The kinetics of thiyl radical-induced reactions of monounsaturated fatty acid esters
The time-dependent isomerizations and thiol additions of several Z- and E-monounsaturated fatty acid methyl esters catalyzed by alkanethiyl radicals during γ-radiolysis of tert-butyl alcohol solutions are analyzed on the basis of the radiation chemical yield of radicals and established rate data. This provides room-temperature rate constants for the reversible thiyl addition. Within experimental errors, they do not depend on the double bond position in the alkyl chains. Particularly noteworthy is the very fast β-elimination of thiyl radicals from alkyl radicals which carry a second β-substituent. It is supported by additional evidence obtained with a radical clock methodology, and the large preference of fragmentation to the E-isomers is attributed to different barriers for the formation of the E- and Z-transition states from the equilibrium radical structure.
Desulfuration Using Plasma Techniques, III. - Reaction of Thioethers
Plasma desulfurations were tested with nine thioethers.While aliphatic, as well as aromatic thioethers and thiophene react easily, benzothiophenes are hard to desulfurize.Predominant reaction products are low molecular alkenes and alkanes (Table 1).Addition of oxygen greatly improves the results (Table 2).
Suhr, Harald,Henne, Peter,Iacocca, Diodoro,Ropero, Marcos J.
p. 441 - 446
(2007/10/02)
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