Oxetane

Oxetane

Names
Preferred IUPAC name Oxetane [1]
Systematic IUPAC name 1,3-Epoxypropane Oxacyclobutane
Other names 1,3-Propylene oxide Trimethylene oxide
Identifiers
CAS Number	503-30-0  Y
3D model (JSmol)	Interactive image
Beilstein Reference	102382
ChEBI	CHEBI:30965  Y
ChemSpider	9994  Y
ECHA InfoCard	100.007.241
EC Number	207-964-3
Gmelin Reference	239520
PubChem CID	10423
UNII	I279Q16FU6  Y
UN number	1280
CompTox Dashboard (EPA)	DTXSID8025969
InChI InChI=1S/C3H6O/c1-2-4-3-1/h1-3H2 Y Key: AHHWIHXENZJRFG-UHFFFAOYSA-N Y InChI=1/C3H6O/c1-2-4-3-1/h1-3H2 Key: AHHWIHXENZJRFG-UHFFFAOYAE
SMILES C1CCO1
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:
Pictograms
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 [77 °F], 100 kPa). N  verify  (what is  YN ?) 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]

Yield of oxetane made this way is c. 40%, as the synthesis can lead to a variety of by-products including water, allyl alcohol, 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.^{[ citation needed ]} 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]
3,3-Bis(chloromethyl)oxetane		198 [4]
3,3-Bis(azidomethyl)oxetane		165 [5]
2-Methyloxetane		60[ citation needed ]
3-Methyloxetane		67[ citation needed ]
3-Azidooxetane		122 [6]
3-Nitrooxetane		195 [7]
3,3-Dimethyloxetane		80[ citation needed ]
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. ^[8] 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. ^[8]

Reactions

Oxetanes are less reactive than epoxides, and generally unreactive in basic conditions, ^[9] although Grignard reagents at elevated temperatures ^[10] and complex hydrides will cleave them. ^[11] However, the ring strain does make them much more reactive than larger rings, ^[12] and oxetanes decompose in the presence of even mildly acidic nucleophiles. ^[13] In non-nucleophilic acids, they mainly isomerize to allyl alcohols. ^[14]

Noble metals tend to catalyze isomerization to a carbonyl. ^[15]

In industry, the parent compound, oxetane polymerizes to polyoxetane in the presence of a dry acid catalyst, ^[16] although the compound was described in 1967 as "rarely polymerized commercially". ^[17]

See also

• β-Propiolactone or 2-oxetanone.
• 3-Oxetanone

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.