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Epoxide

Epoxides, also known as oxiranes, are a class of cyclic ethers characterized by a strained three-membered ring consisting of two adjacent carbon atoms and one oxygen atom.^[1] This structural motif imparts significant ring strain, making epoxides highly reactive toward nucleophilic ring-opening reactions under both acidic and basic conditions.^[2] The simplest epoxide, ethylene oxide, is a major industrial chemical. Epoxides are typically synthesized through the epoxidation of alkenes. The most common laboratory method is the Prilezhaev reaction using peracids such as m-chloroperoxybenzoic acid (mCPBA), which transfers an oxygen atom across the double bond in a stereospecific syn addition.^[1] Other methods include catalytic processes with molecular oxygen and metal catalysts.^[3] Due to their reactivity, epoxides serve as versatile building blocks in organic synthesis, enabling the formation of vicinal diols, amino alcohols, and other functionalized compounds via regioselective ring openings.^[4] In polymer chemistry, epoxides are key monomers for producing epoxy resins, which are thermosetting polymers valued for their adhesion, mechanical strength, and chemical resistance in applications ranging from aerospace composites to dental materials.^[5] Biologically, epoxides function as reactive intermediates in the metabolism of xenobiotics and endogenous compounds, such as arachidonic acid derivatives, where they are often detoxified by epoxide hydrolases to prevent cellular damage from their electrophilic nature.^[6] These enzymes play critical roles in regulating inflammation, blood pressure, and carcinogenesis by converting epoxides to less reactive diols.^[7]

Nomenclature and Structure

Nomenclature

Epoxides are organic compounds classified as three-membered cyclic ethers, in which an oxygen atom is bonded to two adjacent carbon atoms, forming a strained ring structure. The general formula for unsubstituted epoxides is \ce{C_nH_{2n}O}, and the ring strain in this configuration, estimated at about 115 kJ/mol, is a defining feature that enhances their reactivity compared to larger cyclic ethers.^[8]^[9] In IUPAC nomenclature, the parent compound for the simplest epoxide is named oxirane, and derivatives are named by adding prefixes for substituents with locants that provide the lowest possible numbers to the ring carbons. For example, the compound known commonly as propylene oxide is systematically named 2-methyloxirane. When the epoxide ring is part of a larger carbon chain or ring system, it is indicated using the prefix "epoxy-" with appropriate locants, such as 1,2-epoxycyclohexane for the epoxide derived from cyclohexene.^[8]^[10] Common names for epoxides often retain historical terminology or describe the structure relative to the corresponding alkane or alkene, using the "epoxy" prefix or the suffix "oxide." For instance, the simplest epoxide is called ethylene oxide or 1,2-epoxyethane, while propylene oxide is 1,2-epoxypropane. Polymers obtained from the ring-opening polymerization of epoxides, such as those used in resins, are collectively termed epoxies in common nomenclature, exemplified by diglycidyl ether of bisphenol A (DGEBA)-based materials.^[8]^[11] For complex epoxides with stereochemistry, naming incorporates descriptors to specify configuration. Symmetric disubstituted epoxides use cis- or trans- prefixes, as in cis-2,3-dimethyloxirane for the epoxide from cis-2-butene. Chiral epoxides employ the R/S system for absolute configuration at the ring carbons, such as (2R,3R)-2,3-dimethyloxirane. These notations ensure precise identification of stereoisomers, which is critical given the epoxide ring's rigidity.^[10]

Molecular Structure

Epoxides feature a three-membered ring consisting of two carbon atoms and one oxygen atom, resulting in highly strained geometry. The bond angles within the ring are approximately 60° for both the C-C and C-O bonds, significantly deviating from the ideal tetrahedral angle of 109.5° for sp³-hybridized carbons. This angle strain arises from the compressed ring structure, which forces poor orbital overlap and increases the molecule's reactivity compared to larger cyclic ethers.^[12] The bond lengths in the simplest epoxide, oxirane (ethylene oxide), reflect this strain: the C-O bonds measure about 1.435 Å, and the C-C bond is approximately 1.469 Å. In contrast, acyclic ethers exhibit slightly shorter C-O bonds around 1.41 Å, with less compression due to the absence of ring constraints. Larger cyclic ethers like oxetanes (four-membered rings) show even less strain, with C-O bonds at 1.46 Å, C-C bonds at 1.53 Å, and bond angles closer to 90°, highlighting the unique torsional and angle distortions in epoxides that elevate their strain energy to about 27 kcal/mol.^[12]^[13] Electronically, the epoxide ring displays polarization due to oxygen's electronegativity (3.44 on the Pauling scale), which withdraws electron density from the carbons, imparting partial positive charges (δ⁺ ≈ +0.4 to +0.5) on the ring carbons and concentrating negative charge on oxygen's lone pairs. This can be illustrated through resonance structures where one lone pair on oxygen conjugates with an adjacent C-O bond, depicted as O⁻-C⁺, emphasizing the electrophilic nature of the carbons; molecular orbital analysis further reveals bent σ-bonds with elevated LUMO energies at the carbons, facilitating nucleophilic attack.^[14]^[15] The rigid three-membered ring enforces a cis configuration for substituents on the two carbon atoms, as trans geometry is geometrically impossible without breaking the ring. In unsymmetrical epoxides, such as propylene oxide (2-methyloxirane), this leads to chirality at the substituted carbon, resulting in enantiomers: (R)-propylene oxide and (S)-propylene oxide, which are non-superimposable mirror images due to the ring's planarity and the asymmetric substitution.^[16]

Physical and Chemical Properties

Epoxides exhibit a range of physical properties influenced by their molecular weight and substitution patterns. Low molecular weight epoxides, such as ethylene oxide and propylene oxide, are colorless and volatile, appearing as gases or low-boiling liquids at room temperature. For instance, ethylene oxide is a colorless gas with a boiling point of 10.7 °C and a density of 0.871 g/cm³ at 20 °C,^[17] while propylene oxide is a colorless liquid with a boiling point of 34 °C and a density of 0.859 g/cm³.^[18] Higher homologs, including those with longer alkyl chains or aromatic substituents like styrene oxide (density 1.05 g/cm³),^[19] tend to be viscous oils or crystalline solids at ambient conditions. In general, densities of epoxides increase with chain length due to enhanced molecular packing, typically ranging from about 0.85 g/cm³ for simple alkyl epoxides to over 1.0 g/cm³ for more substituted variants. Solubility characteristics of epoxides reflect their polarity. Small epoxides like ethylene oxide are highly soluble in water (miscible) owing to hydrogen bonding capabilities,^[17] but solubility decreases markedly with increasing chain length; for example, propylene oxide has a water solubility of 41 g/100 mL at 20 °C,^[18] while larger epoxides are generally insoluble in water. Conversely, epoxides are broadly soluble in organic solvents such as alcohols, ethers, and hydrocarbons, facilitating their use in synthetic applications. Refractive indices also trend upward with molecular size and substitution, starting at 1.366 for propylene oxide^[18] and reaching 1.50 or higher for polymeric or highly substituted epoxies, due to increased electron density and polarizability. Chemically, epoxides demonstrate notable stability under neutral conditions but possess high reactivity attributable to significant ring strain. The total strain energy in oxirane (the parent epoxide) is approximately 28 kcal/mol, comprising contributions from angle strain (deviation from ideal 109.5° bond angles) and torsional strain in the three-membered ring. This strain renders epoxides inert in neutral media but prone to ring-opening under acidic or basic catalysis. Epoxides act as weak bases, with the pKa of the protonated oxygen (conjugate acid) around -3, indicating protonation occurs only in strongly acidic environments. They exhibit no significant acidity, as the C-H bonds adjacent to the epoxide ring have pKa values exceeding 30, precluding deprotonation under typical conditions. Spectroscopic properties provide diagnostic signatures for epoxides. In infrared (IR) spectroscopy, the symmetric C-O-C stretch appears as a characteristic absorption near 1250 cm⁻¹, while asymmetric stretches occur between 950 and 810 cm⁻¹. Proton nuclear magnetic resonance (¹H NMR) spectra show signals for protons on the epoxide carbons in the range of 2.5-3.5 ppm, typically as multiplets due to coupling within the strained ring. These shifts reflect the deshielding effect of the electronegative oxygen and ring geometry.

Synthesis

Industrial Production

The industrial production of epoxides primarily focuses on commodity-scale processes for ethylene oxide and propylene oxide, which dominate global output due to their use in downstream chemicals like surfactants, glycols, and polyurethanes. Ethylene oxide, the most produced epoxide, is manufactured via the direct catalytic oxidation of ethylene with molecular oxygen in the gas phase over silver-based catalysts. This process operates at temperatures between 210°C and 280°C and pressures of 1-2 MPa, achieving high selectivity through promoters like cesium and chlorine compounds on the catalyst surface. The balanced reaction is:

$2 \ce{CH2=CH2 + O2 -> 2 C2H4O}

This route accounts for over 95% of global ethylene oxide production, with significant byproducts including carbon dioxide (approximately 0.9 kg CO₂ per kg ethylene oxide) from side reactions involving complete combustion. Global capacity for ethylene oxide reached an estimated 37.3 million tonnes in 2025, driven largely by demand in Asia-Pacific regions.^[20]^[21]^[22]^[23] Propylene oxide production employs two main industrial routes: the traditional chlorohydrin process and modern hydroperoxide-based methods. In the chlorohydrin process, propylene reacts with chlorine in water to form propylene chlorohydrin, which is then treated with calcium hydroxide to yield the epoxide and calcium chloride as a byproduct:

\ce{[C3H6](/page/C3H6) + Cl2 + H2O -> [C3H7ClO](/page/C3H6O)} \quad \text{(chlorohydrin formation)}

\ce{[C3H7ClO](/page/C3H6O) + [Ca](/page/CA)(OH)2 -> [C3H6O](/page/C3H6O) + [CaCl2](/page/Calcium_chloride) + H2O}

This method, while cost-effective for large-scale output, generates substantial aqueous salt waste, necessitating extensive treatment to manage environmental impacts. Alternatively, the hydrogen peroxide to propylene oxide (HPPO) process uses hydrogen peroxide as the oxidant in the presence of a titanium silicalite (TS-1) catalyst, offering higher atom efficiency and reduced waste, with water as the primary byproduct. Global propylene oxide capacity stood at approximately 10.1 million tonnes in 2025, with HPPO gaining share due to its sustainability advantages.^[24]^[25]^[26] Other commodity epoxides, such as styrene oxide, are produced on a smaller scale via analogous epoxidation routes, including chlorohydrin methods from styrene and hypochlorous acid followed by base-induced cyclization, though direct peracid oxidation is also employed industrially. Production volumes for styrene oxide remain modest compared to ethylene and propylene oxides, typically integrated into specialty chemical facilities. Process economics emphasize catalyst performance and waste mitigation. For ethylene oxide, modern silver catalysts achieve selectivities exceeding 90%, minimizing ethylene loss and enabling energy-efficient operations with total energy inputs around 25-30 MJ per kg of product, primarily from reaction and distillation steps. Traditional chlorohydrin routes for propylene oxide face higher operational costs due to chlorine handling and salt disposal, with waste management requiring neutralization and brine recycling to comply with regulations, whereas HPPO processes reduce these burdens by avoiding halide byproducts and lowering overall energy demands by up to 20%.^[27]^[23]^[25]

Laboratory Methods

One of the most common laboratory methods for epoxide synthesis is the Prilezhaev reaction, which involves the direct epoxidation of alkenes using percarboxylic acids such as m-chloroperoxybenzoic acid (mCPBA) or peracetic acid.^[28] This electrophilic addition proceeds through a concerted mechanism where the peracid's electrophilic oxygen transfers to the double bond, yielding the epoxide and the corresponding carboxylic acid as byproduct.^[28] The general equation is:

\ce{R2C=CR2 + R'CO3H -> epoxide + R'CO2H}

The reaction is stereospecific, resulting in syn addition that retains the alkene's cis or trans geometry in the product epoxide.^[28] It is particularly suited for electron-rich alkenes, such as allylic alcohols or styrenes, and is often performed in dichloromethane at low temperatures to control exothermicity and selectivity.^[28] Yields typically range from 70-95% for simple substrates, with mCPBA favored in research settings due to its commercial availability and ease of handling.^[28] Another versatile laboratory approach is dehydrohalogenation of halohydrins, where vicinal halohydrins are treated with a base to form epoxides via intramolecular nucleophilic substitution.^[29] For instance, epichlorohydrin is prepared by reacting allyl chloride with hydroxide to form the chlorohydrin intermediate, followed by base-induced cyclization.^[29] The mechanism involves deprotonation of the hydroxyl group, generating an alkoxide that displaces the halide in an S_N2 fashion, often using aqueous NaOH or KOH in a biphasic system.^[29] This method accommodates γ-eliminations from other precursors like β-halo ethers and is effective for both aliphatic and aromatic substrates, providing epoxides in 80-90% yields under mild conditions.^[29] It is especially useful for preparing epoxides from alkenes via prior halohydrin formation, offering regioselectivity controlled by the halide placement. Nucleophilic epoxidation serves as a complementary method for electron-deficient alkenes, such as α,β-unsaturated carbonyls, which are less reactive toward electrophilic peracids.^[30] Alkaline hydrogen peroxide (e.g., 30% H_2O_2 with NaOH) acts as the nucleophilic oxidant, adding oxygen across the double bond under basic conditions in solvents like methanol or water.^[31] Dioxiranes, generated in situ from ketones like acetone and Oxone (potassium peroxymonosulfate), provide an alternative nucleophilic pathway, enabling epoxidation at room temperature with high chemo-selectivity.^[32] These methods invert the typical polarity, with the oxidant attacking the electron-poor alkene, and are applied to chalcones or enones, achieving 60-85% yields while avoiding over-oxidation of sensitive functional groups.^[32] Metal-catalyzed epoxidations expand the scope for laboratory synthesis, exemplified by the Jacobsen-Katsuki process using manganese(III) or cobalt salen complexes with oxidants like NaOCl or iodosylbenzene.^[33] The mechanism involves formation of a high-valent metal-oxo species (e.g., Mn(V)=O), which transfers oxygen to the alkene via a concerted or stepwise pathway, depending on substrate electronics; manganaoxetane intermediates have been proposed for alkyl-substituted olefins.^[33] These catalysts operate at 0-25°C in dichloromethane, accommodating unfunctionalized alkenes with turnover numbers up to 1000, though side reactions like radical pathways can occur with certain substrates.^[33] Variants of peracid methods include in situ generation of peroxycarboxylic acids to enhance safety and efficiency in small-scale reactions.^[34] For example, performic or peracetic acid is formed by mixing hydrogen peroxide with formic or acetic acid, often catalyzed by sulfuric acid, and directly used for epoxidation without isolation.^[34] This approach minimizes handling of unstable peracids and is conducted at 40-60°C, yielding epoxides from unsaturated fatty acids or alkenes in 70-90% with reduced byproduct formation.^[34]

Asymmetric Epoxidation

Asymmetric epoxidation refers to stereoselective methods for synthesizing chiral epoxides from prochiral alkenes, enabling access to enantiopure building blocks essential for pharmaceuticals and natural products. These methods typically employ chiral catalysts or auxiliaries to achieve high enantiomeric excess (ee), often exceeding 90%, and have revolutionized synthetic organic chemistry by providing predictable stereocontrol. One of the most influential approaches is the Sharpless asymmetric epoxidation (SAE), developed in 1980, which targets allylic alcohols using titanium(IV) isopropoxide [Ti(OiPr)₄], tert-butyl hydroperoxide (t-BuOOH) as the oxidant, and a chiral diethyl tartrate (DET) ligand. This stoichiometric process delivers epoxides with predictable stereochemistry guided by the "sticky fingers" mnemonic: when the allylic alcohol is drawn in the plane with the hydroxymethyl group in the lower right, the oxygen is added from the bottom face using (+)-tartrate and from the top with (-)-tartrate. Yields are typically high (>90%), with ee values often >90% for trans-disubstituted allylic alcohols. The reaction for a representative trans allylic alcohol, such as (E)-cinnamyl alcohol, proceeds as follows:

\begin{align*} &\ce{(E)-PhCH=CHCH2OH + t-BuOOH ->[Ti(OiPr)4][(+)-DET] } \\ &\ce{PhCH(O)CHCH2OH + t-BuOH} \end{align*}

where the epoxide has the (2R,3R) configuration.^[35] The Jacobsen hydrolytic kinetic resolution (HKR) complements SAE by resolving racemic terminal epoxides into enantiopure forms using a chiral cobalt(III)-salen complex as catalyst and water as nucleophile. Introduced in 1997 and refined in 2002, this method selectively hydrolyzes one enantiomer to the corresponding diol, leaving the unreacted epoxide with up to 99% ee at 50% conversion, with selectivities (k_rel) often >100 for aliphatic epoxides. The process is operationally simple, scalable, and tolerant of functional groups, making it industrially viable for producing (S)- or (R)-epoxides. Other notable methods include the Shi epoxidation, which uses a chiral ketone-derived dioxirane, generated in situ from Oxone® (potassium peroxymonosulfate) and a fructose-based catalyst, to epoxidize unfunctionalized olefins with ee values up to 99%. This organocatalytic approach is particularly effective for trans-alkenes and avoids metal residues. Phase-transfer catalysis (PTC) with chiral quaternary ammonium salts, such as cinchona alkaloid derivatives, enables asymmetric epoxidation of α,β-unsaturated carbonyls using hydrogen peroxide under biphasic conditions, achieving ee >90% for chalcones and related enones.^[36]^[37] These techniques have found widespread application in total synthesis, notably in constructing the taxol side chain, where SAE of a trans-allylic alcohol intermediate establishes the (2R,3S) stereochemistry required for the β-lactam core with >95% ee. Similarly, SAE has been employed in erythromycin precursor synthesis to install epoxy alcohol motifs in the macrolide ring system, facilitating stereocontrolled fragment assembly. Recent advances post-2020 emphasize greener organocatalytic strategies, including hypervalent iodine-mediated epoxidations that leverage chiral iodosylarenes or peptide-bound iodine catalysts for mild, metal-free oxidations of styrenes with ee up to 92%. Photocatalytic methods, such as those using chiral manganese complexes with visible light and water as the oxygen source, have also emerged for terminal olefins, offering sustainable alternatives with ee >80% under aqueous conditions. These developments prioritize environmental compatibility while maintaining high stereoselectivity.^[38]^[39]

Biosynthesis

Epoxides are biosynthesized in various organisms through enzymatic processes that introduce oxygen across carbon-carbon double bonds in alkenes, primarily via monooxygenases. These pathways are essential for producing bioactive molecules involved in defense, signaling, and structural roles. Cytochrome P450 monooxygenases catalyze the epoxidation of alkenes in diverse substrates, including terpenoids and fatty acids. In terpenoid biosynthesis, enzymes such as CYP15A1 in insects epoxidize the terminal alkene of farnesyl pyrophosphate-derived juvenile hormone III to form the natural (10R)-epoxide enantiomer with high stereoselectivity. In fatty acid metabolism, cytochrome P450 epoxygenases convert arachidonic acid, released from membrane phospholipids by cytosolic phospholipase A2, into four regioisomeric epoxyeicosatrienoic acids (EETs: 5,6-EET, 8,9-EET, 11,12-EET, and 14,15-EET) by inserting an oxygen atom across one of the double bonds. The mechanism involves activation of molecular oxygen by the heme iron center, forming a high-valent iron(IV)-oxo species (Compound I) that transfers the oxo group to the alkene in a concerted manner, yielding the epoxide. These reactions occur in a tissue- and cell-specific manner, with individual P450 isoforms producing regioisomers in varying proportions, such as CYP2J2 predominantly forming 14,15-EET in endothelial cells. Flavoprotein epoxidases in bacteria facilitate epoxide formation during antibiotic biosynthesis, enabling the production of structurally complex natural products. For instance, the flavin-dependent monooxygenase HppE in Streptomyces wedmorensis catalyzes the epoxidation of (S)-2-hydroxypropylphosphonic acid to form the epoxide ring in fosfomycin, a broad-spectrum antibiotic, using FMNH2 and Fe(II) in a cation- and flavin-dependent mechanism that generates a hydroperoxyflavin intermediate for oxygen transfer. Similarly, MonCI in Streptomyces cinnamonensis performs sequential epoxidations on the polyene intermediate premonensin A to introduce three epoxide rings in monensin A, a polyether ionophore antibiotic, via a flavin C4a-hydroperoxide species that selectively targets each alkene. Although the vancomycin biosynthetic pathway in Amycolatopsis orientalis involves extensive oxidations by P450 enzymes like OxyA, B, and C for cross-linking the peptide scaffold, epoxide formation is not a documented step; instead, flavoprotein epoxidases are more prominently featured in polyene-containing antibiotics like monensin. In plants and fungi, epoxy fatty acids are synthesized through P450-mediated epoxidation of unsaturated fatty acids in seed oils. Vernolic acid (12,13-epoxy-9-octadecenoic acid), a major component of Euphorbia lagascae seed oil, is produced by epoxidation of linoleic acid esterified to phosphatidylcholine, catalyzed by a cytochrome P450 monooxygenase in the endoplasmic reticulum, with cytochrome b5 as an electron donor; in vivo labeling studies confirm direct conversion without free linoleic acid intermediates. Fungal pathways similarly employ P450s to epoxidize fatty acids, contributing to oxylipins with antimicrobial properties. Epoxyeicosatrienoic acids (EETs) serve as lipid mediators in inflammation signaling, exerting anti-inflammatory effects by inhibiting cytokine production and NF-κB activation in endothelial and immune cells. For example, 14,15-EET reduces tumor necrosis factor-α-induced inflammation in human bronchial epithelial cells and attenuates lipopolysaccharide-induced responses in macrophages. From an evolutionary perspective, epoxidases such as cytochrome P450 monooxygenases originated as detoxification enzymes for xenobiotics, enabling organisms to metabolize environmental alkenes into epoxides for further conjugation or hydrolysis; this ancient role is conserved across bacteria, plants, and mammals, with P450 diversification driven by selective pressures from plant secondary metabolites and pollutants.

Reactions

Ring-Opening Reactions

Epoxides undergo ring-opening reactions primarily through nucleophilic attack, driven by the inherent ring strain that facilitates cleavage of the strained C-O bond.^[40] Under basic conditions, the reaction proceeds via an SN2-like mechanism where the nucleophile attacks the less substituted carbon of the epoxide, leading to regioselective opening at the terminal position in unsymmetrical cases.^[40] This process is exemplified by the reaction of ethylene oxide with ammonia, yielding ethanolamine as the product.

\ce{(CH2)2O + NH3 -> H2NCH2CH2OH}

^[41] Similar openings occur with other nucleophiles such as water, forming diols like ethylene glycol from ethylene oxide and water, or with amines and thiols to produce amino alcohols and mercapto alcohols, respectively.^[40] In these basic conditions, the nucleophilic attack is backside, resulting in inversion of configuration at the attacked carbon and overall trans stereochemistry in the product from a cis-epoxide starting material.^[42] In contrast, acid-catalyzed ring opening involves protonation of the epoxide oxygen, which enhances the electrophilicity of the carbons and shifts the regioselectivity to favor nucleophilic attack at the more substituted carbon, resembling an SN1-like pathway with partial carbocation character.^[40] This inversion of regioselectivity compared to basic conditions is due to the transition state where the positive charge is stabilized better at the more substituted site after protonation. For instance, acid-catalyzed hydrolysis of propylene oxide with water predominantly yields 1,2-propanediol with the OH group at the secondary carbon.^[40] Stereochemically, the protonated epoxide still undergoes trans addition, with inversion at the site of nucleophilic attack.^[40] Computational studies reveal that these ring openings are exergonic, with the relief of ring strain contributing approximately 13 kcal/mol to the thermodynamics, lowering the overall energy change. Transition state energies for acid-catalyzed openings can be as low as ~10 kcal/mol in the gas phase when assisted by general acids, highlighting the role of strain relief in accelerating the reaction. These insights underscore the mechanistic differences between basic and acidic pathways, guiding selective synthesis of functionalized alcohols.^[40]

Polymerization

Epoxides undergo polymerization through ring-opening mechanisms, primarily via anionic, cationic, or step-growth processes, yielding polyethers, polyols, or cross-linked networks. These reactions exploit the strained three-membered ring to propagate chains or form networks, with control over molecular weight and structure depending on initiation conditions and monomer functionality. Anionic polymerization of epoxides, such as ethylene oxide, is initiated by strong nucleophiles like alkoxide bases (e.g., potassium tert-butoxide or sodium hydroxide), which attack the less substituted carbon of the epoxide ring, generating an alkoxide propagating species that continues chain growth. This base-initiated process produces polyethylene oxide (PEO) or polyethylene glycol (PEG) when terminated with protic species, with molecular weights ranging from oligomers to high polymers depending on monomer-to-initiator ratios. Living anionic polymerization, achieved under anhydrous conditions with crown ether complexed alkali metals or coordinated initiators like calcium or aluminum alkyls, enables precise control over molecular weight and narrow polydispersity, facilitating block copolymer synthesis.^[43]^[44] Cationic polymerization of epoxides employs Lewis acids such as boron trifluoride etherate (BF₃·OEt₂) as initiators, coordinating to the oxygen atom to activate the ring for nucleophilic attack by a growing chain or water/alcohol, often leading to polyether formation from bifunctional epoxides like cyclohexene oxide. This mechanism proceeds via carbocation intermediates, which can rearrange in substituted epoxides, resulting in branched or cyclic byproducts alongside linear chains, and is particularly suited for producing telechelic polyethers with hydroxy end-groups.^[45]^[46] A prominent example of epoxide polymerization is the curing of epoxy resins, such as bisphenol A diglycidyl ether (DGEBA), with diamines like diethylenetriamine via step-growth polyaddition. The primary amine nucleophilically attacks the epoxide, opening the ring to form a β-hydroxy secondary amine, which further reacts with another epoxide, eventually leading to cross-linked thermoset networks as multiple functionalities engage.

\ce{R-NH2 + \chemfig{**3(=-=-)}(-O-)-CH2-CH2 -> R-NH-CH2-CH(OH)-CH2-CH2- \chemfig{**3(=-=-)}(-O-)}

This process, accelerated by heat or catalysts, yields highly cross-linked structures with excellent mechanical properties.^[47]^[48] Oligomerization of epoxides occurs under controlled partial ring-opening conditions, such as mild cationic initiation with Lewis acids and protic co-initiators, producing short-chain hydroxy-terminated polyols (e.g., di- or triethylene glycol from ethylene oxide). These oligomers serve as intermediates for further derivatization, with chain length tuned by reaction stoichiometry to achieve hydroxyl values suitable for polyurethane precursors.^[49] The resulting polymers exhibit versatile properties: PEG functions as a non-ionic surfactant due to its amphiphilic nature, enabling emulsification and solubilization in aqueous systems, while cured epoxy networks provide adhesives with high tensile strength and a glass transition temperature (T_g) around 150°C, conferring thermal stability and rigidity above ambient conditions.^[50]

Deoxygenation and Reduction

Deoxygenation of epoxides to alkenes represents a key transformation for regenerating olefins from oxygenated intermediates while preserving stereochemistry. Metal-mediated methods, such as those employing low-valent titanium species generated from TiCl₄ and Zn, enable stereoretentive deoxygenation under mild conditions. For instance, treatment of epoxides with TiCl₄/Zn in the presence of formamide affords alkenes in good yields, proceeding via radical intermediates that maintain the original alkene geometry. Similarly, molybdenum(VI) dichloride dioxide (MoO₂Cl₂) catalyzed systems, using phosphines as reductants, achieve stereospecific deoxygenation of both cyclic and acyclic epoxides to alkenes with high efficiency and retention of configuration. These processes typically involve the overall reaction:

\ce{epoxide ->[metal cat.] [alkene](/page/Alkene) + H2O}

Hydrogenolysis of epoxides using Pd/C and H₂ provides a regioselective route to alcohols, preferentially cleaving the C-O bond at the less substituted carbon to yield primary alcohols from terminal epoxides. This method operates under mild pressure (1-5 atm H₂) and temperature, with Pd/C catalysts demonstrating high selectivity for anti-Markovnikov products in aryl-substituted cases. Recent reviews highlight its broad applicability to both terminal and internal epoxides, often achieving >90% yields for industrially relevant substrates. Reduction of epoxides to alcohols can be accomplished using LiAlH₄, which delivers hydride to the less hindered carbon, resulting in anti-Markovnikov regioselectivity and formation of primary alcohols from terminal epoxides. This reaction proceeds via SN2-like ring opening, with seminal studies establishing its mechanism through mixed hydride systems that confirm stereospecific inversion at the attacked carbon. Borane reagents (e.g., BH₃·THF) offer complementary regioselectivity, also favoring primary alcohols but under milder conditions, with enhanced selectivity in protic solvents; for example, terminal epoxides yield >95:5 ratios of primary to secondary alcohols. Metallation strategies involve initial insertion of organometallic reagents into the epoxide, followed by elimination to effect deoxygenation. Grignard reagents, such as alkylmagnesium halides, react with benzo-fused 1,4-epoxides in refluxing THF to promote deoxygenation via β-elimination of the magnesium alkoxide, yielding the corresponding alkenes in moderate to high yields. This approach is particularly useful for polycyclic systems where direct ring opening might lead to side products. Recent green methods emphasize sustainable deoxygenation, including nickel-catalyzed processes using silanes as reductants, which avoid stoichiometric metals and operate at room temperature with low catalyst loadings (1-5 mol%). For photocatalytic variants, while Ni-specific examples are emerging, related visible-light-driven systems with earth-abundant metals achieve deoxygenation in aqueous media, aligning with 2020s efforts toward solvent-free and light-mediated transformations.

Other Transformations

Epoxides can participate in [3+2] dipolar cycloaddition reactions as strained dipolarophiles with nitrones, leading to the formation of isoxazolidines, although such reactions are less common than with alkenes due to the ring strain influencing reactivity and regioselectivity.^[51] These transformations typically require activation conditions to facilitate the interaction, yielding five-membered heterocycles that serve as versatile intermediates in natural product synthesis. For example, terminal epoxides react with N-alkyl nitrones under thermal or Lewis acid catalysis to produce trans-isoxazolidines with high diastereoselectivity, attributed to the concerted pericyclic mechanism.^[52] The Payne rearrangement represents a key intramolecular transformation of 2,3-epoxy alcohols under basic conditions, involving deprotonation of the alcohol to form an alkoxide that attacks the epoxide ring, resulting in migration of the epoxide to the adjacent carbon with inversion of configuration at the migration terminus.^[53] This equilibrium process interconverts isomeric epoxy alcohols, often favoring the more stable isomer where the epoxide is positioned away from the hydroxyl group, and is widely exploited for regioselective control in subsequent nucleophilic openings. The reaction is reversible and typically mediated by mild bases like potassium carbonate in protic solvents, with rates influenced by substituents that stabilize the anionic intermediate.^[54] Oxidation of epoxides provides access to α-hydroxy ketones through selective ring cleavage and carbonyl formation, often employing metal-free or catalytic systems to achieve high yields without over-oxidation. For instance, treatment of epoxides with DMSO in the presence of KSF clay under microwave irradiation efficiently opens the ring to deliver α-hydroxy ketones, proceeding via an activated sulfoxonium intermediate that favors the less substituted carbon for cleavage.^[55] Alternatively, ammonium molybdate-catalyzed oxidation with hydrogen peroxide cleaves epoxides regioselectively to α-hydroxy ketones, with the molybdenum species coordinating the oxygen to facilitate nucleophilic attack by peroxide, applicable to both terminal and internal epoxides in aqueous media.^[56] Carbonylation reactions of epoxides with carbon monoxide insert CO into the C-O bond, catalyzed by rhodium complexes to produce β-lactones as strained intermediates for further elaboration. Rhodium(I) catalysts, such as [Rh(cod)Cl]2 combined with phosphine ligands, promote the ring expansion under mild pressures (10-50 atm CO), with the metal coordinating the epoxide oxygen to enhance nucleophilic attack by CO, yielding β-lactones with retention of stereochemistry from cis-epoxides.^[57] This method is particularly effective for propylene oxide, affording β-butyrolactone in high selectivity, and has been extended to copolymerization with additional CO for succinic anhydrides.^[58] Recent advances in epoxide activation have enabled their use in C-H functionalization, leveraging the strained ring for selective alkylation or amidation of inert C-H bonds. In a 2024 development, nickel-catalyzed meta-C-H alkylation of arenes with directing groups employs epoxides as alkylating agents, where the epoxide coordinates to the metal center, facilitating benzylic C-O cleavage and migratory insertion to the arene C-H site with complete regioselectivity.^[59] Post-2020 literature highlights photoinduced protocols, such as visible-light-mediated α-C-H amidation of polyethers derived from epoxide polymerization, where epoxide units activate proximal C-H bonds via radical intermediates for nitrogen insertion without metal catalysts.^[60] These strategies underscore epoxides' role in site-selective C-H transformations, with applications in late-stage functionalization of complex molecules.

Applications

Industrial Uses

Epoxides play a central role in various industrial sectors, with ethylene oxide being one of the most prominent examples due to its versatility in derivative production. Approximately 75% of ethylene oxide consumption is directed toward ethylene glycol, which serves as a foundational material for polyethylene terephthalate (PET) resins used in packaging, textiles, and bottles, as well as antifreeze formulations in automotive applications.^[20] Another significant portion, around 20-25%, undergoes ethoxylation to produce nonionic surfactants essential for detergents, cleaners, and emulsifiers in personal care and industrial cleaning products.^[61] Additionally, ethylene oxide functions directly as a gaseous sterilizing agent for medical devices and equipment, penetrating packaging without residue.^[62] Propylene oxide finds major application in the synthesis of polyether polyols, which constitute about 70% of its global consumption and are key intermediates for polyurethane foams used in furniture, automotive seating, and insulation materials.^[24] It is also hydrolyzed to propylene glycol, a versatile compound employed as a solvent in paints and inks, a humectant in food products, and an antifreeze agent in de-icing fluids.^[63] Epoxy resins represent a cornerstone of epoxide utilization in materials science, with global production reaching approximately 4.64 million tonnes in 2025. These thermosetting polymers excel in adhesives for structural bonding in construction and automotive assembly, protective coatings for corrosion resistance on metal surfaces, and composites reinforced with fibers for lightweight components in aerospace, such as aircraft fuselages and wind turbine blades.^[64] Curing agents like amines or anhydrides cross-link the epoxy groups to form durable networks with high mechanical strength and chemical resistance.^[65] Beyond these, epichlorohydrin-derived epoxides contribute to flame retardants incorporated into polymers and textiles for enhanced fire safety in building materials and electronics.^[66] In response to sustainability demands, the 2020s have seen a shift toward bio-based epoxies derived from epoxidized vegetable oils, such as soybean and castor oil, offering renewable alternatives for coatings and adhesives with comparable performance to petroleum-derived versions.^[67] The global epoxide market, encompassing these applications, is valued at approximately $76.78 billion in 2025, propelled by expansion in construction for infrastructure projects and the automotive industry for lightweight, durable components.^[68]

Pharmaceutical and Biological Roles

Epoxides play a crucial role as synthetic intermediates in the total synthesis of various pharmaceuticals, enabling the construction of complex molecular architectures with high stereocontrol. The Sharpless asymmetric epoxidation, a landmark method for generating enantiopure epoxy alcohols from allylic alcohols, has been widely applied in the synthesis of natural product-derived drugs, including antibiotics like the epothilones, which act as microtubule stabilizers for anticancer therapy.^[69] Similarly, epoxide ring-opening reactions facilitate the assembly of key fragments in the synthesis of other bioactive compounds, though specific routes for agents like etoposide primarily involve glycosidation steps rather than direct epoxide incorporation.^[70] These transformations highlight epoxides' utility in accessing chiral centers essential for biological activity, with ring-opening often proceeding under acidic or basic conditions to yield vicinal diols or amino alcohols.^[29] In biological systems, epoxides function as endogenous signaling molecules, notably the epoxyeicosatrienoic acids (EETs), which are arachidonic acid metabolites produced by cytochrome P450 epoxygenases. EETs exert vasodilatory effects by hyperpolarizing vascular smooth muscle cells through activation of potassium channels and exhibit anti-inflammatory properties by inhibiting NF-κB signaling and cytokine production in endothelial cells and monocytes.^[71] Their levels are regulated by soluble epoxide hydrolase (sEH), an enzyme that hydrolyzes EETs to less active diols; inhibition of sEH thus prolongs EET bioavailability, enhancing cardioprotective outcomes such as reduced blood pressure and attenuated vascular inflammation.^[72] Therapeutically, epoxide-containing drugs like fosfomycin, a broad-spectrum antibiotic, exploit the strained three-membered ring for covalent inhibition of bacterial MurA enzyme, disrupting cell wall biosynthesis via nucleophilic attack by a cysteine residue on the epoxide.^[73] Other epoxide-based inhibitors target proteases and hydrolases, with examples including mechanism-based inhibitors of cysteine proteases that alkylate active-site residues for anti-inflammatory or anticancer effects.^[74] Despite their beneficial roles, epoxides pose significant toxicity risks in biology due to their reactivity as alkylating agents, forming covalent adducts with nucleophilic sites on DNA, proteins, and lipids. This electrophilicity leads to DNA damage, including guanine alkylation and cross-links, which can trigger mutations and carcinogenesis; for instance, epoxides such as benzene oxide and ethylene oxide in cigarette smoke contribute to adduct formation and genotoxicity in exposed tissues.^[75] In recent advances, sEH inhibitors have emerged as promising therapeutics for cardiovascular diseases, with compounds like GSK2256294 demonstrating safety in phase 1b trials for subarachnoid hemorrhage and showing potential to reduce inflammation and improve outcomes in hypertension and ischemic conditions post-2020.^[76] Ongoing preclinical and early clinical studies further support their role in modulating EET signaling for cardioprotection without notable adverse effects.^[77]

Safety and Environmental Considerations

Health Hazards

Epoxides, particularly simple alkyl epoxides like ethylene oxide, act as direct alkylating agents by forming covalent bonds with nucleophilic sites on DNA, RNA, and proteins, which can lead to mutations and genotoxic effects.^[78] This reactivity underlies their carcinogenic potential; for instance, ethylene oxide has been classified by the International Agency for Research on Cancer (IARC) as a Group 1 carcinogen, indicating sufficient evidence of carcinogenicity in humans based on epidemiological and mechanistic data.^[79] Similar genotoxic mechanisms apply to other epoxides, such as those formed metabolically from alkenes, contributing to their role in mutagenesis.^[80] Acute exposure to epoxides primarily causes irritation to the eyes, skin, and respiratory tract, with symptoms including redness, tearing, and coughing at concentrations as low as the odor threshold.^[81] Inhalation of higher levels, such as ethylene oxide at around 1460 ppm for 4 hours, can result in central nervous system depression and potentially fatal pulmonary edema, as evidenced by animal lethality studies (LC<sub>50</sub> ≈ 1460 ppm in rats for 4-hour exposure).^[82] Liquid contact may cause severe burns or frostbite due to its cryogenic properties.^[83] Chronic exposure to epoxides is associated with reproductive toxicity, including menstrual disturbances and reduced fertility in workers, as well as neurological effects such as peripheral neuropathy and cognitive impairment.^[81] To mitigate these risks, the Occupational Safety and Health Administration (OSHA) has set a permissible exposure limit (PEL) of 1 ppm as an 8-hour time-weighted average for ethylene oxide, with additional provisions for monitoring and medical surveillance.^[84] Epoxides are metabolized primarily through conjugation with glutathione via glutathione S-transferases, which detoxifies them by forming excretable mercapturic acids; however, saturation of this pathway during high exposure can lead to unchecked genotoxicity.^[85] Epidemiological studies of sterilization workers exposed to ethylene oxide have documented elevated risks of leukemia, stomach cancer, and pancreatic cancer, with standardized mortality ratios indicating dose-dependent increases.^[86] Industrial accidents, such as leaks or spills in chemical plants, have resulted in acute cases of burns and respiratory distress; for example, a reported incident involving a worker exposed to liquid ethylene oxide led to severe dermal burns requiring medical intervention.^[87] Surveys of hospital sterilizer operators have also linked long-term low-level exposure to symptoms like headaches, nausea, and sensory irritation, underscoring the need for stringent controls.^[88]

Environmental Impact

Epoxide production and utilization contribute to environmental emissions, notably volatile organic compounds (VOCs) released during manufacturing processes, which react with nitrogen oxides under sunlight to form ground-level ozone, a key component of photochemical smog. In epoxy resin production, hazardous air pollutants such as epichlorohydrin are emitted, with regulatory efforts estimating reductions of up to 105 tons per year through emission controls. The chlorohydrin route, historically used for propylene oxide synthesis, generates substantial wastewater laden with salts, necessitating advanced treatment to mitigate salinity impacts on aquatic ecosystems.^[89]^[90]^[91] Simple epoxides like ethylene oxide and propylene oxide exhibit low environmental persistence due to their high reactivity and rapid hydrolysis or biodegradation, limiting long-term accumulation in ecosystems; however, more complex epoxides, such as those derived from pesticides like heptachlor epoxide, demonstrate greater persistence and potential for bioaccumulation in sediments and food chains. Aquatic toxicity varies, with propylene oxide showing moderate effects on fish, evidenced by 96-hour LC50 values of 215 mg/L for species like bluegill sunfish, placing it in the 100-500 mg/L range indicative of low to moderate hazard to aquatic life. Epichlorohydrin, an intermediate in epoxide production, meets persistence criteria in some assessments but has low bioaccumulation potential, with bioconcentration factors below thresholds for significant trophic transfer.^[92]^[93]^[94] Life-cycle assessments of epoxide production highlight high energy demands in oxidation-based routes, such as the hydroperoxide process for propylene oxide, contributing to elevated CO2 emissions from catalyst regeneration and overall process heating; traditional methods can require up to 35% more energy than newer alternatives. Green chemistry advancements address these issues through bio-based feedstocks, including glycerol derived from biodiesel by-products, enabling sustainable epichlorohydrin production with reduced reliance on petrochemicals. Solvent-free epoxidation methods developed post-2020, such as tungsten-catalyzed systems using hydrogen peroxide, minimize waste and solvent emissions while achieving high yields from biorenewable terpenes. The hydrogen peroxide to propylene oxide (HPPO) process exemplifies mitigation, reducing wastewater by up to 80% and energy use by 35% compared to chlorohydrin routes, thereby lowering overall ecological footprints.^[95]^[96]^[97] Regulatory frameworks in the European Union under REACH impose restrictions on epoxides classified as carcinogenic, mutagenic, or reprotoxic, such as epichlorohydrin (Category 1B CMR), limiting their use in consumer mixtures above 0.1% and mandating authorizations for industrial applications. Ethylene oxide's approval for use in biocidal products was withdrawn in June 2025 due to health and environmental risks, via Commission Implementing Decision (EU) 2025/1074, accelerating the shift from older, polluting methods like chlorohydrin processes toward greener alternatives. In the United States, the EPA issued a FIFRA Interim Decision in January 2025 imposing new requirements for ethylene oxide use in medical device sterilization. These measures, including emission limits and substance evaluations, promote sustainable practices across the epoxide lifecycle.^[98]^[99]^[100]

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https://clinicaltrials.gov/study/NCT03318783
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https://www.jacc.org/doi/abs/10.1016/j.jacbts.2024.12.010
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Effect of epoxide hydrolase and glutathione S-tranferase genotypes ...
Its main metabolite, styrene-7,8-oxide (SO), is considered responsible for the genotoxic effects associated with exposure to styrene. SO is detoxified by ...
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Mortality among Workers Exposed to Ethylene Oxide
May 16, 1991 · Those with relatively high levels of exposure include approximately 96,000 exposed in hospitals and 21,000 exposed during the commercial ...
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Ethylene oxide burn in a chemical plant worker: a case report
Jul 1, 2021 · Ethylene oxide is a chemical agent that is widely used for the sterilization of medical equipment and the manufacture of chemicals.Missing: epidemiological | Show results with:epidemiological
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Ethylene Oxide Acute Exposure Guideline Levels - NCBI - NIH
Acute exposure to ethylene oxide at the odor detection level (≥260 ppm) causes eye and upper respiratory tract irritation and signs and symptoms of effects on ...
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Epoxy Resins Production and Non-Nylon Polyamides
The rule is estimated to reduce emissions of hazardous air pollutants (HAP), mainly epichlorohydrin, by approximately 105 tons per year.Missing: smog | Show results with:smog
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Environmental impacts and emission profiles of volatile organic ...
May 3, 2025 · When exposed to sunlight, VOCs react with nitrogen oxides (NOx) to create ozone, a major component of smog. High concentrations of ground-level ...
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Research on treatment of propylene oxide wastewater with high salt ...
There are several routes to produce propylene oxide in the world such as peroxide method and chlorohydrin method [2, 3]. The propylene oxide production ...Missing: epoxides | Show results with:epoxides
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[PDF] ETHYLENE OXIDE PRODUCT STEWARDSHIP GUIDANCE MANUAL
EO aquatic toxicity studies have been conducted using fish and crustaceans. The results indicate that EO has low to moderate aquatic toxicity (Table 4.3 on ...
[86]
Epichlorohydrin - information sheet - Canada.ca
It was also concluded that epichlorohydrin meets the persistence criteria but not the bioaccumulation criteria as set out in the Persistence and Bioaccumulation ...
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[PDF] Propylene Oxide (PO) Product Stewardship Summary - Shell Global
The aquatic toxicity of Propylene Oxide indicates low toxicity, with fish being the most sensitive species with an LC50 of around 50 mg/l.
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Exergy-aided environmental life cycle assessment of propylene ...
Dec 9, 2021 · Propylene oxide has a variety of toxic impacts on the environment and humans. Short-term acute exposure of animals and humans to propylene oxide ...
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[PDF] Green Chemistry - RSC Publishing
This article presents a life cycle assessment for production of CO2-based polyethercarbonate polyols in a real industrial pilot plant. The considered cradle ...
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Recent advances in catalytic and non-catalytic epoxidation of terpenes
Nov 8, 2023 · The cation exchange catalyst showed the greatest selectivity and yield of epoxidation products, despite having a lower conversion of limonene ( ...
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European Commission to Withdraw Approval for Ethylene Oxide in ...
Dec 4, 2024 · The European Commission has announced its intention to withdraw approval for the use of ethylene oxide as a surface disinfectant in biocidal products.
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[PDF] The new HPPO Process for Propylene Oxide - Aidic
HPPO has significant environmental benefits versus the conventional processes: • wastewater is reduced by up to 80%. • Energy use is reduced by 35%. • The ...<|separator|>