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 Boyland-Sims oxidation
Boyland–Sims oxidation
Named after Eric Boyland
Peter Sims
Reaction type Organic redox reaction
Identifiers
RSC ontology ID RXNO:0000181

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 the ortho- sulfate (5), which then hydrolyses to form the ortho-hydroxyl aniline.

The mechanism of the Boyland-Sims oxidation

See also

References
  1. Boyland, E.; Manson, D.; Sims, Peter (1953). "729. The preparation of o-aminophenyl sulphates". Journal of the Chemical Society (Resumed): 3623. doi:10.1039/jr9530003623.
  2. Boyland, E.; Sims, Peter (1954). "The oxidation of some aromatic amines with persulphate". Journal of the Chemical Society (Resumed): 980. doi:10.1039/jr9540000980.
  3. Behrman, E. J. (1988). "The Persulfate Oxidation of Phenols and Arylamines (The Elbs and the Boyland-Sims Oxidations)". Org. React. 35: 421–511. doi:10.1002/0471264180.or035.02. ISBN 0471264180.
  4. Boyland, E.; Sims, P.; Williams, D. C. (1956). "The oxidation of tryptophan and some related compounds with persulphate". Biochem. J. 62 (4): 546–50. doi:10.1042/bj0620546. PMC 1215958. PMID 13315210.
  5. Behrman, E. J. (1992). "The ortho-para ratio and the intermediate in the persulfate oxidation of aromatic amines (the Boyland-Sims oxidation)". J. Org. Chem. 57 (8): 2266–2270. doi:10.1021/jo00034a016.

Further reading
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