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The Isoimide-Imide Rearrangement

DOI: 10.1039/P29800000121

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 121 - 126 (1980)

Update date:2022-07-29

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Authors:

Brady, KieranBrady, Kieran

Hegarty, Anthony F.Hegarty, Anthony F.

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Article abstract of DOI:10.1039/P29800000121

When imidoyl chlorides (8) are solvolysed in the pH range 3-13 in aqueous dioxan in the presence of acetate or benzoate ions, the isoimides (10) are formed in situ.These isoimides undergo acid (pH <4.5) and base (pH >11.5) catalysed acyl transfer to the solvent, giving the amides (12).But at intermediate pH (6-11) rearrangement to the N-acyl form (11) ( the Mumm rearrangement) alone occurs.The specific rate of this O <*> N acyl group migration is pH independent and shows a low solvent effect (m 0.175).Substituents attached to carbon or nitrogen have the same effect (ρ -0.84).When the migrating group R is varied a non-linear Hammet plot is observed, with ρ +0.60 for electron-withdrawing and +1.65 for electron-donating substituents.The changeover point is a function of the migrating terminus varying from R=Ph (when Y=H) to R=p-tolyl (when Y=p-NO2).Rate-determining O <*> N acyl transfer is suggested in all cases, but this is preceded by an equilibrium which favours the Z form (10a) when R is electron donating.

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