Haloform reaction Haloform reaction Definition: Addition of a dihalogen (such as iodine, bromine, or chlorine) to a methyl ketone in the presence of base results in a carboxylic acid and a haloform (iodoform, bromoform, or chloroform). Acetyl chloride and acetamide don't give this test. Haloform Reaction and Iodoform Test We know that base-catalyzed halogenation of aldehydes and ketones replaces all the ɑ hydrogens: The reaction is difficult to stop at monohalogenation because the product, after the first step, is more reactive than the starting carbonyl , and therefore keeps reacting until all the protons are replaced by the halogen. Substrates are broadly limited to methyl ketones and secondary alcohols oxidizable to methyl ketones, such as isopropanol. The base (hydroxide ion) takes out the alpha hydrogen producing enolate. The halogen used may be chlorine, bromine, iodine or sodium hypochlorite. Fluoroform 1,3-Diketones such as acetylacetone also give the haloform reaction. The only primary alcohol and aldehyde to undergo this reaction are ethanol and acetaldehyde, respectively. β-ketoacids such as acetoacetic acid will also give the test upon heating. Then, the reaction between the enolate and the halogen occurs, leading to the formation of the halogenated ketone along with the halogens corresponding anion.

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