Abstract
THE use of Raney metal catalysts for the reductive methylation of amines with formaldehyde and hydrogen is well known1. We wish to report that this reaction is also catalysed by vitamin B12r in vitro, and thus is potentially of biochemical importance. For example, a 1 : 1 mixture of aniline and formaldehyde in methanol and water absorbs hydrogen at room temperature and 1 atm. of pressure if a solution of vitamin B12r is added. N-methylaniline is formed in significant yield (1). Bis-dimethylglyoximato cobalt (II) complexes such as Co(D2H2)·2H2O (‘Diaquocobaloxime (II)’)2 (D = dianion of dimethylglyoxime) which may be regarded as simple models of vitamin B12r were similarly found to be cataly-tically active. Aniline could also be substituted by N-methylaniline which was converted to N,N-dimethylaniline under analogous conditions. In order to isolate or detect intermediates of this reaction, the reductive alkylation of aniline was also carried out using stoichio-metric amounts of the react ants. When 0.4 moles of aniline and 0.25 moles of formaldehyde (in 40 per cent aqueous solution) were added to a suspension of 0.20 moles of Co(D2H2)·2H2O in 1 l. of methanol under 1 atm. of hydrogen, 0.1 mole of hydrogen was rapidly absorbed on stirring and the cobaloxime dissolved completely. On addition of 1 l. of water a crystalline complex precipitated in a yield of 94 per cent, which was dissolved in methanol and reprecipitated by adding water. After drying at 0.1 mm of mercury 25° C it analysed for C21H29N604CoH2O, corresponding to
Similar content being viewed by others
Article PDF
References
Mignonac, G., C. R. Acad. Sci., Paris, 172, 223 (1921).
Schrauzer, G. N., and Windgassen, R. J., Chem. Ber., 99, 602 (1966).
Schrauzer, G. N., and Windgassen, R. J., J. Amer. Chem. Soc., 88, 3738 (1966).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
SCHRAUZER, G., WINDGASSEN, R. Synthesis of Methyl Groups catalysed by Vitamin B12r in vitro. Nature 214, 492 (1967). https://doi.org/10.1038/214492a0
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1038/214492a0
This article is cited by
-
Reductive amination of carbonyl compounds in the presence of cobalt and rhodium complexes
Transition Metal Chemistry (1980)
-
Reductive amination of carbonyl compounds in presence of glyoximate complexes of cobalt and rhodium
Bulletin of the Academy of Sciences of the USSR Division of Chemical Science (1978)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.