Boyland–Sims oxidation

The Boyland-Sims oxidation is the chemical reaction of anilines with alkaline potassium persulfate, which after hydrolysis forms ortho-hydroxyl anilines.[1][2][3]

The ortho-isomer is formed predominantly. However, the para-sulfate is formed in small amounts with certain anilines.[4]

Reaction mechanism

Behrman has shown that the first intermediate in the Boyland-Sims oxidation is the formation of an arylhydroxylamine-O-sulfate (2).[5] Rearrangement of this zwitterionic intermediate forms both the ortho- and para-amino aryl sulfates (3a and 3b).

References

  1. ^ Boyland, E. et al. J. Chem. Soc. 1953, 3623.
  2. ^ Boyland, E.; Sims, P. J. Chem. Soc. 1954, 980.
  3. ^ Behrman, E. J. Org. React. 1988, 35, 421-511. (Review)
  4. ^ Boyland, E.; Sims, P.; Williams, D. C. Biochem. J. 1956, 62, 546.
  5. ^ Behrman, E. J. J. Org. Chem. 1992, 57, 2266. (doi:10.1021/jo00034a016)

6. E. J. Behrman, Chemical Educator, 15, 392-393(2010).

See also