Chandrasekhar, Sosale and Gopalaiah, Kovuru (2003) Ketones to amides via a formal Beckmann rearrangement in 'one pot': a solvent-free reaction promoted by anhydrous oxalic acid. Possible analogy with the Schmidt reaction. In: Tetrahedron Letters, 44 (40). pp. 7437-7439.
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A variety of ketones can be directly converted into the secondary amides expected from a Beckmann rearrangement of the corresponding oximes in high yield, by heating them with hydroxylamine hydrochloride and anhydrous oxalic acid at similar to 100degreesC for 4-12 h. (Aromatic aldehydes afforded mixtures of nitrile and amide.) The transformation is apparently (kinetically) driven by the coupled decomposition of oxalic acid (to CO+CO2) via the fragmentation of an intermediate oxime mono-oxalate. However, an alternative pathway, mechanistically analogous to the Schmidt reaction, is not only equally likely but may well be general for the Beckmann rearrangement.
|Item Type:||Journal Article|
|Additional Information:||Copyright of this article belongs to Elsevier Science.|
|Keywords:||Beckmann rearrangement;ketones;one-pot;oxalic acid; oximes;Schmidt reaction;secondary amides;solvent-free.|
|Department/Centre:||Division of Chemical Sciences > Organic Chemistry|
|Date Deposited:||27 Aug 2009 06:10|
|Last Modified:||19 Sep 2010 04:55|
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