EPR-untersuchungen an carbonsäureestern—II : Radikalanionen der thion- und dithiobenzoesäureester

Alkyl thione (2) and dithiobenzoates (3) as well as their aryl substituted derivatives 4 and 5 may be converted into radical anions by in situ electroreduction.—The EPR spectra of 2–5 are measured. Conclusions about the spin density distribution within the aromatic ring and the functional group are drawn from the hyperfine structure coupling constants, g-values and polarographic half wave potentials, whereby the effect of ortho substituents (twisting of the two halves of the molecule) is especially considered.—The results agree sufficiently with MO calculations of the McLachlan type.Inspection of the alkyl coupling constants

shows that the alkyl groups exhibit conformations of minimum steric hindrance of the thiocarbonyl group.     

Thermal desorption of alcohols and ethers from the surface of aluminum oxide

Conclusions A Chromatographic investigation was made of the thermal desorption of methanol and isopropanol and of diisopropyl ether from the surface of A1₂O₃.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–201, January, 1987.     

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1-Hydro-3-vinylhexamethylcyclotetrasiloxane and its polymerization

1,3-Dimethyl-3-vinyl-1,3-dichlorosiloxane is prepared by partial cohydrolysis of methylvinyldichlorosilane and methyldichlorosilane, and its cohydrolysis with sym-tetra-methyldichlorodisiloxane gives 1-hydro-3-vinylhexamethyl-cyclotetrasiloxane. A study is made of the kinetics of the polymerization of the latter in CCL₄ in the presence of H₂PtCl₆ · 6H₂O     

Submicro methods for the analysis of organic compounds : The determination of hydroxyl groups

Various procedures were examined for the determination of organic hydroxyl groups. Conventional acetylation methods could not be used on the submicro scale, but the spectrophotometric method based on esterification with 3,5-dinitrobenzoyl chloride followed by extraction of the ester and colour development with alkaline acetone proved reasonably satisfactory for aliphatic alcohols. Acidic hydroxyl groups e.g. in phenolic compounds, were titrated accurately with 0.01 M tetrabutylammonium hydroxide in benzene-methanol solution in a pyridine medium ; visual end-points or potentiometricend-points with glass-silver or glass-in-stream platinum electrode pairs were used depending on the strength of the acidic group. Some differentiating titrations were possible. A general submicro bromination method for phenols was not feasible.     

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