5-Cyanovaleramide production

S. M. Cooper, J. E. Gavagan, B. Stieglitz, S. M. Hennessey, and R. DiCosimo, 5-Cyanovaleramide production using immobilized Pseudomonas chlororaphis B23, Bioorgan. Med. Chem. 1999, 7, 2239-2245. 

Hann, E.C., Eisenberg, A., Eager, S.K., et al. 1999.5-Cyanovaleramide production using immobilized Pseudomonas chlororaphis B23. Bioorganic and Medicinal Chemistry, 7 2239-45. 

In basic chemicals, nitrile hydratase and nitrilases have been most successful. Acrylamide from acrylonitrile is now a 30 000 tpy process. In a product tree starting from the addition of HCN to butadiene, nicotinamide (from 3-cyanopyridine, for animal feed), 5-cyanovaleramide (from adiponitrile, for herbicide precursor), and 4-cyanopentanoic acid (from 2-methylglutaronitrile, for l,5-dimethyl-2-piperidone solvent) have been developed. Both the enantioselective addition of HCN to aldehydes with oxynitrilase and the dihydroxylation of substituted benzenes with toluene (or naphthalene) dioxygenase, which are far superior to chemical routes, open up pathways to amino and hydroxy acids, amino alcohols, and diamines in the first case and alkaloids, prostaglandins, and carbohydrate derivatives in the second case. 

DuPont has developed another commercial process, based on catalysis by a nitrilase (E.C. 3.5.5.1), to the solvent l,5-dimethyl-2-piperidone (1,5-DMPD) (Xolvone ) with applications in electronics and coatings (Thomas, 2002). The raw material is 2-methylglutaronitrile (MGN), a by-product during the manufacture of adipodinitrile (ADN) for nylon 6,6 discussed in the previous section. Such a raw material situation leads to coupling of nylon-6,6, 5-cyanovaleramide, and l,5-dimethyl-2-piperidone production, a situation that most likely is specific to DuPont and thus not prone to much competition. 

Similarly, DuPont employs a nitrile hydratase (as whole cells of P. chlororaphis B23) to convert adiponitrile to 5-cyanovaleramide, a herbicide intermediate [122]. In the Lonza nitrotinamide (vitamin B6) process [123] the final step (Fig. 1.42) involves the nitrile hydratase (whole cells of Rh. rhodocrous) catalysed hydration of 3-cyanopyridine. Here again the very high product purity is a major advantage as conventional chemical hydrolysis affords a product contaminated with nicotinic acid, which requires expensive purification to meet the specifications of this vitamin. 

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