Steroido[3,2-b](carbazole-1-oxonium) salts

The reaction of 2-hydroxymethylene-3-ketosteroids with 2-ketoindoline in the presence of hydrogen chloride gives steroido[3,2-b](carbazole-1-oxonium) chlorides, which split out a 2-ketoindoline molecule under the influence of phenylhydrazine and are converted to steroido[3,2-c]-1-phenylpyrazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 219–221, February, 1973.     

Synthesis of 1,2,4-triazolo[3,2-b]-1,3-thiazines

1,2,4-Triazolo[3,2-b]-1,3-thiazines were obtained by the reaction of 1,2,4,-triazole-3-thiones with an equimolar amount of 1-phenyl-2-cyanoacetylene in the presence of triethylamine or potassium hydroxide. It is shown that triazolethiones form N,S diadducts upon reaction with a twofold excess of cyanoacetylene. The nature of the heteroatom in the exo position of the heteroring affects the direction of addition to phenylcyanoacetylene. 2,4-Bis(1-phenyl-2-cyanovinylene)-1,2,4-triazol-3-one was synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1051–1053, August, 1982.     

Synthesis and reactions of 3-(3-ethoxycarbonyl-1-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-4-yl)propenic acid

The reaction of ethyl 4-formyl-1-phenyl-1H-pyrazole-3-carboxylate with the malonic acid led to the formation (2E)-3-(3-ethoxycarbonyl-1-phenyl-1H-pyrazol-4-yl)propenic acid. In reactions of this acid chloride with 4-amino-5-aryl(hetaryl)-4H-1,2,4-triazole-3-thiols were obtained ethyl 4-[(E)-2-{3-aryl(hetaryl)[1,2,4]triazolo[3,4-b][1,3,4]thiadiazol-6-yl}ethenyl]-1-phenyl-1H-pyrazoe-3-carboxylates, with 5-aryltetrazoles, ethyl 4-[(E)-2-(5-aryl-1,3,4-oxadiazol-2-yl)-ethenyl]-1-phenyl-1H-pyrazole-3-carboxylates, with 1-(2-hydroxy-3,5-dimethylphenyl) followed by the Baker-Venkataraman rearrangement and the cyclization, ethyl 4-[(E)-2-(6,8-dimethyl-4-oxo-4Hchromen-2-yl)ethenyl]-1-phenyl-1H-pyrazole-3-carboxylate.     

Chemistry of acyl(imidoyl)ketenes. 8*. Thermolysis of 3-alkoxycarbonyl- 5-phenyl-1,2,4,5-tetrahydropyrrolo[1,2-a]- quinoxaline-1,2,4-triones. Structure of 2-(3-oxo-4-phenyl-3,4-dihydro-2-quinoxalinyl)- 2,4-di(ethoxycarbonyl)-6-phenyl-2,3,5,6-tetrahydro- 1h-pyrido[1,2-a]quinoxaline-1,3,5-trione

3-Alkoxycarbonylmethylene-1-phenyl-1,2,3,4-tetrahydro-2-quinoxalones, obtained by the interaction of dialkyl esters of oxaloacetic acid and N-phenyl-o-phenylenediamine, react with oxalyl chloride with the formation of 3-alkoxycarbonyl-5-phenyl-1,2,4,5-tetrahydropyrrolo[1,2-a]quinoxaline-1,2,4-triones. Alkoxycarbonyl(2-oxo-1-phenyl-1,2-dihydro-3-quinoxalinyl)ketenes, generated on thermal decarbonylation of the latter, are stabilized by participation in a [4+2] cyclodimerization reaction with the formation of 2,4-di(alkoxycarbonyl)-2-(3-oxo-4-phenyl-3,4-dihydro-2-quinoxalinyl)-6-phenyl-2,3,5,6-tetrahydro-1H-pyrido[1,2-a]quinoxaline-1,3,5-triones. The crystal and molecular structure of the di(ethoxycarbonyl) derivative have been investigated by X-ray structural analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1501–1506, October, 2004.     

Formation of 5-oxoindeno[1,2-b]pyran derivatives in cyclization of 1,5-diketones of the indian-1,3-dione series

Indeno[1,2-b]pyrans, including 2-methylene and 2-acetoxy derivatives of 3-ethoxy-carbonyl-4-phenyl-5-oxo-3,4-dihydroindeno[1,2-b]pyran, are formed in the cyclization of 4-(indan-1,3-dion-2-yl)-4-phenyl-2-butanone and its 3-ethoxycarbonyl derivative in acetic anhydride in the presence of sulfuric acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 178–183, February, 1988.     

3-Furylchromones

-[2-(5-Methoxycarbonyl)furyl]-2,4-dihydroxy- and 2,4,6-trihydroxyacetophenones were obtained by the condensation of polyphenols with (2-methoxycarbonyl-5-furyl)acetonitrile. 7-Acetoxy- and 5,7-diacetoxy-2-methyl-3-[2-(5-methoxycarbonyl)furyl]chromones were obtained from them by reaction with acetic anhydride in the presence of triethylamine and were subsequently deacylated to 7-hydroxy and 5,7-dihydroxy compounds. 7-Hydroxy- and 5,7-dihydroxy-2-ethoxycarbonyl-3-[2-(5-methoxycarbonyl)furyl]chromones were obtained from the indicated acetophenones by reaction with ethoxalyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1317–1320, October, 1972.     

Synthesis of 2-acylmethyl- and 2-acylmethylene-1,3-dithiolo[4,5-b]quinoxalines from α-acetylenic ketones

A number of 2-acylmethyl-1,3-dithiolo[4,5-b]quinoxaline derivatives were synthesized on the basis of the reaction of -acetylenic ketones with quinoxaline-2,3-dithiol in dimethyl sulfoxide (DMSO) in the presence of K₂CO₃. Their monohydrochlorides were obtained. A new series of 2-acylmethylene-1,3-dithiolo[4,5-b]quinoxalines was obtained by the reaction of 1-bromo-2-acylacetylenes with quinoxaline-2,3-dithiol in DMSO in the presence of triethylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1489–1491, November, 1982.     

The reactions of 4-dicyanomethylene-2-phenyl-4H-1-benzopyran and some benzologs with nucleophiles

4-Dicyanomethylene-2-phenyl-4H-1-benzopyran (1) reacts with primary amines under mild conditions to give 4-imino-3-alkyl-5-alkylimino-2-phenyl-3,4-dihydro-5H-[1]benzopyrano[3,4-c]-pyridine derivatives which, in turn, are hydrolyzed with acid to 4-imino-3-alkyl-2-phenyl-3,4-dihydro-5H-[1]benzopyrano[3,4-c]pyridin-5-ones. When more vigorous conditions are employed for the reactions of 1 with primary amines, Dimroth rearrangements take place and the products are derivatives of 4-alkyl- (or aryl)amino-5-alkyl- (or aryl)imino-2-phenyl-5H-[1]benzopyrano-[3,4-c]pyridine. The latter compounds are hydrolyzed by acid to the corresponding 5-pyridone derivatives. The reaction of 1 with piperidine gives 2-phenyl-4-piperidyl-5H-[1]benzopyrano-[3,4-c]pyridin-5-one. Sodium methoxide reacts with 1 to give 3-cyano-2-methoxy-4-(2-hydroxyphenyl)-6-phenylpyridine. Two benzologs of 1 have been allowed to react with primary and secondary amines and the products are analogous to those obtained from 1 .     

Investigation of nitrogen- and sulfur-containing heterocycles. 38. Reactions of 2-mercapto-3-ureidopyridines with halo β-diketones

The reaction of 2-mercapto-3-ureido-6-chloropyridine with chlorodibenzoylmethane in the presence of alkali leads to 2-(benzoylmethylthio)-3-benzamido-6-chloropyridine, whereas the reaction in the absence of alkali leads to 2-chloro-6-phenyl-7-benzoylpyrido[2,3-b] [1,4]thiazine. Under similar conditions 2-(diacetylmethylthio)-3-ureido-6-chloropyridine, 2-(acetylmethylthio)-3-ureido-6-chloropyridine, and 2-chloro-6-methyl-7-acetylpyrido[2,3-b][1,4]thiazine were obtained from 2-mercapto-3-ureido-6-chloropyridine and chloroacetylacetone. Treatment of 2-(diacetylmethylthio)-3-ureido-6-chloropyridine with alcoholic alkali leads to 2-(acetylmethylthio)-3-ureido-6-chloropyridine. 2-Chloro-6-phenyl-7-acetylpyrido-[2,3-b] [1,4]thiazine and 2-(benzoylmethylthio)-3-ureido-6-chloropyridine are formed in the reaction of 2-mercapto-3-ureido-6-chloropyridine with chlorobenzoylacetone in the presence of an equimolar amount of alkali, while 2-(benzoylmethylthio)-3-acetamido-6-chloropyridine is formed when excess alkali is used. See [1] for communication 37. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 787–790, June, 1980.     

Synthesis of 3-phenyl- and 3-phenyl-1-methylimidazo [5, 1-b] benzoxazoles

Reduction of 2-benzoylbenzoxazole oxime gives 2-(-aminobenzyl) benzoxazole, converted to the formyl or acetyl derivative by treatment with, respectively, ethyl formate or acetic anhydride. Thiourea derivatives are obtained by treating 2-(-aminobenzyl) benzoxazole with arylisothiocyanates. Heating the above formyl or acetyl derivative with phosphorus oxychloride converts them to 3-phenyl- and 3-phenyl-1-methylimidazo [5, 1-b]-benzoxazole, which are representative members of a new tricyclic system. It did not prove possible to cyclize 1-[-(benzoxazolyl-2) benzyl]-3-phenylthiourea.     

Reactions of 2-aryl (hetaryl) methylene-3-oxoquinuclidines with bifunctional nucleophilic reagents

The reactions of 2-aryl(hetaryl)methylene-3-oxoquinuclidines with hydrazine hydrate, thiourea, and phenylhydrazine gave, respectively, 7-phenyl-7,7a,dihydropyrazolo[3,4-b]quinuclidine, 7-(4-methoxyphenyl)-7,7a-dihydropyrazolo[3,4-b]quinuclidine, 7-(2-thienyl)-7,7a-dihydropyrazolo-[3,4-b]quinuclidine, 3,3-azinobis (2-benzylidenequinuclidine), 3,3-azinobis[2-(4-methoxybenzylidene)quinuclidine], 6-thio-8-phenyl-5,6,7,8-tetrahydropyrimido[5,4-b]quinuclidine, 2-benzylidene -3-oxoquinuclidine phenylhydrazone, and 2-(4-methoxybenzylidene)-3-oxoquinuclidine phenylhydrazone. The structures of the compounds were confirmed by the IR and ¹H and ¹³C NMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 793–797, June, 1982.     

Synthesis of some substituted imidazo [5, 1-b] benzothiazoles

Cyclization of formylated and acetylated -substituted 2-aminomethylbenzothiazoles with phosphorus oxychloride gives 3-substituted imidazo [5, 1-b] benzothiazoles, and 3-substituted 1-methylimidazo [5, 1-b] benzothiazoles. Treatment of 2-benzothiazolyl-4-pyridylaminomethane with formic acid gives 3-(4-pyridyl) imidazo [5, 1-b] benzothiazole. 1-Mercapto-3-phenylimidazo [5, 1-b] benzothiazole is converted into 3-phenylimidazo [5, 1-b] benzothiazole by elimination of the mercapto group.     

Synthesis of Some New Fused and Polyfused [1,2,4]Triazolo-[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazepines

7-[1,3-Dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4-b][1,3,4]thiadiazepine-6,8-dione and 7-[5-oxo-1,3-dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4-b][1,3,4]-thiadiazepine-6,8-diones were obtained by treating 3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo-[3,4-b][1,3,4]thiadiazepine-6,8-diones with CS₂ and chloroacetyl chloride, respectively. Treatment of the above compounds with mercaptoacetic acid gave 1,2-dibromoethane or the corresponding spiro polyfused heterocycles. Some other triazolothiadiazepine derivatives including spiro polyfused compounds were also synthesized. __________ Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 8, 1256–1264, August, 2005.     

Condensed pyridine bases. A new approach to the synthesis of 3-phenacylbenzo[b]thiophenes and 3-phenacyl-5-ethylthieno[2,3-b]thiophene. Synthesis of new derivatives of benzothieno[2,3-c]pyrylium and thieno[2′,3′:5,4]thieno-[2,3-c]pyrylium and pyridine bases

A new method is proposed for the production of substituted 3-phenacylbenzo[b]thiophenes by the intramolecular cyclization of 1-phenyl-4-phenylthio-1,3-butanediones in polyphosphoric acid. The analogous cyclization of 1-phenyl-4-(5-ethyl-2-thienylthio)-1,3-butanedione leads to 3-phenacyl-5-ethylthieno[2,3-b]thiophene. The acylation of substituted 3-phenacylbenzo[b]thiophenes and 3-phenacyl-5-ethylthieno[2,3-b]thiophene by the anhydrides of aliphatic acids in the presence of perchloric acid leads to 1-alkyl-3-phenylbenzothieno[2,3-c]pyrylium perchlorates and 2-ethyl-5-phenyl-7-methylthieno[2′,3′:5,4]thieno[2,3-c]pyrylium perchlorate. The action of ammonium acetate on the obtained salts gives the corresponding pyridine bases. L. M. Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, Donetsk 340114. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1335–1339, October, 1998.     

Investigation of nitrogen- and sulfur-containing heterocycles

The reaction of 5-amino-4-chloro- and -4-methoxy-6~mercaptopyrimidines with 4-methoxy-, 4-amino-, and 2,4-diethoxyphenacyl chlorides has yielded 5-amino-4-chloro- and -4-methoxy-6-phenacylthiopyrimidines. The reaction of 2, 5-diamino-4-methyl-6-mercaptopyrimidine with 4-methoxyphenacyl chloride has yielded 2-amino-6-hydroxy-6-(4-methoxyphenyl)-4-methyl-5, 6-dihydropyrimido[4, 5-b]-1,4-thiazine, and that with 4-aminophenacyl chloride has yielded the corresponding 7H-pyrimido[4, 5-b]-1,4-thiazine.For part IV, see [1].     

Synthesis and antimicrobial activity of novel phosphorus heterocycles with exocyclic p-C link

Several new class of phosphorus heterocyclic compounds containing exocyclic P-C link such as 6-(2'-chloroethyl)/(allyl)/(benzyl)-1,2,4,8,10,11-hexachloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxides (5-7), 2-(2"-chloroethyl)/(allyl)-6-(1,1-dimethylethyl)-3-cyclohexyl-3,4-dihdro-2H-1,3,2-benzoxazaphosphorin 2-oxides (9, 10), 2-(2"-chloroethyl-2,3-dihydro-3-(4'-bromophenyl)-1H-naphth[1,2-e][1,3,2]-oxazaphosphorin 2-oxide (12), 2-(2"-chloroethyl)/(allyl)-2,3-dihydro-5-benzoyl-1H-1,3,2-benzodiazaphosphole 2-oxides (14, 15), 4-phenyl-2-(2"-chloroethyl)-1H-1,3,3a,5,6-pentaza-2-phosphapentalene 2-oxide (17) and 4-benzyl-2-(2"-chloroethyl)-1H-1,3,3a,5,6-pentaza-2-phospha-pentalene 2-oxide (19) were synthesized by reacting equimolar quantities of corresponding diol (4)/diamines (13, 16, 18), 2-cyclohexylaminomethyl-4-t-butylphenol (8) and 1-(4'-bromoanilinomethyl)-2-naphthol (11), with respective phosponyl dichlorides (1-3) in dry toluene/toluene-tetrahydro-furan/pyridine in the presence of triethylamine at various temperatures. Their structures were established by IR, (1)H-, (13)C- and (31)P-NMR spectral data. The mass spectral data were given for compounds 9, 12 and 15. The title compounds were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and antifungal activity on Aspergillus niger and Helminthosporium oryzae. Most of the compounds possess significant activity.     

Investigations in the imidazole series

2,3-Dihydro derivatives of naphth[1,2-d]imidazo[3,2-b]imidazole were synthesized by the reaction of 2-chloro-3-(-haloalkyl)naphth[1,2-d]imidazole with ammonia and primary amines and by the reaction of 2-chloro-3-(-hydroxyaIkyl)naphth[1,2-d]imidazole with ammonia and amines with subsequent cyclization of the resulting 2-amino(alkylamino, arylamino)-3-(-hydroxyalkyl)naphth[1,2-d]imidazoles under the influence of thionyl chloride or phosphorus oxychloride. Dihydro derivatives of the condensed naphth[1,2-d]imidazo[3,2-b]imidazole system have not been described in the literature.See [1] for communication LX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1125–1127, August, 1971.     

Synthesis of dimethylamino derivatives of some condensed heterocycles from dimethylphosgeneimmonium chloride

Diazo coupling of indazole-3-diazonium chloride with 1-(2,4-dinitrophenyl)-3,5-bis(dimethylamino)pyrazole, obtained from dimethylphosgeneimmonium chloride, and subsequent cyclization of the azo compound lead to the formation of the dimethylamino derivatives of a new polycyclic system — benzo[h]dipyrazolo[3,2-c:3,4-e]-1,2,4-triazine. Previously unknown 3-dimethylamino derivatives of 1,2,4-triazolo-[3,4-b]benzothiazole were synthesized by reaction of dimethylphosgeneimmonium chloride with 2-hydrazinobenzothiazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 403–406, March, 1978.     

Synthesis of 2-mercaptobenzthiazole derivatives

The reactions of 2, 3-dihydrothiazolo- (I) and 2, 3-dihydrothiazino-1, 3-[2, 3-b]benzthiazolium chlorides (II) with water, aqueous sodium hydroxide, aqueous alcoholic ammonia, and hydrazine hydrate are investigated. Excess alcoholic potassium hydroxide cleaves I and II to o-(-mercaptoalkylamino) thiophenols, condensation of which with acetyl chloride followed by treatment of the reaction products with potassium iodide gives 2-methyl-3-(-mercaptoalkyl)benzthiazolium iodides. A series of dyes is prepared from these compounds.For Part V see [1]     

Synthesis and properties of 1-aroyl-5,5-dialkyl-2,3,5,6-tetrahydropyrrolo[ 2,1-<Emphasis Type="Italic">a</Emphasis>]isoquinoline-2,3-diones

Acylation of 1-methyl-3,3-dialkyl-3,4-dihydroisoquinolines with acid chlorides afforded enaminoketones. Enaminophenylketones from the obtained series were reacted with oxalyl chloride to provide 1-benzoyl-5,5-dialkyl-2,3,5,6- tetrahydropyrrolo[2,1-a]isoquinoline- 2,3-diones. The reaction of the latter with binucleophiles leads to the opening of the pyrrole ring and to the heterocyclization: Under the effect of o-phenyldiamine qinoxaline is formed, 1,2-cyclohexanediamine provides the hexahydro-benzimidazole system, о-aminophenol gives benzoxazole, 3-hydroxy-2-amino-pyridine furnishes oxazolo[4,5-b]pyridine. In the reaction with hydrazine hydrate the acylation occurs with hydrazide formation.