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Dimethyl sulfide

(Redirected from Dimethyl thioether)

Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. It is the simplest thioether and has a characteristic disagreeable odor. It is a flammable liquid that boils at 37 °C (99 °F). It is a component of the smell produced from cooking of certain vegetables (notably maize, cabbage, and beetroot) and seafoods. It is also an indication of bacterial contamination in malt production and brewing. It is a breakdown product of dimethylsulfoniopropionate (DMSP), and is also produced by the bacterial metabolism of methanethiol.

Dimethyl sulfide
Skeletal formula of dimethyl sulfide with all implicit hydrogens shown
Spacefill model of dimethyl sulfide
Space-filling model of the molecular structure[1][2]
Names
Preferred IUPAC name
(Methylsulfanyl)methane[3]
Other names
  • (Methylthio)methane[3]
  • Dimethyl sulfide[3]
  • Dimethyl thioether[4]
Identifiers
3D model (JSmol)
3DMet
1696847
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.770 Edit this at Wikidata
EC Number
  • 200-846-2
KEGG
MeSH dimethyl+sulfide
RTECS number
  • PV5075000
UNII
UN number 1164
  • InChI=1S/C2H6S/c1-3-2/h1-2H3 checkY
    Key: QMMFVYPAHWMCMS-UHFFFAOYSA-N checkY
  • Key: QMMFVYPAHWMCMS-UHFFFAOYAH
  • CSC
Properties
(CH3)2S
Molar mass 62.13 g·mol−1
Appearance Colourless liquid
Odor Stench: cabbage, sulfurous, unpleasant
Density 0.846 g·cm−3
Melting point −98 °C; −145 °F; 175 K
Boiling point 35 to 41 °C; 95 to 106 °F; 308 to 314 K
log P 0.977
Vapor pressure 53.7 kPa (at 20 °C)
−44.9×10−6 cm3/mol
1.435
Thermochemistry
−63.9 to −66.9 kJ⋅mol−1
−2.1812 to −2.1818 MJ⋅mol−1
Hazards
GHS labelling:
GHS02: Flammable GHS05: Corrosive GHS07: Exclamation mark
Danger
H225, H315, H318, H335
P210, P261, P280, P305+P351+P338
Flash point −36 °C (−33 °F; 237 K)
206 °C (403 °F; 479 K)
Explosive limits 19.7%[clarification needed]
Safety data sheet (SDS) osha.gov
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Occurrence and production

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DMS originates primarily from DMSP, a major secondary metabolite in some marine algae.[5] DMS is the most abundant biological sulfur compound emitted to the atmosphere.[6][7] Emission occurs over the oceans 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.[8]

DMS is oxidized in the marine atmosphere to various sulfur-containing compounds, such as sulfur dioxide, dimethyl sulfoxide (DMSO), dimethyl sulfone, methanesulfonic acid and sulfuric acid.[9] 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 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.[10][11] The CLAW hypothesis suggests that in this manner DMS may play a role in planetary homeostasis.[12]

Marine phytoplankton also produce dimethyl sulfide,[13] and DMS is also produced by bacterial cleavage of extracellular DMSP.[14] DMS has been characterized as the "smell of the sea",[15] 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 pheromones such as dictyopterenes.[16]

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 pollinators that feed on carrion, such as many species of flies.[17]

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."[18]

Industrial processes

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In industry dimethyl sulfide is produced by treating hydrogen sulfide with excess methanol over an aluminium oxide catalyst:[19]

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

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Dimethyl sulfide is normally present at very low levels in healthy people, namely less than 7 nM in blood, less than 3 nM in urine and 0.13 to 0.65 nM on expired breath.[20][21]

At pathologically dangerous concentrations, this is known as dimethylsulfidemia. This condition is associated with blood borne halitosis and dimethylsulfiduria.[22][23][24]

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

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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 ppm[clarification needed] 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.[25] Dimethyl sulfide is also available as a food additive to impart a savory flavor; in such use, its concentration is low. Beetroot,[26] asparagus,[27] cabbage, maize and seafoods produce dimethyl sulfide when cooked.

Dimethyl sulfide is also produced by marine planktonic microorganisms such as the coccolithophores and so is one of the main components responsible for the characteristic odor of sea water aerosols, 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.[28]

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 pigs and detection dogs) sniff out when searching for them.[29]

Industrial uses

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Dimethyl sulfide is considered the most important thioether produced industrially. One major use is for the production of borane dimethyl sulfide from diborane:[19]

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

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As illustrated above by the formation of its adduct with borane, dimethyl sulfide is a Lewis base. It is classified as a soft ligand (see also ECW model). It forms 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:

SO2Cl2 + (CH3)2S → SO2 + HCl + ClCH2SCH3

Like other methylthio compounds, DMS is deprotonated by butyl lithium:[30]

CH3CH2CH2CH2Li + (CH3)2S → CH3CH2CH2CH3 + LiCH2SCH3

Safety

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

See also

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References

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  1. ^ Moorthy, J.N.; Natarajan, P.; Venugopalan, P. (2010). "CSD Entry TUYLOP: 1,3,6,8-tetrakis(4-Methoxy-2,6-dimethylphenyl)pyrene bis(dimethyl sulfide) clathrate". Cambridge Structural Database: Access Structures. Cambridge Crystallographic Data Centre. doi:10.5517/ccscgn7. Retrieved 3 November 2021.
  2. ^ Moorthy, J. N.; Natarajan, P.; Venugopalan, P. (2009). "Abundant Lattice Inclusion Phenomenon with Sterically Hindered and Inherently Shape-Selective Tetraarylpyrenes". J. Org. Chem. 74 (22): 8566–8577. doi:10.1021/jo901465f. PMID 19831423.
  3. ^ a b c "Chapter P-6. Applications to Specific Classes of Compounds". Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 706. doi:10.1039/9781849733069-00648. ISBN 978-0-85404-182-4.
  4. ^ "Dimethyl sulfide".
  5. ^ Stefels, J.; Steinke, M.; Turner, S.; Malin, S.; Belviso, A. (2007). "Environmental constraints on the production and removal of the climatically active gas dimethylsulphide (DMS) and implications for ecosystem modelling". Biogeochemistry. 83 (1–3): 245–275. Bibcode:2007Biogc..83..245S. doi:10.1007/s10533-007-9091-5.
  6. ^ Kappler, U.; Schäfer, H. (2014). "Chapter 11. Transformations of Dimethylsulfide". In Kroneck, P. M. H.; Sosa Torres, M. E. (eds.). The Metal-Driven Biogeochemistry of Gaseous Compounds in the Environment. Metal Ions in Life Sciences. Vol. 14. Springer. pp. 279–313. doi:10.1007/978-94-017-9269-1_11. ISBN 978-94-017-9268-4. PMID 25416398.
  7. ^ Simpson, D.; Winiwarter, W.; Börjesson, G.; Cinderby, S.; Ferreiro, A.; Guenther, A.; Hewitt, C. N.; Janson, R.; Khalil, M. A. K.; Owen, S.; Pierce, T. E.; Puxbaum, H.; Shearer, M.; Skiba, U.; Steinbrecher, R.; Tarrasón, L.; Öquist, M. G. (1999). "Inventorying emissions from nature in Europe". Journal of Geophysical Research. 104 (D7): 8113–8152. Bibcode:1999JGR...104.8113S. doi:10.1029/98JD02747. S2CID 54677953.
  8. ^ Glindemann, D.; Novak, J.; Witherspoon, J. (2006). "Dimethyl Sulfoxide (DMSO) Waste Residues and Municipal Waste Water Odor by Dimethyl Sulfide (DMS): the North-East WPCP Plant of Philadelphia". Environmental Science and Technology. 40 (1): 202–207. Bibcode:2006EnST...40..202G. doi:10.1021/es051312a. PMID 16433352.
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  11. ^ Gunson, J.R.; Spall, S.A.; Anderson, T. R.; Jones, A.; Totterdell, I.J.; Woodage, M.J. (1 April 2006). "Climate sensitivity to ocean dimethylsulphide emissions". Geophysical Research Letters. 33 (7): L07701. Bibcode:2006GeoRL..33.7701G. doi:10.1029/2005GL024982.
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  13. ^ "The Climate Gas You've Never Heard Of". Oceanus Magazine.
  14. ^ Ledyard, K. M.; Dacey, J. W. H. (1994). "Dimethylsulfide production from dimethylsulfoniopropionate by a marine bacterium". Marine Ecology Progress Series. 110: 95–103. Bibcode:1994MEPS..110...95L. doi:10.3354/meps110095.
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  16. ^ Itoh, T.; Inoue, H.; Emoto, S. (2000). "Synthesis of Dictyopterene A: Optically Active Tributylstannylcyclopropane as a Chiral Synthon". Bulletin of the Chemical Society of Japan. 73 (2): 409–416. doi:10.1246/bcsj.73.409. ISSN 1348-0634.
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  18. ^ "Webb Discovers Methane, Carbon Dioxide in Atmosphere of K2-18 b". 12 September 2023. Retrieved 12 September 2023.
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  20. ^ Gahl, W. A.; Bernardini, I.; Finkelstein, J. D.; Tangerman, A.; Martin, J. J.; Blom, H. J.; Mullen, K. D.; Mudd, S. H. (February 1988). "Transsulfuration in an adult with hepatic methionine adenosyltransferase deficiency". The Journal of Clinical Investigation. 81 (2): 390–397. doi:10.1172/JCI113331. PMC 329581. PMID 3339126.
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  22. ^ Tangerman, A.; Winkel, E. G. (September 2007). "Intra- and extra-oral halitosis: finding of a new form of extra-oral blood-borne halitosis caused by dimethyl sulphide". J. Clin. Periodontol. 34 (9): 748–755. doi:10.1111/j.1600-051X.2007.01116.x. PMID 17716310.
  23. ^ Tangerman, A.; Winkel, E. G. (March 2008). "The portable gas chromatograph OralChroma: a method of choice to detect oral and extra-oral halitosis". Journal of Breath Research. 2 (1): 017010. doi:10.1088/1752-7155/2/1/017010. PMID 21386154. S2CID 572545.
  24. ^ Tangerman, A.; Winkel, E. G. (2 March 2010). "Extra-oral halitosis: an overview". Journal of Breath Research. 4 (1): 017003. Bibcode:2010JBR.....4a7003T. doi:10.1088/1752-7155/4/1/017003. PMID 21386205. S2CID 5342660.
  25. ^ Morton, T. H. (2000). "Archiving Odors". In Bhushan, N.; Rosenfeld, S. (eds.). Of Molecules and Mind. Oxford: Oxford University Press. pp. 205–216.
  26. ^ Parliment, T. H.; Kolor, M. G.; Maing, I. Y. (1977). "Identification of the Major Volatile Components of Cooked Beets". Journal of Food Science. 42 (6): 1592–1593. doi:10.1111/j.1365-2621.1977.tb08434.x.
  27. ^ U., Detlef; Hoberg, E.; Bittner, T.; Engewald, W.; Meilchen, K. (2001). "Contribution of volatile compounds to the flavor of cooked asparagus". European Food Research and Technology. 213 (3): 200–204. doi:10.1007/s002170100349. S2CID 95248775.
  28. ^ Highfield, R. (2 February 2007). "Secrets of 'bracing' sea air bottled by scientists". Daily Telegraph. ISSN 0307-1235. Retrieved 27 March 2020.
  29. ^ Talou, T.; G aset, A.; Delmas, M.; Kulifaj, M.; Montant, C. (1990). "Dimethyl sulphide: the secret for black truffle hunting by animals?". Mycological Research. 94 (2): 277–278. doi:10.1016/s0953-7562(09)80630-8. ISSN 0953-7562.
  30. ^ Reich, Hans J. (2013). "Role of Organolithium Aggregates and Mixed Aggregates in Organolithium Mechanisms". Chemical Reviews. 113 (9): 7130–7178. doi:10.1021/cr400187u. PMID 23941648.
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