Synthesis of imidazolino [1,2-f]xanthin-2-ones and their methylene-group-substituted derivatives

8-Amino-7-theophyllylacetic acids and their esters were obtained by reaction of 8-amino(alkylamino, arylamino)theophyllines with haloacetic acids and their esters. The structures of the products were established, and the conditions for cyclization to imidazolino[1,2-f]xanthin-2-one derivatives were studied. The corresponding methylene-group-substituted derivatives were synthesized by reaction of the imidazolino[1,2-f]xanthin-2-one derivatives with aldehydes, isatin, aromatic nitroso compounds, and arenediazonium salts. The ylidene derivatives of this threering system were also obtained by reaction of 8-amino-7-theophyllylacetic acids or their esters with carbonyl compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1132–1135, August, 1976.     

Investigation of nitrogen- and sulfur-containing heterocycles

A number of derivatives of a new heterocyclic system — pyrimido[5,4-b][1,4]-7-oxazinone- were obtained by the reaction of substituted 5-hydroxy-6-aminopyrimidines with ethyl esters of-halocarboxylic acids.See [1] for communication XXIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1285–1288, September, 1972.     

The nitration of sym-triazolo[3,4-b]benzothiazole

The nitration of sym-triazolo[3,4-b]benzothiazole (I) with a mixture of nitric and sulfuric acids has given 6-nitro-sym-triazolo[3,4-b]benzothiazole (II). The structure of II was established by comparing its properties (mp, PMR spectrum) with those of the 7-nitro-sym-triazolo[3,4-b]-benzothiazole (III) obtained by the ring closure of 2-hydrazino-6-nitrobenzothiazole (VI) with orthoformic ester. Compounds II and III have been converted into the corresponding acetylamino derivatives. Saponification of the acetyl groups has given amino derivatives of I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 7, pp. 913–915, July, 1970.     

Heterocyclic analogs of pleiadiene. 50. Sulfonation of perimidines,perimidones, and 2,3-dihydroperimidines

The action of concentrated sulfuric acid on perimidine and 2-substituted perimidines, 1,3-dimethylperimidinium perchlorate, and the 1,3-dimethyl derivatives of perimidone and 2,3-dihydroperimidine gave the 6(7)-sulfonic acids of these compounds.See [1] for communication 49.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 691–696, May, 1980.     

Indole derivatives

7-Nitroindole, 5-methoxyindole, and 6-methoxyindole were synthesized by oxidation of 2-naphthol derivatives with hydrogen peroxide to the corresponding o-carboxycinnamic acids and cyclization of their amides under the conditions of the Hofmann reaction.See [1] for communication LXXXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 207–210, February, 1974.     

Synthesis of fused systems containing an angular nitrogen atom from substituted 2-benzyl-4-hydrazinopyridimines

The condensation of substituted 2-benzyl-4-hydrazinopyrimidines with phenylpyruvic acid gave the corresponding hydrazones, which cyclize upon the action of POCl, to give derivatives of pyrimido[6,1-c][1,2,4]-triazine. The substituted 2-benzylpyrimidinylhydrazides of some carboxylic acids react with POCl, to give 1,2,4-triazolo[4,3-c]pyrimidines. The reaction of 7-benzyl-5-methyl-l-phenyl-1,2,4-triazolo[2,3-c]pyrimidine with sodium ethylate leads to rearrangement and formation of 7-benzyl-5-methyl-2-phenyl-1,2,4-triazolo[2,3-c]pyrimidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 225–229, February, 2000.     

Synthesis of Substituted dihtydro-5H-pyrano[4,-3-b]pyridin-3-carboxamides and -3-carboxylic acids

Optimal conditions were established for the hydrolysis of 2-amino-3-cyanodihydropyranopyridines to give substituted dihydro-5H-pyrano-[4,3-b]pyridine-3-carboxylic acids. Two convenient routes also were developed for the synthesis of the 3-carboxamide derivatives of substi-tuted dihydro-5H-pyrano[4,3-b]pyridine from the corresponding 2-chlorocyano derivatives.A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan, 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7. pp. 995–998, July, 1994.Original article submitted February 15, 1994.     

Benzindoles

The previously undescribed tetrahydro[4, 5]- and tetrahydro[6, 7]benzindoles and some of their derivatives were synthesized by Fischer cyclization of pyruvic acid 5- and 6-tetralinylhydrazones. A linear isomer — tetrahydro[5, 6]benzindole^–and its derivatives were obtained only in a mixture with tetrahydro[4, 5]-benzindole. The geometrical isomers of the pyruvic acid hydrazones were isolated and characterized. A method for the separation of the mixtures of 5- and 6-aminotetralins was developed. The structures of the isolated compounds were confirmed by the PMR and IR spectral data.See [1] for communication XIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 634–640, May, 1978.     

Imidazo[1,2-α]quinoxaline and its transformations

7-Substituted imidazo [1,2-a]quinoxalines were synthesized. Transformations of compounds of this series — quaternization, reduction to 4,5-dihydro derivatives, and behavior toward oxidizing agents — were studied.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1558–1560, November, 1972.     

Study of Nitrogen- and Sulfur-Containing Heterocycles. 57. Synthesis and Conversion of 4′-Substituted 5-(5-Amino-6-Pyrimidylthio)-2,2-Dimethyl-4,6-Dioxo-1,3-Dioxanes

By reaction of 4-substituted 5-amino-6-mercaptopyrimidines with 5-bromo-2,2-dimethyl-4,6-dioxo-1,3-dioxane, we have obtained 4′-substituted 5-(5-amino-6-pyrimidylthio)-2,2-dimethyl-4,6-dioxo-1,3-dioxanes. We have studied diazotization of these compounds by isoamyl nitrite. In the case of 4′-methoxy- and 4′-dimethylamino-substituted derivatives, we have obtained derivatives of novel heterocyclic systems: pyrimido[5,4-e][1,3,4]thiadiazine and pyrimido[5,4-e][1,3,4]thiadiazine-7-spiro-5′-1,3-dioxane, and in the case of the 4′-isopropylamino-substituted derivative we obtained 4-isopropyl-7-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)-1,2,3-triazolo[5,4-d]pyrimidin-7-ylidene.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 613–623, April, 2005.     

Synthesis and isomeric conversions of several 2-substituted 1,4-dihydro-4-oxo-3-quinolinecarboxylic acid derivatives

Ethyl ester derivatives of 6- and 8-substituted 2-methyl-1,4-dihydro-4-oxo-3-quinolinecarboxylic acids have been synthesized by treatment of the diethyl ester of acetylmalonic acid with 2- or 4-substituted anilines. Condensation of these newly synthesized quinolinecarboxylic acid derivatives with 4-nitrobenzaldehyde resulted in the formation of 6- and 8-substituted 2-[2-(4-nitrophenyl)-vinyl]-1, 4-dihydro-4-oxo-3-quinolinecarboxylic acids and ethyl esters of 6- and 8-substituted 2-[2-(4-nitrophenyl)vinyl]-4-acetoxy-3-quinolinecarboxylic acids. The tautomeric and conformational transformations of these newly synthesized compounds have also been investigated, using IR, NMR, and UV spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 931–938, July, 1988.     

Research in the imidazole series

The reduction of pyrrolo[1,2-a]imidazole-2-one and pyrrolo[1,2-a]benzimidazole derivatives, which leads to the formation of 2,3-dihydropyrrolo[1,2-a]imidazole derivatives and derivatives of the previously unknown 1,2,3,3a-tetrahydropyrrolo[1,2-a]benzimidazole, was studied. A method was developed for the preparation of 5- and 7-amino derivatives of pyrrolo[1,2-a]imidazole by reduction of the corresponding nitroso- and arylazo-substituted pyrrolo[1,2-a]-imidazoles.See [1] for communication XCI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 225–228, February, 1977.     

Synthesis of indenoindoles on the basis of 2-aminofluorene and 2-aminofluorenone

Ethyl esters of 2-carboxylic acids of 3H,10H-indeno[2,1-e]-1H,9H-indeno[1,2-f]indoles and their keto derivatives were obtained on the basis of 2-aminofluorene and its 9-keto derivative via the Japp-Klingemann and Fischer reactions. Saponification with subsequent decarboxylation of these products leads to unsubstituted cyclic systems and their keto derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1358–1362, October, 1982.     

Application of pentafluorophenyl hydrazine derivatives to the analysis of nabumetone and testosterone in human plasma by liquid chromatography–atmospheric pressure chemical ionization–tandem mass spectrometry

Two carbonyl compounds, nabumetone and testosterone, were derivatized with pentafluorophenyl hydrazine (PFPH) and analyzed by atmospheric-pressure chemical-ionization mass spectrometry. The PFPH derivatives underwent dissociative electron capture in negative-ion APCI (ECAPCI) and gave intense [M–20]^– ions in the mass spectra. In positive-ion APCI, the PFPH derivatives underwent efficient protonation and gave intense [M+H]⁺ ions in the mass spectra. In CID, the major product ions of the [M–20]^– ions in ECAPCI corresponded to the partial moiety of PFPH. In contrast, the major product ions of [M+H]⁺ corresponded to the partial moiety of the analyte. By using selected reaction monitoring (SRM) detection, low pg of nabumetone (1 pg) and testosterone (7 pg) could be detected in both ECAPCI and positive-ion APCI. In comparison with the detection limits (SRM) of the underivatized analytes, use of the PFPH derivatives resulted in 2500-fold and 35-fold sensitivity enhancements for nabumetone and testosterone, respectively. The PFPH derivatives were applied to the analysis of nabumetone and testosterone in human plasma by both ECAPCI and positive-ion APCI and were found to enable detection of 0.1 ng mL^–1 nabumetone in spiked plasma. For testosterone, endogenous testosterone in female plasma was detected in both ECAPCI and positive-ion APCI.     

Synthesis of methyl esters of 5-amino-4-(substituted amino)-2-methylthio-7H-pyrrolo[2,3d]-pyrimidine-6-carboxylic acids

The optimum route for the synthesis of methyl esters of N-[(4-substituted amino)-5-cyano-2-methylthiopyrimidin-6-yl]amino acids (which are starting materials for preparing the methyl esters of the corresponding 5-amino-4-(substituted amino)pyrrolo[2,3-d]pyrimidine-6-carboxylic acids) is via subsequent reactions of 4,6-dichloro-2-methylthiopyrimidine-5-carbonitrile with amines and methyl glycinate. In some examples, the reaction of methyl N-(4-chloro-2-methylthio-6-pyrimidinyl)aminoacetate with amines occurs to give the corresponding acid amides. The previously unknown synthesized derivatives of pyrimidin-6-yl amino acids and 4,5-diaminopyrrolo[2,3-d]pyrimidine- 6-carboxylic acids possess fungicidal properties.Vilnius University, Vilnius 2006, Lithuania. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No 7, pp. 955–961, July, 2000.     

Synthesis of furo[3,2-c]pyridine and furo[2,3-d]pyrimidine derivatives from butyrolactone diethylacetal

The reaction of butyrolactone acetal with CH acids was used to synthesize 2-methylenetetrahydrofuran derivatives. The latter react with dimethylformimide acetal to give a dieneamine that is capable of undergoing cyclization to furo [3,2-c]pyrimidine derivatives. This two-ring system was also synthesized by the reaction of cyanacetamide with 3-dimethylaminomethylenebutyrolactone acetal. The indicated acetal can also react with amidine components to give furo [2,3-d]pyrimidine derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 68–71, January, 1982.     

Synthesis and structure of mesomorphic 2-cyano-5-[p-alkyl(alkoxy)phenyl]-pyridines

Liquid-crystal 2-cyano-5-[p-alkyl(alkoxy)phenyl]pyridines were synthesized by the reaction of 1-dimethylamino-3-dimethylimmonia-2-[p-alkyl (alkoxy)phenyl]propene perchlorates with 2-acetylfuran and subsequently through 2-furyl-5-[p-alkyl(alkoxy)phenyl]pyrylium perchlorates and 2- (2-furyl)-5-[p-alkyl (alkoxy)phenyl]pyridines by conversion of the latter to 5-alkyl(alkoxy)phenylpyridine-2-carboxylic acids, from which the cyano derivatives were obtained by the usual scheme through the amides. The intermediate arylfurylpyridines and arylpyridine-2-carboxylic acid imides also display liquid-crystal properties.Translated from Khimiya Geterotskilicheskikh Soedinenii, No. 7, pp. 888–891, July, 1980.     

Condensation of N-methyl-4-iodopyra zolecarboxylic acids with copper acetylides

Conclusions The condensation of N-methyl-4-iodopyrazolecarboxylic acids with substituted copper acetylides gave derivatives of two new heterocyclic systems, and specifically of 1-oxo-6-methylpyrano[3,4,-c]- and 1-oxo-5,7-dimethylpyrano [3,4-d]pyrazole.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1175–1177, May, 1978.     

N-p-[di-(2-chloroethyl)amino]phenacetyl dicarboxylic amino acids and their derivatives

Conclusions N-p-[Di-(2-chloroethyl)amino]phenacetylglutaniic and aspartic acids and their derivatives have been synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2150–2153, September, 1970.