Complex formation of O-carboxymethylcalix[4]resorcinolarene with alkaline metal and ammonium ions

Complex formation of 3,5,10,12,17,19,24,26-octa(carboxymethoxy)-1,8,15,22-tetraundecylcalix[4]arene (H₈X) with Li⁺, Na⁺, K⁺, and NH₄ ⁺ ions was studied by ¹H NMR spectroscopy and pH-metry in water—DMSO solutions. Binding of one cation occurs during the stepped deprotonation of four carboxymethyl groups in H₈X. The K⁺ ion was found to be bound more efficiently than Li⁺ and Na⁺. The further deprotonation to the penta- and hexaanion leads to the coordination with two cations. The most stable binuclear complex is formed with the Li⁺ ion.     

A Watersoluble Sulfonatomethylated Calix[4]resorcinarene as Artificial Receptor of Metal Complexes

The binding of different sized and shaped metal complexes [Co(His)₂]ClO₄(1), [Co(en)₂C₂O₄]Cl (2) and [K18-crown-6]SCN (3)(en-ethylendiamine, His-L-histidynate-anion) with a new tetrasulfonatomethylcalix[4]resorcinarene([H₈X]Na4) was investigated in neutral and alkaline aqueous media by NMR and pH-metrictitration methods and compared with those of recently studied NMe₄Br (4). The resultsobtained indicate that the outer-sphere coordination of complexes 1–3 by[H₈X]^4- proceeds via the interaction of hydrophobic fragments of the guestswith both the negatively charged rim and the hydrophobic cavity as a -base. Thenature of binding does not change for cations 1, 2 and 4 on going from[H₈X]^4- in neutral to [H₄X]^8- in alkaline media, while the inclusionof 3 decreases on going from [H₈X]^4- to [H₄X]^8-.     

N-硫脲基套索杯[4]冠醚与四硫脲基杯[4]芳烃的合成

控制反应物的物质的量比, 杯式对叔丁基杯[4]-1,3-二乙酸乙酯衍生物1与5或50倍二乙烯三胺反应, 分别得到杯[4]氮杂冠醚2和开链的氮杂杯[4]芳烃衍生物3. 化合物2和3进一步与异硫氰酸苯酯反应得到首例侧链含硫脲基的套索杯[4]氮杂冠醚4和含4个硫脲基的杯[4]芳烃衍生物5, 产率为92%和87%. 新化合物的结构与构象经元素分析、红外、质谱、核磁共振谱等表征证实.     

Synthesis of （p-Formylphenyl）azo Calix[4]arenes

Five novel azo calix[4]arenes were reported. The p-aminobenzaldehyde was diazotized with sodium nitrite in aqueous hydrochloride solution. Mono-, bis-, tris- and tetrakis(p-formylphenyl)azo calix[4]arenes (including proximal and distal isomers) were obtained respectively by diazo-coupling in different molar ratio to calix[4]arene(1) under pH=7.5--8.5 at 0-5℃. All (p-formylphenyl)azo calix[4]arenes were characterized by ^1H NMR, ^13C NMR, IR, MS (ESIMS) spectroscopies and elemental analysis.     

杯[4]芳烃黄原酸酯衍生物的合成与阳离子萃取性能

以二氧六环作溶剂, 杯[4]芳烃二甲氧基二羟乙氧基衍生物2与氢氧化钾、二硫化碳作用合成了杯芳烃黄原酸盐衍生物3, 并进一步与碘甲烷或氯化苄反应首次合成了含黄原酸酯基的杯芳烃衍生物4a和4b. 阳离子萃取试验表明该新型杯芳烃衍生物比单硫杂杯芳烃衍生物具有更好的过渡金属离子萃取性能.     

1,3-取代杯[4]芳烃三联吡啶配体的合成及其离子识别性能的研究

设计合成了1,3-取代杯[4]芳烃三联吡啶新型配体L1, 通过紫外吸收光谱的变化研究了配体L1对于Fe(II), Zn(II), Ni(II)等离子的识别作用.     

Synthesis of New Calix[4]arenes Functionalizated by Acetylhydrazide Groups

A series of new calix[4]phenols, calix[4]resorcinols and calix[4]pyrogallols with acetylhydrazide substitutes has been␣synthesized with high yields by hydrazinolysis of ester group containing calix[4]arenes. The synthesized calix[4]phenols adopt the cone conformation while the calix[4]resorcinol and calix[4]pyrogallol derivatives prefer the boat conformation. The amide fragment of the hydrazide groups predominantly exists in the trans-conformation. The binding ability of synthesized calix[4]arenes toward transition and alkali metals by solvent extraction has been investigated.     

含酰胺和席夫碱单元的杯[4]芳烃衍生物的合成与配合性能

杯[4]-1,3-二乙酸乙酯衍生物1与水合肼反应生成杯[4]芳烃酰肼衍生物2, 然后进一步与相应的芳醛反应, 高产率地合成了三个新型的含酰胺和席夫碱单元的杯[4]芳烃衍生物3a～3c和一例新型杯[4]冠醚4. 阳离子萃取实验表明新型杯芳烃衍生物比只含有酰胺基或席夫碱基的杯芳烃衍生物有更强的软金属离子配合性能, 杯[4]冠醚4还对Ag^＋有较好的选择性萃取能力.     

Synthesis and Complexing Properties of Four New Tetraamido-type p-tert-Butyl Calix[4]arenes Presenting Two Proximal Binding Subunits

The synthesis of four new tetraamido-type p-tert-butylcalix[4]arenes presenting two proximal binding subunits is reported. Complexation of alkalimetals and zinc picrates with these ligands have been carried out and monitored by ¹H-NMR inCDCl₃. It is shown that hard cations are included in the tetraamido cavity while thezinc cation is chelated to the pyridine rings of one of the ligands. The formation of a 1:1:1heterobinuclear complex is also described     

杯[4]芳烃四丁醚的选择性硝化

硝化反应;杯[4]芳烃四丁醚的选择性硝化     

Calix[4] crowns with Methoxynaphthoylmethyl Pendant Groups

The novel calix [4] crowns with two pendant groups were prepared by the alkylation of calix 141 crowns with 6-methoxy-2-bromoacetylnaphthalene. ^1H NMR titration and picrate extraction experiments indicated that they exhibit higher complexing efficiency than their parent compounds and possess obvious selectivity for Na^ or K^ , respetively, and that the cation is encapsulated inside the preorganized ionophoric cavity defined by carbonyl oxygens, the crown ether and the phenoxy oxygens.From UV and fluorescent spectra it is revealed that calix [4]crown-4 3a with 6-methoxy-2-naphthoylmethyl pedant groups exhibits remarkable cation-induced photophysical effects and it could be utilized as a selective fluorescent sensor for Ca^2 .     

丙醛间苯二酚杯[4]芳烃烷基化衍生物的合成

以间苯二酚和丙醛为原料合成了丙醛杯[4]芳烃(1),1经不同的烷基化反应合成了新的丙醛杯[4]芳烃烷基化衍生物,其结构经1H NMR和IR表征。     

Ternary Complexes of Lanthanide–Calix[4]Arene with Sulphophthalein Dyes

The formation of ternary complexes of lanthanide–calix[4]arene with sulphophthalein dyes was studied. The extraction of model system Gd(III)–calix[4]arene–bromothymol blue was characterized and the distribution, extraction, and stability constants were determined. The applicability of studied system for spectrophotometric determination of lanthanides was demonstrated and parameters of calibration dependences were calculated.     

一锅法合成含两种桥联链的杯[4]双冠醚和双杯[4]冠醚

报道了"一锅法"合成含两种桥联链的新型杯[4]双冠醚和双杯[4]冠醚.杯[4]芳烃先与N,N’-乙撑基-二(2-氯乙酰胺)发生"1+1"缩合反应,然后直接加入三甘醇双对甲苯磺酸酯继续进行"2+2"缩合反应,合成了含两种桥联链的新型双杯[4]冠醚4.按照相似程序,杯[4]芳烃先后与N,N’-乙撑基-二(2-氯乙酰胺)、溴乙酸乙酯和二乙烯三胺反应,得到含两种桥联链的新型杯[4]双冠醚5.化合物5进一步与异硫氰酸苯酯反应合成带硫脲支链的杯[4]双冠醚6.所有新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

新型杯[4]芳烃衍生物的合成

以对叔丁基杯[4]芳烃为起始原料,通过一步或两步取代反应合成了对叔丁基杯[4]芳烃的衍生物(1和2),其结构经FT-IR,^1H NMR,FAB-MS表征．     

The Synthesis of Sodium and Potassium Complexes of Two Calix[4]arene Derivatives

Two compounds (1 and 2) which have calix[4]arene units and their Na⁺ and K⁺-complexes were prepared. All the complexes have a metal-ligand ratio of 1 : 1. The newly prepared compounds were characterized on the basis of their ¹H NMR, IR, UV-visible as well as elemental analysis.     

Synthesis of New Rigid Dimeric Calix[4]arene

A new Dimeric calixarene from the head to head linkage of two calix[4]arene units fixed in the cone conformation was synthesized via Sonogashira cross-coupling reaction. The structure of 10 was confirmed by NMR, MS and IR-spectroscopy.     

四硫脲基杯[4]芳烃衍生物的合成

对叔丁基杯[4]-1,3-二乙酸乙酯与过量的二乙基三胺反应,生成含有游离氨基的杯芳烃酰胺衍物(2),2再与异硫氰酸苯酯反应合成了含4个硫脲基的杯[4]芳烃衍生物,其结构经1H NMR,IR,MS和元素分析表征。     

Thermochemical Investigation of Some Selected Solvates of Calix[4]resorcinarene

Lipophilic calix[4]resorcinarene derived from lauryl aldehyde forms stable crystalline solvates with a range of organic solvents: acetone, 1,4-dioxane, methylethylvketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, butyronitrile, methanol, 1,2-dimethoxybenzene and acetonitrile. The composition and thermal stability of these solvates was followed by thermogravimetric method, indicating a stoichiometry ranging from 1 to 3 (calixresorcinarene/solvent). The activation energy was evaluated for the selected solvates. Molecular modelling, using Hyperchem 5.0 software, was applied to the selected solvates. This revised version was published online in August 2006 with corrections to the Cover Date.     

基于杯[4]芳烃的手性识别*

手性杯芳烃是一类重要的主体化合物,在手性识别、对映体分离和不对称催化等方面有着广泛的用途。[4]芳烃引其稳定的构象和易于修饰的特点,成为研究最为广泛的杯芳烃分子,其中大量的文献报道了能够用于对映体识别和检测的手性[4]芳烃。在手性识别的研究中,荧光、紫外和核磁是3中最常见的研究方法,本文根据这3种方法进行分类,综述了近年来以杯[4]芳烃为分子骨架的手性受体的合成及其在手性识别中的应用。最后对手性[4]芳烃的发展前景作了展望。