Oxidative rearrangement of trismethylene‐trinitrobenzene: Nucleophilic aromatic addition VI

Abstract

AbstractTrismethylene‐trinitrobenzene I undergoes ring contraction when oxidised under mild, alkaline conditions to give stereoisomeric hydroxy‐acids IVa and IVb. Both isomers yield the same cyclic ketone V when oxidatively decarboxylated. This ketone can be subjected to a similar rearrangement as I by successive treatment with selenium dioxide and copper sulphate in pyridine, resulting in another pair of stereoisomeric hydroxy‐acids, VIIIa and VIIIb. Both these isomers are oxidatively decarboxylated to the cyclic ketone IX. V and IX, both α‐nitro‐ketones, undergo ring fission with alkali. The resulting carboxylic acids are identical with acids obtained previously from I by different routes.