Platinum oxide reduction

Figure 11.27. Cyclic voltammograms to illustrate the eharge associated with hydrogen adsorption Qh and that associated with platinum oxide reduction Qo- Nafion 112 membrane Pt/C cathode catalyst T = 100 °C scan rate = 30 mV s [62]. (Reproduced by permission of ECS—The Electrochemical Society, from Xu H, Kunz R, Fenton JM. Investigation of platinum oxidation in PEM fuel cells at various relative humidities.)...

CATALYTIC REDUCTION WITH ADAMS PLATINUM OXIDE CATALYST... 

Hydrocinnamic acid may also be prepared by the reduction of cinnamic acid with sodium and alcohol or with sodium amalgam or with hydrogen in the presence of Adams platinum oxide catalyst (Section 111,150) ... 

The Adams platinum oxide catalyst gives satisfactory results in the reduction of ozonidea. 

Reduction. Quinoline may be reduced rather selectively, depending on the reaction conditions. Raney nickel at 70—100°C and 6—7 MPa (60—70 atm) results in a 70% yield of 1,2,3,4-tetrahydroquinoline (32). Temperatures of 210—270°C produce only a slightly lower yield of decahydroquinoline [2051-28-7]. Catalytic reduction with platinum oxide in strongly acidic solution at ambient temperature and moderate pressure also gives a 70% yield of 5,6,7,8-tetrahydroquinoline [10500-57-9] (33). Further reduction of this material with sodium—ethanol produces 90% of /ra/ j -decahydroquinoline [767-92-0] (34). Reductions of the quinoline heterocycHc ring accompanied by alkylation have been reported (35). Yields vary widely sodium borohydride—acetic acid gives 17% of l,2,3,4-tetrahydro-l-(trifluoromethyl)quinoline [57928-03-7] and 79% of 1,2,3,4-tetrahydro-l-isopropylquinoline [21863-25-2]. This latter compound is obtained in the presence of acetone the use of cyanoborohydride reduces the pyridine ring without alkylation. 

Isoquinoline can be reduced quantitatively over platinum in acidic media to a mixture of i j -decahydroisoquinoline [2744-08-3] and /n j -decahydroisoquinoline [2744-09-4] (32). Hydrogenation with platinum oxide in strong acid, but under mild conditions, selectively reduces the benzene ring and leads to a 90% yield of 5,6,7,8-tetrahydroisoquinoline [36556-06-6] (32,33). Sodium hydride, in dipolar aprotic solvents like hexamethylphosphoric triamide, reduces isoquinoline in quantitative yield to the sodium adduct [81045-34-3] (25) (152). The adduct reacts with acid chlorides or anhydrides to give N-acyl derivatives which are converted to 4-substituted 1,2-dihydroisoquinolines. Sodium borohydride and carboxylic acids combine to provide a one-step reduction—alkylation (35). Sodium cyanoborohydride reduces isoquinoline under similar conditions without N-alkylation to give... 

Dihydrocholesterol has been prepared by the reduction of cholestenone with sodium and amyl alcohoP and by the hydrogenation of cholesterol. In the presence of platinum black or platinum oxide, yields varying from 6.5 per cent to 40 per cent have been obtained in ether, acetone, ethyl acetate, and acetic acid. ... 

The hydrogenation of 5a-cholestanone (58) in methanolic hydrobromic acid over platinum gives 3j5-methoxycholestane ° (61). This compound is also obtained from the palladium oxide reduction of (58) in methanol in the absence of acid. Hydrogenation of 5 -cholestanone also gives the 3j5-methoxy product under these conditions. Reduced palladium oxides are quite effective for the conversion of ketones to ethers. The use of aqueous ethanol as the solvent reduces the yield of ether. Ketals are formed on attempted homogeneous hydrogenation of a 3-keto group in methanol. ... 

The reduction of iminium salts can be achieved by a variety of methods. Some of the methods have been studied primarily on quaternary salts of aromatic bases, but the results can be extrapolated to simple iminium salts in most cases. The reagents available for reduction of iminium salts are sodium amalgam (52), sodium hydrosulfite (5i), potassium borohydride (54,55), sodium borohydride (56,57), lithium aluminum hydride (5 ), formic acid (59-63), H, and platinum oxide (47). The scope and mechanism of reduction of nitrogen heterocycles with complex metal hydrides has been recently reviewed (5,64), and will be presented here only briefly. 

There have been only a few examples of reduction of the C=N+ function of catalytic hydrogenation since the reductions with complex hydrides are so easy to do in the laboratory. A possible reduction of an iminium salt 45 to 46 with platinum oxide was reported by McKay et al. (91). A report that platinum oxide reduces 2l tio).jgj yjj.Qqyjp Qjj2idijjjujn perchlorate (25) in quantitative yield to 47 indicates that such reduction should be facile (47). 

Support for this suggestion comes from many quarters. Reduction of the jS-carboline anhydro-bases with sodium and alcohol or with tin and hydrochloric acid gives the 1,2,3,4-tetrahydro derivatives, as does catalytic reduction over platinum oxide in an alkaline medium. On the other hand, catalytic reduction with platinum oxide in acetic acid results in the formation of the 5,6,7,8-tetrahydro-j3-carbolinium derivatives (see Section III,A,2,a). It should be noted, however, that reduction of pyrido[l,2-6]indazole, in which the dipolar structure 211 is the main contributor to the resonance hybrid, could not be effected with hydrogen in the presence of Adams catalyst. 

Platinum, especially platinum oxide, has been used by many investigators (5), Platinum oxide, when used with aldehydes is apt to be deactivated before reduction is completed. Deactivation is inhibited by small amounts of ferrous or stannous chlorides (59,82). This type of promoter can also sharply curtail hydrogenolysis if it is a troublesome reaction (Rylander and Starrick, 1966). Deactivated systems can often be regenerated by shaking the reaction mixture with air (2,8,21 J3,96). The usefulness of this regenerative technique transcends aldehyde reductions it frequently is worth resorting to. 

Platinum oxide may show induction periods (13) in reductive alkylation and prereduction has been recommended (37,47), but it is not always necessary (19). 

The solubility of the resulting product may dictate the choice of solvent. Reductive alkylation of norepinephrine with a series of keto acids proceeded smoothly over platinum oxide in methanol-acetic acid mixtures. However, when n = 4 or 5, the product tended to precipitate from solution, making catalyst separation difficult. The problem was circumvented by using glacial acetic acid as solvent 38). 

Selective reduction of 11 to 12 is achieved in high yield by the use of 5% Rh-on-C in DMF containing NH OH. Reduction essentially stops after absorption of 3 mol of hydrogen. Yields were lower in ethanol. Platinum oxide in ammonical DMF showed fair selectivity, but Pd-on-C none. In a typical experiment, 0.1 mol of 11 in 250 ml DMF containing 3 ml 28% NH4OH solution and 0.7 g 5% Rh-on-Al O was reduced at 40 psig until 0.3 mol of hydrogen were absorbed (2). 

Platinum, especially as platinum oxide, has been used by many investigators. If this catalyst contains residual alkali, it is apt to be ineffective for aromatic ring reduction unless an acidic solvent is used (1,3,19) or unless the compound also contains a carbonyl group, as in acetophenone, where 1,4-and 1,6-addition are possible (46). Nickel, unless especially active, requires vigorous conditions—conditions that may promote side reactions. 

Nowadays, rhodium or ruthenium are often the preferred catalysts. Rhodium can be used under mild conditions, whereas ruthenium needs elevated pressures. If pressure is available, it might as well be used even with rhodium, for increased pressure makes more efficient use of the catalyst, as well as decreases whatever hydrogenolysis might occur at lower pressure. Rhodium 7,8,12 20,21,38,39,45,65,66,68,69,75) and ruthenium 18,26 8,52,68,69,72,74) are especially advantageous in reductions of sensitive phenols and phenyl ethers that undergo extensive hydrogenolysis over catalysts such as platinum oxide. 

Hydrogenation of 3-pyridinecarboxylic acids is apt to be accompanied by extensive decarboxylation (2S), but this unwanted reaction can be prevented by carrying out the reaction in the presence of one equivalent of base (33,79). Ruthenium (33), rhodium (29), platinum oxide (2S,59), and palladium (30) have all proved effective catalysts for reduction of pyridinecarboxylic acids to the saturated acid. 

Extreme differences between 5% palladium-on-carbon and platinum oxide were found on reduction of the 5-aryl substituted oxazole 14. Over palladium, 15 was formed in quantitative yield by hydrogenolysis of the benzyl hydroxyl, whereas over Pt, scission of the oxazole occurred to give 13 quantitatively (48). Hydrogenation of 15 over platinum oxide gave the phenethylamide 16. 

The reaction product (1-carbethoxymethyM-carbomethoxy-pyridinium bromide) was obtained in crystalline form. (It formed prisms melting at 166°-169°C after recrystallization from a mixture of isopropanol and acetone.) It was not necessary to isolate it. For the following reduction step, the reaction mixture was brought into solution by the addition of about 1 liter of warm ethyl alcohol. It was then hydrogenated at about 30 atm pressure in the presence of 2 g of platinum oxide. The temperature rose during this reaction to about 40°C. 

Oxidation-reduction potential Because of the interest in bacterial corrosion under anaerobic conditions, the oxidation-reduction situation in the soil was suggested as an indication of expected corrosion rates. The work of Starkey and Wight , McVey , and others led to the development and testing of the so-called redox probe. The probe with platinum electrodes and copper sulphate reference cells has been described as difficult to clean. Hence, results are difficult to reproduce. At the present time this procedure does not seem adapted to use in field tests. Of more importance is the fact that the data obtained by the redox method simply indicate anaerobic situations in the soil. Such data would be effective in predicting anaerobic corrosion by sulphate-reducing bacteria, but would fail to give any information regarding other types of corrosion. 

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