Syntheses,characterisation and solid state thermal studies of 1-(2-aminoethyl)piperidine (L), 1-(2-aminoethyl)pyrrolidine (L′) and 4-(2-aminoethyl)morpholine (L″) complexes of nickel(II): X-ray single crystal structure analyses of trans-[NiL2(CH3CN)2](ClO4)2, trans-[NiL2(NCS)2] and trans-[NiL″2(NCS)2]

Reactions of nickel(II) salts with substituted ethane-1,2-diamine where one of the amine nitrogens is a part of a flexible cyclic ring, e.g. 1-(2-aminoethyl)piperidine (L), 1-(2-aminoethyl)pyrrolidine (L′) and 4-(2-aminoethyl)morpholine (L″) produce a number of complexes of the type: (i) Ni(AA)₂X₂ (where X=CF₃CO₂ ⁻, SCN⁻ and NO₂ ⁻; AA represents L/L′/L″); (ii) Ni(AA)₂(CH₃CN)₂X₂ (X=ClO₄ ⁻ and NO₃ ⁻); (iii) Ni(AA)₂(H₂O)₂X₂ (X=CF₃SO₃ ⁻, Cl⁻, Br⁻ and I⁻); and (iv) Ni(AA)₂(H₂O)₄X₂ (X=0.5SO₄ ²⁻, 0.5SeO₄ ²⁻ and CF₃SO₃ ⁻). The complexes possess octahedral geometry. The major complexes upon desolvation retain trans-geometry, some of which are cis with respect to the counter-anion and a few of them are square planar. X-ray single crystal structure analyses of trans-[NiL₂(CH₃CN)₂](ClO₄)₂, trans-[NiL₂(NCS)₂] (violet) and trans-[NiL″₂(NCS)₂] (sky-blue) have been done. The violet and sky-blue thiocyanato species have blue and green coloured isomers, respectively, and these pairs of isomers are proposed to be conformational isomers. Solid state thermal investigation of the complexes has been carried out. The complexes show thermochromism due to deaquation–anation/deaquation reaction/change of conformation. Only [NiL₂](ClO₄)₂, [NiL′₂(CF₃CO₂)₂] and [NiL″₂(NO₂)₂] undergo thermally induced phase transition. The effect of flexible ring size on diamine has been discussed.     

[Ru(bpy)2L]2+、[Ru(phen)2L]2+(L=pytp,pztp)电子结构与抗癌活性研究

Theoretical studies on the complexes Ru(bpy)2L2+, Ru(phen)2L2+ (L=pytp,pztp) were carried out by using the density functional theory (DFT) method at B3LYP/LanL2DZ level. The relation between electronic structures and anti-cancer activities of complexes was investigated. The increasing of N in the main ligand can strengthen the interaction of complexes with DNA and anti cancer activities of complexes. The calculation results show that for complexes I-IV, their energies of LUMO orbital are in the order of εI>εII, εIII>εIV, the electron cloud components of LUMO come mainly from main ligands and the content distributing is in the order of I相似文献   

Synthesis of 1-[6-Fluoro-(2S)-3H,4H-dihydro-2H-2-chromenyl]-(1R)-1,2- ethanediol and 1-[6-Fluoro-(2R)-3H,4H-dihydro-2H-2-chromenyl]- (1R)-1,2-ethanediol

Benzopyran compounds possess diverse pharmacological properties such as β-blockade, anticonvulsant and antimicrobial.[1,2] Our interest has been focused on the synthesis of 1-[6-Fluoro-2S]-3H,4H-dihydro-2H-2-chromenyl]-(1R)-1,2-ethanediol (6) and 1-[6-fluoro-(2R)-3H,4H-dihydro-2H-2-chromenyl]-(1R)-1,2-ethanediol (7) which are particularly convenient precursor to (S,R,R,R)-NE (8). 8 containing four asymmetrical carbon atoms was reported to be the most active isomer.[3] Chandrasekhar[4] has reported on the synthesis of 8. The key step to synthesize this compound is to obtain the chiral chromanone 6 and 7. 6 was accomplished in 8 steps by the Clasien rearrangement and a one-pot Sharpless asymmetric epoxidation, but the compound 7 was accomplished in 10 steps. Johannes[5] used Zr-catalytic kinetic resolution of allylic ethers and Mo-catalyzed chromene formation to synthesize 8 in 14 steps. However both of the methods request many synthetic steps and expensive reagents.     

Synthesis of binuclear complexes of PdCl2 with chiral α,α′-diamino-meta-xylene dioximes H2L1, H2L2, and H2L3, the derivatives of the terpenes (+)-3-carene, (R)-(+)-limonene, and (S)-(−)-α-pinene. Crystal structure of [Pd2(H2L1)Cl4]

Chiral α,α′-diamino-meta-xylene dioximes H₂L¹, H₂L², and H₂L³ were obtained from the naturally occurring terpenoids (+)-3-carene, (R)-(+)-limonene, and (S)-(?)-α-pinene, respectively. Reactions of these ligands with PdCl₂ gave the diamagnetic complexes Pd₂(H₂L¹)Cl₄ (I), Pd₂(H₂L²)Cl₄ (II), and Pd₂(H₂L³)Cl₄ (III). According to X-ray diffraction data, the crystal structure of complex I consists of acentric binuclear molecules [Pd₂(H₂L¹)Cl₄]. The coordination polyhedron PdN₂Cl₂ is a square distorted in a tetrahedral manner (trapezium) made up of two N atoms of the tetradentate bridging cyclic ligand H₂L¹ and two Cl atoms. The fragments PdCl₂ in the complex are cis to each other. According to the ¹H NMR spectra of complexes I–III in CDCl₃, the organic ligands are coordinated through the N atoms; in solution, the complexes exist in several forms.     

The coordination chemistry of mono and bis(di-2-pyridylamine)copper(II) complexes: preparation,characterization and crystal structures of [Cu(L)(NO2)2], [Cu(L)(H2O)2(SO4)], [Cu(L)2(NCS)](SCN)·0.5DMSO and [Cu(L)2(SCN)2]

The crystal structures of two mono(dpyam)copper(II) complexes, [Cu(dpyam)(NO₂)₂] (1) and [Cu(dpyam)(H₂O)₂(SO₄)] (2) and two dithiocyanate compounds containing bis(dpyam)copper(II) units, [Cu(dpyam)₂(NCS)](SCN)·0.5DMSO (3) and [Cu(dpyam)₂(SCN)₂] (4) have been determined by X-ray crystallography. The second orthorhombic form of the monomeric Cu(II) complex 1 was obtained by the reaction of di-2-pyridylamine (dpyam) with CuCl and NaNO₂ in water–methanol solution. Each copper(II) ion in 1 exhibits a tetrahedrally-distorted square base of the CuN₂O₂ chromophore, with off-the-z-axis coordinated nitrito groups weakly bound in approximately axial positions. Complex 2 is an example of a polymeric copper(II) derivative containing the bidentate bridging sulfate ligand in the long-bonded axial positions. Each copper(II) ion in 2 shows an elongated tetragonal octahedral stereochemistry. The CuN₄N′ chromophore of 3 involves a square-based pyramidal structure, slightly distorted towards a trigonal bipyramidal stereochemistry, τ=0.13. One of the SCN⁻ anions is bonded to the copper(II) ion via the N atom in the axial position of the square pyramid. Complex 4 is centrosymmetric and octahedrally elongated, with the SCN⁻ anions coordinating in axial positions via the S atom. The structures of complexes 1–4 and their ESR and electronic reflectance spectra are compared with those of related complexes.     

Electrochemical studies of the bis (triphenyl phosphine) ruthenium(II) complex,cis -[RuCl2(L)(PPh3)2], with L = 2-(2′-pyridyl)quinoxaline

Electrochemical studies of the newly synthesized bis(triphenyl phosphine) ruthenium(II) complex, cis-[RuCl₂(L)(PPh₃)₂] (1, with L = 2-(2′-pyridyl)quinoxaline, C₁₃N₃H₉), were performed in acetonitrile (ACN). For this purpose, cyclic voltammograms (CVs) as well as electrochemical impedance spectra (EIS) were recorded on either glassy carbon (GC), platinum (Pt), gold (Au), or multi-walled carbon nanotube (MWCNT) electrodes. Qualitative examination of solutions of 1 in ACN was performed on the basis of conductivity measurements and electrospray ionization mass spectrometry (ESI–MS). The conductivity data suggest that 1 is a 1 : 1 type electrolyte in ACN. The ESI spectra further demonstrate that upon dissolution of 1 in ACN progressive replacement of chloro- and PPh₃-ligands by ACN occurs, leading to formation of [RuCl(L)(PPh₃)(CH₃CN)₂]⁺Cl^?, [2 ⁺ Cl ^? ]. The CVs recorded for [2 ⁺ Cl ^? ] on various working electrodes demonstrate that the reversibility of the redox couple 2^{2 +/+} enhances with the order: Au < Pt < MWCNT < GC. The EI spectra verify that GC and MWCNT electrodes provide insignificant barrier for interfacial electron transfer since they afford less charge-transfer resistance.     

Synthesis, crystal, and molecular structure of the solvated complex [MoO2(L)] · DMF (L2− = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol anion)

A new dioxomolybdenum(VI) complex, [MoO₂(L)] · DMF, where L^2? = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol, has been synthesized. Its structure has been determined by X-ray diffraction analysis. The Mo atom is octahedrally coordinated by two oxo ligands that are in cis-positions with respect to each other, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) ligand L, and the DMF oxygen atom.     

SYNTHESIS, CHARACTERIZATION OF 2-[2-(3-NITRO-4-METHOXYLPHENYL) VINYLI-1-ME

ＳＹＮＴＨＥＳＩＳ，ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦ２－［２－（３－ＮＩＴＲＯ－４－ＭＥＴＨＯＸＹＬＰＨＥＮＹＬ）ＶＩＮＹＬＩ－１－ＭＥＴＨＹＬＰＹＲＩＤＩＮＩＵＭＰＥＮＴＡＡＮＤＨＥＸＡＮＩＴＲＡＴＯＲＡＲＥＥＡＲＴＨ（Ⅲ）ＣＯＭＰＬＥＸＥＳＨ...     

3-取代-(1H)-嘧啶[1, 2-a]喹啉-1-酮和2-取代嘧啶[1, 2a]苯骈 咪唑-4-(10H)- 酮的简便合成法

本文利用2-氨基喹啉和2-氨基苯骈咪唑作为亲核试剂,与5-(双甲硫基亚甲基)丙二酸亚异丙酯(1)、5-(甲硫基亚烃基)丙二酸亚异丙酯(3)反应,开发出3-取代-(1H)-嘧啶-[1,2-a]喹啉-1-酮(5)和2-取代嘧啶[1,2-a]苯骈咪唑-4-(10H)-酮(6)通用的简便合成法。     

CRYSTAL STRUCTURE OF μ-[meso-1, 2-BIS(PHENYLSULFINYL)-ETHANE]-(O,O'''')-BIS[DIPHENYLTIN(Ⅳ) DICHLORIDE]

<正> The title complex is of triclinic system space group P1 with its cell parameters: a = 9. 386(1), b = 9. 412(2), c=11. 549(2)(?), α=97. 91(2), β = 81.70(1), γ= 102. 63(1)°, V= 979.2(?)3, Z = l, Mr = 966. 01, Dx =1. 638 gcm-3, μ(MoKα) = 16. 896cm-1, F (000) = 478, final R = 0. 033 and Rw = 0. 046 for 3424 reflections with I≥3σ(I). The two O atoms of the ligand are bonded to two Sn atoms to form a bridged binuclear species which lies on the crystallographic centre of symmetry situated at the centre of the ethylene C -C bond. The unique Sn atom exhibits a trigonalbipyramidal geometry.     

Tansition metal complexes with 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL): Synthesis and crystal structure of [Co(L)2(H2O)4] · 6H2O and [Cu(L)2(H2O)2] · 4H2O

Transition metal complexes of 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL), namely [Co(L)₂(H₂O)₄] · 6H₂O (I) and [Cu(L)₂(H₂O)₂] · 4H₂O (II), have been synthesized by a hydrothermal procedure and characterized by X-ray crystallography, CIF files CCDC nos. 1007524 (I), 1007525 (II). Both I and II are mononuclear molecules. In I, the Co²⁺ ion is in octahedral coordiantion environment and surrounded by four O atoms from water molecules and two carboxylate O atoms of two deprotonated ligand (L^?) occupied six culmination. While in II, the Cu²⁺ ion is located in a square-planar geometry, bounded to two aqua O atoms and two carboxylate O atoms from L^?.     

Synthesis,halogenation and structural characterization of (Z)-1-[2-(triphenylstannyl)vinyl]-l-cyclododecanol

Synthesis and characterization of (Z)-1-[2-(triphenylstannyl)vinylj-l-cyclododecanol,c-(CH2)11C(OH)CH=CHSnPh3,are reported,together with its halogenation by I2,Br2 and IC1 to yield derivatives of the types c-(CH2)11C(OH)CH=CHSnPh3_nXn (n=1,2; X=I,Br,Cl,respectively).The molecular structures of two compounds have been determined by X-ray diffraction analysis.The tin atom exhibits a distorted tetrahedral geometry in the crystal of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cyclododecanol,but a trigonal bipyramidal geometry in the monoiodo-derivative (Z)-1-[2-(diphenyliodo-stannyl)vinyl]-l-cyclododecanol and other derivatives,in which significant intramolecular coordinative interaction HO→Sn is observed.And the formation of a five-membered tin containing ring is significant for their antitumour activities.     

Crystal Structure of 1, 1-Dichloro-la, 3-diphenyl-1, la, 2, 3-tetrahydro-azirino [2, 1-d ] [1, 5]benzothiazepine (C_(22),H_(17)Cl_2NS )

1INTR0DUCTI0NBenzoheteroazepinecompoundsareimportantpharmaceuticalagents"-".Inre-centyears,ithasbeenfoundthatbenzoheter0azepinetricyclicderivatives,especiallythosefusedwithotherfiveorsix-memberedheterocycle,area1soofpotentialphar-maceuticalinterestst4-6j.Hence,muchattentionhasbeenpaidtothesynthesesofthem,suchasl,3-oxazino[3,2-djt1,5jbenzothia/diazepin-l-onet"'J,1,2,4-tria-zolo[4,3-dj[1,5jbenzothia/diazepine"',1,2,4-oxadiazolo[4,5-dj[l,5jbenzothia/diazepine',',andsoon.Meanwhiletheirstructur…     

Syntheses,molecular structures,and antiviral activities of 1- and 2-(2′-deoxy-d-ribofuranosyl)cyclohepta[d][1,2,3]triazol-6(1H)-ones and 1-(2′-deoxy-d-ribofuranosyl)cyclohepta[b]pyrrol-8(1H)-one

The synthesis of a novel class of 2′-deoxyribonucleosides possessing tropone-fused nitrogen heterocycles as nucleobases was developed. The reaction of alkali metal salts of 1H-cyclohepta[d][1,2,3]triazol-6-one with 2-deoxy-3,5-di-O-(p-toluoyl)-α-d-ribofuranosyl chloride (α-chlorosugar) afforded an anomeric mixture of N1- and N2-coupled glycosylation products. Good stereospecificity in relation to the amount of the β-anomer was achieved in the less polar solvent DME. The reactions of the sodium salt of 1H-cyclohepta[b]pyrrol-8-one and its 3-methyl derivative with an α-chlorosugar in DME gave the β-anomer of the N1-coupled glycosylation products. The glycosylation products were treated with NaOMe in MeOH to produce the desired 2′-deoxyribonucleosides. X-ray structural analyses of the three nucleosides prepared confirmed their anomeric configuration and revealed that their sugars were puckered. The β-anomers of the nucleosides had weak antiviral activities for herpes simplex virus type 1 and herpes simplex virus type 2 in comparison with those of acyclovir (ACV). These nucleosides showed no cytotoxicity on a lung (A549) and two colon (HT-29 and HCT-116) cancer cell lines.     

Crystal Structure of 3- (4-Methoxyphenyl )- 1-methylpyrrolo [2, 1-b] benzothiazole

lINTR0DUCTI0NSincebiologicalandpharmacol0gicalactivitieshavebeenwellknownfornumer-ousheterocyc1icar0matictricyc1es""',muchattenti0nhasbeenpaidtothesynthesisoftheheterocycliccompoundswithnovelringsystem(').Inrecentyears,ourwork-inggr0uphassynthesizedaseries0f1,5-benzothiazepineandl,5-benz0diazepinetri-cyclicderivativesandstudiedtheirstructurest4~10i.l,3-Disubstituded-pyrr0l0F2,1-bjbenz0thiazo1eshavebeenobtainedasmainbyproductsinthecycloadditionreactionofl,5-benzothiazepineswithdichl0rocarbe…     

Synthesis, crystal structure, and luminescent property of [Zn2(Ox)3]H2L · 4H2O (L = 2,2′-(1,4-butanediyl-bis(1H-benzimidazole))

A new complex [Zn₂(Ox)₃]H₂L · 4H₂O (L = 2,2??-(1,4-butanediyl)-bis(1H-benzimidazole)) (I) has been hydrothermally synthesized and characterized by the elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. It crystallizes in monoclinic space group P2₁/c with a = 10.108(2), b = 15.600(4), c = 9.768(2) ?, ?? = 105.289(3)·, V = 1485.7(6) ?³, Z = 4. Complex I is a 2D honeycomb-like polymer with pro-toned L and water molecules intercalating in the cavities. The luminescent spectra shows the emission peak of complex I is at 455 nm which is attributed to ligand-to-metal charge transfer.     

Syntheses,Structure and Biological Activities of 2-(1H-Benzo [1,2,3]triazole-1-yl)-1-(3-methyl-4-bromobiphenyl)-2-(1H-1,2,4-triazole-1-yl)ethanone

Introduction1,2,4-Triazole derivatives represent an interesting class of heterocyclic compounds[1]and have become the most rapidly expanding group of antifungal compounds with the advantages of toxicity, high oral bioavailabi-lity, and broad spectrum of a…     

(S)-1-[2-(3-羟基金刚烷-1-氨基)乙酰基]吡咯烷-2-甲酰胺的合成

为了对维格列汀进行质量控制,合成了其相关物质:(S)-1-[2-(3-羟基金刚烷-1-氨基)乙酰基]吡咯烷-2-甲酰胺(1)。本文以L-脯氨酸和盐酸金刚烷胺为原料,经仲N-氯乙酰化,酰胺化,氨基取代3步反应合成,合成的物质其结构经MS、1H-NMR和13C-NMR确证,纯度经HPLC检测亦符合国家药品生物制品检定所的规定。应用星点设计-效应面法优化工艺后,提高了其收率和纯度,具有重要的应用价值。