Chemistry:Dimethyl sulfide

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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
EC Number
  • 200-846-2
KEGG
MeSH dimethyl+sulfide
RTECS number
  • PV5075000
UNII
UN number 1164
Properties
(CH
3)
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
−66.9 tp −63.9 kJ⋅mol−1
−2.1818 to −2.1812 MJ⋅mol−1
Hazards
Safety data sheet osha.gov
GHS pictograms GHS02: Flammable GHS05: Corrosive GHS07: Harmful
GHS Signal word DANGER
H225, H315, H318, H335
P210, P261, P280, P305+351+338
Flash point −36 °C (−33 °F; 237 K)
206 °C (403 °F; 479 K)
Explosive limits 19.7%[clarification needed]
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☑Y verify (what is ☑Y☒N ?)
Infobox references

Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH
3)
2S. The simplest thioether, it is a flammable liquid that boils at 37 °C (99 °F) 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 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.

Occurrence and production

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

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

2 CH
3OH + H
2S → (CH
3)
2S + 2 H
2O

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 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

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

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

B
2H
6 + 2 (CH
3)
2S → 2 BH
3 · S(CH
3)
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 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:

SO
2Cl
2 + (CH
3)
2S → SO
2 + HCl + ClCH
2SCH
3

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

CH
3CH
2CH
2CH
2Li + (CH
3)
2S → CH
3CH
2CH
2CH
3 + LiCH
2SCH
3

Safety

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

See also

References

  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 Crystallographic Data Centre. doi:10.5517/ccscgn7. https://dx.doi.org/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. ↑ 3.0 3.1 3.2 "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. ↑ https://pubchem.ncbi.nlm.nih.gov/compound/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. doi:10.1007/s10533-007-9091-5. 
  6. ↑ Kappler, U.; Schäfer, H. (2014). "Chapter 11. Transformations of Dimethylsulfide". The Metal-Driven Biogeochemistry of Gaseous Compounds in the Environment. Metal Ions in Life Sciences. 14. Springer. pp. 279–313. doi:10.1007/978-94-017-9269-1_11. ISBN 978-94-017-9268-4. 
  7. ↑ Simpson, D.; Winiwarter, W.; Börjesson, G.; Cinderby, S.; Ferreiro, A.; Guenther, A.; Hewitt, C. N.; Janson, R. et al. (1999). "Inventorying emissions from nature in Europe". Journal of Geophysical Research 104 (D7): 8113–8152. doi:10.1029/98JD02747. Bibcode: 1999JGR...104.8113S. http://www.escholarship.org/uc/item/9qv1m5k7. 
  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. doi:10.1021/es051312a. PMID 16433352. Bibcode: 2006EnST...40..202G. 
  9. ↑ Lucas, D. D.; Prinn, R. G. (2005). "Parametric sensitivity and uncertainty analysis of dimethylsulfide oxidation in the clear-sky remote marine boundary layer". Atmospheric Chemistry and Physics 5 (6): 1505–1525. doi:10.5194/acp-5-1505-2005. Bibcode: 2005ACP.....5.1505L. https://hal.archives-ouvertes.fr/hal-00295675/file/acp-5-1505-2005.pdf. 
  10. ↑ Malin, G.; Turner, S. M.; Liss, P. S. (1992). "Sulfur: The plankton/climate connection". Journal of Phycology 28 (5): 590–597. doi:10.1111/j.0022-3646.1992.00590.x. 
  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. doi:10.1029/2005GL024982. Bibcode: 2006GeoRL..33.7701G. 
  12. ↑ Charlson, R. J.; Lovelock, J. E.; Andreae, M. O.; Warren, S. G. (1987). "Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate". Nature 326 (6114): 655–661. doi:10.1038/326655a0. Bibcode: 1987Natur.326..655C. 
  13. ↑ "The Climate Gas You've Never Heard Of". Oceanus Magazine. http://www.whoi.edu/oceanus/feature/dms--the-climate-gas-youve-never-heard-of. 
  14. ↑ Ledyard, K. M.; Dacey, J. W. H. (1994). "Dimethylsulfide production from dimethylsulfoniopropionate by a marine bacterium". Marine Ecology Progress Series 110: 95–103. doi:10.3354/meps110095. Bibcode: 1994MEPS..110...95L. 
  15. ↑ "Cloning the smell of the seaside". University of East Anglia. 2 February 2007. http://www.uea.ac.uk/mac/comm/media/press/2007/feb/Cloning+the+smell+of+the+seaside. 
  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. 
  17. ↑ Stensmyr, M. C.; Urru, I.; Collu, I.; Celander, M.; Hansson, B. S.; Angioy, A.-M. (2002). "Rotting Smell of Dead-Horse Arum Florets". Nature 420 (6916): 625–626. doi:10.1038/420625a. PMID 12478279. Bibcode: 2002Natur.420..625S. 
  18. ↑ "Webb Discovers Methane, Carbon Dioxide in Atmosphere of K2-18 b". 12 September 2023. https://www.nasa.gov/goddard/2023/webb-discovers-methane-carbon-dioxide-in-atmosphere-of-k2-18b. 
  19. ↑ 19.0 19.1 Roy, K.-M. (15 June 2000). "Thiols and Organic Sulfides". Ullmann's Encyclopedia of Industrial Chemistry. p. 8. doi:10.1002/14356007.a26_767. ISBN 978-3-527-30673-2. 
  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. PMID 3339126. 
  21. ↑ Tangerman, A. (15 October 2009). "Measurement and biological significance of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices.". Journal of Chromatography B 877 (28): 3366–3377. doi:10.1016/j.jchromb.2009.05.026. PMID 19505855. 
  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. 
  24. ↑ Tangerman, A.; Winkel, E. G. (2 March 2010). "Extra-oral halitosis: an overview". Journal of Breath Research 4 (1): 017003. doi:10.1088/1752-7155/4/1/017003. PMID 21386205. Bibcode: 2010JBR.....4a7003T. 
  25. ↑ Morton, T. H. (2000). "Archiving Odors". 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. 
  28. ↑ Highfield, R. (2 February 2007). "Secrets of 'bracing' sea air bottled by scientists". Daily Telegraph. ISSN 0307-1235. https://www.telegraph.co.uk/news/uknews/1541342/Secrets-of-bracing-sea-air-bottled-by-scientists.html. 
  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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