Synthése par deux voies différentes d'un systéme dihétérocyclique apparenté aux peltogynoides

5-Oxo-5H,7H-[2]benzopyrano[4,3-b][1]benzopyran ( 2 ) has been synthesized from 3-(o-hydroxybenzylidene)isochroman-1,4-dione ( 3 ) by reductive cyclization, and from 5H,7H[2]benzo-pyrano[4,3-b][1]benzopyran-5,7-dione ( 4 ) by selective hydro-genation. This second method affords the dihydro compound 6 or 6a,12a-dihydro-5H,7H-[2]benzopyrano[4,3-b] [1 ]benzopyran-5-one as reaction time increases.     

Recherches en série triazépine-1,2,4: II — Etude de la réaction de l'acétylacétate d'éthyle avec les diamino-3,4 oxo-5 dihydro-4,5 triazines-1,2,4

The reaction of 3,4-diamino-5-oxo-4,5-dihydro-l,2,4-triazine or its 6-methyl or 6-phenyl substituted derivatives and ethyl acetoacetate gave three compounds: 4,7-dioxo-9-methyl-1,4,6,7-tetrahydro-as-triazino[4,3-b]-1,2,4-triazepine in poor yield, isomeric 4,9-dioxo-7-methyl-1,4,8,9-tetrahydro-as -triazino[4,3-b]-1,2,4-triazepine and by competitive cyclisation, 2-methyl-7-oxo-3,7-dihydro-s-triazolo[3,2-c]-1,2,4-triazine. By condensation of 3-methylamino-4-amino-5-oxo-4,5-dihydro-1,2,4-triazine with ethyl acetoacetate, the formation of 4,9-dioxo-7,10-dimethyl-4,8,9,10-tetrahydro-as-triazino[4,3-b]-1,2,4-triazepine was strongly favored.     

Recherches en série azabenzodiazepine V. Synthése de bis s-triazolo[4,3-b:4,3-d] triaze'pines-1,2,4

Several new bis-s-triazolo[4,3-b:4,3-d]-1,2,4-triazepines were synthesized from appropriate 8-hydrazino-s-triazolo[4,3-b]-1,2,4-triazepines by condensation with formic and acetic acid.     

Sur quelques analogues fluores des [1] benzothiopyrano[4,3-b]indoles et des 6H[1] benzothiopyrano[4,3-b] quinoleines

2-, 3-, and 4-Fluorinated analogs of the carcinogenic [1]-benzothiopyrano[4,3-b]indoles and of 6H[1]benzothiopyrano-[4,3-b]quinolines have been synthesized from the corresponding fluorothiochromanones. Nmr spectral data (at 60 Mc) of the six base molecules are reported. Biological tests for the possible carcinogenic activity of these new compounds, currently under way, have already shown one of them to be a powerful sarcomagen.     

Azaindoles. V. Pyrido(4,3-b]indoles (γ-carbolines) fonctionnalisés sur leur sommet 4: Synthèse en une seule étape

In boiling diphenylether phenylhydrazine reacts with 1,2-dihydro-2-oxo-4-hydroxypyridines to give 3,4-dihydro-4-oxo(9H)-pyrido[4,3-b]indoles (γ-carbolines) in one step. Nucleophilic displacement of their 4-chloro derivatives by secondary amines affords both 3,4-disubstituted γ-carbolines and chlorination of 2,3-dimethyl-4-oxo(9H)pyrido[4,3-b]indoles, as well as methylation of 2-methyl-4-chloro-(9H)pyrido[4,3-b]indole leads to derivatives in the (3H)4-substituted pyrido[4,3-b] indole series.     

New one-step procedure for the synthesis of 6H-chromeno[4,3-b]quinolines and 8a,9,14,14a-tetrahydro-8H-benzo[5,6]chromeno[4,3-b]quinolines

Schiff bases generated in situ from substituted anilines and 2-allyloxybenzaldehyde underwent acid-catalyzed intramolecular Diels-Alder reaction followed by dehydrogenation to give 6H-chromeno[4,3-b]-quinolines. Under analogous conditions, derivatives of 2-allyloxynaphthalene-1-carbaldehyde were converted into 8a,9,14,14a-tetrahydro-8H-benzo[5,6]chromeno[4,3-b]quinolines. Possible dehydrogenation mechanisms are discussed. Original Russian Text ? M.M. Tomashevskaya, O.A. Tomashenko, A.A. Tomashevskii, V.V. Sokolov, A.A. Potekhin, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 1, pp. 75–80.     

Synthesis of some pyrimido[4′,5′:4,5]thieno[2,3-b]quinolines and related heterocycles

Several thieno[2,3-b]quinolines 6a-i have been synthesized. These compounds were used as key intermediates in the synthesis of oxazino[4′,5′:4,5]thieno[2,3-b]quinoline 8 , pyrimido[4′,5′:4,5]-thieno[2,3-b]quinolines 9–12 , triazino[4′,5′:4,5]thieno[2,3-b] quinolines 14 and imidazo[4′,5′:4,5]-thieno[2,3-b]quinolines 17 .     

The synthesis and transformations of 9H-imidazo[1,2-b]pyrazolo[4,3-d]-pyridazine and 9H-pyrazolo[4,3-d]-s-triazolo[4,3-b]pyridazine derivatives

The nucleophilic and electrophilic substitutions of 6-substituted 9,9-dimethyl-9H-imidazo[1,2-b]pyrazolo- [4,3-d]pyridazines 2 , nucleophilic substitutions of 6-substituted 9,9-dimethyl-9H-pyrazolo[4,3-d]-s-triazolo- [4,3-b]pyridazines 7 and some other transformations to give compounds 3 and 8 , respectively, were studied. It was shown that both heterocyclic systems are stable under the conditions employed in these transformations.     

Synthesis and antiviral evaluation of some novel [1,2,4]triazolo[4,3-β][1,2,4]triazole nucleoside analogs

Ribosylation of 3-amino-5H-[1,2,4]triazolo[4,3-b][1,2,4]triazole ( 1 ) with l-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose and stannic chloride resulted in the following protected nucleoside analogs: 3-amino-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)[1,2,4]triazolo[4,3-β][1,2,4]triazole ( 4 ), 3-amino-1-(2,3,5-tri-O-benzoyl-α-D-ribofuranosyl)[1,2,4]triazolo[4,3-β][1,2,4]triazole ( 5 ), 3-amino-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)[1,2,4]triazolo[4,3-β][1,2,4]triazole ( 5 ), and 3-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl) amino-5H-[1,2,4]triazolo[4,3-b]-[1,2,4]triazole ( 7 ). Compounds 4–6 were deprotected to 3-amino-1-β-D-ribofuranosyl[1,2,4]triazolo[4,3-b][1,2,4]-triazole ( 3 ), 3-amino-1-α-D-ribofuranosyl[1,2,4]triazolo[4,5-b][1,2,4]triazole ( 8 ), and 3-imino-2H-2-β-D-ribo-furanosyl[1,2,4]triazolo[4,3-b][1,2,4]triazole ( 9 ), while 7 could not be deprotected without decomposition. Compounds 1, 4, 6, 7 , and 9 were screened and found to have no antiviral activity.     

Syntheses of substituted pyrazolo[3,4-b]quinolines, 3,4-dihydro-4-oxopyrimido[4′,5′:4,5]theino[2,3-b]quinoline and pyrido[1′,2′:1,2]pyrimido[4,5-b]quinoline

Syntheses of substituted pyrazolo[3,4-b]quinolines, 3,4-dihydro-4-oxopyriraido[4′,5′:4,5]theino[2,3-b]quinoline and 12-phenylpyrido[1′,2′:1,2[pyrimido[4,5-b]quinoline are described.     

Nouvelle voie de synthèse des dérivés de l'ellipticine et analogues alcaloïdes à activité antitumorale

A new snythesis of 6H-pyrido[4,3-b]carbazoles is described starting from substituted cyclohexanones involving the combination of Borsche's carbazole preparation and Cranwell and Saxton's ellipticine synthesis where the starting materials are easily available. The dehydrogenation step is accomplished at an early stage. In some cases (11-desmethyl ellipticines derivatives), 7H-pyrido[3,4-c]carbazoles were also obtained.     

Recherches en série triazepine-1,2,4: 1 - détermination de la structure de la triazolotriazépinone obtenue par action de l'acétylacétate d'éthyle sur le diamino-3,4 triazole-1,2,4

The condensation of 3,4-diamino 1,2,4-triazole with ethyl aceloacelate gave 6-methyl-8,9-dihydro(7H)-s-triazolo[4,3-b]-1,2,4-triazepin-8-one ( 2 ); 2 has been caracterized by nmr spectroscopy and by comparison with its methylated derivative prepared in an unambigous manner.     

2-Dicyanomethylidene-3-ethoxymethylidene-2,3-dihydroindole in the synthesis of fused tri- and tetracyclic systems

The reactions of 2-dicyanomethylidene-3-ethoxymethylidene-2,3-dihydroindole with hydrazine hydrate and phenylhydrazine afforded 2,3-diamino-4-cyanopyrido[4,3-b]indole and 3-amino-2-anilino-4-cyanopyrido[4,3-b]indole, respectively, and the reactions of the latter compounds with dimethylformamide diethyl acetal were studied. The reactions of 2,3-diamino-4-cyanopyrido[4,3-b]indole with benzaldehyde, ethyl acetoacetate, and acetylacetone were investigated. First representatives of new heterocyclic systems, viz., [1,2,4]triazolo[1’,5’:1,6]-pyrido[4,3-b]indole and pyrazolo[1’,5’:1,2]pyrido[4,3-b]indole, were synthesized. The structure of ethyl 6-cyano-5-[(E)-(dimethylamino)methylideneamino]-2-methyl-7H-pyrazolo-[1’,5’:1,2]pyrido[4,3-b]indole-1-carboxylate was established by X-ray diffraction.     

Synthesis of dihydrochromeno[4,3-b]pyrrolo[3,2-f]quinolines via intramolecular aza Diels-Alder reaction

An efficient and convenient one-pot intramolecular aza Diels-Alder approach for the synthesis of dihydrochromeno[4,3-b]pyrrolo[3,2-f]quinolines has been reported. Particularly valuable features of this methodology include simple execution, inexpensive catalyst, and good product yields.     

Hydrogénation de sels de flavylium: formation de composés heptacycliques; structure radiocristallographique du [tétrahydro-10b,10c,16,16a-diméthyl-16,16a-méthylène-10b,16-5aH-di(benzo[1]pyranno)[4,3-b:3′,4′,-c;2,3:2′,3′]-benz[1]oxépinyl-5a]-2-phénol

Hydrogenation of Flavylium Salts: Formation of Heptacyclic compounds; X-Ray Crystal Structure of 2-[10b,10c,16,16a-Tetrahydro-16,16a-dimethyl-10b,16-methylene-5aH-di[1]benzopyrano[4,3-b:3′,4′ -c; 2,3:2′,3′][1]benzoxepin-5a-yl]phenol The hydrogenation of flavylium salts 1 either by catalytic reduction or by chemical reduction afforded the unexpected heptacyclic compound 2 , the structure of which was determined by X-ray analysis. The latter was confirmed by ¹H-NMR and mass spectra.     

Synthesis of 2-substituted cinchoninic acid amides and their cyclization into 1,2,4-triazolo[4,3-α]-quinoline-9-and 1,2,4-triazino[4,3-a]quinoline-10-carboxylic acid amides

Substituted amides of 2-hydrazino- and 2-ethylhydrazinocinchoninic acids react with pyruvic acid and its ethyl ester to give amides of 3-methyl-4-oxo-1,2,4-triazino[4,3-a]quinoline-10-carboxylic acid. On reaction with aromatic aldehydes they are converted into amides of 2-ethyl-3-phenyl-2,3-dihydro-1,2,4-triazolo[4,3-a]quinoline-9-carboxylic acid, or, in the case of unsubstituted hydrazines, into amides of 2-arylidene-hydrazinocinchoninic acid, which was oxidized to substituted 1,2,4-triazolo[4,3-a]quinolines.Perm Pharmaceutical Academy, Perm 614600. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 701–705, May, 1977.     

5-Arylidene Derivatives of <Emphasis Type="Italic">Meldrum</Emphasis>’s Acid as Synthons in Pyrano[4,3-<Emphasis Type="Italic">b</Emphasis>]pyran Synthesis

Summary. The reactions of 5-arylidene derivatives of Meldrum’s acid with ethyl vinyl ether or N-vinyl-2-oxazolidinone yielded trans-trans-(2,4:4,7)-pyrano[4,3-b]pyrans, cis-trans-(2,4:4,7)-pyrano[4,3-b]pyrans, or diastereoisomeric mixtures of pyrano[4,3-b]pyrans and reactions with 3,4-dihydro-2H-pyran afforded Michael adducts. The reactions of 5-arylidene derivatives of Meldrum’s acid with cyanoacetic acid derivatives do not provide appropriate pyrans.     

A new approach to the synthesis of pyrido[4,3-<Emphasis Type="Italic">b</Emphasis>]indole derivatives (γ-carbolines) <Emphasis Type="Italic">via</Emphasis> cyclization of enamino dinitriles

Reactions of 2-dicyanomethylidene-3-ethoxymethylidene-2,3-dihydroindole with various amines afforded enamino dinitriles and the corresponding pyrido[4,3-b]indoles (γ-carbolines). 3-Amino-4-cyano-5H-pyrido[4,3-b]indole reacted with cyclohexanone to give pentacyclic 13-amino-2,3,4,12-tetrahydro-1H-benzo[b]indolo[2,3-f]-1,8-naphthyridine. Alkylation of pyrido[4,3-b]indoles with various alkylating agents was studied.     

Synthesis of 2,10,11-Trisubstituted Indolo[3,2-b]quinolines

A new method has been developed for the synthesis of derivatives of indolo[3,2-b]quinolines-11 based on N-oxidization of 2-nitro-10-substituted indolo[3,2-b]quinolines with subsequent conversion of the mixtures obtained into 2-nitro-11-substituted indolo[3,2-b]quinolinones-11. A series of 2-nitro-11-substituted indolo[3,2-b]quinolines was prepared.     

4,5-Diamino-1-phenyl-1,7-dihydro-6<Emphasis Type="Italic">H</Emphasis>-pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]pyridin-6-one in the synthesis of fused tricyclic systems

Starting from the substituted 4,5-diaminopyrazolo[3,4-b]pyridine, derivatives of a number of tricyclic systems, viz., imidazo[4,5-d]pyrazolo[3,4-b]pyridine, pyrazolo[3,4-b][1,2,5]thiadiazolo[3,4-d]pyridine, pyrazolo[3,4-b][1,2,3]triazolo[4,5-d]pyridine, and [1,3]oxazolo[5,4-b]pyrazolo[4,3-e]pyridine, were synthesized and reaction schemes for the processes were proposed.