Synthesis of new pyridazino[4′,3′:4,5]-thieno[3,2-d]-1,2,3-triazine and pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives

Summary 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).

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Synthese neuer Pyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-und Pyrimido[4,5:4,5]thieno[2,3-c]pyridazin-Derivate

Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).

     

Phenolic derivatives of 2-pyrone

The cyclization of 1,1-dichloro-5-(2,5-dimethoxyphenyl)-1,3-pentadien-5-one and the product of its partial demethylation leading to the corresponding derivatives of 2-pyrone and 2-(,-dichlorovinyl)-6-methoxy-4-chromanone has been studied. Irradiation causes the dimerization of 1,1-dichloro-5-(2,5-dimethoxyphenyl)-1,3-pentadien-5-one.For part I, see [1].     

Chemistry of 2-hetarylbenzimidazoles. 8. Synthesis and properties of 1-methyl-2-(5′-methyl-2′-selenienyl)benzimidazole

1-Methyl-2-(5-methyl-2-selenienyl)benzimidazole was synthesized and subjected to electrophilic-substitution reactions: nitration, bromination, sulfonation, chloromethylation, formylation, and acylation. The substituent usually enters the 4 position of the selenophene ring, but nitration with acetyl nitrate leads to a mixture of 5-nitro and 4-nitro derivatives. Oxidation of 2-selenienylbenzimidazole with potassium permanganate leads to the 5-carboxy derivative, while oxidation with selenium dioxide leads to the 5-hydroxymethyl and 5-formyl derivatives.See [1] for Communication 7.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1636–1639, December, 1987.     

N-acetylindoxyl in the synthesis of new condensed heterocycles

Derivatives of a new heterocyclic system thieno[2,35,6]pyrimido[3,4-a]indole, were obtained by the reaction of substituted N,O-diacetylindoxyls with excess N-(2-methyl-3-ethoxycarbonyl-4-thienyl)hydrazine. The reaction of N-acetylindoxyl and 4-hydrazinouracil forms 12-amino-1,3-dioxo-2,4,6-trimethylpyrimido[5,45,6]pyrimido[3,4-a]indole.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1343–1345, October, 1987.     

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.     

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.     

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 and some properties of the methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid

The methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid were obtained by the reaction of the corresponding 4-substituted 2-hydrazino-5-phenylthiazole with NaNO₂ in acid media. IR and UV spectroscopy were used to show that the compounds synthesized retain azide form in both the crystalline state and in solution. The reaction of azides with dicarbonyl compounds gave derivatives of 2-[5-methyl-4-acetyl-or 2-[5-methyl-4-ethoxycarbonyl-1,2,3-triazol-1-yl]-5-phenylthiazole-4-carboxylic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 710–714, May, 1993.     

Pyrimidines. 70. Relative reactivities of the chlorine atoms of 2,2′,4-trichloro-4′,5-dipyrimidinyl in its reaction with piperidine

2,2,4-Trichloro-6-phenyl-4,5-dipyrimidinyl, for which nucleophilic substitution with piperdine under various conditions was studied, was obtained from 2,2,4-trioxo-6-phenyl-1, 1,2,2,3,4-hexahydro-4,5-dipyrimidinyl. It is shown that there is an appreciable difference in the rates of substitution of the first, second, and third chlorine atoms, and this made it possible to obtain reaction products that contain one, two, and three piperidino groups. The chlorine atom in the 4 position is replaced initially, after which the chlorine atom in the 2 position undergoes substitution. The structures of the compounds were proved by chemical transformations and analysis of the PMR spectra.See [1] for communication 69.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 821–826, June, 1979.     

Direct nitration and acetylation of the furan nucleus of 1-alkyl-2-[Β -(2′-furyl) vinyl]-benzimidazoles

The direct nitration and acetylation of 1-methyl-, 1-ethyl-, and 1-benzyl-2-[-(2-furyl)vinyl]benzimidazoles has given the corresponding 1-alkyl- and 1-benzyl-2-[-(5-nitro-2-furyl)vinyl]benzimidazoles and 1-alkyl- and 1-benzyl-2-[-(5-acetyl-2-furyl)vinyl]benzimidazoles. The UV spectra of these compounds have been recorded and their ionization constants have been determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 832–834, June, 1970.     

A new method for the synthesis of macrocyclic ketones

Summary We have described the synthesis of macrocyclic diacetylene ketones by oxidative condensation of aliphatic ,-diacetyiene ketones.     

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.     

Darstellung von 2′,3′-Dideoxy-2′-hydroxymethyl-nucleosiden

Zusammenfassung Die Synthese von geschützten 2,3-Dideoxy-2-hydroxymethyl-nucleosiden wird beschrieben. Die durch ein Mehrstufenverfahren aus Isopropylidenglycerol erhaltenen Nucleoside können als Bausteine zur Darstellung von Oligonucleotiden verwendet werden, deren 2- und 5-Positionen über eine Etherbrücke verbunden sind.

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Synthesis of 2,3-dideoxy-2-hydroxymethyl nucleosides

Summary The synthesis of protected 2,3-dideoxy-2-hydroxymethyl nucleosides is presented. The nucleosides, obtained in a multi-step procedure starting from isopropylideneglycerol, may be used as building blocks for the synthesis of 2,5-ether linked oligonucleotides.

     

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.     

Isoflavones of the roots of Lupinus luteus

Conclusions For the first time in the isoflavone series, a compound which has the structure of 5,7-dihydroxy-3,4-methylenedioxyisoflavone (3,4-methylenedioxyorobol) and two of its glucosides — 3,4-methylenedioxyorobol 7-O--D-glucoside and 3,4-methylenedioxyorobol 7-O--D-glucosylglucoside — and also a genistein C-monoglucoside, have been described. The isoflavones were isolated from the roots ofLupinus luteus L. by preparative chromatography on paper and on columns of polyamide. In addition, the previously known genistein, genistein 7-O--D-glucoside (genistin), and genistein 7-O--D-glucosylglucoside have been obtained.V. F. Kuprevich Institute of Experimental Botany, Academy of Sciences of the Belorussian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 162–166, March–April, 1974.     

Über Dihydro-bzw. Tetrahydrospiro([1]benzopyran-2,4′(1′H)-pyrimidin)-2′(3′H)-one

On reaction of dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone1 with o-hydroxybenzaldehydes, dihydro- and tetrahydrospiro([1]-benzopyran-2,4(1H)-pyrimidin)-2(3H)-ones resp.5, 6, 7 are formed.     

The structure of xanthalin

Conclusions From the roots ofXanthogalum purpurascens growing in the Transcaucasus, we have isolated a new coumarin, C₂₄H₂₆O₇ with mp 111–113°C, [] _D ²⁰ –164.2° (c 0.97; ethanol) which we have called xanthalin. On the basis of the NMR spectrum it has been established that xanthalin is 3, 4-diangeloyl-2, 2-dimethyl-3, 4-dihydropyrano-5, 6:6, 7-coumarin.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 5, pp. 280–283, 1968