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In organosulfur chemistry, a sulfenyl chloride is a
Sulfenyl chlorides are typically prepared by chlorination of R2S2 + Cl2 -> 2 R-SCl
This reaction is sometimes called the Zincke disulfide reaction, in recognition of Theodor Zincke. Typically, sulfenyl halides are stabilized by
CCl3SCl + R2NH -> CCl3SNR2 + HCl
This method is used in the production of the fungicides Captan and Folpet.
Sulfenyl chlorides add across CH2=CH2 + R-SCl -> R-SC2H4Cl
They undergo chlorination to the trichlorides:
:R-SCl + Cl2 -> -SCl2l
Sulfenyl chlorides react with water and R-SCl + H2O -> R-SOH + HCl
:R-SCl + R'-OH -> R-SO-R' + HCl
2 R-SI -> (R-S)2 + I2
Sulfenyl iodides can be isolated as stable compounds if they bear alkyl steric protecting groups as part of a cavity-shaped framework, illustrating the technique of kinetic stabilization of a reactive functionality, as in the case of
In organosulfur chemistry, a sulfenyl chloride is a functional group
In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the res ...
with the connectivity , where R is alkyl
In organic chemistry, an alkyl group is an alkane missing one hydrogen.
The term ''alkyl'' is intentionally unspecific to include many possible substitutions.
An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloal ...
or aryl
In organic chemistry, an aryl is any functional group or substituent derived from an aromatic ring, usually an aromatic hydrocarbon, such as phenyl and naphthyl. "Aryl" is used for the sake of abbreviation or generalization, and "Ar" is used as ...
. Sulfenyl chlorides are reactive compounds that behave as sources of . They are used in the formation of and bonds. According to IUPAC
The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
nomenclature they are named as alkyl thiohypochlorites, i.e. ester
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ...
s of thiohypochlorous acid.
Preparation
Sulfenyl chlorides are typically prepared by chlorination of disulfide
In biochemistry, a disulfide (or disulphide in British English) refers to a functional group with the structure . The linkage is also called an SS-bond or sometimes a disulfide bridge and is usually derived by the coupling of two thiol groups. In ...
s:
:electronegative
Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the d ...
substituents. This trend is illustrated by the stability of obtained by chlorination of carbon disulfide
Carbon disulfide (also spelled as carbon disulphide) is a neurotoxic, colorless, volatile liquid with the formula and structure . The compound is used frequently as a building block in organic chemistry as well as an industrial and chemical ...
.
Some thioether
In organic chemistry, an organic sulfide (British English sulphide) or thioether is an organosulfur functional group with the connectivity as shown on right. Like many other sulfur-containing compounds, volatile sulfides have foul odors. A sul ...
s () with electron-withdrawing substituents undergo chlorinolysis of a bond to afford the sulfenyl chloride.
Reactions
Perchloromethyl mercaptan
Perchloromethyl mercaptan is the organosulfur compound with the formula CCl3SCl. It is mainly used as an intermediate for the synthesis of dyes and fungicides (captan, folpet). It is a colorless oil, although commercial samples are yellowish. It ...
() reacts with bonds in the presence of base to give the sulfenamides:
:alkene
In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond.
Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...
s, for example ethylene
Ethylene ( IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene ...
:
:alcohols
In chemistry, an alcohol is a type of organic compound that carries at least one hydroxyl () functional group bound to a saturated carbon atom. The term ''alcohol'' originally referred to the primary alcohol ethanol (ethyl alcohol), which i ...
to give sulfenyl esters ():
:Route to sulfinyl halides
Sulfenyl chlorides can be converted to sulfinyl chlorides (RS(O)Cl). In one approach, the sulfinyl chloride is generated in two steps starting with reaction of athiol
In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...
() with sulfuryl chloride
Sulfuryl chloride is an inorganic compound with the formula SO2Cl2. At room temperature, it is a colorless liquid with a pungent odor. Sulfuryl chloride is not found in nature, as can be inferred from its rapid hydrolysis.
Sulfuryl chloride is ...
(). In some cases the sulfenyl chloride results instead, as happens with 2,2,2-trifluoro-1,1-diphenyl ethanethiol. A trifluoroperacetic acid
Trifluoroperacetic acid (trifluoroperoxyacetic acid, TFPAA) is an organofluorine compound, the peroxy acid analog of trifluoroacetic acid, with the condensed structural formula . It is a strong oxidizing agent for organic oxidation reactions, suc ...
oxidation then provides a general approach to formation of sulfinyl chlorides from sulfenyl chlorides:
Related compounds
Sulfenylfluoride
Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts ...
s and bromide
A bromide ion is the negatively charged form (Br−) of the element bromine, a member of the halogens group on the periodic table. Most bromides are colorless. Bromides have many practical roles, being found in anticonvulsants, flame-retardan ...
s are also known. Simple sulfenyl iodide
An iodide ion is the ion I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine def ...
s are unknown because they are unstable with respect to the disulfide
In biochemistry, a disulfide (or disulphide in British English) refers to a functional group with the structure . The linkage is also called an SS-bond or sometimes a disulfide bridge and is usually derived by the coupling of two thiol groups. In ...
and iodine
Iodine is a chemical element with the Symbol (chemistry), symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , ...
:
:sulfenic acid
In chemistry, a sulfenic acid is an organosulfur compound and oxoacid with the general formula . It is the first member of the family of organosulfur oxoacids, which also include sulfinic acids () and sulfonic acids (), respectively. The base me ...
s.
A related class of compounds are the alkylsulfur trichlorides, as exemplified by methylsulfur trichloride, .
The corresponding selenenyl halides, , are more commonly encountered in the laboratory. Sulfenyl chlorides are used in the production of agents used in the vulcanization
Vulcanization (British: Vulcanisation) is a range of processes for hardening rubbers. The term originally referred exclusively to the treatment of natural rubber with sulfur, which remains the most common practice. It has also grown to include ...
of rubber.
References
{{functional groups Organosulfur compounds Functional groups