The Use of tert-Butyl Vinyl Ether in Stepwise Electrophilic Addition Reactions

tert-Butyl vinyl ether (1) reacts with p-TolSCl to give 2-tert-butoxy-2-chloroethyl p-tolyl sulfide (2). In the presence of SnCl₄, 2 reacts with silyl enol ethers, allyltrimethylsilane, and vinyl ethers to form a C-C bond. In the case of vinyl ethers, the reaction proceeds through the formation of the 5-membered sulfonium salt intermediate which in turn can react with H₂O, TMSCN, allyltrimethylsilane, and Grignard reagents.     

A Comparative Study of Biocathodes Based on Multiwall Carbon Nanotube Buckypapers Modified with Three Different Multicopper Oxidases

14 Single‐ and multi‐walled carbon nanotubes from different sources were characterized in detail, and the characteristics obtained were carefully analyzed. The carbon material with the highest capacitance, and also other superior properties (“Taunit‐M” from “NanoTechCenter”, Russia), was chosen for further modification and fabrication of buckypaper based electrodes. These electrodes were biomodified with plant and fungal laccases, as well as fungal bilirubin oxidase. The designed biocathodes were investigated in simple buffers and also in a complex physiological fluid (human serum). Biocathodes based on immobilized fungal laccase were bioelectrocatalytically inactive in chloride containing media at neutral pH. In spite of the quite high current densities realized using biodevices based on plant laccase and fungal bilirubin oxidase, the limited thermal stability of the enzymes renders the biocathodes inadequate for practical applications in implanted situations.     

Radical Anions,Radical-Anion Salts,and Anionic Complexes of 2,1,3-Benzochalcogenadiazoles

By means of cyclic voltammetry (CV) and DFT calculations, it was found that the electron-acceptor ability of 2,1,3-benzochalcogenadiazoles 1 – 3 (chalcogen: S, Se, and Te, respectively) increases with increasing atomic number of the chalcogen. This trend is nontrivial, since it contradicts the electronegativity and atomic electron affinity of the chalcogens. In contrast to radical anions (RAs) [ 1 ]^.− and [ 2 ]^.−, RA [ 3 ]^.− was not detected by EPR spectroscopy under CV conditions. Chemical reduction of 1 – 3 was performed and new thermally stable RA salts [K(THF)]⁺[ 2 ]^.− ( 8 ) and [K(18-crown-6)]⁺[ 2 ]^.− ( 9 ) were isolated in addition to known salt [K(THF)]⁺[ 1 ]^.− ( 7 ). On contact with air, RAs [ 1 ]^.− and [ 2 ]^.− underwent fast decomposition in solution with the formation of anions [ECN]⁻, which were isolated in the form of salts [K(18-crown-6)]⁺[ECN]⁻ ( 10 , E=S; 11 , E=Se). In the case of 3 , RA [ 3 ]^.− was detected by EPR spectroscopy as the first representative of tellurium–nitrogen π-heterocyclic RAs but not isolated. Instead, salt [K(18-crown-6)]⁺₂[ 3 -Te₂]²⁻ ( 12 ) featuring a new anionic complex with coordinate Te−Te bond was obtained. On contact with air, salt 12 transformed into salt [K(18-crown-6)]⁺₂[ 3 -Te₄- 3 ]²⁻ ( 13 ) containing an anionic complex with two coordinate Te−Te bonds. The structures of 8 – 13 were confirmed by XRD, and the nature of the Te−Te coordinate bond in [ 3 -Te₂]²⁻ and [ 3 -Te₄- 3 ]²⁻ was studied by DFT calculations and QTAIM analysis.     

Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

Reactions of P(III)-Halides with Calix[4]Resorcinarenes

Abstract

Reactions of calix[4]resorcinarenes, bearing aliphatic radicals of different length, with P(III)-halides results in the formation of cyclic chlorophosphites and chlorophosphates.     

Novel trialkylsilyl(germyl)-substituted thienyl- and furylbenzimidazoles and their N-substituted derivatives – synthesis,structure and cytotoxic activity

The reaction of 1,2-phenylenediamine with a variety of silicon- or germanium-containing 2-furaldehydes or 2-thienylcarbaldehydes in DMFA gave the corresponding benzimidazole derivatives in moderate yields (36–49%) in the presence of sodium hydrogen sulfite. As a result, a new series of silyl, germyl substituted hetarylbenzimidazoles were synthesized and their in vitro cytotoxicity was studied. The quaternisation of N-substituted benzimidazoles by heating with various alkyl, allyl and propargyl chlorides and bromides leads to the formation of benzimidazolinium salts. Potential cytotoxic activity of synthesized new benzimidazoles and benzimidazolinium salts was tested in vitro on two monolayer tumour cell lines: MG-22A (mouse hepatoma), HT-1080 (human fibrosarcoma) and normal mouse fibroblasts (NIH 3T3) and compared with corresponding benzimidazoles.     

N‐phosphorylated 3,5‐bis(arylidene)4‐piperidones: Synthesis,X‐ray structure,and evaluation of antitumor activity

In a search for cytotoxic fluorescent materials, a series of N‐phosphorylated compounds 2a–c were prepared by phosphorylation of 3,5‐bis(4‐N,N‐dimethylbenzylidene)‐4‐piperidone 1 . According to X‐ray investigations, molecule 2a is E,E‐isomer with axial position of the P(O)(OCH₂CF₃)₂ substituent. Fluorescence of compounds 2a–c was found to be similar to fluorescence of nonphosphorylated compound 1 . The cytotoxicity of the compounds 2a–c was estimated on several human tumor cell lines (H9, K562, and MCF7). © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:497–502, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20147     

Solvent‐Free Iodination of Arenes using Iodine–Silver Nitrate Combination

A simple and environmentally safe general method of iodination of aromatic substrates under sovent‐free conditions using the I₂/AgNO₃ combination in a solid state is reported. Both activated and deactivated aromatic compounds afford the respective aryl iodides in generally high yields (80–90%).     

Polymorphism of methyl 4‐amino‐3‐phenylisothiazole‐5‐carboxylate: an experimental and theoretical study

Being a close analogue of amflutizole, methyl 4‐amino‐3‐phenylisothiazole‐5‐carboxylate (C₁₁H₁₀N₂O₂S) was assumed to be capable of forming polymorphic structures. Noncentrosymmetric and centrosymmetric polymorphs have been obtained by crystallization from a series of more volatile solvents and from denser tetrachloromethane, respectively. Identical conformations of the molecule are found in both structures. The two polymorphs differ mainly in the intermolecular interactions formed by the amino group and in the type of stacking interactions between the π‐systems. The most effective method for revealing packing motifs in structures with intermolecular interactions of different types (hydrogen bonding, stacking, dispersion, etc.) is to study the pairwise interaction energies using quantum chemical calculations. Molecules form a column as the primary basic structural motif due to stacking interactions in both polymorphic structures under study. The character of a column (straight or zigzag) is determined by the orientations of the stacked molecules (in a `head‐to‐head' or `head‐to‐tail' manner). Columns bound by intermolecular N—H…O and N—H…N hydrogen bonds form a double column as the main structural motif in the noncentrosymmetric structure. Double columns in the noncentrosymmetric structure and columns in the centrosymmetric structure interact strongly within the ab crystallographic plane, forming a layer as a secondary basic structural motif. The noncentrosymmetric structure has a lower density and a lower (by 0.59 kJ mol^?1) lattice energy, calculated using periodic calculations, compared to the centrosymmetric structure.     

Catalytic Sandmeyer cyanation as a synthetic pathway to aryl nitriles

Aryl nitriles ArCN were obtained by the Cu(I)/Cu(II) catalysed reaction of aryl diazonium salts with KCN in good yields.