2-Carbethoxy-4H-3,1-benzoxazin-4-one. 2. Hydrazinolysis

3-Amino-2-carboxymethylquinazolin-4(3H)-one was obtained by hydrazinolysis of 2-carbethoxymethyl-4H-3,1-benzoxazin-4-one. Its transformations into 2-hydroxypyrazolo[5,1-b]quinazolin-9(1H)-oneand3-amino-2-hydrazido-(orbenzylamido)carbonylmethylquinazoline-4(3H)-ones were studied.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1128–1130, August, 1991.     

4-hydroxy-2-quinolones. 34. Structure of photocondensation products of 3-amino-1R-2-oxo-4-hydroxyquinolines

3-Amino-2-oxo-4-hydroxyquinolines when exposed to light are quantitatively converted to di(1R-2-oxo-4-hydroxyquinolin-3-yl)amines. We have carried out an x-ray diffraction study of one such compound.For Communication 33, see [1].Ukrainian Pharmaceutical Academy, Kharkov 310002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 933–940, July, 1997.     

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. 26. Bromination of 3-substituted 2-oxo-4-hydroxyquinolones

The bromination of 3-alkyl- and 3-ethoxycarbonyl-2-oxo-4-hydroxyquinolones by molecular bromine gave 3-bromo-3-R-2,4-dioxoquinolones. Under analogues conditions, 1-R-2,4-dioxo-3H-quinolone-3-carboxylic acids form 1-R-3-bromo-2-oxo-4-hydroxyquinolones. The results of the study of the antimicrobial activity of the compounds synthesized are presented.For Communication 25, cf. [1].Ukrainian Pharmaceutical Academy, Khar'kov, 310002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 204–207, February, 1995. Original article submitted November 8, 1994.     

Photochemistry of 4-Thia-2-cycloalkenones. Part 2

Methyl 2-allyl-3-oxo-2,3-dihydrothiophene-2-carboxylate ( 2 ) photocyclizes selectively to methyl 2-oxo-7-thiatricyclo[3.2.1.0^3,6]octane-1-carboxylate ( 4 ). In contrast, 4-thia-2-cyclohexenone 3 , on irradiation, affords only low yields of dimers, cycloadducts (2-methylpropene) or RH reduction products (i-ProH).     

4-hydroxy-2-quinolones. 33. Novel approach to synthesis of 1H-2-oxo-4-hydroxyquinoline-3-acetic acid

We propose a novel method for obtaining the methyl ester of 1H-2-oxo-4-hydroxyquinoline-3-acetic acid.Communication 32, see [1].Ukrainian Pharmaceutical Academy, Kharkov 310002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 928–932, July, 1997.     

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.     

2-Carbethoxymethyl-4H-3,1-benzoxazin-4-one. 3. Condensation of o-phenylenediamive

3-(2-Benzimidazolyl)-4-hydroxy-2-quinolone was unexpectedly obtained as the principal reaction product on fusion of 2-carbethoxymethyl-4H-3,1-benzoxazin-4-one with o-phenylenediamine. A possible mechanism of its formation is presented.For Communication 2 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 239–241, February, 1992.     

Cyanoacetylene and Its Derivatives. 30. Reactions of 2,3-Dimercaptoquinoxaline with 3-Phenyl-2-propynonitrile and 4-Alkyl-4-hydroxy-2-alkynonitriles

The reaction of 2,3-dimercaptoquinoxaline with 3-phenyl-2-propynonitrile (~10 mass % KOH, 20-25°C, 5 h, dioxane) gave the S,S-diadduct (as with unsubstituted acetylene). 2,3-Dimercaptoquinoxaline reacted with 4-alkyl-4-hydroxy-2-alkynonitriles to give 2-cyanomethyl-2-(1-hydroxy-1-alkyl)-1,3-dioxolano[4,5-b]quinoxalines or 3-cyanomethylene-8-imino-2,2,6,6-tetramethyl-1,7-dioxa-4-thiaspiro[4.4]nonane.     

Synthesis of nitrogen-containing heterocycles. 4. A facile route to new 1, 2, 4-triazole derivatives

The reaction of amino-N(4),N(4)-dimethylaminornethylenehydrazones 1 of some aliphatic carbonyl compounds with ethyl ethoxymethylenecyanoacetate 2 gave directly symmetrical gem-bis(3-dimethylamino-1, 2, 4-triazol-1-yl)alkanes 4 and (3-dimethylamino-1, 2, 4-triazol-1-yl)alkenes 5 at room temperature, with the former being major product. On the other hand, the reaction of amino- N (4)-methylaminomethylenehydrazone homologue 1 of aliphatic ketone with 2 gave ethyl 2-alkyl-5-methylamino[1, 2, 4]triazolo[1, 5-c]pyrimidine-8-carboxylate 7 as the only product with elimination of alkane.     

4-Hydroxy-2-quinolones. 112. Reaction of 2-ethoxycarbonylmethyl-4H-3,1-benzoxazin-4-one with active methylene compounds

The reaction of 2-ethoxycarbonylmethyl-4H-3,1-benzoxazin-4-one with malononitrile in dry pyridine leads to 1-hydroxy-3,6-dioxo-4,6-dihydro-3H-pyrimido[1,2-a]quinoline-5-carbonitrile. Acetoacetic and cyanoacetic esters under analogous conditions form anilides of 4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid while diethyl malonate gives N,N′-di-2-carboxyanilides of malonic acid. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 75–79, January, 2007.     

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.     

4-Hydroxy-2-quinolones. 2. Simple synthesis of arboricine

Acylation of methyl N-methylanthranilate with phenylacetyl chloride with subsequent intramolecular cyclization of the resulting anilide was used to synthesize 1-methyl-3-phenyl-4-hydroxy-2-quinolone (arboricine).See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 522–524, April, 1992.     

4-Hydroxy-2-quinolones. 31. 3-Amino-ir-2-oxo-4-hydroxyquinolines and their acyl derivatives

Abstarct An alternative method has been developed for preparing and studying the antioxidant activity of 3-acylamino-2-oxo-4-hydroxyquinolones. Results are presented from an investigation of the antithyroid and antimicrobial action of the intermediate 2-oxo-3-(1 pyridinio)quinotin-4-olates and the 3-amino-2-oxo-4-hydroxyquinolines.For communication 30, see [1].Ukrainian Pharmaceutical Academy, Khar'kov 310002. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1113–1123, August, 1996. Original article submitted June 10, 1996.     

4-hydroxy-2-quinolones 151. Reaction of 4-chloro-3-ethoxycarbonyl-2-oxo-1,2-dihydroquinolines with p-toluenesulfonylhydrazide

The reaction of ethyl 4-chloro-1-methyl-2-oxo-1,2-dihydroquinoline-3-carboxylate with p-toluene-sulfonylhydrazide at room temperature in the system DMSO/K₂CO₃ gives 5-methyl-2-(toluene-4-sulfonyl)-1,2-dihydro-5H-pyrazolo[4,3-c]quinoline-3,4-dione, alkylation of which using ethyl iodide gives the 1N-substituted derivative. For Communication 150 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 59-66, January, 2009.     

[4 + 2]-Cycloadditionen von α, β- ungesättigten hydrazonen. Teil3. Isothiazolo[4,5-b]pyridin-3(2H)-on-1,1-dioxide (= 4-azasaccharine)

[4 + 2] Cycloaddition of α, β-Unsaturated Hydrazones: Isothlazolo[4,5-b]pyridin-3(2H)-on 1,1-Dioxides (= 4-Azasaccharine Derivatives) The [4 + 2] cycloaddition of α, β -unsaturated hydrazones of type 1 (1-azabuta-1,3-dienes) with isothiazol-3(2H)-on 1,1-dioxide derivatives 10 affords, depending on the solvent used, picolinamides 15 or 17 , 4,7-dihydro-4-azasaccharine 14 or 4-azasaccharine derivatives 16 (Scheme 4). The course of the reaction is mainly influenced by the substituent R of the dienophile 10 .     

Chinazolincarbonsäuren. XII. Mitteilung. Synthese von [2-(Ethoxycarbonyl)-3,4-dihydro-4-oxochinazolin-3-yl]-, [2-(Ethoxycarbonyl)chinazolin-4-yloxy]- und (5,6,7,8-Tetrahydro-2-phenylchinazolin-4-ylthio)alkansäure-estern

Quinazolinecarboxylic Acids. Synthesis of Alkyl [2-(Ethoxycarbonyl)-3,4-dihydro-4-oxoquinazolin-3-yl]-, [2-(Ethoxycarbonyl)quinazolin-4-yloxy]- and (5,6,7,8-Tetrahydro-2-phenylquinazolin-4-ylthio)alkanoates The [(2-aminobenzoyl)amino]alkanoic acids and their esters 1 showed a different reaction behaviour with diethyl oxalate. Compound 1 (n = 2,3) was converted into the quinazolinylalkanoates 3 . o-Aminohippurate yielded with ethyl (chloroformyl)formate a mixture of the amide 4 and the cyclized quinazolinone 7b . Ethyl 3,4-dihydro-4-oxoquinazoline-2-carboxylate ( 6 ) reacted with 2-bromoalkanoates, in the presence of NaH, to the [2-(ethoxycarbonyl)-3,4-dihydro-4-oxoquinazolin-3-y1]acetates 7 in the case of alkyl bromoacetate, and to the O-alkylated derivatives 8 with the ethyl 2-bromopropionate and -butyrate. 2-Aminobenzamide ( 5 ) gave with ethyl 3-(chloroformyl)-2-propenoate and methyl 3-(chloroformyl)propionate the amides 9 or 11 , respectively, and not the expected quinazolinones. The cyclized product 12 was obtained from 11 and ethyl bromoacetate. Tetrahydroquinazolin-4(3H)-thione 14 was synthesized by the reaction of 13 with NH₃, and it was alkylated at the S-atom with bromoalkanoates to 15 . The hydrazide 16 was synthesized from 15b with hydrazine hydrate.     

Synthesis and reactions of 3-aminothiazolidine-2-thion-4-one derivatives. 2. 3-[R-(Alkylthio)methylene]aminothiazolidine-2-thion-4-ones

3-[R-(Alkylthio)methylene]aminothiazolidine-2-thion-4-ones were obtained by the reaction of 3-aminorhodanine with thioimino ester hydriodides.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 199–201, February, 1981.     

Zur Photodimerisierung von 3-Phenyl-2H-azirinen. Vorläufige Mitteilung

Irradiation of 3-phenyl-2H-azirine ( 2 ) in benzene solution with a high-pressure mercury lamp yields 4,5-diphenyl-1,3-diazabicyclo[3,1,0]hex-3-ene ( 4 ) and not 3-phenylimino-4-phenyl-1-azabicyclo[2,1,0]pentane ( 1 ), as had been reported previously by others [2]. 2-Methyl-3-phenyl-2H-azirine ( 3 ) yields on irradiation a 2:1 mixture of 2-exo, 6-exo- and 2-exdo, 6-exo-dimethyl-4,5-diphenyl-1,3-diazabicyclo[3,1,0]hex-3-ene (2-exo,6-exo- and 2-endo, 6-exo- 5 ). Irradiation of 2,3-diphenyl-2H-azirine ( 8 ) leads to the formation of 2,4,5-triphenyl-imidazole ( 9 ) and tetra-phenylpyrazine ( 10 ). The suggested reaction path for the generation of 9 and 10 is shown in Scheme 2.     

Electrospray-Ionization Mass Spectrometry. Part 2. Neighboring-Group Participation in the Mass-Spectral Decomposition of 4-Hydroxycinnamoyl-spermidines

The three mono substituted N-[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines 1–3 have been studied by positive-ion electrospray-ionization tandem mass spectrometry (ESI-MS/MS). Because of the neighboring-group participation, the MS/MS of [ 1 + H]⁺ and [ 2 + H]⁺ are essentially similar, while compound 3 can be easily distinguished from 1 and 2 because of the characteristic ions at m/z 218. However, with the source collision-induced dissociation (source-CID) MS/MS technique, the compounds 1 and 2 can be unambiguously distinguished by the signal of the pyrrolidinium ion (m/z 72) from their daughter ion (m/z 275). The source-CID MS/MS of the labeled compound N-(4-aminobutyl)-N-(3-aminopropyl)-N-[3-(4- hydroxyphenyl)prop-2-en[¹⁵N]amide] ([¹⁵N(4)]- 2 ) provide more information on the decomposition mechanisms and proved the occurrence of a partial transamidation reaction 2→1 during the measurement.