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Electrophilic halogenationIn 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. Additional recommended knowledgeA 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 attacks the benzene ring. Reaction mechanismThe reaction mechanism for chlorination of benzene is the same as bromination of benzene. Ferric bromide and ferric chloride become inactivated if they react with water, including moisture in the air. Therefore, they are generated in situ by adding iron fillings to bromine or chlorine. 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 [1]. In another series of studies the powerful reagent obtained by using a mixture of iodine and potassium iodate dissolved in concentrated sulphuric acid was used. Here the iodinating agent is the tri-iodine cation I3+ and the base is HSO4-. In these studies both the 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.[2]. [3]
ScopeIf the ring contains a strongly activating substituent such as -OH, -OR or amines, a catalyst is not necessary, for example in the bromination of p-cresol:[4] 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. Chlorination of toluene with chlorine without catalyst requires a polar solvent as well such as acetic acid. The ortho to para selectivity is low:[5] No reaction takes place when the solvent is replaced by tetrachloromethane. In contrast, when the reactant is 2-phenyl-ethylamine, 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.
This reaction is driven by sodium bicarbonate [6]. References
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This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Electrophilic_halogenation". A list of authors is available in Wikipedia. |