Alumina supports, reactions

Among a wide range of other applications, the combination of alumina-supported reactions and microwave irradiation was successfully applied to the cleavage of esters, a commonly used strategy to deprotect alcoholic groups in multi-step organic synthesis. Deacylation of alcoholic and phenolic ac-... 

Alkylthiazoles can be oxidized to nitriles in the presence of ammonia and a catalyst. For example, 4-cyanothiazole was prepared from 4-methylthiazole by a one-step vapor-phase process (94) involving reaction with a mixture of air, oxygen, and ammonia at 380 to 460°C. The catalyst was M0O3 and V Oj or M0O3, VjOj, and CoO on an alumina support. 

When catalysts are used in a highly exothermic reaction, an active phase may be diluted with an inert material to help dissipate heat and moderate the reaction. This technique is practiced in the commercial oxychlorination of ethylene to dichloroethane, where an alumina-supported copper haUde catalyst is mixed with a low surface area inert diluent. 

An alumina-supported trifluoromethylthiocopper reagent gave improved yields of trifluoromethyl aryl sulfides in coupling reactions with this reagent [26 ] (equation 184). 

A great many materials have been used as catalyst supports in hydrogena-tion, but most of these catalyst have been in a quest for an improved system. The majority of catalyst supports are some form of carbon, alumina, or silica-alumina. Supports such as calcium carbonate or barium sulfate may give better yields of B in reactions of the type A- B- C, exemplified by acetylenes- cjs-olefins, apparently owing to a weaker adsorption of the intermediate B. Large-pore supports that allow ready escape of B may give better selectivities than smaller-pore supports, but other factors may influence selectivity as well. 

In a study on the influence of supports on rhodium, the amount of dicyclohexylamine was found to decrease in the order carbon > barium carbonate > alumina > barium sulfate > calcium carbonate. Plain carbon added to rhodium-on-alumina-catalyzed reactions was found to cause an increase in the amount of dicyclohexylamine, suggesting that carbon catalyzes the formation of the intermediate addition product (59). 

Alumina supported sodium metaperiodate, which can be prepared by soaking the inorganic support with a hot solution of sodium metaperiodate, was also found to be a very convenient reagent for the selective and clean oxidation of sulphides to sulphoxides79. The oxidation reaction may be simply carried out by vigorous stirring of this solid oxidant with the sulphide solution at room temperature. As may be expected for such a procedure, solvent plays an important role in this oxidation and ethanol (95%) was found to be... 

For instance, bromination of toluene in carbon tetrachloride did not proceed at reflux, even though pentamethylbenzene was brominated at 30°C to give bromopentamethylbenzene quantitatively. Toluene and copper(II) bromide reacted at reflux for 72 h. to give benzyl bromide as the main product. In a similar reaction with alumina-supported copper(II) bromide, bromotoluene (o/p = l) was obtained in good yield and no side-chain-brominated compounds were detected. 

The reaction of anisole with copper(II) bromide in benzene at 50°C yielded no detectable products after 10 h. In contrast, in a similar reaction using alumina-supported copper(II) bromide, p-bromoanisole in 90 % yield was obtained from the reaction run at 30°C for 2 h. (eqn. 1). No dibromides were detected. 

The yield increased with increasing the ratio of alumina-supported copper(II) bromide to alkoxybenzenes. The size of alkoxy group did not influence significantly the yield and the ratio of p/o. Nonpolar solvents such as benzene and hexane were better than polar solvent. Polar solvents such as chloroform and tetrahydrofiiran decreased the yield. It is suggested that these polar solvents may be strongly adsorbed on the surface of the reagent. The reaction did not proceed in ethanol to be due to the elution of copper(II) bromide from the alumina to the solution. It is known that the reaction of aromatic hydrocarbons with copper(II) halides in nonpolar solvents proceeds between aromatic hydrocarbons and solid copper(II) halides and not between hydrocarbons and dissolved copper(II) halides (ref. 6). 

The reaction of 1-alkoxynaphtalenes with copper (II) bromide in benzene produced a mixture of 4-bromo-1-alkoxynaphtalenes and 4,4 -dialkoxy-l,l -binaphtyls. For instance, the reaction of 1-methoxynaphtalene 4 with copper(II) bromide in refluxing benzene for 2 h. gave a mixture of 4-bromo-1-methoxy-naphtalene 5 (47 %) and 4,4 -dimethoxy-l,l -binaphtyl 6 (45 %). In contrast, in similar reaction using alumina-supported copper(II) bromide at 30°C, only dimerization occurred and no brominated compounds were obtained. 

Reaction experiments were performed at the substrate to catalyst ratios between 250 and 5000 (Table 1). The immobilized catalyst showed a rather constant values of TOP and enantioselectivity in spite of the increase in the S/C ratio, even though these values were slightly lower than those of the homogeneous Ru-BINAP catalyst. After the reaction, the Ru content in the reaction mixture was measured by ICP-AES and was found to be under 2 ppm, the detecting limit of the instrument, indicating the at Ru metal didn t leach significantly during the reaction. These results show that the immobilized Ru-BINAP catalyst had stable activity and enantioselectivity and that the Ru metal complex formed a stable species on the alumina support. 

More recently, Chang reported a ruthenium-based Heck-type reaction in DME/H20 (1 1) by using alumina-supported ruthenium catalysts.154... 

Figure 10.3. Proposed mechanism for the C8H18—NO—02 reaction in the low [C8H18]/[02] (a) and in the high [C8H18]/[02] concentration region (b). Reactions above the dotted line occur on the Pt surface, while reactions below occur on the alumina support (reproduced with permission from Ref. [62]).

Oh, S.H. (1990) Effects of cerium addition on the CO-NO reaction kinetics over alumina-supported rhodium catalysts, J. Catal. 124, 477. 

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