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1.
Ravindra V. Patel Jayesh G. Panchal Shobhana K. Menon 《Journal of inclusion phenomena and macrocyclic chemistry》2010,67(1-2):63-71
The binuclear Co(II) complexes of calix[4]arene substituted 2-vanillin (R1) and 2-hydroxy naphthaldimine (R2), Schiff bases (Co2L1 and Co2L2) have been synthesized, characterized and employed as models to mimic monooxygenase in the catalytical oxidation of olefins. The kinetic mathematical model (oxygen rebound mechanism) for olefin cleavage catalyzed by the complexes has been proposed. The results show that, compared to the calix[4]arene-free analogous, the mono and multinuclear complexes of calix[4]arene Schiff bases as catalyst exhibit high activity in the olefin catalytic oxidation. 相似文献
2.
The strategy of bridging the anisole units at the upper rim of calix[6]arene has been applied to strain the conformations of calix[6]arene. Based on the selective formylation of the 1,3,5-tri-p-tert-butylcalix[6]arene, several new calix[6]arene derivatives with different 1,3-bridged chains or a 1,3,5-tripod bridge at the upper rim have been prepared with moderate yields. The 1H NMR spectra indicate that these calix[6]arene derivatives adopt a cone conformation, which has also been confirmed by the theoretical calculation at AM1 level. X-ray crystal structure of 1,3,5-tripod bridged compound 5 discloses that the calix[6]arene host stands in a cone conformation with approximate C3v symmetry, and that a methanol molecule is enclosed in its hydrophobic cavity and stabilized by multi hydrogen bonds. 相似文献
3.
In the present study, the synthesis and liquid phase extraction properties towards some amino acid methylesters and amino alcohols of Schiff base and amino alcohol substituted calix[4]arene are reported. The Schiff base substituted calix[4]arene 5 has been synthesized via condensation reaction involving 5,17-diformyl-11,23-di-tert-butyl-25,27-di[3-(4-formylphenoxy)propoxy]-26,28 dihydroxycalix[4]arene 4 and (R)-(?)-2-phenylglycine methyl ester in CHCl3:MeOH. To give the amino alcohol substituted calix[4]arene 6, the synthesized chiral compound 5 was reduced by LiAlH4. The new chiral Schiff base and amino alcohol derivatives of calix[4]arene have been characterized by a combination of FT-IR, 1H NMR, 13C NMR, FAB-MS and elemental analysis. Also, the extraction behaviors of 5 and 6 towards some selected amino acid methylesters and amino alcohols have been studied by liquid–liquid extraction. 相似文献
4.
Viktoriya Skripacheva Vladimir Burilov Asiya Mustafina Olga Kataeva Margit Gruner Vitaliy Yanilkin Alexey Stepanov Viktor Syakaev Rustem Zairov Svetlana Soloveva Wolf Habicher Alexander Konovalov 《Journal of inclusion phenomena and macrocyclic chemistry》2011,69(1-2):191-199
The comparative study of the ion-pairing of Co(III) sepulchrate ([Co(sep)]3+) with p-sulfonatothiacalix[4]arene and p-sulfonatocalix[4]arene tetracarbonic acid by 1H NMR and pH-metric data in solution and X-ray data in solid state elucidates pH dependent effect of carboxylate groups on the stoichiometry and the mode of the ion pairing. The electrochemical data of [Co(sep)]3+ bound with both calix[4]arenes have been analyzed in the correlation with stoichiometry and the mode of their binding. The pH-dependent effect of tetracarboxy-p-sulfonatocalix[4]arene on the electrochemical behavior of [Co(sep)]3+ has been found to correlate with the participation of carboxylate groups in the host?Cguest binding. 相似文献
5.
In this study, 5,11,17,23-tetrakis[(N-ethylpiperazine)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(4-carboethoxy-N-piperidino) methyl]-25,26,27,28-tetrahydroxycalix[4]arene (4) were synthesized in one step according to the Mannich reaction by the treatment of calix[4]arene with a secondary amine (N-ethylpiperazine, ethyl-4-piperidincarboxylate) and formaldehyde. The calix[4]arene derivatives (3, 4) were characterized by a combination of FTIR, 1H NMR and elemental analyses. The synthesized compounds were used in an esterification reaction as the phase transfer catalyst. The catalytic efficiency of the calix[4]arenes 3 and 4 was evaluated by carrying out the ester-forming reaction of alkali metal carboxylates (sodium butyrate or sodium caprylate) with p-nitrobenzyl bromide. It was observed that the ester-forming reaction of alkali metal carboxylates with p-nitrobenzyl bromide, using calix[4]arene-based catalyst 3 as a phase-transfer catalyst in dichloromethan, provided the best yields. 相似文献
6.
Two novel carboxylphenyl-modified calix[4]arenes, tetrakis-carboxylphenylcalix[4]arene (TCPC) and 1,3-bis-carboxylphenylcalix[4]arene (BCPC), as well as a corresponding analogue for comparison, tetrakis-phenylcalix[4]arene (TPC), have been synthesized by palladium-catalyzed Suzuki cross-coupling of arylboronic acid and tetrabromocalix[4]arene as a key step. The binding properties of these calix[4]arene derivatives with bovine heart cytochrome c (cyt c) in dimethylformamide (DMF) was investigated by fluorescence spectroscopy. The binding affinity in the order of TCPC > BCPC ? TPC reflects a clear dependence on the number of carboxyl ligating groups attached onto a receptor and suggests the electrostatic force may be the predominant factor driving the complexing process. The stable 1:1 complexes of TCPC and BCPC with cyt c were evidenced with the binding constants of 3.15 × 106 and 5.85 × 105 L mol−1, respectively. Due to a large overlap between the emission spectrum of TCPC and the absorption spectrum of cyt c, and a short interaction distance (estimated to be 5.6 nm) between them, the fluorescence quenching of TCPC upon complexation with cyt c is attributed to an efficient energy transfer. 相似文献
7.
Cone, partial cone and 1,3-alternate conformers of tetrathiacalix[4]arene tetraethylacetate were synthesized and subjected to aminolysis with alkyl amines [CH3(CH2)nNH2; n=2, 3, 5] to yield mono-, di-, tri- or tetrasubstituted p-tert-butyltetrathiacalix[4]arene amides which were characterized by detailed analysis of their NMR spectral and single crystal X-ray crystallography. It has been observed that while the 1,3-alternate and cone conformers of the tetrathiacalix[4]arene tetraethylacetate gave corresponding tetrathiacalix[4]arene tetraamides under different experimental conditions, the corresponding partial cone conformer undergoes a cascade of regioselective reactions with the same amines. Variable temperature 1H NMR experiments allowed the determination of relative stability of different conformers within the temperature range of 298-333 K. The synthesized derivatives were evaluated as molecular extractants for cations and anions and were determined to facilitate extraction of oxyanions (CrO42− and Cr2O72−) from aqueous to the organic phase. The studies have a significance in the design of tetrathiacalix[n]arene based molecular receptors for innovative applications. 相似文献
8.
Ezgi AkceylanMustafa Yilmaz 《Tetrahedron》2011,67(34):6240-6245
This study reports the synthesis of calix[4]arene-based phase-transfer catalysts derived from the reaction of 5,17-di-tert-butyl-25,27,26,28-tetrahydroxycalix[4]arene with N-ethylpiperazine, diallylamine or 4-benzylpiperidine. The catalytic efficiency of the calix[4]arenes alkylamine derivatives was evaluated by carrying out the ester-forming reaction of alkali metal carboxylates (sodium butyrate or sodium caprylate) with p-nitrobenzyl bromide. It has been observed that the ester-forming reaction of alkali metal carboxylates with p-nitrobenzyl bromide, using the N-ethylpiperazine amine derivative of calix[4]arene as a phase-transfer catalyst in dichloromethane at 25 °C, provided the best yields. 相似文献
9.
Sergey N. Podyachev Nadezda E. Kashapova Victor V. Syakaev Svetlana N. Sudakova Railya R. Zainullina Margit Gruner Wolf D. Habicher Tatiana A. Barsukova Fafu Yang Alexander I. Konovalov 《Journal of inclusion phenomena and macrocyclic chemistry》2014,78(1-4):371-380
The extraction ability of phenyl hydrazone derivatives of cone- and 1,3-alternate tetrathiacalix[4]arenes towards to some alkali, alkaline earth, transition and heavy metal ions has been investigated by picrate extraction method. The synthesized cone-tetrathiacalix[4]arene hydrazones show a high efficiency coupled with an excellent selectivity towards for Ag+ and Hg2+ ions. The stoichiometry of complexes and the extraction constants have been determined. The influence of calix[4]arene platform’s structure and the electron donor substituents in phenyl fragments on the extraction efficiency has been discussed. 相似文献
10.
Lijuan Jiao 《Tetrahedron》2007,63(19):4011-4017
Six new functionalized oxacalix[4]arene porphyrins have been synthesized via a high-yielding ‘3+1’ condensation between meso-(3,5-dihydroxyphenyl)triphenylporphyrin and readily available new fluorodinitrobenzene-containing trimers. The X-ray structure of one linear trimer is presented. The synthesis of a porphyrin containing two oxacalix[4]arene moieties is also reported using a similar strategy. 1H NMR data and computer calculations using the AM1 semiempirical method incorporated into the Spartan program indicate that the oxacalix[4]arene porphyrins adopt 1,3-alternating conformations. The photophysical properties of the oxacalix[4]arene porphyrins were investigated. 相似文献
11.
Narinder Singh 《Tetrahedron》2004,60(25):5393-5405
New podands based on the p-tert-butylcalix[4]arene unit with substitution at the lower rim incorporating imine units, have been synthesized in high yield by simple condensation method. These podands have been shown to extract and transport Ag+ selectively over alkali, alkaline earth metal cations, Zn2+, Pb2+ and Hg2+ ions, from neutral aqueous phase to organic phase. In all the ligands the calix unit has been found to be present in a cone conformation except for the one having pyridine as end group, at the ortho position. It has been isolated in two conformations; cone and 1,2-alternate. To the best of our knowledge, this may be the first 1,3-lower rim substituted calix[4]arene to exist in a 1,2-alternate conformation and is among a few known compounds with this conformation in the general class of calix[4]arenes. A complex of this ligand, which happens to be the highest extractant of Ag+ has been isolated and characterized using mass, 1H and 13C NMR spectroscopy's and elemental analysis. The spectroscopic evidence and molecular modelling studies performed on the complex suggest a participation of the imine and pyridine nitrogens and two of the ether oxygens in coordination to the metal ion. The X-ray crystal structures of three of the ligands establish the formation of inclusion complexes with polar acetonitrile solvent molecules. The 1H and 13C NMR spectra of all the compounds, taken in CDCl3, show the presence of acetonitrile molecules in the cavity of the calix[4]arene, indicating inclusion of the neutral guest molecules in the solution phase as well. For one of the podands X-ray crystal structure has shown a formation of clatharate complex of chloroform with the ligand which has rarely been found in the case of calix[4]arenes. 相似文献
12.
Yu Liu 《Tetrahedron》2003,59(40):7967-7972
A series of novel double-armed calix[4]arene derivatives, i.e. 5,11,17,23-tetra-tert-butyl -25,27-bis[2-[(2-hydroxy-5-(4-nitroazo)benzylidene)amino]ethoxy]-26,28-dihydroxy-calix[4]-arene (4), 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[(2-hydroxy-5-(2-nitroazo)benzylidene) amino]ethoxy]-26,28-dihydroxycalix[4]arene (5), 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[(2-hydroxy-5-(4-chloroazo)benzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (6), have been synthesized as an selective chromoionophore for Na+. The complexation behavior of ligands 4-6 with alkali metal ions Na+, K+, Rb+and Cs+ has been evaluated by using UV-Vis spectrometry in CH3CN-H2O (99:1/V:V) solution at 25°C. The UV-Vis spectra show that the complexation of 4-6 with Na+exhibits obvious bathochromic shifts (λmax 379→480 nm) and there is a unique color change in the solution from yellow to red upon complexation. The binding constants for Na+ are higher than that of other alkali metal ions, giving the highest cation selectivity up to 7 for Na+/K+. The binding ability and photophysical behavior of alkali cations by calix[4]arene derivatives 4-6 are discussed from the point of view of substituted effects at the lower rim of parent calix[4]arene and size-fit concept between host calix[4]arenes and guest cations. 相似文献
13.
Lukesh Bajaj H. M. Chawla Satish Kumar Geeta Hundal M. S. Hundal 《Journal of inclusion phenomena and macrocyclic chemistry》2014,78(1-4):89-96
C-acylation of calix[n]arenes is an important reaction which has been primarily utilized for their further functionalization to provide conformers with varying shapes, cavity dimensions and molecular receptor characteristics that can bind ionic and neutral species in a selective and specific manner. The length of the alkyl chain at the upper or the lower rim of calixarenes can be adjusted as required to give derivatives which can span the channels and membranes and majorly influence transport phenomenon. As a part of our program to obtain calixarene based derivatives that can span and scan artificial membranes, C-acylation of calix[4]arene has been examined to yield peracylated and partially acylated calixarene ethers. 5,11,17,23-Tetraacetyl-25,26,27,28-tetramethoxycalix[4]arene has been obtained in 80 % yield by treatment of tetramethoxycalix[4]arene with acetyl chloride in the presence of aluminum chloride using dichloromethane as the solvent. The structure was established by the conversion to corresponding phenyl hydrazones and oximes. The tetraacetyltetramethoxycalix[4]arene 2a crystallized in a monoclinic lattice, space group P21/C with a = 10.320(2) Å, b = 18.928(4) Å, c = 18.421(4) Å, β = 95.44(3)o, Z = 4. The corresponding methyl substituted O7 directs inwards towards the cavities of calix[4]arene to give an inward flattened partial cone conformation. Molecular packing shows the presence of intermolecular C–H···O, H-bonding interactions between methyl and methylene hydrogens and oxygens of the acetyl groups. 相似文献
14.
Yannick Tauran Moez Rhimi Ryohei Ueno Marie Grosso Arnaud Brioude Erwann Janneau Kinga Suwinska Rima Kassab Patrick Shahgaldian Alessandro Cumbo Bernard Fenet Beomjoon Kim Anthony W. Coleman 《Journal of inclusion phenomena and macrocyclic chemistry》2013,77(1-4):213-221
The molecular recognition by para-sulphonato-calix[4]arene of cytosine, occurs in solution, in the solid-state and by assembly on the surface of para-sulphonato-calix[4]arene capped silver nanoparticles. Each of these states shows different modes of assembly; in solution a 1:1 complex is formed; in the solid state a 4:1 assembly exists, however some of the cytosine molecules are present as space fillers and do not participate in the host (guest complexes, finally on the surface of the hybrid silver/para-sulphonato-calix[4]arene nanoparticles a 2:1 cytosine/para-sulphonato-calix[4]arene assembly is observed. The assembly processes have been studied by DOSY NMR, fluorescence spectroscopy, Dynamic Light Scattering (DLS), Single Crystal Solid State Diffraction, Visible Spectroscopy and Electron Microscopy. The results demonstrate how cytosine initiates the aggregation of the hybrid silver/para-sulphonato-calix[4]arene hybrid nanoparticles. 相似文献
15.
Xin-long Ni Hirotsugu Tomiyasu Tomoe Shimizu Carol Pérez-Casas Zeng Xi Takehiko Yamato 《Journal of inclusion phenomena and macrocyclic chemistry》2010,67(1-2):99-108
A novel thiacalix[4]arene ditopic receptor with 1,3-alternate conformation and possessing two complexation sites for hard and soft cations, 5,11,17,23-tetra-tert-butyl-25,27-bis[(N,N-diethylaminocarbonyl)methoxy]-26,28-bis[(pyridylmethyl)oxy]-2,8,14,20-tetrathiacalix[4]arene is prepared. Regioselective synthesis of distal-bis[(N,N-diethylaminocarbonyl)methoxy]thiacalix[4]arene is accomplished by a protection-deprotection method using benzyl groups as a protecting group. The deprotection of benzyl group was succeeded in the presence of solid superacid (Nafion-H) under refluxing benzene. Its complexation behavior is examined by 1H-NMR titration experiments. The formation of 1:2 homo- and heteronuclear complexes demonstrates that the preorganization, subtle conformational changes and affinity have a pronounced effect on the complexation of the receptor. 相似文献
16.
Serkan Elçin Murat Muzaffer İlhan Hasalettin Deligöz 《Journal of inclusion phenomena and macrocyclic chemistry》2013,77(1-4):259-267
In this study, the synthesis and characterization of two new upper rim functionalized azocalix[4]arene dyes have been obtained by coupling calix[4]arene with different diazo compounds of 3,5-dicarboxyaniline and 4-aminobenzene sulphon amide. The characterization of these dyes has been carried out by elemental analysis, FT-IR and 1H NMR spectra. The effect of varying dielectric constants of solvents on the absorption spectra of azocalix[4]arenes (1, 2, 3, 4) and commercial Isolan Gelb SGL (T) have been examined by UV–Vis spectrophotometer. These azocalix[4]arene dyes have also been used for dyeing textile fibers like cotton, wool, acetate, polyester and polyamide fibers. Their dyeing and fastness properties have also been discussed. 相似文献
17.
A family of six new variously substituted calix[4]arene dithianes has been prepared from respective formyl and acetyl derivatives. Shorter reaction time, mild conditions, and facile isolation of desired products are attractive features of the described method. The new 1,2-dithiane derivatives have been characterized by 1H NMR, 13C NMR spectroscopy, and FABMS analysis. The crystal structure of one of the acetyl calix[4]arene dithiane was determined by X-ray diffraction analysis, which revealed a dithiane capped linear molecular organization. Preliminary evaluation of bis (dithiane) calix[4]arene derivatives as molecular receptor for transition metal ions has revealed strong interaction with Hg2+ in 1:1 stoichiometry. 相似文献
18.
Si-Zhe Li Ke Yang Hong-Bing Liu Yu-Xiang Xia Rong-Xiu Zhu Jun Luo Qian Wan 《Tetrahedron letters》2013
Inherently chiral biscalixarenes with hetero-cavities were synthesized by a covalent assembly of p-tert-butylcalix[5]arene with a 1,3-substituted calix[4]arene via 1,3-alkylation reaction and subsequent desymmetrization. The racemates were resolved by chiral HPLC method. 1H NMR spectra, VT-NMR spectra, and theoretical calculations support that the calix[5]arene subunit of the inherently chiral calix[4][5]arene ester adopts a cone-in conformation, with the aromatic ring bearing the CH2CO2Et group tilting inward the calix[5]arene cavity. By contrast, such a cone-in structural feature of the calix[5]arene subunit disappears for the corresponding inherently chiral calix[4][5]arene carboxylic acid, due to the intramolecular hydrogen bonding between the carboxyl group and an ethereal oxygen of the glycolic chain. 相似文献
19.
MCM-41 mesoporous silica has been functionalized with two kinds of macrocylic calixarene derivatives Calix[4] and Calix[4]Br (Calix[4]=P-tert-butylcalix[4]arene, Calix[4]Br=5.11,17.23-tetra-tert-butyl-25.27-bihydroxy-26.28-bibromopropoxycalix[4]arene) through condensation approach of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as a template. Novel organic-inorganic mesoporous luminescent hybrid containing RE3+ (Eu3+, Tb3+) complexes covalently attached to the functionalized ordered mesoporous MCM-41, which are designated as RE-Calix[4]-MCM-41 and RE-Calix[4]Br-MCM-41, respectively, are obtained by sol-gel process. It is found that they all have high surface area, uniform in the mesostructure and good crystallinity. Measurement of the photoluminescence properties show the mesoporous material covalently bonded Tb3+ complexes (Tb-Calix[4]-MCM-41 and Tb-Calix[4]Br-MCM-41) exhibit the stronger characteristic emission of Tb3+ and longer lifetime than the corresponding Eu-containing materials Eu-Calix[4]-MCM-41 and Eu-Calix[4]Br-MCM-41 due to the triplet state energy of modified organic ligands Calix[4]-Si and Calix[4]Br-Si match with the emissive energy level of Tb3+ very well. 相似文献
20.
Mustafa Durmaz 《Journal of inclusion phenomena and macrocyclic chemistry》2012,74(1-4):361-368
Novel chiral calix[4]arene derivatives functionalized at the lower rim have been prepared from the reaction of p-tert-butylcalix[4]arene diamine or acylhydrazine derivative with mandelic acid or hydroxyisovaleric acid. The structures of these receptors were characterized by FTIR, 1H, 13C and 2D COSY NMR spectroscopy and elemental analysis. The transport of amino acid derivatives (phenylalanine, phenylglycine and tryptophan methyl ester hydrochlorides) was studied through bulk liquid membrane in the presence of chiral calix[4]arene derivatives. The receptors have been found to act as carriers for transport of aromatic amino acid methylesters from the aqueous source phase to the aqueous receiving phase. The transport rate and L/D selectivity of amino acid esters studied depend strongly upon the structure of the chiral receptors and guests. The best enantioselectivity was obtained in the case of phenylglycine methyl ester for all chiral carriers. 相似文献