In organic chemistry, an electrophilic aromatic halogenation is a type of electrophilic aromatic substitution. This organic reaction is typical of aromatic compounds and a very useful method for adding substituents to an aromatic system.
A few types of aromatic compounds, such as phenol, will react without a catalyst, but for typical benzene derivatives with less reactive substrates, a Lewis acid catalyst is required. Typical Lewis acid catalysts include AlCl3, FeCl3, FeBr3, and ZnCl2. These work by forming a highly electrophilic complex which is attacked by the benzene ring.
The reaction mechanism for chlorination of benzene is the same as bromination of benzene. Iron(III) bromide and iron(III) chloride become inactivated if they react with water, including moisture in the air. Therefore, they are generated by adding iron filings to bromine or chlorine. Here is the mechanism of this reaction:
The mechanism for iodination is slightly different: iodine (I2) is treated with an oxidizing agent such as nitric acid to obtain the electrophilic iodine (2 I+). Unlike the other halogens, iodine does not serve as a base since it is positive. In one study the iodinization reagent is a mixture of iodine and iodic acid.
In another series of studies the powerful reagent obtained by using a mixture of iodine and potassium iodate dissolved in concentrated sulfuric acid was used. Here the iodinating agent is the triiodine cation I+
3 and the base is HSO−
4. In these studies both the kinetics of the reaction and the preparative conditions for the iodination of strongly deactivated compounds, such as benzoic acid and 3-nitrobenzotrifluoride, were investigated.
Halogenation of aromatic compounds differs from the halogenation of alkenes, which do not require a Lewis Acid catalyst. The formation of the arenium ion results in the temporary loss of aromaticity, which has a higher activation energy compared to carbocation formation in alkenes. In other words, alkenes are more reactive and do not need to have the Br–Br or Cl–Cl bond weakened.
However, if a catalyst is used with excess bromine, then a tribromide will be formed.
Halogenation of phenols is faster in polar solvents due to the dissociation of phenol, with phenoxide ions being more susceptible to electrophilic attack as they are more electron-rich.
No reaction takes place when the solvent is replaced by tetrachloromethane. In contrast, when the reactant is 2-phenylethylamine, it is possible to employ relatively apolar solvents with exclusive ortho- regioselectivity due to the intermediate formation of a chloramine making the subsequent reaction step intramolecular.
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