Hydrogenolysis of Sulfur Compounds by Raney Nickel Catalyst

Mozingo, R. W.; Wolf, Donald E.; Harris, Stanton A.; Folkers, Karl

doi:10.1021/ja01246a005

Cited by 269 publications

(94 citation statements)

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“…As was observed with the primary benzyl in Table 1, some dehydromethylation occurs simultaneously with the hydrogenolysis reaction of the primary alcohols found in Table 3 ( Raney nickel is known to contain adsorbed hydrogen which is formed in the activation of the catalyst. One estimate places the amount of adsorbed hydrogen per gram of catalyst at 2-5 mmol [3,27]. By reducing ethyl trans-cinnamate to the ethyl ester of 3-phenylpropanoic acid with Raney nickel in 2-propanol at room temperature we determined that our Raney catalyst contains 1.2 mmol/g of available hydrogen.…”

Section: Raney Nickel Reductionsmentioning

confidence: 99%

Transfer hydrogenolysis of aromatic alcohols using Raney catalysts and 2-propanol

Gross

Mebane

Armstrong

2001

Applied Catalysis A: General

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Raney nickel in refluxing 2-propanol is an effective catalytic system for cleaving C-O bonds in aromatic alcohols by transfer hydrogenolysis. Deoxygenation of alcohols substituted at the ␣-, ␤-, ␥-, ␦-, and ε-positions was accomplished. The reaction appears not to be sensitive to substitution about the carbinol carbon. Aliphatic alcohols do not undergo hydrogenolysis with this system. Some dehydromethylation is found in the hydrogenolysis of primary alcohols. With extended reaction times, ring reduction accompanies hydrogenolysis of alcohols containing more than one aromatic ring. Raney cobalt is shown to catalyze hydrogen transfer from 2-propanol. Raney cobalt in refluxing 2-propanol is an effective system for deoxygenating ␣-substituted alcohols only. Although Raney cobalt is less reactive than Raney nickel in transfer hydrogenolysis, it exhibits greater selectivity as illustrated by the lack of ring reduction in alcohols containing more than one aromatic ring.

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Section: Raney Nickel Reductionsmentioning

confidence: 99%

Transfer hydrogenolysis of aromatic alcohols using Raney catalysts and 2-propanol

Gross

Mebane

Armstrong

2001

Applied Catalysis A: General

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“…Hydrogenolysis with Rainey-niickel breaks the carbon-sulfur bond in miiercaptide linkages (20). If the BSP metabolites are conjugated with cysteine through the cysteine-sulfur bond, Raneyniickel treatment should result in the degradation of the cysteine and the release of desulfurated cysteine (alaiiine).…”

Section: Raney-ntickel Liydrogenolysismentioning

confidence: 99%

Identification of Metabolites of Sulfobromophthalein *

Grodsky¹,

Carbone²,

Fanska³

1959

J. Clin. Invest.

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Sulfobromophthalein (BSP) is normally cleared from the blood by the liver and excreted into the bile. Brauer, Krebs and Pessotti (1) originally reported that part of the pigment appearing in dog bile was chromatographically different from the injected dye. Our studies using differenlt chromatographic techniques indicate that in man the bulk of the recovered pigments (65 to 75 per cent, according to estimates based on their absorption at 575 nu) consists of two metabolites. Similar metabolites are normally found in the urine and trace amounts also appear in the serum. The absorption spectra in the visible range and the indicator characteristics of BSP and the metabolic products were indistinguishable (2).The Isolationt of the cruide mtetabolites. In initial experimenits, the metabolites were isolated as follows. The total BSP pigments were extracted from bile with three volumes of acetone. The acetone extract was taken to dryniess ini vacuo, then dissolved in water (approximately 0.2 ml. per ml. of initial bile). The solution was chromatographed on Whatman 3 MM paper in an ascending system employing tert-butanol-water (1.73: 1 v/v) for six to 15 hours. The BSP bands were developed with ammonia fumes (or if permanent records were desired, by dipping the paper in a fresh saturated solution of sodium hydroxide in 90 per cent ethanol). After the position of the metabolites had been determined with ammonia, the bands were cut out and individually eluted with water. The resultant solutions were then taken to dryness.Putrification of the inetabolites. Purified pigments were prepared by chromatography in three systems. Activated alumina (Alcoa, 80 to 200 mesh) was washed 10 times in two volumes of water and once in acetone. During each washing period, the larger particles were allowed to settle for one minute; the supernatant was then decanted and discarded. The dried alumina was suspended in a loading solution consisting of two volumes of acetone to one volume of water. Columns, 3.4 cm. (outer diameter) by 6 cm., were prepared by gravity packing.The dried acetone extract from 60 ml. of bile was sus-1981

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“…The methods most commonly used for deoxygenation of carbonyl groups to alkanes are the Clemmensen reduction, 1 the Wolff-Kishner reaction, 2,3 and the Mozingo reduction. 4 Although both the Clemmensen and Wolff-Kishner conversions work well, they are carried out under strongly acidic and basic conditions respectively. The Mozingo reduction of dithioketals using Raney-Nickel overcomes some of these problems but requires formation of the dithioketal and the undesirable use of a heavy metal.…”

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confidence: 99%