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Hell-Volhard-Zelinsky halogenation
Introduction
The Hell-Volhard-Zelinsky halogenation reaction halogenates carboxylic acids at the α carbon.
Scheme
Scheme
The reaction is initiated by addition of a catalytic amount of PBr3, after which one molar equivalent of Br2 is added.
PBr3 replaces the carboxylic OH with a bromide, resulting in a carboxylic acid bromide. The acyl bromide can then tautomerize to an enol, which will readily react with the Br2 to brominate a second time at the α position.
In neutral to slightly acidic aqueous solution, hydrolysis of the α-bromo acyl bromide occurs spontaneously, yielding the α-bromo carboxylic acid in an example of a nucleophilic acyl substitution. If an aqueous solution is desirable, a full molar equivalent of PBr3 must be used as the catalytic chain is disrupted.
If little nucleophilic solvent is present, reaction of the α-bromo acyl bromide with the carboxylic acid yields the α-bromo carboxylic acid product and regenerates the acyl bromide intermediate. In practice a molar equivalent of PBr3 is often used anyway to overcome the slow reaction kinetics.
References
References
- Hell C. (1881). Berichte. 14: 891. Missing or empty
|title=(help) - Volhard J. (1887). Annalen der Chemie. 242: 141. Missing or empty
|title=(help) - Zelinsky N. (1887). Berichte. 20: 2026. Missing or empty
|title=(help) - Allen C. F., Kalm M. J. (1958). “2-Methylenedodecanoic Acid”. Organic Syntheses. 38: 47.
Editor-In-Chief: C. Michael Gibson, M.S., M.D. [1]