Numford
Name reaction

Hell-Volhard-Zelinsky reaction

Carboxylic acids with alpha hydrogen react with chlorine or bromine in the presence of red phosphorus to give alpha-halo acids.

Class 12, Chapter 8 Aldehydes, Ketones and Carboxylic Acids

  1. OOH
    Ethanoic acidCH₃COOHCarboxylic acid
  2. Step 1

    (i) Cl₂, red P (ii) H₂O

    Hell-Volhard-Zelinsky reaction
    i

    Hell-Volhard-Zelinsky reaction halogenates only the alpha carbon.

    OHOCl
    Chloroethanoic acidClCH₂COOHCarboxylic acid

Reagents: (i) X₂ / red P (ii) H₂O

Mechanism

How it works

  1. Red phosphorus and the halogen form PX₃, which converts the acid to the acyl halide.
  2. The acyl halide enolises and is halogenated at the alpha carbon.
  3. Water hydrolyses the acyl halide to the alpha-halo acid.
Used to prepare

What it makes

Alpha-halo acids such as chloroethanoic acid.

Limitations

Where it fails

The acid needs at least one alpha hydrogen.

Which chapter

Class 12, Chapter 8 Aldehydes, Ketones and Carboxylic Acids

Questions

Hell-Volhard-Zelinsky reaction: quick answers

What is the role of red phosphorus?

It forms PX3 with the halogen, which makes the acyl halide that is halogenated.

Where does halogenation occur?

At the alpha carbon.

Can methanoic acid or benzoic acid undergo HVZ?

No, they have no alpha hydrogen.

Plan an organic conversion