Showing papers on "Triazene published in 2015"
TL;DR: The chemical reactivity of 1-alkynyltriazenes has been investigated and is found to parallel the reactions of ynamides, suggesting that these compounds should become valuable reagents in synthetic organic chemistry.
Abstract: The chemical reactivity of 1-alkynyltriazenes has been investigated and is found to parallel the reactivity of ynamides. The similarity in reactivity of these two classes of compounds is demonstrated by addition reactions with acids, by cycloaddition reactions with ketenes, tetracyanoethene, and cyclopropanes, as well as by intramolecular cyclization reactions. The presence of reactive triazene groups in the products enables subsequent transformations. Overall, our results suggest that 1-alkynyltriazenes should become valuable reagents in synthetic organic chemistry.
43 citations
TL;DR: The reaction of 1-[(2-carboxyethyl)benzene]-3-[benzothiazole]triazene (HL) and CuCl gives a trinuclear copper(I) complex, which has been structurally characterized by X-ray crystallography as discussed by the authors.
34 citations
TL;DR: In this article, the first representatives of a new class of promising exogenous nitric oxide (NO) donors, which can release NO in living organisms, were developed, which involves the reactions of salts of 1-hydroxy-3,3-dialkyl-1-triazene 2-oxides with either dibromomethane or 1-chloromethoxy-3.3-dioxene 2 -oxides.
Abstract: Synthetic procedures towards methylene-bis(1-oxy-3,3-dialkyl-1-triazene 2-oxides), the first representatives of a new class of promising exogenous nitric oxide (NO) donors, which can release NO in living organisms, were developed. Synthesis involves the reactions of salts of 1-hydroxy-3,3-dialkyl-1-triazene 2-oxides with either dibromomethane or 1-chloromethoxy-3,3-dialkyl-1-triazene 2-oxides.
17 citations
TL;DR: In this article, a trinuclear copper(I) complex was synthesized and characterized by single crystal X-ray diffraction (XRD) studies and the complex was then immobilized on the surface of Au electrode through Au-S covalent bonds.
16 citations
TL;DR: A simple and efficient fluorous coupling reagent TriTFET (2,4, 6-tris-(2,2, 2-trifluoro-ethoxy)-[1,3, 5] triazene) has been designed and synthesized for the direct amidation as mentioned in this paper.
12 citations
TL;DR: In this paper, a synthetic approach to 2-hydroxyethyl derivatives of methylene-bis(1-oxy-3, 3-dialkyl-1triazene 2-oxides), promising NO donors, which can release NO in living organisms was developed.
Abstract: Synthetic approach to 2-hydroxyethyl derivatives of methylene-bis(1-oxy-3, 3-dialkyl-1triazene 2-oxides), promising NO donors, which can release NO in living organisms was developed. Some transformations of the hydroxyethyl moiety of the synthesized compounds were studied.
12 citations
TL;DR: In this paper, an efficient synthesis of fluorinated alkyl and aryl ethers was achieved by the use of s-triazene derived fluorinated reagent 2,4,6-tris-(2,2, 2-trifluoro-ethoxy)-[1,3,5] triazene (TriTFET).
Abstract: An efficient synthesis of fluorinated alkyl and aryl ethers was achieved by the use of s-triazene derived fluorinated reagent 2,4,6-tris-(2,2,2-trifluoro-ethoxy)-[1,3,5] triazene (TriTFET). The procedure offers a very attractive alternative for the synthesis of fluorinated motifs that are found in various bioactive molecules. Moreover, TriTFET is a synthetic non-toxic, non-ozone depleting and stable reagent. All compounds were characterized by 1H, 13C and 19F NMR.
10 citations
TL;DR: In this paper, a method for the synthesis of 1-alkoxy-3-methyl-1-triazene 2-oxides and their salts with alkali metals was developed.
Abstract: A method for the synthesis of 1-alkoxy-3-methyl-1-triazene 2-oxides and their salts with alkali metals was developed. 3, 3´-Methylene-bis(1-alkoxy-3-methyl-1-triazene 2-oxides) were obtained for the first time. Some properties of the synthesized compounds were studied. These compounds can be of interest as new NO and HNO donors in living organisms.
9 citations
TL;DR: The triazene group is removed with trifluoroacetic acid and, because of the low barrier to rotation, affords sharp (1)H NMR spectra at room temperature.
7 citations
TL;DR: In this article, an attractive way to in situ create noble metal nanoparticles in block copolymer matrixes through the UV-triggered photodecomposition of the photolabile triazene units without the use of any conventional reducing agent was described.
Abstract: This article describes an attractive way to in situ create noble metal nanoparticles in block copolymer matrixes through the UV-triggered photodecomposition of the photolabile triazene units without the use of any conventional reducing agent. The poly(isodecyl methacrylate-co-triazene urethane methacrylate) random copolymer containing pendent photocleavable triazene junctions (COP-1) was synthesized under RAFT conditions and subsequently employed as macroinitiator to obtain a block copolymer, namely poly(isodecyl methacrylate-co-triazene urethane methacrylate)-block-poly(acrylic acid) (COP-2). The photogeneration of silver/gold metal nanoparticles (NPs) from noble metal precursors (1 wt% AgNO3 or AuBr3 metal salts) induced through the UV decomposition of triazene units with the formation of some radical active species was monitored in solution and thin films. The in situ growth of Ag/Au nanostructures into polymer matrixes for which the light is a key element has been confirmed by UV spectroscopy and TEM analysis. The TEM images allowed the visualization of the silver NPs (sizes of 4–16 nm in COP-1 and of 2–6 nm in COP-2) as well as of the gold NPs (sizes between 10 and 20 nm in COP-1 and from 15 to 25 nm in COP-2), which are mainly spherical in shape, even though there is some triangular or hexagonal gold nanoparticles.
6 citations
TL;DR: In this article, the triazene oxide sodium salts with 3,3-dialkyl-1,chloromethoxy-1-triazene 2-oxides produces a complex mixture of product bearing the oxytriazenes moieties of the starting alkoxy-3-methyl-3-(methylthiomethyl)-1-oxide bonded with the methylene group as a key structural fragment.
Abstract: 1-Alkoxy-3-methyl-1-triazene 2-oxide sodium salts react with chloromethyl methyl sulfide to give a mixture of 1-alkoxy-3-methyl-3-(methylthiomethyl)-1-triazene 2-oxides and 3-alkoxy-1-methyl-3-(methylthiomethyl)-1-triazene 2-oxides. The reaction of these triazene oxide sodium salts with 3,3-dialkyl-1-chloromethoxy-1-triazene 2-oxides produces a complex mixture of product bearing the oxytriazene moieties of the starting alkoxy-1-triazene 2-oxides bonded with the methylene group as a key structural fragment.
TL;DR: In this article, a planar planar anthraquinone fragment was inserted between the parallel pairs of nucleic acids for the preparation of alkyltriazene derivatives of 9,10-anthraquinones.
Abstract: Some alkyltriazenes are used in clinical practice as cytotoxic drugs in chemotherapy of cancer [1–4]. Amino derivatives of 9,10-anthraquinone possess similar properties, they inhibit the tumor growth through intercalation, the insertion of a planar anthraquinone fragment between the parallel pairs of nucleic acids [5, 6]. The target of this work was the preparation of alkyltriazene derivatives of 9,10anthraquinone combining presumably the useful qualities of these classes of compounds.
TL;DR: In this article, a modular synthesis of highly substituted indazoles via a strategy on solid supports is presented, where the heterocyclic nitrogen atoms originate from diazonium salts, being cleaved from triazene containing resins.
Abstract: Indazoles are important heterocycles as they are a substantial part in many drugs. In this study, we present a modular synthesis of highly substituted indazoles via a strategy on solid supports. The heterocyclic nitrogen atoms originate from diazonium salts, being cleaved from triazene containing resins. The scope and limitations of this process are explored, considering especially the competitive occurrence of triazines and the cleavage of hydrolyzed and traceless side products.
TL;DR: In this paper, an efficient chiral organocatalyst was prepared from readily available cyanuric chloride for the alkylation of a glycinate Schiff base, which provides a useful procedure for the enantioselective synthesis of structurally diverse natural and unnatural α-alkyl-α-amino acids.
Abstract: A very efficient chiral organocatalyst was prepared from the readily available cyanuric chloride. The asymmetric catalyst exhibited a highly enantioselective catalytic performance for the alkylation of a glycinate Schiff base, which provides a useful procedure for the enantioselective synthesis of structurally diverse natural and unnatural α-alkyl-α-amino acids.
TL;DR: In this paper, asymmetric triazenes consisting 1-(2methoxycarbonylphenyl)-3-(2-methylphenyl)triazene and their related HgII complexes were reported, and the characterizations were performed by FT-IR, 1H NMR and 13C NMR spectroscopies.
Abstract: Syntheses of some ligands based on asymmetric triazenes consisting 1-(2-methoxycarbonylphenyl)-3-(2-methylphenyl)triazene (1), 1-(2-methoxycarbonylphenyl)-3-(3-methylphenyl)triazene (2), 1-(2-methoxycarbonylphenyl)-3-(4-methylphenyl)triazene (3), 1-(2-methoxycarbonylphenyl)-3-(3,5-dichlorophenyl)triazene (4), 1-(4-chlorophenyl)-3-(4-methylphenyl)-triazene (5) and their related HgII complexes were reported. The characterizations were performed by FT-IR, 1H NMR and 13C NMR spectroscopies. In (3) and (4), both triazenes possess trans-conformation around the (–N=N–) bond and monomeric moieties are linked to pairs and wave-like chains through C–H···O and C–H···N hydrogen bonds which are further assembled by stacking through secondary π···π interactions [3.829(1) and 3.736(1) A]. The reaction of (1) and Hg(NO3)2 in methanol produces the corresponding HgII complex (6) where each triazenide binds to the HgII atom through two nitrogen atoms of triazenide and one oxygen atom of pendant methoxycarbonyl group forming distorted MN4O2 octahedral around the HgII atom. The stoichiometry and formation of complex (6) and (8) in methanol solution were investigated by UV–Vis titration. Moreover, Reaction of substituted 1,3-diaryltriazenes (2) and (5) with HgII salts afford a family of orange complexes (7) and (8), respectively. Finally, the chemical structures of the investigated ligands were correlated to their pharmacokinetic behaviour using five pre-calculated models implemented in VolSurf program. Polyhedron around HgII atom coordinated by two triazenide ligands in an octahedron fashion.
TL;DR: Chlorides and anhydrides of carboxylic acids react with salts of 1-methoxy-3-methyl-1-triazene 2-oxides to give the corresponding 3-acyl-1.
Abstract: Chlorides and anhydrides of carboxylic (including dicarboxylic) acids react with salts of 1-methoxy-3-methyl-1-triazene 2-oxides to give the corresponding 3-acyl-1-methoxy-3-methyl-1-triazene 2-oxides.
TL;DR: In this article, the authors describe the direct synthesis of polysubstituted indolo[2,1-a]isoquinoline analogues via a double C-H annulation cascade using triazene as an internally cleavable directing group.
Abstract: Indole-containing polyaromatic scaffolds are widely found in natural products, pharmaceutical agents, and π-conjugated functional materials. Often, the synthesis of these highly valuable molecules requires a multistep sequence. Therefore, a simple, one-step protocol to access libraries of polyaromatic indole scaffolds is highly desirable. Herein we describe the direct synthesis of polysubstituted indolo[2,1-a]isoquinoline analogues via a double C–H annulation cascade using triazene as an internally cleavable directing group. Evidence from HRMS and theoretical calculations suggests that an unprecedented 1,2-alkyl migration might be responsible for the in situ cleavage of the directing group. Both kinetic isotope effects and DFT calculations suggested that the alkyne insertion step is rate-limiting for the second C,N annulation reaction.
TL;DR: In this article, various fluorinated alkyl and aryl ethers are eco-friendly obtained using the synthetic non-toxic, non-ozone depleting, and stable 2,4,6-tris-(2,2, 2-trifluoroethoxy)-[1,3,5]triazene (II) reagent.
Abstract: Various fluorinated alkyl and aryl ethers are eco-friendly obtained using the synthetic non-toxic, non-ozone depleting, and stable 2,4,6-tris-(2,2,2-trifluoroethoxy)-[1,3,5]triazene (II) as trifluoroethylation reagent.
01 Jan 2015
TL;DR: The study has brought about a novel application of this class of analytical reagents as an emerging class of bioactive chemicals.
Abstract: Antibacterial activities of four hydroxytriazenes namely 3-hydroxy-3-m-chlorophenyl-1-(4sulphonamidophenyl)triazene, 3-hydroxy-3-n-propyl-1-(4-sulphonamidophenyl)triazene, 3-hydroxy-3-isopropyl-1(4-sulphonamidophenyl) triazene, and 3-hydroxy-3-m-tolyl-1-p-chlorophenyltriazene and their ternary complexes with vanadium (V) using thiourea as second ligand have been screened against four bacterial strains viz.: Pseudomonas aeruginosa, Proteus mirabilis, Klebsiella pneumoniae and Escherichia coli at 100 and 200 ppm. Thus the study has brought about a novel application of this class of analytical reagents as an emerging class of bioactive chemicals.
TL;DR: In this article, 1-alkylpiperazine was treated with a diazonium salt solution to produce the new triazenes, which have been characterized by proton and carbon-13 NMR spectroscopy, IR and mass spectrometric analysis.
Abstract: New triazenes derived from the 1-alkylpiperazines have been synthesized. Each 1-alkylpiperazine was treated with a diazonium salt solution to produce the new triazenes, which have been characterized by proton and carbon- 13 NMR spectroscopy, IR spectroscopy and by mass spectrometric analysis. Assignment of the chemical shifts to specific protons and carbons in the piperazine ring was facilitated by comparison with the chemical shifts in the previously reported 1-methyl-4-(2-aryl-1-diazenyl)piperazines (1).
TL;DR: In this article, the asymmetric ligands [1-(phenyl)-3-(2-nitro-4-methylphenyl)]triazene (1), [1-ethylphenyl]-3-( 2-nitrogen-4 -methyl-phenyl) triazene(2), [ 1-(4-ethoxyphenyl)-1-3-2-n-methyl-4]-triazenes (3) and [
Abstract: In this work, the asymmetric ligands [1-(phenyl)-3-(2-nitro-4-methylphenyl)]triazene (1), [1-(4- methylphenyl)-3-(2-nitro-4-methylphenyl)]triazene (2), [1-(4-ethylphenyl)-3-(2-nitro-4-methylphenyl)]triazene (3) and [1-(4-ethoxyphenyl)-3-(2-nitro-4-methylphenyl)]triazene (4), were synthesized. The reaction of the ligand (3) with HgCl 2 in methanol resulted in the formation of the [HgL 2] complex, (5). All compounds were characterized by means of CHN analysis, FT-IR, 1H NMR, 13C NMR spectroscopy. In addition, the crystal structures of the ligands (2) to (4) were investigated by single crystal X-ray analysis. In the solid state, all ligands exhibited trans conformation about the –N =N– double bond. The Hg II complex (5) crystallized in monoclinic system with C2/c space group. The triazene ligand was found to be deprotonated prior to coordination and acts as monodentate ligand. The Hg II which lies on inversion center (site symmetry i), is surrounded by two N atoms from L ligands forming a linear geometry. The other two Hg–N bonds are relatively longer and can only be regarded as weak secondary bonds. Also, Hg- η
3-arene π-interactions are present in this compound. Hydrogen bonds, π⋯π and C–H ⋯π stacking interactions help in the stabilization of the resulted frameworks. These C–H ⋯π edge-to-face interactions are present with H ⋯π distance of 3.00 A.
Patent•
25 Mar 2015
TL;DR: In this article, the authors described the preparation process of triazamidine and a preparation process thereof, which consists of a series of diazotization reaction, coupling reaction and salt formation reaction on p-amino-benzamidine hydrochloride to synthesize triazene, enabling the triazenes to react with aceturic acid and synthesize a crude product of triazoamidine, finally refining the crude product to obtain a pure product.
Abstract: The invention discloses triazoamidine and a preparation process thereof. The preparation process of the triazoamidine comprises the following steps: firstly carrying out a series of diazotization reaction, coupling reaction and salt formation reaction on p-amino-benzamidine hydrochloride to synthesize triazene, enabling the triazene to react with aceturic acid and synthesize a crude product of triazoamidine, finally refining the crude product of triazoamidine to obtain a pure product. The preparation process of the triazoamidine is simple to operate, is safe, and is free of highly toxic substances and low in use amount of an organic solvent; the solvent residue is reduced to the minimum extent; and the preparation process of the triazoamidine has the advantages of being environmentally-friendly, high in yield and low in cost.
Patent•
08 Jul 2015
TL;DR: In this paper, a triazene-nickel (II) mononuclear complex Ni(C14H8N5S2) was synthesized, representation is carried out on a complex crystal structure through X-ray monocrystalline diffraction, the complex belongs to a triclinic crystal system, and has P1space group.
Abstract: In the invention, the invention takes 1,3-dibenzo thiazolyl triazene as a ligand, and a triazene-nickel (II) mononuclear complex Ni(C14H8N5S2)2 which is unreported is synthesized, representation is carried out on a complex crystal structure through X-ray monocrystalline diffraction, the complex belongs to a triclinic crystal system, and has P1space group; of which crystal has the crystal cell parameters as follows: a= 10.256(8) A, b= 10.256(8) A, c= 13.160(10) a, alpha= 90 DEG, beta = 90 DEG, gamma= 90 DEG, a molecular formula is C28H16N10NiS4, Mr= 679.46, V=1384.2(19) A , Z=2, Dc = 1.630 Mgm , R1 = 0.0678, and wR2 = 0.1619[I is greater than 2sigma(I)].
TL;DR: Its structural characterization by X-ray analysis and 1H NMR spectroscopy is performed to determine molecular overall conformation in view of its possible interaction to DNA.
Abstract: Biologically active 4-nitro-substituted 1,3-diaryltriazene, a chemical analogue of 1,3- bis (4'-amidinophenyl)-triazene-berenil ® , belongs to the novel, chemically modified class of potent antitumor agents. Its structural characterization by X-ray analysis and 1 H NMR spectroscopy is performed to determine molecular overall conformation in view of its possible interaction to DNA
01 Jan 2015
TL;DR: In this article, 3-Hydroxy-3-4-methylphenyl)-1-(4-sulphonato (sodium salt) phenyl) triazene (HPST) has been studied using weight loss techniques at temperatures ranging from 303 to 343 K.
Abstract: Corrosion inhibition of copper in 1N HCl solution by 3-Hydroxy-3-(4-methylphenyl)-1-(4-sulphonato (sodium salt) phenyl) triazene (HPST) has been studied using weight loss techniques at temperatures ranging from 303 to 343 K. It is observed that the proposed organic compound exhibit 84.4% inhibition efficiency at 303 K temperature in 1N HCl solution . Increase the concentration of HPST inhibition efficiency increases whereas increase in temperature decreases inhibition efficiency. The inhibitior show maximum inhibition efficiency for 0.002 M concentration of HPST at 303 K temperature. Activation energy (E a), Enthalpy ( ∆H),Entropy ( ∆S) and Gibbs free energy have also been reported. The Langmuir isotherm was found to accurately describe the adsorption behavior of the compound.
TL;DR: In this paper, an efficient chiral organocatalyst was prepared from readily available cyanuric chloride for the alkylation of a glycinate Schiff base, which provides a useful procedure for the enantioselective synthesis of structurally diverse natural and unnatural α-alkyl-α-amino acids.
Abstract: A very efficient chiral organocatalyst was prepared from the readily available cyanuric chloride. The asymmetric catalyst exhibited a highly enantioselective catalytic performance for the alkylation of a glycinate Schiff base, which provides a useful procedure for the enantioselective synthesis of structurally diverse natural and unnatural α-alkyl-α-amino acids.
TL;DR: A series of substituted triazene dyes were synthesized by coupling functionalized imidazol-2-ylidenes with various azides (alkyl, vinyl, aryl, and heteroaryl), in moderate to excellent yields.
Abstract: A series of substituted triazene dyes were synthesized by coupling functionalized imidazol-2-ylidenes with various azides (alkyl, vinyl, aryl, and heteroaryl), in moderate to excellent yields. Their structures were confirmed by spectroscopic studies (IR, NMR, UV–vis, and HRMS). Additionally, the solid-state structure of triazene dye 7 was secured by single crystal X-ray diffraction. Electron delocalization between the two coupled components was studied using UV–vis spectroscopy. The respective triazenes were found to exhibit λmax values ranging between 294 and 450 nm.
TL;DR: Alkyl, benzyl, aryl, and hetaryl carboxylic acids are successfully coupled with primary aliphatic and aromatic amines as well as secondary aliphastic amines as mentioned in this paper.
Abstract: Alkyl, benzyl, aryl, and hetaryl carboxylic acids are successfully coupled with primary aliphatic and aromatic amines as well as secondary aliphatic amines.
Patent•
22 Mar 2015
TL;DR: In this article, an unreported triazene-cobalt (III) mononuclear complex Co(C13H11N4O2)3 is synthesized through X-ray single crystal diffraction, the crystalline structure of the complex is characterized; the complex belongs to a triclinic crystal system and a P1 space group.
Abstract: With 2-aminopyridyl triazene as a ligand, an unreported triazene-cobalt (III) mononuclear complex Co(C13H11N4O2)3 is synthesized; through X-ray single crystal diffraction, the crystalline structure of the complex is characterized; the complex belongs to a triclinic crystal system and a P1 space group; crystal cell parameters are as shown in the description; the molecular formula is C39H33N12CoO6; data are obtained according to formulas as shown in the description; the final deviation factors are as shown in the description; all data are shown in the description.