Competitive -Cycloaddition versus -Hydrogen Sigmatropy in a Cycloheptatriene. An Efficient Route to 3-Azatricyclo4,10>undeca-5,8-diene

Article abstract of DOI:10.1021/jo00247a001

Thermal rearrangements of N-acyl-7-aminocyclohepta-1,3,5-trienes 7b-e in octane or xylene provide <4+2>-cycloaddition products 8b-e and <1,5>-hydrogen sigmatropic rearrangement products 9b-e.The relative rate of formation for 8e/9e is 1.5 in refluxing octane.At a higher reaction temperature in xylene and longer reaction times, 7b afforded a second hydrogen-shift product 10b.No thermal <3,3>-carbon shift products were observed from N-allyl cycloheptatrienes 9b-e or 10b in octane or xylene.The thermal behavior of 7b-e can be contrasted with that of O-allyl cyclohepta-1,3,5-triene 1.