Palladium(II) and platinum(II) complexes of bidentate 2-pyridyl-1,2,3-triazole “click” ligands: Synthesis,properties and X-ray structures

The synthesis and characterization of palladium(II) and platinum(II) complexes of isomeric bidentate 2-pyridyl-1,2,3-triazole “click” ligands is reported. The complexes have been fully characterized by elemental analysis, HRESI-MS, IR, UV–Vis, ¹H and ¹³C NMR spectroscopy. Additionally, the molecular structures of the Pd(II) and Pt(II) complexes of the 2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]pyridine ligand are confirmed by X-ray crystallography. Solution studies indicate the 2-(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine ligand forms more stable complexes with Pd(II) and Pt(II) than the isomeric 2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]pyridine ligand.     

Synthesis and molecular docking studies of novel 1,2,3-triazole ring-containing 4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol derivatives as COX inhibitors

Research on Chemical Intermediates - A series of novel 3-phenyl-1-(4-(4-((4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy)methyl)-1H-1,2,3-triazol-1-yl)phenyl)prop-2-en-1-one derivatives 6a–j...     

Photoluminescent copper(I) complexes with amido-triazolato ligands

A series of heteroleptic copper(I) complexes incorporating amido-triazole and diphosphine ligands, [Cu(I)(N-phenyl-2-(1-phenyl-1H-1,2,3-triazol-4-yl)aniline)(dppb)] (1), [Cu(I)(N-(4-methylphenyl)-2-(1-phenyl-1H-1,2,3-triazol-4-yl)aniline)(dppb)] (2), [Cu(I)(N-(4-methoxyphenyl)-2-(1-phenyl-1H-1,2,3-triazol-4-yl)aniline)(dppb)] (3), [Cu(I)(N-(4-chlorophenyl)-2-(1-phenyl-1H-1,2,3-triazol-4-yl)aniline)(dppb)] (4), [Cu(I)(2,6-dimethyl-N-[2-(1-phenyl-1H-1,2,3-triazol-4-yl)phenyl]aniline)(dppb)] (5), [Cu(I)(2,6-dimethyl-N-[2-(1-benzyl-1H-1,2,3-triazol-4-yl)phenyl]aniline)(dppb)] (6), (dppb = 1,2-bis(diphenylphosphino)benzene), have been prepared. The complexes adopt a distorted tetrahedral geometry in the solid state with the amido-triazole ligand forming a six-member ring with the Cu(I) ion. The complexes exhibit long-lived photoluminescence with colors ranging from yellow to red-orange in the solid state, in frozen glass at 77 K, and in fluid solution with modest quantum yields of up to 0.022. Electrochemically, complexes 1-4 show irreversible oxidation waves while 5 and 6 are characterized by quasi-reversible oxidations as determined by cyclic voltammetry. For 1-4, the emission energy and oxidation potential are found to vary linearly with the Hammett parameter σ(p) of the substituent in the para position of the amido ligand, while in 5 and 6, large differences in emission are observed because of the nature of N3 substitution in the triazole ring. Density functional theory calculations have been performed on the singlet ground states (S(o)) of all complexes at the BP86/6-31G(d) level to assist in assignment of the excited states. On the basis of both experimental and computational results, we have assigned the excited states as intraligand + metal-to-ligand charge transfer (3)(ILCT+MLCT) or ligand-to-ligand charge transfer mixed with MLCT (3)(MLCT +LLCT) in these complexes.     

三唑类白杨素衍生物的设计、合成及其抗增殖活性研究

合成了2个系列的白杨素衍生物,采用噻唑蓝(MTT)法测试了所有化合物针对六种肿瘤细胞的体外抗增殖活性,包括MGC-803, BEL-7402, HepG2, HeLa, A549以及SGC-7901细胞.实验结果显示, 7-[1-(3-氟苯基)-1H-1,2,3-三唑-4-甲氧基]-白杨素(1c)与7-[1-(2-氯苯基)-1H-1,2,3-三唑-4-甲氧基]-白杨素(1g)针对MGC-803细胞的活性与先导化合物白杨素及阳性对照药5-氟尿嘧啶相比显著提高.因此,化合物1c与1g具有深入研究用以开发抗癌药物的潜能.     

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.     

Synthesis and molecular docking studies of novel 2-phenyl-4-{4-[(1-phenyl-1H-1,2,3-triazol-4-yl)methoxy]benzylidene}oxazol-5(4H)-one derivatives

Russian Journal of General Chemistry - 2-Phenyl-4-{4-[(1-phenyl-1H-1,2,3-triazol-4-yl)methoxy]benzylidene}oxazol-5(4H)-one derivatives were synthesized by click chemistry reactions. Exploration of...     

Synthesis and in-vitro antioxidant activities of some coumarin derivatives containing 1,2,3-triazole ring

A new green protocol was developed for the S-alkylation of 2-mercapto-1,3,4-oxadiazole by the reaction of 5-substituted-2-mercapto-1,3,4-oxadiazole with propargyl bromide in sodium bicarbonate in water. The newly synthesized 5-[(substitutedphenoxy)methyl]-2-[(prop-2-yn-1-yl)sulfanyl]-1,3,4-oxadiazole when reacted with azidomethyl coumarins underwent regioselective reaction yielding 4-(((4-((5-((substitutedphenoxy)methyl)-1,3,4-oxadiazol-2-yl)sulfanylmethyl)-1H-1,2,3-triazol-1-yl)methyl)-6-methyl)-2H-chromene-2-one or 1-((4-((5-((substitutedphenoxy)methyl)-1,3,4-oxadiazol-2-yl)sulfanylmethy)-1H-1,2,3-triazol-1-yl-)methyl)-3H-benzo[f]chromene-3-one. Structures of the newly synthesized compounds were confirmed by spectral and analytical data. The compounds were screened for their in-vitro antioxidant property.     

Synthesis and Antimicrobial Activity of (E)-2-[(1-Substituted Phenyl-1H-1,2,3-triazol-4-yl)methylene]-2,3-dihydro-1H-inden-1-ones

Russian Journal of General Chemistry - A series of novel (E)-2-[(1-phenyl-1H-1,2,3-triazol-4-yl)methylene]-2,3-dihydro-1H-inden-1-one derivatives has been synthesized by condensation of...     

超声辐射法在新型含双杂环芳酰基硫脲合成中的应用

以2-苯基-1,2,3-三唑-4-甲酸、氨基硫脲为原料在三氯氧磷中反应得到2-氨基-5-(2-苯基-1,2,3-三唑-4-基)-1,3,4-噻二唑,然后分别采用超声辐射法和常规加热法与芳酰基异硫氰酸酯反应合成了一系列的N-[5-(2-苯基-1,2,3-三唑-4-基) 1,3,4-噻二唑-2-基\]-N′-酰基硫脲。 通过与常规方法比较,采用超声辐射法反应时间只有原来的12.5%,反应产率提高了4%~17%,减少了副反应。 所有化合物的结构经元素分析、MS、IR、1H NMR测试技术确证。     

Synthesis of 1H-1,2,3-triazole derivatives by the cyclization of aryl azides with 2-benzothiazolylacetonone, 1,3-benzo-thiazol-2-ylacetonitrile,and (4-aryl-1,3-thiazol-2-yl)acetonitriles

The cyclization of aryl azides with 2-benzothiazolylacetone, 1,3-benzothiazol-2-ylacetonitrile, and (4-aryl-1,3-thiazol-2-yl)acetonitriles in methanol in the presence of sodium methylate gives high yields of new products, 2-(5-methyl(amino)-1-aryl-1H-1,2,3-triazol-4-yl)-1,3-benzothiazoles and 1-aryl-(4-aryl-1,3-thiazol-2-yl)-1H-1,2,3-triazole-5-amines. 1,3-Benzothiazol-2-ylacetonitrile undergoes an anionic domino reaction with methyl 2-azidobenzoate or 2-azidobenzonitrile to give [1,2,3]triazolo[1,5-a]quinazoline derivatives. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 612–618, April, 2009.     

Synthesis of azoles from 3-[(3-hydrazino-3-oxopropyl)anilino]-and 3-[(3-hydrazino-3-oxopropyl)-4-methylanilino]propane hydrazides

Condensation of 3-[(3-hydrazino-3-oxopropyl)anilino]-and 3-[(3-hydrazino-3-oxopropyl)-4-methylanilino]propane hydrazides with 2,4-pentanedione, phenyl isocyanate or phenyl isothiocyanate (with subsequent work up of the semicarbazides obtained by base), and carbon disulfide gave respectively: 1-(3,5-dimethyl-1H-1-pyrazolyl)-3-[3-(3,5-dimethyl-1H-1-pyrazolyl)-3-oxopropylanilino]-1-propanone, 3-(2-{[2-(5-oxo-4-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)ethyl]anilino}ethyl)-4-phenyl-4,5-dihydro-1H-1,2,4-triazol-5-one and its thio analog, and 5-(2-{[2-(2-thioxo-2,3-dihydro-1,3,4-oxadiazol-5-yl)ethyl]anilino}ethyl)-2,3-dihydro-1,3,4-oxadiazole-2(3H)-thione plus their methyl derivatives. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1353–1358, September, 2007.     

New tetradentate N,N,N,N-chelating α-diimine ligands and their corresponding zinc and nickel complexes: synthesis, characterisation and testing as olefin polymerisation catalysts

A series of zinc complexes of the general formula {[ZnCl(ArN=C(An)-C(An)=NAr)](+)}(2)[Zn(2)Cl(6)](2-) (where Ar = 2-(1-benzyl-1H-1,2,3-triazol-4-yl)phenyl 2a, 2-(1-(1-phenylethyl)-1H-1,2,3-triazol-4-yl)phenyl 2b, 2-(1-phenyl-1H-1,2,3-triazol-4-yl)phenyl 2c; An = acenaphthene backbone) were prepared by the condensation of acenaphthenequinone with the corresponding o-triazolyl-substituted anilines (2-(1-benzyl-1H-1,2,3-triazol-4-yl)aniline 1a, 2-(1-(1-phenylethyl)-1H-1,2,3-triazol-4-yl)aniline 1b, 2-(1-phenyl-1H-1,2,3-triazol-4-yl)aniline 1c) which were formed by the copper(I)-catalyzed Huisgen[3+2] dipolar cycloaddition between 2-ethynylaniline and the corresponding azides in high yields, using anhydrous ZnCl(2) as the metal template, in boiling glacial acetic acid. Zinc complexes of the type [ZnCl(ArN=C(An)-C(An)=NAr)](+)[ZnCl(3)(NCCH(3))](-) (4a-c) were synthesized by crystallisation of the corresponding complexes 2a-c in acetonitrile, at -20 °C. After removal of zinc dichloride from complexes 2a-c by the addition of potassium oxalate, in dichloromethane, the tetradentate N,N,N,N-chelating α-diimine ligands of the type ArN=C(An)-C(An)=NAr (5a-c) were obtained. The new ligand precursors and zinc complexes were characterised by elemental analysis, (1)H and (13)C{(1)H} NMR spectroscopy, two-dimensional NMR spectroscopy, and X-ray diffraction. Reaction of the ligand precursors 5a-c with [NiBr(2)(DME)], in dichloromethane, gave nickel complexes of the type [NiBr(2)(ArN=C(An)-C(An)=NAr)] (6a-c). The results of single crystal X-ray diffraction characterisation and magnetic susceptibility measurements demonstrated that nickel complexes 6a-c possess octahedral geometries around the nickel atoms with variable configurations, the Br atoms of which can be ionized when dissolved in methanol. In preliminary catalytic tests, complexes 6a-c revealed to be active as catalysts for the polymerisation of norbornene and styrene, when activated by cocatalyst MAO. The characterisation of the polymers by (1)H and (13)C{(1)H} NMR spectroscopy, gel permeation chromatography/size-exclusion chromatography (GPC/SEC) revealed that these polymers were formed by a coordination addition mechanism.     

Cyclization of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(prop-2-yn-1-yl)methanesulfonamides to <Emphasis Type="Italic">N</Emphasis>-(hydroxymethyl)-1,2,3-triazoles

Three-component heterocyclizations of trifluoro-N-(prop-2-yn-1-yl)methanesulfonamide, trifluoro-N-pheny-N-(prop-2-yn-1-yl)methanesulfonamide, and trifluoro-N,N-di(prop-2-yn-1-yl)methanesulfonamide with formaldehyde and sodium azide afforded N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-, N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-N-phenyl-, and N,N-bis{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}trifluoromethanesulfonamides as the major products together with minor 1-(hydroxymethyl)-1H-1,2,3-triazole isomers.     

Homogeneous oxidation reactions catalysed by in situ-generated triazolylidene copper(I) complexes

Transition Metal Chemistry - Four new Cu complexes bearing triazolylidene ligands 1-(R)-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium-5-yl: R?=?phenyl (2a), mesitylenyl (2b), propyl (2c),...     

Synthesis and biological activity of new 2,6-diphenyl-4-(1-phenyl-1H-1,2,3-triazol-4-yl)pyridines

Russian Journal of General Chemistry - An efficient one-pot synthesis of new 2,6-diphenyl-4-(1-phenyl-1H-1,2,3-triazol-4-yl)pyridines is presented. This involves the three-component reaction of...     

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, insecticidal activity and DFT study on the geometry and vibration of O-(E)-1-{1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-phenylphosphorothioate

The title compound, O-(E)-1-{1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-1,2,3-triazol-4-yl}ethyleneamino-O-ethyl-O-phenylphosphorothioate, has been synthesized via the condensation reaction of 1-{1-[(6-chloropyridin-3-yl)methyl]-5-methyl-1H-1,2,3-triazol-4-yl}ethanone oxime and O-ethyl-O-phenylphosphorochloridothioate in the presence of NaOH powder in refluxing EtOH. Its structure was characterized by (1)H NMR, FTIR, Raman, elemental analysis and X-ray single crystal diffraction. The results of preliminary bioassays indicated that the title compound displays good insecticidal activity. Density functional (DFT) calculations have been carried out for the title compound by using the Becke-Lee-Yang-Parr's three-parameter hybrid functional (B3LYP) method at 6-31G and 6-31G basis sets. The calculated results show that the predicted geometry can well reproduce the structural parameters. The vibrational wave numbers of the title compound were calculated at same level. Predicted vibrational frequencies have been assigned and compared with experimental IR and Raman spectra and they are supported each other.     

Synthetic transformation of higher terpenoids 31. Synthesis of 1,2,3-triazolyl-containing furan labdanoids and studies of their cytotoxic activity

16-(1-R-1,2,3-Triazol-4-ylethyl)-, 16-(1-R-1,2,3-triazol-4-ylmethoxymethyl)-, and 16-{2-(1-R-1,2,3-triazol-4-yl)-1-[(1-R-1,2,3-triazol-4-ylmethoxy)ethyl]}-substituted derivatives of methyl lambertianate were synthesized by 1,3-cycloaddition of labdanoid alkynes with azides. The compounds obtained possess considerable cytotoxicity toward the human tumor cell lines CEM-13, MT-4, and U-937. The most active compound, methyl 16-(2-{2-[(1-benzyl-1H-1,2,3-triazol-4-yl)acetyl]furan-3-yl}ethyl)lambertianate, was found to inhibit the viability of the tumor cells by 50% (CCID₅₀) in the concentration of 7–12 μmol L^?1.     

Synthesis of 1,2,4- and 1,3,4-oxadiazoles from 1-aryl-5-methyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazole-4-carbonyl chlorides

5-Substituted 2-(1-aryl-5-methyl-1H-1,2,3-triazol-4-yl)-1,3,4-oxadiazoles were synthesized by reaction of 1-aryl-5-methyl-1H-1,2,3-triazole-4-carbonyl chlorides with the corresponding 5-substituted 1H-tetrazoles. 5-Methyl-1-phenyl-1H-1,2,3-triazole-4-carbonyl chloride reacted with N′-hydroxybenzimidamides to give 3-aryl-5-(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)-1,2,4-oxadiazoles. Reactions of 4-(5-methyl-1H-1,2,3-triazol-1-yl)benzoic acid with N′-hydroxybenzimidamides resulted in the formation of 3-aryl-5-[4-(5-methyl-1H-1,2,3-triazol-1-yl)phenyl]-1,2,4-oxadiazoles.     

Azolyl-substituted 1,2,3-triazoles

Huisgen reaction of (E)-1,5-diarylpent-2-en-4-yn-1-ones and (E)-1,5-diarylpent-1-en-4-yn-3-ones afforded 1-aryl-3-(5-aryl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones and 3-aryl-1-(5-aryl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones, respectively. (E)-1-Aryl-3-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones reacted with hydrazine hydrate and phenylhydrazine to give 72–93% of 4-(3-aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles which underwent dehydrogenation on heating in boiling acetic acid with formation of the corresponding pyrazole derivatives. The molecular structures of (E)-3-phenyl-1-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-one and 4-[3-(4-methylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-5-yl]-5-phenyl-1H-1,2,3-triazole were studied by X-ray analysis. 4-(3-Aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles showed toxicity against Daphnia magna.