Fluorinated [1,2,4]triazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]pyrimidines and [1,2,4]triazolo[5,1-<Emphasis Type="Italic">c</Emphasis>][1,2,4]triazines*

The reaction of 3-R-5-amino-1,2,4-triazoles with the ethyl ester of 2-fluoroacetoacetic acid gave 2-R-fluoro[1,2,4]triazolo[1,5-a]pyrimidin-7(4H)-ones. The reaction of a 3-R-1,2,4-triazolyl-5-diazonium salt with the ethyl ester of 2-fluoroacetoacetic acid and subsequent cyclization of the triazolylhydrazones lead to 7-R-3-fluoro[1,2,4]triazolo[5,1-c][1,2,4]triazin-4(1H)-ones.     

4-Hydroxy-2-quinolones. 3. Synthesis and physicochemical properties of 1-R-3-carbethoxy-4-hydroxy-2-quinolones

1-R-3-Carbethoxy-4-hydroxy-2-quinolones were synthesized by intramolecular cyclization of N-R-2-carbalkoxymalonanilic acids by the Dieckmann reaction. The possibility and advantages of conducting this reaction in aqueous medium were demonstrated. The mutually perpendicular orientation of the heterocyclic and aryl fragments was demonstrated for the 1-phenyl derivative by ESR spectroscopy.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 636–639, May, 1992.     

4-Hydroxy-2-quinolones. 152*. 3-acetyl-4-hydroxy-2-oxo-1,2-dihydroquinoline and its biologically active derivatives

A synthesis and study of the spatial structure of 3-acetyl-4-hydroxy-2-oxo-1,2-dihydroquinoline have been carried. 1-R-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acids [1-(4-hydroxy-2-oxo-1,2-dihydroquinolin-3-yl)ethylidene]hydrazides were prepared from this compound by two routes. A comparative analysis of the antitubercular properties of the synthesized compounds and of the closely structurally related N,N′-di(1-R-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carbonyl)hydrazines has been performed. *For Communication 151 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 214–222, February, 2009.     

Synthesis of [5-(1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazol-4-yl)-1,3,4-oxadiazol-2-yl]pyridines

2-, 3-, and 4-[5-(1-Aryl-5-R-1H-1,2,3-triazol-4-yl)-1,3,4-oxadiazol-2-yl]pyridines were synthesized from the corresponding 1-aryl-5-R-1H-1,2,3-triazole-4-carbonyl chlorides and 2-, 3-, and 4-(1H-tetrazol-5-yl)-pyridines.     

Synthesis of heterocycles based on arylation products of unsaturated compounds: XVII. Arylation of 2-acetylfuran and synthesis of 3-R-6-(5-aryl-2-furyl)-7<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazolo[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazines

Reaction of 2-acetylfuran with arenediazonium chlorides under Meerwein reaction conditions led to the formation of 5-aryl-2-acetylfurans. The bromination of these compounds gave 2-bromo-1-(5-aryl-2-furyl)-ethanones that reacted with 4-amino-4H-5-R-1,2,4-triazole-3-thiols to form 3-R-6-(5-aryl-2-furyl)-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines.     

Aminolysis of 2-Aryl-5-R-5,6-dihydro-7H-[1,2,4]triazolo[5,1-<Emphasis Type="Italic">b</Emphasis>]1,3]thiazin-7-ones

We have established that the products of aminolysis of 2-aryl-5-R-5,6-dihydro-7H-[1,2,4]triazolo-[5,1-b][1,3]thiazin-7-ones in boiling ethanol are 3-R-3-(5-aryl-4H-1,2,4-triazol-3-ylsulfanyl)-propanamides, and at 180°C–210°C (depending on the structure of the substituent R): 3-phenyl-4,5-dihydro-1H-1,2,4-triazoline-5-thione and 3-arylacrylamides or 3-(3-aryl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)propanamides. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1587–1592, October, 2005.     

2-Alkyl-4-oxohexahydropyrimido[4,5-<Emphasis Type="Italic">d</Emphasis>]- and -[5,4-<Emphasis Type="Italic">d</Emphasis>]azocines

It has been established that 2-R-4-oxotetrahydropyrido[4,3-d]pyrimidines, under the action of activated alkynes in methanol, form a mixture of 2-R-4-oxohexahydropyrimido[4,5-d]azocines and products of decomposition of the tetrahydropyridine ring, the 2-R-5-methoxymethyl-4-oxo-6-vinylaminoethyl-pyrimidines. Tetrahydropyrido[3,4-d]pyrimidine, isomeric at the junction of the pyrimidine and tetrahydropyridine rings, forms only the corresponding pyrimido[5,4-d]azocine, the product of expansion, under the action of methyl propiolate.     

4-Hydroxy-2-quinolones 7. Synthesis and biological properties of 1-R-3-(2-benzimidazolyl)-4-hydroxy-2-quinolones

Condensation of 1-R-3-carbethoxy-4-hydroxy-2-quinolones with o-phenylene diamine gives the corresponding 1-R-3-(2-benzimidazolyl)-4-hydroxy-2-quinolones. Data on a study of the antithyroid activity of the synthesized compounds is presented.For Communication 6, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 105–108, January, 1993.We express our sincere thanks to A. A. Kirichenko and T. S. Bozhko for the study of the antithyroid activity.     

4-hydroxy-2-quinolones. 18. Synthesis and antithyroid activity of 1-R-2-oxo-3-(4-oxo-3H-quinazolin-2-yl)-4-hydroxyquinolines

Preparative methods for the synthesis of 1-R-2-oxo-3-(4-oxo-3H-quinazolin-2-yl)-4-hydroxyquinolines based on ethyl esters or nitrites of 1-R-2-oxo-4-hydroxyqidnoline-3-carboxylic acids and anthranilamide or ethyl anthranilate correspondingly were proposed. The antithyroid activity of the compounds synthesized was studied.For Communication 17, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1223–1226, September, 1993.     

1,2-Diacyl-1-arylhydrazines. 1. Derivatives of 2-hydroxy- and 2-halogenobenzoic acids

New 1,2-diacyl-1-arylhydrazines, containing a hydroxy group or a mobile halogen atom in the 1-acyl fragment, were obtained by the reaction of the arylhydrazones of acetyl and benzoyl chlorides with the salts of 2-hydroxy-, 2-acetoxy-, and 2-halogeno-3-nitrobenzoic acids. 1-(2-Hydroxybenzoyl)-1-aryl-2-acylhydrazines could not be converted into cyclic products. On heating in alkaline and acidic media elimination of the more hindered salicyloyl group and not dehydration occurred. When boiled in DMF in the presence of bases, 1-(2-halogeno-3-nitro-5-R-benzoyl)-1-aryl-2-acylhydrazines gave 2-aryl-5-R-7-nitroindazol-3-ones and not the expected 4,5-dihydrobenzo[f]-1,3,4-oxadiazepin-5-ones.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1424–1430, June, 1992.     

Unusual amino acids. 5. Synthesis of 3,5-dioxopyrazolidine derivatives

Monohydrazides of 2-R-4-methyl-4-cyclohexene-1,1-dicarboxylic acids react with trifluoroacetic acid anhydride to give 4-substituted 3,5-dioxopyrazolidines, with phosphorus trichloride to give 4-(2-R-5-chloro-4-methylcyclohexane)-3,5-dioxopyrazolidines, and with acetic anhydride to give 4-(2-R-4-methyl-4-cyclohexene)-3,5-diacetoxypryazoles.For Communication 4, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 903–907, July, 2000.     

Azines and azoles: CXXVI. First example of a novel heterocyclic system: Pyrimido[1,6-<Emphasis Type="Italic">a</Emphasis>][1,5]benzodiazepines

4-Hydroxy-5-(2-R-2,3-dihydro-1H-1,5-benzodiazepin-4-yl)-2H-1,3-thiazine-2,6-diones readily undergo acylation at the N¹ atom of the benzodiazepine system by the action of acetic anhydride. Heating of the acetylated products in boiling dimethylformamide leads to the formation of 75–93% of the corresponding 7-acetyl-6-R-6,7-dihydropyrimido[1,6-a][1,5]benzodiazepine-1,3-diones that are derivatives of hitherto unknown fused heterocyclic system, pyrimido[1,6-a][1,5]benzodiazepine. 4-Hydroxy-5-(2-R-2,3-dihydro-1H-1,5-benzodiazepin-4-yl)-2H-1,3-thiazine-2,6-diones are converted into 1-(2-aminophenyl)-6-(2-R-vinyl)uracils on heating in boiling DMF.     

4-hydroxy-2-quinolones. 43. Thermolysis of ethyl esters of 1-R-2-oxo-4-hydroxy-quinoline-3-carboxylic acids

Ethyl esters of 1-R-2-oxo-4-hydroxyquinoline-3-carboxylic acids under thermolysis conditions are converted to 5,9-di-R-6,7,8-trioxodiquinolino[3,4-b;3,4-e]-4H-pyrans. One of the synthesized compounds was studied by X-ray diffraction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 516–522, April, 2000.     

Synthesis of 8-R-9c-alkyl-1-aryl-2-benzyl-1-hydroxy-1,2,9b,9c-tetrahydro-5-oxa-2-aza-cyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones and reaction thereof with acetic anhydride

The reaction of zinc enolates synthesized from 1-aryl-2,2-dibromoalkanones and zinc with 6-R-2-oxochromene-3-carboxylic acid N-benzylamide affords 8-R-9c-alkyl-1-aryl-2-benzyl-1-hydroxy-1,2,9b,9c-tetrahydro-5-oxa-2-aza-cyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones. Acylation of these compounds is accompanied by an unexpected rearrangement producing a sole geometrical isomer of 4′-alkyl-5′-aryl-1′-benzyl-3,4,2′,3′-tetrahydro-2,2′-dioxospiro[chroman-3,3′-pyrrol]-4-yl acetates.     

Fused polycyclic nitrogen-containing heterocycles: IX. Synthesis and molecular structure of methyl 3-(2-R-5-phenylthiazol-4-yl)-7-phenyl-7<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazolo-[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazine-6-carboxylates

4-Amino-3-(2-R-5-phenylthiazol-4-yl)-1,2,4-triazole-5-thiones react with methyl 3-chloro-2-oxo-3-phenylpropionate to give methyl 3-(2-R-5-phenylthiazol-4-yl)-7-phenyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine-6-carboxylates. According to the X-ray diffraction data, the thiazole ring in the products is planar, while the thiadiazine ring has a distorted unsymmetrical boat conformation. Depending on the substituent in the thiazole ring, methyl 3-(2-R-5-phenylthiazol-4-yl)-7-phenyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine-6-carboxylates in crystal give rise to different supramolecular structures, lamellar and cylindrical.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1358–1365.Original Russian Text Copyright © 2004 by Mamedov, Mustakimova, Gubaidullin, Litvinov, Levin.     

Pyrimidines

The reaction of methylenebisurea with 5-amino-1-R-pyrazoles and 3-ureido-1-phenylpyrazole gives 1- and 2-R-6-oxo-4,5,6,7-tetrahydropyrazolo[3,4-d]pyrimidines, respectively. The 1-R-6-oxo-4,5,6,7-tetrahydropyrazolo[3,4-d]pyrimidines are readily dehydrogenated to 1-R-6-hydroxypyrazolo[3,4-d]pyrimidines. The 2-R-6-oxo-4,5,6,7-tetrahydropyrazolo[3,4-d]pyrimidines could not be dehydrogenated.See [1] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1696–1699, December, 1972.     

New method for the annelation of a pyridine ring on derivatives of imidazole and benzimidazole

The interaction of (Z)-1,3-diaryl-4-bromo-2-buten-1-ones with 1-substituted (benz)imidazoles in benzene gave (Z)-1-R-3-(2,4-diaryl-4-oxo-2-butenyl)-1H-imidazolium bromides and (Z)-1-R-3-(2,4-diaryl-4-oxo-2-butenyl)-1H-benzimidazolium bromides which readily cyclize in the presence of base to form derivatives of 7,9-diarylpyrido[1,2-a]benzimidazole and 6,8-diarylpyrimidazo[1,2-a]pyridine. The effects of the nature of substituents in the benzene ring of the diarylbutenones and the substituent at N(1) in the (benz)imidazoles on the alkylation and cyclization reactions has been studied. The optimum conditions for the synthesis of the 5-R-4-hydroxy-2,4-diphenyl-4,5-dihydro-1H-pyrido[1,2-a]benz-imidazol-10-ium, 5-R-2,4-diaryl-4-hydroxy-4,5-dihydro-3H-pyrido[1,2-a]benzimidazol-10-ium, and 5-R-2,4-diaryl-5H-pyrido[1,2-a]benzimidazol-10-ium have been found.     

4-Hydroxy-2-quinolones. 84. Synthesis of 5-R-5H-5,7a,12-Triazabenzo[a]anthracene-6,7-diones

2-Aminopyridines react under thermolysis conditions with ethyl 1-R-4-chloro-2-oxoquinoline-3-carboxylates exclusively in the imino form to give the corresponding 5-R-5H-5,7a,12-triazabenzo[a]anthracene-6,7-diones and 4-(pyridyl-2-amino)-1-R-quinolin-2-ones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1060–1070, July, 2005.     

Synthesis of azepino[1,2-<Emphasis Type="Italic">a</Emphasis>]benzimidazoles and imidazo[1,2-<Emphasis Type="Italic">a</Emphasis>]azepines

Fusion of 4-bromo-1,3-diphenyl-2-buten-1-ones (γ-bromodypnones) with 1,2-dimethyl-1H-benzimidazole and further treatment of the reaction product with a base (morpholine) gives 7,9-diaryl-5-methyl5,10-dihydroazepino[1,2-a]benzimidazol-11-ium bromides. The reaction of γ-bromodypnone with 1-alkyl-2-methyl-1H-imidazoles in benzene at 25 °C gives quaternary azolium salts. Upon heating their solutions in alcohol in the presence of K₂CO₃ the latter cyclize to 1-R-6,8-diaryl-1,5-dihydroimidazo[1,2-a]azepin-4-ium bromides or 1-R-6,8-diaryl-1H-imidazo[1,2-a]azepines depending on the nature of the substituent in the benzene rings and the substituent at the N(1) atom of the imidazole.     

Dual reactivity of diazonium salts derived from 1-amino-2-ethynyl-9,10-anthraquinones

Diazotization of vicinal 1-amino-2-ethynyl-4-R-9,10-anthraquinones followed by a reaction with NaN₃ gave 5-hydroxy-3-R-1H-naphtho[2,3-g]indazole-6,11-diones or 3-ethynyl-5-R-6H-anthra[1,9-cd]isoxazol-6-ones, depending on the substituents at the triply bonded C atom and in position 4 of the anthraquinone framework.