Zinc-catalyzed Williamson ether synthesis in the absence of base

Zinc powder was found to be a highly efficient catalyst for the synthesis of aromatic ethers using microwave heating in the presence of N,N-dimethylformamide as well as under stirring in an oil-bath using tetrahydrofuran as solvent without any inorganic base. This method can be used for selective mono-, di- or tri-O-alkylations.     

Preparation of enol ethers by carbonyl olefination utilizing an alkoxymethyl chloride-titanocene(II) system

Aldehydes, ketones, esters and lactones are transformed into enol ethers or 1,2-dialkoxy-1-alkenes by treatment with organotitanium species prepared from alkoxymethyl chlorides and a titanocene(II) complex.     

A simple, efficient and highly selective deprotection of t-butyldimethylsilyl (TBDMS) ethers using silica supported sodium hydrogen sulfate as a heterogeneous catalyst

t-Butyldimethylsilyl (TBDMS) ethers have been efficiently and selectively deprotected using silica supported sodium hydrogen sulfate (NaHSO₄·SiO₂) as a heterogeneous catalyst at room temperature to regenerate the parent alcohols in high yields.     

A conductance study of the association of alkali cations with 1,13-dibenzo-24-crown-8 in acetonitrile

A conductance study concerning the association of Na⁺, K⁺, Rb⁺, and Cs⁺ with 1,13-dibenzo-24-crown-8 in acetonitrile has been carried out at 35, 30, 25, 20, and 15°C. The observed molar conductivities were found to decrease significantly for mole ratios less than unity. A model involving 11 stoichiometry has been used to analyze the conductivity data. The stability constant, K, and the molar conductivity _C for each 11 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of log K at 25°C, is found to be Rb⁺>Cs⁺>K⁺>Na⁺. Values of H^o and S^o are reported and their significance is discussed.     

A General, Highly Efficient Ullmann C-O Coupling Reaction under Microwave Irradiation and the Effects of Water

A general, rapid and highly efficient method for the synthesis of diaryl ethers under the assistance of microwave irradiation was described. A series of diaryl ethers were prepared by direct coupling of phenols and aryl halides in good to excellent yields in anhydrous DMF or NMP at 150 ℃ within 20 rain. The presence of water was found to have a significant impact on the Ullmann C-O coupling reaction between aryl halides and phenols under microwave irradiation.     

Synthesis and characterization of maleimide polymers with pendant pyrazole groups. IV. Copolymerization of pyrazole-modified maleimides with vinyl ethers

The synthesis of maleimides that have pyrazolic or bipyrazolic pendant groups is described. Their homopolymerization and their copolymerization with 2-chloroethyl vinyl ether (CEVE) is reported. The homopolymerizations of such maleimides were performed under various conditions and led to low molecular-weight polymers. However, alternating copolymers were obtained from CEVE as comonomers whatever the monomers feed compositions. A similar behavior was also observed for maleimides that do not exhibit any spacer, whereas for bulky vinyl ethers, random copolymers were produced. A comparison of the thermal behavior between these copolymers (glass transition temperatures, T_g, and decomposition temperatures) and other copolymers having different spacers between the nitrogenated cycles and the chain are related. Thus, an important decrease of T_g, was observed when C₃H₆CO₂CH₂ groups were used as the spacer instead of methylene groups. Moreover, the thermal weakness of these copolymers may come from the substituents of the vinyl ether and is discussed. © 1994 John Wiley & Sons, Inc.     

Intramolecular Dynamics and Molecular Structure of Europium(III) Chelate Complexes with Crown Ethers as Studied by NMR Spectroscopy

Earlier the intramolecular inversion of the 18-crown-6 molecules was found in the complex ion pairs [Ln(ptfa)₂ (18-crown-6)]⁺ [Ln(ptfa)₄]⁻ (H₂O)₄ where Ln = La(1), Ce (2), Pr (3), Nd (4), and ptfa is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. In this work the peculiarities of the molecular structure and dynamics were studied for [Eu(ptfa)₂ (18-crown-6)]⁺ [Eu(ptfa)₄]⁻ (H₂O)₄ (5) by NMR spectroscopy techniques. Through VT-NMR spectra analysis the temperature dependence was obtained for the rate constant. The free energy ΔG^‡(320) of 18-crown-6 ring inversion activation was found to be 65 ± 5 kJ mol⁻¹ for 5 in CDCl₃. This result is comparable with the earlier data [S.P. Babailov and D.A. Mainichev: J. Inclusion Phenom. Macrocyclic Chem. 43, 187–193 (2002)] for complexes 2, 3, 4 in deuterated toluene (ΔG^‡(320)=65 ± 9, 64 ± 9, 64 ± 9 kJ mol⁻¹ respectively). It was found by relaxation NMR spectroscopy that the effective distance between Ln and protons of the crown molecule is 4.5 ± 0.2 Å. The analysis of structural parameters testifies that the crown ether and chelated anions are in the first coordination sphere of a Ln cation. Obtained geometrical parameters show that the complex cations of Eu, Ce and Pr have similar spatial structures.This revised version was published online in July 2005 with a corrected issue number.     

Direct vinylation of glucose derivatives with acetylene

Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, methyl 4,6-O-benzylidene-α-d-glucopyranoside, 1,2-O-cyclohexylidene-α-d-glucofuranose, methyl α-d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH-DMSO, t-BuOK-DMSO). The complete vinylation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and methyl α-d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH-THF as well.     

Properties of monolayers of crown ethers bearing an azo and azoxy group in the macrocycle

Two methods are described for preparing monomolecular layers of crown ethers with an azo or azoxy group in the macrocycle. When the molecules used to build the monolayer are soluble in aqueous solutions, adsorptive preconcentration on mercury electrodes was used to prepare the monolayer coating. The monolayer was electroactive due to the presence of the azo or azoxy unit in the molecules. Monolayers of crown ethers bearing an azo group in the macrocycle were shown to recognize alkali metal cations present in the solution. Changes of the parameters of the voltammetric reduction peaks - peak potential and peak width, served as an indication of specific interactions of the monolayer of 13-membered and 16-membered azocrown ethers with Na⁺ and K⁺ cations, respectively.The monolayers capable of recognizing cations have also been prepared on the aqueous solution-air interface, using the Langmuir technique. In this approach, amphiphilic derivatives of the azocrowns were synthesized and the monolayer has been assembled on the subphase containing metal cations. Binding of the cation by the macrocycle has a stabilizing effect on the monolayer and higher collapse pressures are achieved than on the pure water subphase. The monolayer was transferred from the air-water interface on the solid substrate using the Langmuir-Blodgett technique. Thin mercury film electrodes on the Ag substrate, or An films evaporated on glass slides were employed as the electrode substrates. The former gave monolayer modified electrodes of higher stability.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Conductance study of the thermodynamics of ammonium ion complexes with several crown ethers in acetonitrile solution

A conductance study concerning the interaction between ammonium ion and several crown ethers in acetonitrile solution has been carried out at different temperatures. The stability constants of the resulting 11 complexes at various temperatures were determined from the molar conductance-mole ratio data and found to vary in the order DC18C6>18C6>DB30C10>DB21C7>DB24C8>DB18C6>15C5>B15C5. The enthalpy and entropy of complexation were determined from the temperature dependence of the formation constants. The influence on the thermodynamic data of different parameters such as cavity size and dimensionality of crown ethers, nature of substituents in the polyether ring, conformations of the free and complexed ligands, solvent-ligand interaction and number of N–H bonds available for hydrogen bonding are discussed.