Search for a nonelectrocyclic cyclization of nitrosostyrene: Rearrangements of Michael adducts from DMAD and $alpha$-dialkylamino oximes

The aza-Claisen rearrangement product of the Michael adducts 2 from $alpha$-dialkylaminoacetophenone oximes and DMAD underwent fragmentation to give dialkylaminomaleate, and benzonitrile at reflux in acetonitrile. The fragmentation was assumed to proceed through an unstable 4H-1,2-oxazete 6. The same reaction performed at room temperature, in addition to the nitrile and maleate, gave the corresponding 2-(2-dialkylamino-1-phenylethylideneaminooxy)-but-2- enedioic acid dimethyl esters 8 and 9. Compounds 9 isomerized to 8 on heating in acetonitrile.

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