Oxidation of perfluoro-substituted derivatives of 1,3-diazines and 1,2,4-triazoles

Oxidation of 6-perfluoro-substituted 2-amino-4-methylpyrimidines and 5-amino-3-perfluoro(1,4-dimethyl-2,5-dioxaoctyl)-1,2,4-triazole with potassium permanganate and of 3-perfluoro-substituted 5-mercapto-and 5-amino-1,2,4-triazoles with hydrogen peroxide in alkaline solution was studied.     

4(3H)-Quinazolinones containing heterocyclic group in position 3

The corresponding 2,3-substituted 4(3H)-quinazolinones were obtained in the reactions of 2-methyl- and 2-phenyl-4-oxo-3,1-benzoxazines with 1-amino-1,2,4-triazole, 4-amino-2,3-dimethyl-1-phenyl-5-pyrazolone, 2-amino-5-ethyl-1,3,4-thiadiazole, 3-amino-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole, 1-amino-3-cyano-4,6-dimethyl-2-pyridone, and 1-amino-3-cyano-6-phenyl-4-trifluoromethyl-2-pyridone. The formation of N-benzolyanthranilamides in the reactions of 2-phenyl-4-oxo-3,1-benzoxazine with 2-amino-5-ethyl-1,3,4-thiadiazole and 1-amino-3-cyano-6-phenyl-4-trifluoromethyl-2-pyridones was exceptional. The structures of two of the products have been confirmed by X-ray crystallography.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 936–943, July, 2000.     

On the preparation of substituted 4H- 1,3,4-thiadiazolo[2,3-c]-1,2,4-triazin-4-ones and 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles

The reaction of benzoyl isothiocyanates and methoxycarbonyl isothiocyanate with 4-amino-4,5-dihydro-3-(methylthio)-1,2,4-triazin-5-ones in acetonitrile gave several substituted 4H-1,3,4-thiadiazolo[2,3-c]-1,2,4-triazin-4-ones VIa-h instead of the expected thioureas. In addition, benzoyl isothiocyanate reacted with 4-amino-3-(methylthio)-5-(trifluoromethyl)-4H-1,2,4-triazole to give the benzoyl thiourea IX and with 4-amino-3-mercapto-5-(trifluoromethyl)-4H-1,2,4-triazole to give the bicyclic compound N-[3-(trifluoromethyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazol-6-yl]benzamide IX .     

Synthesis and Physicochemical Properties of Heterocyclic Compounds Based on 5,7-Diimino-2,5,6,7-tetrahydro-1H-cyclopenta[cd]phenalene

N,N'-Bis(7-amino-2,5-dihydro-1H-cyclopenta[cd]phenalen-5-ylidene)-substituted derivatives of 2,5-diamino-1,3,4-thiadiazole, 2,6-diaminopyridine, and 3,5-diamino-1-phenyl-1,2,4-triazole were synthesized. The products are soluble in water, and they attract interest as potential biologically active substances.     

1,2,4-Triazoles. Improved synthesis of 5-substituted 4-amino-3-mer-cato-(4H)-1,2,4-triazoles and a facile route to 3,6-disubstituted 1,2,4-triazolo[3,4-b][1,3,4]thiadiazoles

The reaction of thiocarbohydrazide with carboxylic acids at the melting temperature allows an improved preparation of the S-substituted 4-amino-3-mercapto-1,2,4-triazole heterocycles. The crude 4-amino-5-mercapto-1,2,4-triazoles react easily with carboxylic acids or carboxylic acid chlorides to afford the 1,2,4-triazolo[3,4-fc][1,3,4]thiadiazole ring system.     

Synthesis of 4-hetaryl-substituted 5-amino- and 5-sulfanyl-1,3-oxazole derivatives

Previously unknown 5-amino- and 5-sulfanyl-1,3-oxazole derivatives containing a 1,3,4-oxadiazole, 1,3,4-thiadiazole, or 1,2,4-triazole fragment at C⁴ were synthesized from accessible 1,3-oxazole-4-carboxylic acid hydrazides.     

6-硝基苯并咪唑杂环衍生物的合成

以６－硝基苯并咪唑－１－乙酰肼和５－（６－硝基苯并咪唑－１－亚甲基）－３－巯基－４－氨基－１,２,４－三唑为原料,在不同条件下合成了一系列新的均三唑〔３,４－ｂ〕－１,３,４－噻二唑,１,２,４－三唑和１,３,４－恶二唑衍生物。化合物的结构均经元素分析、＾１Ｈ ＮＭＲ、ＩＲ和ＭＳ确证,并对其波谱性质进行了讨论。     

微波促进下3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑

微波辐射条件下, 首先由2-苯并呋喃甲酰肼依次与二硫化碳和水合肼反应合成3-(2-苯并呋喃基)-4-氨基-5-巯基- 1,2,4-三唑, 进一步在微波辐射条件下由4-氨基-5-巯基-1,2,4-三唑分别与芳甲酸/芳氧基乙酸、α-溴代苯乙酮及芳醛反应以较高产率制得了相应的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑、1,2,4-三唑并[3,4-b]-1,3,4-噻二嗪及4-芳亚甲基亚胺基-5-巯基-1,2,4-三唑. 产物结构经IR, ¹H NMR, MS及元素分析进行了表征.     

H14[NaP5W30O110] as a Heterogeneous Recyclable Catalyst for the Synthesis of 6,8-Dimethyl-3-aryl-[1,2,4]triazolo[3,4-b][1,3,4]thiazepine Derivatives

6,8-Dimethyl-3-aryl-[1,2,4]triazolo[3,4-b][1,3,4]thiazepine derivatives were synthesized by cyclodehydration of 3-aryl-4-amino-5-mercapto-1,2,4-triazole with 2,4-pentanedione in the presence of a catalytic amount of Preyssler catalyst under very mild conditions.     

Reaction of 3-Formylchromones with 4-Amino-3-Mercapto-5-Phenyl-4H-1,2,4-Triazole Under Phase Transfer Catalysis Conditions - Synthesis of 7-(2′-Hydroxybenzoyl)-3-Phenyl-1,2,4-Triazolo[3,4-b][1,3,]Thiadiazpins

Several substituted 7-(2′-hydroxybenzoyl)-3-phenyl-1,2,4-triazolo[3,4-b][1,3,4]thiadiazepines are synthesised by reacting 3-formylchromones with 4-amino-3-mercapto-5-phenyl-1,2,4-triazole under phase transfer catalysis conditions.     

Syntheses of some new 4-amino-5-(N-methyl-arylsulfonamido)methyl-1,2,4-triazole-3-thiones and their derivatives

The cyclization of 4-amino-5-(N-methyl-arylsulfonamido)methyl-1,2,4-triazole-3-thiones II , synthesized by the Reid and Heindel approach, with α-chloroacetophenone yields 7II-6-aryl-3-(N-methyl-arylsulfon-amido)methyl-s-triazolo[3,4-b][1,3,4]-thiazines III . Novel compounds II also react with benzyl chloride to afford 4-amino-3-benzylthio-5-(N-methyl-arylsulfonamido)methyl-1,2,4-triazole IV . © 1996 John Wiley & Sons, Inc.     

Synthesis of Partially Hydrogenated 1,2,4-Triazoloquinazolines by Condensation of 3,5-Diamino-1,2,4-triazole with Aromatic Aldehydes and Dimedone

Three-component condensation of 3,5-diamino-1,2,4-triazole with aromatic aldehydes and dimedone in dimethylformamide gives 2-amino-5-aryl-8,8-dimethyl-5,6,7,8,9,10-hexahydro[1,2,4]triazolo[3,2-b]quinazolin-6-ones. The reaction of 3,5-diamino-1,2,4-triazole with dimedone in the absence of aldehyde involves dimethylformamide as one of the carbonyl components to afford 2-amino-8,8-dimethyl-6,7,8,9-tetrahydro[1,2,4]triazolo[2,3-a]quinazolin-6-one.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 115–120.Original Russian Text Copyright © 2005 by Lipson, Desenko, Borodina, Shirobokova, Musatov.     

Synthon-Based Approach to the Design of Macroheterocyclic Compounds Using Diaminothiadiazoles and Diamonotriazoles

Russian Journal of General Chemistry - Synthesis and properties of 2,5-diamino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-thiadiazole, 3,5-diamino-1H-1,2,4-triazole,...     

Synthesis of 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazepines and 4-amino-3-acylvinylthio-1,2,4-triazoles by reaction o acylacetylenes with 4-amino-3-mercapto-1,2,4-triazole

1,2,4-Triazolo[3,4-b]-1,3,4-thiadiazepines have been prepared by treating -acetylenic ketones with 4-amino-3-mercapto-1,2,4-triazole in glacial acetic acid. Terminal acetylenic ketones react with the triazole to form 4-amino-3-acylvinylthio-1,2,4-triazoles. Heating the latter with hydrazine hydrate in alcohol yields substituted pyrazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 990–994, July, 1991.     

Chemistry of biureas—I: Cyclisation of ethoxycarbonyl derivatives of thiobiureas and bithioureas

The interaction of ethoxycarbonyl isothiocyanate with semicarbazides or thiosemicarbazides produces 1-ethoxycarbonyl-2-thiobiureas or bithioureas, respectively. The former are cyclisable to 2-ethoxycarbonamido-5-hydroxy-l,3,4-thiadiazole in acid, or to 2(H)-carbamoyl-3-hydroxy-5-alkylthio-1,2,4-triazoles, and thence to 3-hydroxy-5-mercapto-1,2,4-triazole in alkaline media. The ring-closure of the 1-ethoxycarbonylbithioureas proceeds similarly affording, under the influence of acids, 5-amino (or mercapto)-2-ethoxycarbonamido-1,3,4-thiadiazoles. The action of alkali produces compounds derived from 3-hydroxy-5-mercapto-1,2,4-triazole; the isolation, in a selected example, of the 2(H)-phenylthiocarbamoyl-derivative, elucidates the course of this reaction. Hydrazinolysis of 1-ethoxycarbonylbithiourea yields 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole.     

Synthesis and biological activity of some novel derivatives of 4-amino-3-(D-galactopentitol-1-yl)-5-mercapto-1,2,4-triazole

To discover new 1,2,4-triazole derivatives which may possess significant biological activities, we synthesized a series of novel 6-aryl-3-(D-galactopentitol-1-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines and 4-(arylmethylidene)amino-5-(D-galactopentitol-1-yl)-3-mercapto-4H-1,2,4-triazoles from 4-amino-3-(D-galactopentitol-1-yl)-5-mercapto-1,2,4-triazole. All the title compounds were characterized by elemental analysis, IR, 1H- and 13C-NMR. Plant growth-regulating activity tests showed that these compounds have remarkable effects on the growth of radish and wheat.     

Interaction of aminoazoles with Meldrum’s acid and dialkyl ketones or cyclohexanone

Interaction of 3-amino-5-methylpyrazole, 3-amino-5-methylthio-, and 3,5-diamino-1,2,4-triazole with Meldrum’s acid, acetone, ethyl methyl ketone, and cyclohexanone leads to alkyl-substituted pyrazolo[3,4-b]pyridin-6-ones and 1,2,4-triazolo[1,5-a]pyrimidin-7-ones respectively. The structure of 5,5-dimethyl-2-methylthio-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidin-7-one was demonstrated by an X-ray structural investigation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 595–601, April, 2007.     

Synthesis of 9-Aryl-6,6-dimethyl-5,6,7,9-tetrahydro-1,2,4-triazolo[5,1-b]quinazolin-8(4H)ones

The reaction of 3-amino-1,2,4-triazole with arylidene derivatives of dimedone and their potential synthetic equivalents leading to the formation of 9-aryl-6,6-dimethyl-5,6,7,9-tetrahydro-1,2,4-triazolo[5,1-b]quinazolin-8(4H)ones has been studied. The direction of heterocyclization has been established, and the possible mechanisms for the formation of the pyrimidine heterocycle have been analysed.     

Synthesis and Tautomeric Structure of 7-Arylhydrazono-7H-[1,2,4]Triazolo[3,4-b][1,3,4]Thiadiazines

Two synthetic approaches were developed for the title compounds 8a-g via coupling of diazotized anilines with 7-acetyl-6-methyl-3-phenyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine 7 , and reaction of N-aryl 2-oxopropanehydrazonoyl chlorides 9 with 4-amino-3-mercapto-5-phenyl-1,2,4-triazole 1 . The tautomeric structures of 8 were elucidated by their spectral analyses and correlation of their acid dissociation constants with Hammett equation.     

Acid-mediated cycloalkylation of C-aminoazoles with 2,5-dimethylhexane-2,5-diol

Alkylation of 5-aminotetrazole with 2,5-dimethylhexane-2,5-diol in perchloric acid was found to proceed on an endocyclic nitrogen atom as well as on the amino group, giving 5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-4H-tetrazolo[1,5-a][1,3]diazepine. Under analogous conditions, 3-amino-1,2,4-triazole undergoes cycloalkylation of the neighboring N1 and N2 atoms of the heterocycle resulting in 1-amino-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-[1,2,4]triazolo[1,2-a]pyridazinium perchlorate. The crystal structures of the products were determined by single crystal X-ray analysis.