Nitrile reduction

From Wikipedia, the free encyclopedia
Jump to: navigation, search

In nitrile reduction a nitrile is reduced to either an amine or an aldehyde with a suitable chemical reagent.[1]

Hydrogenation[edit]

The largest scale application of nitrile reduction is their hydrogenation. Under idealized conditions, the reaction can afford either the primary amine

Nitrile reduction

Depending on conditions, the intermediate imine can undergo attack by amine products to afford secondary and tertiary amines. Such reactions proceed via the intermediacy of enamines.[2] Commercial applications of this technology is in the production of fatty amines and precursors to nylon.

Non-catalytic routes to amines[edit]

Reagents for the conversion to amines are sodium,[3] lithium aluminium hydride, Raney nickel / hydrogen / [4][5][6] or diborane [7] This organic reaction is one of several nitrogen-hydrogen bond forming reactions.

Noncatalytic routes to aldehydes[edit]

Nitriles can also be reduced to aldehydes. One method is called the Stephen aldehyde synthesis (Tin(II) chloride, hydrochloric acid and hydrolysis of the iminum salt). Aldehydes also form by reduction with hydrogen with in-situ hydrolysis of the imine. Reagents are Raney nickel,[8] lithium aluminium hydride and sodium borohydride.

Electrochemical methods[edit]

Nitriles can also be reduced electrochemically[9][10]

References[edit]

  1. ^ March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York: Wiley, ISBN 0-471-85472-7 
  2. ^ J. Barrault, Y. Pouilloux "Catalytic Amination Reactions Synthesis of fatty amines. Selectivity control in presence of multifunctional catalysts" Catalysis Today 1997 Volume Pages 137–153. doi:10.1016/S0920-5861(97)00006-0
  3. ^ Suter, C. M.; Moffett, Eugene W. (1934). "The Reduction of Aliphatic Cyanides and Oximes with Sodium and n-Butyl Alcohol". Journal of the American Chemical Society 56 (2): 487–487. doi:10.1021/ja01317a502. 
  4. ^ Organic Syntheses, Coll. Vol. 3, p.229 (1955); Vol. 27, p.18 (1947). Link
  5. ^ Organic Syntheses, Coll. Vol. 3, p.358 (1955); Vol. 27, p.33 (1947). Link
  6. ^ Organic Syntheses, Coll. Vol. 3, p.720 (1955); Vol. 23, p.71 (1943). Link
  7. ^ Organic Syntheses, Coll. Vol. 6, p.223 (1988); Vol. 53, p.21 (1973). Link
  8. ^ Organic Syntheses, Coll. Vol. 6, p.631 (1988); Vol. 51, p.20 (1971). Link
  9. ^ V. Krishnan, A. Muthukumaran, H. V. K. Udupa (1979). "The electroreduction of benzyl cyanide on iron and cobalt cathodes". Journal of Applied Electrochemistry 9 (5): 657–659. doi:10.1007/BF00610957. 
  10. ^ V. Krishnan, A. Muthukumaran, H. V. K. Udupa (1983). Process for Electrochemical Preparation of beta phenylethylamine using cobalt black cathode (PDF). Calcutta: India Patent Office.