16967-04-7Relevant articles and documents
Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided Mo-Ni/Al2O3 catalysts
Shen, Zhibing,Ke, Ming,Yu, Pei,Hu, Haiqiang,Song, Zhaozheng,Jiang, Qingzhe
, p. 120 - 127 (2015/02/02)
The thioetherification reaction of 1-butanethiol and 1-hexene dissolved in n-hexane was investigatedover sulfided Mo-Ni/Al2O3catalysts. The experimental results showed the catalysts have good cat-alytic performance for thioetherification reaction, but the isomerization and hydrogenation reactions of olefins over the catalysts can inhibit thioetherification reaction. As reaction temperature increases,the isomerization and hydrogenation reactions of olefins increase rapidly, however, the inhibition of thioetherification reaction also increases. The sulfur distribution and molecular structures of sulfurcompounds in the products were analyzed by the gas chromatograph with sulfur chemiluminescencedetector (GC-SCD) and the gas chromatograph/mass spectra spectrometry (GC/MS). Two possible routesof thioetherification reaction could be observed. At low temperature, the major pathway involves a directaddition of 1-butanethiol to the terminal carbon of double bond of 1-hexene. In this mechanism, the mainproduct is anti-Markovnikov adduct. At a higher temperature, the C S bond of 1-butanethiol can be sub-sequently cleaved, and the adsorbed -SH species can be formed on the catalysts. On the same time,abundant 1-hexene can be absorbed on the catalysts, as well. Therefore, the adsorbed SH species canthen recombine with adsorbed 1-hexene to form new hexyl-mercaptans, which can continue to produceanother kind of thioether (di-hexyl sulfide) with adsorbed 1-hexene. Similar with the first reaction route,the thioether of the anti-Markonikov adduct still dominates in the product.
Metalation of 1,3-Dithiolanes. Mercaptan Synthesis and Carbonyl Transposition
Wilson, Stephen R.,Georgiadis, Gregory M.,Khatri, Hiralal N.,Bartmess, John E.
, p. 3577 - 3583 (2007/10/02)
The reaction of 1,3-dithiolanes with n-butyllithium results in fragmentation to the corresponding thiocarbonyl compound followed by furhter reaction with n-butyllithium.All four types of thiocarbonyl reactions are observed: reduction, S-addition, C-addition, double addition.Synthetic applications of this reaction for the synthesis of secondary mercaptans and 1,2-carbonyl transposition (23 -> 24a-c) are described.
