Chemistry: molecular biology and microbiology – Micro-organism – tissue cell culture or enzyme using process... – Preparing heterocyclic carbon compound having only o – n – s,...
Patent
1996-05-17
1999-01-12
Lilling, Herbert J.
Chemistry: molecular biology and microbiology
Micro-organism, tissue cell culture or enzyme using process...
Preparing heterocyclic carbon compound having only o, n, s,...
435122, 435232, 4352521, 435227, C12P 1710, C12P 1712
Patent
active
058587365
ABSTRACT:
A process for the preparation of five-membered or six-membered ring lactams from aliphatic .alpha.,.omega.-dinitriles has been developed. In the process an aliphatic .alpha.,.omega.-dinitrile is first converted to an ammonium salt of an .omega.-nitrilecarboxylic acid in aqueous solution using a catalyst having an aliphatic nitrilase (EC 3.5.5.7) activity, or a combination of nitrile hydratase (EC 4.2.1.84) and amidase (EC 3.5.1.4) activities. The aimnonium salt of the .omega.-nitrilecarboxylic acid is then converted directly to the corresponding lactam by hydrogenation in aqueous solution, without isolation of the intermediate .omega.-nitrilecarboxylic acid or .omega.-monocarboxylic acid. When the aliphatic .alpha.,.omega.-dinitrile is also unsymmetrically substituted at the .alpha.-carbon atom, the nitrilase produces the .omega.-nitrilecarboxylic acid ammonium salt resulting from hydrolysis of the .omega.-nitrile group with greater than 98% regioselectivity, thereby producing only one of the two possible lactam products during the subsequent hydrogenation. A heat-treatment process to select for desirable regioselective nitrilase or nitrile hydratase activities while destroying undesirable activities is also provided.
REFERENCES:
patent: 4329498 (1982-05-01), Demmin et al.
patent: 4599199 (1986-07-01), Fuchs
patent: 4625023 (1986-11-01), Mares et al.
patent: 4730040 (1988-03-01), Vagt et al.
patent: 5449780 (1995-09-01), Kosak
Bargar et al., Rapid and Efficient Method for Dehydration of Primary Amides to Nitriles, Chemical Abstracts, 94, No. 3, Abstract No. 14593, Jan. 19, 1981.
M. Cushman et al., A Synthesis of 2-alkyl and 2-benzyl Substituted Acrylonitriles from 2-alkyl and 2-benzylidenecyanoacetate Esters under Mild Conditions, Chemical Abstracts, 113, No. 25, Abstract No. 230773, Dec. 17, 1990.
J. Lange et al., Direct Pyradazine Ring Synthesis from Beta-cyano Esters, Chemical Abstracts, 119, No. 21, Abstract No. 225898, Nov. 22, 1993.
Kobayashi, et al., Tetrahedron, vol. 46, 5587-5590 (1990).
Kobayashi, et al., J. Bacteriology, vol. 172, 4807-4815 (1990).
Levy-Schil, S., et al., Gene vol. 161, 15-20 (1995).
Gradley, M.L. and Knowles, C.J., Biotechnology Lett., vol. 16, 41-46 (1994).
Bengis-Garber, C. and Gutman, A.L., Appl. Microbiol. Biotechnol., vol. 32, 11-16 (1989).
Honicke-Schmidt, P. and Schneider, M.P., J. Chem. Soc., Chem. Commun., 648-650 (1990).
Blakely, A.J., et al., FEMS Microbiology Lett., vol. 129, 57-62 (1995).
Yamada, H., et al. J.Ferment. Technol., vol. 58, 495-500 (1980).
Yamamoto, K., et al. J. Ferment, Bioengineering, vol. 73, 125-129 (1992).
Moreau, J.L., et al. Biocatalysis, vol. 10; 325-340 (1994).
Kerridge, A., et al., Biorg. Medicinal Chem., vol. 2, 447-455 (1994).
Asano, Y., et al., Agric. Biol. Chem., vol. 44, 2497-2498 (1980).
Taylor, E.C., et al., J. Am. Chem. Soc., vol. 87, 1984-1990 (1965).
Taylor, E.C., et al., J. Am. Chem. Soc., vol. 87, 1990-1995 (1965).
Blade-Font, A., Tetrahedron Letters, vol. 21, 2443-2446 (1980).
Frank, R.L., et al., Org. Sytheses, Coll. vol. 3, 328-329 (1954).
Zienty, F.B. and Steahly, G.W., J. Am. Chem. Soc., vol. 69, 715-716 (1947).
Di Cosimo Robert
Fallon Robert Donald
Gavagan John Edward
Herkes Frank Edward
E. I. Du Pont de Nemours and Company
Lilling Herbert J.
LandOfFree
Preparation of lactams from aliphatic .alpha.,.omega.-dinitriles does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Preparation of lactams from aliphatic .alpha.,.omega.-dinitriles, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Preparation of lactams from aliphatic .alpha.,.omega.-dinitriles will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-1514397