Synthesis of alkynylbenzo-15-crown-5 ethers

Reactions of 4"-iodobenzo-15-crown-5 ether with ethynylarenes or 4"-ethynylbenzo-15-crown-5 ether with haloarenes in the presence of catalytic amounts of Pd^IIcomplex salts, CuI, and Et₃N gave 4"-(arylethynyl)benzo-15-crown-5 ethers in 55—80% yields.     

Separation of common monovalent and divalent cations by ion chromatography on calcined silica gel cation-exchange stationary phases, with tyramine-oxalic acid-containing crown ether mobile phases and indirect photometric detection

Summary Pure silica gels (Pia Seed 5S-60-SIL) calcined at 200, 400, 600, 800 and 1000°C for 5 h have been used as cation-exchange stationary phases in ion chromatography with indirect photometric detection for common monovalent and divalent cations (Li⁺, Na⁺, NH₄ ⁺, K⁺, Mg²⁺ and Ca²⁺); 0.75mm tyramine (4-(2-aminoethyl)phenol)-0.25mm oxalic acid, pH 5.0, containing crown ethers (18-crown-6 (1,4,7,10,13,15-hexaoxacyclooctadecane) or 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane)) was used as mobile phase. With increasing calcination temperature, the amounts of the crown ethers adsorbed on the calcined silica gel column increased and, consequently, the effect of the crown ethers as retention modifiers for these cations increased. Excellent simultaneous separation and highly sensitive detection of these cations at 275 nm were achieved in 17 min by use of a 150 mm×4.6 mm i.d. column packed with silica gel calcined at 1000°C and use of 0.75mm tyramine-0.25mm oxalic acid, pH 5.0, containing either 0.5mm 18-crown-6 or 5.0mm 15-crown-5 as mobile phase.     

15-Hydroxybenzomonothia-15-crown-5 with the sulfur atom linked with the benzene ring and the derived sulfoxide: synthesis,structure, and complexation with the metal cations

Novel 15-hydroxybenzomonothia-15-crown-5 containing the sulfur atom linked with the benzene ring and its S-oxide were synthesized. The stability constants for the complexes of the obtained benzocrown ethers and a reference 15-hydroxybenzo-15-crown-5 with Na, Ca, Ag^I, Cd, Hg^II, and Pb^II perchlorates were determined by ¹H NMR titration. In MeCN-d₃, the benzothiacrown ether demonstrates a high selectivity towards the thio- and oxothiophilic Hg²⁺ (logK ₁ = 7.1) and Pb²⁺ ions (logK ₁ = 7.4). In MeCN-d₃-D₂O mixtures, the stabilities of the most of complexes decrease sharply due to competitive hydration of the metal cations except for the “soft” Ag⁺ and Hg²⁺ ions having low affinity for the “hard” oxygen atoms and, on the contrary, very high affinity for the “soft” S^II atoms. This results in the change in selectivity of complexation: at the water content in solution of 20%, the benzothiacrown ether binds preferably the Hg²⁺ (logK ₁ = 5.0) and Ag⁺ ions (logK ₁ = 2.7). In MeCN-d₃, the benzothiacrown-derived sulfoxide is a weak and non-selective complexing agent towards all the metal cations under study; the reference 15-hydroxybenzo-15-crown-5 forms more stable complexes with the oxophilic sodium, calcium, and lead(ii) cations. The conformational features of the benzocrown ethers and their metal complexes established by NMR spectroscopy and X-ray diffraction are discussed. The found characteristics of the complexing ability of benzomonothia-15-crown-5 where the sulfur atom is in conjugation with the benzene ring reveal that the macrocyclic ligands with such a structure are promising as high-selective and efficient complexing agents for the “soft” mercury(ii) and silver(i) cations in acetonitrile-water mixtures.     

Test Films for the Determination of Aromatic Amines and Hydrazines in Aqueous Solutions

Conditions of the test determination of toxic aniline (I), N,N-dimethylaniline (II), N,N-diethylaniline (III), 2,2,4-trimethyl-1,2-dihydroquinoline (IV), 1,1-dimethylhydrazine (V), and phenylhydrazine (VI) as their 4,6-dinitrobenzofuroxan (I) and 5,7-dinitrobenzofurazan (II, III, IV, V, VI) derivatives in aqueous solutions were found. Visual and spectrophotometric measurement of the signal was used. The reagents were immobilized in nitrocellulose films. Optimal results of visual determination of color development in test films were obtained with reagents immobilized in nitrocellulose at their concentration of 5 mass % and pH of the test solution in the range 6.0–7.5. The spectrophotometric measurement of the signal of test films was performed at wavelengths of 500–560 nm for I, V, and VI and 610–620 nm for II, III, and IV. The detection limit for spectrophotometric measurement was 0.01, 0.18, 0.13, 0.15, 0.16, and 0.04 mg/L for I, II, III, IV, V, and VI, respectively. The analytical range of the toxicants was 0.05–6.0 mg/L. Test determination is possible in the presence of alkylamines, ammonia, phenols, carboxylic acids, and inorganic salts.     

<Emphasis Type="Italic">N,N</Emphasis>′-bis(<Emphasis Type="Italic">ortho</Emphasis>-acylaryl)diaza-18-crown-6 ethers: Synthesis,complexation in solution,and crystal structure of the complex with lead perchlorate

Two new lariat ethers were obtained from N,N′-diaryldiaza-18-crown-6 (Ar = 2-formyl-4-methylphenyl (II) and 2-benzoyl-4-methylphenyl (III)). In the ethers obtained, the carbonyl O atoms act as additional electron-donating sites. Complexation of lariat ethers II and III with metal cations in solution was studied by ¹H NMR spectroscopy (acetone-d₆, methanol-d₄). The stability constants of the resulting complexes were determined. For lariat ether III and its complexes, the magnetic anisotropy of the benzoyl groups substantially influences the chemical shifts of the protons of the macrocycle. The stability of the complexes increases from ether II to III and in the order K⁺ < Ba²⁺ < Pb²⁺. Complexes with La³⁺ were not obtained. The complex of lariat ether II(L) with Pb(ClO₄)₂, [PbL(H₂O)](ClO₄)₂ · H₂O, was characterized by X-ray diffraction. The Pb²⁺ cation is in the cavity of the lariat ether and is coordinated by the formyl O atoms on one side of the macrocycle plane and by the water molecule on the other side (C.N. 9).     

Decomposition of vinyl ethers by alkalide K, K(15-crown-5)2 via organopotassium intermediates

The structure of vinyl ethers determines the direction of the C-O bond cleavage by alkalide K⁻, K⁺(15-crown-5)₂1. Highly reactive organopotassium compounds are intermediate products formed in the system containing phenyl vinyl ether, butyl vinyl ether, ethylene glycol butyl vinyl ether or triethylene glycol methyl vinyl ether. Vinylpotassium and butylpotassium react with 15-crown-5. The oxacyclic ring of the latter is opened in this case. Organopotassium ethers possessing CH₂CH₂O units eliminate ethylene. It results in various potassium alkoxides. The reaction of 1 with butyl vinyl ether occurs very slow as compared to other vinyl ethers and most of other reagents used till now.     

Change in regioselectivity in the monoreduction of 2,4,6-trinitrotoluene with titanium(III) and vanadium(II) ions in the presence of iron(II) and copper(II) salts

Small additives of iron(II) or copper(II) salts change the regioselectivity of 2,4,6-trinitrotoluene monoreduction with titanium(III) chloride affording predominantly less accessible 2-amino-4,6-dinitrotoluene over 4-amino-2,6-dinitrotoluene (from 25% when the reduction occurs in the absence of the iron and copper salts to 70% in the presence of these salts). A possible mechanism of the process is discussed. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1172–1176, May, 2005.     

Thiocarbamoyl chitosan as a novel sorbent with high sorption capacity and selectivity for the ions of gold(III), platinum(IV), and palladium(II)

Thiocarbamoyl chitosan (TCC) was synthesized by grafting thiourea on chitosan backbone in eutectic composition of ammonium thiocyanate—thiourea. Insoluble products with the amno group functionalization degree of 0.3–1.1 can be prepared by varying the conditions of polymer-analogous (synthesis in a gel) transformation. Structure of the synthesized chitosan derivatives was characterized by elemental analysis, diffuse reflectance infrared spectroscopy, and the solid state ¹³C NMR. Study of sorption properties of TCC shows high sorption capacity and selectivity for the ions of gold(III), platinum(IV), and palladium(II) as evidenced by results obtained at pH 2 in the presence of 100–1000-fold excess of iron(III), copper(II), zinc(II), and nickel(II). Sorption capacity of TCC for all ions increases with the increase in the degree of substitution and changes in the series: Au^III > Pd^II > Pt^IV.     

Synthesis and electrochemical properties of amphiphilic crown ether langmuir-blodgett films [1]

4-Octadecanoylbenzo-15-crown-5 (I) and four 4-alkylbenzo-15-crown-5 ligands [4-XB15C5 where X =n-C₁₈H₃₇ (II), X =n-C₁₆H₃₃ (III), X =n-C₁₄H₂₉ (IV), and X =n-C₁₂H₂₅ (V)] have been synthesized. The -A isotherms ofI andII were systematically investigated. The results indicated that the Langmuir-Blodgett (LB) films have high stability where the ratios ofI/SA andII/SA were 1 : 1 and 1 : 10, respectively, with a 6.2 pH subphase. The LB films of the crown ethers were deposited onto graphite electrodes pretreated by immersing them in liquid wax. The peak current reached the maximum value when the electrode surface was modified with five layers of the amphiphilic crown ethers.     

Ion-pair extraction of tetravalent plutonium from hydrochloric acid medium using crown ethers

Ion-pair extraction behaviour of plutonium (IV) from varying concentrations of HCl solution was studied employing crown ethers (benzo-l5-crown-5 (B15C5), 18-crown-6, (18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6, (DC18C6), dibenzo-24-crown-8 (DB24C8) and dicyclohexano-24-crown-8 (DCH24C8)) in nitrobenzene as the extractant. Ammonium metavanidate was used as the holding oxidant in the aqueous phase and the conditions necessary for the quantitative extraction of the tetravalent ion were found. The co-extraction of species of the type [HL⁺].[HPu(Cl) ₆ ^– ] and [HL⁺]2·[Pu(Cl) ₆ ^2– ] as ion-pairs (where L represents the crown ether) is suggested.     

Copper (II) complexes of sterically hindered o-diphenol derivatives: synthesis, characterization and microbiological studies

Cu (II) complexes with the sterically hindered diphenol derivatives 3,5-di(tert-butyl)-1,2-benzenediol (I), 4,6-di(tert-butyl)-1,2,3-benzenetriol (II) and the sulfur-containing 4,6-di(tert-butyl)-3-(2-hydroxyethylsulfanyl)-1,2-benzenediol (III) and 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid (IV) have been synthesized and characterized by elemental analysis, TG/DTA, FT-IR, ESR, XPS, XPD and conductivity measurements. Compounds I–III can coordinate in their singly deprotonated forms and act as bidentate ligands. These compounds yield Cu (II) complexes of the stoichiometry Cu(L)₂, which have square planar geometry (g_| > g_⊥ > g_e). Unlike them, compound IV behaves as a terdentate ligand, and its complex Cu(L^IV)₂ has distorted octahedral geometry. According to ESR data, only the Cu(L^II)₂ complex contains a very small amount of phenoxyl radicals. Antimicrobial activities of these ligands and their respective Cu (II) complexes have been determined with respect to Gram-positive and Gram-negative bacteria, as well as on yeasts. Their phytotoxic properties against Chlorella vulgaris 157 were also examined.     

A “sodium trap” based on benzo-15-crown-5 with an exocyclic N-(thiophosphoryl)thiourea moiety

For N-(thio)phosphorylthioureas of the common formula RC(S)NHP(X)(OiPr)₂HL^I (R = N-(4′-aminobenzo-15-crown-5), X = S), HL^II (R = N-(4′-aminobenzo-15-crown-5), X = O), HL^III (R = PhNH, X = S), HL^IV (R = PhNH, X = O), and (N,N′-bis-[C(S)NHP(S)(OiPr)₂]₂-1,10-diaza-18-crown-6) H₂L^V, salts LiL^I,III,IV, NaL^I–IV, KL^I–IVM₂L^V (M = Li⁺, Na⁺, K⁺), Ba(L^I,III,IV)₂, and BaL^V have been synthesized and investigated. Compounds NaL^I,II quantitatively drop out as a deposit in ethanol medium, allowing the separation of Na⁺ and K⁺ cations. This effect is not displayed for the other compounds. The crystal structures of HL^III and the solvate of the composition [K(Me₂CO)L^III] have been investigated by X-ray crystallography.     

New carbofunctional organosilicon monomers and polymers possessing sorption and metal chromatic properties

Monomeric and polymeric β-naphthylamine and dithizone organosilicon derivatives were synthesized. The organosilicon polymers were studied as sorbents of heavy (Fe^III, Hg^II) and noble (Ag^I, Au^III, Rh^III, Pd^II, Pt^IV) metal ions, as well as of Ce^III and Tb^III. They were found to possess high sorption activity toward platinum group metals and iron. The monomers and polymers obtained exhibit metal chromatic properties. Their reactions virtually with all the elements studied, except cerium and terbium, are accompanied by coloration.     

Selective determination of 4-aminobenzoic and 4-aminosalicylic acid derivatives in mixtures by flow-injection analysis

The working conditions were found for the determination of medicinal substances anesthesin (benzocaine,I), novocaine (II), novocainamide (procainamide,III), and sodium 4-aminosalicylate (IV) as their 4,6-dinitrobenzofuroxan derivatives by flow-injection analysis with spectrophotometric detection (λ 510 nm). The best conditions were attained using a mixture of ethanol (methanol) and a buffer solution of pH 6.68 (30: 70 vol %). The analytical range for the analytes was 0.08-5.0 μg/mL. The detection limits (3σ,n = 4) were 0.04 (I), 0.05 (II), 0.07 (III), and 0.03 (IV) μg/mL. Procedures for determining 4-aminobenzoic and 4-aminosalicylic acid derivatives in pharmaceuticals containing ephedrine, atropine, dimedrol, and inorganic salts and in biological fluids (protein hydrolyzate, blood plasma, and whole blood) were developed.     

Mechanistic Study of the Reactions of l-ascorbic Acid and Oxalic Acid with an Octahedral Manganese(IV) Complex of 1,8-bis(2-hydroxybenzamido)-3,6-diazaoctane

The Mn^IV complex of 1,8-bis(2-hydroxybenzamido)-3,6-diazaoctane (Mn^IVL) with phenolate-amido-amine coordination is reduced by l-ascorbic acid and oxalic acid obeying overall 1:1 stoichiometry. The reactions are biphasic and Mn^IIIL⁻ is the reactive intermediate. The product of oxidation of ascorbic acid (H₂Asc) is dehydroascorbic acid and that of oxalic acid (H₂OX) is CO₂, while Mn^II is the end product from Mn^IV. Both Mn^IVL and Mn^IIIL⁻ form outer sphere adducts with H₂Asc and H₂OX with high values of equilibrium constants of formation (Q>10² dm³ mol⁻¹, I = 0.5 mol dm⁻³, 25.8 °C, 1.5% v/v MeOH+H₂O). The adduct formation is diffusion controlled and is attributed to hydrogen bonding interactions between the reactants. The rate constants for the electron transfer in (Mn^IV/^IIIL, H₂A), (Mn^IV/^IIIL, HA⁻) (H₂A = H₂Asc, H₂OX) and for (Mn^IVL, H₂Asc)+H₂Asc, (Mn^IIIL⁻, HAsc⁻)+HAsc⁻ are reported. There was no evidence of direct coordination of the reductants to the Mn^IV/III center indicating an outer sphere (ET) mechanism.     

(18-Crown-6)potassium tetrachloroferrate(III), dibromodichloroferrate(III), and tetrabromoferrate(III): Synthesis and crystal structures

Three new crystalline complexes are synthesized: [K(18-crown-6)]⁺ · An, where An = [FeCl₄]^?(I), [FeBr₂Cl₂]^? (II), and [FeBr₄]^? (III). The crystals of compounds I–III are cubic and isomorphic, space group Fd $ \bar 3 Three new crystalline complexes are synthesized: [K(18-crown-6)]⁺ · An, where An = [FeCl₄]⁻(I), [FeBr₂Cl₂]⁻ (II), and [FeBr₄]⁻ (III). The crystals of compounds I–III are cubic and isomorphic, space group Fd (Z = 16): a = 20.770(2) ? for I, 20.844(3) ? for II, and 20.878(4) ? for III. Structures I–III are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.047 (I), 0.059 (II), and 0.098 (III) for all 680 (I), 684 (II), and 686 (III) independent reflections. In two tetrahedral anions [Fe(1)X₄]⁻ and [Fe(2)X₄]⁻ in structures I–III, all halogen atoms (X = Cl and Br) are randomly disordered over three close positions relative to the crystallographic axes 3. Structures I–III contain the [K(18-crown-6)]⁺ host-quest complex cation. The K⁺ cation (CN = 8) resides in the cavity of the 18-crown-6 ligand and coordinated by its six O atoms and two disordered halogen X atoms. The coordination polyhedron of the K⁺ cation in complexes I–III is a distorted hexagonal bipyramid. Original Russian Text ? A.N. Chekhlov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 9, pp. 1566–1570.     

Synthesis, complex-formation, and extracting ability of new derivatives of dithia-13(16)-crown-4(5) ethers

Various methods of synthesizing functional derivatives of dithia-13(16)-crown-4(5) ethers are proposed. Complex-formation of the obtained compounds with Ag⁺ and Pb²⁺ ions has been studied using ¹H NMR. A radiometric method was used to investigate the extracting ability of substituted dithia-13(16)-crown-4(5) ethers in relation to Ag⁺ and Cd²⁺ ions from aqueous solution in the presence of anions of various degree of hardness, with determination of the metal content. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 233–243, February, 2006.     

REACTIONS OF THE SUBSTITUTED THIOUREAS WITH PLATINUM COMPOUNDS

Abstract

Thiourea and its derivatives easily form the complexes with compounds of Cu^II, Fe^III, Pt^IV etc. By the formation of complexes as a rule redoxprocess proceeds to give an appropriate thiourea disulphide. It has been shown, that redoxprocess goes on prejudice on the derivatives of thiourea in that case when the thion-thiol tautomerism is possible.     

Alkali Metal- and Ammonium Picrate Extraction and Complex Forming Capabilities of d-Glucose and d-Mannose-based Lariat Ethers

The alkali metal- and ammonium picrate extracting ability of d-glucose- and d-mannose-based 15-crown-5 ethers and related lariat ethers was investigated in dichloromethane – water system. A heteroatom was waried in the crown ether containing a 4,6-O-benzylidene-α-d-glucopyranoside unit 6, (X=O), 2 (X=S) and 8a (X=NH). Extracting ability of the latter species (8a) was excellent (97–99%) in regard of all cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄⁺) examined, it was not, howewer, selective. Introduction of a side arm on the nitrogen atom of 8a decreased the extracting ability, but increased the selectivity. In this series of compounds (8b–f, 4), 4 with a pyridylethyl substituent allowed the extraction of sodium picrate in 72%. The glucose-based macrocycles 8a, 8e and 8f formed a stronger complex with the cations examined than the mannose-based analogues 9a, 9e and 9f, that can be explained by the all-gauche conformation of the former ones. It was pointed out that in the case of crowns with tertiary amine moieties, the basicity increases the quantity of the picrates extracted. According to complex forming measurements by FAB-MS, the best sodium ion selectivity was achieved by the γ-hydroxypropyl substituted lariat ether (8e). Possible structures of the complexes formed by the two types of monosacharides with sodium cation were evaluated by molecule modelling calculations.