Hydrogenation of nitriles

Complexes of ruthenium and rhodium have been identified that catalyze the hydrogenation of nitriles under mild conditions with very good selectivities to the primary amine. In particular, Otsuka and co-workers showed that [RhHfP Prj) ] catalyzes the hydrogenation of a variety of nitriles to amines under mild conditions (1 atm pressure, 20 °C, 2 h Equation 15.119). The reaction is reversible primary amines undergo dehydrogenation in the presence of [Rl iHfP Prj) ] to form nitriles (Equation 15.120). Iridium catalysts for the dehydrogenation of nitriles have also been reported recently.  

Hydrogenation with achiral catalysts has been widely used and is likely to experience increased development in the coming years. The concept of directed hydrogenation led to an increase in the ability to control diastereoselectivity, which is often as important to control in synthetic sequences as enantioselectivity. Furthermore, the drive for cleaner chemical processes is likely to make the hydrogenation of functional groups such as esters, adds, nitriles, and nitro groups important for the production of achiral products without the use of main group metal hydrides. 

Tolman, C. A. Faller, J. W. In Homogeneous Catalysis with Metal Phosphine Complexes Pignolet, L., Ed. Plenum Press New York, 1983 p 13. 

Campbell, M. L In Ullmann s Encyclopedia of Industrial Chemistry (Online) TOley-VCH Weinheim, 2002 p DOt 10.1002/14356007.al2 629. 

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As a class of compounds, nitriles have broad commercial utility that includes their use as solvents, feedstocks, pharmaceuticals, catalysts, and pesticides. The versatile reactivity of organonitnles arises both from the reactivity of the C=N bond, and from the abiHty of the cyano substituent to activate adjacent bonds, especially C—H bonds. Nitriles can be used to prepare amines, amides, amidines, carboxyHc acids and esters, aldehydes, ketones, large-ring cycHc ketones, imines, heterocycles, orthoesters, and other compounds. Some of the more common transformations involve hydrolysis or alcoholysis to produce amides, acids and esters, and hydrogenation to produce amines, which are intermediates for the production of polyurethanes and polyamides. An extensive review on hydrogenation of nitriles has been recendy pubHshed (10). 

Adiponitrile undergoes the typical nitrile reactions, eg, hydrolysis to adipamide and adipic acid and alcoholysis to substituted amides and esters. The most important industrial reaction is the catalytic hydrogenation to hexamethylenediarnine. A variety of catalysts are used for this reduction including cobalt—nickel (46), cobalt manganese (47), cobalt boride (48), copper cobalt (49), and iron oxide (50), and Raney nickel (51). An extensive review on the hydrogenation of nitriles has been recendy pubUshed (10). 

The principal iadustrial production route used to prepare fatty amines is the hydrogenation of nitriles, a route which has been used since the 1940s. Commercial preparation of fatty amines from fatty alcohols is a fairly new process, created around 1970, which utilizes petrochemical technology, Ziegler or Oxo processes, and feedstock. 

Solvents influence the hydrogenation of oximes in much the same way as they do hydrogenation of nitriles. Acidic solvents prevent the formation of secondary amines through salt formation with the initially formed primary amine. A variety of acids have been used for this purpose (66 ), but acids cannot always be used interchangeably (43). Primary amines can be trapped also as amides by use of an anhydride solvent (2,/5,57). Ammonia prevents secondary amine formation through competition of ammonia with the primary amine in reaction with the intermediate imine. Unless the ammonia is anhydrous hydrolysis reactions may also occur. 

This chapter mainly aims at describing the various methods and processes developed for hydrogenation of nitrile rubber. The characterization, physical properties, and application of hydrogenated nitrile rubber are also discussed. Another small section on hydroformylation of nitrile rubber has been included. 

Table 3 Heterogeneous Catalytic Hydrogenation of Nitrile Rubber...

It can be summarized from the available data in Table 3 that supported palladium catalysts selectively hydrogenated carbon-carbon double bonds in the presence of the nitrile group in NBR. However, there is no detailed fundamental study on heterogeneous catalytic hydrogenation of nitrile rubber in the literature that can provide an insight into the reaction. The available information is limited since most of the literature is patented. 

Table 6 Hydrogenation of Nitrile Rubber in Presence of Palladium Catalyst...

The available studies indicate that diimide has been used as a reducing agent for the preparation of HNBR. It has been used mainly as an alternative for hydrogenation of nitrile rubber latex. The use of diimide to hydrogenate low-molecular weight olefines is well known in the organic literature [93]. Diimide can be conveniently generated in situ by thermal treatment of solutions of p-tolu-enesulfonyl hydrazide or oxidation of hydrazine. 

Drawing heavily from prior experience in hydrogenation of nitriles (7-10) and of ADN to ACN and/or HMD (11), in particular, we decided to restrict the scope of this investigation to Raney Ni 2400 and Raney Co 2724 catalysts. The hydrogenation reactions were initially carried out in a semi-batch reactor, followed by continuous stirred tank reactor to study the activity, selectivity, and life of the catalyst. 

While the desired product of the hydrogenation of nitriles is often the primary amines, the proportion of primaiy/secondary/tertiary amines in the product is strongly affected by the nature of metal. In the hydrogenation of nitriles on Group VIII metals, the selectivity of primary amine decreases in the order Co>Ni>Ru>Rh>Pd>Pt [1], The difference between Group VIII metals in selectivity to primary amine is explained by the difference in the electronic... 

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