Syntheses, Crystal Structures and Complexing Properties of 1,3-Distal Calix[4]arene Schiff Bases

Novel 1,3-distal p-tert-butylcalix[4]arene Schiff bases were efficiently synthesized in three steps. At first p-tert-butylcalix[4]arene was reacted with N-2-hydroxyethylphthalimide catalyzed by TPP/DEAD or alkylated with ω-haloalkylphthalimide in the system of K2CO3/KI/CH3COCH3 to give 1,3-distal diphthalimidoalkyl calixarenes, which were in turn hydrazinolyzed to give diaminoalkyl calixarenes. Then with the aid of the condensation of active calixarene amines with salicylaldehyde, 2-hydroxy-1-naphthaldehyde or pyridine-2-carboxaldehyde, a series of 1,3-distal calixarene Schiff bases was prepared in satisfied yields. The single crystal structures and complexing properties of these Schiff bases for transition metal ions were studied.     

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.     

Synthesis of Calix[4]resorcinarene Schiff Bases

Introduction Calix[4]resorcinarenes are cyclic tetramers in which four resorcinol units are linked via alkylmethylene bridges in the o-position to each resorcinic hydroxyl group[1]. Their structures resemble that of p-butylcalix[n]arenes and render them of interest as host compounds in many contemporary fields of supramolecular chemistry.     

Synthesis of Schiff Base Calix [4] arene Crowns

This letter reports the synthesis of Schiff base calix [4] arene crowns containing m-xylylene phenol subunit, in which calix [4] arene Schiff base crowns 2a,2b and 2c were formed by 1:1 condensation of calix [4] arene diamine 1 with dialdehydes (2,6-diformyl-4-chlorophenol 3a,2,6-diformyl-4-methylphenol 3b,2,6-diformyl-4-tert-butylphenol 3c)under high dilute condition in refluxing anhydrous ethanol in 65-70% yield.     

新型多重氮杂杯[4]芳烃衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与水杨酰肼、烟酰肼、异烟酰肼反应, 合成了具有开链结构新型杯[4]多重氮杂衍生物2a～2c, 产率分别为88%, 85%和90%. 化合物1与乙二酰肼、丙二酰肼、己二酰肼反应, 得到具有桥联结构的新型杯[4]多重氮杂衍生物3a～3c, 产率分别为86%, 89%和90%. 新化合物的结构经元素分析、质谱、核磁共振谱等表征证实, 杯[4]芳烃单元均为1,3-取代且采取锥式构象.     

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.     

杂金属杯[4]配位聚合物的合成与表征

合成了4个杂金属杯[4]配位聚合物{[Cd（L）（tpa）]·3H₂O}_n（1）,{[Zn₂（L）₂（tpa）₂]·3H₂O}_n（2）,{[Co（L）（oba）]·2DMA·0.5H₂O}_n（3）和{[Zn（L）（oba）]·DMA}_n（4）（L=2-（1H-咪唑基-甲基）-6-（3-（1H-咪唑基-甲基）-5-叔丁基-2-羟基）苄基-4-叔丁基苯酚,H₂tpa=对苯二甲酸,H₂oba=4,4''-二苯醚二甲酸）,并通过元素分析、热重、红外光谱、固态紫外、单晶X射线衍射和粉末X射线衍射对其进行了表征。单晶结构分析表明晶体1是单斜晶系,P2₁/n空间群,而晶体2,3和4均为三斜晶系,P1空间群。化合物1,2,3和4是由0维[M（N₄O₂C₂₉H₃₆）]（M=Zn,Co,Cd）的杂金属杯[4]与配体对苯二甲酸和4,4''-二苯醚二甲酸形成的一维配位聚合物。     

稀土氧化膦取代杯芳烃配合物的合成与结构

合成了一种新的氧化膦取代杯芳烃衍生物的稀土离子(La³⁺,Eu³⁺)硝酸盐配合物.通过元素分析和红外光谱对配合物进行了表征.在无水甲醇中培养出了配合物的单晶,用X射线单晶衍射法测定了其晶体结构.硝酸镧配合物晶体[L·La(OH₂)(NO₃)₂]NO₃{L为四(亚甲基二苯基氧化膦)杯[4]芳烃}属四方晶系,空间群P4₃2₁2,晶胞参数a=b=1.8977(4)nm,c=3.1087(11)nm;Z=4;V=11.196(5)nm³;D_c=1.097g/cm³,F(000)=3712,μ=0.491mm^-1,R₁=0.1181,wR₂=0.1930.硝酸铕配合物晶体[L·Eu(OH₂)(NO₃)₂]NO₃·CH₃OH属单斜晶系,空间群C2/c,晶胞参数a=2.88172(11)nm,b=5.4015(2)nm,c=2.01189(7)nm;β=133.4067(9)°,Z=8;V=22.7511(14)nm³,D_c=1.106g/cm³,F(000)=7464,R₁=0.0671,wR₂=0.1794.2个配合物的晶体结构相类似,配合物中配体的4个磷氧键上的氧原子、2个双齿配位的硝酸根中的4个氧原子还有1个水分子中的氧原子分别参与了配位.中心离子配位数为9,配位多面体为单帽四方反棱柱体.另外在铕配合物的杯芳烃中还包合了1个甲醇分子.     

Syntheses of Chiral Calix [4] arene Derivatives Bearing Amino Acid Residue

The syntheses of chirai calix[4]arene derivatives bearing amino acid residue at the lower rim or upper rim by three different methods were reported.     

Calix[4]arene Schiff bases—potential ligands for fluorescent studies

A series of novel double-armed calix[4]arene derivatives incorporating imine substituents were synthesised from the Schiff-base reaction of 25,27-bis[2-[(1-formyl-2-phenyl)oxy]ethyl]-p-tert-butylcalix[4]arene (1) with the appropriate amine or hydrazone. All compounds were characterised by various spectroscopic and analytical techniques, and in three cases, by X-ray crystallographic studies. In the case of compound 2, inclusion compounds were synthesised with both m-xylene and dimethylformamide and their X-ray structures revealed these inclusion sites—between the pendant arms and in the upper cavity, respectively. In all cases, the pendant arms are bent away from each rather than adopting a face-to-face conformation.     

Calix[4]arene based dendrimers

The synthesis of calix[4]arene based dendrimers containing up to seven calix[4]arene moieties is described, including the X-ray crystal structure of a tris-calix[4]arene branching derivative.     

Ultramacrocycle with Four Calix[4]arenes: Synthesis and X-Ray Crystal Structure of A Quadruple Calix[4]arene

A quadruple calix[4]arene has been synthesized efficiently from the known diaminocalix[4]arene and 4,4′-biphenyldisulfonyl chloride in just one step (38% yield). The compound has been fully characterized including the determination of the X-ray crystal structure.     

Crystal and Molecular Structure of Calix[4]arene Originating from Pyrogallol

First example of X-ray diffraction analysis of the crystal structure of calix[4]pyrogallolarene is reported. The compound was prepared by acid-catalyzed condensation of pyrogallol with propionaldehyde in a water-alcohol medium, and it gave rise to a system of host-guest type. Calixarene molecules in a cone conformation are packed in molecular layers; therewith each host molecule contains an ethanol molecule in the cavity. Hydroxy groups, ethanol and water molecules form a hydrophilic layer between two layers; as a result arises an endless bilayer structure.     

Syntheses and Structures of Binaphthyl-bridged Schiff Bases

The reaction of dinaphthofuran with lithium in anhydrous diethyl ether led to a solution of the corresponding C,O-dilithiated intermediate which, upon treatment with DMF at ？78 oC, afforded, after hydrolysis, 2＇-hydroxy-1,1＇-binaphthyl-2-carbaldehyde in a good yield. Then binaphthyl-bridged Schiff bases were prepared by the condensation of 2＇-hydroxy-1,1＇-binaphthyl-2-carbaldehyde with the corresponding aromatic amines.     

Polymer Supported Calix[4]arene Schiff Bases: A Novel Chelating Resin for Hg2+ and Dichromate Anions

This article describes the synthesis and characterization of two new calix[4]arene Schiff bases and their polymeric resins. The extraction properties of these “proton switchable extractants” with alkali, transition, post transition metal cations and for dichromate anions are reported. The two new calix[4]arene based Schiff bases (5 and 6) have been synthesized from 5,17‐diformyl‐25,27‐dipropoxy‐26,28‐dihydroxycalix[4]arene (4) by treatment with 3‐amino‐methylpyridine and 1,8‐diaminooctane in two separate reaction flasks following the same procedure. Compounds 5 and 6 have been appended to a polymeric resin by treatment with Merrifield resin through a nucleophilic substitution reaction. The receptor compounds (3 and 5–8) do not extract alkali metal cations, but show some selectivity toward transition metal cations, and a particularly high selectivity to Hg²⁺ and Pb²⁺. The protonated forms of all of the calixarene‐based receptors are good extractants for transferring Cr₂O₇ ^2?/HCr₂O₇ ^? anions from an aqueous into a dichloromethane layer.     

Syntheses and Binding Properties of Novel Calix[4]arene Derivatives Containing Multiple Azo-groups

Introduction Calixarenes are excellent scaffolds that can bemodified by introducing various functional groups tocreate specific interactions between the host and guestmolecules. Thus, many calixarene derivatives contai-ning special functional groups, such as ester, amideand thiourea, have been synthesized and their excellentcomplexing capability for cations have also been stud-ied[1—4]. Lately, calixarene derivatives containing twoor more sorts of functional groups have attracted muchattentio…     

Chlorination of Calix[4]arene Derivatives

New convenient method for synthesis of p-chlorinated calix[4]arenes is reported. The sulfuryl chloride was used for chlorination of unsubstituted at the lower rim calix[4]arenes. The products of this reaction were very suitable for further O-alkylation.     

一些新型含氮、硫杂官能团的杯[4]芳烃衍生物的合成

以杯[4]芳烃-1,3-二溴乙氧基衍生物1为合成平台,在K2CO3/MeCN体系中分别与乙醇胺、L-亮氨醇、2-巯基苯并咪唑、巯基乙酸乙酯反应,以49%～76%的产率合成了4种新型含氮、硫杂官能团的杯[4]芳烃衍生物2,4,5和6.化合物2进一步与异硫氰酸苯酯反应,以84%的产率得到了新型树枝状杯[4]芳烃氮、硫杂衍生物3.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.     

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.