Misplaced Pages

Oxetane

Article snapshot taken from[REDACTED] with creative commons attribution-sharealike license. Give it a read and then ask your questions in the chat. We can research this topic together.
Oxetane
Names
Preferred IUPAC name Oxetane
Systematic IUPAC name 1,3-Epoxypropane
Oxacyclobutane
Other names 1,3-Propylene oxide
Trimethylene oxide
Identifiers
CAS Number
3D model (JSmol)
Beilstein Reference 102382
ChEBI
ChemSpider
ECHA InfoCard 100.007.241 Edit this at Wikidata
EC Number
  • 207-964-3
Gmelin Reference 239520
PubChem CID
UNII
UN number 1280
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C3H6O/c1-2-4-3-1/h1-3H2Key: AHHWIHXENZJRFG-UHFFFAOYSA-N
  • InChI=1/C3H6O/c1-2-4-3-1/h1-3H2Key: AHHWIHXENZJRFG-UHFFFAOYAE
SMILES
  • C1CCO1
Properties
Chemical formula C3H6O
Molar mass 58.08 g/mol
Density 0.8930 g/cm
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:
Pictograms GHS02: FlammableGHS07: Exclamation mark
Signal word Danger
Hazard statements H225, H302, H312, H332
Precautionary statements 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 , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

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:

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 as well as through decarboxylation of a six-membered cyclic carbonate.

Derivatives

More than a hundred different oxetanes have been synthesized. 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
3,3-Bis(chloromethyl)oxetane 198
3,3-Bis(azidomethyl)oxetane 165
2-Methyloxetane 60
3-Methyloxetane 67
3-Azidooxetane 122
3-Nitrooxetane 195
3,3-Dimethyloxetane 80
3,3-Dinitrooxetane –

Taxol

Paclitaxel with oxetane ring at right.

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. 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.

Reactions

Oxetanes are less reactive than epoxides, and generally unreactive in basic conditions, although Grignard reagents at elevated temperatures and complex hydrides will cleave them. However, the ring strain does make them much more reactive than larger rings, and oxetanes decompose in the presence of even mildly acidic nucleophiles. In non-nucleophilic acids, they mainly isomerize to allyl alcohols.

Noble metals tend to catalyze isomerization to a carbonyl.

In industry, the parent compound, oxetane polymerizes to polyoxetane in the presence of a dry acid catalyst, although the compound was described in 1967 as "rarely polymerized commercially".

See also

References

  1. 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. ISBN 978-0-85404-182-4.
  2. C. R. Noller (1955). "Trimethylene Oxide". Organic Syntheses. 29: 92; Collected Volumes, vol. 3, p. 835.
  3. Patai 1967, pp. 411–413.
  4. "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.
  5. 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.
  6. 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.
  7. "3-Nitrooxetane | C3H5NO3 | ChemSpider". www.chemspider.com. Retrieved 2022-12-28.
  8. ^ 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.
  9. Patai 1967, p. 425.
  10. Patai 1967, pp. 63, 425.
  11. Patai 1967, pp. 67–68.
  12. Patai 1967, pp. 376–377.
  13. 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.
  14. Patai 1967, p. 696.
  15. Patai 1967, pp. 697, 700.
  16. Penczek & Penczek (1963), "Kinetics and mechanism of heterogeneous polymerization of 3,3-bis(chloromethyl)oxetane catalyzed by gaseous BF3" in Die Makromolekuläre Chemie. Wiley.
  17. Patai 1967, p. 380.
Category:
Oxetane Add topic