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Dimethyldioxirane

Dimethyldioxirane (DMDO), also known as Murray's reagent, is a three-membered cyclic organic peroxide with the molecular formula C₃H₆O₂ and the structure featuring a triangular dioxirane ring consisting of a carbon atom bearing two methyl groups bonded to two oxygen atoms.^[1] This volatile, yellow compound exists only as a dilute solution in acetone (typically 0.07–0.1 M) and is renowned as a mild, selective electrophilic oxidant that transfers oxygen under neutral conditions without requiring catalysts or metals.^[2] First isolated in 1985 through the oxidation of acetone with potassium caroate (Oxone),^[1] DMDO's dioxirane structure was confirmed by ¹⁷O NMR spectroscopy in 1987,^[3] marking a breakthrough in non-metal-based oxidation chemistry. DMDO is synthesized by reacting acetone with Oxone in aqueous solution buffered with sodium bicarbonate, followed by low-temperature vacuum distillation to isolate the peroxide as a stable solution at −25°C; this procedure yields concentrations of 0.07–0.09 M with high purity when unreacted peroxides are carefully managed.^[2] As a strong yet chemoselective oxidant, it exhibits high reactivity toward electron-rich substrates, enabling stereospecific epoxidation of alkenes (e.g., cis-alkenes to cis-epoxides in near-quantitative yields), Baeyer-Villiger oxidation of ketones to esters, and conversion of sulfides to sulfones, often at room temperature and with minimal over-oxidation.^[4] Its electrophilic nature allows selective oxidation of secondary alcohols over primary ones and has been applied in the dearomatization of indoles and furans to form epoxides or quinone methides, facilitating downstream transformations in natural product synthesis.^[5] Due to its peroxide instability, DMDO must be handled in a fume hood with safety shields, and it decomposes exothermically if concentrated or heated.^[2] Beyond traditional batch processes, recent advances include continuous-flow generation of DMDO^[6] for scalable epoxidations, enhancing safety and efficiency in polymer and monomer synthesis, such as epoxidizing imidazolium salts for advanced materials with improved thermal properties.^[7]

Properties

Structure and nomenclature

Dimethyldioxirane possesses the molecular formula C₃H₆O₂ and features a strained three-membered ring structure consisting of a central carbon atom bonded to two oxygen atoms, with two methyl groups attached to the carbon atom.^[8] This triangular dioxirane ring can be viewed as derived from acetone, where the carbonyl group has been converted to the cyclic peroxide moiety.^[9] The IUPAC name for the compound is 3,3-dimethyldioxirane, reflecting the geminal dimethyl substitution at the 3-position of the dioxirane parent scaffold.^[8] It is commonly referred to as DMDO (an abbreviation for dimethyldioxirane) or Murray's reagent, in honor of Robert W. Murray, who first isolated it in pure form.^[10] Another synonym is monoperoxyacetone, emphasizing its structural relation to acetone peroxide. Compared to the parent dioxirane (CH₂OO), which is highly unstable and decomposes rapidly at room temperature, the two methyl substituents in dimethyldioxirane significantly enhance kinetic stability by reducing ring strain through geminal substitution effects. This stabilization arises from hyperconjugative interactions and steric factors that lower the strain energy by approximately 6-10 kcal/mol relative to the unsubstituted analog.^[11] Computational studies indicate that the O-O bond length in dimethyldioxirane is about 1.51 Å, while the C-O bonds are around 1.40 Å, values similar to those in the parent dioxirane (O-O ≈ 1.51 Å, C-O ≈ 1.39 Å) but with altered reactivity due to the electron-donating methyl groups that weaken the peroxide bond slightly and facilitate oxygen transfer.^[12]^[13]

Physical and chemical properties

Dimethyldioxirane (DMDO) is handled exclusively as a dilute solution in acetone, appearing as a pale yellow liquid with typical concentrations ranging from 0.08 to 0.10 M.^[14] The pure compound has not been isolated owing to its inherent instability and tendency to decompose.^[15] Its molar mass is 74.08 g/mol.^[16] The predicted boiling point of pure DMDO is approximately -22 °C, while the density of the acetone solution is approximately 0.8 g/mL (similar to acetone).^[16] DMDO exhibits good solubility in acetone and other organic solvents such as dichloromethane, but it is immiscible with water.^[16] As a cyclic peroxide, DMDO functions primarily as an electrophilic oxygen transfer agent, facilitating selective oxidations under mild conditions.^[17] Its peroxide nature precludes typical acidity measures like pKa, as it lacks ionizable protons in the conventional sense. Thermodynamically, DMDO is endothermic, with a ring strain energy of about 11 kcal/mol that enhances its reactivity compared to less strained analogs; this strain is moderated relative to the parent dioxirane due to geminal dimethyl substitution.^[18]

Stability and reactivity

Dimethyldioxirane (DMDO) exhibits limited thermal stability, particularly in its typical acetone solutions, where it remains viable for practical use only under controlled low-temperature conditions. Solutions are stable for weeks when stored at -20 °C, allowing for extended shelf life in refrigerated environments.^[19] At higher temperatures, such as around room temperature (approximately 22 °C), DMDO persists for about 7 hours before significant decomposition occurs.^[19] Above 0 °C, decomposition accelerates primarily through homolysis of the O-O bond, leading to an activation energy of approximately 24.9 kcal/mol for the process.^[20] This thermal instability is attributed to the strained three-membered ring structure, which facilitates bond breaking, though the gem-dimethyl substitution provides some kinetic stabilization compared to unsubstituted dioxiranes.^[19] Photochemical and catalytic factors further compromise DMDO's stability, making careful storage essential. Exposure to light, including visible wavelengths up to 450 nm due to UV tailing upon standing, promotes decomposition.^[19] Similarly, trace heavy metals such as iron or copper catalyze rapid breakdown, as do basic conditions, where the half-life drops dramatically—less than 30 minutes under neutral pH and even shorter in alkaline media.^[21] In the absence of these accelerators, such as in dark storage at -20 °C, solutions maintain stability for weeks, underscoring the importance of inert, low-light, and metal-free conditions for longevity.^[19] As a reactive species, DMDO functions as a mild and selective oxidant, primarily through concerted oxygen atom transfer mechanisms that avoid radical intermediates under standard conditions.^[22] This electrophilic process involves a spiro-like transition state, enabling precise oxidations without the harshness of traditional peracids.^[22] Decomposition pathways yield products such as acetone (from ring opening), methyl acetate (via isomerization), and reactive oxygen species including singlet oxygen, particularly in nucleophile-catalyzed variants.^[23] Radical channels, stemming from O-O homolysis, contribute modestly (about 23% at 56 °C) but are not dominant in typical reactivity scenarios.^[23]

Synthesis

Preparation from peroxymonosulfate

Dimethyldioxirane (DMDO) is primarily prepared in the laboratory through the reaction of acetone, which serves as both solvent and substrate, with potassium peroxymonosulfate (commercially available as Oxone, 2KHSO₅·KHSO₄·K₂SO₄) in the presence of a sodium bicarbonate buffer.^[1]^[14] This method was first reported by Robert W. Murray and Ramasubbu Jeyaraman in 1985, representing a significant improvement over earlier approaches using sodium hypochlorite, which suffered from lower yields and poorer control over reaction conditions.^[1] The reaction proceeds via nucleophilic attack of the ketone oxygen on the electrophilic peroxo moiety of the peroxymonosulfate anion, forming the three-membered dioxirane ring:

(\ce{CH3})_2\ce{C=O} + \ce{HSO5^-} \rightarrow \ce{(CH3)2C(O2)} + \ce{HSO4^-}

This process generates DMDO in situ as a dilute solution in acetone, typically without isolation of the pure compound due to its thermal instability.^[1]^[14] Standard conditions involve suspending excess Oxone in a mixture of acetone and water, buffered to pH 7–8 with sodium bicarbonate to maintain neutrality and prevent decomposition.^[14] The mixture is cooled to 0–5 °C and stirred vigorously for 10–15 hours to ensure complete conversion, with the temperature controlled to minimize side reactions such as acetone epoxidation or peroxymonosulfate decomposition.^[14] After reaction, the mixture is subjected to vacuum distillation to collect the acetone solution, which is dried over anhydrous sodium sulfate to yield a clear, pale yellow solution of DMDO.^[14] Yields are typically 0.08–0.1 M in DMDO (corresponding to 2–3% based on available Oxone), limited by the equilibrium nature of the formation and competing hydrolysis pathways.^[14] The concentration of the resulting solution is determined by iodometric titration, which quantifies active oxygen content through reaction with iodide to liberate iodine, or by gas chromatography (GC) analysis, often using phenyl methyl sulfide as a substrate to monitor epoxidation efficiency via sulfoxide formation.^[14] These assays confirm the solution's potency, with iodometry providing a direct measure of peroxo species and GC offering structural specificity.^[14]

Alternative synthetic routes

A modern adaptation for safer and larger-scale production employs continuous flow generation using Oxone in microreactors. In this process, a 0.8 M solution of Oxone and 0.33 M K₃PO₄ in a 70:30 water:acetone mixture is used in a continuous stirred tank reactor at ambient temperature with residence times of 1-5 minutes, followed by filtration and reaction in a PFA coil, generating DMDO in situ for epoxidation and enabling gram-scale production of epoxidized materials at rates of 0.8 g/hour without the need for hazardous storage or distillation.^[24] This method addresses safety concerns by minimizing the accumulation of the explosive reagent and facilitates on-demand generation for applications like polymer epoxidation. Other oxidants, such as Caro's acid (H₂SO₅), have been employed in historical syntheses by adding a 50% K₂CO₃ solution dropwise to the acid at 0 °C to form the dioxirane in acetone solution.^[25] Attempts with peroxyacids like mCPBA, following the general reaction (CH₃)₂C=O + mCPBA → DMDO + PhCO₂H, suffer from low efficiency due to competing side reactions and poor selectivity.^[15] All alternative routes yield dilute solutions of dimethyldioxirane (typically 0.04-0.18 M), and isolation of pure material remains unviable owing to the compound's high explosion risk when concentrated, necessitating in situ use or careful handling in solvent.^[26]^[27]

Applications

Epoxidation of alkenes

Dimethyldioxirane (DMDO) serves as an effective reagent for the epoxidation of alkenes, converting them to the corresponding epoxides while producing acetone as a byproduct. The reaction proceeds under mild, neutral conditions, typically at temperatures between 0 and 25 °C, without the need for catalysts or additional reagents. It involves a stereospecific syn addition of oxygen to the double bond, preserving the alkene's stereochemistry in the product.^[28] The mechanism of DMDO-mediated epoxidation is a concerted process involving direct oxygen transfer from the dioxirane ring to the alkene through a spiro transition state. In this transition state, the alkene's π-bond interacts with one of the peroxide oxygens, leading to simultaneous formation of the two C-O bonds and cleavage of the O-O bond, without involvement of radical or stepwise intermediates. This pathway ensures no skeletal rearrangement occurs and provides high regioselectivity, particularly favoring electron-rich alkenes due to the electrophilic nature of the oxygen atom being transferred.^[29]^[30] DMDO exhibits broad scope for epoxidizing terminal, internal, and aryl-substituted alkenes, accommodating a variety of functional groups under conditions that avoid over-oxidation. For instance, cyclohexene is converted to cyclohexene oxide in approximately 90% yield within minutes at room temperature. Similarly, cis-3-hexene undergoes epoxidation nearly quantitatively, reacting eight times faster than the trans isomer due to steric accessibility in the spiro transition state. Aryl alkenes like phenanthrene yield the 9,10-epoxide in 93% isolated yield at -20 °C. These examples highlight DMDO's efficiency for both aliphatic and aromatic systems. Recent developments include continuous-flow generation of DMDO for scalable epoxidations in polymer and monomer synthesis, such as epoxidizing limonene or imidazolium salts for advanced materials with improved thermal properties, enhancing safety and efficiency as of 2022.^[28]^[4]^[6]^[31] Compared to peracids such as mCPBA, DMDO offers advantages including higher selectivity for acid-sensitive substrates, operation under neutral pH to prevent side reactions like Baeyer-Villiger oxidation, and a recyclable acetone byproduct that simplifies workup. Unlike peracids, which can lead to over-oxidation or ring-opening of sensitive epoxides, DMDO's mild reactivity minimizes such issues, making it preferable for complex natural product syntheses.^[4]

Other oxidation reactions

Dimethyldioxirane (DMDO) selectively oxidizes sulfides to the corresponding sulfoxides without further oxidation to sulfones, owing to the reagent's controlled reactivity. For instance, the oxidation of thioanisole (methyl phenyl sulfide) proceeds in high yield, typically 80-95%, under mild conditions at low temperatures in acetone solvent. This transformation is widely used for the preparation of sulfoxides due to its high selectivity and avoidance of over-oxidation, even with one equivalent of DMDO. Recent applications include post-polymerization modification of conjugated polymers containing sulfides, achieving selective sulfoxide formation to tune optical properties as of 2019.^[32]^[33] DMDO also facilitates the oxidation of amines, converting tertiary amines to amine N-oxides in quantitative yields at 0 °C, often within less than one hour.^[34] For primary amines, DMDO effects a two-step oxidation to nitro compounds under controlled conditions, such as low temperatures to minimize side reactions like hydroxylation.^[35] These reactions highlight DMDO's utility in nitrogen-containing functional group interconversions, providing clean access to oxidized derivatives without metal catalysts. In C-H bond activations, DMDO enables the oxidation of unactivated alkanes to alcohols or ketones, targeting tertiary sites preferentially. A representative example is the conversion of adamantane to 1-adamantanol via tertiary C-H oxidation, achieving yields of approximately 20-30% under standard conditions. This method demonstrates DMDO's capability for direct functionalization of saturated hydrocarbons, though selectivity for secondary over tertiary sites can vary with substrate sterics. DMDO mediates a variant of the Nef reaction by oxidizing nitronate anions derived from primary nitroalkanes, leading to the corresponding carbonyl compounds under mild, neutral conditions.^[36] This approach offers an efficient alternative to classical Nef protocols, accommodating sensitive substrates and proceeding in good yields without acidic workup.^[37] Despite these applications, DMDO's efficacy diminishes for electron-poor substrates, where reaction rates slow and alternative oxidants may be preferred. Additionally, many transformations require excess DMDO to achieve satisfactory conversion due to its dilute solutions and peroxide nature.

Safety and handling

Hazards

Dimethyldioxirane (DMDO) is a highly reactive organic peroxide that poses significant explosive risks due to its unstable three-membered ring structure containing a weak O-O bond. Neat or concentrated DMDO is shock-sensitive and can detonate upon mechanical impact or heating, with solutions above approximately 0.1 M becoming increasingly hazardous and prone to violent decomposition. ^[38] ^[39] As a volatile peroxide, DMDO exhibits thermal instability, decomposing exothermically at elevated temperatures and potentially leading to runaway reactions if not properly controlled. ^[40] Health hazards associated with DMDO primarily stem from its irritant nature. Contact with skin causes irritation, while exposure to eyes results in serious damage requiring immediate flushing and medical attention. Inhalation of vapors or mist can irritate the respiratory tract. Ingestion may cause gastrointestinal irritation, though specific data for DMDO are limited. ^[41] Environmental risks arise from DMDO's decomposition products, which include acetone—a flammable volatile organic compound—contributing to fire hazards and potential air quality issues in confined spaces. Peroxide residues from incomplete reactions can form explosive concentrates in waste streams, necessitating careful containment to prevent release into soil or water systems. ^[40] ^[41] Toxicity data for DMDO remain limited, with no established LD50 values; it is classified under GHS as a skin irritant (Category 2) and causing serious eye irritation (Category 2). Analogous organic peroxides are often rated as oxidizing liquids (Category 1). ^[41] ^[42]

Storage and disposal

Dimethyldioxirane (DMDO) is typically generated in situ for use due to its instability, but if stored, it should be as a dilute solution in acetone at concentrations below 0.1 M to minimize risks associated with its reactivity as an organic peroxide.^[40] Solutions are maintained at low temperatures such as -20 °C in a freezer to prevent decomposition, which is accelerated at higher temperatures, with stability observed for up to several weeks under these conditions (though some commercial guidance suggests 10–25 °C).^[43] Storage containers should be made of glass and protected from light, as photodecomposition occurs, and kept away from heavy metals that catalyze breakdown; periodic monitoring of concentration via iodometric titration is recommended to ensure integrity.^[19] Long-term studies indicate that properly stored solutions can retain significant active content for over a year, though fresh preparations are preferred for optimal performance. Handling of DMDO requires strict precautions due to its volatile and oxidizing nature. All operations, including preparation and use, must be conducted in a well-ventilated fume hood to avoid inhalation of vapors.^[40] Personnel should wear appropriate personal protective equipment, including chemical-resistant gloves, safety goggles, and protective clothing, to prevent skin and eye contact.^[44] Distillation or attempts to concentrate the solution are strictly prohibited, as they can lead to hazardous exothermic reactions; excess reagent should be quenched immediately after use with a reducing agent such as sodium thiosulfate to decompose residual peroxide.^[40] Disposal of DMDO solutions follows established protocols for organic peroxides to ensure safe environmental release. Solutions should first be diluted extensively and neutralized using reducing agents like sodium bisulfite or sodium thiosulfate, followed by testing for residual peroxides using standard kits; neutralized waste may then be discharged to sewer systems in accordance with local regulations.^[44] If peroxide tests remain positive, residues must be treated via controlled incineration with flue gas scrubbing at a licensed facility to prevent contamination of water sources or ecosystems.^[44] DMDO is not available as a commercial product due to its instability and is generated in situ or on-demand in laboratory settings only. Handling and storage practices must comply with OSHA standards for organic peroxides and laboratory chemical hygiene, including those outlined in 29 CFR 1910.1450 for occupational exposure limits and safe work practices.

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