Boyland–Sims Oxidation on:
[Wikipedia]
[Google]
[Amazon]
The Boyland–Sims oxidation is the
chemical reaction
A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and break ...
of aniline
Aniline is an organic compound with the formula C6 H5 NH2. Consisting of a phenyl group attached to an amino group, aniline is the simplest aromatic amine. It is an industrially significant commodity chemical, as well as a versatile start ...
s with alkaline potassium persulfate, which after hydrolysis
Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile.
Biological hydrolysis ...
forms ''ortho''-hydroxyl anilines. The reaction is generally performed in water at room temperatures or below, using equimolar quantities of reagents.
The ''ortho''-isomer is formed predominantly. However, the ''para''-sulfate is formed in small amounts with certain anilines.
Scope and mechanism
The reaction is disadvantaged by moderate to lowchemical yield
In chemistry, yield, also referred to as reaction yield, is a measure of the quantity of moles of a product formed in relation to the reactant consumed, obtained in a chemical reaction, usually expressed as a percentage. Yield is one of the ...
s, 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). Rearrangement of this zwitterion
In chemistry, a zwitterion ( ; ), also called an inner salt or dipolar ion, is a molecule that contains an equal number of positively- and negatively-charged functional groups.
: With amino acids, for example, in solution a chemical equilibrium w ...
ic intermediate forms the ortho- sulfate (5), which then hydrolyses to form the ortho-hydroxyl aniline.
See also
*Elbs persulfate oxidation
The Elbs persulfate oxidation is the organic reaction of phenols with alkaline potassium persulfate to form ''para''-diphenols. The reaction is generally performed in water at room temperatures or below, using equimolar quantities of reagents.
...
References
Further reading
* {{Organic reactions Organic oxidation reactions Name reactions