Oxetane
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Names | |||
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Preferred IUPAC name Oxetane[1] | |||
Systematic IUPAC name 1,3-Epoxypropane Oxacyclobutane | |||
Other names 1,3-Propylene oxide Trimethylene oxide | |||
Identifiers | |||
CAS Number |
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3D model (JSmol) |
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Beilstein Reference | 102382 | ||
ChEBI |
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ChemSpider |
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ECHA InfoCard | 100.007.241 ![]() | ||
EC Number |
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Gmelin Reference | 239520 | ||
PubChem CID |
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UNII |
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UN number | 1280 | ||
CompTox Dashboard (EPA) |
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InChI
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Properties | |||
Chemical formula | C3H6O | ||
Molar mass | 58.08 g/mol | ||
Density | 0.8930 g/cm3 | ||
Melting point | −97 °C (−143 °F; 176 K) | ||
Boiling point | 49 to 50 °C (120 to 122 °F; 322 to 323 K) | ||
Refractive index (nD) | 1.3895 at 25 °C | ||
Hazards | |||
GHS labelling: | |||
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Danger | |||
H225, H302, H312, H332 | |||
P210, P233, P240, P241, P242, P243, P261, P264, P270, P271, P280, P301+P312, P302+P352, P303+P361+P353, P304+P312, P304+P340, P312, P322, P330, P363, P370+P378, P403+P235, P501 | |||
Flash point | −28.3 °C; −19.0 °F; 244.8 K (NTP, 1992) | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). ![]() ![]() ![]() Infobox references |
Oxetane, or 1,3-propylene oxide, is a heterocyclic organic compound with the molecular formula C
3H
6O, having a four-membered ring with three carbon atoms and one oxygen atom.
The term "an oxetane" or "oxetanes" refer to any organic compound containing the oxetane ring.
Production
A typical well-known method of preparation is the reaction of potassium hydroxide with 3-chloropropyl acetate at 150 °C:[2]
![](http://upload.wikimedia.org/wikipedia/commons/thumb/2/2d/Synthesis_of_trimethylene_oxide.png/440px-Synthesis_of_trimethylene_oxide.png)
Yield of oxetane made this way is c. 40%, as the synthesis can lead to a variety of by-products including water, potassium chloride, and potassium acetate.
Another possible reaction to form an oxetane ring is the Paternò–Büchi reaction. The oxetane ring can also be formed through diol cyclization[3] as well as through decarboxylation of a six-membered cyclic carbonate.[citation needed]
Derivatives
More than a hundred different oxetanes have been synthesized.[4] Functional groups can be added into any desired position in the oxetane ring, including fully fluorinated (perfluorinated) and fully deuterated analogues. Major examples are:
Name | Structure | Boiling point, Bp [°C] |
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3,3-Bis(chloromethyl)oxetane | ![]() | 198[5] |
3,3-Bis(azidomethyl)oxetane | ![]() | 165[6] |
2-Methyloxetane | ![]() | 60[4][failed verification] |
3-Methyloxetane | ![]() | 67[4][failed verification] |
3-Azidooxetane | ![]() | 122[7] |
3-Nitrooxetane | ![]() | 195[8] |
3,3-Dimethyloxetane | ![]() | 80[4][failed verification] |
3,3-Dinitrooxetane | ![]() | – |
Taxol
![](http://upload.wikimedia.org/wikipedia/commons/thumb/5/59/Taxol.svg/220px-Taxol.svg.png)
Paclitaxel (Taxol) is an example of a natural product containing an oxetane ring. Taxol has become a major point of interest among researchers due to its unusual structure and success in the involvement of cancer treatment.[9] The attached oxetane ring is an important feature that is used for the binding of microtubules in structure activity; however little is known about how the reaction is catalyzed in nature, which creates a challenge for scientists trying to synthesize the product.[9]
Oxetane is used in one of the syntheses of Disparlure (Gypsy moth sexual pheromone).[10]
Reactions
Oxetanes are less reactive than epoxides, and generally unreactive in basic conditions,[11] although Grignard reagents at elevated temperatures[12] and complex hydrides will cleave them.[13] However, the ring strain does make them much more reactive than larger rings,[14] and oxetanes decompose in the presence of even mildly acidic nucleophiles.[15] In non-nucleophilic acids, they mainly isomerize to allyl alcohols.[16]
Noble metals tend to catalyze isomerization to a carbonyl.[17]
In industry, the parent compound, oxetane polymerizes to polyoxetane in the presence of a dry acid catalyst,[18] although the compound was described in 1967 as "rarely polymerized commercially".[19]
See also
- β-Propiolactone or 2-oxetanone.
- 3-Oxetanone
References
- ^ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 147. doi:10.1039/9781849733069-FP001 (inactive 2024-04-15). ISBN 978-0-85404-182-4.
{{cite book}}
: CS1 maint: DOI inactive as of April 2024 (link) - ^ C. R. Noller (1955). "Trimethylene Oxide". Organic Syntheses. 29: 92; Collected Volumes, vol. 3, p. 835.
- ^ Patai 1967, pp. 411–413.
- ^ a b c d Goethals, Lucien; Sioen, Philip (2000). "Dialogos. Lucien Goethals in gesprek met Philip Sioen". Revue belge de Musicologie / Belgisch Tijdschrift voor Muziekwetenschap. 54: 49–71. doi:10.2307/3686877. ISSN 0771-6788. JSTOR 3686877.
- ^ "78-71-7 CAS MSDS (3,3-BIS(CHLOROMETHYL)OXETANE) Melting Point Boiling Point Density CAS Chemical Properties". www.chemicalbook.com. Retrieved 2022-12-28.
- ^ Akhtar, Tauseef; Berger, Ronald; Marine, Joseph E; Daimee, Usama A; Calkins, Hugh; Spragg, David (2020-08-13). "Cryoballoon Ablation of Atrial Fibrillation in Octogenarians". Arrhythmia & Electrophysiology Review. 9 (2): 104–107. doi:10.15420/aer.2020.18. ISSN 2050-3377. PMC 7491081. PMID 32983532.
- ^ Baum, Kurt; Berkowitz, Phillip T.; Grakauskas, Vytautas; Archibald, Thomas G. (September 1983). "Synthesis of electron-deficient oxetanes. 3-Azidooxetane, 3-nitrooxetane, and 3,3-dinitrooxetane". The Journal of Organic Chemistry. 48 (18): 2953–2956. doi:10.1021/jo00166a003. ISSN 0022-3263.
- ^ "3-Nitrooxetane | C3H5NO3 | ChemSpider". www.chemspider.com. Retrieved 2022-12-28.
- ^ a b Willenbring, Dan; Tantillo, Dean J. (April 2008). "Mechanistic possibilities for oxetane formation in the biosynthesis of Taxol's D ring". Russian Journal of General Chemistry. 78 (4): 723–731. doi:10.1134/S1070363208040336. S2CID 98056619.
- ^ Hans Jürgen Bestmann; Otto Vostrowsky; Werner Stransky (1976). Pheromone, X. Eine stereoselektive Synthese des (Z)-7,8-Epoxy-2-methyloctadecans (Disparlure). , 109(10), 3375–3378. doi:10.1002/cber.19761091015
- ^ Patai 1967, p. 425.
- ^ Patai 1967, pp. 63, 425.
- ^ Patai 1967, pp. 67–68.
- ^ Patai 1967, pp. 376–377.
- ^ Patai, Saul, ed. (1967). The Chemistry of the Ether Linkage. The Chemistry of Functional Groups. London: Interscience / William Clowes and Sons. pp. 28–30. LCCN 66-30401.
- ^ Patai 1967, p. 696.
- ^ Patai 1967, pp. 697, 700.
- ^ Penczek & Penczek (1963), "Kinetics and mechanism of heterogeneous polymerization of 3,3-bis(chloromethyl)oxetane catalyzed by gaseous BF3" in Die Makromolekuläre Chemie. Wiley.
- ^ Patai 1967, p. 380.