Multiple decomposition pathways for the oxenium ion precursor O-(4-(4'-methylphenyl)phenyl)-N-methanesulfonylhydroxylamine.
Although O-arylhydroxylamine derivatives have been claimed to be sources of oxenium ions in a large number of studies, it is not clear that the products of these reactions are due to oxenium ions. Previously, we had shown through azide trapping studies that the quinol ester 2a and the title compound 3a generate the oxenium ion 1a. The ester 2a exclusively generates 1a in water and is also a photoprecursor of 1a in water. This is not true of 3a. The oxenium ion pathway accounts for a significant fraction of the reaction of 3a under neutral and acidic pH conditions, but there are three other pathways that account for hydrolysis of 3a. Both 3a and its conjugate base 3a(-) are present in aqueous solution under mild pH conditions. In addition to the oxenium ion product 4a, two other significant products are generated: the phenol 6a and the rearrangement product 8a. Both 4a and 8a are generated exclusively from 3a, whereas 6a is generated from both 3a and 3a(-). Azide trapping studies show that 6a and 8a are not generated from the oxenium ion. The phenol 6a is generated by two paths, one involving an apparent radical intermediate 7a and the other through a stepwise alpha-elimination pathway through 3a(-). The rearrangement product 8a is generated either through a concerted rearrangement or via an ion-pair rearrangement. Photolysis of 3a does not generate 1a. The only products of photolysis of 3a in water are 6a (major) and 8a (minor). The weak O-N bond of 3a is susceptible to homolysis under photolysis conditions, and the radical 7a is observed after laser flash photolysis of 3a. The cation 1a that is observed during laser flash photolysis experiments on 2a cannot be detected during similar experiments on 3a. These results suggest that the previous attribution of oxenium ions as the source of the decomposition products of other O-arylhydroxylamine derivatives in aromatic solvents via thermolysis or acid-catalyzed decomposition may not be correct.
Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, USA.
Yue-Ting
YT
Wang
Michael
M
Novak