Sulfenyl chloride

A sulfenyl chloride is a functional group with the connectivity R-S-Cl, where R is alkyl or aryl. Sulfenyl chlorides are reactive compounds that behave as sources of RS+. They are used in the formation of RS-N and RS-O bonds.

According to IUPAC nomenclature they are named as alkyl thiohypochlorites, i.e. esters of thiohypochlorous acid.

Preparation and reactions

Sulfenyl chlorides are typically prepared by chlorination of disulfides:[1][2]

R2S2 + Cl2 → 2 RSCl

This reaction is sometimes called the Zincke disulfide reaction, in recognition of Theodor Zincke.[3][4] Typically, sulfenyl halides are stabilized by electronegative substituents.

Sulfenyl chlorides add across alkenes:

CH2=CH2 + RSCl → RSCH2CH2Cl

Related compounds

Sulfenyl bromides are also known.[5] Sulfenyl iodides, however, are not known, but are unstable with respect to the disulfide and iodine:

2 RSI → (RS)2 + I2

The corresponding selenyl halides, e.g. C6H5SeCl, are more commonly encountered in the laboratory. Sulfenyl chlorides are used in the production of agents used in the vulcanization of rubber.

References

  1. ^ Max H. Hubacher (1943), "o-Nitrophenylsulfur chloride", Org. Synth., http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV2P0455 ; Coll. Vol. 2: 455 
  2. ^ Methyl sulfenyl chloride: Irwin B. Douglass and Richard V. Norton (1973), "Methanesulfinyl Chloride", Org. Synth., http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV5P0709 ; Coll. Vol. 5: 709 
  3. ^ Zincke, Th. (1911). "Über eine neue Reihe aromatischer Schwefelverbindungen". Chemische Berichte 44 (1): 769–771. doi:10.1002/cber.191104401109. 
  4. ^ Zincke, Th., Fr. Farr (1912). "Über o-Nitrophenylschwefelchlorid und Umwandlungsprodukte". Justus Liebig's Annalen der Chemie 391 (1): 57–88. doi:10.1002/jlac.19123910106. 
  5. ^ Daniel S. Reno and Richard J. Pariza (1998), "Phenyl Vinyl Sulfide", Org. Synth., http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV9P0662 ; Coll. Vol. 9: 662