Dimethyl sulfide

Dimethyl sulfide
Names
Preferred IUPAC name
methylthiomethane
Systematic IUPAC name
(Methylsulfanyl)methane[1]
Identifiers
75-18-3 YesY
3DMet B00138
1696847
ChEBI CHEBI:17437 YesY
ChEMBL ChEMBL15580 YesY
ChemSpider 1039 YesY
EC Number 200-846-2
Jmol 3D model Interactive image
KEGG C00580 YesY
MeSH dimethyl+sulfide
PubChem 1068
RTECS number PV5075000
UNII QS3J7O7L3U YesY
UN number 1164
Properties
C2H6S
Molar mass 62.13 g·mol−1
Appearance Colourless liquid
Odor Cabbage, sulfurous
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)
1.435
Thermochemistry
-66.9--63.9 kJ mol−1
-2.1818--2.1812 MJ mol−1
Hazards
Safety data sheet osha.gov
GHS pictograms
GHS signal word DANGER
H225, H315, H318, H335
P210, P261, P280, P305+351+338
F Xn
R-phrases R11, R22, R37/38, R41
S-phrases S7, S9, S16, S26, S29, S33, S36/39
Flash point −36 °C (−33 °F; 237 K)
206 °C (403 °F; 479 K)
Explosive limits 19.7%
Related compounds
Dimethyl ether (dimethyl oxide)

Dimethyl selenide
Dimethyl telluride

Related compounds
 Dimethyl sulfoxide

Dimethyl sulfone

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. Dimethyl sulfide is a water-insoluble 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.

Natural occurrence

DMS originates primarily from DMSP, a major secondary metabolite in some marine algae.[2] DMS is the most abundant biological sulfur compound emitted to the atmosphere.[3][4] 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.[5]

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.[6] Among these compounds, sulfuric acid has the potential to create new aerosols which act as cloud condensation nuclei. 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.[7] The CLAW hypothesis suggests that in this manner DMS may play a role in planetary homeostasis.[8]

Smell

Dimethyl sulfide has a characteristic smell 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 between different persons, but it has been suggested that the odor attributed to dimethyl sulfide may in fact be due to di- and polysulfides and thiol impurities, since the odor of dimethyl sulfide is much less disagreeable after it is freshly washed with saturated aqueous mercuric chloride.[9] Dimethyl sulfide is also available as a food additive to impart a savory flavor; in such use, its concentration is low. Beetroot,[10] asparagus,[11] cabbage, corn and seafoods produce dimethyl sulfide when cooked.

Marine phytoplankton also produces dimethyl sulfide. DMS has been characterized as the "smell of the sea",[12] 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.[13]

Dimethyl sulfide also is an odorant emitted by kraft pulping mills, and it is a byproduct of Swern oxidation.

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.[14]

Preparation

In industry dimethyl sulfide is produced by treating hydrogen sulfide with excess methanol over an aluminum oxide catalyst.[15]

Industrial uses

Dimethyl sulfide has been used in petroleum refining to pre-sulfide hydrodesulfurization catalysts, although other disulfides or polysulfides are preferred and easier to handle. It is used as a presulfiding agent to control the formation of coke and carbon monoxide in ethylene production. DMS is also used in a range of organic syntheses, including as a reducing agent in ozonolysis reactions. It also has a use as a food flavoring component. It can also be oxidized to dimethyl sulfoxide, (DMSO), which is an important industrial solvent.

The largest single commercial producer of DMS in the world is Gaylord Chemical Corporation, which until mid-2010 was a significant economic component of the paper industry of Bogalusa, Louisiana. The Bogalusa DMS plant operated continuously until this date, since its startup in 1961 by the now defunct Crown Zellerbach Corporation. The process technology practiced at the Bogalusa plant (alkylation of sulfur using Kraft lignin) is no longer in operation anywhere in the world. All DMS manufacturers currently use hydrocarbon-based feedstocks. Gaylord has no production of any kind at the old Louisiana site after opening its expanded DMS / Dimethyl sulfoxide operation in Tuscaloosa, Alabama in 2010.[16]

ChevronPhillips Chemical Company is another major manufacturer of DMS. CP Chem produces this material at their facilities in Borger, Texas, USA and Tessenderlo, Belgium.

Other uses

Dimethyl sulfide finds a niche use as a displaceable ligand in chloro(dimethyl sulfide)gold(I) and other coordination compounds. Dimethyl sulfide is also used in the ozonolysis of alkenes, reducing the intermediate trioxolane and oxidizing to DMSO.

alkene + ozone + DMS → aldehyde(1) + aldehyde(2) + DMSO

Safety

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

Physiology of dimethyl sulfide

Dimethyl sulfide is normally present at very low levels in healthy people, namely < 7nM in blood, < 3 nM in urine and 0.13 - 0.65 nM on expired breath.[17][18]

When dimethyl sulfide becomes pathologically increased, this is known as dimethylsulfidemia, which is associated with blood borne halitosis and dimethylsulfiduria.[19][20][21]

See also

References

  1. ↑ "dimethyl sulfide (CHEBI:17437)". Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. 17 October 2009. Main. Retrieved 19 October 2011.
  2. ↑ 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.
  3. ↑ Kappler, Ulrike; Schäfer, Hendrik (2014). "Chapter 11. Transformations of Dimethylsulfide". In Peter M.H. Kroneck and Martha E. Sosa Torres. 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.
  4. ↑ 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.
  5. ↑ 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.
  6. ↑ 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.
  7. ↑ 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.
  8. ↑ 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. Bibcode:1987Natur.326..655C. doi:10.1038/326655a0.
  9. ↑ Morton, T. H. (2000). "Archiving Odors". In Bhushan, N.; Rosenfeld, S. Of Molecules and Mind. Oxford: Oxford University Press. pp. 205–216.
  10. ↑ 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.
  11. ↑ http://www.springerlink.com.libproxy.tkk.fi/content/djbrepd4mjpjqgwn/
  12. ↑ "Cloning the smell of the seaside". University of East Anglia. 2007-02-02.
  13. ↑ 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.
  14. ↑ 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. Bibcode:2002Natur.420..625S. doi:10.1038/420625a. PMID 12478279.
  15. ↑ Roy, Kathrin-Maria (15 June 2000). "Thiols and Organic Sulfides". Ullmann's Encyclopedia of Industrial Chemistry: 8. doi:10.1002/14356007.a26_767. Retrieved 2003.
  16. ↑ "Locations". Gaylord Chemicals.
  17. ↑ Gahl, WA; Bernardini, I; Finkelstein, JD; Tangerman, A; Martin, JJ; Blom, HJ; Mullen, KD; Mudd, SH (February 1988). "Transsulfuration in an adult with hepatic methionine adenosyltransferase deficiency.". The Journal of Clinical Investigation 81 (2): 390–7. doi:10.1172/JCI113331. PMC 329581. PMID 3339126.
  18. ↑ Tangerman, A (Oct 15, 2009). "Measurement and biological significance of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices.". Journal of chromatography. B, Analytical technologies in the biomedical and life sciences 877 (28): 3366–77. doi:10.1016/j.jchromb.2009.05.026. PMID 19505855.
  19. ↑ "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): 748–55. September 2007. doi:10.1111/j.1600-051X.2007.01116.x. PMID 17716310.
  20. ↑ Tangerman, A; Winkel, EG (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.
  21. ↑ Tangerman, A; Winkel, EG (Mar 2, 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.

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