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21.1.5.3 Method 3: Schmidt Reaction from Ketones with Hydrazoic Acid

DOI: 10.1055/sos-SD-021-00115

Judd, W. R.; Katz, C. E.; Aubé, J.Science of Synthesis, (200521146.

The Schmidt reaction of ketones with hydrazoic acid (HN3) is a very useful method for the preparation of amides and N-unsubstituted lactams (Scheme 17).[‌36‌‌38‌] The overall transformation results in the formal insertion of an NH group between the carbonyl function and one of the ketone α-carbons. The Schmidt reaction is related in many ways to the Beckmann rearrangement of ketone-derived oximes (see Section 21.1.5.4); however, the former process is more succinct, allowing the direct conversion of the ketone into an amide. The ketone-to-amide conversion with hydrazoic acid requires the presence of an acid catalyst. Concentrated sulfuric acid is most commonly employed for this purpose, although Lewis acids can also be used. Hydrazoic acid is usually prepared in situ by treatment of sodium azide with concentrated sulfuric acid. An alternative method of generating hydrazoic acid involves the reaction of polyphosphoric acid with sodium azide.[‌39‌]

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References