Synthesis of Calix[4]arene Derivatives with NLO Properties

The new chromophore compounds with NLO properties were prepared by Knoevenagel condensation from forrnyl or diformyl calix[4/arene and isophorone derivatives in the presence of piperidine and acetic acid, respectively. In these chromophore calix[4]arenes, the ring locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The NMR spectra demonstrated that they existed in a cone conformation and consequently non-conjugated D-π-A units could be oriented at nearly the same direction.     

四对-乙酰胺苯磺酰氧基杯[4]芳烃的合成

以对叔丁基苯酚为起始原料,通过缩合、取代反应合成了25,26,27,28-四对-乙酰胺苯磺酰氧基对叔丁基杯[4]芳烃,其结构经FT—IR,^1H NMR和FAB-MS表征。     

对叔丁基杯[n]芳烃酰胺衍生物的合成及其对某些金属离子的萃取性能

对叔丁基杯[n]芳烃酰胺衍生物的合成及其对某些金属离子的萃取性能;杯芳烃; 酰胺衍生物; 金属离子; 萃取; 离子识别     

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．     

Synthesis and Chiral Recognition of a New Type of Chiral Calix[4]-arene Derivatives

Two new chiral calix[4] arenes bearing chiral pendants,which were from by-product of the antibiotic industry,were synthesized and characterized by ^1H NMR.MS-FAB and elemental analysis,Studies of ^1H NMR of the two calix[4] arene derivatives indicate that they exist in cone conformation in solution.Results of chiral recognition of the two chiral ligands 2a and 2b towards the tartaric acid derivative 3 show that ligand 2a exhibited good chiral recognition abilities compared to ligand 2b.     

羧基苯偶氮基杯[8]芳烃衍生物的合成及表征

以邻、间或对氨基苯甲酸和杯[8]芳烃为原料，经重氮化一偶联反应合成了新型有色邻、间或对羰基苯偶氮基杯[8]芳烃，产物的结构经元素分析，IR，UV－Vis和1H NMR表征，并研究了它们的生色原理和光谱性能，实验结果表明它们是一类新型指示剂和具有新型配位空腔的主体分子。     

新型大环分子受体: 四同二氧杂杯[6]芳烃衍生物的合成及其络合性质

Several tetrahomodioxacalix[6]arene hexaesters, hexaacid and hexaamide derivatives were synthesized from tetrahomodioxacalix[6]arene by etherification with ethyl bromoacetate. It was found that p-tert-butyltetrahomodioxacalix[6]arene hexaethylester exhibited high selectivity towards lithium ion. p-tert-Butyltetrahomodioxacalix[6]arene hexaamides showed high ion-binding ability towards transition metal ions.     

羧基苯偶氮基杯[6]芳烃衍生物的合成及表征

近几年,随着对主客体化学研究的深入,杯芳烃的功能化修饰成为该领域的研究热点[1-6]。本文以邻、间、对氨基苯甲酸和杯[6]芳烃为原料,经重氮化 偶联反应合成了新型有色邻、间、对羧基苯偶氮基杯[6]芳烃,产物的结构经IR,1HNMR和元素分析表征;并研究了它们生色原理和光谱性能。结果表明它们是一类新型指示剂和具有新型配位空腔的主体分子。合成路线如下:图1　邻、间、对羧基苯偶氮基杯[6]芳烃的合成Fig.1　Fig1:Synthesisofp (o,m,p carboxylbenzeneazo)calix[6]arenes1　实验部分1 1　仪器与试剂Nicolet 460型傅里叶红外光谱仪(KBr…     

Synthesis and Extraction Properties of 1,3,5-O-trimethyl-2,4,6-tri-O-hydroxamic Acid p-tert-butyl Calix[6]arene

A calix[6]arene bearing three hydroxamic acid groups arranged in aC₃ symmetry has been synthesized. Extraction properties towards transition metal ions are presented and compared with other proton-ionizable related calix[6]arenes and with a monomeric hydroxamic acid analog.     

一种新型含喹啉环杯[4]芳烃衍生物的合成

以对叔丁基苯酚为起始原料,把酯基和具有荧光性质的喹啉环引入杯芳烃大环分子中,通过缩合,两步取代反应,获得了具有荧光性质的新型含喹啉环杯[4]芳烃衍生物。其结构经1H NMR,IR,MS和元素分析表征。     

Extraction Behavior of Amino Acids by Calix[6]arene Carboxylic Acid Derivatives

A series of calixarene carboxylic acid derivatives were synthesized for the extraction of amino acids. A calix[6]arene carboxylic acid derivative showed the highest extractability to the target tryptophan ester. The main driving forcefor the complexation was the interaction between the ammonium cation of the aminoacid and the oxygen atoms of the host molecule. Stripping of amino acids was alsoaccomplished by contacting the organic solution with a fresh acidic solution. Basedon slope and Job method analyses, it was confirmed that the calix[6]arene formsa 1 : 1 complex with the amino acid ester. The structure of the complex between the calix[6]arene and the amino acid was investigated by ¹H-NMR and CD spectra. The calix[6]arene includes a guest molecule in the cavity, and the inclusion induces the asymmetrization of the host molecule. This host compound functions as a novel recognition tool for amino acids.     

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.     

Two Novel Self-Assemblies of the Calix[4]arene Derivatives and Their Structures

Two newly identified supramolecule structures arise from self-assembly of theCalix[4]arenes derivatives 1 and 2: one ethyl ester of 1 (or 2) enters into the cavity of another 1 (or 2) forming a 1D long chain structure. The interaction force of the molecules and the crystallization energy might be an important driving force for forming theself-assembled calix[4]arene. Supplementary Data relating to this article (atomic coordinates, hydrogen coordinates, isotropic displacement parameters, anisotropic displacement parameters, selected geometrical parameters and observed and calculated structure factors) are deposited in the British Library.     

新型正丁醛杯[4]芳烃醚衍生物的合成

以正丁醛间苯二酚杯[4]芳烃为原料,经酯化、水解、酰氯化后再与9-蒽甲醇反应,合成了蒽单取代的正丁醛间苯二酚型杯[4]芳烃醚衍生物。其结构经1H NMR和IR表征。     

Synthesis,Crystal Structure and Complexing Properties of Calix[4]arene Schiff Bases

Four p‐tert‐butylcalix[4]arene derivatives with different Schiff base groups at the lower rim were efficiently prepared in three steps. p‐tert‐Butylcalix[4]arene was firstly O‐peralkylated with ω‐haloalkylphthalimide in the system of NaH/DMF to give calixarene tetraalkylphthalimides, which were in turn hydrazinolyzed to give tetraaminoalkylcalixarenes. Then by condensation of the latter with salicylaldehyde and 2‐hydroxy‐1‐naphthaldehyde, a series of calixarene Schiff bases were obtained in satisfying yields. The complexing properties of these Schiff bases for transition metal ions were investigated with UV spectroscopy.     

一类芳香族偶氮化合物的合成及表征

采用重氮偶合反应合成了一系列不同对位取代的4-[N，N-(二羟乙基)]氨基偶氮苯化合物，其结构用元素分析，IR，1HNMR，DSC，DSC等进行表征和确认。     

A Novel Type of Lower-Rim-Connected Double-Calix[6]arenes Composed of A 1,2,4-Triply Bridged and A Normal Calix[6]arene

Calixareneshavebeenprovedtobeusefulbuildingblockstoconstructmolecularreceptorsinsupramolecularchemistry.Chemicalmodificationsofcalixarenesattheupperrimorthelowerrimcanaffordpreorganizedligandsabletocomplexmetalionsandneutralmolecules,oftenwithspecialselectivitiesl.Inordertoimprovethebindingpropertiesofcalixarenes,double-calixareneshavebeenpreparedandattractedmuchmoreattentionduetothecombinationoftwobuildingblockswithenforcedcavitiesandspecialmolecularrecognitionabilitiesbyco-operationeffects2.…     

Syntheses and Properties of New Pendant‐armed Calix[4]arene Derivatives as Cesium Selective Ionophore

Two new pendant‐armed calix[4]arene derivatives 5 and 6 have been synthesized. The study of alkali metal picrates extraction indicates that both compounds show preference of cesium cation, compound 6 in 1,3‐alternate conformation has better extractibility for Cs⁺ than compound 5. The coordination behavior of compound 6 with cesium cation was studied by ¹H NMR spectroscopy. The Cs⁺ selective electrode based on compound 6 exhibits a linear, near Nernstian response characteristics, the slope is 56.4 mV/decade in me concentration range of 10^?4—10^?1 mol/L, the selectivity coefficient (logK^pot_Cs.Na) is ?3.39.     

Pinched-cone Calix[6]arene: New Synthesis of p- (1,1,3,3-tetramethylbutyl)calix[6]arene. Structure of its 1 : 3 Complex with Chloroform

A new method is described for the synthesis of p-(1,1,3,3-tetramethylbutyl)calix[6]arene isolated ina 30 % yield. For the first time the crystal structure isgiven. The crystals are monoclinic, space group C2/c,a = 24.144(5) Å, b = 14.093(3) Å,c = 26.972(5) Å, = 93.36(3)^circ, V = 9162(3) ų, Z = 4. The macrocycle with C2symmetry presents the pinched-cone conformation. It crystallizes with three chloroform molecules, two of them are positioned in the cones shaped by the phenol moieties; the third chloroform is located in the cavity near the hydroxyl groups; this solvent molecule is disordered around the 2 axis. The packing of the complex is described.