Boyland–Sims oxidation
{{Reactionbox
|Name = Boyland–Sims oxidation
|Type = Organic redox reaction
|NamedAfter = Eric Boyland
Peter Sims
|Section3 = {{Reactionbox Identifiers
| RSC_ontology_id = 0000181
}}
}}
The Boyland–Sims oxidation is the chemical reaction of anilines with alkaline potassium persulfate, which after hydrolysis forms ortho-hydroxyl anilines.{{cite journal|last1=Boyland|first1=E.|last2=Manson|first2=D.|last3=Sims|first3=Peter|title=729. The preparation of o-aminophenyl sulphates|journal=Journal of the Chemical Society (Resumed)|date=1953|pages=3623|doi=10.1039/jr9530003623}}{{cite journal|last1=Boyland|first1=E.|last2=Sims|first2=Peter|title=The oxidation of some aromatic amines with persulphate|journal=Journal of the Chemical Society (Resumed)|date=1954|pages=980|doi=10.1039/jr9540000980}}{{cite journal|author=Behrman, E. J. |journal=Org. React.|year=1988|volume=35|pages= 421–511|doi=10.1002/0471264180.or035.02|title=The Persulfate Oxidation of Phenols and Arylamines (The Elbs and the Boyland-Sims Oxidations)|isbn=0471264180}} The reaction is generally performed in water at room temperatures or below, using equimolar quantities of reagents.
Image:Boyland-Sims Oxidation Scheme.png
The ortho-isomer is formed predominantly. However, the para-sulfate is formed in small amounts with certain anilines.{{cite journal|author1=Boyland, E. |author2=Sims, P. |author3=Williams, D. C. |journal=Biochem. J.|year=1956|volume=62|pages= 546–50|pmid=13315210|title=The oxidation of tryptophan and some related compounds with persulphate|issue=4|doi=10.1042/bj0620546 |pmc=1215958}}
Scope and mechanism
The reaction is disadvantaged by moderate to low chemical yields, but is simple to perform and uses mild conditions. Some competitive oxidation of the nitrogen has been observed.
Behrman has shown that the first intermediate in the Boyland–Sims oxidation is the formation of an arylhydroxylamine-O-sulfate (2).{{cite journal|author=Behrman, E. J. |journal=J. Org. Chem.|year=1992|volume=57|pages= 2266–2270|doi=10.1021/jo00034a016|title=The ortho-para ratio and the intermediate in the persulfate oxidation of aromatic amines (the Boyland-Sims oxidation)|issue=8}} Rearrangement of this zwitterionic intermediate forms the ortho- sulfate (5), which then hydrolyses to form the ortho-hydroxyl aniline.
See also
References
{{Reflist}}
Further reading
- {{cite journal |last=Behrman |first=Edward J. |title=On the Mechanism of the Boyland-Sims Oxidation |journal=Progress in Reaction Kinetics and Mechanism |publisher=Science Reviews 2000 Ltd |volume=39 |issue=3 |year=2014 |pages=308–310 |doi=10.3184/146867814X14062204626705 |s2cid=101779652 |doi-access=free }}
{{Organic reactions}}
Category:Organic oxidation reactions
{{DEFAULTSORT:Boyland-Sims oxidation}}