The synthesis of bis(benzo-15-crown-5) derivatives and their use in potassium-PVC membrane electrodes

Five new bis(benzo-15-crown-5) derivatives with different connecting groups were synthesized. Potassium ion-selective PVC membrane electrodes based on these bis(crown ether)s were prepared and their selective properties were measured. The results showed that most of these electrodes are stable over a wide pH range and their selectivity coefficients were better than those of an electrode based on natural valinomycin.     

Synthesis of benzo-13-crown-4 derivatives

A series of nine, new benzo-13-crown-4 compounds which bear one or two substituents on the three-carbon bridge has been prepared in good yields by cesium fluoride-assisted cyclization reactions of catechol with ditosylates of the appropriate glycols. The solid state structure of 9,9-dibenzyl-2,3-benzo-13-crown-4 is determined and compared with the reported structure for the unsubstituted crown ether.     

Cation selectivity of 13-crown-4 and bis(13-crown-4) derivatives

The cation selectivity of liquid-membrane electrodes based on 18 derivatives of 13- crown-4 and bis(13-crown-4) is reported. When these compounds are dissolved in 1,2-dichlorobenzene, the electrodes exhibit MgCl⁺ selectivity which depends on the nature of the bonds connecting the crown ether rings.     

Mass-spectrometric investigation of ionophoric derivatives of benzo- and dibenzocrown ethers. 4. 4′-Acyl derivatives of benzo-15-crown-5 and benzo-18-crown-6

The mass spectra of 4-acyl derivatives of benzo-15-crown-5 and benzo-18-crown-6 were studied by the method of direct analysis of the daughter ions (DADI). It was established that the fragmentation of the M⁺ ions of the investigated compounds under electron impact proceeds via the scheme of the McLafferty rearrangement with the simultaneous elimination of ethylene oxide. The degree of occurrence of the McLafferty rearrangement increases with an increase in the length of the side chain.See [3] for communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 989–901, July, 1987.     

A benzo-21-crown-7/secondary ammonium salt [c2]daisy chain

A [c2]daisy chain has been constructed from a heteroditopic monomer based on the benzo-21-crown-7/secondary ammonium salt recognition motif as shown by single crystal X-ray analysis. It has been further demonstrated that the complexation behavior of this heteroditopic monomer in solution can be controlled by changing the solution pH or adding/removing K(+).     

双羟甲基-18-冠-6及其衍生物的合成

报道了双羟甲基-18-冠-6及其正丁基、烯丙基、酯基、羧酸基衍生物的合成。所合成的八种新冠醚化合物的结构已经IR、MS、NMR、元素分析证实。     

Molecular structure and properties of benzo-12-crown-4 and acetylbenzo-12-crown-4

Conclusion Significant differences were found in the conformational states of B12C4 and acB12C4 in solution, which are capable of affecting the complexation properties and physiological activity of these polydentate ligands.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1051–1055, May, 1988.     

Synthesis of quinazoline derivatives containing veratrole and benzo-15-crown-5 moieties

The condensation of (benzo-15-crown-5)-4-thiocarboxamide with anthranilic acid is studied for the first time. Novel representative of crown ethers incorporating the quinazoline moiety is synthesized. Methylation of (benzo-15-crown-5)-4-thiocarboxamide proceeds anomalously giving (benzo-15-crown-5)-4-carbonitrile. (Benzo-15-crown-5)-4-thiocarboxamide is reacted with thioveratramide in order to compare the reaction paths.Mirzo Ulugbek Tashkent State University, Tashkent 700095, Republic of Uzbekistan; Institute of Plant Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent 700170. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 937–940, July, 1999.     

Synthesis and structures of nitromethane complexes of furanotribenzo-21-crown-7 and dibenzo-21-crown-7

Single crystal X-ray diffraction analyses of two nitromethane complexes of furanotribenzo-21-crown-7 (1 and2) and the nitromethane complex of dibenzo-2l-crown-7 (3) are reported. The two nitromethane complexes1 and2 are polymorphic in that the macrocyclic ring adopts the dentist's chair conformation in both structures, with a single nitromethane molecule coordinating to either the lower, concave (1) or upper, convex (2) face of the crown ether. Complex3 adopts an entirely different conformation with a coplanar arrangement of the crown ether oxygen atoms binding a single nitromethane molecule. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. 82209 (31 pages).The U.S. Government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Potassium and cesium thiocyanate complexes with diphenyloxa-21-crown-7: Synthesis and vibration spectra. Selective properties of dipnehyloxa-21-crown-7

Novel K and Cs complexes with diphenyloxa-21-crown-7 (2,3,5,6-dibenzo-1,4,7,10,13,16,19-heptaoxacyclo-heneicosadiene-2,5; DPO21C7) are synthesized and isolated in a solid state, and their IR spectra (4000–400 cm^–1) are studied. Only four ether O atoms of crown ether are involved in coordination. Conformation of a macrocycle in the complexes depends on the cation size. The potentiometric selectivity of diphenyloxa-21-crown-7 toward Cs⁺ ions was found to be the greatest.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 163–167.Original Russian Text Copyright © 2005 by Ivanova, Dorokhov, Pyatova, Galkina, Yakshin, Tsivadze.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Syntheses, spectroscopic characterization and metal ion binding properties of benzo-15-crown-5 derivatives and their sodium and nickel(II) complexes

New benzo-15-crown-5 derivatives containing nitro, amine and imine groups were prepared. Nitro compound (1) was prepared after the reaction?4′,5′-bis(bromethyl)benzo-15-crown-5 and o-nitrophenol in the presence of NaOH. After reduction process by using hydrazine hydrate and Pd/C amine compound (2) was formed. New crown ether imine compounds (3–5) were synthesized by the condensation of corresponding crown ether diamine (2) with salicylaldehyde derivatives. Sodium complexes of the crown compounds (1a–5a) form crystalline 1:1 (Na⁺: ligand) complexes with sodium perchlorate. Nickel(II) complexes (3b–5b) with 1:1 (Ni²⁺:ligand) stoichiometries were also been synthesized from the Schiff bases (3–5). The results indicated that the Schiff base ligands coordinated through the azomethine nitrogen and phenolic oxygen. The extraction ability of compounds (1, 3, 4 and 5) were also evaluated in chloroform by using several alkali and transition metal picrates such as Li⁺, Na⁺, K⁺, Cr³⁺, Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pb²⁺.     

12-Membered crown ethers. Lipophilic derivatives of benzo- and naphtho-12-crown-4 and their membrane electrode properties. Crystal structures of benzo-12-crown-4 NaI and KI complexes

Lipophilic derivatives of benzo-12-crown-4 and naphtho-12-crown-4 have been synthesized. The behavior of the parent compounds and their derivatives in membrane ion-selective electrodes have been studied. Selectivity changes have been observed with the rise in lipophilicity. Crystal structures of the NaI and KI complexes of benzo-12-crown-4 (1 and2) have been determined by X-ray analysis. The alkali metal and iodide ions are in direct contact in2 but not in1. Compound1 [Na(benzo-12-crown-4)₂]·I is triclinic, witha=13.368(8),b=10.727(7),c=10.325(4) Å; =73.56(4),=77.73(4), =108.70(5)°;Z=2, space group is . Compound2 [K(benzo-12-crown-4)₂·I] is monoclinic, witha=15.807(8),b=12.043(4),c=15.601(6) Å,=117.74(3)°;Z=4, space groupC2/c. In both compounds the cations interact with all oxygen atoms of two crown ether molecules. Correlation of the crystal structures and behavior of the crown ethers in ion-selective membrane electrodes is discussed. Supplementary Data related to this article have been deposited with the British Library as Supplementary Publication No. 82185 (15 pages).     

Polymethine dyes based on (benzo-15-crown-5) thiazole

Several monomethinecyanine, merocyanine and styryl dyes were synthesized using a 5,6-(1,4,7,10,13-pentaoxacyclotridecane)-benzothiazole derivative as the starging reageni. A study was made of their spectral characteristics and the effect which complexing with alkaline and alkaline-earth metal salts had on their chromaticity.Organic Chemistry Institute, National Academy of Sciences of Ukraine, Kiev. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 992–996. Original article submitted March 12, 1996.     

Preparation of a fixed-tetraphenylethylene motif bridged ditopic benzo-21-crown-7 and its application for constructing AIE supramolecular polymers

Benzo-21-crown-7(B21 C7) is one of the most important crown ethers,which not only shows excellent physicochemical properties but also exhibits promising binding capability with dialkylammonium salts.In this paper,we designed and synthesized a fixed-tetraphenylethylene(FTPE) motif bridged ditopic benzo-21-crown-7 molecule(H).The fixed tetraphenylethylene motif endows H with aggregation induced emission(AIE) prope rty.In the presence of a ditopic dialkylammonium salt guest molecule(G),a fluorescent supramolecular polymer with golden luminescent property could be fabricated.This B21 C7-based host-guest supramolecular polymer with golden fluorescence may have potential application in dynamic luminescent materials.     

Synthesis and properties of bis(pyridylmethylene)mercury derivatives

The action of ammonia on - and -monomercurimethylenePyrylium perchlorates gave bis(pyridylmethylene)mercury derivatives, which undergo decomposition to the corresponding pyridine derivatives and mercuric chloride.See [1] for our preceding communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 887–888, July, 1981.     

苯并-15-冠-5和二苯并-18-冠-6萃取分离铟(III)的研究

本文用斜率法、饱和法以及通过与萃取合物相对应的冠醚配合物晶体的制备及其性质研究, 探讨了In^3^+的萃取机理, 测定并计算了表观萃取平衡常数, 将此萃取体系应用于铟和某些体系应用于铟和某些金属离子的萃取分离, 亦获得较好的结果.     

Hydration to benzo-15-crown-5, benzo-18-crown-6 and the benzo-18-crown-6-potassium ion complex in the low-polar organic solvents.

The coextraction of water with benzo-15-crown-5 (B1SC5), benzo-18-crown-6 (B18C6) and the B18C6-K+ complex into seven low-polar solvents, i.e., carbon tetrachloride (CTC), chloroform (CF), dichloromethane (DCM), 1,2-dichloroethane (1,2-DCE), benzene (BZ), chlorobenzene (CB) and o-dichlorobenzene (o-DCB), has been investigated. The mean hydration number, nH2O, of these solutes in the water-saturated organic solvents was determined. There is a trend that the nH2O values for any solutes increase with increasing the water concentration in the solvents. Those of B18C6 and B15C5 converge at almost 0.8 for B18C6 and 0.4 - 0.5 for B15C5 in the solvents with the relatively high water concentration, i.e., CF, 1,2-DCE, DCM, and nitorobenzene (NB). The nH2O value of B15C5 is about one-half of that of B18C6 for a given organic solvent. The dominant species of the B18C6-K+ complex in these solvents is non-hydrated. From these results, the hydration equilibrium constants, KH2O, in the organic solvents were estimated.