Raney nickel, Table

Experiment HGR-14. The reactor was packed with 2 ft of parallel plates sprayed with Raney nickel (Table I) catalyst spraying and activation were as described under catalyst preparation. Operating conditions were practically the same as in experiment HGR-13 except for the periodic changes in the CGR ratio (see Figure 8 for reactor conditions and Figure 9 for product gas characteristics). 

Several substituted pyridines have been examined using the degassed Raney nickel, and the results are summarized in Table I. As all the biaryls obtained formed colored chelates with either ferrous or cuprous ions, they must be derivatives of 2,2 -bipyridine. Structural ambiguities cannot arise with 2,2 -bipyridines derived from 2- and 4-substituted pyridines but 3-substituted pyridines could conceivably give three isomeric 2,2 -bipyridines (e.g., 3, 4, 5). In fact, however, each 3-substituted pyridine so far examined has given only one 2,2 -bipyridine. 

Inspection of Table I shows that the yields of 2,2 -bipyridines obtainable from a substituted pyridine in the reaction with degassed Raney nickel depend on the nature of the substituents and their positions in the ring. 

Table II shows that, at least for the reactions with quinoline and with 4-methylquinoline (lepidine), nickel-alumina and degassed Raney nickel catalysts are of similar efficiency but better yields have been obtained with degassed Raney nickel, and only this catalyst produces the biaryl from 7-methyIquinoIine.

Most of the reactions with quinolines and degassed Raney nickels have been carried out at the atmospheric boiling point (above 230 C), a condition which is known to favor the formation of by-products. With quinoline and 4-methylquinoline (lepidine), however, the yields of the 2,2 -biquinolines were increased three to four times by heating in vacuo at 150° C, and it seems probable that other quinolines will behave similarly. Table II also shows that the yields of 2,2 -biquino-lines obtained under comparable conditions vary with the position of the methyl group in a fashion reminiscent of the trends observed with the pyridines (Table I). This similarity extends to the behavior of the two 2-methyl substituted quinolines studied, which undergo loss of the 2-methyl group to some extent and form traces of 2,2 -biquinolines. 

Table III. Iron and Carbon Content of Raney Nickel Catalyst Grids after Experiment HGR-10...

Experiment HGR-13. A 2-ft bed of commercial catalyst was tested as a packed bed of 0.25-in. pellets (see Table I for bed properties). This test was similar to experiment HGR-14 in which the catalyst bed consisted of parallel plates sprayed with Raney nickel. The experiment was... 

That the reaction with a lower rate constant is taking place preferentially and that the rate increases during the reaction are phenomena that can also occur with parallel reactions. As an example, Wauquier and Jungers (48), when studying competitive hydrogenation of a series of couples of aromatic hydrocarbons on Raney-nickel, have observed these phenomena for the couple tetraline-p-xylene (Table I). The experimental result was... 

If, for the purpose of comparison of substrate reactivities, we use the method of competitive reactions we are faced with the problem of whether the reactivities in a certain series of reactants (i.e. selectivities) should be characterized by the ratio of their rates measured separately [relations (12) and (13)], or whether they should be expressed by the rates measured during simultaneous transformation of two compounds which thus compete in adsorption for the free surface of the catalyst [relations (14) and (15)]. How these two definitions of reactivity may differ from one another will be shown later by the example of competitive hydrogenation of alkylphenols (Section IV.E, p. 42). This may also be demonstrated by the classical example of hydrogenation of aromatic hydrocarbons on Raney nickel (48). In this case, the constants obtained by separate measurements of reaction rates for individual compounds lead to the reactivity order which is different from the order found on the basis of factor S, determined by the method of competitive reactions (Table II). Other examples of the change of reactivity, which may even result in the selective reaction of a strongly adsorbed reactant in competitive reactions (49, 50) have already been discussed (see p. 12). 

Raney-nickel catalysts - The effect of NH3 and base modifier on the activity and selectivity of RNi-C catalyst is shown in Table 1. The addition of NH3 significantly decreased the pseudo first-order rate constants, the conversion of RCN and the selectivity to R2NH. Upon increasing the reaction time (t) on... 

The catalysts used in these experiments included those already employed in the infrared measurements in addition to some others. The results are presented in Tables VI and VII along with some older measurements on Raney-nickel and a nickel-on-kieselguhr catalyst. These older measurements are slightly less accurate because the cyclohexane content of the reaction product was determined by mass spectrometry. The surface area of catalyst E was not determined hence, its reaction rates per unit of surface area could not be calculated. 

Chiral amines were always considered important targets for synthetic chemists, and attempts to prepare such compounds enantioselectively date back to quite early times. Selected milestones for the development of enantioselective catalysts for the reduction of C = N functions are listed in Table 34.1. At first, only heterogeneous hydrogenation catalysts such as Pt black, Pd/C or Raney nickel were applied. These were modified with chiral auxiliaries in the hope that some induction - that is, transfer of chirality from the auxiliary to the reactant -might occur. These efforts were undertaken on a purely empirical basis, without any understanding of what might influence the desired selectivity. Only very few substrate types were studied and, not surprisingly, enantioselectivities were... 

Many catalysts, certainly those most widely used such as platinum, palladium, rhodium, ruthenium, nickel, Raney nickel, and catalysts for homogeneous hydrogenation such as tris(triphenylphosphine)rhodium chloride are now commercially available. Procedures for the preparation of catalysts are therefore described in detail only in the cases of the less common ones (p. 205). Guidelines for use and dosage of catalysts are given in Table 1. 

A related method for the synthesis of aldehydes from nitriles has also been studied.8 This method, which has been found to be extremely effective for the reduction of hindered nitriles to aldehydes, uses moist, preformed Raney nickel catalyst in formic acid. Compounds synthesized by this method are illustrated in Table II. 

Naphthol has been reduced to 1-decalol using platinum,5 Raney nickel,6 and Raney copper.7 The reactions catalyzed by nickel and copper required elevated temperatures and pressure. The present procedure allows the preparation of substantial quantities of 1-decalol under much more convenient conditions and shorter reaction times. Previous methods5-7 require costly catalysts or high-pressure equipment and frequently result in a high degree of hydrogenolysis. The submitters have found that the present method is applicable to a wide variety of aromatic nuclei, some of which are listed in Table I. 

Table 3 Isomerization of ds-4-aminocyclohexane carboxylic acid on Raney nickel catalyst (Metalyst). Effect of the amount of catalyst, temperature and H2 pressure...

In the catalytic isomerization of pure cis isomer the yield of the trans isomer estimated from H-NMR results are listed in Table 4. Results obtained on Raney nickel catalyst (B 113 W, nickel content 90%) indicate that the yield of the trans isomer significantly increases with the temperature and also affected by the hydrogen pressure (compare experiment No. 1 - No. 9 in Table 4). However the highest yield of the trans isomer was reached at 1 MPa H2 pressure (see experiments No. 10 - No. 13 in Table 4). Upon increasing the amount of catalyst from 100 to 150 mg the yield of the trans isomer slightly increased. 

Reduction of alkylated aldehyde-derived SAMP-hydrazones, followed by reductive N —N cleavage of the resulting hydrazines with Raney nickel, furnishes /(-substituted primary amines in good chemical yields and without racemization in 94-99% ee (see Table 5)31. 

Table 7 Desulfurization of Thietane Derivatives with Raney Nickel...

Only a limited number of examples are known of applications of thietanes in organic synthesis. Prominent among these examples would be electrophilic ring opening reactions leading to polyfunctional sulfur compounds (33)-(37), utilization of 3-thietanones (55) and metal complexes (87) derived therefrom as oxyallyl zwitterion equivalents in cycloaddition reactions, synthesis of dipeptide (63) with a /3-thiolactone, Raney nickel desulfurization of thietanes (e.g. 120 cf. Table 7) as a route to gem-dimethyl compounds, and desulfurization of thietanes (e.g. 17) in the synthesis of cyclopropanes (also see Table 7). 

---