Synthesis of 2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine and its 1-α-L-arabinopyranoside

A new type of isatin analog-2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine — was obtained by oxidation of 4-methyl-6-chloro-1H-pyrrolo(2,3-b]pyridine. Condensation of L-arabinose with 4-methyl-6-chloro-2,3-dihydropyrrolo[2,3-b]pyridine and subsequent acetylation and dehydrogenation gave 1-(2,3,4-tri-O-acetyl--L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine, which served as the starting compound for the synthesis of 1--L-arabinopyranosyl-4-methyl-6-chloropyrrolo[2,3-b]pyridine. Oxidation of 1-(2,3,4-tri-O-acetyl-L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine gave 1-(2,3.4-tri-O-acetyl--L-arabinopyranosyl)-2,3-dioxo-2,3-dihydro-4-methyl-6-chloropyrrolo [2,3-b]pyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1083–1086, August, 1977.     

Polymethine dyes — Benzofuro[2,3-b]pyridine and selenonaphtheno[2,3-b]pyridine derivatives

Polymethine dyes — benzofuro[2,3-b]pyridine and selenonaphtheno[2,3-b]pyridine derivatives — were synthesized, and their spectral properties are discussed. Replacement of a vinylene group by an oxygen or selenium atom in one benzene ring of the 2-benzo[h]quinoline residue in the cyanines causes a large bathochromic shift of the absorption maxima of the dyes as compared with replacement by a sulfur atom. The dyes derived from benzofuro[2,3-b]pyridine derivatives are more deeply colored than the derivatives of both thionaphtheno[2,3-b]-pyridine and selenonaphtheno[2,3-b]pyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp.1611–1614, December, 1972.     

Synthesis of furo[2,3-f]- and furo[3,2-e]indole derivatives

Two compounds — the diethylamides of 1,2-dimethyl-3-carbethoxy-6-carboxyfuro[2,3-f]- and 1,2-dimethyl-3-carbethoxy-5-carboxvfuro[3,2-e]indoles — are formed in the reaction of 1,2-dimethyl-3-carbethoxy-5-hydroxyacetic acid (I) with dimethylformamide and phosphorus oxychloride as a result of subsequent intramolecular cyclization of the intermediates. This constitutes evidence for formylation of the starting acid in the 6 and 4 positions. Formylation of the ethyl ester of acid I gives only the 6-formyl derivative, the intramolecular cyclization of which under the influence of sodium ethoxide gives 1,2-dimethyl-3,6-dicarbethoxyfuro[2,3-f]-indole. Hydrolysis of the latter with alcoholic alkali gives the corresponding dicarboxylic acid. The structures of the synthesized compounds were confirmed by the PMR, IR, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 766–769, June, 1977.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 8 . [1]Benzothieno[2,3-c]naphtho[1,2-h]quinoline and [1]benzothieno[2,3-c]naphtho[1,2-h][1,2,4]triazolo[4,3-a]quinoline

The previously unknown polycyclic heterocyclic ring systems, namely, [1]benzothieno[2,3-c]naphtho[1,2-h]-quinoline and [1]benzothieno[2,3-c]naphtho[1,2-h][1,2,4]triazolo[4,3-a]quinoline were synthesized via photocyclization of 3-chloro-N-(1′-phenanthryl)benzo[b]thiophene-2-carboxamide.     

Selenonaphtheno[2,3-d]thiazole derivatives as polymethine dyes

New polymethine dyes — selenonaphtheno[2,3-d]thiazole derivatives — were synthesized. It is shown that all of the synthesized dyes which have a selenonaphtheno[2,3-d]thiazole residue are more deeply colored than the corresponding 6,7-benzobenzothiazole and thionaphtheno[2,3-d] thiazole derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 459–461, April, 1971.     

Polymethine dyes — Furo[2,3-b]-6-pyridine derivatives

Polymethine dyes — furo[2,3-b]-6-pyridine derivatives — were synthesized. Replacement of the vinylene group in the benzene ring of the quinoline residue by an oxygen atom and by a sulfur atom causes a bathochromic shift of the absorption maximum of the corresponding cyanine dyes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475– 479, April, 1975.     

Synthesis of 2-methylthie no [3,2-b]thieno-[2,3-d]thiazole

A new heterocyclic base — 2-methylthieno[3,2-b]thieno[2,3-d]thiazole — was synthesized by heating 2-acetamido-3-hydroxythieno[3,2-b]thiophene with phosphorus pentasulfide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1039–1041, August, 1976.     

Saturated heterocycles, 75. Preparation of tetracyclic thiophene derivatives with bridgehead nitrogen. Synthesis of polymethylenethieno[2,3—d]dihydropyrrolo-, tetrahydropyrido- and tetrahydroazepino[1,2—a]pyrimidin-4-ones and -4-thiones

The following tetracyclic ring systems and their derivatives have been synthesized for pharmacological investigations: Trimethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and -4-thione (1 a, 5 a); Tetramethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and -4-thione (1 b, 1 j, 5 b); Pentamethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and-4-thione (1 c, 5 c); Trimethylenethieno[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one and -4-thione (1 d, 5 d); Tetramethylenethieno[2,3—d]tetrahydropyrido[1,2,—a]pyrimidin-4-one and -4-thione (1 e, 5 e); Pentamethylenethieno[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one and -4-thione (1 f, 5 f); Trimethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one and -4-thione (1 g, 5 g); Tetramethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-on and -4-thione (1 h, 5 h); Pentamethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one and -4-thione (1 i, 5 i); Tentamethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one (7 b); Pentamethylenethieno-[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one (7 c).Compounds1 a–i were synthesized from 2-amino-3-ethoxycarbonyl-4,5-polymethylenethiophene2 a–c with the corresponding lactim ethers (3 a–c) in chlorobenzene in the presence of polyphosphoric acid (PPA). Compounds7 b and7 c were obtained in the reaction of -amino acid esters2 b and2 c with 2-bromopyridine (6). The thione derivatives (5 a–i) were prepared from compounds1 a–i with phosphorus(V) sulphide.Part 74:Szabó J, Fodor L, Szcs E, Bernáth G, Sohár P (1984) Pharmazie 39: 347.     

Synthesis and cytotoxic activity of benzo[a]pyrano[3,2-h] and [2,3-i]xanthone analogues of psorospermine, acronycine, and benzo[a]acronycine

Condensation of 2-hydroxy-1-naphthalenecarboxylic acid with phloroglucinol afforded 9,11-dihydroxy-12H-benzo[a]xanthen-12-one (6). Construction of an additional dimethylpyran ring onto this skeleton, by alkylation with 3-chloro-3-methyl-1-butyne followed by Claisen rearrangement, gave access to 6-hydroxy-3,3-dimethyl-3H,7H-benzo[a]pyrano[3,2-h]xanthen-7-one (12) and 5-hydroxy-2,2-dimethyl-2H,6H-benzo[a]pyrano[2,3-i]xanthen-6-one (13), which were methylated into 6-methoxy-3,3-dimethyl-3H,7H-benzo[a]pyrano[3,2-h]xanthen-7-one (14) and 5-methoxy-2,2-dimethyl-2H,6H-benzo[a]pyrano[2,3-i]xanthen-6-one (15), respectively. Osmium tetroxide oxidation of 14 and 15 gave the corresponding (+/-)-cis-diols 16 and 17, which afforded the corresponding esters 18-21 upon acylation. Similarly, condensation of 2-hydroxy-1-naphthalenecarboxylic acid with 3,5-dimethoxyaniline gave 11-amino-9-methoxy-12H-benzo[a]xanthen-12-one (23) which was converted into 11-amino-9-hydroxy-12H-benzo[a]xanthen-12-one (24) upon treatment with hydrogen bromide in acetic acid. Alkylation with 3-chloro-3-methyl-1-butyne followed by Claisen rearrangement afforded 6-amino-3,3-dimethyl-3H,7H-benzo[a]pyrano[3,2-h]xanthen-7-one (25) and 5-amino-2,2-dimethyl-2H,6H-benzo[a]pyrano[2,3-i]xanthen-6-one (26). The new benzopyranoxanthone derivatives only displayed marginal antiproliferative activity when tested against L1210 and KB-3-1 cell lines. The only compounds found significantly active against L1210 cell line, 16 and 20, belong to the benzo[a]pyrano[3,2-h]xanthen-7-one series, which possess a pyran ring fused angularly onto the xanthone basic core.     

Benzindoles. 24. Reduction of nitro-2,3-dimethyl[4,5]- and nitro-2,3-dimethyl[6,7]benzindoles

The reduction of nitro-2,3-dimethyl[4,5]- and -[6,7]benzindoles was studied; Benzindoles were obtained with an amino group in the benzene ring. Individual isomers can be separated as the acyl derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1481–1484, November, 1986.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 7. [1]Benzothieno[2,3-c]naphtho[2,1-h]quinoline and [1]benzothieno[2,3-c]naphtho[2,1-h][1,2,4]triazolo[4,3-a]quinoline

The synthesis of two novel polycyclic heterocyclic ring systems via photocyclization is described. These are [1]benzothieno[2,3-c]naphtho[2,1-h]quinoline and [1]benzothieno[2,3-c]naphtho[2,1-h][1,2,4]triazolo[4,3-α]-quinoline. In the ¹H nmr spectrum the proton at position 6 is strongly deshielded in the first ring system while the proton at position 6 in the second ring system is shifted considerably upfield while the proton at position 8 in the second ring system is the most deshielded proton in that ring system. The bay regions in both ring systems are severely congested.     

Condensed pyridine bases synthesis of some benzo[b]furo[2,3-c]-, benzo[b]- thieno[2,3-c]-, and benzo[b]selenopheno[2,3-c]-quinolines

Summary Condensation of benzo[b]furan-3(2H-one, benzo[b]thiophen-3(2H)-one and benzo[b]selenophen-3(2H)-one with dimedone gives 2-(3-heteryl)dimedones. Acylation of the latter leads to the corresponding tetracyclic pyrylium salts, from which condensed quinolines are obtained. Some condensed quinoline derivatives are obtained by reaction of 1-oxo-1,2,3,4-tetrahydroheterene[2,3-c]quinolines with sodium borohydride, hydrazine, and hydroxylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 321–326, March, 1994.     

2,5-Dihydro-1H-4-methylnaphtho[2,3-b]-1,4-diazepine-2,6,11-trione. Reaction with methanol

The reaction of 2,3-diamino-1,4-naphthoquinone with acetoacetic ester in toluene (with water separation) gave 2,5-dihydro-1H-4-methylnaphtho[2,3-b]-1,4-diazepine-2,6,11-trione, which adds a molecule of methanol to the C=C bond of the diazepine ring to give 2,3,4,5-tetrahydro-1H-4-methyl-4-methoxynaphtho-[2,3-b]-1,4-diazepine-2,6,11-trione.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 121–123, January, 1979.     

Condensed imidazo-1,2,4-azines. 21. Synthesis of 2-arylfuro(pyrrolo-, thieno-)[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles by cyclization of 2-aroyl-1,2,4-triazino[2,3-a]benzimidazol-4H-3-ones

2-[(-Ethyl-, arylimino)phenethyl]-1,2,4-triazino[2,3-a]benzimidazoles were obtained by reaction of 2-aroylmethyl-1,2,4-triazino[2,3-a]benzimidazol-4H-3-ones with ethyl(aryl)amines or urea. By the action of phosphorus oxychloride, these benzimidazoles cyclize into substituted pyrrolo[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles, heating of which in polyphosphoric acid leads to the formation of furo[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles, while by the action of P₄S₁₀, they are transformed into thieno[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles.For Communication 20, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1109–1113, August, 1989.     

Studies on the esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one with acid chlorides under different conditions

The esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one （4） with acid chlorides afforded normal oxime-esters 3a-e in 35-78% yields in presence of excessive 4-dimethylaminopyridine as the acid scavenger, whereas the reactions gave unexpected 8-substituted products N-（8-chloro-4-methyl-2-oxo-2H-furo-[2,3-h]chromen-9-yl）amides （5a-c） and 4-methyl-2,9-dioxo-8,9-dihydro-2H-furo[2,3-h]chromen-8-ylcarboxyloates （6d-e） by using excessive acid chlorides. The structures of 10 new compounds were determined by 1H NMR, 13C NMR, MS and HRMS, and the possible mechanism for the formation of unexpected products 5a--c and 6d-e was also proposed.     

Syntheses in the benzo-2, 1,3-thiadiazole series. II. Derivatives of 1,2,5-thiadiazolo]3,4-h]quinoline and benzo-2, 1, 3-thiadiazolo]4, 5-h]-1,6-naphthyridine

Derivatives of l,2,5-thiadiazolo[3,4-h]quinoline and benzo- 2,1,3-thiadiazolo-[4, 5-h]-1, 6-naphthyridine were synthesized from 4-aminobenzo-2, 1, 3-thiadiazole.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 61–64, January, 1976.     

Synthesis of 2-methyl-5-phenylthieno[2,3-d]thiazole

The synthesis of a new heterocyclic base — 2-methyl-5-phenylthieno[2,3-d]thiazole — is described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, 1624–1625, December, 1970.     

Pyrazolo[5,4-h]quinazolines

The reaction of 1-phenyl- and 4-chloro-5-formyl-3-methyl-1-(2-pyridyl)-6,7-dihydroindazoles with carbamidinopyrrolidine, 4-carbamidinomorpholine, creatine, 2-carbamidinopyrazine, and 2-carbamidino-5-trifluoromethylpyridine gives the corresponding 3,8-substituted 1-methyl-4,5-dihydropyrazolo-[5,4-h]quinazolines and with 2-aminobenzimidazole gives 3-phenyl- and 3-(2-pyridyl)-1-methyl-4,5-dihydrobenzo[b]indazolo[4,5-e]imidazolo[1,2-a]pyrimidines.Riga Technical University, Riga LV-1658, Latvia; e-mail; marina@osi.lv . Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 962–965, July, 2000.     

Investigation of nitrogen- and sulfur-containing heterocycles. 44. New heterocyclic systems. Derivatives of imidazolidino-[3,2-f]pyrido[2,3-b]-and imidazolidino[3,2-f]pyrimido[4,5-b]-1,4-thiazines. Synthesis and structure

New representatives of heterocyclic systems, imidazolidino[3,2-f]-pyrido-[2,3-b]- and imidazolidino[3,2-f]pyrimido[4,5-b]-1,4-thiazines, have been obtained. Intermediate compounds of 5N-oxalamides-6-hydroxy-7H-pyrido[2,3-b]-1,4-thiazine have been isolated and characterized. Amides of N-(pyridyl-3)- and N-(pyrimidyl-5)-oxaminic acids have been obtained.For communication 43, see [1].Translated from Khimiya Geterotsiklicheskikh Soedininii, No. 7, pp. 992–997, July, 1986.     

Synthese von [1]Benzothieno[2,3—d]isoxazol-Derivaten

Derivatives of [1]benzothieno[2.3—d]isoxazole, a new heterocyclic ring system, were synthesized by 1.3-dipolar cyclisations: benzo[b]thiophene-1.1-dioxide and its 3-methyl derivative reacted with nitrile oxides and nitrones to the corresponding substituted [1]benzothieno[2.3—d]isoxazolines and-isoxazolidines. Hydrogenolysis of the latter cleaved the isoxazolidine ring, yielding the corresponding 2-(-phenylamino-benzyl)-3-hydroxy-2.3-dihydro-benzo[b]thiophene-1.1-dioxides.

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Herrn Prof. Dr.E. Hardegger zum 60. Geburtstag gewidmet.