Thietane

Thietane
Names
	Preferred IUPAC name Thietane
	Systematic IUPAC name Thiacyclobutane
	Other names Trimethylene sulfide
Identifiers
CAS Number	287-27-4 [chemspider];
3D model (JSmol)	Interactive image;
Beilstein Reference	102383
ChEBI	CHEBI:87565;
ChemSpider	8895 ;
ECHA InfoCard	100.005.469
EC Number	206-015-0;
PubChem CID	9251;
UNII	1O7C19QQDB;
UN number	1993
CompTox Dashboard (EPA)	DTXSID7059773 ;
	InChI InChI=1S/C3H6S/c1-2-4-3-1/h1-3H2 Key: XSROQCDVUIHRSI-UHFFFAOYSA-N ;
	SMILES C1CSC1;
Properties
Chemical formula	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:
Pictograms
Signal word	Danger
Hazard statements	H225, H302
Precautionary statements	P210
NFPA 704 (fire diamond)	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). verify (what is ?) Infobox references

Thietane is a heterocyclic compound containing a saturated four-membered ring with three carbon atoms and one sulfur atom.^[1]^[2] Some derivatives are of interest as drugs.^[3]

Thietane, and its derivative 2-propylthietane, are strong-smelling mouse alarm pheromones and predator scent analogues.^[4]^[5] Both the mouse and human olfactory receptors MOR244-3 and OR2T11, respectively, were found to respond to thietane in the presence of copper.^[6]

Synthesis

Thietanes are the subject of many preparative studies.^[7]^[8] They are traditionally produced in modest or poor yields from 1,3-difunctionalized alkanes.^[9] One example is the reaction of trimethylene carbonate and potassium thiocyanate.^[10]

C₄H₆O₃ + KSCN → C₃H₆S + KOCN + CO₂

An improved synthesis method is the reaction of 1,3-dibromopropane and sodium sulfide.^[11]

Br−(CH₂)₃−Br + Na₂S → C₃H₆S + 2 NaBr

Reactions

Nucleophiles like butyllithium can open the ring in thietane.^[12] Thietane also reacts with bromine.^[13]

References

^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ Sander, Manfred (1966). "Thietanes". Chemical Reviews. 66 (3): 341–353. doi:10.1021/cr60241a005.
^ 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.
^ 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.
^ 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.
^ 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.

[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] 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.

[13] 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.

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