# Sulfene

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> Markdown URL: https://mediated.wiki/source/Sulfene.md
> Source: https://en.wikipedia.org/wiki/Sulfene
> Source revision: 1354279914
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{{Chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 470473600
| ImageFileL1 = Thioformaldehyde-S,S-dioxide-2D.png
| ImageClassL1 = skin-invert 
| ImageFileL1_Ref = {{chemboximage|correct|??}}
| ImageSizeL1 = 121
| ImageNameL1 = Skeletal formula of sulfene with both explicit hydrogens added
| ImageFileR1 = Thioformaldehyde-S,S-dioxide-3D-vdW.png
| ImageClassR1 = bg-transparent 
| ImageFileR1_Ref = {{chemboximage|correct|??}}
| ImageSizeR1 = 121
| ImageNameR1 = Spacefill model of sulfene
| OtherNames = Thioformaldehyde-''S'',''S''-dioxide{{Citation needed|date = September 2011}}; Methanethione dioxide; Methylidene-λ<sup>6</sup>-sulfanedione
|Section1={{Chembox Identifiers
| CASNo_Ref = {{cascite|correct|pubchem}}
| CASNo = 917-73-7
| PubChem = 12244237
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 10645700
| SMILES = C=S(=O)=O
| StdInChI = 1S/CH2O2S/c1-4(2)3/h1H2
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| InChI = 1/CH2O2S/c1-4(2)3/h1H2
| StdInChIKey = LZOZLBFZGFLFBV-UHFFFAOYSA-N
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| InChIKey = LZOZLBFZGFLFBV-UHFFFAOYAF
}}
|Section2={{Chembox Properties
| Formula = {{Chem|CH|2|SO|2|}}
| MolarMass = 78.090 g mol<sup>−1</sup>
}}
|Section3={{Chembox Structure
| MolShape = trigonal planar at C and S
}}
}}

'''Sulfene''' is an extremely reactive [chemical compound](/source/chemical_compound) with the [formula](/source/chemical_formula) H<sub>2</sub>C=SO<sub>2</sub>. It is the simplest member of the '''sulfenes''', the group of compounds which are ''S'',''S''-dioxides of [thioaldehydes](/source/thial) and [thioketone](/source/thioketone)s, and have the general formula R<sub>2</sub>C=SO<sub>2</sub>.<ref>{{GoldBookRef | file = S06095 | title = sulfenes}}</ref><ref>{{cite journal |last=Zwanenburg|first=B |title=S,S-Dioxides of Thioaldehydes and Thioketones (Sulfenes and Derivatives) |journal =Sci. Synth. |year=2004 |volume=27 |pages=123–134}}</ref><ref>{{cite journal |last=King|first=JF |title=Return of Sulfenes |journal =Acc. Chem. Res. |year=1975 |volume=8|issue=1|pages=10–17|doi=10.1021/ar50085a002}}</ref>

==Preparation==
The first general method for preparation of sulfene as an intermediate, reported simultaneously in 1962 by [Gilbert Stork](/source/Gilbert_Stork)<ref>{{cite journal|last=Stork|first=G|author2=Borowitz, IJ |title=Four-membered Sulfones from Enamines and Aliphatic Sulfonyl Halides|journal=J. Am. Chem. Soc.|year=1962|volume=84|issue=2|page=313|doi=10.1021/ja00861a042}}</ref> and by Günther Optiz,<ref>{{cite journal|last=Opitz|first=G|author2=Adolph, H |title=Cycloaddition of Sulfenes to Enamines|journal=Angew. Chem. Int. Ed. |year=1962|volume=1|issue=2|pages=113–114|doi=10.1002/anie.196201133}}</ref> involved the removal of [hydrogen chloride](/source/hydrogen_chloride) from [methanesulfonyl chloride](/source/methanesulfonyl_chloride) using [triethylamine](/source/triethylamine) in the presence of an [enamine](/source/enamine) as trapping agent. The formation of a [thietane](/source/thietane) 1,1-dioxide derivative was taken as evidence for the intermediacy of sulfene. Because of the highly [electrophilic](/source/electrophilic) character of sulfene, the use of amines presents difficulties, since they can intercept the sulfene to form [adduct](/source/adduct)s. A simple alternative which avoids the use of amines involves [desilylation](/source/desilylation) of trimethylsilylmethanesulfonyl chloride with [cesium fluoride](/source/cesium_fluoride) in the presence of trapping agents.<ref>{{cite journal|last=Block|first=E|author2=Aslam, M |title=A New Sulfene Synthesis|journal=Tetrahedron Lett.|year=1982|volume=23|issue=41|pages=4203–4206|doi= 10.1016/S0040-4039(00)88704-3}}</ref>

: (CH<sub>3</sub>)<sub>3</sub>SiCH<sub>2</sub>SO<sub>2</sub>Cl + CsF → [CH<sub>2</sub>=SO<sub>2</sub>] + (CH<sub>3</sub>)<sub>3</sub>SiF + CsCl

Alternatively, sulfenes can be stabilized by installing amido substituents on the alkylidene substituent.  The extreme case is [thiourea dioxide](/source/thiourea_dioxide), which features planar amido groups.
:thumb|left|Structure of thiourea dioxide ((H<sub>2</sub>N)<sub>2</sub>CSO<sub>2</sub>). Selected distances and angles: r<sub>S=O</sub> = 1.49, r<sub>S=C</sub> = 1.85.1, r<sub>C-N</sub> = 1.31 Å, sum of angles around S = 312.4°.<ref>{{cite journal|journal=Acta Crystallogr.|year=1962|volume=15|pages=675–682|doi=10.1107/S0365110X62001851|title=The Crystal and Molecular Structure of Thiourea Dioxide|author=R. A. L. Sullivan |author2=A. Hargreaves |issue=7 |doi-access=free|bibcode=1962AcCry..15..675S }}</ref>

==Reactions==
Sulfenes react with [enamines](/source/enamines), ynamines, and 1,3-cyclopentadienes to give [thietane](/source/thietane)s, [thiete](/source/thiete)s and [Diels-Alder](/source/Diels-Alder) adducts, respectively. In the presence of a [chiral](/source/chiral) tertiary amine complex, several sulfenes could be trapped with trichloroacetaldehyde ([chloral](/source/chloral)) in a catalytic asymmetric synthesis of β-[sulfone](/source/sulfone)s (four-membered ring sulfonate esters).<ref>{{cite journal|last=Koch|first=FM|author2=Peters, R |title=Lewis Acid/Base Catalyzed [2+2]-Cycloaddition of Sulfenes and Aldehydes: A Versatile Entry to Chiral Sulfonyl and Sulfinyl Derivatives|journal=Chem. Eur. J.|year=2011|volume=17|issue=13 |pages=3679–3692|doi=10.1002/chem.201003542|pmid=21365709 }}</ref> Sulfene can also undergo insertion into metal–hydrogen bonds.<ref name="Lorenz">{{cite journal|author=Ingo-Peter Lorenz |title= Demonstration of "Sulfene" Insertion into the Metal–Hydrogen Bond |journal = Angew. Chem. Int. Ed. |volume=17|issue=4 |pages=285–286|date=April 1978 | doi = 10.1002/anie.197802851}}</ref>

==See also==
* [Sulfine](/source/Sulfine) - related functional group with the formula H<sub>2</sub>C=S=O

== References ==
{{reflist}}

Category:Organosulfur compounds

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Adapted from the Wikipedia article [Sulfene](https://en.wikipedia.org/wiki/Sulfene) by Wikipedia contributors ([contributor history](https://en.wikipedia.org/wiki/Sulfene?action=history)). Available under [Creative Commons Attribution-ShareAlike 4.0 International](https://creativecommons.org/licenses/by-sa/4.0/). Changes may have been made.