143406-35-3Relevant articles and documents
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.
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 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+.
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.
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
Lower-Rim-Modified Calix[4]arene-Pyrrolotetrathiafulvalene Molecular Tweezers
Azov, Vladimir A.,Korsching, Kai R.,Schlüter, Dirk
supporting information, p. 4469 - 4476 (2021/08/30)
An approach for the lower rim modification of the calix[4]arene-based molecular tweezes with monopyrrolo-tetrathiafulvalene (MPTTF) arms attached to the upper rim of calixarenes is described. First, calixarene-MPTTF conjugates with free hydroxyl on the lower rim are synthesized using the Ullmann reaction, then hydroxyl groups are substituted by propargyl groups, which can be used for further modification by the click reaction. The new calixarene-TTF derivatives displayed reversible redox processes, as well as demonstrated binding affinity for electron-deficient molecular guests such as tetracyanoquinodimethane. The described synthetic approach will be used for the modular synthesis of molecular receptors tailored for specific applications.
