Boyland-Sims oxidation

The Boyland-Sims oxidation is the chemical reaction of anilines with alkaline potassium persulfate, which after hydrolysis forms "ortho"-hydroxyl anilines.Ref|Boyland1953Ref|Boyland1954Ref|Behrman1988

The "ortho"-isomer is formed predominantly. However, the "para"-sulfate is formed in small amounts with certain anilines.Ref|Boyland1956

Reaction mechanism

Behrman has shown that the first intermediate in the Boyland-Sims oxidation is the formation of an arylhydroxylamine-O-sulfate (2).Ref|Behrman1992 Rearrangement of this zwitterionic intermediate forms both the ortho- and para-amino aryl sulfates (3a and 3b).

References

# Boyland, E. "et al." "J. Chem. Soc." 1953, 3623.
# Boyland, E.; Sims, P. "J. Chem. Soc." 1954, 980.
# Behrman, E. J. "Org. React." 1988, "35", 421-511. (Review)
# Boyland, E.; Sims, P.; Williams, D. C. "Biochem. J." 1956, "62", 546.
# Behrman, E. J. "J. Org. Chem." 1992, "57", 2266. (DOI|10.1021/jo00034a016)

ee also

* Elbs persulfate oxidation