82833-69-0Relevant articles and documents
Photolysis and Thermolysis of Phenyl Azide in Acetic Acid
Takeuchi, Hiroshi,Koyama, Kikuhiko
, p. 202 - 204 (1981)
The photolysis and thermolysis of phenyl azide in acetic acid gave 2,3-dihydro-1H-azepin-2-one via 1-azacyclohepta-1,2,4,6-tetraene, and ring-disubstituted products via a resonance-stabilized ion formed by attack of singlet phenylnitrene on acetic acid.
Photolysis and Thermolysis of Phenyl Azide in Acetic Acid. Trapping of 1-Azacyclohepta-1,2,4,6-tetraene and Nucleophilic Aromatic Substitution
Takeuchi, Hiroshi,Koyama, Kikuhiko
, p. 1269 - 1274 (2007/10/02)
Photolysis and thermolysis of phenyl azide in acetic acid yielded 1H-azepin-2(3H)-one (4), 2-methylbenzoxazole (15), 2- and 4- acetamidophenyl acetates (16) and (12), 2- and 4- acetamidophenols (14) and (13), acetanilide, and azobenzene.Addition of ethanol to the system caused a linear decrease in the yield of (4) and a more remarkable decrease in total yield for the para-products than that for the ortho-products to give 2- and 4- acetamidophenyl ethyl ethers (9) and (8).Photolysis of the azide in ethanol in the presence of phenol afforded 2-phenoxy-3H-azepine (5) and aniline, but no 2- and 4-phenetidines.The yield of compounds (4) and (12)-(16) was independent of the presence of penta-1,3-diene(0.01 M), and somewhat decreased by an addition of bromobenzene.The rate of decomposition of azide in acetic acid was not accelerated as compared with that in 1,4-dioxan, and the activation parameters varied little in the two solvents.The results suggest that 1-azacyclohepta-1,2,4,6-tetraene (1) formed via singlet phenylnitrene or via singlet excited phenyl azide is trapped by acetic acid or phenol to give (4) or (5), and that a resonance-stabilized ion (3) neighbouring acetate anion is formed by an attack of the singlet nitrene on acetic acid to give aromatic nucleophilic substitution.
