二氧化硅固载硫、氮杂冠醚铂配合物的合成及其催化烯烃硅氢化性能

二(β-氯乙基)烯丙胺与3,6-二氧杂辛-1,8-二硫醇在乙醇钠存在下关环缩合,得到具有烯基侧链的1,7-二硫杂-10,13-二氧杂-4-氮杂-4-烯丙基环十五烷.后者通过硅氢加成、二氧化硅固载.再与氯亚铂酸钾反应,合成了一种新型有机硅聚合物负载硫、氮杂冠醚及其铂配合物.该配合物对于烯烃硅氢加成反应具有良好的催化性能.     

Application of Crown Ether in Chemical Analysis Extraction of Copper(II)-Zincon Chelate Anion with Crown Ether Complex

Abstract

Crown ether-potassium ion complex extracts selectively copper-zincon anion complex as ion-pairs into chloroform phase in the presence of copper-zincon and zinc-zincon chelate anion, whereas quarternary ammonium ion extracts both anions. By measuring the absorbance of the chloroform phase at 615 nm, copper in the presence of zinc has been determined spectrophotometrically. The composition of extracted species was estimated to be Cu²⁺-zincon^4?-(KL⁺)₂.     

一种新型四氮杂取代三环冠醚的晶体结构及其配合物的合成与表征

合成了一种新型的四氮杂取代的三环结构冠醚4,13-二氧-1,7,10,16-四氮杂三环[14.2.1.1^7,10]二十烷(L7), 低温条件下在乙醚中培养出其单晶, 用X射线衍射法测定了晶体结构. 该晶体属单斜晶系, 空间群P2₁/n, 晶胞参数a＝0.8984(7) nm, b＝1.0805(9) nm, c＝1.1040(9) nm; Z＝2, β＝111.707(13)°; V＝0.9958(14) nm³, D_c＝1.189 g/cm³, μ＝0.092 mm^－1, F(000)＝392, R₁＝0.0649, wR₂＝0.1714. 制备了配体L7与金属盐的配合物, 分析结果表明, 配体L7与金属离子形成1∶1型的配合物.     

查尔酮冠醚PVC膜钾离子选择性电极的初步研究

查尔酮冠醚ＰＶＣ膜钾离子选择性电极的初步研究李廷盛，蔡汉临，王传林，张建明，魏旭东，胡宏纹（华中师范大学化学系武汉４３００７０））（南京大学化学系南京）关键词查尔酮冠醚ＰＶＣ膜，钾离子电极，性能钾离子在生物细胞膜内外的浓度梯度对生物膜的能量传输等起着...     

一类新型冠醚稀土配合物的合成、表征及与DNA作用研究

合成了四种双(N,N′-乙基,苯基)-2,3-萘-二(氧杂乙酰胺)(L=C30H30N2O4)稀土配合物。通过元素分析、红外光谱、差热-热重及摩尔电导值的分析,确定配合物的组成为[RE(pic)3L],RE=Eu(Ⅲ),Tb(Ⅲ),Ce(Ⅲ),Y(Ⅲ)。电化学实验表明:配体无电化学活性,配合物则呈现出一准可逆的氧化还原过程,在10～1000 mV.s-1扫速范围内配合物的氧化还原峰电流与扫描速度的平方根(ν1/2)呈良好的线性关系,表明其在玻碳电极(GCE)上的伏安行为受扩散控制。另外,通过循环伏安法、光谱法及粘度法研究了配合物与DNA的作用方式,结果表明:配合物均以插入方式与DNA作用,并且作用大小次序是Ce(pic)3L>Tb(pic)3L>Y(pic)3L>Eu(pic)3L。在pH=3.0适宜酸度条件下,建立了以Ce(pic)3L为探针定量测定DNA的分析方法。     

Calix[4]arenes Bridged with Two Different Crown Ether Loops: Influence of Crown Size on Metal Ion Recognition

A series of calix[4]arene-bis-crownethers were synthesized in a fixed 1,3-alternateconformation with good yields by the reaction of amonocyclic calixcrown ether with multi-ethyleneglycoldi-p-toluenesulfonate in the presence of cesiumcarbonate. In the preparation of the monocycliccalixcrown ethers (1 and 2), the use ofpotassium carbonate as a base provided the best yieldregardless of the template concept. In two phaseextraction and competitive transport experiments forligand-metal complexation, calix[4]arene biscrown(5) provided the best selectivity for potassiumion. When a calixbiscrown ether (4) bearingdifferent sized crown ether loops coordinates to K⁺and Cs⁺, respectively, the changes of peak splittingpatterns and chemical shift on ¹H NMR spectra aredependent on the complexed metal ion species.     

含二苯并-18-冠-6酰胺型液晶冠醚钾配合物的合成和性质

合成了2个系列酰胺型液晶冠醚钾配合物，配合物的结构通过元素分析、IR、UV-Vis和AAS等方法表征。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明，所有配合物均具有热致液晶性，且随分子末端烷氧基碳原子数增加，其熔点和清亮点呈规律性变化。与配体相比，配合物液晶态温度范围变宽。液晶相态类型发生改变，配体只有近晶相，而配合物既有近晶相，又有向列相。     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的合成与表征

以顺(反)-4,4＇-双[4-(4＇-正烷氧基联苯基-4-羧基) 苯亚氨基] 二苯并-18-冠-6（I和II）为配体合成了2个系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%~92.1%和88.7%~90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等方法确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的液晶行为

以顺(反)-4,4′-双[4-(4′-正烷氧基联苯基-4-羧基)苯亚氨基]二苯并-18-冠-6(Ⅰ和Ⅱ)为配体合成了2种系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%～92.1%和88.7%～90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等测试技术确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽。     

二芳基大环冠醚共轭8-羟基喹啉的合成及光致发光性质

设计并合成了两种新型二芳基大环冠醚共轭8-羟基喹啉衍生物7a和7b及其锌配合物, 通过核磁共振(1H NMR, 13C NMR)、质谱(MS)、红外光谱(FT-IR)和紫外光谱(UV)等对7a和7b进行了结构表征. 初步研究了7a和7b及其锌配合物在溶液中的光致发光性质. 结果表明, 相对于2-甲基-8-羟基喹啉, 化合物7a和7b的荧光光谱向长波方向有明显的移动, 分别在460和467 nm处出现发射峰, 处于蓝光的范围. 配合物8a和8b的荧光发射峰分别为562和665 nm, 属黄光范围, 但荧光强度较弱.     

Construction of Crown Ether‐Stoppering [3]Rotaxanes Based on N‐Hetero Crown Ether Host

Crown ether usually plays the role of macrocyclic host in supramolecular chemistry, but here the crown ether is also utilized as the stoppers in rotaxanes. In this work, we designed and synthesized two [3]rotaxanes containing four crown ether components by using an approach of template‐directed clipping reaction, of which, two crown ether components were employed as the macrocyclic hosts to assemble the mechanically interlocked framework while another two crown ether units located on the two ends of ammonium template acting as the stoppering groups of rotaxanes. Their self‐assembling process was monitored by the ¹H NMR and one of the single crystal structures of [3]rotaxane was obtained.     

联萘冠醚的合成新方法

一种用于合成含联萘基冠醚的新方法。以消旋，手性联萘酚为起始原料，先与氯乙醇反应制得2,2'-二（2－羟基乙氧基）－1,1'－联二苯，再与二甘醇或三甘醇对二对甲苯磺酸酯反应，成功制得了4种联萘冠醚。     

Two-dimensional Network Crown Ether Complex. Synthesis and Crystal Structure of 18-Crown-6 Complex: [K(18-C-6)]_2[Cd-(mnt)_2]

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偶氮喹啉-镍离子配合物应用于HSO-4识别研究

考察了5-(4'-氰基苯)偶氮-8-羟基喹啉(1)-镍配合物的光谱特性并将其应用于阴离子识别研究中.研究结果表明,1-Ni2+金属配合物可选择性识别不同的阴离子,并对HSO-4具有独特的光谱响应.化合物1在乙腈中为无色溶液,与Ni2+可形成稳定常数为9.2×10 6mol-1·L的1∶1型红色配合物,在此配合物中加入HSO-4后,红色的溶液逐渐褪色,而加入CH3CO-2,F-和H2PO-4却产生增色效应,Cl-和Br-加入后主体溶液无明显颜色和光谱变化,据此建立了选择性识别HSO-4新体系,并探讨其作用机理.     

王冠高聚物担载四核钴羰基簇催化剂的醛化反应活性

本文用二苯并-18-冠-6高聚物作因相化载体,通过化学健合,合成了担载的四核钴羰基簇催化剂Crown-Co_4。,并对该催化剂进行了元素分析、红外光谱及X射线光电子能谱(XPS)等方面的测试分析;还考察了不同温度、不同极性溶剂及不同类型烯烃对醛化活性的影响。实验证明,该催化剂对直链端位烯烃的醛化活性高于均相的苯基-四核钴羰基簇催化利Ph-Co_4。。二苯并-18-冠-6高聚物载体能明显改善催化性能。     

Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether

A comparative quantitative analysis of the effect of solventmodifiers on the ion-pair extraction of an inorganic salt by a crown ether was conducted with the aim of advancing the understanding of transport of highly hydrophilic metal ions from aqueous salt solutions. Two classes of solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (compound 1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenylacetamide—the enhancement of the NaNO₃ extraction by compound 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier as quantified by the β solvatochromic parameter. A HBD modifier 3,5-di-t-butylphenol (compound 8), which forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO₃ extraction by compound 1. The determined extraction constants were correlated with the β- or α-solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between compound 8 and nitrate anion in the presence of the sodium-loaded crown ether in the extraction phaseswas studied by vibrational spectroscopy.     

套索冠醚固定相的气相色谱研究

用一种新合成的套索冠醚Ｎ，Ｎ′－双（乙酰苄胺）－二氮杂－１８－冠－６作为固定相，涂渍在弹性石英毛细管内，测其柱效、惰性、热稳定性、平均极性及选择性等性质。实验表明，它具有良好的色谱性能，中等极性，分离选择性高，适用于对醇、卤代烃、芳香烃等各类异构体的分离，并从分子结构和热力学参数等探讨了保留机理。     

三维网状冠醚配合物（Bu4N){[K(18-C-6)][Cd4(dmit)2(dmt)3]}的合成与结构

研究了18-冠-6（18-C-6）与KSCN，CdCl2.2.5H2O,(Bu4N2)[Zn(dmit)2] (dmit=4,5-dimercapto-1,3-dithiole-2-thione,C3S5^2-)的反应，生成的标题配 合物（1）通过元素分析，红外光谱，单晶X射线衍射进行了表征，配合物属单斜晶 系，空间群C2/c，晶体学数据：a=3.4780(7)nm,b=1.5170(3)nm,c=2.8440(6)nm,β =105.93(3)°,V=14.427(3)nm^3,Z=8,F(000)=7872,R1=0.0425,wR2=0.0739,配合物 由一个Bu4N^+阳离子和一个{[K(18-C-6)][Cd4(dmit)2(dmt)3]}-(dmt=4,5- dimercapto-1,2-dithiole-3-thione,C3S5^2-)配阴离子组成，{[K(18-C-6)[Cd4 (dmit)2(dmt)3]}-通过K…S，S…S弱相互作用形成三维网状结构。     

Synthesis and Selective Coloration of Monoaza Crown Ethers Bearing Picrylamino－type Side Arms for Alkali Metal Salts and Methylamine

N-pivot lariat ethers with picrylamino group as a chromophore (1, 2 and 3) have been prepared by reaction of N-(4-aminoaryl)monoaza crown ethers with picryl chrolide,and the selective coloration of 1, 2 and 3 for alkali metal salts and amines has been studied by UV-Vis spectra.     

A Novel Type of Crown Ether‐Containing Metal Ions Optical Sensors Based on Polymer‐Stabilized Cholesteric Liquid Crystalline Films

For the first time, the films based on polymer‐stabilized cholesteric composites containing crown ether fragments with the optical properties sensitive to the complexation with potassium and barium ions were obtained. The complexation with these ions leads to blue spectral shift of the selective light reflection of planar cholesteric texture of composite films. Peculiarities of spectral changes and kinetics of selective light reflection shift were studied. The proposed approach can be used for the creation of the effective and selective sensor materials for different ions or groups of ions.