Sulfenyl chloride

Short description: Chemical group (R–S–Cl)

General structural formula of sulfenyl chlorides, RSCl

In organosulfur chemistry, a sulfenyl chloride is a functional group with the connectivity R–S–Cl, where R is alkyl[1] 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.

## Contents

* 1 Preparation
* 2 Reactions
* 2.1 Route to sulfinyl halides
* 3 Related compounds
* 4 References

## Preparation

Trichloromethane­sulfenyl chloride is a stable sulfenyl chloride

Sulfenyl chlorides are typically prepared by chlorination of disulfides:[2][3]

[math]\ce{ R2S2 + Cl2 -> 2 R-SCl }[/math]

This reaction is sometimes called the Zincke disulfide reaction, in recognition of Theodor Zincke.[4][5] Typically, sulfenyl halides are stabilized by electronegative substituents. This trend is illustrated by the stability of CCl
3SCl obtained by chlorination of carbon disulfide.

Some thioethers (R–S–R’) with electron-withdrawing substituents undergo chlorinolysis of a C–S bond to afford the sulfenyl chloride.[6][7]

## Reactions

Perchloromethyl mercaptan (CCl
3SCl) reacts with N–H bonds in the presence of base to give the sulfenamides:

[math]\ce{ CCl3SCl + R2NH -> CCl3SNR2 + HCl }[/math]

This method is used in the production of the fungicides Captan and Folpet.

Sulfenyl chlorides add across alkenes, for example ethylene:[8]

[math]\ce{ CH2=CH2 + R-SCl -> R-SC2H4Cl }[/math]

They undergo chlorination to the trichlorides:[3]

[math]\ce{ R-SCl + Cl2 -> [R-SCl2]Cl }[/math]

Sulfenyl chlorides react with water and alcohols to give sulfenyl esters (R–S–O–R′):[9]

[math]\ce{ R-SCl + H2O -> R-SOH + HCl }[/math]
[math]\ce{ R-SCl + R'-OH -> R-SO-R' + HCl }[/math]

### 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 a thiol (–SH) with sulfuryl chloride (SO
2Cl
2). In some cases the sulfenyl chloride results instead, as happens with 2,2,2-trifluoro-1,1-diphenylethanethiol. A trifluoroperacetic acid oxidation then provides a general approach to formation of sulfinyl chlorides from sulfenyl chlorides:[10]

## Related compounds

Sulfenyl fluorides and bromides are also known.[11] Simple sulfenyl iodides are unknown because they are unstable with respect to the disulfide and iodine:

[math]\ce{ 2 R-SI -> (R-S)2 + I2 }[/math]

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 acids.[12]

A related class of compounds are the alkylsulfur trichlorides, as exemplified by methylsulfur trichloride, CH
3SCl
3.[13]

The corresponding selenenyl halides, R–SeCl, are more commonly encountered in the laboratory. Sulfenyl chlorides are used in the production of agents used in the vulcanization of rubber.

## References

1. ↑ Drabowicz, J.; Kiełbasiński, P.; Łyżwa, P.; Zając, A.; Mikołajczyk, M. (2008). Kambe, N.. ed. Alkanesulfenyl Halides. Science of Synthesis. 39. pp. 544–550. ISBN 9781588905307.
2. ↑ Hubacher, Max H. (1943). "o-Nitrophenylsulfur chloride". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=CV2P0455. ;  Collective Volume, 2, pp. 455
3. ↑ 3.0 3.1 Douglass, Irwin B.; Norton, Richard V. (1973). "Methanesulfinyl Chloride". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=CV5P0709. ;  Collective Volume, 5, pp. 709–715
4. ↑ "Über eine neue Reihe aromatischer Schwefelverbindungen" (in de). Chemische Berichte 44 (1): 769–771. 1911. doi:10.1002/cber.191104401109. https://zenodo.org/record/1426425.
5. ↑ "Über o-Nitrophenylschwefelchlorid und Umwandlungsprodukte" (in de). Justus Liebig's Annalen der Chemie 391 (1): 57–88. 1912. doi:10.1002/jlac.19123910106. https://zenodo.org/record/1427597.
6. ↑ F. B. Wells, C. F. H. Allen (1935). "2,4-Dinitroaniline". Organic Syntheses 15: 22. doi:10.15227/orgsyn.015.0022.
7. ↑ Norman Kharasch, Robert B. Langford (1964). "2,4-Dinitrobenzenesulfenyl Chloride". Organic Syntheses 44: 47. doi:10.15227/orgsyn.044.0047.
8. ↑ Brintzinger, H.; Langheck, M., "Synthesen mit Alkylschwefelchloriden (X. Mitteil. über organische Schwefelchloride)", Chemische Berichte 1954, volume 87, 325-330. doi:10.1002/cber.19540870306
9. ↑ Petrovic, Goran; Saicic, Radomir N.; Cekovic, Zivorad (2005). "Phenylsulfenylation of Nonactivated Carbon Atom by Photolysiis of Alkyl Benzenesulfenated: Preparation of 2-Phenylthio-5-heptanol". Organic Syntheses 81: 244. doi:10.15227/orgsyn.081.0244.
10. ↑ Page, P. C. B.; Wilkes, R. D.; Reynolds, D. (1995). "Alkyl Chalcogenides: Sulfur-based Functional Groups". in Ley, Steven V.. Synthesis: Carbon with One Heteroatom Attached by a Single Bond. Comprehensive Organic Functional Group Transformations. Elsevier. pp. 113–276. ISBN 9780080423234. https://books.google.com/books?id=BPcxrmIgLKMC&pg=PA173.
11. ↑ Reno, Daniel S.; Pariza, Richard J. (1998). "Phenyl Vinyl Sulfide". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=CV9P0662. ;  Collective Volume, 9, pp. 662
12. ↑ Sase, S.; Aoki, Y.; Abe, N.; Goto, K. (2009). "Stable Sulfenyl Iodide Bearing a Primary Alkyl Steric Protection Group with a Cavity-shaped Framework". Chemistry Letters 38 (12): 1188–1189. doi:10.1246/cl.2009.1188.
13. ↑ Braverman, S.; Cherkinsky, M.; Levinger, S. (2008). "Alkylsulfur Trihalides". Sci. Synth. 39: 187–188. ISBN 9781588905307.

* v
* t
* e

Functional groups

| Only carbon,
hydrogen,
and oxygen|

| Hydrocarbons|

* Allene
* Alkene (Allyl group

|

Other|

* Acetoxy
* Acetyl
* Acryloyl
* Acyl
* Aldehyde
* Alkoxy (Methoxy)
* Benzoyl
* Carbonyl
* Carboxyl
* Carboxylic anhydride
* Dioxirane
* Epoxide
* Ester
* Ether
* Ethylenedioxy
* Hydroxy
* Ketone
* Methylenedioxy
* Peroxide (Organic)
* Ynone

Only one
element
apart from
C, H, O|

| Nitrogen|

* Amine
* Azo compound
* Cyanate
* Hydrazone
* Imide
* Imine
* Isocyanate
* Isonitrile
* Nitrene
* Nitrile
* Nitro compound
* Nitroso compound
* Organic amide
* Oxime

|

Phosphorus|

* Phosphonate
* Phosphonous

Sulfur|

* Disulfide
* Sulfone
* Sulfonic acid
* Sulfoxide
* Thial
* Thioester
* Thioether
* Thioketone
* Thiol

Selenium|

* Selenol
* Selenonic acid
* Seleninic acid
* Selenenic acid
* Selone

Tellurium|

* Tellurol
* Telluroketone

Other|

* Isothiocyanate
* Phosphoramide
* Sulfenyl chloride
* Sulfonamide
* Thiocyanate

See also chemical classification, chemical nomenclature ([[Chemistry:IUPAC nomenclature of inorganic, IUPAC nomenclature of organic chemistry|organic]])

0.00

(0 votes)

Original source: https://en.wikipedia.org/wiki/Sulfenyl chloride. Read more

|

Retrieved from "https://handwiki.org/wiki/index.php?title=Chemistry:Sulfenyl_chloride&oldid=3322624"
*[v]: View this template
*[t]: Discuss this template
*[e]: Edit this template