Ketone To amide

WILLGERODT- KINDLER Rearrangement Rearrangement ot ketones to amides by heating with sulfur and ammonia or amines. 

The reaction of hydrazoic acids converts ketones to amides. 

Conversion of ketones to amides using HN3 (hydrazoic acid). 

Conversion of oximes derived from cyclobutyl ketones to amides represents the classic Beckmann rearrangement. One example of this reaction is the formation of optically active 7,7-dimethyl-2-azabicyclo[4.1.1]octan-3-one (1) from 6,6-dimethylbicyclo[3.1.1]heptan-2-one oxime, which is readily derived from /3-pinene.40... 

The conversion of ketones to amides by the Schmidt reaction has been mentioned elsewhere (method 362). Since the hydrolysis of the amides so obtained proceeds readily, the two steps provide a convenient synthesis of amines from ketones. The yields are often higher than those obtained from the Beckmann rearrangement with subsequent hydrolysis (method... 

Chandrasekhar, S., Gopaiaiah, K. 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. Tetrahedron Lett. 2003,44, 7437-7439. 

J Direct conversion of ketones to amides 5.222.4 Misceiianeous reactions... 

When the Schmidt reaction is applied to a,j8-unsaturated carboxylic acids, the product of the rearrangement is an enamine, which hydrolyzes to the corresponding ketone. Entry 3 in Scheme 8.9 is an example of this type of reaction. Reaction with hydrazoic acid converts ketones to amides, and is thus an alternative method for effecting the same transformation as the Beckmann rearrangement. A drawback of... 

Conversion of aryl alkyl ketones to amides and/or the ammonium salts of the corresponding acids by aqueous ammonium polysulfide or by sulfur and a primary or secondary amine ... 

The direct aldol reaction of carboxylic acid derivatives and aldehydes (or ketones) is very difficult. Recently, Kobayashi and co-workers (146) extended the ketones to amides as suitable candidates successfully for the direct aldol reaction. The screening of metal sources revealed that Ba(0-tBu)2 was the better catalyst than Sr(0-iPr)2, Ca(0-iPr)2, or Mg(0-iPr)2, whereas rare earth metals (eg, La(0-iPrls) are catalytically inactive in the presence of p-methoxyphenol. In this aldol reaction, barium enolate formed in situ from barium alkoxide and acylamide and... 

The Schmidt reaction of carboxylic acids with hydrazoic acid has the advantage over Curtius rearrangement that it is only one step from the acid to the amine, but the conditions are more drastic (usually sulphuric acid plus sodium azide). Under these harsh conditions, the isocyanate intermediate is rarely isolated. For these reasons, the Curtius rearrangement is frequently employed to convert acids to amines. The Schmidt reaction of ketones with hydrazoic acid is a powerful method for the synthesis of amides and lactams. TTiis process is somewhat related to the Beckmann rearrangement of oximes however, the Schmidt reaction is more succinct, allowing the conversion of ketones to amides in a single operation. Considering its widespread... 

Scheme 3.12 Copper catalyzed transformation of aryl alkyl ketones to amides with NaNa...

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