Coordination Compounds of Copper(II) with Bis(5-amino-1,2,4-triazol-3-yl)alkanes

Procedures for synthesis of coordination compounds of copper(II) with bis(5-amino-1,2,4-triazol-3-yl)alkanes as ligands. A conclusion was drawn that the coordination polyhedron of copper(II) has different configurations depending on the structure of the ligand and on the coordination mode.     

3-(4-Phenyl-1,2,4-triazol-3-yl)chromones

The condensation of 4-phenyl-1,2,4-triazol-3-ylacetonitrile with 2-methyl-, 4-ethylresorcinol, and with pyrogallol gave α-(4-phenyl-1,2,4-triazol-3-yl)-2,4-dihydroxyacetophenones. Upon treatment with acid anhydrides and chlorides and subsequent hydrolysis these form 7-hydroxy-3-(4-phenyl)-1,2,4-triazol-3-yl)chromones with different substituents in both the benzene and the pyrone rings. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1676–1684, November, 2005.     

Synthesis of 5-azaadenine derivatives from N-(1,2,4-triazol-5-yl)amidines

A method is proposed for the synthesis of N-substituted 5-azaadenines. The condensation of N-(1,2,4-triazol-5-yl)amidines with trichloroacetonitrile gives trichloromethyl derivatives of 1,2,4-triazolo[1,5-a]-1,3,5-triazines, which are converted by the action of primary or secondary amines into N-alkylamino- or N,N-dialkylamino-1,2,4-triazolo-[1,5-a]-1,3,5-triazines (5-azaadenines).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 241–243, January, 1991.     

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.     

Synthesis,Crystal Structure,and Luminescence of Cadmium(II) and Silver(I) Coordination Polymers Based on 1,3-Bis(1,2,4-triazol-1-yl)adamantane

Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO₃]_n, in which metal ions are linked by 1,3-bis(1,2,4-triazol-1-yl)adamantane ligands, coordinated by nitrogen atoms at positions 2 and 4 of 1,2,4-triazole rings. Layers of the coordination polymer consist of rare 18- and 30-membered {Ag₂L₂} and {Ag₄L₄} metallocycles. Cadmium(II) nitrate formed two kinds of one-dimensional coordination polymers depending on the metal-to-ligand ratio used in the synthesis. Coordination polymer [Cd(L)₂(NO₃)₂]_n was obtained in case of a 1:2 M:L ratio, while for M:L = 2:1 product {[Cd(L)(NO₃)₂(CH₃OH)]·0.5CH₃OH}_n was isolated. All coordination polymers demonstrated ligand-centered emission near 450 nm upon excitation at 370 nm.     

Synthesis of N-(1,2,4-triazol-5-yl)amidines from 5-amino-1,2,4-triazole and nitriles using tributylborane

A method is proposed for the synthesis of N-(1,2,4-triazol-5-yl)amidines not previously described in the literature from 5-amino-1,2,4-triazole and nitriles using tributylborane as an auxiliary reagent. The structures of the products were indicated by physicochemical methods.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2353–2355, October, 1989.     

Synthesis, Structure and Biological Activities of 2- （4-Met hoxybenzoyl ）-N-phenyl- 2- （ 1,2,4-triazol- 1-yl ） thioacetamide

The title compound, 2-(methoxybenzoyl)-N-phenyl-2-(1,2,4-triazol-l-yl) thioacetamide was synthesized by several reactions from 4-methoxyacetophenone, triazole and phenyl isothiocyanate. The structure was identified by elemental analysis, ^1H NMR, MS and IR. The single crystal structure of 2-(methoxybenzoyl)-N-phenyl-2-(1,2,4-triazol-l-yl)thioacetamide was determined withX-ray diffraction. The preliminary bioassays show that the title compound exhibits weak antifungal activities and plant-growth regulatory activity.     

Optimization of the synthesis of 5-amino-1,2,4-triazol-3-ylacetic acid and bis(5-amino-1,2,4-triazol-3-yl)methane

The influence of the molar ratio and concentration of the reactants and of the temperature and time of the synthesis on the yield of malonic acid guanylhydrazides in the reaction of aminoguanidine with malonic acid in acidic aqueous solutions was examined, and improved procedures for preparing 5-amino-1,2,4-triazol-3-ylacetic acid and bis(5-amino-1,2,4-triazol-3-yl)methane were suggested.     

New derivatives of N-vinyltriazoles: 1,3-diaryl-3-(1H-1,2,4-triazol-1-yl)-2-propen-1-ones

We have synthesized previously unknown N-vinyltriazoles:1,3-diaryl-3-(1H-1,2,4-triazol-1-yl)-2 propen-1-ones. We discuss a hypothesis for a probable reaction mechanism. Institute of Chemistry, Academy of Sciences of the Moldavian Republic, Kishinev 277028. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 910–914, July, 1995. Original article submitted March 24, 1995.     

Recyclization of 7-hydroxy-3-(4-phenyl-1,2,4-triazol-3-yl)-chromones using binucleophiles

The recyclization of 2-R-7-hydroxy-3-(4-phenyl-1,2,4-triazol-3-yl)chromones using the binucleophiles hydroxylamine, hydrazine, or guanidine gave isoxazoles, 2-aminochromones, pyrazoles, or pyrimidines with a 4-phenyl-1,2,4-triazol-3-yl substituent. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 571–578, April, 2006.     

Quantum-chemical study of the structure and magnetic properties of mono- and binuclear Cu(II) complexes with 1,3-bis(3-(pyrimidin-2-yl)-1<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazol-5-yl)propane

On the basis of X-ray crystallographic data on molecular copper complexes with 1,3-bis(3-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl)propane, quantum-chemical optimization of their equilibrium structure has been performed by the density functional theory method with subsequent analysis of the electron density distribution by Bader’s atoms in molecules method and g-factor anisotropy calculation. The topological parameters of electron density at the Cu–N bond critical points have been considered, and the bond energies have been estimated using the Espinosa equation. A phenomenon of variable coordination of nitrate ions with Cu(II) ions in the inner coordination sphere of the mononuclear copper complex with 1,3-bis(3-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl)propane has been revealed. The contributions of different components to the gfactor anisotropy have been analyzed in the framework of the gauge-independent atomic orbital method. The largest contribution to the g-factor is made by the orbital (Zeeman) and spin–orbit components accounting for very high averaged g-factor values of 2.1413 and 2.5636 for the doublet state of the mononuclear complex and the triplet state of the binuclear complex, respectively.     

Spacer-Armed Copper(II) Complex Based on Bis(2-pyidyl-1,2,4-triazol-3-yl)butane and 1-Aminoethane-1,1-Diphosphonic Acid

Russian Journal of Coordination Chemistry - The new complex [Cu4L2(H2AEDP)2(H2O)4] · 34H2O was prepared by the reaction of CuSO4 with bis(2-pyridyl-1,2,4-triazol-3-yl)butane (H2L) and...     

Reactivity of 3,5-bis-(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole

Alkylation of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole with haloalkanes afforded N-CH₂R derivatives, and nitration furnished the corresponding bis-N-nitramine isolated as a trisodium salt. Treatment of the latter with CH₃I resulted in denitration. Diazotization and oxidation of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4- triazole, its N-methyl and N-carboxy derivatives gave rise to the corresponding azido and nitro derivatives. Salts of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazol-5-acetic acid with nitrogen-containing bases were synthesized. It was established that the character of reaction products of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole with formaldehyde depended on the acid-base properties of the medium.__________Translated from Zhurnal Organicheskoi Khirmii, Vol. 41, No. 2, 2005, pp. 270–276.Original Russian Text Copyright © 2005 by Sergievskii, Romanova, Mel’nikova, Tselinskii.     

1,2,4-Triazolium-5-ylidene and 1,2,4-triazol-3,5-diylidene as new ligands for transition metals

Ab initio calculations show the 1,2,4-triazolium-5-ylidene (3a) and 1,2,4-triazol-3,5-diylidene (4a) are true minima on the potential surface. As expected, 4a is much higher in energy than its triazole isomers 5a, 6a and 8a and the 1,2,4-triazol-3-ylidene (7a). Sodium methoxyde adds to the diquaternary salt of 1,2,4-triazoles (9b,c) to give the corresponding monocationic heterocycles 10b,c in 70 and 50% yield, respectively. One equivalent of silver(I) acetate reacts with 9b leading to the bis(1,2,4-triazolium-5-ylidene)silver(I) complex (11b) in 80% yield. Under the same experimental conditions, but using two equivalents of silver(I) acetate, solid-state one-dimensional polymers 12′b,c featuring the coplanar 1,2,4-triazol-3,5-diylidene ligands coordinated to silver(I) are obtained in 90% yield. 12′c has been fully characterized including a single-crystal X-ray diffraction study.     

(Z)-3,3-二甲基-1-(1H-1,2,4-三唑-1-基)-2-丁酮肟(5-芳基-1,3,4-噁二唑-2-基)甲基醚的合成和抑菌活性

以3,3-二甲基-1-（1H-1,2,4-三唑基）-2-丁酮肟为原料,经醚化、肼解及腙化3步反应得到（E）-N'-（取代苯亚甲基）-2-[（Z）-3,3-二甲基-1-（1H-1,2,4-三唑-1-基）丁基-2-亚甲氨氧基]乙酰肼（3a~3u）,化合物3与二乙酸碘苯（IBD）反应,合成了21个（Z）-3,3-二甲基-1-（1H-1,2,4-三唑-1-基）-2-丁酮肟-（5-芳基-1,3,4-噁二唑-2-基）甲基醚（4a~4u）,化合物4的化学结构经核磁共振谱、高分辨质谱和元素分析确证.采用单晶X射线衍射仪测定了化合物4c的晶体结构.抑菌活性测试结果表明,在500 mg/L浓度下,化合物4k,4f,4j和4n对纹枯病菌的防效率分别为70.9%,60.2%,60.0%和60.6%;在25 mg/L浓度下,化合物4b,4c,4d和4e对菌核病菌的抑制率为71.8%~76.9%.     

手性1-芳基-2-(1H-1,2,4-三唑-1-基)乙醇衍生物的合成与生物活性

取代苯乙烯1与KHSO₅在手性催化剂2存在的条件下反应, 生成1-芳基环氧化物3, 3与1H-1,2,4-三唑在固体碳酸钾催化下作用, 得到手性的1-芳基-2-(1H-1,2,4-三唑-1-基)乙醇衍生物4. 部分4对甾醇14α-脱甲基化酶表现出强结合作用.     

3-芳基-1-(吡啶-3-基)-2-(1H-1,2,4-三唑-1-基)-2-丙烯-1-醇的合成及生物活性研究

用硼氢化钠还原3-芳基-1-(吡啶-3-基)-2-(1H-1,2,4-三唑-1-基)丙烯酮, 合成了10个新型含吡啶基的三唑醇类化合物. 所有化合物均经核磁、元素分析确证. 生物活性测试结果表明, 部分化合物具有一定的杀菌活性及植物生长调节活性.     

Synthesis and biological activity of (3,5-disubstituted-1H-1,2,4-triazol-1-yl)benzophenone derivatives

The synthesis of (5-acylaminomethyl-3-carbamoyl-1H-1,2,4-triazol-1-yl)benzophenone derivatives 4a-i, 14a-d, 15a-d, 16a-c , is described. Acylation of the key intermediate, 1-benzoylphenylazo-1-aminoacetamide 7, followed by cyclization in the presence of acid afforded 1H-1,2,4-triazole derivatives. These compounds were evaluated for their central nervous system (CNS) activity. Some of these compounds exhibited high activities in anti-pentylene tetrazole and rotarod test in mice when orally administered.     

Kinetics of rearrangement of 2,4-dichlorophenyl-(1H-1,2,4-triazol-1-ylmethyl)ketone enol acetate

The kinetics of rearrangement of 2,4-dichlorophenyl(1H-1,2,4-triazol-1-ylmethyl)ketone enol acetate into 2,4-dichlorophenyl(5-acetyl-1H-1,2,4-triazol-l-ylmethyl)ketone were investigated by¹H NMR spectroscopy. It was shown that this rearrangement is a first-order reaction. The rate constant was measured in the 129–156°C range and the activation parameters of the reaction were determined. A hypothesis concerning the intramolecular character of the observed rearrangement was drawn based on the kinetic data.Institute of Chemistry, Academy of Sciences of the Moldovian Republic, 277014 Kishinev. All-Union Scientific-Research Institute of Chemical Agents for the Protection of Plants, Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2284–2287, October, 1992.     

Some features of the crystal and molecular structure of N-(1,2,4-triazol-5-yl)benzamidine and its hydrochloride

The crystal and molecular structures of N-(1,2,4-triazol-5-yl)benzamidine (1) and its hydrochloride (2) were determined by x-ray crystallography. In compound 1 both independent molecules are Z isomers of the anidine substituted in the imino group and 5-substituted 1H-1,2,4-triazoles. In the crystal the molecules of compound 1 are linked into a stable dimer by intermolecular hydrogen bonds. An undissociated HCl molecule was unexpectedly found in the structure of compound 2, while the structure of the base corresponded to the Z isomer of the amidine substituted in the amino group and to 2H-1,2,4-triazole substituted at position 5. The structures of compounds 1 and 2 are stabilized by an intramolecular hydrogen bond. The HCl molecule participates in the formation of intermolecular hydrogen bonds in compound 2.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1380–1386, June, 1992.