Thietane

Thietane
Structural formula of thietane
Ball-and-stick model of the thietane molecule
Names
Preferred IUPAC name
Thietane
Systematic IUPAC name
Thiacyclobutane
Other names
Trimethylene sulfide
Identifiers
3D model (JSmol)
102383
ChEBI
ChemSpider
ECHA InfoCard 100.005.469 Edit this at Wikidata
EC Number
  • 206-015-0
UNII
UN number 1993
  • InChI=1S/C3H6S/c1-2-4-3-1/h1-3H2 checkY
    Key: XSROQCDVUIHRSI-UHFFFAOYSA-N checkY
  • C1CSC1
Properties
C3H6S
Molar mass 74.14 g·mol−1
Appearance Colourless liquid
Odor Sulfurous
Density 1.028 g cm−3
Boiling point 94 to 95 °C (201 to 203 °F; 367 to 368 K)
Hazards
GHS labelling:
GHS02: FlammableGHS07: Exclamation mark
Danger
H225, H302
P210
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
4
1
Flash point −11(9) °C
Related compounds
Other anions
 Oxetane, Azetidine, Phosphetane
Related compounds
 Thiirane, Dithietane, Tetrahydrothiophene, Thiane, Thiepane, Thiocane, Thionane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Thietane is a heterocyclic compound containing a saturated four-membered ring with three carbon atoms and one sulfur atom. Some derivatives are of interest as drugs.

Thietane, and its derivative 2-propylthietane, are strong-smelling mouse alarm pheromones and predator scent analogues. Both the mouse and human olfactory receptors MOR244-3 and OR2T11, respectively, were found to respond to thietane in the presence of copper.

Synthesis

Thietanes are the subject of many preparative studies. They are traditionally produced in modest or poor yields from 1,3-difunctionalized alkanes. One example is the reaction of trimethylene carbonate and potassium thiocyanate.

C4H6O3 + KSCN → C3H6S + KOCN + CO2

An improved synthesis method is the reaction of 1,3-dibromopropane and sodium sulfide.

Br−(CH2)3−Br + Na2S → C3H6S + 2 NaBr

Alternatively, phosphines desulfurize 1,2-dithiolanes to thietanes.

Reactions

Nucleophiles like butyllithium can open the ring in thietane. Thietane also reacts with bromine.

References

  1. ↑ Leśniak, S; Lewkowski, J; Kudelska, W; Zając, A (2008). "Thietanes and Thietes: Monocyclic". Comprehensive Heterocyclic Chemistry III. 2 (7): 389–428. doi:10.1016/B978-008044992-0.00207-8.
  2. ↑ Block, E; DeWang, M (1996). "Thietanes and Thietes: Monocyclic". Comprehensive Heterocyclic Chemistry II. 1 (24): 773–802. doi:10.1016/B978-008096518-5.00024-1.
  3. ↑ Francisco, Karol R.; Ballatore, Carlo (2022). "Thietanes and Derivatives thereof in Medicinal Chemistry". Current Topics in Medicinal Chemistry. 22 (15): 1219–1234. doi:10.2174/1568026622666220511154228. PMID 35546768.
  4. ↑ Sievert, Thorbjörn; Laska, Matthias (2016). "Behavioral responses of CD-1 mice to six predator odor components". Chem. Senses. 41 (5): 399–406. doi:10.1093/chemse/bjw015. PMID 26892309.
  5. ↑ Brechbuhl, J; Moine, F; Klaey, M; Nenniger-Tosato, M; Hurni, N; Sporkert, F; Giroud, C; Broillet, MC (2013). "Mouse alarm pheromone shares structural similarity with predator scents". Proc. Natl. Acad. Sci. U.S.A. 110 (12): 4762–4767. Bibcode:2013PNAS..110.4762B. doi:10.1073/pnas.1214249110. PMC 3607058. PMID 23487748.
  6. ↑ Li, Shengju; Ahmed, Lucky; Zhang, Ruina; Pan, Yi; Matsunami, Hiroaki; Burger, Jessica L; Block, Eric; Batista, Victor S; Zhuang, Hanyi (2016). "Smelling sulfur: Copper and silver regulate the response of human odorant receptor OR2T11 to low molecular weight thiols". Journal of the American Chemical Society. 138 (40): 13281–13288. Bibcode:2016JAChS.13813281L. doi:10.1021/jacs.6b06983. PMID 27659093.
  7. ↑ Xu, Jiaxi (2020). "Synthesis of Thietanes from Saturated Three-membered Heterocycles". Asian Journal of Organic Chemistry. 9 (7): 1008–1017. doi:10.1002/ajoc.202000219.
  8. ↑ Xu, Jiaxi (2020). "Recent synthesis of thietanes". Beilstein Journal of Organic Chemistry. 16: 1357–1410. doi:10.3762/bjoc.16.116. PMC 7323639. PMID 32647542.
  9. ↑ Sander, Manfred (1966). "Thietanes". Chemical Reviews. 66 (3): 341–353. doi:10.1021/cr60241a005.
  10. ↑ Searles, Scott; Lutz, Eugene F. (1958). "A New Synthesis of Small Ring Cyclic Sulfides". Journal of the American Chemical Society. 80 (12): 3168. Bibcode:1958JAChS..80.3168S. doi:10.1021/ja01545a071. ISSN 0002-7863.
  11. ↑ Nagasawa, Kazuo; Yoneta, Akemi (1985). "Organosulfur chemistry. II. Use of dimethyl sulfoxide; A facile synthesis of cyclic sulfides". Chemical and Pharmaceutical Bulletin. 33 (11): 5048–5052. doi:10.1248/cpb.33.5048. ISSN 0009-2363.
  12. ↑ Harpp, David N.; Gleason, John G. (1970) [19 Jan 1970]. "The chemistry of small-ring sulfur compounds". J. Org. Chem. 56 (10): 3259–3263. doi:10.1021/jo00835a018.
  13. ↑ Bordwell, F. G.; Andersen, Harry M.; Pitt, Burnett M. (1954). "The Reaction of Thiacyclopropanes (Olefin Sulfides) and Thiacyclobutanes with Organolithium Compounds". Journal of the American Chemical Society. 76 (4): 1082–1085. Bibcode:1954JAChS..76.1082B. doi:10.1021/ja01633a045. ISSN 0002-7863.
  14. ↑ Stewart, John M.; Burnside, Charles H. (1953). "Reactions of Trimethylene Sulfide with Chlorine and Bromine". Journal of the American Chemical Society. 75 (1): 243–244. Bibcode:1953JAChS..75..243S. doi:10.1021/ja01097a517. ISSN 0002-7863.