Dimethyl sulfide: Difference between revisions

{{Use dmy dates|date=June 2017}}

{{Chembox

| verifiedrevid = 443690574

| ImageFile_Ref = {{chemboximage|correct|??}}

| ImageName = Skeletal formula of dimethyl sulfide with all implicit hydrogens shown

| ImageFile1 = Dimethyl-sulfide-3D-vdW.png

| ImageFile1_Ref = {{chemboximage|correct|??}}

| ImageName1 = Spacefill model of dimethyl sulfide

| ImageCaption1 = [[Space-filling model]] of the molecular structure<ref>{{ Cite journal | url = https://dx.doi.org/10.5517/ccscgn7 | title = CSD Entry TUYLOP: 1,3,6,8-tetrakis(4-Methoxy-2,6-dimethylphenyl)pyrene bis(dimethyl sulfide) clathrate | website = [[Cambridge Structural Database]]: Access Structures | year = 2010 | publisher = [[Cambridge Crystallographic Data Centre]] | doi = 10.5517/ccscgn7 | access-date = 3 November 2021 | last1 = Moorthy | first1 = J.N. | last2 = Natarajan | first2 = P. | last3 = Venugopalan | first3 = P. }}</ref><ref>{{ cite journal | title = Abundant Lattice Inclusion Phenomenon with Sterically Hindered and Inherently Shape-Selective Tetraarylpyrenes | first1 = J. N. | last1 = Moorthy | first2 = P. | last2 = Natarajan | first3 = P. | last3 = Venugopalan | journal = [[Journal of Organic Chemistry|J. Org. Chem.]] | volume = 74 | pages = 8566–8577 | year = 2009 | issue = 22 | doi = 10.1021/jo901465f | pmid = 19831423 }}</ref>

| PIN = (Methylsulfanyl)methane<ref name=iupac2013>{{cite book | title = Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = [[Royal Society of Chemistry|The Royal Society of Chemistry]] | date = 2014 | location = Cambridge | page = 706 | doi = 10.1039/9781849733069-00648 | isbn = 978-0-85404-182-4| chapter = Chapter P-6. Applications to Specific Classes of Compounds }}</ref>

| OtherNames = {{ubl|(Methylthio)methane<ref name=iupac2013/>|Dimethyl sulfide<ref name=iupac2013/>|Dimethyl thioether<ref name=pubchem>{{cite web | url=https://pubchem.ncbi.nlm.nih.gov/compound/Dimethyl-sulfide | title=Dimethyl sulfide }}</ref>}}

| CASNo = 75-18-3

| CASNo_Ref = {{cascite|correct|CAS}}

| PubChem = 1068

| ChemSpiderID = 1039

| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

| UNII_Ref = {{fdacite|correct|FDA}}

| EINECS = 200-846-2

| UNNumber = 1164

| KEGG_Ref = {{keggcite|correct|kegg}}

| MeSHName = dimethyl+sulfide

| ChEBI = 17437

| ChEBI_Ref = {{ebicite|correct|EBI}}

| ChEMBL_Ref = {{ebicite|correct|EBI}}

| RTECS = PV5075000

| Beilstein = 1696847

| 3DMet = B00138

| SMILES = CSC

| StdInChI_Ref = {{stdinchicite|correct|chemspider}}

| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

| InChIKey = QMMFVYPAHWMCMS-UHFFFAOYAH

| Formula = {{chem2|(CH3)2S}}

| C=2|H=6|S=1

| Appearance = Colourless liquid

| Odor = Stench: cabbage, sulfurous, unpleasant

| Density = 0.846{{nbsp}}g·cm⁻³

| MeltingPtK = 175

| BoilingPtK = 308 to 314

| LogP = 0.977

| VaporPressure = 53.7{{nbsp}}kPa (at 20&nbsp;°C)

| RefractIndex = 1.435

| MagSus = {{val|−44.9e-6|u=cm³/mol}}

}}

| Section3 = {{Chembox Thermochemistry

| DeltaHf = −63.9 to −66.9{{nbsp}}kJ⋅mol⁻¹

| DeltaHc = −2.1812 to −2.1818{{nbsp}}MJ⋅mol⁻¹

}}

| ExternalSDS = [http://www.osha.gov/dts/chemicalsampling/data/CH_236505.html osha.gov]

| GHSPictograms = {{GHS flame}} {{GHS corrosion}} {{GHS exclamation mark}}

| GHSSignalWord = '''DANGER'''

| HPhrases = {{H-phrases|225|315|318|335}}

| PPhrases = {{P-phrases|210|261|280|305+351+338}}

| FlashPtC = −36

| AutoignitionPtC = 206

| ExploLimits = 19.7%{{clarify|reason=Define "%"! Without unambiguous explanation, it can be mass/mass, mass/volume, volume/mass, volume/volume, mole/mole or who knows what. Readers have no ability to read the author's mind. Using ambiguous units of measurement like "%" or "ppm" without unambiguous explanation what those units stand for is unacceptable, and irritates non-expert readers!|date=August 2023}}

}}

| Section9 = {{Chembox Related

| OtherFunction_label = [[chalcogen]]ides

| OtherFunction = {{ubl|[[Dimethyl ether]] (dimethyl oxide)|[[Dimethyl selenide]]|[[Dimethyl telluride]]}}

| OtherCompounds = {{ubl|[[Dimethyl sulfoxide]]|[[Dimethyl sulfone]]}}

}}

'''Dimethyl sulfide''' ('''DMS''') or methylthiomethane is an [[Organosulfur compounds|organosulfur]] compound with the formula {{chem2|(CH3)2S}}. The simplest [[thioether]], it is a [[flammable liquid]] that boils at {{convert|37|°C}} and has a characteristic disagreeable odor. It is a component of the smell produced from cooking of certain vegetables, notably [[maize]], [[cabbage]], [[beetroot]], and [[seafoods]]. It is also an indication of [[bacteria]]l contamination in [[malt]] production and [[brewing]]. It is a breakdown product of [[dimethylsulfoniopropionate]] (DMSP), and is also produced by the bacterial metabolism of [[methanethiol]].

==Occurrence and production ==

DMS originates primarily from DMSP, a major secondary metabolite in some [[marine algae]].<ref>{{cite journal|author1=Stefels, J. |author2=Steinke, M.|author3=Turner, S.|author4=Malin, S.|author5=Belviso, A.|title=Environmental constraints on the production and removal of the climatically active gas dimethylsulphide (DMS) and implications for ecosystem modelling|journal=Biogeochemistry|year=2007|volume=83|issue=1–3|pages=245–275|doi=10.1007/s10533-007-9091-5|doi-access=free|bibcode=2007Biogc..83..245S }}</ref> DMS is the most abundant biological sulfur compound emitted to the [[Earth's atmosphere|atmosphere]].<ref>{{cite book

|first1=U.

|last1=Kappler

|first2=H.

|last2=Schäfer

|editor1=Kroneck, P. M. H.

|editor2=Sosa Torres, M. E.

|title=The Metal-Driven Biogeochemistry of Gaseous Compounds in the Environment

|series=Metal Ions in Life Sciences

|volume=14

|year=2014

|publisher=Springer

|chapter=Chapter 11. Transformations of Dimethylsulfide

|pages=279–313

|doi=10.1007/978-94-017-9269-1_11

|pmid=25416398

|isbn=978-94-017-9268-4

}}</ref><ref>{{cite journal|author1=Simpson, D.|author2=Winiwarter, W.|author3=Börjesson, G.|author4=Cinderby, S.|author5=Ferreiro, A. |author6=Guenther, A.|author7=Hewitt, C. N.|author8=Janson, R.|author9=Khalil, M. A. K.|author10=Owen, S.|author11=Pierce, T. E.|author12=Puxbaum, H.|author13=Shearer, M.|author14=Skiba, U.|author15=Steinbrecher, R.|author16=Tarrasón, L.|author17=Öquist, M. G.|title=Inventorying emissions from nature in Europe|journal=Journal of Geophysical Research|year=1999|volume=104|issue=D7|pages=8113–8152|doi=10.1029/98JD02747|bibcode=1999JGR...104.8113S|s2cid=54677953 |url=http://www.escholarship.org/uc/item/9qv1m5k7|doi-access=free}}</ref> Emission occurs over the [[ocean]]s by [[phytoplankton]]. DMS is also produced naturally by bacterial transformation of [[dimethyl sulfoxide]] (DMSO) waste that is disposed of into sewers, where it can cause environmental odor problems.<ref>{{cite journal|author1=Glindemann, D.|author2=Novak, J.|author3=Witherspoon, J.|title=Dimethyl Sulfoxide (DMSO) Waste Residues and Municipal Waste Water Odor by Dimethyl Sulfide (DMS): the North-East WPCP Plant of Philadelphia|journal=Environmental Science and Technology|year=2006|volume=40|issue=1|pages=202–207|doi=10.1021/es051312a|pmid=16433352|bibcode=2006EnST...40..202G}}</ref>

DMS is oxidized in the marine atmosphere to various sulfur-containing compounds, such as [[sulfur dioxide]], [[dimethyl sulfoxide]] (DMSO), [[Methylsulfonylmethane|dimethyl sulfone]], [[methanesulfonic acid]] and [[sulfuric acid]].<ref>{{cite journal|author1=Lucas, D. D. |author2=Prinn, R. G.|title=Parametric sensitivity and uncertainty analysis of dimethylsulfide oxidation in the clear-sky remote marine boundary layer|journal=Atmospheric Chemistry and Physics|year=2005|volume=5|issue=6|pages=1505–1525|doi=10.5194/acp-5-1505-2005|bibcode=2005ACP.....5.1505L|url=https://hal.archives-ouvertes.fr/hal-00295675/file/acp-5-1505-2005.pdf|doi-access=free}}</ref> Among these compounds, sulfuric acid has the potential to create new [[aerosols]] which act as [[cloud condensation nuclei]]. It usually results in the formation of [[Sulfate aerosol|sulfate particles]] in the troposphere. Through this interaction with [[cloud]] formation, the massive production of atmospheric DMS over the oceans may have a significant impact on the Earth's [[climate]].<ref>{{cite journal|author1=Malin, G.|author2=Turner, S. M.|author3=Liss, P. S.|title=Sulfur: The plankton/climate connection|journal=Journal of Phycology|year=1992|volume=28|issue=5|pages=590–597|doi=10.1111/j.0022-3646.1992.00590.x|bibcode=1992JPcgy..28..590M |s2cid=86179536}}</ref><ref>{{Cite journal|title=Climate sensitivity to ocean dimethylsulphide emissions|journal = Geophysical Research Letters|last1=Gunson|first1=J.R.|last2=Spall, S.A.|date=1 April 2006|doi=10.1029/2005GL024982|last3=Anderson, T. R.|last4=Jones, A.|last5=Totterdell, I.J.|last6=Woodage, M.J.|bibcode=2006GeoRL..33.7701G|volume=33|issue = 7|pages = L07701|doi-access=free}}</ref> The [[CLAW hypothesis]] suggests that in this manner DMS may play a role in planetary [[homeostasis]].<ref name="CLAW87">{{cite journal|author1=Charlson, R. J.|author2=Lovelock, J. E.|author3=Andreae, M. O.|author4=Warren, S. G.|authorlink1=Robert Jay Charlson|authorlink2=James Lovelock|title=Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate|journal=Nature|year=1987|volume=326|issue=6114|pages=655–661|doi=10.1038/326655a0|bibcode=1987Natur.326..655C|s2cid=4321239}}</ref>

Marine phytoplankton also produce dimethyl sulfide,<ref>{{cite web|url=http://www.whoi.edu/oceanus/feature/dms--the-climate-gas-youve-never-heard-of|title=The Climate Gas You've Never Heard Of|publisher=Oceanus Magazine}}</ref> and DMS is also produced by bacterial cleavage of extracellular DMSP.<ref>{{Cite journal|year=1994|title=Dimethylsulfide production from dimethylsulfoniopropionate by a marine bacterium|journal=Marine Ecology Progress Series|volume=110|pages=95–103|doi=10.3354/meps110095|bibcode=1994MEPS..110...95L|last1=Ledyard|first1=K. M.|last2=Dacey|first2=J. W. H.|doi-access=free}}</ref> DMS has been characterized as the "smell of the sea",<ref>{{cite web|publisher=University of East Anglia|url=http://www.uea.ac.uk/mac/comm/media/press/2007/feb/Cloning+the+smell+of+the+seaside|title=Cloning the smell of the seaside|date=2 February 2007|access-date=24 May 2012|archive-date=12 November 2013|archive-url=https://web.archive.org/web/20131112091408/http://www.uea.ac.uk/mac/comm/media/press/2007/feb/Cloning+the+smell+of+the+seaside|url-status=dead}}</ref> though it would be more accurate to say that DMS is a component of the smell of the sea, others being chemical derivatives of DMS, such as oxides, and yet others being algal [[pheromone]]s such as [[dictyopterene]]s.<ref>{{cite journal|author1=Itoh, T.|author2=Inoue, H.|author3=Emoto, S.|title=Synthesis of Dictyopterene A: Optically Active Tributylstannylcyclopropane as a Chiral Synthon|journal=Bulletin of the Chemical Society of Japan|issn=1348-0634|year=2000|volume=73|issue=2|pages=409–416|doi=10.1246/bcsj.73.409}}</ref>

Dimethyl sulfide, [[dimethyl disulfide]], and [[dimethyl trisulfide]] have been found among the volatiles given off by the fly-attracting plant known as [[dead-horse arum]] (''[[Helicodiceros muscivorus]]''). Those compounds are components of an [[odor]] like rotting meat, which attracts various [[Pollination|pollinators]] that feed on carrion, such as many species of flies.<ref>{{cite journal|author1=Stensmyr, M. C. |author2=Urru, I.|author3=Collu, I.|author4=Celander, M.|author5=Hansson, B. S.|author6=Angioy, A.-M.|title=Rotting Smell of Dead-Horse Arum Florets|journal=Nature|year=2002|volume=420|issue=6916|pages=625–626|doi=10.1038/420625a|pmid=12478279|bibcode=2002Natur.420..625S|s2cid=1001475}}</ref>

On September 12, 2023, [[NASA]] announced that their investigation into [[exoplanet]] [[K2-18b]] revealed the possible presence of dimethyl sulfide, noting "On Earth, this is only produced by life."<ref>{{cite web|url=https://www.nasa.gov/goddard/2023/webb-discovers-methane-carbon-dioxide-in-atmosphere-of-k2-18b|title=Webb Discovers Methane, Carbon Dioxide in Atmosphere of K2-18 b|date=12 September 2023|access-date=12 September 2023}}</ref>

===Industrial processes===

In industry dimethyl sulfide is produced by treating [[hydrogen sulfide]] with excess [[methanol]] over an [[aluminium oxide]] [[catalyst]]:<ref name=Ullmann>{{cite book|last=Roy|first=K.-M.|chapter=Thiols and Organic Sulfides|title=Ullmann's Encyclopedia of Industrial Chemistry|date=15 June 2000|page=8|doi=10.1002/14356007.a26_767|isbn=978-3-527-30673-2 }}</ref>

:{{chem2|2 CH3OH + H2S → (CH3)2S + 2 H2O}}

Dimethyl sulfide is emitted by [[kraft pulping]] mills as a side product from [[delignification]].

=== Physiology of dimethyl sulfide ===

Dimethyl sulfide is normally present at very low levels in healthy people, namely less than 7&nbsp;[[Molar concentration|nM]] in blood, less than 3&nbsp;nM in urine and 0.13 to 0.65&nbsp;nM on expired breath.<ref>{{cite journal|last=Gahl|first=W. A.|author2=Bernardini, I.|author3=Finkelstein, J. D.|author4=Tangerman, A.|author5=Martin, J. J.|author6=Blom, H. J.|author7=Mullen, K. D.|author8= Mudd, S. H.|title=Transsulfuration in an adult with hepatic methionine adenosyltransferase deficiency.|journal=The Journal of Clinical Investigation|date=February 1988|volume=81|issue=2|pages=390–397|pmid=3339126|doi=10.1172/JCI113331|pmc=329581}}</ref><ref>{{cite journal|last=Tangerman|first=A.|title=Measurement and biological significance of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices.|journal=Journal of Chromatography B |date=15 October 2009|volume=877|issue=28|pages=3366–3377|pmid=19505855|doi=10.1016/j.jchromb.2009.05.026}}</ref>

At pathologically dangerous concentrations, this is known as dimethylsulfidemia. This condition is associated with [[halitosis|blood borne halitosis]] and [[dimethylsulfiduria]].<ref>{{cite journal|pmid=17716310|doi=10.1111/j.1600-051X.2007.01116.x|volume=34|issue=9|title=Intra- and extra-oral halitosis: finding of a new form of extra-oral blood-borne halitosis caused by dimethyl sulphide|date=September 2007|journal=J. Clin. Periodontol.|pages=748–755|last1=Tangerman|first1=A.|last2=Winkel|first2=E. G.}}</ref><ref>{{cite journal|last=Tangerman|first=A.|author2=Winkel, E. G.|title=The portable gas chromatograph OralChroma: a method of choice to detect oral and extra-oral halitosis.|journal=Journal of Breath Research|date=March 2008|volume=2|issue=1|pages=017010|pmid=21386154|doi=10.1088/1752-7155/2/1/017010|s2cid=572545 }}</ref><ref>{{cite journal|last=Tangerman|first=A.|author2=Winkel, E. G.|title=Extra-oral halitosis: an overview|journal=Journal of Breath Research|date=2 March 2010 |volume=4 |issue=1 |pages=017003 |pmid=21386205 |doi=10.1088/1752-7155/4/1/017003|bibcode=2010JBR.....4a7003T|s2cid=5342660 }}</ref>

In people with chronic liver disease (cirrhosis), high levels of dimethyl sulfide may be present in the breath, leading to an unpleasant smell ([[fetor hepaticus]]).

== Odor ==

Dimethyl sulfide has a characteristic odor commonly described as [[cabbage]]-like. It becomes highly disagreeable at even quite low concentrations. Some reports claim that DMS has a low olfactory threshold that varies from 0.02 to 0.1&nbsp;ppm{{clarify|reason=Define "ppm"! Without unambiguous explanation, it can be mass/mass, mass/volume, volume/mass, volume/volume, mole/mole or who knows what. Readers have no ability to read the expert's mind. Using ambiguous units of measurement like "%" or "ppm" without unambiguous explanation what those units stand for is unacceptable, and irritates non-expert readers!|date=August 2023}} between different persons, but it has been suggested that the odor attributed to dimethyl sulfide may in fact be due to disulfides, polysulfides and thiol impurities, since the odor of dimethyl sulfide is much less disagreeable after it is freshly washed with saturated aqueous mercuric chloride.<ref>{{cite book|author=Morton, T. H.|year=2000|chapter=Archiving Odors|editor1=Bhushan, N.|editor2=Rosenfeld, S.|title = Of Molecules and Mind|pages=205–216|location=Oxford|publisher=Oxford University Press}}</ref> Dimethyl sulfide is also available as a food additive to impart a savory flavor; in such use, its concentration is low. [[Beetroot]],<ref>{{cite journal|author1=Parliment, T. H.|author2=Kolor, M. G.|author3=Maing, I. Y.|title=Identification of the Major Volatile Components of Cooked Beets|journal=Journal of Food Science|year=1977|volume=42|issue=6|pages=1592–1593|doi=10.1111/j.1365-2621.1977.tb08434.x}}</ref> [[asparagus]],<ref>{{cite journal|title=Contribution of volatile compounds to the flavor of cooked asparagus|first1=Detlef|last1=U.|first2=E.|last2=Hoberg|first3=T.|last3=Bittner|first4=W.|last4=Engewald|first5=K.|last5=Meilchen|journal=European Food Research and Technology|volume=213|issue=3|pages=200–204|doi=10.1007/s002170100349|year=2001|s2cid=95248775}}</ref> [[cabbage]], [[maize]] and [[seafoods]] produce dimethyl sulfide when cooked.

Dimethyl sulfide is also produced by marine [[plankton]]ic microorganisms such as the [[coccolithophore]]s and so is one of the main components responsible for the characteristic odor of [[sea water]] [[aerosol]]s, which make up a part of [[sea air]]. In the [[Victorian era]], before DMS was discovered, the origin of sea air's 'bracing' aroma was attributed to [[ozone]].<ref>{{Cite news|first=R.|last= Highfield|url=https://www.telegraph.co.uk/news/uknews/1541342/Secrets-of-bracing-sea-air-bottled-by-scientists.html|title=Secrets of 'bracing' sea air bottled by scientists|journal=Daily Telegraph|date=2 February 2007|access-date=27 March 2020|issn=0307-1235}}</ref>

Dimethyl sulfide is the main volatile chemical produced by various species of [[truffle]], and is the compound that animals trained to uncover the fungus (such as [[pig]]s and [[detection dogs]]) sniff out when searching for them.<ref name="TruffleSulfide">{{Cite journal|last1= Talou|first1= T.|last2=G aset|first2= A.|last3= Delmas|first3= M.|last4= Kulifaj |first4= M.|last5=Montant|first5=C.|date=1990|title=Dimethyl sulphide: the secret for black truffle hunting by animals? |journal= Mycological Research|volume= 94|issue= 2|pages= 277–278|doi= 10.1016/s0953-7562(09)80630-8|issn=0953-7562}}</ref>

== Industrial uses ==

Dimethyl sulfide is considered the most important thioether produced industrially. One major use is for the production of [[borane dimethyl sulfide]] from [[diborane]]:<ref name=Ullmann/>

:{{chem2|B2H6 + 2 (CH3)2S → 2 BH3*S(CH3)2}}

Oxidation of dimethyl sulfide gives the solvent [[dimethyl sulfoxide]]. Further oxidation affords [[dimethyl sulfone]].

== Chemical reactions==

As illustrated above by the formation of its adduct with borane, dimethyl sulfide is a Lewis base. It is classified as a [[HSAB theory|soft ligand]] (see also [[ECW model]]). It forms [[transition metal thioether complex|complexes]] with many transition metals but such adducts are often labile. For example, it serves a displaceable ligand in [[chloro(dimethyl sulfide)gold(I)]].

Dimethyl sulfide is used in the workup of the [[ozonolysis]] of [[alkenes]]. It reduces the intermediate trioxolane. The [[Swern oxidation]] produces dimethyl sulfide by reduction of dimethylsulfoxide.

With chlorinating agents such as [[sulfuryl chloride]], dimethyl sulfide converts to [[chloromethyl methyl sulfide]]:

:{{chem2|SO2Cl2 + (CH3)2S → SO2 + HCl + ClCH2SCH3}}

Like other methylthio compounds, DMS is deprotonated by [[butyl lithium]]:<ref>{{cite journal |doi=10.1021/cr400187u|title=Role of Organolithium Aggregates and Mixed Aggregates in Organolithium Mechanisms |year=2013 |last1=Reich |first1=Hans J. |journal=Chemical Reviews |volume=113 |issue=9 |pages=7130–7178 |pmid=23941648 }}</ref>

:{{chem2|CH3CH2CH2CH2Li + (CH3)2S → CH3CH2CH2CH3 + LiCH2SCH3}}

== Safety ==

Dimethyl sulfide is highly [[flammable]] and an eye and skin [[irritation|irritant]]. It is harmful if swallowed. It has an [[unpleasant odor]] at even extremely low concentrations. Its ignition temperature is 205&nbsp;°C.

== See also ==

* ''[[Emiliania huxleyi]]'', a coccolithophorid producing DMS

* [[Phosphine]], another molecule that is associated with biological processes and thus used as a [[biosignature]] in [[astrobiology]]

* [[Geosmin]], the substance responsible for the odour of earth

* [[Petrichor]], the earthy scent produced when rain falls on dry soil

== References ==

{{Reflist}}

== External links ==

* [https://web.archive.org/web/20050427100311/http://saga.pmel.noaa.gov/underwaydms/why.html Dimethylsulfide (DMS) in the Bering Sea and Adjacent Waters: In-situ and Satellite Observations]

* [https://web.archive.org/web/20150214081038/http://saga.pmel.noaa.gov/review/dms_climate.html DMS and Climate]

* [https://archive.today/20130119003450/http://www.chemicalland21.com/arokorhi/industrialchem/solalc/DIMETHYL%20SULFIDE.htm Industrial chemicals]

{{Authority control}}

[[Category:Foul-smelling chemicals]]

[[Category:Trace gases]]