Sulfenyl chloride
Encyclopedia
A sulfenyl chloride is a functional group
Functional group
In organic chemistry, functional groups are specific groups of atoms within molecules that are responsible for the characteristic chemical reactions of those molecules. The same functional group will undergo the same or similar chemical reaction regardless of the size of the molecule it is a part of...

 with the connectivity R-S-Cl, where R is alkyl or aryl
Aryl
In the context of organic molecules, aryl refers to any functional group or substituent derived from an aromatic ring, be it phenyl, naphthyl, thienyl, indolyl, etc....

. 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. ester
Ester
Esters are chemical compounds derived by reacting an oxoacid with a hydroxyl compound such as an alcohol or phenol. Esters are usually derived from an inorganic acid or organic acid in which at least one -OH group is replaced by an -O-alkyl group, and most commonly from carboxylic acids and...

s of thiohypochlorous acid.

Preparation and reactions

Sulfenyl chlorides are typically prepared by chlorination
Chlorination
Chlorination is the process of adding the element chlorine to water as a method of water purification to make it fit for human consumption as drinking water...

 of disulfide
Disulfide
In chemistry, a disulfide usually refers to the structural unit composed of a linked pair of sulfur atoms. Disulfide usually refer to a chemical compound that contains a disulfide bond, such as diphenyl disulfide, C6H5S-SC6H5....

s:
R2S2 + Cl2 → 2 RSCl

This reaction is sometimes called the Zincke disulfide reaction, in recognition of Theodor Zincke
Theodor Zincke
Theodor Zincke was a German chemist and the academic adviser of Otto Hahn.-Life:Theodor Zincke was born in Uelzen on 19 May 1843. He became a pharmacist and graduated in Göttingen with his Staatsexamen. He began studying chemistry with Friedrich Wöhler and received his Ph.D in 1869...

. Typically, sulfenyl halides are stabilized by electronegative substituents.

Sulfenyl chlorides add across alkenes:
CH2=CH2 + RSCl → RSCH2CH2Cl

Related compounds

Sulfenyl bromides are also known. Sulfenyl iodides, however, are not known, but are unstable with respect to the disulfide and iodine
Iodine
Iodine is a chemical element with the symbol I and atomic number 53. The name is pronounced , , or . The name is from the , meaning violet or purple, due to the color of elemental iodine vapor....

:
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
Vulcanization
Vulcanization or vulcanisation is a chemical process for converting rubber or related polymers into more durable materials via the addition of sulfur or other equivalent "curatives." These additives modify the polymer by forming crosslinks between individual polymer chains. Vulcanized material is...

of rubber.
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