Synthesis of first representatives of 5-diazo-1,2,3-triazol-4-ones

Russian Chemical Bulletin - A new intramolecular reaction involving neighboring (tert-butyl-NNO-azoxy) and N-nitroamine groups was found, which gave the first representatives of...     

Synthesis of 4-methylthio-1,2-dithiolane and 5-methylthio-1,2,3-trithiane. Two naturally occurring bioactive compounds

Syntheses of the title compounds are described. A method has been developed for the synthesis of 2-methylthio-1,3-propanedithiol, which on treatment with iodine or sulphurdichloride yields 4-methylthio-1,2-dithiolane and 5-methylthio-1,2,3-trithiane respectively.     

N-alkylation of 4-chloro-5-cyano-1,2,3-triazole with orthoformic acid derivatives

The N-alkylation of 4-chloro-5-cyano-1,2,3-triazole with methyl and ethyl orthoformate, and the dimethyl, diethyl and ethylene acetals of DMF has been examined. Methylation gives all three N-methyl isomers, whereas ethylation and hydroxyethylation gives the 2-N-alkyl derivatives only. It has been shown for the first time that it is possible to use DMF ethylene acetal to obtain N-hydroxyethylazoles. The structures of the products were established by¹³C NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 920–924, July, 1988.     

Synthesis and evaluation of the influence of 5-sulfanyl-1,2,3-triazol-1-ylaminocarboxylic acid derivatives on kinetics of ascorbic acid oxidation

1,2,3-Thiadiazolylureas containing amino acid residues were synthesized. These compounds were converted to 5-sulfanyl-1,2,3-triazol-1-ylaminocarboxylic acid sodium salts under alkaline conditions. These salts were found to inhibit the oxidation of ascorbic acid with air oxygen. In the presence of the equimolar amount of 5-sulfanyl-1,2,3-triazoles, the rate of diminution of ascorbic acid decreased by 1.5—3 times, whereas in the case of their two-fold excess by a factor of 5.     

Triple Equilibrium in N'-Aryl-N-tosyldiazomalonimidolates, 1-Tosyl-1,2,3-triazol-5-olates, and 1-Aryl-1,2,3-triazol-5-olates

A series of 1-tosyl-substituted 4-arylcarbamoyl-1,2,3-triazol-2-olates, which can undergo rearrangement to isomeric 1-aryl-4-tosylcarbamoyl-1,2,3-triazol-5-olates and N-tosyl-N'-aryldiazomalonimidolates, were synthesized. An equilibrium between these compounds is observed in solutions in DMSO. The introduction of an electron-withdrawing substituent into the aryl residue increases the stability of the 1-tosyl-1,2,3-triazoles but reduces the stability of the 1-aryl-1,2,3-triazoles. -Donating substituents increase the stability of the open-chain structure.     

Recyclization of substituted furoxans into 1,2,3-triazol-1-oxide derivatives

The effect of the position and nature of substituents on the recyclization of substituted furoxans has been established.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences (RAN), Moscow 117913, Russia Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences (RAN), Chernogolovka 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 202–209, February, 1999.     

Synthesis of isomerically pure 3-(5-trifluoromethyl-1,2,3-triazol-4-yl)cinnamic acid derivatives via the reaction of 4-aryl-6-trifluoromethyl-2-pyrones with sodium azide

Treatment of 4-aryl-6-trifluoromethyl-2-pyrones with sodium azide in DMSO afforded the corresponding (Z)-3-(5-trifluoromethyl-1,2,3-triazol-4-yl)cinnamic acids in good yields. Similarly, 4-aryl-3-carbethoxy-6-trifluoromethyl-2-pyrones smoothly reacted with sodium azide in acetonitrile to produce (E)-2-ethoxycarbonyl-3-(5-trifluoromethyl-1,2,3-triazol-4-yl)cinnamic acids in high yields, whereas their reactions in ethanol, accompanied by a configurational change, gave the thermodynamically more stable (Z)-2-ethoxycarbonyl-3-(5-trifluoromethyl-1,2,3-triazol-4-yl)cinnamic acids.     

Synthesis and Properties of 1-Arylsulfonyl-1,2,3-triazol-5-olates

A series of 1-arylsulfonyl-4-carbamoyl-1,2,3-triazol-5-olates has been synthesized. The cyclization of diazoacetamides by the action of base has been shown to be reversible for the first time. 1-Arylsulfonyl-1,2,3-triazol-5-olates undergo rearrangement upon heating to give isomeric N-sulfonylcarbamoyldiazoacetimidolates. An equilibrium exists between these isomers in DMSO solution, which is shifted toward the acyclic derivative.     

Quantum chemical computational studies on 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester

The optimized molecular geometry, vibrational frequencies, and gauge including atomic orbital (GIAO) (1)H and (13)C NMR shift values of 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester have been calculated by using Hartree-Fock (HF) and density functional method (DFT/B3LYP) with 6-31G(d), 6-31G(d,p) and LANL2DZ basis sets. The optimized molecular geometric parameters were presented and compared with the data obtained from X-ray diffraction. In order to fit the calculated harmonic wavenumbers to the experimentally observed ones, scaled quantum mechanics force field (SQM FF) methodology was proceeded. Correlation factors between the experimental and calculated (1)H chemical shift values of the title compound in vacuum and in CHCl(3) solution by using the conductor-like screening continuum solvation model (COSMO) were reported. The calculated results showed that the optimized geometry well reproduces the crystal structure. The theoretical vibrational frequencies and chemical shifts are in very good agreement with the experimental data. In solvent media the energetic behavior of the title compound was also examined by using the B3LYP method with the 6-31G(d) basis set, applying the COSMO model. The obtained results indicated that the total energy of the title compound decreases with increasing polarity of the solvent. Furthermore, molecular electrostatic potential (MEP), natural bond orbital (NBO) and frontier molecular orbitals (FMOs) of the title compound were performed by the B3LYP/LANL2DZ method, and also thermodynamic parameters for the title compound were calculated at all the HF and B3LYP levels.     

3-Nitro-1,2,4-triazol-5-one derivatives

3-Nitro-1,2,4-triazol-5-one and its monomethyl derivatives react with methyl vinyl ketone to give products of addition to the ring N₁ and N₄ atoms. The reaction with formaldehyde and N-methylolacetamide proceeds only at the N₁ atom. The keto derivatives of 3-nitro-1,2,4-triazol-5-one undergo the Schmidt reaction to give the corresponding acetamides. A number of compounds that include functional groups in the N₁-alkyl substituent of the 3-nitro ring were obtained by treatment of the bases of N₁-substituted 3,5-dinitro-1,2,4-triazoles in aprotic media.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 552–558, April, 1981.     

Synthesis and Antibacterial Activities of 4-Amino-3-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-5-mercapto-1,2,4-triazoles/2-Amino-5-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-1,3,4-thiadiazoles and Their Derivatives

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Crystal Structure of Ethyl 2-Methylthiamethylene-5-(4-bromoanilino)- 2H-1,2,3-triazol-4-carbonate

Compound ethyl 2-methylthiamethylene-5-(4-bromoanilino)-2H-1,2,3-triazol-4-carbonate (6), C13H17BrN4O2S,Mr=373.28, crystallizes in the monoclinic P21/n space group with unit cell parameters a=0.55220(10) nm, b=2.6996(5)nm, c= 1.0596(2) nm, α= 90.00°, β= 103.83(3)°, γ=90.00°, V= 1.5338(5) nm3, Z=4, Dx= 1.617 Mg·m-3. The final Rwas 0.0488.     

Synthesis of 1-Substituted 3-Alkyl-1,2,3-triazol-3-ium-5-olates

Alkylation of 1-substituted sodium 1,2,3-triazol-5-olates with halogen derivatives occurs at the nitrogen atom in position 3 of the heteroring to give zwitterionic 1,2,3-triazol-3-ium-5-olates.     

3-(4-Thiocarbamoyl-1,2,3-triazol-1-yl)benzo-15-crown-5: synthesis and properties

A reaction of 1,2,3-thiadiazole-4-carbaldehyde with 3-aminobenzo-15-crown-5 involves the Cornforth rearrangement of the 1,2,3-thiadiazole ring, which leads to 1,2,3-triazole-4-carbothioamide containing the benzocrown ether substituent in position 1 of the triazole ring. Reversible formation of the isomeric thiadiazole occurs in aprotic nonpolar solvents such as deuterated chloroform. These compounds are suitable for extraction of α-amino acids from an aqueous phase.     

Deep blue luminescent cyclometallated 1,2,3-triazol-5-ylidene iridium(iii) complexes

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Synthesis and selected transformations of 1-(5-methyl-1-aryl-1H-1,2,3-triazol-4-yl)ethanones and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl]ethanones

By cycloaddition of arylazides to acetylacetone are obtained derivatives of 1,2,3-triazole. In the reaction of 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] ethanones (VIIa-VIIe) with isatin are obtained 2-[1-(R-phenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-4-quinolinecarboxylic acids (IIIa–IIIe) and 2-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] -4-quinolinecarboxylic acids (IXa, IXb), respectively. We found that 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) readily transform into [5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] acetic acids (IVa–IVc) by the method of Wilgerodt-Kindler. The (5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)acetic acid reacts with 5-phenyl-4-amino-4H-1,2,4-triazol-3-thiol affording 6-[(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl) methyl]-3-phenyl[1,2,4] triazolo[3,4-b] [1,3,4] thiadiazole (VI). Original Russian Text ? N.T. Pokhodylo, R.D. Savka, V.S. Matiichuk, N.D. Obushak, 2009, published in Zhurnal Obshchei Khimii, 2009, vol. 79, no. 2, pp. 320–325.     

A tandem of the Cornforth rearrangements of 4-(1,2,3-triazol-1-yl)iminomethyl-1,2,3-thiadiazole

The method for the synthesis of 5-(2,6-dimethylmorpholino)-1,2,3-thiadiazole-4-carbaldehyde was proposed. Its reaction with sodium 1-amino-4-(N-methyl)carbamoyl-1,2,3-triazol-5-olate proceeds through a tandem of the Cornforth rearrangements. The initially formed azomethine isomerizes into sodium 4"-(2,6-dimethylmorpholino)thiocarbonyl-4-(N-methyl)carbamoyl-1,1"-bis[1,2,3]triazolyl-5-olate, which then rearranges to give sodium 4-{N-[4-(2,6-dimethylmorpholinothiocarbonyl)-1,2,3-triazol-1-yl]carbamoyl}-1-methyl-1,2,3-triazol-5-olate.