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Naturalmacrocycliclactonesandlactamsastheionophoreshaveabsorbedextensiveinterestsbecauseoftheirveryhighselectiverecognitionforalkalimetals.rorexample,nactinslandvalinomycin'havethehighestselectivityforpotassiumamongalltheionopohores.Artificialmacrocycliclactonesalsoshowedselectivityforcanons,althoughthebindingstrengthwaslowerthanthatofcommoncrownethers3.Calixareneswereaveryimportantkindofartificialreceptors,whosederivativeshaveshowedthehighestselectivityforNa ,K andCs amongthesynthesizedmacro… 相似文献
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Synthesis of Schiff Base Calix [4] arene Crowns 总被引:2,自引:0,他引:2
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. 相似文献
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De Salvo G Gattuso G Notti A Parisi MF Pappalardo S 《The Journal of organic chemistry》2002,67(3):684-692
A series of tri-O-substituted 1,3-bridged calix[5]arene crown-6 ethers bearing alkyl, arylalkyl, alkoxyalkyl, and alkoxycarbonylmethyl residues at the lower rim and either (t)()Bu or H substituents at the upper rim have been synthesized. (1)H NMR studies have shown that p-tert-butylcalix[5]crowns, irrespective of the size and nature of their lower rim pendant groups, adopt preorganized conelike conformations, whereas p-H-calix[5]crowns with bulky substituents preferentially exist in solution as partial cone conformers (C(1) symmetry). Calix[5]crown derivatives behave as mono- or ditopic receptors for isomeric butylammonium ions, forming endo-cavity (inside the calixarene cup) and/or exo-cavity (at the crown ether moiety) 1:1 complexes according to the shape of the guest. These two binding modes can be clearly distinguished and monitored by (1)H NMR titration experiments. 相似文献
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Rudzevich Y Rudzevich V Moon C Brunklaus G Böhmer V 《Organic & biomolecular chemistry》2008,6(13):2270-2275
Calix[4]arenes substituted at their wide rim by four aryl urea residues (1) form hydrogen-bonded dimers in apolar solvents. Replacement of one urea residue by an acetamido moiety leads to calix[4]arene derivatives (5) which form hydrogen-bonded tetramers under the same conditions. Both self-assembly processes occur independently. Therefore, molecules have been prepared in which a tetra-urea calix[4]arene and a tri-urea mono acetamide derivative are covalently connected between their narrow rims by a long, mainly aliphatic chain [-O-(CH(2))(n)-C(O)-NH-(CH(2))(m)-O-] (7). In the presence of an equimolar amount of tetra-tosyl urea calix[4]arene () they form dendritic assemblies since the well known heterodimerization of tetra-tosyl and tetra-aryl urea calix[4]arenes prevents the formation of a cross-linked structure. Covalent connection of adjacent urea residues leads to tetra-loop derivatives (3) that cannot form homodimers, but instead form heterodimers with tetra-aryl or tetra-tosylureas. Therefore, similar dendrimers should be available using the selective dimerization observed for 3. The formation of a single, structurally uniform dendrimer from eight building blocks is confirmed by (1)H NMR spectra, showing only peaks that are also found for respective model assemblies. Translational diffusion coefficients of the assemblies have been determined using (1)H DOSY NMR. 相似文献
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Serkan Erdemir Ozlem Sahin Arzu Uyanik Mustafa Yilmaz 《Journal of inclusion phenomena and macrocyclic chemistry》2009,64(3-4):273-282
Synthesis of the glutaraldehyde derivatives calix[n]arene (n = 4,6,8) (Calix[n]-GA) and using as cross-linkers for immobilization of Candida rugosa lipase (CRL) have been discussed in this paper. The amino functional calix[n]arene derivatives (Calix[n]-NH 2) were synthesized via reduction of dinitrile, hexanitrile and octanitrile derivatives of calix[n]arenes. These amino functional calix[n]arene derivatives (Calix[n]-NH 2) were converted to their aldehyde derivativatives with glutaraldehyde. The calix[n]arene derivatives were used in lipase immobilization in order to see the role of calix[n]arene binding site on the lipase activitiy and stability. The activity recovery of calix[n]arene-supported lipases (Calix[n]-CRL) based on the Calix[4]-CRL, Calix[6]-CRL and Calix[8]-CRL reaches to 53.5, 66.1 and 76.4%, respectively. 相似文献
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Calixarenes have absorbed considerable interests for their outstanding abilities of recognition for cations, anions and organic molecules1. In order to include larger and more complex molecules, polytopic receptors were designed from two or more host macrocycles linked by one or several links. Therefore, double-calixarenes and oligocalixarenes have been synthesized and reviewed2. Among these polytopic receptors, double-calixarenes can be used as the mimic of ion channel or to self-organize koi… 相似文献
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Binding of a calix[5]arene containing a single phosphorus ligand and three hydroxyl groups, calix[5]PNMe2(OH)3, 1, toward titanium and zirconium is investigated to yield insight into the factors that determine the strength of the phosphorus/metal interaction within the constraint of the calix[5]arene. Treatment of 1 with tetrakis(dimethylamino)titanium yields three complexes, 4a, 4b, and 4c, each of which shows the loss of 3 mol of dimethylamine in the reaction with the titanium bound to three oxygens. Treatment of 1 with tetrakis(diethylamino)zirconium proceeds similarly, although only two products, 5a and 5b, were isolated. X-ray structures of the products were obtained. Complexes 4a and 5a show similar geometries, with the calix[5]arene in an approximate cone conformation and the phosphorus lone pair directed toward the metal. The P...M distances are, however, markedly different: 3.69 A in 4a and 3.18 A in 5a, the former indicative of no interaction and the latter a weak one. Complexes 4b and 5b each are dimers, featuring a planar four-membered M-O-M-O ring; however, the titanium is five-coordinate in 4b with no phosphorus/metal bond, while the zirconium in 5b is six-coordinate with a P-Zr distance of 2.95 A. Complex 4c is monomeric with the calix[5]arene in an approximate 1,2-alternate conformation with a P...Ti distance of 2.90 A. The two most significant aspects controlling the phosphorus/metal contact are the metal, with the larger zirconium showing stronger interaction, and the calix[5]arene conformation, with the cone conformation showing the weaker interaction. 相似文献
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Cavalleri O Vignolo M Strano G Natale C Rolandi R Thea S Prato M Gonella G Canepa M Gliozzi A 《Bioelectrochemistry (Amsterdam, Netherlands)》2004,63(1-2):3-7
We investigate the self-assembly of modified calix[4]arene on gold surfaces. Calix[4]arene was modified through a reaction sequence which led to assembling of the crown-5 moiety and to the insertion of two thioether groups into the starting molecule. The so-obtained calix[4]arene-crown-5 bis(7-thiatridecyloxy) (hereafter called calix[4]arene) was in the stable 1,3-alternate conformation. The calix[4]arene/gold interface was investigated by means of spectroscopic ellipsometry (SE), scanning tunneling microscopy (STM) and cyclic voltammetry (CV). SE data indicate a layer thickness compatible with the formation of a monomolecular layer. This result is confirmed by STM imaging which shows the formation of a high density of small pits, one gold layer deep, a typical feature of self-assembled organosulphur monolayers on gold. CV measurements performed in presence of the [Ru(NH(3))(6)(2+/3+)] redox couple indicate a passivation of the metal electrode, resulting in a reduction of the redox current, after the layer deposition. CV has also been used to investigate the selectivity properties of calix[4]arene-covered gold electrodes by measuring the redox current decrease in the presence of different salt solutions. It is found that calix[4]arene-covered electrodes are able to complex K(+) and Ba(2+), while no complexation is observed in the case of Li(+), Na(+), Cs(+), Mg(2+) and Ca(2+). 相似文献
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Unprecedented synthesis of chiral (aza)crown ethers of calix[4]arene derivatives bearing a carboxyl amide bridge was described. The synthesis proceeds through condensation of the corresponding dinitriles with optically active 1,2-aminoalcohols,and is catalyzed by the ZnCl2 Lewis acid at elevated temperature in a very efficient one-pot process. The cavity of calix[4](aza)crowns can encapsulate methanol molecules by O—H...π interaction,which has been confirmed by X-ray crystal structures and ESI-MS. 相似文献
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Fan M Shevchenko IV Voorhies RH Eckert SF Zhang H Lattman M 《Inorganic chemistry》2000,39(21):4704-4712
Treatment of calix[4]arene (1b) with trichloromethylsilane yields two conformers of calix[4]SiMe(OH), the cone 2b-C and the partial cone 2b-PC. These are isolated and structurally characterized, and their thermodynamic activation parameters are determined in solution [Ea = 117(3) kJ/mol, delta H = 5(4) kJ/mol]. Similar parameters are found for the p-tert-butylcalix[4]arene analogues 2a-C and 2a-PC. Deprotonation of 2b with butyllithium yields calix[4]SiMe(OLi) (8b). The structure of 8b is solvent dependent: 8b contains a five-coordinate silicon in THF and a four-coordinate silicon in benzene. Similar behavior is found for the p-tert-butylcalix[4]arene analogues. The five-coordinate phosphorus analogue of the anion in 8, p-tert-butylcalix[4]PMe (11a), is synthesized from the phosphonium triflate salt p-tert-butylcalix[4]PMe(OH)OTf (10a(OTf)) via treatment with butyllithium. The structure of 11a shows the geometry around phosphorus to be very close to a pure trigonal bipyramid. The X-ray structure of 10a(OTf) cannot be obtained, but its iodide analogue 10a(T) is synthesized and structurally characterized. The cation in 10a(I) adopts the partial cone conformation in the solid state, similar to 2b-PC. Treatment of 8b with methyl trifluoromethanesulfonate yields the methyl phenyl ether calix[4]SiMe(OMe) (3b). This species and its p-tert-butyl analogue 3a are structurally characterized. Both adopt the partial cone conformation. The SiMe group in 3b can be removed via treatment with fluoride to yield the monomethylated calix[4]arene 4b in 50-60% overall yield based on 1b. 相似文献
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The three-step synthesis of a calix[6]arene capped with a TAC unit is presented. The novel C(3v)-symmetrical calix[6](aza)cryptand displayed an exceptionally high affinity for small ammoniums. NMR and X-ray diffraction analyses demonstrated the formation of endo-complexes. These complexes are stabilized thanks to (i) hydrogen bonding to both the aza cap and one phenolic unit of the calixarene and to (ii) cationic and CH-pi interactions between the ammonium and the aromatic walls of the host. Combined extraction and competitive binding experiments yielded the free energies of bindings DeltaG degrees in chloroform. The values are the highest ever obtained with a calixarene-type host. Calix[6]TAC displayed the best affinity for EtNH(3)(+). Comparison with other small ammoniums emphasizes the high selectivity of the recognition process. 相似文献
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Two calix[4]arene derivatives containing 1,2,3-triazole moiety were synthesized via K2CO3-catalyzed1,3-dipolar cycloaddition reaction between calix[4]arene-based azide and active methylene compounds in good yields.The structures of the two compounds synthesized herein were fully confirmed by 1HNMR,,(13)C NMR,and MS(ESI).The thermal analysis showed that the mass losses of the synthesized compounds 4 and 5 containing 1,2,3-triazole groups are similar to each other. 相似文献
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Vovk AI Kalchenko VI Cherenok SA Kukhar VP Muzychka OV Lozynsky MO 《Organic & biomolecular chemistry》2004,2(21):3162-3166
Calix[4]arenes bearing one or two methylenebisphosphonic acid fragments were prepared via addition of diethylphosphite to the parent calix[4]arene aldehydes. The resulting compounds displayed stronger inhibition of calf intestine alkaline phosphatase than simple methylenebisphosphonic or 4-hydroxyphenyl methylenebisphosphonic acids. The action of these phosphorylated calix[4]arenes is concordant with partial mixed-type inhibition. The inhibition constants Ki and Ki' for the calix[4]arene bis(methylenebisphosphonic) acid in Tris-HCl buffer at pH 9 are 0.38 microM and 2.8 microM respectively. The replacement of the phosphoric acid moieties on the macrocycle with diethylphosphonates results in a sharp decrease of its inhibitory action. Preorganizing phosphonic acid fragments using a calixarene platform therefore provides a promising approach for the design of efficient alkaline phosphatase inhibitors. 相似文献
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《Electroanalysis》2004,16(24):2073-2081
Calix[4]pyrrole liquid membrane electrodes display a potentiometric response towards the neutral form of phenol derivatives. They do not respond towards the corresponding anionic forms. The mechanism of the generation of the potentiometric signal relies on: (1) The creation of supramolecular complex calix[4]pyrrole? nitrophenol at the organic/aqueous interface; (2) The increasing of the acidity of OH group from nitrophenol molecules due to formation of hydrogen bond between calix[4]pyrrole? nitrophenol at the interface; (3) The dissociation of the OH group from calix[4]pyrrole? nitrophenol complex and the ejection of H+ to the aqueous layer adjusted to the membrane organic phase boundary. The sensitivity and selectivity of the calix[4]pyrrole liquid membrane electrodes are governed by the lipophilicity and acidity of the phenolic guests. Also, the affinity to create a hydrogen bond between the host and the target molecule is a parameter which has a strong influence on the phenomena studied. 相似文献