Reaction of 2‐[(2‐aminoethyl)amino]ethanol with pyridine‐2‐carbaldehyde and complexation of the products with CuII and CdII along with docking studies

The reaction between 2‐[2‐(aminoethyl)amino]ethanol and pyridine‐2‐carbaldehyde in a 1:2 molar ratio affords a mixture containing 2‐({2‐[(pyridin‐2‐ylmethylidene)amino]ethyl}amino)ethanol (PMAE) and 2‐[2‐(pyridin‐2‐yl)oxazolidin‐3‐yl]‐N‐(pyridin‐2‐ylmethylidene)ethanamine (POPME). Treatment of this mixture with copper(II) chloride or cadmium(II) chloride gave trichlorido[(2‐hydroxyethyl)({2‐[(pyridin‐2‐ylmethylidene)amino]ethyl})azanium]copper(II) monohydrate, [Cu(C₁₀H₁₆N₃O)Cl₃]·H₂O or [Cu(HPMAE)Cl₃]·H₂O, 1 , and dichlorido{2‐[2‐(pyridin‐2‐yl)oxazolidin‐3‐yl]‐N‐(pyridin‐2‐ylmethylidene)ethanamine}cadmium(II), [CdCl₂(C₁₆H₁₈N₄O)] or [CdCl₂(POPME)], 2 , which were characterized by elemental analysis, FT–IR, Raman and ¹H NMR spectroscopy and single‐crystal X‐ray diffraction. PMAE is potentially a tetradentate N₃O‐donor ligand but coordinates to copper here as an N₂ donor. In the structure of 1 , the geometry around the Cu atom is distorted square pyramidal. In 2 , the Cd atom has a distorted octahedral geometry. In addition to the hydrogen bonds, there are π–π stacking interactions between the pyridine rings in the crystal packing of 1 and 2 . The ability of PMAE, POPME and 1 to interact with ten selected biomolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II and B‐DNA) was investigated by docking studies and compared with doxorubicin.     

Ruthenium‐catalyzed synthesis of quinolines via reductive heteroannulation of nitroarenes with 3‐amino‐1‐propanols

Nitroarenes are reductively cyclized with 3‐amino‐1‐propanols in dioxane/H₂O in the presence of a ruthenium catalyst and tin(II) chloride dihydrate together with isopropanol to afford the corresponding quinolines. A reaction pathway involving initial reduction of nitroarenes to anilines, propanol group transfer from 3‐amino‐1‐propanols to anilines, N‐alkylation of anilines by 3‐anilino‐1‐propanols and heteroannulation of 1,3‐dianilinopropanes is proposed.     

Simple,Convenient Method for the Synthesis of Substituted Furan-2(5H)-one Derivatives Using Tin(II) Chloride

Furan-2(5H)-one derivatives have been synthesized by a simple, efficient, one-pot, three-component condensation of anilines, dimethylacetylenedicarboxylate, and aromatic aldehydes in the presence of a catalytic amount of tin(II) chloride in excellent yields.     

The structure of di-μ-chloro- bis - {chloro( N,N -diethylethane-1,2-diamine-κ 2)copper(II)}

Dichloro(N,N-diethyl-ethane-1,2-diamine)copper(II) has copper(II) ions in square pyramidal coordination. The two nitrogen atoms of the diamine {Cu–N_primary?=?1.979(3), Cu–N_tertiary?=?2.108(2)?Å} and two chloride ions are in the basal plane {Cu–Cl1?=?2.2680(9), Cu–Cl2?=?2.2989(8)?Å}. A centrosymmetrical dimer di-μ-chloro-bis{chloro(N,N-diethylethane-1,2-diamine-κ²)copper(II)}, C₆H1₆Cl₂CuN₂, is formed by axial coordination by Cl2, trans to the tertiary nitrogen, to a second copper(II) ion, with Cu?···?Cuⁱ?=?3.4855(9) and Cl2–Cuⁱ?=?2.7860(8)?Å. The dimer is also linked by H-bond N1–H?···?Cl1ⁱ.     

Application of a wall jet disk electrode combined with an electrochemical quartz crystal microbalance to the study of the dissolution of copper in acidic chloride media

An electrochemical quartz crystal microbalance (EQCM) system combined with a wall jet disk electrode (WJDE) was applied to the investigation of copper dissolution in acidic chloride media. The average valence of dissolved ions, n, was calculated from the resonant frequency of the quartz crystal and the applied current. The value of n between 1 and 2 indicates that both Cu(I) and Cu(II) dissolved from the copper electrode at the same time. The formation rate of Cu(II) increased with decreasing chloride concentration. The influence of the hydrodynamic conditions on the dissolution behaviour was discussed.     

以手性相转移催化剂为配体的单分子Cu (II)配合物及其不对称催化反应

在加热条件下,手性相转移催化剂氯化- N -（4-乙烯基苄基）辛可尼定（L1）与氯化铜在2-丁醇中反应,可得到一个单一手性的二价铜单分子配合物 N -（4-乙烯基苄基）辛可尼定三氯化铜(1)。配合物（1）和配体(L1)都可用于催化 N -（二苯基亚甲基）氨基乙酸叔丁基酯（3）烷基化反应,催化结果表明：使用配合物N-（4-乙烯基苄基）辛可尼定三氯化铜的反应对映体选择性比使用配体的更高,配合物催化能力的提高可能与配合物中喹啉环的N原子与铜配位、分子刚性增加有关。     

Ligand‐free CuTC‐catalyzed N‐arylation of amides,anilines and 4‐aminoantipyrine: synthesis of N‐arylacrylamides, 4‐amido‐N‐phenylbenzamides and 4‐amino(N‐phenyl)antipyrenes

N‐Arylation of amides and anilines with aryl iodides was efficiently catalyzed by copper thiophenecarboxylate under ligand‐free conditions with good to excellent yields. A variety of substituted aryl iodides, amides, anilines and 4‐aminoantipyrine were found to be applicable to the simple catalytic system. Furthermore, some practical, unique secondary amides, such as N‐arylacrylamides and 4‐amido‐N‐phenylbenzamides, and 4‐amino(N‐phenyl)antipyrenes, which are difficult to obtain by the classical methods, were prepared. Copyright © 2013 John Wiley & Sons, Ltd.     

The solvent effect on the isotropic hyperfine interaction in some aliphatic polyamine copper(II) complexes

ESR and optical absorption studies are described for a number of copper(II) chelates with aliphatic polyamines, exhibiting both square pyramidal and square bipyramidal coordination around the copper ion. The complexes studied were bis(N,N′-dimethylethylenediamine)copper(II) sulphate tetrahydrate, bis(N,N′-diethylethylenediamine)copper(II) nitrate, diaquosulphato(N,N,N′,N′-tetramethylethylenediamine)copper(II) hydrate, dinitrato(N,N,N′,N′-tetramethylethylenediamine)copper(II), dichloro(N,N,N′,N′-tetramethylethylenediamine)copper(II) and dithiocyanato(N,N,N′,N′-tetramethylethylenediamine)copper(II). The ESR measurements were carried out in methanol, dimethyl sulphoxide, dimethylformamide and pyridine, at room and liquid nitrogen temperatures. The molecular orbital coefficients were estimated assuming an axial symmetry. The parameter χ proportional to the hyperfine constants shows a variation with the solvent for all these complexes. The χ values in solution are lower than the corresponding average χ values reported in the solid state for each complex. The solvent effect and the influence of 4s character in the ground state are discussed. The χ values, either calculated or reported, for a number of copper complexes for [4O], [3O, N], [2O, 2N], [O, 3N] and [4N] environments around copper(II) are presented.     

Copper Complexes of Dicarboxy‐Functionalized Tetramethylcyclam. Crystal Structures of Complexes with the Axial Ligands Perchlorate,Chloride, and Iodide

6,13‐Dicarboxy‐1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane‐copper(II) perchlorate ( 2 a ) was synthesized via one‐step cyclocondensation from bis(N,N′‐dimethyl‐ ethylenediamine‐copper(II) perchlorate, formaldehyde and malonic acid. Anion exchange yielded the analogous copper(II) chloride ( 2 b ) and iodide ( 2 c ) complexes. Crystal structures of 2 a – 2 c show a square‐planar N₄‐co‐ordination of the copper(II) ion with RRSS configuration of the nitrogens and perchlorate, chloride or iodide ions weakly co‐ordinated axially. Relating to the macroring, the carboxy groups are in trans‐position. In 2 a , the packing is typical of parallel strands of complex subunits effected by dimerization of the carboxy groups, while in 2 b and 2 c formation of the supramolecular strands involve hydrogen bond interactions between carboxy groups and halide anions.     

Structural and spectral studies of di-2-pyridyl ketone N(4)-methyl- and N(4)-dimethylthiosemicarbazone and their metal complexes

Cobalt(II), nickel(II) and copper(II) complexes of di-2-pyridyl ketone N(4)-methyl- and N(4)-dimethylthiosemicarbazone have been prepared and characterized by physical and spectral methods. Use of different ligand-to-metal chloride molar ratios in the preparation of the complexes has produced both mononuclear and polynuclear species for the three metal ions. Crystal structures of the uncomplexed di-2-pyridyl ketone N(4)-methylthiosemicarbazone and a nickel(II) complex, di-2-pyridyl ketone N(4)-dimethylthiosemicarbazone, have been determined and aid the assignments of the i.r., n.m.r., u.v.–vis.–n.i.r. and e.s.r. spectra.     

Efficient Aromatization of 4,5-Dihydro-3(2H)-Pyridazinones Substituted at 5 Position by Using Anhydrous Copper (II) Chloride

An efficient conversion of 5-substituted-4,5-dihydro-3(2H)-pyridazinones into their corresponding dehydrogenated derivatives was achieved by treatment with anhydrous copper(II) chloride in acetonitrile.     

Competitive complexation in the copper(II) chloride-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylformamide-Aerosil system

Competitive complexation in the copper(II) chloride-N,N-dimethylformamide (DMF)-Aerosil system was studied by IR spectroscopy. It was found that adsorption from organic solutions containing copper(II) chloride and DMF resulted in the formation of the following three types of DMF complexes: self-associates of DMF, DMF complexes with surface hydroxyl groups, and DMF complexes with Cu(II) ions. The removal of DMF resulted in the sequential degradation of, initially, self-associates; next, complexes with silanol groups; and, finally, complexes with copper ions.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 917–920.Original Russian Text Copyright © 2004 by Golubeva, Zubareva.     

Impact of Substituents Attached to N-Heterocyclic Carbenes on the Catalytic Activity of Copper Complexes in the Reduction of Carbonyl Compounds with Triethoxysilane

By using functionalized imidazolium salts such as 1‐allyl‐3‐alkylimidazolium or 1‐alkyl‐3‐vinylimidazolium salts as carbene ligand precursors, the reduction of aryl ketones with triethoxysilane may be catalyzed by copper salt/imidazolium salt/KO^tBu systems. The functional substituents attached to the N‐heterocyclic carbene (NHC) serve to enhance the catalytic activity. Different copper salts also have an effect on the catalytic activity, with copper(II) acetate monohydrate being superior to copper(I) chloride.     

Cyclocopolymerization of allyl‐acrylate quaternary ammonium salts with diallyldimethylammonium chloride

A series of copolymers of N,N‐dialkyl‐N‐2‐(methoxycarbonyl)allyl allyl ammonium chloride, N,N‐dialkyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride, and N,N‐dialkyl‐N‐2‐(t‐butoxycarbonyl)allyl allyl ammonium bromide with diallyldimethylammonium chloride (DADMAC) were prepared in water at 60 °C with 2,2′‐azo‐bis(2‐amidinopropane)dihydrochloride. A strong effect of ester substituents on cyclopolymerization was observed. The methyl and ethyl ester monomers showed high cyclization efficiencies during homopolymerizations and copolymerizations. Unexpectedly, the t‐butyl ester derivatives showed high crosslinking tendencies. Water‐soluble copolymers were obtained only with a decrease in the molar fraction of t‐butyl ester monomer below 30%. Relative reactivities of the allyl‐acrylate monomers in photopolymerizations were compared with the relative reactivity of DADMAC. Allyl‐acrylate monomers were much more reactive than DADMAC; the photopolymerization rate decreased in the following order: N,N‐morpholine‐N‐2‐(t‐butoxycarbonyl)allyl allyl ammonium bromide > N,N‐piperidyl‐N‐2‐(t‐butoxycarbonyl)allyl allyl ammonium bromide > N,N‐dibutyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride > N,N‐piperidyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride ∼ N,N‐morpholine‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride ∼ N,N‐piperidyl‐N‐2‐(methoxycarbonyl)allyl allyl ammonium chloride > N‐methyl‐N‐butyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride. Intrinsic viscosities of the polymers measured in 0.09 M NaCl ranged from 1.06 to 3.20 dL/g. The highest viscosities were obtained for copolymers of the t‐butyl ester monomers with piperidine and morpholine substituents. The copolymer of the t‐butyl ester with piperidine substituent and DADMAC was hydrolyzed in acid to give a polymer with zwitterionic character. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 640–649, 2001     

Halido-bridged Copper(II) Complexes with 1-tert-Butyl-1H-tetrazole: Crystal Structure and Magnetic Properties

Complex [Cu(tbt)Cl₂]_n (tbt = 1-tert-butyl-1H-tetrazole) was prepared by reaction of tbt with copper(II) chloride in solution. According to single-crystal X-ray analysis, this complex presents 1D coordination polymer, formed at the expense of double chlorido bridges between neighboring pentacoordinate copper(II) cations. 1-tert-Butyl-1H-tetrazole acts as monodentate ligand coordinated by Cu^II cations via the heteroring N⁴ atoms. The temperature-dependent magnetic susceptibility measurements of novel complex [Cu(tbt)Cl₂]_n as well as described previously 1D coordination polymer [Cu(tbt)₂Cl₂]_n, and linear trinuclear complex [Cu₃(tbt)₆Br₆], were carried out. Magnetic studies revealed that the copper(II) ions were weakly ferromagnetically coupled in polymeric copper(II) chloride complexes, whereas complex [Cu₃(tbt)₆Br₆] showed antiferromagnetic coupling.     

Synthesis, Crystal Structure and Properties of Polyamine Copper(II) Complexes

Two polyamine copper(II) complexes were synthesized by the reaction between N,N,N′,N′-tetrakis(2′-aminoethyl)propane-1,2-diamine hexahydrochloride and copper(II) perchlorate under almost the same conditions except for reaction temperature. The crystal structures of two complexes were determined by X-ray diffraction techniques, which shows that one of the complexes is unexpected and is a double chlorine or chloride-bridged dinuclear copper(II) complex formed by two diethylenetriamines, and another is a pentadentate mononuclear copper(II) complex composed of homo-protonated N,N,N′,N′-tetrakis(2′-aminoethyl)propane-1,2-diamine. The mechanism of the reaction leading to form the unexpected complex was discussed. The UV-visible spectra and cyclic voltammogram of the complexes were measured.     

Interaction of Co(II), Ni(II), Cu(II), and Zn(II) with N,N′-(aldose)2-thiocarbohydrazide: synthesis,electrochemistry, and spectral characterization

Complexes of Co(II), Ni(II), Cu(II), and Zn(II) with N,N′-(aldose)₂–thiocarbohydrazide (LH₂) were synthesized, isolated as solid products and characterized by analytical means as well as by spectral techniques, FTIR, ¹H NMR, EPR, UV spectroscopy, and CD. All the metal ions formed M[LH]X complexes. Molar conductance values in DMF indicate non-electrolytic complexes. In DMSO with tetramethylammonium chloride supporting electrolyte, the copper complex displays irreversible cyclic voltammetric responses with E _p near ?0.621 and 0.461 V versus Ag/AgCl at scan rate of 0.1 V s^?1. Probable structures for the complexes are proposed.     

Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridine. Part 4. The 3-piperidinyl derivative

Summary Metal ion complexes of the thiosemicarbazone, 3-piperidinyl-3-thiocarboxylic acid-2-[1-(2-pyridyl)ethylidene]hydrazide (HLpip) have been prepared and spectrally characterized. HLpip coordinates both as the deprotonated ligand (i.e., pyridylN, azomethineN, and thione sulphur) and the neutral ligand (i.e., pyridylN and azomethineN) with the sulphur possibly weakly coordinating in [Ni(HLpip)₂](BF₄)₂. All three preparative cobalt(II) salts yielded cobalt(III) cationic complexes. The nickel(II) and copper(II) chloride salts gave [M(Lpip)Cl] solids while complexes involving the neutral ligand were prepared with the corresponding bromide salts. Significant differences in the spectral properties of the various complexes are observed when compared to other thiosemicarbazones prepared from 2-acetylpyridine.     

One-pot synthesis of N-methylindoles from N-methylanilines and of benzofurans from phenols using transition-metal carbene X-H insertion reactions

Transition-metal carbene X-H insertion reactions (X=N or O) have been employed in the simple conversion of anilines and phenols into indoles and benzofurans, respectively. Thus copper(II) catalyzed N-H insertion reactions of α-diazo-β-ketoesters with N-methylanilines followed by treatment with acidic ion-exchange resin gives indoles. In a similar manner, dirhodium(II) catalyzed O-H insertion reactions of α-diazo-β-ketoesters with phenols followed by treatment with PPA gives benzofurans.     

Three transition‐metal complexes with the macrocyclic ligand meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane (L): [Cu(ClO4)2(L)], [Zn(NO3)2(L)] and [CuCl(L)(H2O)]Cl

The three transition‐metal complexes, (meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane‐κ⁴N)bis(perchlorato‐κO)copper(II), [Cu(ClO₄)₂(C₁₈H₄₀N₄)], (I), (meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane‐κ⁴N)bis(nitrato‐κO)zinc(II), [Zn(NO₃)₂(C₁₈H₄₀N₄)], (II), and aquachlorido(meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane‐κ⁴N)copper(II) chloride, [CuCl(C₁₈H₄₀N₄)(H₂O)]Cl, (III), are described. The molecules display a very similarly distorted 4+2 octahedral environment for the cation [located at an inversion centre in (I) and (II)], defined by the macrocycle N₄ group in the equatorial sites and two further ligands in trans‐axial positions [two O–ClO₃ ligands in (I), two O–NO₂ ligands in (II) and one chloride and one aqua ligand in (III)]. The most significant difference in molecular shape resides in these axial ligands, the effect of which on the intra‐ and intermolecular hydrogen bonding is discussed. In the case of (I), all strong hydrogen‐bond donors are saturated in intramolecular interactions, while weak intermolecular C—H...O contacts result in a three‐dimensional network. In (II) and (III), instead, there are N—H and O—H donors left over for intermolecular interactions, giving rise to the formation of strongly linked but weakly interacting chains.