New preorganized calix[4]arenes. Part II. Double Schiff-based calix[4]arenes derived from 4,6,10,12,16,18,22,24,25,26,27,28-dodecamethyl-5,11,17,23-tetrahydroxycalix[4]arene

We describe the condensation of an appropriate tetraaldehyde derivative of mesitol calix[4]arene with 1,n-diaminoalkanes to afford double Schiff-base calix[4]arene receptors in the 1,3-alternate conformation.     

Isolation and X-ray crystal structure of a stable calix[4]arene monohemiketal

The formation of a stable calix[4]arene monohemiketal is described. X-ray crystallographic data provide conclusive evidence for the presence of a stabilizing hydrogen bond. Supplementary Data. Lists of H-atom parameters and bond lengths and angles involving hydrogens have been deposited with the British Library Document Supply Centre as Supplementary Publication No. SUP 82159 (5 pp.).     

一种新型杯[4]芳烃的合成

本文通过对特丁基杯[4]芳烃的酚羟基烷基化和苯环特丁基位上的IPSO-硝化制备了一系列对硝基杯[4]芳烃烷基醚,烷基分别是n-C~4H~9(3a)、n-C~8H~1~7(3b)、n-C~1~2H~2~5(3c)和n-C~1~6H~3~3(3d)。^1HNMR表明所有新的杯[4]芳烃都具有锥形(cone)构象。     

The synthesis of metallocene calix[4]arenes

The condensation of 1,1-bis(chlorocarbonyl)metallocenes andp-tert-butylcalix[4]arene in toluene leads to novel metallocene calix[4]arenes in which the metallocene subunit bridges the opposite hydroxy groups of the parent calixarene.Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

Evidence of Hydrogen Bonding in Stabilizing the Cone Conformation of a Monoalkylated Calix[4]arene. X-ray Structure of 25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene

The synthesis of25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene3 as a byproduct of the preparation of 1,3-dialkylated25,27-di-[2-(ethoxy-1p-toluene-sulfonate)phenyl]-26,28-dihydroxy calix[4]arene 2 is reported. Compound 3 is a monoalkylatedcalix[4]arene in the cone conformation. The X-ray structure of 3 showed that this conformation is stabilized by intramolecular hydrogen bonding.     

Extraction of technetium(vii) by calix[4]arene tetraketones and tetraesters from acidic and basic media

Tetrasubstituted on the lower rim calix[4]arenes, containing carbonyl and ester groups, and existing in a cone conformation are selective and efficient extracting agents for Tc^VII extraction from both acidic and basic solutions.     

Controlled solvothermal synthesis of PbS quasi-nanorods by calix[4]arene

A new idea of the nanorods preparation and a novel application of calixarenes are presented. Calix[4]arene was introduced into solvothermal system to produce one-dimensional inorganic nanomaterial. The obtained product was characterized by XRD and TEM. Results of the XRD analysis showed that the product was pure cubic phase of PbS with high crystallinity. TEM images revealed that the diameter and length of the PbS nanorods were about 200 nm and up to 3.5 μm, respectively. Optical properties of the product were also studied. PL emission image showed that the product exhibited an emission peak at 308 nm in ultraviolet region showing a blue shift of 14 nm compared to the bulk material. The formation mechanism of PbS nanorods in the presence of calix[4]arene is discussed.     

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．     

A New Efficient Synthesis of p-Nitrocalix[4]arene

A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described.The compound is an useful intermediates for the introduction of other functional groups to obtain N containing substituted calix[4]arene.The reaction mechanism is briefly discussed.     

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.     

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.     

Synthesis and Conformational Properties of Bis（calix [4] arene）

The bis(calix [4] arene)3 was synthesized in moderate yield by the reaction of p-tert-butylcalix [4] arene (1) with 1,4-bis(chloromethyl) benzene (2). The conformation of all alkylated product 4 was investigated by the variable-temperature ^1H-NMR.     

Synthesis of a functionalised calix[4]arene and its interactions with hemicucurbit[6,7]urils and cucurbit[8]uril

In the present work, we synthesised a functionalised calix[4]arene with 5,11-di(N-methyl-E-(4-pyridylethylene) moiety (CX[4]), and investigated interactions of it with HemiMeQ[6], HemiMeQ[7], and Q[8]) in both water and DMSO using fluorescence spectrophotometry and ¹H NMR spectroscopy. Titration ¹H NMR spectra revealed that Q[n]s prefers to include the N-methyl-E-(4-pyridylethylene) moiety. In particular, the interaction of CX[4] with Q[8] in water resulted in intense fluorescence emission, and this interaction system can respond to compounds such as amantadine.     

Polymeric membrane sodium-selective electrodes based on calix[4]arene ionophores

Six kinds of tetra alkylester type calix[4]arene derivatives, (R₁=R₂=CH₃1, C₂H₅2, C₃H₇3,n-C₄H₉4,t-C₄H₉5,n-C₁₀H₂₁6), a diethyl-didecyl mixed ester type (R₁=C₂H₅, R₂ =C₁₀H₂₁7), and three kinds of lower rim bridged types (R₁=C₂H₅, R₂–R₂=(CH₂)₁₀8, (CH₂)₁₂9, (CH₂)₂(OCH₂CH₂)₃10) were characterized by electrochemical measurement to elucidate the effect of the length of the alkyl group of alkoxycarbonyl substituents on Na⁺ selectivity. To obtain excellent Na⁺ selective ionophores, introduction of short chain alkyl groups rather than long chain ones, such as a decyl group, and maintenance of sufficient solubility of the calix[4]arene derivatives in the membrane solvent are required concurrently. Among the calix[4]arenes tested, 25,26,27,28-tetrakis[(ethoxycarbonyl)methoxy]-p-tert-butylcalix[4]arene2, and the diethyl-didecyl mixed ester type derivative7 are the best ionophores for a Na⁺ selective electrode. On the other hand, sodium selectivity of the bridged type derivative9 is comparable or even superior to that of the known bis(12-crown-4).This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

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.     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

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.     

25,26,27,28-羟乙氧基-杯[4]芳烃的合成

以对叔丁基苯酚为原料,经4步反应合成了新的杯[4]芳烃衍生物--25,26,27,28-羟乙氧基-杯[4]芳烃,其结构经~1H NMR和MS表征.     

Tetra-CMPO-derivatives of calix[4]arenes fixed in the 1,3-alternate conformation

Calix[4]arene derivatives fixed in the 1,3-alternate conformation and substituted at one side by four carbamoylmethylphosphine oxide (CMPO) residues were synthesised. Two CMPO groups are directly attached to the wide rim, while the second pair is bound to the narrow rim via a tri- or tetramethylene spacer. Similar compounds, in which two CMPO groups at the wide rim are combined with two picolinamide groups or two ionisable carboxylic groups at the narrow rim, were also prepared. Some of these calixarene derivatives were studied as extractants for lanthanides (La³⁺, Eu³⁺, Yb³⁺) and thorium (Th⁴⁺) from acidic solution into methylene chloride. For selected samples, stability constants in methanol were determined by spectrophotometric titrations. Three compounds (1b′, 13, 17) in the 1,3-alternate conformation and one intermediate in the cone conformation (18) were confirmed by a crystal structure.