Reaction of 3-Amino-5H- and 3-Amino-5-sulfanyl-1,2,4-triazoles with 1,2,4-Triazine-5-carbonitriles

Russian Journal of Organic Chemistry - 1,2,4-Triazines with an unsubstituted (1,2,4-triazol-3-yl)amine residue in the C5 position were synthesized by the solvent-free ipso-amination reaction...     

On triazoles. VIII The reaction of 5-amino-1,2,4-triazoles with ethyl 2-cyano-3-ethoxyacrylate and 2-cyano-3-ethoxyacrylonitrile

The reaction of different 5-amino-3-Q-1H-1,2,4-triazoles 1 with ethyl 2-cyano-3-ethoxyacrylate ( 5a ) and 2-cyano-3-ethoxyacrylonitrile ( 5b ) to yield either the a type 5-amino-, or the b type 7-amino-1,2,4-triazolo[1,5-a]-pyrimidine derivatives 6–10 was studied. The structure of compounds 6 and 9 was proved by their degradation to the corresponding derivatives 17a and 18a , respectively, through intermediates 11a, 12a, 13a, 14a, 15a and 16a , respectively. The structure of derivatives 7, 8 and 10 was proved on the basis of the analogy of their uv spectra with those of 6a and 9a , respectively. The isolation of the intermediates 19 and 20 helped to prove the mechanism of the reactions leading to the formation of 6a and 9a , respectively. In the reaction of the N-substituted 5-amino-1,2,4-triazoles with 5a the expected condensed ring products were not formed. Instead the aminoacrylates 22 and 24 were obtained. The “Z”-“E” isomeric structure of derivatives 19, 20, 22 and 24 was proved with the help of their pmr spectra. The “Z” isomeric structure of the thermodynamically stabile 22 was corroborated with the help of its proton coupled cmr spectra, too.     

Reaction of 3-oxo-N-phenylbutanethioamide with 5-amino-1H-1,2,4-triazoles

Reactions of 3-oxo-N-phenylbutanethioamide with 3-substituted 5-amino-1H-1,2,4-triazoles in acetic acid led to the formation of 5-methyl-7,8-dihydro[1,2,4]triazolo[1,5-a]pyrimidine-7-thiones, 7-methyl-5,8-dihydrol[1,2,4]triazolo[1,5-a]pyrimidine-5-thiones and 7-methyl-5-phenylamino[1,2,4]triazolo[1,5-a]pyrimidines. The structure of the products was proved by the ¹H and ¹³C NMR spectra, X-ray diffraction data, and chemical transformations.     

Reaction of Unsymmetrically Substituted Hydrazines with 5-Nitromethyl-3-phenyl-1,2,4-oxadiazoles

Russian Journal of Organic Chemistry -     

Reaction of 3(5) -diazo-1,2,4-triazoles with nitroalkane anions

The 1,2,4-triazolylhydrazones of the corresponding nitro aldehydes were obtained by the reaction of the anions of nitromethane, nitroethane, and 1-nitropropane with diazo-1,2,4-triazoles. 2-Nitropropane, 1,1-dinitroethane, 1,1-dinitropropane, and trinitromethane form 1,2,4-triazolylazonitro compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 713–717, May, 1972.     

Reaction of 1,1,2,2-tetrafluoropropanal with phenylhydrazine

Conclusions The reaction of 1,1,2,2-tetrafluoropropanal with phenylhydrazine gave difluoromethyl-glyoxal bis(phenylhydrazone) and mesoxaldehyde tris(phenylhydrazone); reaction with phenylhydrazine acetate in aqueous medium gave 1-phenyl-4-phenylazopyrazole. The dehydrofluorination of perfluoroethylglyoxal bis(phenylhydrazone led to 1-phenyl-4-phenylazo-5-trifluoro-methylpyrazole.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1912–1916, August, 1977.The authors express their gratitude to P. V. Petrovskii for taking and interpreting the¹³C NMR spectra.     

Neue acetonylsubstituierte Azole II. 3-Acetonyl-1,2,4-oxadiazole, 2-Acetonyl-1,3,4-oxadiazole und 5-Acetonyl-1,2,4-thiadiazole

3-Acetonyl-1,2,4-oxadiazoles and 2-acetonyl-1,3,4-oxadiazoles are accessible starting with the ketal of acetoacetamide oxime and the ketal of acetoacetic acid hydrazide, respectively. 5-Acetonyl-1,2,4-thiadiazoles are obtained from 5-chloro-1,2,4-thiadiazoles andtert.-butyl acetoacetate. These Acetonyl-azoles are starting materials for three series of azolylvinyl phosphates and phosphonates.

Herrn Prof. Dr.Klaus Weissermel zu seinem 60. Geburtstag.     

Reaction of 4-cyano-5-aminopyrazole and 3,4-dicyano-5-aminopyrazole with dimethylformamide diethylacetal

The condensation of 4-cyano-5-aminopyrazole or 3,4-dicyano-5-aminopyrazole with dimethylformamide diethylacetal was studied. It was shown that, in addition to the formation of dimethylaminomethyleneamino derivatives, alkylation of the pyrazole ring occurs under severe conditions without a solvent. Only the corresponding formamidino derivatives are formed when the same reactions are carried out in methanal under milder conditions. The site of addition of an ethyl group to the pyrazole ring in the N-alkyl derivatives obtained was established by ¹³C NMR and PMR spectroscopy. The possibility of the synthesis of 4-amino- or 4-methylmercaptopyrazolo[3,4-d]pyrimidines by cyclization of the corresponding dimethylamino- methyleneaminopyrazoles with a cyano group in the ortho position was demonstrated for the first time.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 259–264, February, 1984.     

Reaction of ethyl cyanoacetate with 4-amino-3 mercapto-5R-1,2,4-triazole

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 137–138, January, 1994.     

Effects of some 5-anilino-1,2,4-thiadiazole derivatives onto leukemic cells

Russian Chemical Bulletin - The antileukemic activities of some thiadiazole derivatives in the forms of hydrochlorides and salicylates have been determined. The insertion of salicylate ion in the...     

Reaction of ethyl 4-aryl-6-bromomethyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates with N-methylmorpholinium 3-cyano-1,4-dihydro- and 3-cyano-1,4,5,6-tetrahydropyridine-2-thiolates

Alkylation of N-methylmorpholinium 4-Ar¹-3-cyano-6-oxo-1,4,5,6-tetrahydropyridine-2-thiolates using ethyl 4-Ar-6-bromomethyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates (10 % KOH, DMF) gives mixtures of diastereomers of ethyl 4-Ar-6-[(4-Ar¹-3-cyano-1,4,5,6-tetrahydropyridin-2-ylthio)methyl]-1-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates in overall 30-58 % yield. Under these conditions the N-methylmorpholinium 4-Ar1-5-(N-Ar²-carbamoyl)-3-cyano-6-methyl-1,4-dihydropyridine-2-thiolates undergo aromatization of the dihydropyridine ring to give ethyl 4-Ar-6-[4-Ar¹-5-(N-Ar²-carbamoyl)-3-cyano-6-methylpyridin-2-ylthio)methyl]-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates (37-51 %). In the absence of KOH, only the substituted pyridine-2(1 H)-thione is formed as a product of oxidation of the dihydropyridine ring in the starting substrate. Some of the alkylation products obtained possess weak or moderate antibacterial activity towards the specific strains of Escherichia coli and Bacillus subtilis but are inactive towards Candida albicans and Staphylococcus aureus.     

3-芳基-5-巯基-1,2,4-三唑衍生物的亲核反应研究

研究了碱性条件下3-芳基-5-巯基-1,2,4-三唑与丙烯腈或丙烯酸甲酯的亲核反应,得到31个新的3-芳基-1,2,4-三唑-5-硫酮类衍生物,其结构经NMR, IR, MS和元素分析表征.     

Reaction of 1,2,4-triazole-3-thione with acetylene

A mixture of 1,2,4-triazol-3-yl vinyl sulfide and N,S-divinyl derivatives is formed in the reaction of 1,2,4-triazole-3-thione with acetylene under pressure. The mixture of N,S-divinyl derivatives was separated into two isomers by gas-liquid chromatography. The hydrogenation, polymerization, and complexing of 1,2,4-triazol-3-yl vinyl sulfide were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1561–1563, November, 1977.     

Palladium(II) recovery in extraction and sorption systems with 5-amino-1,2,4-thiadiazole derivatives

The distribution of palladium(II) between the solutions of hydrochloric and nitric acids and the solutions of 5-amino-1,2,4-thiadiazole derivatives in 1,2-dichloroethane depending on acid and extractant concentrations in the aqueous and organic phases, respectively, was studied. The stoichiometry of the extracted complexes was determined, and the concentration constants of extraction were calculated. The applicability of macroporous polymer sorbents noncovalently modified with the test reagents to the sorption recovery of palladium(II) from nitric acid solutions was demonstrated.     

5-Phenyl-1,3,4-thiadiazole and 5-phenyl-1,2,4-triazoline-3-thione as products of dehydrogenation of cyclic tautomeric forms of benzaldehyde thiosemicarbazone

5-Pkenyl-1,3,4-thiadiazole and 5-phenyl-1,4-triazoline-3-thione are produced from heterocyclic tautomeric forms of benzaldehyde thiosemicarbazone in the gas phase under conditions existing in a mass spectrometer, and also in the solid phase in the course of thermolysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1554–1560, November, 1993.