Copper-chromite nitriles

Hydrolysis of primary amides cataly2ed by acids or bases is very slow. Even more difficult is the hydrolysis of substituted amides. The dehydration of amides which produces nitriles is of great commercial value (8). Amides can also be reduced to primary and secondary amines using copper chromite catalyst (9) or metallic hydrides (10). The generally unreactive nature of amides makes them attractive for many appHcations where harsh conditions exist, such as high temperature, pressure, and physical shear. 

Previous works have shown that copper catalysts are selective in the dehydrogenation of esters (5-7), in the hydrolysis of nitrile (8), in the selective hydrogenation of nitrile or in alcohol amination (10). The catalyst systems such as copper chromite are often used for the preparation of substituted amines. These solids, however, are very sensitive to the presence of water and ammonia (formation of copper nitrides... 

In the first, a previously dried mixture of butadiene and hydrochloric acid is sent to the reactor with hydrogen cyanide entrained by nitrogen. The butadiene/HCN/N HC1 molar ratio is 1/1/1/0.2. Residence time remains less than one hour, at between 210 and 220 C, in the presence of copper chromite and magnesium as catalyst. A mixture of 3- and 4-pentene nitriles (88 per cent) and branched 3-methyl 1- and 2-butene nitriles (12 per cent) is obtained with virtually total once-througb conversion ... 

Copper-chromite type catalysts supported by alumina or graphite and promoted with barium were used for the one step synthesis of tertiary fatty amines (R2NCH3 or RN(CH3)2) from nitrile, methanol and hydrogen. The surface composition of the catalysts was studied by XPS and by adsorption experiments. A correlation was found between the selectivity and the presence of a well-dispersed CUC1O2 phase, stabilized with barium. Moreover the elements influencing the stability of the copper catalysts were also studied and we remarked the effect of the promoter or/and of the support on the variation of the copper surface area in the presence of water or ammonia. These modifications were examined in relation with the change of the catalytic properties with time-on-stream. 

DL-Serine is synthesized in 51% over-all yield by Redemann and Icke s (661) modification of the method of Dunn et al. (212). Ethoxy-acetaldehyde (A) is prepared in aqueous solution by oxidizing ethylene glycol monoethyl ether (ethyl cellosolve) with copper chromite catalyst at 310-330°C. DL-Serine is prepared by reaction of NaCN, NH Cl and NH, in methanol with (A) and hydrolysis of the intermediate ethoxy nitrile with HBr. Other methods for the preparation of ethoxyacet-aldehyde have been described by the authors referred to by Dunn (203, p. 21) and by other workers (196-198, 412, 226). This synthesis... 

---