Possibility of the Intarmolecularity of Triazene Rearrangement

Article abstract of DOI:10.1246/bcsj.54.2853

The mechanism for the ortho-rearrangement of diaryltriazenes still remains equivocal.An interesting result suggesting an intramolecular nature of the triazene rearrangement was obtained on the basis of the effect of concentration of added N,N-dimethylaniline in the ortho-rearrangement of 1,3-bis(4-methylphenyl)triazene (1).The ortho/para ratio for the rearrangement of 1,3-diphenyltriazene (4) tends to increase with an increase of the viscosity.The results are discussed on the basis of increasing nucleophilicity of free amine by H-bonding with dimethylaniline and favoring ortho-migratrion with viscosity, respectively.