Thiacalixarenes-A New Class of Synthetic Receptors

The review summarizes and analyzes published data on the synthesis, modification, and com- plexing properties of sulfur-bridged analogs of calixarenes, which constitute a new class of metacyclophanes.     

Crystal and molecular structure of (2)-4-(3-trifluormethyl-phenyl)-1-hydroxyadamantane

Moscow State University Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 5, pp. 153–158, September–October, 1991.     

Intramolecular co-operative hydrogen bond in calix[<Emphasis Type="Italic">n</Emphasis>]arenes (<Emphasis Type="Italic">n</Emphasis> = 4, 6, 8) bearing bulky substituents

Based on the Fourier transform IR spectroscopy together with the published NMR and X-ray data, it was shown that cyclic co-operative intramolecular hydrogen bond in calix[n]arene (n = 4, 6, 8) molecules is mainly responsible for their conformational state irrespective of the presence or absence of bulky substituents at the upper rim of the molecules. In accordance with the size of a macrocycle (n = 4, 6, 8), the stable conformation, secured by such a hydrogen bond, constitutes a cone, a pinched cone, and a pleated loop, respectively. The new, potentially competing system of hydrogen bonds in calix[6]arenes with 3-carboxymethyl-1-adamantyl substituents does not affect the conformational state of the macrocycle and its H-bonding. Six carboxy groups at the upper rim form in pairs three cyclic dimers, which does not disturb the hydrogen bonds of the hydroxy groups and the conformation of the macrocycle. In addition, the cavity of the molecule is considerably enlarged. The removal or rearrangement of the guest molecules in the solid calixarene by heating up to 180 °C only slightly affects the conformational state of macrocycles bearing bulky substituents, whereas in calixarenes devoid of such substituents, the similar procedure leads to somewhat of a distortion of the macrocycles (judging from the IR spectral indications of hydrogen bonding). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1062–1068, June, 2007.     

Ion-Selective Electrodes Based on Adamantylcalix[4,8]arenes for the Determination of Alkali Cations

Calix[4,8]arenes bearing adamantyl substituents in the upper rim and ethoxycarbonylmethoxy groups in the lower rim of the macrocycle were proposed as ionophores in membranes of ion-selective electrodes (ISEs) for determining alkali cations. Depending on the number of phenolic fragments (n) in the calixarene molecule, ISEs respond to either sodium (n = 4) or cesium (n = 8) ions. Sensors based on membranes that, along with ionophores, contain tetraphenyl borate ions as a lipophilic additive are selective for Na and Cs ions in the presence of other alkali metals. They exhibit almost theoretical responses over the concentration range from 1 × 10^–4 to 1 × 10^–1 M at pH 5.5–12 for Na-SE and pH 3–11 for Cs-SE, respectively.     

Substituent control of potassium and rubidium uptake by asymmetric calix[4]-thiacalix[4]tubes

Herein we report on the synthesis and ionophore properties of the first asymmetric p-tert-butylcalix[4]-p-R-thiacalix[4]tubes 7a-c (R = t-Bu, H, 1-adamantyl). The target compounds were obtained by the condensation of tosyloxyethoxy-p-tert-butylcalix[4]arene with the corresponding p-R-thiacalix[4]arenes in the presence of K2CO3 in acetonitrile. The complexation with sodium, potassium and rubidium iodides was studied in CDCl3-CD3OD (4:1) medium by means of 1H NMR measurements. It was found that the ionophore properties of calixtubes 7a-c are controlled by the character of the substituents at the upper rim of the thiacalix[4]arene fragment and it was shown that only the molecular tube 7c with an adamantane-containing thiacalixarene unit is capable of quantitatively binding potassium (swiftly) and rubidium (slowly) cations.     

Synthesis of Adamantylated Salicylic Acids

Russian Journal of Organic Chemistry - 5-[3(4)-R-Adamantan-1-yl]salicylic acids [R = H, Alk, Ar, OH, NHC(S)NH2] have been synthesized by electrophilic substitution reactions of hydroxy- and...     

Homooxacalixarenes: I. Structure,Synthesis, and Chemical Reactions

Data published on the structure, preparation, and chemical reactions of homooxacalixarenes with various number of aromatic fragments and dihomooxabridges in macrocycles were analysed and summarized.     

Erratum to: “Asymmetric Calix[4]-thiacalix[4]arene Tubes: Synthesis and Ionophore Properties”

Russian Journal of Organic Chemistry -