2,2-Bis(trifluoromethyl)oxirane
[CAS# 31898-68-7]

Identification

• Classification: Chemical reagent >> Organic reagent >> Epoxide
• Name: 2,2-Bis(trifluoromethyl)oxirane
• Synonyms: 3,3,3,-Trifluoro-2-(trifluoromethyl)-1,2-propenoxide
• Molecular Formula: C₄H₂F₆O
• Molecular Weight: 180.05
• CAS Registry Number: 31898-68-7
• EC Number: 803-996-2
• SMILES: C1C(O1)(C(F)(F)F)C(F)(F)F

Properties

• Melting point: -85.83 °C
• Boiling point: 41-42 °C

Safety Data

• Hazard Symbols: GHS07;GHS02
• Risk Statements: H315-H319-H335-H302-H312-H226-H332
• Safety Statements: P210-P233-P240-P241-P242-P243-P261-P264-P270-P271-P280-P330-P301+P312-P302+P352-P303+P361+P353-P304+P340-P305+P351+P338-P362+P364-P370+P378-P405-P403+P233-P403+P235-P501

Hazard Classification

Hazard	Class	Category Code	Hazard Statement
Acute toxicity	Acute Tox.	4	H302
Eye irritation	Eye Irrit.	2	H319
Flammable liquids	Flam. Liq.	3	H226
Specific target organ toxicity - single exposure	STOT SE	3	H335
Acute toxicity	Acute Tox.	4	H332
Skin irritation	Skin Irrit.	2	H315
Acute toxicity	Acute Tox.	4	H312

Discovery and Applications

2,2-Bis(trifluoromethyl)oxirane is a perfluorinated epoxide compound that has been studied primarily for its unique chemical reactivity and its role as a building block in fluorinated organic synthesis. Its molecular structure consists of a three-membered oxirane ring, also known as an epoxide, substituted at the 2-position with two trifluoromethyl groups (–CF₃). The presence of these highly electronegative fluorinated substituents imparts exceptional stability and resistance to nucleophilic attack compared to non-fluorinated epoxides.

The discovery of 2,2-bis(trifluoromethyl)oxirane can be traced back to mid-20th century efforts in organofluorine chemistry, which intensified during and after World War II due to interest in fluorinated compounds for materials, refrigerants, and agrochemical applications. The compound is typically synthesized through the epoxidation of hexafluoropropylene, a commercially available fluorinated olefin. One of the most common routes involves oxidation of hexafluoropropylene oxide (HFPO) or fluorinated peracids to yield 2,2-bis(trifluoromethyl)oxirane under controlled conditions. Because of the electron-withdrawing nature of the –CF₃ groups, the oxirane ring in this compound is less reactive than typical epoxides, allowing it to persist under conditions where ordinary epoxides might readily undergo ring-opening reactions.

Applications of 2,2-bis(trifluoromethyl)oxirane are centered around its utility as a precursor or intermediate in the synthesis of fluorinated molecules. It has been employed in the preparation of specialty monomers and polymers that require high thermal stability, chemical inertness, and hydrophobic properties. The incorporation of perfluoroalkyl moieties, such as those present in this compound, is known to enhance the surface activity and non-stick characteristics of materials, making it useful in the development of coatings and high-performance elastomers.

In academic research, 2,2-bis(trifluoromethyl)oxirane has been used as a model compound to study the effects of fluorination on ring strain, reactivity, and stereoelectronic properties of epoxides. Its resistance to nucleophilic ring-opening has provided insights into the influence of fluorinated substituents on reaction mechanisms in epoxide chemistry. Additionally, its reactions with nucleophiles, though less common, have been studied under forcing conditions, sometimes leading to rearranged or ring-opened fluorinated products of interest in fluorine-rich molecular scaffolds.

Due to its high fluorine content and small ring structure, 2,2-bis(trifluoromethyl)oxirane has also attracted interest in the field of gas-phase ion chemistry and mass spectrometry, where its fragmentation patterns provide data useful for the development of fluorinated compound libraries and analytical techniques. Furthermore, it is sometimes examined in computational studies focused on ring strain energies and the thermodynamics of fluorinated heterocycles.

Although 2,2-bis(trifluoromethyl)oxirane does not have widespread industrial applications, its role as a chemical intermediate and its contribution to the understanding of fluorinated small-ring compounds remain significant. It continues to serve as a foundational compound in organofluorine chemistry, particularly in synthetic investigations where high fluorine content and structural rigidity are desirable features.

The handling of this compound, like other perfluorinated chemicals, requires appropriate safety precautions. While it is not highly reactive under ambient conditions, the volatility and potential for releasing hazardous decomposition products under high temperatures or combustion necessitate the use of personal protective equipment and proper ventilation. Environmental considerations are also relevant, as persistent perfluorinated compounds are the subject of increasing regulatory attention due to their stability and potential bioaccumulation. Therefore, use of 2,2-bis(trifluoromethyl)oxirane in laboratory and industrial settings is typically limited to well-defined applications with suitable containment and waste management protocols.

References

2007 Features of reaction between fluorine-containing glycidyl ethers and alcohols in basic medium. Russian Journal of Organic Chemistry, 43(5).
DOI: 10.1134/s1070428007050041

2010 Dithiodiolate Ligands: Group 4 Complexes and Application in Lactide Polymerization. Inorganic Chemistry, 49(9).
DOI: 10.1021/ic100390x

2014 Synthesis by Rearrangement of 2,2-Bis(trifluoromethyl)-2-(trimethylsiloxy)ethyl Thiocyanate. Science of Synthesis.
URL: https://science-of-synthesis.thieme.com/app/text/?id=SD-118-00475