Preparation of lactams from aliphatic .alpha.,.omega.-Dinitiles

Details Preparation of lactams from aliphatic .alpha.,.omega.-Dinitiles Preparation of lactams from aliphatic .alpha.,.omega.-Dinitiles

1998-07-01

1999-07-13

Lilling, Herbert J.

Chemistry: molecular biology and microbiology

Micro-organism, per se ; compositions thereof; proces of...

Bacteria or actinomycetales; media therefor

435121, 435122, 435227, 435232, C12N 120, C12P 1710, C12P 1712

Patent

active

059225890

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 ammonium 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.-aminocarboxylic 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: 4730040 (1988-03-01), Vagt et al.
patent: 5449780 (1995-09-01), Kosak
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).
Bargar et al., Rapid and Efficient Method for Dehydration of Primary Amides to Nitriles, Chemical Abstract, 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-benzylidenecyanacetate 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.

Affiliated with

Also associated with

Rating

Preparation of lactams from aliphatic .alpha.,.omega.-Dinitiles 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.-Dinitiles, 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.-Dinitiles will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2275264