70593-66-7Relevant articles and documents
Oxidative Cyclizations. VIII. Mechanisms of Oxidation of ortho-Substituted Benzenamines and Improved Cyclizations by Bis(acetato-O)phenyliodine
Dyall, Leonard K.,Harvey, Jacqueline J.,Jarman, Tony B.
, p. 371 - 384 (1992)
Published reports describe the oxidative cyclization of suitable ortho-substituted arenamines to form such products as 2,1-benzisoxazoles, benzofurazan 1-oxides and benzotriazoles, by using bis(acetato-O)phenyliodine at room temperature.However, the reactions are often inconveniently slow.We now report attempts to achieve short reaction times with more powerful iodine(III) oxidants.These often failed to give cyclic products, but the results enable us to argue that the reaction competing with cyclization involves the arenaminyl cation ArN+H.When such cations are predicted to be relatively unstable, the parent arenamine can be rapidly cyclized in high yield by oxidation with bis(acetato-O)phenyliodine in boiling benzene.
Pyrolysis of Aryl Azides. V. Characterization of Phenylazo, Benzoyl and Formyl as Neighbouring Groups
Dickson, Noel J.,Dyall, Leonard K.
, p. 91 - 99 (2007/10/02)
The enhancements of thermolysis rate of azidobenzene produced by ortho phenylazo, benzoyl and formyl substituents are 21180, 70.0 and 22.8 at 393.2 K (decalin solutions).The same ortho substituents produce much smaller enhancements (169, 8.56 and 10.7 respectively) in the pyrolysis rate of 1-azido-2,4-dibromobenzene.These results are interpreted as steric effects on an electrocyclic thermolysis mechanism, and are not consistent with the alternative pathway of intramolecular 1,3-dipolar addition which continues to be advocated by Hall and Dolan.
