Divinyl Sulfoxide: XI. Selective Addition of Carbonodithioate Anions to Divinyl Sulfoxide in the Water-Benzene System

Selective monoaddition of carbonodithioate anions to divinyl sulfoxide gives rise to O-alkyl S-[2-(vinylsulfinyl)ethyl] carbonodithioates [ROC(S)SK, R = Et, Bu; 42–50°C, 6 h, NaHCO₃, aqueous benzene].     

Calorimetric and Thermal Investigation of Metal Derivatives of 6-aminopicolinic Acid

The comparison of thermal and calorimetric properties of metal derivatives of 6-aminopicolinic acid (APH) is presented. The salts and complexes of APH with Cr(III), Cd(II), Cu(II), Ni(II), Pb(II), Co(II)and Ag(I) have been studied by TG-DTA and DSC methods up to 1200°C in a nitrogen atmosphere. Decomposition processes are proposed. The decarboxylation, deamination and carbonation of the organic fragments of molecules take place. The compounds decompose to metal or to metal oxides. The values of the transition enthalpy were determinated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Enantioseparations using capillary electromigration techniques in nonaqueous buffers

This review summarizes recent developments in the field of enantioseparations in capillary electromigration techniques using nonaqueous background electrolytes. The more established and rather intensively reviewed field of nonaqueous chiral capillary electrophoresis (NAQ-CE) is covered in less detail whereas more attention is paid to the relatively new field of nonaqueous capillary electrochromatography (NAQ-CEC).     

Pulsed photothermal phase-shift spectroscopy for weak absorption measurement

A novel photothermal phase-shift spectroscopy configuration based on the retro-reflected beam interference has been developed and its operational principle is described. The weak absorption measurement ability of this technique is experimentally proven with a water/ethanol solution of standard Pyronine G dye and the limit of detection is found to be 1.8 x 10(-6) absorbance. Potential applications of the technique are discussed.     

Catalytic Properties of Acid Solutions and the Structure of Acid–Base Complexes with Strong Hydrogen Bonds

The catalytic action of acid solutions involves an equilibrium step in the formation of a reactive complex of reactant molecules with catalyst entities. The relative concentrations of these complexes are determined by using thermodynamic parameters (acidity functions and activities of catalyst components). Data on the structure of complexes with strong H-bonds can be obtained from the vibrational spectra of these species. These data are required for establishing the mechanisms of catalytic reactions and for predicting the catalytic properties of acid solutions containing these complexes.     

A Study of Amorphous Precursors for PbZrO3-PbTiO3 Based Ceramic Materials

Amorphous precursors for PbZrO₃ and PbTiO₃ ceramics were prepared from lead acetate and the transition metaln-propoxide inn-propanol orn-butoxide inn-butanol and hydrolysed with an excess of water. According to GLC and TGA/EGA analyses, the type of alkoxide group influences distinctly the structure of heterometallic precursors, i.e., oxo or acetate bridging, and the amounts of hydroxyl and organic groups bound to the metal network. The local environments of metal atoms in the amorphous precursors were also studied by EXAFS. The analysis reveals that in Pb−Zr precursors alkoxide groups modify the coordination spheres of the zirconium atoms. Conversely, local environments of both lead and titanium atoms within the analysed range of 3.4 A depend weakly on the type of alkoxide used.     

1,2,2-Trimethyldisilane-1,1,2-triol: intermediate formation and conversion to condensation products

1,2,2-Trimethyldisilane-1,1,2-triol (1) is formed as an unstable intermediate upon hydrolysis of oligo(trimethyldisilanylsesquiazane). In the absence of trapping agents it undergoes rapid condensation to give ether-soluble poly(trimethyldisilanyloxane) which contains silanol groups. Treatment of the hydrolysis products with chlorotrimethylsilane in the presence of triethylamine affords trimethylsiloxy derivatives, (Me₃SiO)₂MeSiSiMe₂(OSiMe₃),5,6, and [Si₂Me₃O _x (OSiMe₃) _y ] _n . The isolation of these products indicates that disilanetriol1 readily undergoes condensation to form hydroxylcontaining six-membered rings and polysiloxanes. The condensation of compound1 in the presence of Me₃SiOH has been studied. The ratio between the isomeric cyclosiloxanes5 and6 has been determined both by¹H NMR spectroscopy and by a chemical method (chlorinolysis). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1788–1792, October, 1993.     

Kinetics of Hydroperoxide Epoxidation of 1-Octene in the Presence of MoB2

We have studied the kinetics of the process of epoxidation of 1-octene by tert-butyl hydroperoxide in the presence of molybdenum boride MoB₂. We have studied the effect of the concentrations of starting materials and reaction products on the process. We suggest a kinetic scheme and we calculate the kinetic parameters of the process.