2.4- Dinitrobenzenesulfonamides 2,4-dinitrobenzenesulfonyl chloride

The a- and /3-cyclodextrins have been found to accelerate the Smiles rearrangement of 4-nitrophenyl salicylate. The reaction of 2,4-dinitrobenzenesulfonamide with acyl chlorides in the presence of excess triethylamine has been found to produce the corresponding nitrile in good yield. Mechanistic studies have indicated that the reaction proceeds via a Smiles rearrangement of the initially formed iV-(2,4-dinitrobenzenesulfonyl)amide to form the nitrile, 2,4-dinitrophenol, and sulfur dioxide (see Scheme 12). l-Chloro-3-fluorophenothiazines have been prepared by Smiles rearrangement of 3-chloro-5-fluoro-2-formamido-2 -nitrophenyl sulfides in alcoholic... 

An interesting version of the rearrangement [76] is presented in Scheme 51. The base-induced reaction of 2,4-dinitrobenzenesulfonamide with various acyl chlorides provides AT-(2,4-dinitrobenzenesulfonyl) acylamide derivatives 159 that rearrange and fragment in situ to afford the respective nitriles 160. The reaction has been used for derivatization of complex crown ethers. 

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See also in sourсe #XX -- [ ]

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