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'''Tetrahydrothiophene''' is an [[organosulfur compound]] with the formula (CH<sub>2</sub>)<sub>4</sub>S. The molecule consists of a five-membered saturated ring with four [[Methylene group|methylene]] groups and a [[sulfur]] atom. It is the [[Saturated and unsaturated compounds|saturated]] [[structural analog|analog]] of [[thiophene]] or the sulfur analog of [[Tetrahydrofuran|THF]]. It is a volatile, colorless liquid with an intensely unpleasant [[odor]]. It is also known as '''thiophane''', '''thiolane''', or '''THT'''.
'''Tetrahydrothiophene''' is an [[organosulfur compound]] with the formula (CH<sub>2</sub>)<sub>4</sub>S. The molecule consists of a five-membered saturated ring with four [[Methylene group|methylene]] groups and a [[sulfur]] atom. It is the [[Saturated and unsaturated compounds|saturated]] [[structural analog|analog]] of [[thiophene]] and is therefore the sulfur analog of [[Tetrahydrofuran|THF]]. It is a volatile, colorless liquid with an intensely unpleasant [[odor]]. It is also known as '''thiophane''', '''thiolane''', or '''THT'''.


==Synthesis and reactions==
==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.<ref>Loev, B; Massengale, JT U. S. Patent 2,899,444, "Synthesis of Tetrahydrothiophene", 8/11/1959</ref><ref name="Ullmann">{{Ullmann|author=Jonathan Swanston|title=Thiophene|year=2006|doi=10.1002/14356007.a26_793.pub2}}</ref>
Tetrahydrothiophene is prepared by the reaction of [[tetrahydrofuran]] with [[hydrogen sulfide]]. This vapor-phase reaction is catalyzed by alumina and other heterogenous acid catalysts.<ref>Loev, B; Massengale, JT U. S. Patent 2,899,444, "Synthesis of Tetrahydrothiophene", 8/11/1959</ref><ref name="Ullmann">{{Ullmann|author=Jonathan Swanston|title=Thiophene|year=2006|doi=10.1002/14356007.a26_793.pub2}}</ref>


This compound is a [[ligand]] in [[coordination chemistry]], an example being the complex [[chloro(tetrahydrothiophene)gold(I)]].<ref>{{cite book|vauthors = Uson R, Laguna A, Laguna M, Briggs DA, Murray HH, Fackler JP|title=Inorganic Syntheses|chapter=(Tetrahydrothiophene)Gold(I) or Gold(III) Complexes|year=2007|volume=26 |pages=85–91|issn=1934-4716|doi=10.1002/9780470132579.ch17|isbn=9780470132579}}</ref>
This compound is a [[ligand]] in [[coordination chemistry]], an example being the complex [[chloro(tetrahydrothiophene)gold(I)]].<ref>{{cite book|vauthors = Uson R, Laguna A, Laguna M, Briggs DA, Murray HH, Fackler JP|author6-link=John P. Fackler Jr.|title=Inorganic Syntheses|chapter=(Tetrahydrothiophene)Gold(I) or Gold(III) Complexes|year=2007|volume=26 |pages=85–91|issn=1934-4716|doi=10.1002/9780470132579.ch17|isbn=9780470132579}}</ref>


Oxidation of THT gives the sulfone [[sulfolane]], which is of interest as a polar, odorless solvent:
Oxidation of THT gives the sulfone [[sulfolane]], which is of interest as a polar, odorless solvent:
Line 67: Line 67:


==Natural occurrence==
==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)<ref>{{cite journal|last=Aissani|first=N|year=2006|title=Nematicidal Activity of the Volatilome of ''Eruca sativa'' on ''Meloidogyne incognita''|journal=[[Journal of Agricultural and Food Chemistry]]|volume=63|issue=27|pages=6120–6125|doi=10.1021/acs.jafc.5b02425|pmid=26082278|display-authors=etal }}</ref> while monocyclic substituted tetrahydrothiophenes have been isolated from ''[[Allium fistulosum]]'' 'Kujou',<ref>{{cite journal|last=Fukaya|first=M|year=2018|title=Rare Sulfur-Containing Compounds, Kujounins A1 and A2 and Allium Sulfoxide A1, from ''Allium fistulosum'' 'Kujou'|journal=[[Organic Letters]]|volume=20|issue=1|pages=28–31|doi=10.1021/acs.orglett.7b03234|pmid=29227665|display-authors=etal}}</ref> ''[[Allium sativum]]'' (garlic),<ref>{{cite journal |last=Block |first=E |display-authors=etal |year=2018 |title=Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (''Allium sativum''). |url=https://www.osti.gov/servlets/purl/1490686 |journal=[[Journal of Agricultural and Food Chemistry]] |volume=66 |issue=39 |pages=10193–10204 |doi=10.1021/acs.jafc.8b03638 |osti=1490686 |pmid=30196701 |s2cid=52178061}}</ref> ''[[Allium cepa]]'' (onion),<ref>{{cite journal|last=Aoyagi|first=M|year=2011|title=Structure and Bioactivity of Thiosulfinates Resulting from Suppression of Lachrymatory Factor Synthase in Onion|journal=[[Journal of Agricultural and Food Chemistry]]|volume=59|issue=20|pages=10893–10900|doi=10.1021/jf202446q|pmid=21905712|display-authors=etal}}</ref> ''[[Allium schoenoprasum]]'' (chives),<ref>{{cite journal|last=Fukaya|first=M|year=2019|title=Cyclic Sulfur Metabolites from ''Allium schoenoprasum'' var. ''foliosum''|journal=[[Phytochemistry Letters]]|volume=29|pages=125–128|doi=10.1016/j.phytol.2018.11.018|bibcode=2019PChL...29..125F|s2cid=104387714|display-authors=etal}}</ref> and ''[[Salacia (plant)|Salacia prinoides]].''<ref>{{cite journal|last=Tanabe|first=G|year=2008|title=Synthesis and Elucidation of Absolute Stereochemistry of Salaprinol, another Thiosugar Sulfonium Sulfate from the Ayurvedic Traditional Medicine ''Salacia prinoides''|journal=[[Tetrahedron (journal)|Tetrahedron]]|volume=64|issue=43|pages=10080–10086|doi=10.1016/j.tet.2008.08.010|display-authors=etal}}</ref> [[Albomycin]]s are a group of tetrahydrothiophene-ring containing antibiotics from [[streptomyces]] while [[biotin]] and [[neothiobinupharidine]] (and other [[nuphar]] alkaloids
Both unsubstituted and substituted tetrahydrothiophenes are reported to occur in nature. For example, tetrahydrothiophene occurs as a volatile from ''[[Eruca sativa]]'' Mill. (salad rocket)<ref>{{cite journal|last=Aissani|first=N|year=2006|title=Nematicidal Activity of the Volatilome of ''Eruca sativa'' on ''Meloidogyne incognita''|journal=[[Journal of Agricultural and Food Chemistry]]|volume=63|issue=27|pages=6120–6125|doi=10.1021/acs.jafc.5b02425|pmid=26082278|display-authors=etal }}</ref> while monocyclic substituted tetrahydrothiophenes have been isolated from ''[[Allium fistulosum]]'' 'Kujou',<ref>{{cite journal|last=Fukaya|first=M|year=2018|title=Rare Sulfur-Containing Compounds, Kujounins A1 and A2 and Allium Sulfoxide A1, from ''Allium fistulosum'' 'Kujou'|journal=[[Organic Letters]]|volume=20|issue=1|pages=28–31|doi=10.1021/acs.orglett.7b03234|pmid=29227665|display-authors=etal}}</ref> ''[[Allium sativum]]'' (garlic),<ref>{{cite journal |last=Block |first=E |display-authors=etal |year=2018 |title=Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (''Allium sativum''). |url=https://www.osti.gov/servlets/purl/1490686 |journal=[[Journal of Agricultural and Food Chemistry]] |volume=66 |issue=39 |pages=10193–10204 |doi=10.1021/acs.jafc.8b03638 |osti=1490686 |pmid=30196701 |bibcode=2018JAFC...6610193B |s2cid=52178061}}</ref> ''[[Allium cepa]]'' (onion),<ref>{{cite journal|last=Aoyagi|first=M|year=2011|title=Structure and Bioactivity of Thiosulfinates Resulting from Suppression of Lachrymatory Factor Synthase in Onion|journal=[[Journal of Agricultural and Food Chemistry]]|volume=59|issue=20|pages=10893–10900|doi=10.1021/jf202446q|pmid=21905712|bibcode=2011JAFC...5910893A|display-authors=etal}}</ref> ''[[Allium schoenoprasum]]'' (chives),<ref>{{cite journal|last=Fukaya|first=M|year=2019|title=Cyclic Sulfur Metabolites from ''Allium schoenoprasum'' var. ''foliosum''|journal=[[Phytochemistry Letters]]|volume=29|pages=125–128|doi=10.1016/j.phytol.2018.11.018|bibcode=2019PChL...29..125F|s2cid=104387714|display-authors=etal}}</ref> and ''[[Salacia (plant)|Salacia prinoides]].''<ref>{{cite journal|last=Tanabe|first=G|year=2008|title=Synthesis and Elucidation of Absolute Stereochemistry of Salaprinol, another Thiosugar Sulfonium Sulfate from the Ayurvedic Traditional Medicine ''Salacia prinoides''|journal=[[Tetrahedron (journal)|Tetrahedron]]|volume=64|issue=43|pages=10080–10086|doi=10.1016/j.tet.2008.08.010|display-authors=etal}}</ref> [[Albomycin]]s are a group of tetrahydrothiophene-ring containing antibiotics from [[streptomyces]] while [[biotin]] and [[neothiobinupharidine]] (and other [[nuphar]] alkaloids
<ref>{{cite journal|last=Korotkov|first=A|year=2015|title=Total Syntheses and Biological Evaluation of Both Enantiomers of Several Hydroxylated Dimeric Nuphar Alkaloids|journal=[[Angewandte Chemie International Edition]]|volume=54|issue=36|pages=10604–10607|doi=10.1002/anie.201503934|pmid=26205039|display-authors=etal|pmc=4691328}}</ref>), are examples of bicyclic and polycyclic tetrahydrothiophene-ring containing natural products, respectively.
<ref>{{cite journal|last=Korotkov|first=A|year=2015|title=Total Syntheses and Biological Evaluation of Both Enantiomers of Several Hydroxylated Dimeric Nuphar Alkaloids|journal=[[Angewandte Chemie International Edition]]|volume=54|issue=36|pages=10604–10607|doi=10.1002/anie.201503934|pmid=26205039|display-authors=etal|pmc=4691328}}</ref>), are examples of bicyclic and polycyclic tetrahydrothiophene-ring containing natural products, respectively.


Latest revision as of 19:19, 10 December 2024

Tetrahydrothiophene
Names
Preferred IUPAC name
Thiolane
Other names
Tetrahydrothiophene,
thiophane, tetramethylene sulfide
Identifiers
3D model (JSmol)
Abbreviations THT
102392
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.391 Edit this at Wikidata
EC Number
  • 203-728-9
RTECS number
  • XN0370000
UNII
UN number 2412
  • InChI=1S/C4H8S/c1-2-4-5-3-1/h1-4H2 checkY
    Key: RAOIDOHSFRTOEL-UHFFFAOYSA-N checkY
  • InChI=1/C4H8S/c1-2-4-5-3-1/h1-4H2
    Key: RAOIDOHSFRTOEL-UHFFFAOYAY
  • S1CCCC1
Properties
C4H8S
Molar mass 88.17 g·mol−1
Appearance colorless liquid
Density 0.997 g/mL[1]
Melting point −96 °C (−141 °F; 177 K)
Boiling point 119 °C (246 °F; 392 K)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Stench, flammable, irritant
GHS labelling:
GHS02: FlammableGHS07: Exclamation mark
Danger
H225, H302, H312, H315, H319, H332, H412
P210, P233, P240, P241, P242, P243, P261, P264, P270, P271, P273, P280, P301+P312, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P312, P321, P322, P330, P332+P313, P337+P313, P362, P363, P370+P378, P403+P235, P501
Flash point 12 °C (54 °F; 285 K)
200 °C (392 °F; 473 K)
Safety data sheet (SDS) Oakwood
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).
checkY verify (what is checkY☒N ?)

Tetrahydrothiophene is an organosulfur compound with the formula (CH2)4S. The molecule consists of a five-membered saturated ring with four methylene groups and a sulfur atom. It is the saturated analog of thiophene and is therefore the sulfur analog of THF. 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 sulfone sulfolane, which is of interest as a polar, odorless solvent:

C4H8S + 2 O → C4H8SO2

Sulfolane is, however, 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.

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

See also

[edit]

References

[edit]
  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. ^ a b Jonathan Swanston (2006). "Thiophene". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a26_793.pub2. ISBN 978-3527306732.
  4. ^ Uson R, Laguna A, Laguna M, Briggs DA, Murray HH, Fackler JP (2007). "(Tetrahydrothiophene)Gold(I) or Gold(III) Complexes". Inorganic Syntheses. Vol. 26. 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. Bibcode:2018JAFC...6610193B. doi:10.1021/acs.jafc.8b03638. OSTI 1490686. PMID 30196701. S2CID 52178061.
  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. Bibcode:2011JAFC...5910893A. 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. Bibcode:2019PChL...29..125F. doi:10.1016/j.phytol.2018.11.018. S2CID 104387714.
  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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