Synthesis of N-Mesyl- and N-Tosyl-o-allylanilines by Amido-Claisen Rearrangement

Abstract

The thermal reaction of N-allyl-N-mesyl- and N-allyl-N-tosyl-substituted anilines in N, N-dibutylaniline containing a small amount of triphenylphosphine gave the Claisen-type rearranged products, o-allylsulfonanilides, in highly pure states and excellent yields, except for N-allyl-N-mesyl-p-dimethylaminoaniline. The rearrangement of the latter was accompanied by the formation of a considerable amount of the deallylated product. Anilides, whose methyl groups exist at the ortho-position, gave no para-rearranged products in contrast to expectation. As to the effect of substituento at para-position, it was found that electron donative groups promote the rearrangement and electron attractive groups retard it.
The effect of sulfonyl group on amino nitrogen atom in the rearrangement was discussed in comparison with the thermal rearrangement of N-allylanilines.