99419-74-6Relevant articles and documents
Chromium(III) and indium(III) 3,6-di-tert-butyl-o-semiquinolate complexes as redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes
Berberova,Shinkar,Smolyaninov,Shvetsova,Sediki
, p. 578 - 582 (2017/09/23)
The electrochemical oxidation of the chromium(III) and indium(III) complexes with 3,6-di-tert-butyl-o-semiquinolate leading to the formation of active monocationic species is studied by cyclic voltammetry. The reactions of the latter with hydrogen sulfide generate the radical cation of H2S, whose fragmentation affords the proton and thiyl radical. These complexes are proposed for the first time as redox mediators for the one-pot thiolation of inert cycloalkanes C6–C8, which decreases the activation energy of hydrogen sulfide compared to that for direct electrochemical oxidation. The major products of cycloalkane functionalization involving H2S are thiols and organic di- and trisulfides. The yield of the synthesized compounds depends on the type of the mediator: the chromium(III) complex exhibits the highest efficiency in the electrocatalytic transformations.
Role of hydrogenolysis and nucleophilic substitution in hydrodenitrogenation over sulfided NiMo/γ-Al2O3
Prins,Rota
, p. 195 - 199 (2007/10/03)
The HDS of cyclohexanethiol and 2-methylcyclohexanethiol was studied over a sulfided NiMO/γ-Al2O3 catalyst. About 66% of the thiols reacted by elimination to (methyl)cyclohexene and 33% by hydrogenolysis of the C-S bond to (methyl)cyclohexane. These values were slightly lower than those for the selectivity to methylcyclohexene and slightly higher than those for the selectivity to methylcyclohexane in the HDN of 2-methylcyclohexylamine. HDN occurred predominantly in aliphatic molecules that contained H atoms in the β position relative to the nitrogen atom by elimination of ammonia. Part of the remaining HDN occurred by nucleophilic substitution of the amine by H2S, followed by elimination of H2S from the resulting thiol and, to a lesser extent, by C-S bond hydrogenolysis, the rest of the remaining HDN occurred by direct hydrogenolysis of the C-N bond.
