The Action of Raney Nickel on Organic Sulfur Compounds.

Hauptmann, Heinrich; Walter, Wolfgang

doi:10.1021/cr60219a001

Cited by 127 publications

(29 citation statements)

References 134 publications

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“…Raney nickel catalysts possess high catalytic activity due to its highly porous microstructure and high surface area. It is extensively used in various industrial processes and also in organic synthesis process [20,21].Fe 3 O 4 (magnetite) acts as a catalyst for water gas shift reaction (CO (g) + H 2 O (g)  CO 2 (g) +H 2 (g), ΔH = −41.1kJ/mol) [22,23].…”

Section: Open Accessmentioning

confidence: 99%

Catalytic Studies of Sodium Hydroxide and Carbon Monoxide Reaction

2012

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Abstract:We have studied the effect of ball milling on alumina mixed nickel, magnetite and Raney nickel on the reaction: 2NaOH(s) + CO (g) = Na 2 CO 3 (s) + H 2 (g) and determined the optimum particle size for the catalysts. The best performance was shown by a 2 h ball milled Raney nickel with average crystallite size of 209 Å. This reaction serves the dual purpose of carbon sequestration and yielding hydrogen gas.

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Section: Open Accessmentioning

confidence: 99%

Catalytic Studies of Sodium Hydroxide and Carbon Monoxide Reaction

2012

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“…As the reaction proceeded over noble‐metal‐based catalysts in the presence of 3‐mercapto‐1,2‐propanediol as sulfur source, the mechanism elucidation should be started by the well‐established thiol desulfurization by hydrogen over noble‐metal catalysts 45. During the hydrogenation/directed isomerization process of safflower oil over Rh/SBA‐15 catalyst, the 3‐mercapto‐1,2‐propanediol underwent desulfurization as depicted in Scheme .…”

Section: Resultsmentioning

confidence: 99%

Sulfur Promotion in Conjugated Isomerization of Safflower Oil over Bifunctional Structured Rh/SBA‐15 Catalysts

et al. 2013

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The sulfur effect on conjugated linoleic acid isomer (CLA) formation during the combined hydrogenation/directed isomerization of safflower oil over a bifunctional (hydrogenation and isomerization) highly structured rhodium‐based catalyst (Rh/SBA‐15) was investigated either by direct addition of increased concentrations of 3‐mercapto‐1,2‐propanediol to the reaction medium or by doping Rh/SBA‐15 with the same sulfur‐based compound yielding the sulfur‐doped Rh‐catalyst (S–Rh/SBA‐15). These catalysts exhibited interesting activity, stability, and recyclability. The maximum CLA contents obtained during the combined reactions with 0, 0.2, 1, 2, 5, and 10 ppm sulfur additions were 73, 99, 131, 110, 105, and 68 mgCLA goil−1, respectively, whereas the amount of harmful trans monoenes remained below 8 %. The safflower oil after partially hydrogenation under the same conditions over S–Rh/SBA‐15 catalyst contained up to 110 mgCLA goil−1. These results showed clear evidence of the sulfur promotion effect on CLA formation during the dual hydrogenation/directed isomerization of safflower oil. A mechanism for the sulfur promotion of the heterogeneous catalyst Rh/SBA‐15 for the conjugated isomerization activity during hydrogenation/directed isomerization of safflower oil was determined by solid‐state 1H NMR analysis of the fresh and spent catalysts. This was also confirmed by liquid‐state 2H NMR analysis of deuterium‐labeled product aliquots withdrawn throughout the reaction. The sulfur promotion towards the double bond conjugation of linoleic acid to form CLA isomers could be explained mechanistically through the preferable formation of the more nucleophilic rhodium sulfide (RhSH) over that of the hydride (RhH). However, both types of Rh clusters constituted distinct catalytic sites leading to the formation of hydrogenation as well as conjugated and geometric isomerization products. The lumped kinetics model described the experimental data well and complied simply with the proposed mechanism.

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“…1) gave mainly proposed in Schemes 1-4. According to this mechtetraphenylthiophene (97% yield) in addition to anism, the rearrangement products seem to be benzene (15%), biphenyl (lo%), benzyl thiol(5%), formed through an intermolecular process involving a homolytic fission of C-S linkages (5,6 …”

Section: Introductionmentioning

confidence: 94%

Molecular rearrangements. III. Thermal decomposition of some selected thioesters

Abdel‐Wahab¹,

El‐Khawaga²,

Ismail³

1982

Can. J. Chem.

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Four selected thioesters (1–4) were prepared and pyrolyzed in the absence of promoters either alone or in isoquinoline solvent. These esters include benzyl thiobenzoate (1), phenyl phenylthioacetate (2), benzyl phenylthioacetate (3), and phenyl thiobenzoate (4). Pyrolysis of 1 gave mainly 2,3,4,5-tetraphenylthiophene in addition to benzene, biphenyl, benzyl thiol, and benzoic acid. Thermal decomposition of 1 under nitrogen gave benzaldehyde, benzil, and only a trace of benzoic acid in addition to the former products. Compound 2 afforded essentially toluene and dibenzyl in addition to benzene, biphenyl, phenyl sulphide, thiophenol, and phenyl acetic acid. Thermolysis of 3 gave toluene and stilbene beside small quantities of benzyl thiol and phenylacetic acid. Finally, thermal decomposition of 4 in isoquinoline gave benzene, biphenyl, phenyl sulphide, thianthrene, thiophenol, benzoic acid, and 1-phenylisoquinoline. H2S and CO are also produced in all cases. In these rearrangements, the C—S bonds undergo homolytic fission either simultaneously or selectively. No isomer redistribution precedes the coupling reactions. Plausible mechanisms for the above facts are proposed.

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The Action of Raney Nickel on Organic Sulfur Compounds.

Cited by 127 publications

References 134 publications

Catalytic Studies of Sodium Hydroxide and Carbon Monoxide Reaction

Catalytic Studies of Sodium Hydroxide and Carbon Monoxide Reaction

Sulfur Promotion in Conjugated Isomerization of Safflower Oil over Bifunctional Structured Rh/SBA‐15 Catalysts

Molecular rearrangements. III. Thermal decomposition of some selected thioesters

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