All-Solid-State PVC Membrane Ag+-Selective Electrodes Based on Diaza-18-Crown-6 Compounds

Two diaza-crown ether compounds were synthesized and evaluated as Ag⁺-selective carriers in polyvinylchloride (PVC) membrane electrodes of solid-state type. The all-solid-state PVC membrane electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 exhibited a super-Nernstian response (75±10mV per decade) over the concentration range of 1×10^–1 to 7×10^–6M of Ag⁺ ion and a detection limit of 3×10^–6M, at a wide range of pH (pH 4–7). The response time of the electrode was fast (less than 10s), and it can be used for three months without any significant deviation in potential. The proposed all-solid-state PVC membrane electrodes revealed high selectivity toward Ag⁺ ion with respect to alkali, alkaline earth, heavy and transition metal ions. A flow-through cell of all-solid-state PVC membrane Ag⁺-selective electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 has also been prepared and applied for flow-injection analysis of Ag⁺ ion in solution.     

Non-catalytic Addition of 1,2,4-Triazole to Nucleophilic and Electrophilic Alkenes

Non-catalytic addition of 1,2,4-triazole to vinyl ethers and esters occurs on heating (65-175°C, 4-20 h) to give Markovnikov adducts (yield 30-100%). Electron-deficient alkenes (acrylonitrile, acrylic acid, 4-phenyl-3-buten-2-one) react with 1,2,4-triazole (78-190°C, 4-20 h) to give anti-Markovnikov adducts in yields of 45-83%.     

Synthesis of trifluoroethyl ethers from 2,2,2-trifluoroethyl chloride (HCFC-133a) in high temperature aqueous medium

Treatment of 2,2,2-trifluoroethyl chloride (HCFC-133a) with alcohols (phenols) and aqueous KOH in autoclave at 240-280 °C gives the corresponding 2,2,2-trifluoroethyl (2-chloro-1,1-difluoroethyl) ethers in good yields.     

Stabilization of a K+-(bis-Cage-Annulated 20-Crown-6) Complex by Bidentate Picrate

Bis-cage-annulated 18-crown-6 and 20-crown-6 macrocyclic ethers (i.e., 1 and 2, respectively) have been synthesized, and their alkali metal picrate extraction profiles have been determined. Host system 1 proved to be a significantly more avid alkali metal cation complexant than 2 and somewhat more avid than 18-crown-6. Both 1 and 18-crown-6 display modest selectivity toward K⁺ and Rb⁺. A stable host–guest complex was prepared by slow evaporation of a CH₂Cl₂–hexane solution of an equimolar mixture of 2 and potassium picrate. The X-ray crystal structure of this complex reveals that picrate anion functions as a bidentate ligand therein. The gas-phase interaction energy between the 2 K⁺ complex and picrate anion was calculated to be ca. –64.9 kcal mol^–1, thereby indicating that participation of picrate anion as an additional bidentate ligand results in significant stabilization of complex 10.     

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.