Reactions of mercury salts with benzo- and tetrafluorobenzobarrelenes

Regiochemistry and stereochemistry of the addition of mercury salts to benzobarrelene and tetrafluorobenzobarrelene have been studied in acetic acid and methanol. The effect of the substrate structure on the regiochemistry of the reaction is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1105–1108, June, 1994.     

Effect of structural variation within cationic azo-surfactant upon photoresponsive function in aqueous solution

The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R₂=C₂H₄, R₃=C₄H₉) and 9 (R₂=C₄H₈, R₃=C₂H₅) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation.     

19F NMR study of relative polarities and reactivities of N-H,N-Hg,and N-Au bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and Ph3PAu derivatives in intermolecular exchange

It has been shown by the¹⁹F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh₃Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528).     

带作用的群系的临界结构

在本文中，我们讨论了带作用群的群系的临界结构，给出了处理允许某些作用群的群的问题的一般方法，作为应用，我们特别给出了关于幂零群及ｐ－幂零群的一些结果。     

On the Donor Ability of the Phosphaneiminato Substituent and Cube Formation with Transition Metal Fragments

The particular role of the phosphaneiminato ligand as a donor is investigated for a) nitrenes (phosphinidenes) and carbenes and b) cubane formation with transition metals. Accordingly, and as shown for the case a) the ligand is a stronger π‐donor than an amino group and can be considered as a special case of imine‐type substituents. The latter are very effective in π‐donation. In the case b), i.e. the cubane formation with transition metals, one has to consider transition metals with a partially or completely filled d‐shell (with electrons). Hence depending on the transition metal, cubanes are build with weak ferromagnetic coupled or closed shell systems. For the cubanes with closed shell character the matter of insertion of halide anions is discussed. In the last chapter of the review the bond stretching in the dithionitrosyl complexes with rhenium is characterized.     

An efficient phosphine-free palladium coupling for the synthesis of new 2-arylbenzo[b]thiophenes

Straightforward and rapid access to 2-arylbenzo[b]thiophenes has been developed. It involved a catalytic coupling of 3-activated benzo[b]thiophenes with several aryl halides in the presence of a phosphine-free palladium system. In case of fragile functional groups such as aldehydes, a quaternary ammonium was used as an additive as with the other substrates, the coupling performed better and faster in the presence of a crown ether, the best one being DCH-18-C-6, with good yields and low reaction times. This method would provide a direct access to novel structures of biological interest.     

Crystallographic report: Crystal structure of tetra(4‐methyl‐5‐imidazole‐carboxyaldehyde)zinc(II) diperchlorate

The central zinc(II) atom in the title complex is tetrahedrally coordinated by four nitrogen atoms derived from 4‐methyl‐5‐imidazolecarboxyaldehyde ligands with Zn? N in the range 2.007(3) to 2.026(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

Preparation of a new hydrophilic copolymer from a polylactone and the structure analyses

A new hydrophilic copolymer having three kinds of hydroxyl groups, i.e. primary OH on -hydroxy allyl alcohol component, secondary OH on cyclic hemiacetal component and tertiary OH on -hydroxy acrylate component, was prepared by reducing a ‘polylactone’, poly(1-oxa-2-oxobutane-1,4:3,3-tetrayl), with NaBH₄ in mixed solvents containing an alcohol. The structural analyses were performed by the solution ¹H NMR and the solid state ¹³C NMR spectroscopies of the reduced samples. The composition of the three components turned out to be variable to the alcohol species used for the mixed solvent.