion trans-2-Methoxymethoxy-2,4,6-trinitrostilben, das sich in saurem Milieu in das trans-2-Hydroxy-2,4,6-trinitrostilben überführen läßt.Auch einige andere Substitutionsprodukte des 2-Hydroxystilbens werden vom Salicylaldehydmethoxymethyläther aus dargestellt.Mit 4 AbbildungenHerrn Prof. Dr. Dr. e. h.B. Helferich, meinem verehrten Lehrer der organischen Chemie, zum 75. Geburtstage gewidmet. H.