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.     

Cu K-edge EXAFS on copper(I) complexes containing dihydridobis(3-nitro-1,2,4-triazol-1-yl)borate and bis(1,2,4-triazol-1-yl)acetate ligand: Evidence for the Cu–O interaction

X-ray absorption spectroscopy (XAS) has been used to probe the local structure of copper(I) complexes containing the dihydridobis(3-nitro-1,2,4-triazol-1-yl)borate and the bis(1,2,4-triazol-1-yl)acetate ligands. The material is polycrystalline and no crystal structure is available in the literature. The EXAFS analysis has permitted the identification of the local environment of the copper site. Copper is found to be 4-fold coordinated with two sets of Cu–N and Cu–P interactions describing a quasi planar figure. An additional coordination is revealed for the copper(I) complex of bis(1,2,4-triazol-1-yl)acetate due to the interaction of the copper with the acetate of the scorpionate ligand. XANES spectra of the studied samples show a resolved pre-edge peak at about 8983 eV which is assigned to the 1s → 4p transition, whose intensities can be explained considering the copper in a 4-fold coordination.     

Solvatochromic parameters for binary mixtures of 1-(1-butyl)-3-methylimidazolium tetrafluoroborate with some protic molecular solvents

The solvatochromic parameters (ET(N), normalized polarity parameter; pi*, dipolarity/polarizability; beta, hydrogen-bond acceptor basicity; alpha, hydrogen-bond donor acidity) were determined for binary solvent mixtures of 1-(1-butyl)-3-methylimidazolium tetrafluoroborate ([bmim]BF4) with water, methanol, and ethanol at 25 degrees C over the whole range of mole fractions. In nonaqueous solutions, the value of the mixture increases with mole the fraction of [bmim]BF4 and then decreases gradually to the value of pure [bmim]BF4. Positive deviation from ideal behavior was observed for the solvent parameters ET(N), pi*, and alpha, whereas the deviation of the beta parameter is negative. The applicability of the combined nearly ideal binary solvent/Redlich-Kister equation for the correlation of various solvatochromic parameters with solvent composition was proved too for the first time. This equation provides a simple computational model to correlate and/or predict various solvatochromic parameters for many binary solvent systems. The correlation between the calculated and the experimental values of various parameters was in accordance with this model. Solute-solvent and solvent-solvent interactions have been applied for interpretation of the results.     

Solvation in binary mixtures of water and polar aprotic solvents: theoretical calculations of the concentrations of solvent-water hydrogen-bonded species and application to thermosolvatochromism of polarity probes

Thermo-solvatochromism of two polarity probes, 2,6-diphenyl-4-(2,4,6-triphenyl- pyridinium-1-yl)phenolate, RB, and 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl) phenolate, WB, in aqueous acetone, Me2CO, and aqueous dimethylsulfoxide, DMSO, has been studied. The data obtained have been analyzed according to a recently introduced solvation model that explicitly considers the presence of 1:1 organic solvent-water hydrogen-bonded species, S-W, in the bulk binary mixture and its exchange equilibria with (S) and (W) in the solvation shell of the probe. Calculations require reliable values of Kdissoc, the dissociation constant of S-W. Previously, this has been calculated from the dependence of the densities of binary solvent mixtures on their composition. Using iteration, the volume of the hydrogen-bonded species, VS-W, and Kdissoc were obtained simultaneously from the same set of experimental data. This approach may be potentially suspect because Kdissoc, and VS-W are highly correlated. Therefore, we extended a recently introduced approach for the calculation of Valcohol-W to binary mixtures of water with acetone, acetonitrile, N,N-dimethylformamide, DMSO, and pyridine. This approach includes: Determination of VS-W from ab initio calculations by the COSMO solvation model; correction of these volumes for the nonideal behavior of the binary solvent mixtures at different temperatures; use of corrected VS-W as a constant (not an adjustable parameter) in the equation that is employed to calculate Kdissoc (from density versus binary solvent composition). Solvation of RB and WB by Me2CO-W showed different behavior from that of aqueous DMSO. Thus, water is able to displace Me2CO more efficiently than DMSO from the probe solvation shell. Me2CO-W and DMSO-W displace their corresponding precursor solvents; this is more efficient for the former case because the strong DMSO-W interactions attenuate the solvation capacity of this species. Temperature increase resulted in desolvation of both probes, due to concomitant decrease of the structures of the component solvents.     

Synthesis and crystal structure of 2-{5-[2-(2,6-dichlorophenylamino)benzyl]-4-p-tolyl-4H-1,2,4-triazol-3-ylthio}acetate

The compound 2-{5-[2-(2,6-dichlorophenylamino)benzyl]-4-p-tolyl-4H-1,2,4-triazol-3-ylthio}acetate has been prepared and characterized by IR, ¹H NMR, ¹³C NMR and mass spectra. The crystal and molecular structure were further confirmed using single crystal X-ray diffraction. The crystal structure has been found to be stabilized by intermolecular C–H···O interaction generating bifurcated hydrogen bonds whereas the C–H···N interactions generate chain of molecules. The intramolecular N–H···N hydrogen bond forms a ring with S(7) graph-set motif.     

Preferential Solvation in Aqueous–Organic Mixed Solvents Using Solvatochromic Indicators

Solvatochromism of the twisted intramolecular charge-transfer (TICT) fluorescence of 4-(N,N-dimethylamino)benzonitrile (DMABN) in pure water, methanol, ethanol, 1-propanol, 2-propanol, acetone, acetonitrile, and in the corresponding aqueous–organic binary mixed solvents was systematically studied and an empirical solvent polarity scale (F _B) based on the DMABN solvatochromism was defined. The F _B parameters of the explored binary mixed solvents as a function of solvent composition were analyzed by a stepwise solvent-exchange (SSE) model to clarify the preferential solvation (PS) of the probe dye in these binary mixed solvents. Solvation diagrams toward DMABN in the mixed solvents, i.e., the local solvent composition in the solvation shell of DMABN molecules was depicted as a function of bulk solvent composition to visualize the PS in these mixed solvents. For comparison, a similar PS analysis was applied to the solvatochromism of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1- yl)phenolate (ET-30) and pyrene (Py) in these mixed solvents; the responsive PS pattern of the mixed solvents toward the specific indicator dye of DMABN, ET-30, and Py was then discussed in terms of the chemical properties of the probe dye, the properties of the mixed solvents, and the solute–solvent and solvent–solvent interactions.     

α-Oxides in reaction with N-H acids of the heterocyclic series

Anumber of 1-methyl-4-(2-hydroxyalkyl)-3-nitro-1,2,4-triazol-5-ones and their derivatives were obtained by reaction of 1-methyl-3-nitro1,2,4-triazol-5-one with -epoxides. The fact of intramolecular nucleophilic substitution of the nitro group in hydroxy derivatives of 3-nitro-1,2,4-triazol-5-one with cyclization to 2-methyl-3-oxo-5,6-dihydrooxazolo[3,2-b]-1,2,4-triazoline was established.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1407–1410, October, 1977.     

One-potCuAAC synthesis of (1H-1,2,3-triazol-1-yl)methyl-1,3,4/1,2,4-oxadiazoles starting from available chloromethyl-1,3,4/1,2,4-oxadiazoles

The one-pot CuAAC synthesis of (1H-1,2,3-triazol-1-yl)methyl-1,3,4-oxadiazole and (1H-1,2,3-triazol-1-yl)methyl-1,2,4-oxadiazole derivatives via three-component reaction of consequent nucleophilic substitution of chlorine, with azide, and its further “click” reaction, with alkynes, in the presence of CuI was studied. The utility of newly synthesized 2-(azidomethyl)-1,3,4/1,2,4-oxadiazoles and chloromethyl-1,3,4/1,2,4-oxadiazole derivatives was explored, and their limitations were determined. Novel 5-([4-aryl-1H-1,2,3-triazol-1-yl]methyl)-3-(aryl)-1,2,4-oxadiazoles, 2-([4-aryl-1H-1,2,3-triazol-1-yl]methyl)-5-(aryl)-1,3,4-oxadiazoles were obtained in good yields.     

含三唑基希夫碱的锰配合物的合成及结构

合成了4-(4-氯苯基亚甲基)亚胺-1,2,4-三唑希夫碱配体(L),以及希夫碱的配合物[Mn(SO4)(H2O)2L]n,并对配合物进行了结构表征。该配合物是1个用硫酸根桥连而成的一维链状配位聚合物,相邻的链通过水分子和硫酸根的氢键相互作用形成了二维超分子结构。利用DSC技术测试了配合物和固体推进剂主要组分(HMX,NC,RDX)的二元混合体系的热分解行为。本文也对配合物做了元素,红外光谱分析。     

Water-methanol-benzene ternary system. Thermochemical experiment and computer simulation

Solution heats have been measured for benzene dissolved in mixtures of water with methanol at 25°C. The resulting values are compared with data for water-methanol-aniline, water-acetonitrile-benzene, and water-acetonitrile-aniline systems. Computer simulations have been performed for binary mixtures of water with methanol and dilute solutions of benzene in these mixtures. Thermodynamic and structural characteristics of solutions were obtained by calculations. The enthalpy of benzene transfer from water into a mixed solvent correlates with the relative deviation of the local composition from the mean composition of the mixture.     

ORGANISCHE PHOSPHORVERBINDUNGEN 80 HERSTELLUNG VON TRIAZOLYLMETHYL-PHOSPHONATEN UND VON TRIAZOLYL-METHYLPHOSPHONIUMSALZEN UND DEREN VERWENDUNG IN DER WITTIG-HORNER REAKTION

Abstract

Attempts to prepare 1H-1,2,4-triazol-1-ylmethylphosphonates (4 and 5) by a Mannichtype reaction or by transesterification of 1-hydroxymethyl-1H-1,2,4-triazol 1 with tertiary phosphites failed. On the other hand 4 and 5 are obtained by a Michaelis-Becker reaction from 1-chloromethyl-1H-1,2,4-triazol 3 and sodium phosphites in high yield. The Michaelis-Arbuzov reaction is less suited for the preparation of 4 and 5. 3 is obtained in good yield as a water clear liquid, b.p. 52–54°C/0.2 torr, from the interaction of 1 with thionyl chloride followed by treatment with a base. On standing at 0° or 20°C it decomposes within hours and yields the unsymmetrical methylen-bis(triazol) 3a in addition to other products. However an acetonitrile solution of 3 is stable for months. Heating this solution with tertiary phosphines gives triazolylsubstituted phosphoniumsalts 6 to 8. The Wittig-Horner reaction with 4 to 6 gives the olefinically substituted triazols 9–12 as a Z/E mixture in high yield. Alkylation of 4 with methyl-and ethyl iodide gives the corresponding alkylated diethyl-1H-1,2,4-triazol-1-yl-ethyl-1-and-propyl-1-phosphonates 14 and 15 which on hydrolysis with HCI yield 1H-1,2,4-triazol-1-yl-ethyl-1-and propyl-1-phosphonic acids 17 and 18, respectively. Hydrolysis of 4 gives the unsubstituted 1H-1,2,4-triazol-1-ylmethyl-phosphonic acid, 16.     

On triazoles. XXI. Synthesis of 1,2,4-triazolyldithiocarbonates

The reaction of 5-amino-1,2,4-triazoles 1 with carbon disulfide and alkylating agents in basic condition to yield alkyl, aralkyl and aryl (5-amino-3-Q-1,2,4-triazol-1-yl)dithiocarbonates 2 and alkyl (3-Q-1,2,4-triazol-5-yl-amino)dithiocarbonates 3 was studied. The isomeric and tautomeric structure of derivatives obtained was proved with the help of their uv, pmr and cmr spectra using model compounds prepared for this purpose. The results obtained enabled us to correct some confusion in the literature.     

Solvatochromism of Heteroaromatic Compounds: IX. Anions of 3-Nitro-1,2,4-triazol-5-ones

Solvatochromism of the long-wave band in the electronic absorption spectra of 3-nitro-1,2,4-triazol-5-one anions was studied and quantitatively described with the Kamlet-Taft solvent parameters. Azole anions are specifically solvated in amphiprotic solvents. The strength of the hydrogen bond in H complexes with amphiprotic solvents decreases in going to the Franck-Condon excited state. The UV and IR specrta show that 3-nitro-1,2,4-triazol-5-one anions, in contrast to nitroazole anions, are specifically solvated with participation of the carbonyl group. In highly polar organic solvents the 3-nitro-1,2,4-triazol-5-one anion mainly exists in the form of the 1H tautomer.     

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale (E(T)) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.     

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.     

Nitration of Triazolyl-substituted Ketones

By nitration of 3-R-1,2,4-triazol-1-ylalkanones with a mixture of concentrated sulfuric and nitric acids a series of compounds was obtained containing a trinitromethyl fragment at the nitrogen of the ring.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 767–771.Original Russian Text Copyright © 2005 by Kofman, Kartseva, Glazkova, Krasnov.     

Thermosolvatochromism of betaine dyes revisited: theoretical calculations of the concentrations of alcohol-water hydrogen-bonded species and application to solvation in aqueous alcohols

Solvatochromic data of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB) in aqueous methanol, 1-propanol, 2-propanol, and 2-methyl-2-propanol at 25 degrees C were recalculated by employing a recently introduced model that explicitly considers the presence of 1:1 alcohol-water hydrogen-bonded species, ROH-W, in bulk solution and their exchange equilibria with water and alcohol in the probe solvation microsphere. The thermosolvatochromic behavior of RB in aqueous ethanol was measured in the temperature range from 10 to 60 degrees C; the results thus obtained were treated according to the same model. All calculations require reliable values of Kdissoc, the dissociation constant of the ROH-W species. This was previously calculated from the dependence of the density of the binary solvent mixture on its composition. Through the use of iteration, the volume of the hydrogen-bonded species, VROH-W, and Kdissoc are obtained simultaneously from the same set of experimental data. This approach may be potentially problematic because Kdissoc and VROH-W are highly correlated. Therefore, we introduced the following approach: (i) VROH-W was obtained from ab initio calculations, (ii) these volumes were corrected for the nonideal behavior of the binary solvent mixtures at different temperatures, (iii) corrected VROH-W values were employed as a constant in the equation used to calculate Kdissoc (from density vs binary solvent mixture composition). VROH-W calculated by the COSMO-RS solvation model fitted the density data better than those calculated by the IEFPCM model. In all aqueous alcohols, solvation by ROH-W is favored over that by the two precursor solvents. In aqueous ethanol, a temperature increase resulted in a gradual desolvation of RB, due to a decrease in the hydrogen-bonding of both components of the mixture. The microscopic polarities of ROH-W are much closer to those of the precursor alcohols.     

Nitrosation of 4-amino-1-phenacyl-1,2,4-triazolium bromides and ω-(1,2,4-triazol-1-yl)acetophenones

The reaction of 4-amino-1-phenacyl-1,2,4-triazolium bromides with an excess of nitrous acid leads to a mixture of the corresponding -(1,2,4-triazol-1-yl)-acetophenones and -hydroximino--(1,2,4-triazol-1-yl)acetophenones. Products of the latter type are formed during nitrosation at the methylene group of both the intermediate -triazolylacetophenones, and the starting 4-amino-1-phenacyl-1, 2,4-triazolium bromides. The role of Br^– as a catalyst is significant for both nitrosation paths. In the reaction of -(1,2,4-triazol-1-yl)acetophenones with HNO₂, SCN^– is a more active catalyst than Br^–. During the nitrosation of para-substituted 4-amino-1-phenacyl-1,2,4-triazolium bromides, the yield of -hydroximino--(1,2,4-triazol-1-y1)acetophenones increases with increase in the acceptor properties of the aryl substituent, which is explained by the increase in the CH-acidity of the nitrosation substrates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2821–2824, December, 1991.     

Picryl derivatives of 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one

Treatment of 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one ( 1 ) with picryl fluoride (PkF) in 1-methyl-2-pyrrolidinone (NMP) gave a mixture of a monopicryl and a dipicryl derivative of 1 in a ratio of 2 :1 , respectively, regardless of the initial concentrations of 1 and PkF. The products were identified as 5-nitro-2-picryl-2,4-dihydro-3H-1,2,4-triazol-3-one ( 2 ) by X-ray crystallography and 5-nitro-2,4-dipicryl-2,4-dihydro-3H-1,2,4-triazol-3-one ( 4 ) by ¹⁵N labeling experiments.     

Synthetic routes towards tetrazolium and triazolium dinitromethylides

Tetrazolium-5-dinitromethylide sodium salt has been prepared (91%) by cyclization of 1-amino-1-hydrazino-2,2-dinitroethene with nitrous acid in water. 5-Imino-1-(hydroxyiminonitromethyl) derivatives were obtained by nitration of 2-(5-amino-1,3-dimethyl-1H-1,2,4-triazol-4-ium-4-yl)- and 2-(5-amino-4-methyl-1H-tetrazolium-1-yl)acetate complex salts. Treatment of 4-methyl-1-(2-oxopropyl)-1-tetrazolium methylsulfate with nitric and sulfuric acid gave methyl (3-nitro-1,2,4-oxadiazol-5-yl)amine (27%) probably via dinitromethylide followed by cyclization and loss of nitrogen.__________Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 127–134, January, 2005.