143406-35-3Relevant academic research and scientific papers
Syntheses and optical resolution of calix[4]arenes with molecular asymmetry. Systematic classification of all possible chiral isomers derivable from calix[4]arene
Iwamoto, Koji,Shimizu, Hiroyasu,Araki, Koji,Shinkai, Seiji
, p. 3997 - 4006 (1993)
All possible chiral isomers that can be derived from calix[4]arene by modification of the OH groups were systematically classified. Molecular asymmetry can be generated not only by different substituents but also by conformational isomerism. The numbers of chiral isomers are 24 for tetra-O-substituted calix[4]arenes, 10 for tri-O-substituted calix[4]arenes, 3 for di-O-substituted calix[4]arenes, and 0 for mono-O-substituted calix[4]arenes. This implies that calix[4]arene is a useful building block for the design of novel asymmetric ring structures. In order to demonstrate asymmetry in these chiral calix[4]arenes, we synthesized several tetra-, tri-, and di-O-substituted calix-[4]arenes by using the metal template method, the stepwise synthesis method, the protection-deprotection method, etc., which were developed in efforts directed toward regioselective O-alkylation and control of conformational isomerism in calix[4]arenes. Finally, we succeeded in complete optical resolution of chiral calix[4]arenes by an HPLC method using a chiral-packed column or by the formation of diastereomers with the (-)-menthoxyacetyl group. This article thus contains all of the molecular design concepts, syntheses, and optical resolutions of chiral calix[4]arenes.
Modulation of nanotube packing through the controlled self-assembly of tris-p-carboxylatocalix[4]arenes
Kennedy, Stuart,Dalgarno, Scott J.
, p. 5275 - 5277 (2009)
Crystallisation of tris-carboxylatocalix[4]arenes from pyridine affords self-assembled layered and triply helical nanotubular arrays; the latter of these represents a modulation of nanotubule spacing in a persistent self-assembly motif.
Regioselective Friedel-Crafts acylation of calix[4]arenes
Skácel, Jan,Budka, Jan,Eigner, Václav,Lhoták, Pavel
, p. 1959 - 1965 (2015)
Friedel-Crafts acylation of 25,27-dialkoxycalix[4]arenes has been studied. Direct acylation of de-tert-butylated calixarene using acyl chlorides and AlCl3 in 1,2-dichloroethane provided the corresponding diacyl derivatives regioselectively in h
Synthesis, characterization of a novel calixarene having dipyridyl pendants and study of its complexes with Cu(II) and Co(II)
Arena, Giuseppe,Contino, Annalinda,Longo, Elisa,Sciotto, Domenico,Sgarlata, Carmelo,Spoto, Giuseppe
, p. 5415 - 5418 (2003)
Two dipyridyl pendants were attached to the 1,3 positions of a calix[4]arene, with the purpose of having a ligand able to complex Cu(II) and Co(II). Indeed, the new ligand, fixed in its 1,3-alternate conformation, forms stable complexes with both Co(II) and Cu(II), as shown by UV-vis titrations carried out in acetonitrile. However, the data analysis clearly shows that the ligand forms with the two metal ions complexes having different stoichiometries.
Synthesis, characterization and electrochemical properties of two new calix[4]arene derivatives bearing two ferrocene imine or ferrocene amine units at the upper rim
Shaabani, Behrouz,Shaghaghi, Zohreh
, p. 3259 - 3264 (2010)
A novel calix[4]arene derivative with two ferrocenyl Schiff-base groups at the upper rim 3 has been synthesized from 5,17-diformyl-25,27-dipropoxy-26,28-dihydroxy calix[4]arene and 4-ferrocenylaniline via condensation reaction. Reduction of 3 with sodium borohydride led to calix[4]arene derivative 4 with two amino ferrocenyl groups at the upper rim. The ferrocenyl Schiff-base calix[4]arene and its corresponding reduced amine have been purified and characterized by elemental analysis,1H NMR, FTIR, Mass and UV-vis spectral data. Electrochemical properties of compounds 3 and 4 have been investigated. Cyclic voltammograms of 3 and 4 show reversible redox couples of ferrocene/ferrocinium at E1/2=0.401 V and 0.346 V, respectively. Electrochemical studies show these redox active compounds electrochemically recognize trivalent lanthanides La3+ and Ce3+ and divalent Pb2+ and Cu2+cations. With ferrocenyl Schiff-base calix[4]arene 3 an anodic shift as large as 130 mV is observed on addition of one equivalent of Ce3+ ion. Also extraction properties of compound 4 towards some metal cations have been described. It has been observed that compound 4 has a good selectivity for metal cations Fe3+, Cu2+, Pb2+ and Cd2+ against Ni2+ and Co2+.
Regioselective deuteration of 25,27-dialkoxycalix[4]arenes
Ma?Ková, Michaela,Himl, Michal,Miná?ová, Lenka,Lang, Jan,Lhoták, Pavel
, p. 2543 - 2546 (2011)
A direct deuteration of the upper rim of calix[4]arene has been carried out for the first time. 25,27-Dialkoxy derivatives of calix[4]arene (R = Me, Et, n-Pr, n-Bu) were regioselectively deuterated at the para positions of unsubstituted phenolic rings using DCl/D2O in tetrachloroethane. Interestingly, identical reaction conditions do not lead to deuteration of mono- or tri-substituted derivatives where only simple cleavage of alkyl substituents was observed.
Effect of conformation, flexibility and intramolecular interaction on ion selectivity of calix[4]arene-based anion sensors: experimental and computational studies
Maity, Debdeep,Bhatt, Madhuri,Desai, Mittal L.,Suresh,Si, Mrinal Kanti,Boricha, Vinod P.,Ganguly, Bishwajit,Paul, Parimal
, p. 600 - 615 (2017)
A number of calix[4]arene-based molecules were designed incorporating amide moiety with variation in conformation, rigidity at the binding sites and steric crowding at the upper rim to investigate the anion sensing property of this series of ionophores. These compounds were synthesised and characterised, molecular structures of two of the compounds were established by single-crystal X-ray study. Anion binding property of these ionophores, investigated with the aid of 1H NMR and UV–vis spectroscopy, revealed that three (1–3) out of four ionophores strongly interact with F?, in addition, ionophore 2 interacts with CN? and H2PO? 4, ionophore 3 interacts with CH3COO? and H2PO? 4 and ionophore 4 does not interact with any anions. NMR titration was carried out to determine binding constant with strongly interacting anions. Crystal structure analysis revealed that strong intramolecular N ? H · π interaction in 4 prevented the anions to interact with the N–H protons of the amide moiety. Interestingly, 2 with F? and CN? exhibits sharp colour change in acetonitrile–chloroform. Apparently, conformation of the calix moiety, flexibility of the binding sites and intramolecular H-bonding played critical role towards determination of selectivity. Computational study was performed to investigate the interaction site(s) and also to corroborate some of the experimental results.
Calix[4]arene based fluorescent chemosensor bearing coumarin as fluorogenic unit: Synthesis, characterization, ion-binding property and molecular modeling
Patra, Subrata,Lo, Rabindranath,Chakraborty, Ashish,Gunupuru, Ravi,Maity, Debdeep,Ganguly, Bishwajit,Paul, Parimal
, p. 592 - 601 (2013)
A series of calix[4]arene-based fluorescent chemosensors in cone and 1,3-alternate conformations have been synthesised incorporating ethylene glycol units as binding sites and coumarin as fluorescent probe. These compounds have been designed with variation in substituents, conformations of the calixarene unit and steric crowding. The open chain ethylene glycol moieties are flexible so that they can orient themselves in space to make effective interactions with metal ions. Ion-binding study of these fluoroionophores has been carried out using a large number of metal ions and the ion recognition event is monitored by fluorescence and absorption spectroscopy. Substantial quenching in emission intensity in presence of Fe3+ and Cu2+ and enhancement of emission intensity in presence of Ca2+ suggests strong binding of these metal ions with the ionophores. Complexation with these metal ions is also evident from UV-Vis spectral changes. Composition of the complexes formed (1:1) has been confirmed by ESMS analysis. Binding constants with the strongly interacting metal ions have been evaluated from fluorescence titration data. DFT calculations have been carried out to find out the metal binding sites of the calix ionophores and frontier molecular orbital analyses have rationalized the fluorescence behaviors observed upon complexation with metal ions in these cases.
Synthesis, crystal structures and competitive complexation property of a family of calix-crown hybrid molecules and their application in extraction of potassium from bittern
Ramakrishna, Vallu,Suresh,Boricha, Vinod P.,Bhatt, Anjani K.,Paul, Parimal
, p. 706 - 718 (2015)
A family of calix-crown hybrid molecules containing calix[4]arene and crown-5/6, either at lower rim or at both upper and lower rims, have been synthesised, characterised and their competitive complexation property towards alkali and alkaline earth metal
Synthesis of new calix[4]arene based chiral ligands bearing β-amino alcohol groups and their application in asymmetric transfer hydrogenation
Quintard, Adrien,Darbost, Ulrich,Vocanson, Francis,Pellet-Rostaing, Stephane,Lemaire, Marc
, p. 1926 - 1933 (2007)
A new series of chiral calix[4]arenes bearing β-amino alcohol groups have been synthesised. The crucial steps consist of the binding of glycidyl groups on the lower rim of the calix[4]arenas, followed by their regioselective opening with amines. These lig
