Synthesis and Characterization of Novel Arylaldehyde (Arylketone)‐(4‐Substituted phenyl‐5‐Substituted phenoxy‐Methyl‐4H‐1,2,4‐Triazole‐3‐yl)‐Thiol Acetyl Hydrazones

Fourteen novel arylaldehyde (arylketone)‐(4‐substituted phenyl‐5‐substituted phenoxy‐methyl‐4H‐1,2,4‐triazole‐3‐yl)‐thiol acetyl hydrazone derivatives ( 5a‐5g, 6a‐6g ) were synthesized by 4‐substituted phenyl‐5‐substituted phenoxy‐methyl‐1,2,4‐triazole‐3‐thione as starting material according to substructure link principle, followed by thioetherification, hydrazide hydrazone reaction. The structures of these compounds were confirmed by IR, ¹H NMR and elemental analysis. Crystal structure of compounds 1b and 6d were determined by the X‐ray diffraction.     

Synthesis and Molecular Structure of New S‐Nucleosides of 5‐(4‐Pyridyl)‐4‐Aryl‐4H‐1,2,4‐Triazole‐3‐Thiols

The synthesis of some new S‐nucleosides of 5‐(4‐pyridyl)‐4‐aryl‐4H‐1,2,4‐triazole‐3‐thiols ( 4a‐n ) is described. Direct glycosylation of ( 4a‐n ) with tetra‐O‐acetyl‐α‐D‐glucopyranosyl bromide in the presence of potassium hydroxide followed by deacetylation using dry ammonia in methanol gave the corresponding 3‐S‐(ñ‐D‐glucopyranosyl)‐5‐(4‐pyridyl)‐4‐aryl‐4H‐1,2,4‐triazoles ( 6a‐n ) in good yields. All the compounds were fully characterized by means of ¹HNMR, ¹³C NMR spectra and elemental analyses. To assist in the interpretation of the spectroscopic data, the crystal structure of 3‐S‐(2′,3′,4′,6′‐tetra‐O‐acetyl‐β‐D‐glucopyranosyl)‐5‐(4‐pyridyl)‐4‐phenyl‐4H‐1,2,4‐triazole ( 5a ) was determined by X‐ray diffraction.     

Two 1,2,4‐Triazole‐based Zinc(II) Complexes with Aromatic Acid as Coligand: Synthesis,Structure and Fluorescence Properties

Two two‐dimensional (2‐D) trz‐based coordination polymers, {[Zn(trz)(mb)]·H₂O}_n ( 1 ) and {[Zn(trz)(ca)]·H₂O}_n ( 2 ) (Htrz = 1,2,4‐triazole, Hmb = 4‐methylbenzoic acid, and Hca = trans‐cinnamic acid), have been synthesized by diffusion method and fully structural characterized by elemental analysis, FT‐IR, single‐crystal X‐ray crystallography, TG and fluorescence spectra. Structural analysis reveals that both complexes exhibit the analogous 2‐D Zn^II‐trz layer motif with hydrophobic aromatic rings attached on both sides despite their different crystal system and space group (orthorhombic, Pbca for 1 and monoclinic, P2₁/c for 2 ). Interestingly, the discrete water‐dimer and infinite 1‐D water‐chain were observed to be entrapped in the 2‐D layer of 1 and 2 , respectively, resulted from the different orientation of lattice water molecules as well as the patterns of hydrogen bonds involved. In addition, their similiar thermal behaviors and fluorescence emissions originated from intraligand electronic transfer were also investigated and compared.     

The Synthesis of Some New 7‐Methyl‐3‐substituted‐1,2,4‐triazolo[3,4‐b]benzothiazoles

New 7‐Methyl‐3‐substituted‐1,2,4‐triazolo[3,4‐b]benzothiazoles were synthesized from p‐methylaniline to 5 with various aromatic carbonic acids. The yielded product 6a‐j was investigated with Elemental analyses, NMR, MS and IR techniques.     

Synthesis and Antifungal Activities of ω‐[4‐Aryl‐5‐(1‐phenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazol‐3‐thio]‐ω‐(1H‐1,2,4‐triazol‐1‐yl)acetophenones

New 4‐aryl‐5‐(1‐phenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazol‐3‐thiones 3 have been synthesized by the intramolecular cyclization of 4‐aryl‐1‐(1‐phenyl‐5‐methyl‐1,2,4‐triazol‐4‐formyl)thiosemicarbazides 2 with an 8% NaOH solution, and then 3 reacted with ω‐bromo‐ω‐(1H‐1,2,4‐triazol‐1‐yl)acetophenone to afford ω‐[4‐aryl‐5‐(1‐phenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazol‐3‐thio]‐ω‐(1H‐1,2,4‐triazol‐1‐yl)‐acetophenones 4 . The preliminary biological test showed that the representative compounds possess some anti fungal activities.     

Synthesis of Novel Biphenyltetrazole Derivatives Containing 5‐Methylisoxazole Substituted 1,2,4‐Triazole

An efficient route to synthesize the target compounds was developed. Fifteen new 5‐[4′‐(5‐isoxazol‐4‐aryl‐1,2,4‐triazol‐3‐yl‐sulfanylmethyl)‐biphenyl‐2‐yl]‐tetrazoles derivatives were synthesized. The structures of the new compounds synthesized were confirmed by elemental analyses and spectral data.     

Synthesis and Cytotoxicity in Vitro of N‐Aryl‐4‐(tert‐butyl)‐5‐(1H‐1,2,4‐triazol‐1‐yl)thiazol‐2‐amine

A series of novel N‐aryl‐4‐(tert‐butyl)‐5‐(1H‐1,2,4‐triazol‐1‐yl)thiazol‐2‐amines synthesized in a green way. H₂O₂‐NaBr Brominating circulatory system was used in the synthesis of the key intermediate in a mild condition. All of the target compounds were confirmed by ¹H NMR and elemental analysis and tested for their cytotoxicity against two different human cancer cell lines. The cytotoxicity assay revealed that some of the title compounds showed moderate to strong cytotoxic activities. Compound 2i was the most potent compound with the IC₅₀ values of 9 μM against Hela cells and 15 μM against Bel–7402 cells, respectively.     

A 1,2,4‐Triazole‐based Polynuclear Mixed‐valence MnIIMnIII Complex: Synthesis,Characterization, and Magnetic Property

A mixed‐valence Mn complex {[Mn^IIMn^III(HL)₂(4,4′‐bpy)(H₂O)₂] · (ClO₄)(DMF)₃(4,4′‐bpy)_0.5}_n ( 1 ) [H₂L = 3‐(2‐phenol)‐5‐(pyridin‐2‐yl)‐1,2,4‐triazole] was synthesized and characterized by X‐ray single‐crystal structure analysis and magnetic susceptibility. Single‐crystal X‐ray analysis revealed that complex 1 has a dinuclear core, in which adjacent central Mn^III atoms are linked by 4,4′‐bipyridine to form an infinite one‐dimensional (1D) molecular configuration. According to the Mn surrounding bond lengths and bond valence sum (BVS) calculations, we demonstrated that the Mn atom coordinated to the pyridine N atoms is in the +2 oxidation state, while another Mn atom coordinated to the phenolic oxygen atoms is in the +3 oxidation state. Magnetic susceptibility data of the complex 1 indicate that the ferromagnetic interaction dominates in this complex.     

Synthesis,Characterization, and Crystal Structure of the New Schiff‐Bases derived from 1,2,4‐Triazole and the Structure of [(PPh3)2Cu(AMTT)]NO3·EtOH (AMTT = 4‐Amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione)

The reactions of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, L1 ) with 2‐thiophen carbaldehyde, salicylaldehyde and 2‐nitrobenzaldehyde in methanol led to the corresponding Schiff‐bases ( L1a‐c ). The reaction of L1 with [(PPh₃)₂Cu]NO₃ in ethanol gave the ionic complex [(PPh₃)₂Cu(L1)]NO₃·EtOH ( 2 ) All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for L1a at 20 °C: space group P2₁/n with a = 439.6(2), b = 2074.0(9), c = 1112.8(4) pm, β = 93.51(3)°, Z = 4, R₁ = 0.0406, L1b at ?80 °C: space group P2₁/n with a = 1268.9(2), b = 739.3(1), c = 1272.5(1) pm, β = 117.97(1)°, Z = 4, R₁ = 0.0361, L1c at ?80 °C: space group P2₁/n with a = 847.8(1), b = 1502.9(2), c = 981.5(2) pm, β = 110.34(1)°, Z = 4, R₁ = 0.0376 and for 2 at ?80 °C: space group with a = 1247.8(1), b = 1270.3(1), c = 1387.5(1) pm, α = 84.32(1)°, β = 84.71(1)°, γ = 63.12(1)°, Z = 2, R₁ = 0.0539.     

One‐pot Synthesis of 2,5‐Disubstituted‐1,3,4‐oxadiazoles Based on the Reaction of N,N‐Dimethyl Amides with Acid Hydrazides

Convenient and efficient one pot method for the synthesis of 2,5‐disubstituted‐1,3,4‐oxadiazoles based on the reaction of N,N‐dimethyl amides with acid hydrazides has been developed. The methodology is applied to a wide range of difference aryl hydrazide and difference N,N‐dimethyl amides to 2,5‐disubstituted‐1,3,4‐oxadiazoles yield the in good to excellent yields. It will be possible wide useful application in synthesis.     

A Convenient and Efficient Conversion of 4‐Aminobenzophenone into Some New 1,2,3‐Triazole and Benzothiazole Derivatives

Several heterocyclic systems such as 1,2,3‐triazoles ( 5–9 ), pyrimidotriazoles ( 10–13 ), benzothiazole ( 16 ), thiazolo ( 17 ), and pyrimidinone derivative ( 18 ) was obtained from 4‐aminobenzophenone ( 1 ) and the appropriate reagents.     

Synthesis and Visible Spectral Behaviour of Some New N‐Bridgehead Heterocyclic Cyanine Dyes Incorporating Pyrazolo (4,5‐b) Indolizine (Benzoindolizine)

The new unsymmetrical N‐bridgehead, apo (zeromethine), mono‐methine, dimethine, meso substituted tetramethine and styryl cyanine dyes incorporating pyrazolo (4,5‐b) indolizine (benzoindolizine) nuclei were prepared. Structural confirmation was carried out by elemental analyses, IR, H‐NMR, mass spectra and ¹³C‐NMR with the aid of carbon DEPT spectral data. The visible absorption spectra for the newly synthesized cyanines were examined in 95% ethanol.     

A Simple and Efficient Procedure for Synthesis of Optically Active 1,2,4‐Triazolo‐[3,4‐b]‐1,3,4‐Thiadiazole Derivatives Containing l‐Amino Acid Moieties

Some new and optically active 1,2,4‐triazolo thiadiazoles bearing N‐phthaloyl‐l ‐amino acids were synthesized by reaction of 4‐amino‐5‐(3‐ or 4‐)pyridyl‐3‐mercapto‐(4H)‐1,2,4‐triazoles with N‐phthaloyl‐l ‐amino acids in the presence of phosphorus oxychloride. All the newly synthesized compounds were confirmed by IR, ¹H NMR, ¹³C NMR and elemental analysis.     

Synthesis,Characterization and X‐ray Structures of AMTT‐Type Schiff bases and two CuI Complexes (AMTT= 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione)

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT) with 4‐methylbenzaldehyde and 4‐methoxybenzaldehyde in ethanol led to the iminic derivatives ‐4‐(4‐methylbenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)thione ( L1 ) and 4‐(4‐methoxybenzyl‐ideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione ( L2 ). The reaction of L1 with CuCl in the presence of triphenylphosphane as co‐ligand in methanol/chloroform solution gave the Cu^I complex containing L1 , [Cu( L1 )(PPh₃)₂Cl]·0.5CH₃OH·0.25CHCl₃ ( 1 ). Treatment of L2 with the same metal salt in a molar ratio of 1:1 in methanol and further addition of a solution of PPh₃ in chloroform led to the complex [Cu( L2 )(PPh₃)₂Cl]·2.5CHCl₃ ( 2 ). The complexes and L1 were characterized by IR and NMR spectroscopy as well as by X‐ray diffraction studies. In both complexes, the Schiff base ligand is coordinated to the copper ion through its sulfur atom. The other coordination sites around the copper ion are occupied by two triphenylphosphane molecules and one chloride ion. Therefore, each Cu^I ion is in a distorted tetrahedral environment. Crystal data for L1 at ?100 °C: space group P2₁/n with a = 720.5(1), b = 1140.6(1), c = 1426.3(2) pm, β = 91.25(1)°, Z = 4, R₁ = 0.03, for 1 at ?120 °C : space group with a = 1286.3(1), b = 1740.3(1), c = 2060.2(1) pm, α = 79.085(6), β = 83.827(5), γ = 76.688(6)°, Z = 4, R₁ = 0.0649 and for 2 at ?80 °C : space group with a = 1183.7(2), b = 1370.1(2), c = 1812.1(3) pm, α = 85.69(2), β = 88.52(2), γ = 64.89(2)°, Z = 2, R₁ = 0.0488.     

Synthesis,Characterization and Evaluation of Antimicrobial and Antituberculosis Activities of New N‐(Substituted‐thioureido)aminobicyclo Dicarboximide and 3,4‐Disubstituted 1,2,4‐Triazolino‐5‐thione

The novel N‐(substituted‐thioureido)aminobicyclo dicarboximide and 3,4‐disubstituted 1,2,4‐triazolino‐5‐thione were synthesized and their antimicrobial and antituberculosis activities were examined. Selected dicarboxylic acid anhydrides were used to obtain derivatives of thiosemicarbazide and dicarboximide. Dicarboximides were also cyclized in the presence of an alkaline solution giving 1,2,4‐triazolino‐5‐thione. The chemical structure of all compounds was confirmed by IR, ¹H NMR, ¹³C NMR, the X‐ray crystallography ( 6 , 11 ) and elemental analysis. Antimicrobial and antituberculosis activities of the derivatives were measured.     

Synthesis and Antibacterial Activity of s‐Triazoles,s‐Triazolo[3,4‐b]‐1,3,4‐thiadiazines and s‐Triazolo[3,4‐b]‐1,3,4‐thiadiazoles of 5‐Methylisoxazole

The condensation of 4‐amino‐5‐mercapto‐3‐(5‐methylisoxazol‐3‐yl)‐1,2,4‐triazole with substituted phenacyl bromide, aldehydes, p‐bromophenylisothiocyanate, aromatic carboxylic acids and oxalic acid, is described. The antibacterial activity of representative compounds was evaluated.     

Synthesis,Characterization and Crystal Structures of 1,2,4‐Triazole based Schiff‐Bases and their Copper(I) Complexes

The reaction of of 4‐amino‐5‐ethyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AETT, L ) with furfural in methanol led to the corresponding Schiff‐Base ( L1 ). The reaction of L1 with [Cu(PPh₃)₂]Cl in methanol gave to the neutral compound [( L1 )Cu(PPh₃)₂Cl] ( 1 ). By recrystallization of 1 from CH₃CN the complex [( L1 )Cu(PPh₃)₂Cl]·CH₃CN ( 1a ) was obtained. All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for L1 at ?80 °C: space group with a = 788.4(1), b = 830.3(2), c = 928.8(2) pm, α = 84.53(1)°, β = 65.93(1)°, γ = 72.02(1)°, Z = 2, R₁ = 0.0323; for 1 at ?100 °C: space group with a = 1166.3(1), b = 1423.8(2), c = 1489.1(2) pm, α = 62.15(1)°, β = 72.04(1)°, γ = 88.82(1)°, Z = 2, R₁ = 0.0338 and for 1a at ?100 °C: space group P2₁/c with a = 1294.1(1), b = 1019.8(2), c = 3316.9(4) pm, β = 94.73(1)°, Z = 4, R₁ = 0.0435.     

Synthesis,Characterization and Crystal Structures of new 1,2,4‐Triazole based Schiff‐bases and their Copper(I) Complexes

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, 1 ) with 4‐methoxy benzaldehyde and 3‐methoxybenzaldehyde in methanol led to the iminic derivatives 4‐(4‐methoxybenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)thione ( 2 , L1) and 4‐(3‐methoxybenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione ( 3 , L2). The reaction of the latter with [(PPh₃)₂CuCl] in methanol solution gave the first Cu^I complex of 3 , [(PPh₃)₂CuCl(L2)] ( 4 ) and in chloroform solution the complex [(PPh₃)₂CuCl(L2)]·2CHCl₃ ( 5 ). All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at ?80 °C: space group P2₁/c with a = 1351.3(3), b = 399.4(1), c = 2225.2(5) pm, β = 96.50(2)°, Z = 4, R₁ = 0.0667, for 3 at ?80 °C: space group R3c with a = b = 3020.4(2), c = 708.2(1) pm, Z = 18, R₁ = 0.0435, for 4 at ?80 °C: space group P2₁/c with a = 1427.8(1), b = 1129.0(1), c = 2622.8(2) pm, β = 97.19(1)°, Z = 4, R₁ = 0.0517 and for 5 at ?80 °C: space group with a = 1280.5(1), b = 1316.1(1), c = 1731.4(1) pm, α = 78.14(1)°, β = 86.06(1)°, γ = 64.69(1)°, Z = 2, R₁ = 0.0525.