Tetrahydrothiophene

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Tetrahydrothiophene
Tetrahydrothiophene.svg
Tetrahydrothiophene3d.png
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 GHS02: FlammableGHS07: Harmful
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

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.

Synthesis and reactions[edit]

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[edit]

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[edit]

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.

See also[edit]

References[edit]

  1. ^ Armarego WF, Chai CL (2003). "Purification of Organic Chemicals": 361. doi:10.1016/B978-075067571-0/50008-9. Cite journal requires |journal= (help)
  2. ^ Loev, B; Massengale, JT U. S. Patent 2,899,444, "Synthesis of Tetrahydrothiophene", 8/11/1959
  3. ^ a b 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": 85–91. doi:10.1002/9780470132579.ch17. ISSN 1934-4716. Cite journal requires |journal= (help)
  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. 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: 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.