Five new tetradentate ligands [NNNN] with benzimidazolyl‐imine or amine nitrogen donors have been synthesized in good yields under mild conditions from easily available substrates. trans‐N,N′‐bis(1‐Ethyl‐2‐benzimidazolylmethylene)cyclohexane‐1,2‐diimine is the best accelerating ligand in this series that supports the CuI‐catalyzed Ullmann N‐arylation and the direct three‐component azide–alkyne cycloaddition reaction to give the corresponding substituted imidazole, pyrazole, and triazole in high yields. Single‐crystal X‐ray diffraction analysis of its complex with CuI reveals a novel one‐dimensional coordination polymer of the metal chain bridged alternately by the [NNNN] ligand and diiodides. 相似文献
Summary: Novel hyperbranched poly([1,2,3]‐triazole)s were synthesized from several AB2 monomers by a 1,3‐dipolar cycloaddition reaction. The compound 3,5‐bis(propargyloxy)benzyl azide was polymerized thermally at room temperature leading to 1,4‐ and 1,5‐disubstituted poly([1,2,3]‐triazole) and catalytically leading only to the 1,4‐disubstituted poly([1,2,3]‐triazole). Only the thermal reaction led to fully soluble products. The AB2 monomers containing an internal alkyne A unit could be autopolymerized thermally under mild reaction conditions leading to soluble, high‐molecular‐weight hyperbranched poly([1,2,3] triazole)s. All products were characterized by detailed NMR investigations.
The cyclization of 1‐amino‐2‐mercapto‐5‐[1‐(4‐ethoxyphenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐1,3,4‐triazole which was synthesized from p‐ethoxyaniline with various triazole acid in absolute phosphorus oxychloride yields 3,6‐bis(1,2,3‐triazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazole derivatives 9a?j , and their structures are established by MS, IR, CHN and 1H NMR spectral data. 相似文献
The coordination geometry of the NiII atom in the title complex, poly[diazidobis[μ‐1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene‐κ2N4:N4′]nickel(II)], [Ni(N3)2(C12H12N6)2]n, is a distorted octahedron, in which the NiII atom lies on an inversion centre and is coordinated by four N atoms from the triazole rings of two symmetry‐related pairs of 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene (bbtz) ligands and two N atoms from two symmetry‐related monodentate azide ligands. The NiII atoms are bridged by four bbtz ligands to form a two‐dimensional (4,4)‐network. 相似文献
Mononuclear nickel(II) complexes were prepared by reaction of the three ONNO type reduced Schiff bases bis‐N,N′‐(2‐hydroxybenzyl)‐1,3‐propanediamine (LHH2), bis‐N,N′‐(2‐hydroxybenzyl)‐2,2′‐dimethyl‐1,3‐propanediamine (LDMHH2), and bis‐N,N′‐[1‐(2‐hydroxyphenyl)ethyl]‐1,3‐propanediamine (LACHH2) with NiII ions in the presence of pseudo halides (OCN–, SCN– and N3–). The complexes were characterized with the use of elemental analyses, IR spectroscopy, and thermal analyses. The molecular structure of one of the complexes was obtained by single‐crystal X‐ray diffraction. The obtained complexes are mononuclear, and a pseudo halide molecule is attached. One of the oxygen atoms of the ligand is in phenolate and the other was in phenol form. According to the thermogravimetry results, it was thought that the pseudo halide thermally detaches from the structure as hydropseudo halide. In azide‐containing complexes an endothermic reaction was observed although the azide group usually decomposes with an exothermic reaction. 相似文献
Two novel multilevel switchable [2]rotaxanes containing an ammonium and a triazole station have been constructed by a CuI‐catalyzed azide–alkyne cycloaddition reaction. The macrocycle of [2]rotaxane containing a C6‐chain bridge between the two hydrogen bonding stations exhibits high selectivity for the ammonium cation in the protonated form. Interestingly, the macrocycle is able to interact with the two recognition stations when the bridge between them is shortened. Upon deprotonation of both [2]rotaxanes, the macrocycle moves towards the triazole recognition site due to the hydrogen‐bond interaction between the triazole nitrogen atoms and the amide groups in the macrocycle. Upon addition of chloride anion, the conformation of [2]rotaxane is changed because of the cooperative recognition of the chloride anion by a favorable hydrogen‐bond donor from both the macrocycle isophthalamide and thread triazole CH proton. 相似文献
Abstract. Two bis‐triazole‐bis‐amide‐based copper(II) pyridine‐2,3‐dicarboxylate coordination polymers (CPs), [Cu(2,3‐pydc)(dtb)0.5(DMF)] · 2H2O ( 1 ) and [Cu(2,3‐pydc)(dth)0.5(DMF)] · 2H2O ( 2 ) (2,3‐H2pydc = pyridine‐2,3‐dicarboxylic acid, dtb = N,N′‐bis(4H‐1,2,4‐triazole)butanamide, and dth = N,N′‐bis(4H‐1,2,4‐triazole)hexanamide), were synthesized under solvothermal conditions. CPs 1 and 2 show similar two‐dimensional (2D) structures. In 1 , the 2,3‐pydc anions bridge the CuII ions into a one‐dimensional (1D) chain. Such 1D chains are linked by the dtb ligands to form a 2D layer. The adjacent 2D layers are extended into a three‐dimensional (3D) supramolecular architecture by hydrogen‐bonding interactions. The electrochemical properties of 1 and 2 were investigated. 相似文献
Bis(triazolo[3,4‐b]thiadiazine) 4 in which the fused system is linked directly to the benzene core can be synthesized in 75% yield by, firstly, preparation of bis(s‐triazole) 2 followed by reaction with phenacyl bromide 3 in refluxing EtOH/DMF mixture containing piperidine. Bis(s‐triazolo[3,4‐b][1,3,4]thiadiazines) 8 and 11 in which the triazolothiadiazines are linked to benzene core via alkyl or ether linkage were synthesized in 70 and 72% yields, respectively, starting from dicarboxylic acids 5 and 9 upon treatment with two moles of thiocarbohydrazide 6 to give the corresponding bis(4‐amino‐5‐mercapto‐s‐triazolo‐3‐y1) derivatives 7 and 10 and subsequent reaction with two equivalents of phenacyl bromide. Bis(6‐phenyl‐7H‐[1,2,4]triazolo[3,4‐b][1,3,4]thiadiazines) 15a , 15b , 15c , 15d , 15e , 15f , which are linked to arene cores via sulfanylmethylene spacers, were prepared by the reaction of 4‐amino‐4H‐1,2,4‐triazole‐3,5‐dithiol 12 with the appropriate bis(bromomethyl)benzenes 13a , 13b , 13c , 13d , 13e , 13f to give bis(4‐amino‐5‐mercapto‐4H‐3‐sulfanylmethyl)arenes 14a , 14b , 14c , 14d , 14e , 14f and subsequent reaction with phenacyl bromide. Compounds 15a , 15b , 15c , 15d , 15e , 15f were alternatively obtained in 60–70% yields by twofold substitution of 13a , 13b , 13c , 13d , 13e , 13f with two equivalents of 6‐phenyl‐7H‐[1,2,4]triazolo[3,4‐b][1,3,4]thiadiazine‐3‐thiol 16 in refluxing EtOH/DMF mixture containing KOH. Bis(triazolothiadiazine) 22 attached to the benzene core through the thiadiazine ring via an amine linkage was prepared in 70% yield starting from p‐phenylenediamine 19 by, firstly, acylation with chloroacetyl chloride 18 followed by bis‐alkylation with 1,2,4‐triazole 20 and subsequent intramolecular ring closure upon treatment with phosphorus oxychloride. 相似文献
The reaction of 10‐azidoacetyl‐10H‐phenothiazine with olefinic dipolarophiles depends on the reaction temperature. In refluxing toluene, a mixture of enamine and aziridine is formed in 3:1 ratio. The reaction mechanism appears to involve a Michael‐type addition of the nucleophilic N1 azide atom to the olefinic double bond. In chloroform, a cycloaddition reaction takes place with the formation of a 4,5‐dihydro‐1,2,3‐triazole. The heating of dihydrotriazoles in toluene is accompanied by nitrogen elimination leading to a mixture of enamine and aziridine in 1:3 ratio. J. Heterocyclic Chem., 2011. 相似文献
Three photoluminescent complexes containing either ZnII or CdII have been synthesized and their structures determined. Bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(dicyanamido‐κN 1)zinc(II), [Zn(C12H10N6)2(C2N3)2], (I), bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(dicyanamido‐κN 1)cadmium(II), [Cd(C12H10N6)2(C2N3)2], (II), and bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(tricyanomethanido‐κN 1)cadmium(II), [Cd(C12H10N6)2(C4N3)2], (III), all crystallize in the space group P , with the metal centres lying on centres of inversion, but neither analogues (I) and (II) nor CdII complexes (II) and (III) are isomorphous. A combination of N—H…N and C—H…N hydrogen bonds and π–π stacking interactions generates three‐dimensional framework structures in (I) and (II), and a sheet structure in (III). The photoluminescence spectra of (I)–(III) indicate that the energies of the π–π* transitions in the coordinated triazole ligand are modified by minor changes of the ligand geometry associated with coordination to the metal centres. 相似文献
Some 1,4‐bis[(3‐aryl)‐s‐triazolo[3,4‐b]‐[1,3,4]thiadiazole‐6‐yl]benzenes are readily accessible in high yields by reaction of 3‐aryl 4‐amino‐5‐mercapto‐1,2,4‐triazole with p‐phthalic acid. 相似文献
The reaction of 3-allylthio-5-phenyl-4H-1,2,4-triazole with iodine to give a mixture of 5,6-dihydro-5-iodomethyl-3-phenyl[1,3]thiazolo[2,3-c][1,2,4]triazole, 6,7-dihydro-6-iodo-3-phenyl-5H-[1,2,4]triazolo[3,4-b][1,3]thiazine, 5,6-dihydro-6-iodomethyl-2-phenyl[1,3]thiazolo[3,2-b][1,2,4]triazole, and 6,7-dihydro-6-iodo-2-phenyl-5H-[1,2,4]triazolo[5,1-b][1,3]thiazine has been studied. The structure of the products obtained was established using 1H NMR spectroscopy of their dehydriodination products. 相似文献
Synthesizing energetic metal–organic frameworks at ambient temperature and pressure has been always a challenge in the research area of energetic materials. In this work, through in situ controllable synthesis, energetic metal–organic framework gem‐dinitromethyl‐substituted dipotassium 4,5‐bis(dinitromethyl)‐1,2,3‐triazole with a “cage‐like” crystal packing was obtained and characterized. Most importantly, for the first time, we found that it could be successfully afforded with a catalytic effect of trifluoroacetic acid. This new compound exhibited its high density (2.04 g cm?3) at ambient temperature, superior detonation velocity (8715 m s?1) to that of lead azide (5877 m s?1) and comparable to that of RDX (8748 m s?1). Its detonation products are mainly N2 (48.1 %), suggesting it is also a green energetic material. The above‐mentioned performance indicates its potential applications in detonator devices as lead‐free primary explosive. 相似文献
We present herein the synthesis and properties of the largest hitherto unknown graphyne fragment, namely trigonally expanded tetrakis(dehydrobenzo[12]annulene)s (tetrakis‐DBAs). Intramolecular three‐fold alkyne metathesis reactions of hexakis(arylethynyl)DBAs 9 a and 9 b using Fürstner’s Mo catalyst furnished tetrakis‐DBAs 8 a and 8 b substituted with tert‐butyl or branched alkyl ester groups in moderate and fair yields, respectively, demonstrating that the metathesis reaction of this protocol is a powerful tool for the construction of graphyne fragment backbones. For comparison, hexakis(arylethynyl)DBAs 9 c – g have also been prepared. The one‐photon absorption spectrum of tetrakis‐DBA 8 a bearing tert‐butyl groups revealed a remarkable bathochromic shift of the absorption cut‐off (λcutoff) compared with those of previously reported graphyne fragments due to extended π‐conjugation. Moreover, in the two‐photon absorption spectrum, 8 a showed a large cross‐section for a pure hydrocarbon because of the planar para‐phenylene‐ethynylene conjugation pathways. Hexakis(arylethynyl)‐DBAs 9 c – e and 9 g and tetrakis‐DBA 8 b bearing electron‐withdrawing groups aggregated in chloroform solutions. Comparison between the free energies of 9 e and 8 b bearing the same substituents revealed the more favorable association of the latter due to stronger π–π interactions between the extended π‐cores. Polarized optical microscopy observations, DSC, and XRD measurements showed that 8 b and 9 e with branched alkyl ester groups displayed columnar rectangular mesophases. By the time‐resolved microwave conductivity method, the columnar rectangular phase of 8 b was shown to exhibit a moderate charge‐carrier mobility of 0.12 cm2 V?1 s?1. These results indicate that large graphyne fragments can serve as good organic semiconductors. 相似文献
The copper‐iodine based coordination polymer [Cu4I2(bmte)]n ( 1 ) [H2bmte = 1,2‐bis(5‐methyl‐1H‐1,2,4‐triazol‐3‐yl)ethane] was synthesized using cuprous iodide and a flexible 3‐substituted, ethyl‐bridging bis(triazole) ligand under solvothermal conditions. X‐ray diffraction analysis reveals that compound 1 shows a 3D framework containing Cu4I4 clusters and alternating left‐ and right‐handed [Cu(triazole)] helices, which result in a (4,8)‐connected fluorite (flu) topological network. Moreover, compound 1 exhibits orange phosphorescence with the emission maxima at 590 nm in the solid state at room temperature. 相似文献
A series of new chiral 2(5H)‐furanone derivatives containing bis‐1,2,3‐triazole moiety were designed and synthesized from (5S)‐5‐alkoxy‐3,4‐dihalo‐2(5H)‐furanones 1 , dicarboxyl amino acids 2 , propargyl bromide, and organic azides 5 under mild conditions via the sequential three steps, including asymmetric Michael addition‐elimination, substitution and no‐ligand click reaction. Twelve new intermediates, including N‐[5‐alkoxy‐2(5H)‐furanonyl] dicarboxyl amino acids 3 and their corresponding propargyl esters 4 , and twelve target molecules 6 were characterized by FTIR, 1H NMR, 13C NMR, MS and elemental analysis. The influences of different synthetic conditions and substrates in each step were investigated. The research provides a new method and idea for the synthesis of 2(5H)‐furanone compounds with polyheterocyclic structure due to the diversities of four basic unit molecules. 相似文献