organosulfur chemistry Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature abounds with organosulfur compounds—sulfur ...

, 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 ...

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: :R2S2 + Cl2 -> 2 R-SCl This reaction is sometimes called the Zincke disulfide reaction, in recognition of

Theodor Zincke Ernst Carl Theodor Zincke (19 May 1843 – 17 March 1928) 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 ...

. Typically, sulfenyl halides are stabilized by

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

sulfenamide Sulfenamides (also spelled sulphenamides) are a class of organosulfur compounds characterized by the general formula RSNR'2, where R and R' are H, alkyl, or aryl.Capozzi, G., Modena, G., Pasquato, L. in "Chemistry of Sulphenyl Halides and Sulfe ...

s: :CCl3SCl + R2NH -> CCl3SNR2 + HCl This method is used in the production of the fungicides

Captan Captan is a general use pesticide (GUP) that belongs to the phthalimide class of fungicides. It is a white solid, although commercial samples appear yellow or brownish. Applications Although it can be applied on its own, Captan is often adde ...

and

Folpet Folpet is the tradename for the organic compound with the formula C6H4(CO)2NSCCl3. It is a fungicide derived from phthalimide (C6H4(CO)2N-) and trichloromethylsulfenyl chloride. The compound is white although commercial samples can appear brow ...

. Sulfenyl chlorides add across

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 ...

: :CH2=CH2 + R-SCl -> R-SC2H4Cl They undergo chlorination to the

trichloride Trichloride may refer to: * The trichloride ion, a polyhalogen ion * Antimony trichloride, SbCl3 also known as butter of antimony * Arsenic trichloride, AsCl3, also known as arsenous chloride or butter of arsenic *Boron trichloride, BCl3, a colorl ...

s: :R-SCl + Cl2 -> -SCl2l Sulfenyl chlorides react with water and

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 ester 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 m ...

s (): :R-SCl + H2O -> R-SOH + HCl :R-SCl + R'-OH -> R-SO-R' + HCl

Route to sulfinyl halides

Sulfenyl chlorides can be converted to

sulfinyl chloride Sulfinyl halide have the general formula R−S(O)−X, where X is a halogen. They are intermediate in oxidation level between sulfenyl halides, R−S−X, and sulfonyl halides, R−SO2−X. The best known examples are sulfinyl chlorides, thermol ...

s (RS(O)Cl). In one approach, the sulfinyl chloride is generated in two steps starting with reaction of a

thiol 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 Ethanethiol, commonly known as ethyl mercaptan, is an organosulfur compound with the formula CH3CH2SH. is a colorless liquid with a distinct odor. Abbreviated EtSH, it consists of an ethyl group (Et), CH3CH2, attached to a thiol group, SH. Its ...

. 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: Conversion of F3CCPh2SH to F3CCPh2SCl and on to F3CCPh2S(O)Cl

Conversion of F3CCPh2SH to F3CCPh2SCl and on to F3CCPh2S(O)Cl

Related compounds

Sulfenyl

fluoride 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

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 , ...

: :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

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