Nitrobenzamides, rearrangement

Product Compositions for the Rearrangement of N-Benzhydryl-N-nitroso-p-nitrobenzamide and the Reaction of DDM with p-Nitrobenzoic Acid... 

Refluxing a solution of l-(p-nitrobenzoyl)-2-benzylaziridine (63) in toluene for 24 hours produced a 91% yield of N-(frflns-cinnamyl)-p-nitrobenzamide (64, equation 10.89). Propose a mechanism for the rearrangement. 

In a transition metal-free, one-pot, and regioselective process, 2-halo-benzenethiols 195 or 3-chloro-5-(trifluoromethyl)pyridine-2-thiol 196 reacted with N-substituted nitrobenzamides 197 to afford a library of dibenzo[I>,/][l,4]thiazepin-ll(10id)-ones 198 or pyridobenzothiazepines 199, respectively, via a Smiles rearrangement (13ACO130). 

Household bleach has been used to carry out the Hofmann rearrangement of 3-nitrobenzamide to 3-nitroaniline, while the Hofmann rearrangement of N(2)-protected glutamine esters of N(2)-protected (25 )-4-[(2,2,2-trifluoroethoxy)carbonylamino]-2-aminobutyric acid esters has been successfully achieved by an electrochemical method using a trifluoroethanol-methyl cyanide solvent system." ... 

With aromatic amides, hydrolysis prior to rearrangement may occur to such an extent that the yield is lowered seriously. Amides like p-nitrobenzamide, having a substituent which withdraws electrons from O... 

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