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.     

Rearrangements in cobaltic fluoride fluorinations of cycloalkanes with seven or more ring carbons

Cyclo-heptane, -octane, -decane, -dodecane and -octadecane have been fluorinated in the vapour phase with cobaltic fluoride. The perfluorocarbons obtained revealed varying degrees of skeletal rearrangements. Thus, cycloheptane gave perfluoro-cycloheptane and -methylcyclohexane; cyclooctane gave at least eight fluorocarbons including-bicyclo(3,3,0)octane and -cyclooctane; cyclodecane gave a complex mixture from which were isolated perfluoro cis- and trans-bicyclo(4,4,0)decanes but no perfluorocyclodecane; cyclododecane and cyclooctadecane gave complex fluorocarbon mixtures in which none of the fluorocarbons with the original cycloalkene skeleton could be detected.Tetradecafluorobicyclo(3,3,0)octane gave dodecafluorobicyclo (3,3,0)oct-1(5)-ene and decafluorobicyclo(3,3,0)octa-di-1(5), 2-ene when pyrolysed over iron gauze.The fluorination of cyclooctane also afforded 1$\text{H}$-pentadecafluorocyclooctane which was dehydrofluorinated to tetradecafluorocyclooctene. This was converted to a range of derivatives including dodecafluorosuberic acid, 1,2-dichlorotetradecafluorocyclooctane, 1-methoxy tridecafluorocyclooctene and tetradecafluorocyclooctanone.     

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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     

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Über die Bildung kondensierter Borazinderivate bei der Grignardmethylierung von 2,4,6-Trichlorborazin

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