Pyrolysis of Aryl Azides. XIII. Conformational Effects on the Ability of Carbonyl as a Neighbouring Group
Australian Journal of Chemistry
49(11) 1197 - 1202
Published: 1996
Abstract
Our previous claim, that locking an ortho carbonyl group into a favourable conformation causes very large increases in the rate of thermolysis of aryl azides , has been reexamined. In 8-azido-5-methoxy-1-tetralone the rate advantage over an azide with a rotatable ortho acetyl group is estimated to be only 18-fold. Nevertheless, this factor is large enough to invalidate attempts to explain relative neighbouring group abilities on simple electronic effects alone. The very large rate increases we reported previously for 1-azidoacridin-g(10H)-one and 1-azidoanthracene-9,10-dione are partly due to favourable retention of conjugation in the transition state.
https://doi.org/10.1071/CH9961197
© CSIRO 1996