Tetrahydrothiophene

Tetrahydrothiophene is an organosulfur compound with the formula (CH2)4S. It contains a five-membered ring consisting of four carbon atoms and a sulfur atom. It is the saturated analog of thiophene. It is a volatile, colorless liquid with an intensely unpleasant odor. It is also known as thiophane, thiolane, or THT.

Tetrahydrothiophene
Names
IUPAC name
Thiolane
Other names
Tetrahydrothiophene,
thiophane, tetramethylene sulfide
Identifiers
3D model (JSmol)
Abbreviations THT
102392
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.391
EC Number
  • 203-728-9
RTECS number
  • XN0370000
UNII
UN number 2412
Properties
C4H8S
Molar mass 88.17 g·mol−1
Density 0.997 g/mL[1]
Melting point −96 °C (−141 °F; 177 K)
Boiling point 119 °C (246 °F; 392 K)
Hazards
Main hazards Stench, flammable, irritant
Safety data sheet Oakwood
GHS pictograms
GHS Signal word Danger
H225, H302, H312, H315, H319, H332, H412
P210, P233, P240, P241, P242, P243, P261, P264, P270, P271, P273, P280, P301+312, P302+352, P303+361+353, P304+312, P304+340, P305+351+338, P312, P321, P322, P330, P332+313, P337+313, P362
Flash point 12 °C (54 °F; 285 K)
200 °C (392 °F; 473 K)
Related compounds
Related compounds
 Tetrahydrofuran, Thiophene, Selenolane, Thiazolidine, Dithiolane, Thiane
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

Synthesis and reactions

Tetrahydrothiophene is prepared by the reaction of tetrahydrofuran with hydrogen sulfide. This vapor-phase reaction is catalyzed by alumina and other heterogenous acid catalysts.[2][3]

This compound is a ligand in coordination chemistry, an example being the complex chloro(tetrahydrothiophene)gold(I).[4]

Oxidation of THT gives the solvent called sulfolane, a polar solvent with almost no odor. Sulfolane is more conventionally prepared from butadiene.

Natural occurrence

Both unsubstituted and substituted tetrahydrothiophenes are reported to occur in nature. For example, tetrahydrothiophene occurs as a volatile from Eruca sativa Mill. (salad rocket)[5] while monocyclic substituted tetrahydrothiophenes have been isolated from Allium fistulosum 'Kujou',[6] Allium sativum (garlic),[7] Allium cepa (onion),[8] Allium schoenoprasum (chives),[9] and Salacia prinoides.[10] Albomycins are a group of tetrahydrothiophene-ring containing antibiotics from streptomyces while biotin and neothiobinupharidine (and other nuphar alkaloids [11]), are examples of bicyclic and polycyclic tetrahydrothiophene-ring containing natural products, respectively.

Applications

Because of its smell, tetrahydrothiophene has been used as an odorant in LPG,[3] albeit no longer in North America. It is also used as an odorant for natural gas, usually in mixtures containing tert-butylthiol.

Tetrahydrothiophene is a Lewis base classified as a soft base and its donor properties are discussed in the ECW model.

See also

References
  1. Armarego WF, Chai CL (2003). "Purification of Organic Chemicals". Purification of Laboratory Chemicals. p. 361. doi:10.1016/B978-075067571-0/50008-9. ISBN 9780750675710.
  2. Loev, B; Massengale, JT U. S. Patent 2,899,444, "Synthesis of Tetrahydrothiophene", 8/11/1959
  3. Jonathan Swanston (2006). "Thiophene". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a26_793.pub2.
  4. Uson R, Laguna A, Laguna M, Briggs DA, Murray HH, Fackler JP (2007). "(Tetrahydrothiophene)Gold(I) or Gold(III) Complexes". Inorganic Syntheses. pp. 85–91. doi:10.1002/9780470132579.ch17. ISBN 9780470132579. ISSN 1934-4716.
  5. Aissani, N; et al. (2006). "Nematicidal Activity of the Volatilome of Eruca sativa on Meloidogyne incognita". Journal of Agricultural and Food Chemistry. 63 (27): 6120–6125. doi:10.1021/acs.jafc.5b02425. PMID 26082278.
  6. Fukaya, M; et al. (2018). "Rare Sulfur-Containing Compounds, Kujounins A1 and A2 and Allium Sulfoxide A1, from Allium fistulosum 'Kujou'". Organic Letters. 20 (1): 28–31. doi:10.1021/acs.orglett.7b03234. PMID 29227665.
  7. Block, E; et al. (2018). "Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (Allium sativum)". Journal of Agricultural and Food Chemistry. 66 (39): 10193–10204. doi:10.1021/acs.jafc.8b03638. OSTI 1490686. PMID 30196701.
  8. Aoyagi, M; et al. (2011). "Structure and Bioactivity of Thiosulfinates Resulting from Suppression of Lachrymatory Factor Synthase in Onion". Journal of Agricultural and Food Chemistry. 59 (20): 10893–10900. doi:10.1021/jf202446q. PMID 21905712.
  9. Fukaya, M; et al. (2019). "Cyclic Sulfur Metabolites from Allium schoenoprasum var. foliosum". Phytochemistry Letters. 29: 125–128. doi:10.1016/j.phytol.2018.11.018.
  10. Tanabe, G; et al. (2008). "Synthesis and Elucidation of Absolute Stereochemistry of Salaprinol, another Thiosugar Sulfonium Sulfate from the Ayurvedic Traditional Medicine Salacia prinoides". Tetrahedron. 64 (43): 10080–10086. doi:10.1016/j.tet.2008.08.010.
  11. Korotkov, A; et al. (2015). "Total Syntheses and Biological Evaluation of Both Enantiomers of Several Hydroxylated Dimeric Nuphar Alkaloids". Angewandte Chemie International Edition. 54 (36): 10604–10607. doi:10.1002/anie.201503934. PMC 4691328. PMID 26205039.
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