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Darzens halogenation is the chemical synthesis of alkyl halides from alcohols via the treatment upon reflux of a large excess of thionyl chloride or thionyl bromide (SOX₂) in the presence of a small amount of a nitrogen base, such as a tertiary amine or pyridine or its corresponding hydrochloride or hydrobromide salt. The reaction is named after its creator, Auguste Georges Darzens, who first reported it in 1911.

The addition of the amine and use of a large excess of the thionyl halide as compared to the usual halogenation protocol makes this reaction effective for a wide range of alcohols including those that are difficult to halogenate, such as cyclohexanol, which normally decomposes to form cyclohexene if reacted with only SOCl₂. The reaction takes place through an S_N2 mechanism but is also often used in the description of S_Ni mechanisms.

For example, ethanol can be converted into chloroethane (X=Cl) or bromoethane (X=Br) as follows:

CH₃CH₂OH + SOX₂ ${\displaystyle \xrightarrow {\text{pyridine}} }$ CH₃CH₂X + SO₂ + HX

References

1. Darzens, George (1911). "Nouvelle methode d'etherification des alcools par les hydracides" [New method of etherification of alcohols with hydracids]. Compt. Rend. (in French). 152: 1314–1317.
2. Darzens, George (1911). "Action du Chlorure de Thionyle en Presence d'une Base Tertiare sur quelques Ether d'Acides Alcohols" [Action of Thionyl Chloride in the Presence of a Tertiary Base on some Aether of Alcohols]. Compt. Rend. (in French). 152: 1601–1603.
3. "Darzens Halogenation". Comprehensive Organic Name Reactions and Reagents. 2010. pp. 846–847. doi:10.1002/9780470638859.conrr179. ISBN 9780471704508.
4. Libermann, D. (27 December 1947). "Interaction of Thionyl Chloride and Hydroxy Compounds". Nature. 160 (4078): 903–904. Bibcode:1947Natur.160..903L. doi:10.1038/160903a0. PMID 18917309. S2CID 4138548.

• Halogenation reactions
• Substitution reactions
• Name reactions