Platinum sulfide-on-carbon

Platinum catalysts have been shown to be highly selective for the hydrogenation of halonitrobenzenes to haloanilines. A number of effective platinum catalysts or catalyst systems have been described in the literature, mostly in patents.96 Dovell and Greenfield found that the sulfides of the platinum metals and cobalt were highly selective in the hydrogenation of halo-substituted nitrobenzenes.117-119 There was no detectable dechlorination with the sulfides of palladium, platinum, rhodium, ruthenium, and cobalt no detectable debromination occurred with platinum sulfide trace debromination occurred with rhodium sulfide and cobalt sulfide and appreciable debromination occurred with palladium sulfide. Typical hydrogenations with 5% platinum sulfide on carbon catalyst are given in eqs. 9.52 and 9.53 with 2,5-dichloronitrobenzene and p-bromobenzene, respectively.118... 

With platinum sulfide-on-carbon, a catalyst not sensitive to poisons, reductions can be performed with retention of halogen and sulfur-carbon bonds... 

The predominant process for manufacture of aniline is the catalytic reduction of nitroben2ene [98-95-3] ixh. hydrogen. The reduction is carried out in the vapor phase (50—55) or Hquid phase (56—60). A fixed-bed reactor is commonly used for the vapor-phase process and the reactor is operated under pressure. A number of catalysts have been cited and include copper, copper on siHca, copper oxide, sulfides of nickel, molybdenum, tungsten, and palladium—vanadium on alumina or Htbium—aluminum spinels. Catalysts cited for the Hquid-phase processes include nickel, copper or cobalt supported on a suitable inert carrier, and palladium or platinum or their mixtures supported on carbon. 

In past years, metals in dilute sulfuric acid were used to produce the nascent hydrogen reductant (42). Today, the reducing agent is hydrogen in the presence of a catalyst. Nickel, preferably Raney nickel (34), chromium or molybdenum promoted nickel (43), or supported precious metals such as platinum or palladium (35,44) on activated carbon, or the oxides of these metals (36,45), are used as catalysts. Other catalysts have been suggested such as molybdenum and platinum sulfide (46,47), or a platinum—nithenium mixture (48). 

Since arenes are adsorbed much better on carbon than on platinum, it is possible to avoid undesired anodic self-coupling (44e) of bisarene sulfides at carbon anodes but not at Pt anodes. 

Dibutylamine, piperidine, N-ethylcyclohexylamine, N-ethyldicyclohexylamine, and the ketones were reagent grade chemicals. The 5% palladium on carbon, 5% platinum on carbon, sulfided 5% platinum on carbon and sulfided 5% rhodium on carbon catalysts were obtained from Engelhard Industries. The 20% molybdenum sulfide on alumina (Girdler T-318) was obtained from the Chemetron Corp. Palladium chloride was obtained from Matheson, Coleman and Bell. Ruthenium trichloride was obtained from Ventron. 

Malz, Jr. et al. found platinum sulfide supported on carbon to be superior to any of other nonsulfided and sulfided catalysts in the selective hydrogenation of 6-chloro-2(l//)-quinoxalinone-4-oxide to 6-chloro-2(l//)-quinoxalinone.230 The hydrogenation was performed in an aqueous potassium hydroxide solution at 60°C and 0.69-1.38 MPa H2 to give the product containing 92% of the desired compound in 90% isolated yield (eq. 9.79). 

Ozonides are rarely isolated [75, 76, 77, 78, 79], These substances tend to decompose, sometimes violently, on heating and must, therefore, be handled with utmost safety precautions (safety goggles or face shield, protective shield, and work in the hood). In most instances, ozonides are worked up in the same solutions in which they have been prepared. Depending on the desired final products, ozonide cleavage is done by reductive or oxidative methods. Reductions of ozonides to aldehydes are performed by catalytic hydrogenation over palladium on carbon or other supports [80, 81, 82, S3], platinum oxide [84], or Raney nickel [S5] and often by reduction with zinc in acetic acid [72, 81, 86, 87], Other reducing agents are tri-phenylphosphine [SS], trimethyl phosphite [89], dimethyl sulfide (DMS) [90, 91, 92], and sodium iodide [93], Lithium aluminum hydride [94, 95] and sodium borohydride [95, 96] convert ozonides into alcohols. 

Palladium and platinum (5—10 wt % on activated carbon) can be used with a variety of solvents as can copper carbonate on siHca and 60 wt % nickel on kieselguhr. The same is tme of nonsupported catalysts copper chromite, rhenium (VII) sulfide, rhenium (VI) oxide, and any of the Raney catalysts, copper, iron, or nickel. 

CARBON SKELETON. The technique of precolumn catalytic hydrogenation can be applied to reduce certain unsaturated compounds to their parent hydrocarbons. Compounds analyzed by this technique include esters, ketones, aldehydes, amines, epoxides, nitriles, halides, sulfides, and fatty acids. Fatty acids usually give a hydrocarbon that, is the next lower homolag than the parent acid. For most systems utilizing hydrogenation, hydrogen is also used as the carrier gas. Usually 1% palladium or platinum on a non-adsorptive porous support such as AW-Chromosorb P is used as the catalytic packing material. 

Bulk aluminum may undergo the following dangerous interactions exothermic reaction with butanol, methanol, 2-propanol, or other alcohols, sodium hydroxide to release explosive hydrogen gas. Reaction with diborane forms pyrophoric product. Ignition on contact with niobium oxide + sulfur. Explosive reaction with molten metal oxides, oxosalts (nitrates, sulfates), sulfides, and sodium carbonate. Reaction with arsenic trioxide + sodium arsenate + sodium hydroxide produces the toxic arsine gas. Violent reaction with chlorine trifluoride, Incandescent reaction with formic acid. Potentially violent alloy formation with palladium, platinum at mp of Al, 600°C. Vigorous dissolution reaction in... 

Reduction of nitroquinazolines 1 using palladium oncharcoal, - palladium on calcium carbonate,Raney nickel,or platinum oxide catalysts, tin(II) chlo-ride, iron, sodium sulfide, or titaniuni(III) chloride is a facile route to quinazolinamines 2. Under conditions of catalytic reduction of the nitro group, chlorine in positions 2 and/or 4 is reductively removed (cf. Section 6.3.1.1.7.1.1.). 

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