Chemistry:Difluorodioxirane
Difluorodioxirane (CF2O2) is a rare, stable member of the dioxirane family, known for a single oxygen-oxygen bond (O-O). Unlike most dioxiranes that decompose quickly, difluorodioxirane is surprisingly stable at room temperature, making it potentially useful for further research and applications.
Synthesis
Difluorodioxirane was first synthesised by Russo and DesMarteau in 1993 by treating fluorocarbonyl hypofluorite (FCOOF) with X2 (= F2, Cl2 or ClF) over pelletized CsF in a flow system.[1]
It also likely exists as a possible intermediate in reactions involving other fluorine-containing compounds.[2][3]
Properties
Unlike most dioxiranes that decompose quickly, difluorodioxirane is surprisingly stable at room temperature[4] due to the stabilising interaction of two fluorine atoms with the ring. This effect makes the O-O bond less reactive and more stable compared to other dioxiranes. The central F–C–F angle is 109°, approximately a tetrahedral angle.[5]
Difluorodioxirane is known for its ability to perform regiospecific and stereoselective oxidations. This makes it a valuable tool in organic synthesis for precise manipulation of molecules.[6]
Despite its increased stability, difluorodioxirane can still act as an oxidizing agent, transferring oxygen to other molecules. it often leads to cleaner and more predictable reaction outcomes due to its controlled reactivity.
Uses
Difluorodioxirane itself has not yet found widespread applications due to its recent discovery. However, its unique stability and reactivity similar to other dioxiranes suggest potential uses in several areas:
- Organic synthesis: Due to its oxidizing properties, difluorodioxirane could be a valuable reagent in organic reactions, particularly for controlled oxidation processes. Researchers are exploring its potential applications in epoxidation (adding oxygen atoms to create epoxide rings), hydroxylation (adding hydroxyl groups -OH), and other oxidation reactions.
- Development of new catalysts: The stability and reactivity profile of difluorodioxirane make it a promising candidate for the development of new and more efficient catalysts for various organic transformations.
See also
- Dimesityldioxirane
- Dimethyldioxirane
- Shi epoxidation
References
- ↑ Russo, Antonio; DesMarteau, Darryl D. (1993). "Difluorodioxirane" (in en). Angewandte Chemie International Edition in English 32 (6): 905–907. doi:10.1002/anie.199309051. ISSN 0570-0833. https://onlinelibrary.wiley.com/doi/10.1002/anie.199309051.
- ↑ Ma, Xiaoyu; Liu, Xitao; Shang, Xiao; Zhao, Yanwei; Zhang, Zhenguo; Lin, Chunye; He, Mengchang; Ouyang, Wei (2024). "Efficient roxarsone degradation by low-dose peroxymonosulfate with the activation of recycling iron-base composite material: Critical role of electron transfer". Journal of Hazardous Materials (Elsevier BV) 469. doi:10.1016/j.jhazmat.2024.134087. ISSN 0304-3894. PMID 38518697. Bibcode: 2024JHzM..46934087M.
- ↑ Huang, Qun; DesMarteau, Darry D. (2000-09-09). "Difluorodioxirane, a Possible Intermediate in the Reaction of Bis(fluoroxy)difluoromethane with Cesium Trifluoromethoxide". Inorganic Chemistry (American Chemical Society (ACS)) 39 (20): 4670–4672. doi:10.1021/ic0003224. ISSN 0020-1669.
- ↑ Russo, Antonio; DesMarteau, Darryl D. (1993-06-01). "Difluorodioxirane" (in en). Angewandte Chemie International Edition in English 32 (6): 905–907. doi:10.1002/anie.199309051. ISSN 0570-0833. https://onlinelibrary.wiley.com/doi/10.1002/anie.199309051.
- ↑ Sander, Wolfram; Schroeder, Kerstin; Muthusamy, Sengodagounder; Kirschfeld, Andreas; Kappert, Wilhelm; Boese, Roland; Kraka, Elfi; Sosa, Carlos et al. (1997-08-01). "Dimesityldioxirane" (in en). Journal of the American Chemical Society 119 (31): 7265–7270. doi:10.1021/ja964280n. ISSN 0002-7863. Bibcode: 1997JAChS.119.7265S. https://pubs.acs.org/doi/10.1021/ja964280n.
- ↑ Kraka, Elfi; Konkoli, Zoran; Cremer, Dieter; Fowler, Joseph; Schaefer, Henry F. (1996-01-01). "Difluorodioxirane: An Unusual Cyclic Peroxide" (in en). Journal of the American Chemical Society 118 (43): 10595–10608. doi:10.1021/ja961983w. ISSN 0002-7863. Bibcode: 1996JAChS.11810595K. https://pubs.acs.org/doi/10.1021/ja961983w.
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