tert-Butyl hydroperoxide
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Product Description
Tert-butyl hydroperoxide (TBHP) is a high-energy, SN1/SN2-mixed organic peroxide whose weak O–O bond delivers powerful, selective oxidation under mild conditions, enabling epoxidations, C–H activations and biomass conversions at ≥95 % yield in seconds, yet its exothermic synthesis and metal-catalyzed decomposition rank it as a maximum-hazard chemical. Recent advances replace batch reactors with 91 %-yield continuous pipe flow that cuts heat accumulation 40 % and worst-case temperature rise 38 %, while switchable Cu/V catalysts steer site-selective oxidations and magnetically recoverable Ru-on-γ-Fe₂O₃ nanocatalysts give green, reusable epoxidation, positioning TBHP as an essential but rigorously controlled oxidant for fine chemicals, pharmaceuticals and environmental remediation.
Other Information
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Environmental Fate: In the atmosphere, it reacts with hydroxyl radicals (rate constant ~3.00 × 10⁻¹² cm³/molecule-sec).
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Biochemical Role: Serves as a substrate for glutathione peroxidase in cells, used experimentally to induce oxidative stress and study related pathways (e.g., mitochondrial permeability transition leading to necrosis).
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Analytical Methods: Can be analyzed by Gas Chromatography (GC), High-Performance Liquid Chromatography (HPLC), and spectroscopy (IR, NMR, Mass Spec). Special care is needed in mass spectrometry due to dissociative ionization, primarily forming the tert-butyl fragment (C₄H₉⁺, m/z 57).
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Regulatory Status: Appears in various chemical inventories (TSCA, EINECS). Production volume in the U.S. is significant (tens of millions of pounds annually).
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Impurities & Byproducts: Industrial synthesis can produce byproducts like di-tert-butyl peroxide (DTBP), tert-butanol, and acetone.
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Research Frontiers: Current studies focus on developing safer, more efficient catalytic systems (e.g., using Au/CeO₂, magnetic nanoparticles) for TBHP-mediated oxidations, enhancing selectivity, and improving process safety through microreactor technology and detailed kinetic/thermodynamic modeling.
Synthesis and Production
Primary Industrial Method:
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The dominant industrial process is the two-step acid-catalyzed peroxidation of tert-butyl alcohol (TBA) with hydrogen peroxide (H₂O₂).
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Esterification: TBA reacts with concentrated sulfuric acid (H₂SO₄) to form tert-butyl bisulfate.
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Oxidation: The bisulfate intermediate is oxidized by H₂O₂ to yield TBHP.
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Key Process Parameters: Optimized conditions typically involve temperatures of 25-50°C, with a molar ratio of TBA:H₂O₂ around 1:1 and H₂SO₄:TBA around 0.95. Yields can exceed 90%.
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Alternative Routes: Other methods include the direct oxidation of isobutane or isobutene with oxygen, but these are less common due to harsher conditions (high temperature/pressure) or handling difficulties.
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Safety Note: The synthesis is strongly exothermic. Hydrogen peroxide and the product TBHP are thermally unstable, presenting a significant thermal runaway hazard. Process safety evaluations (using calorimetry) are critical for intrinsic safety design.
Product Form:
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Due to safety and stability, TBHP is commonly marketed and handled as aqueous or solvent solutions.
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Common Grades: 70% wt. in water (most common), ~80% solutions (often stabilized with water and phosphoric acid), and solutions in decane or nonane (~5.5 M).
Uses and Applications
TBHP is a versatile chemical with applications across multiple industries due to its role as an oxidant and radical initiator.
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Polymer Industry:
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Initiator for emulsion polymerization (e.g., styrene-butadiene rubber) and radical polymerization of monomers like acrylics.
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Cross-linking/Curing Agent for unsaturated polyester resins and melamine resins.
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Organic Synthesis:
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Oxidizing Agent: Widely used in C-H functionalization and the formation of heteroatom-heteroatom bonds. Its advantages include being cost-effective, efficient, and a greener alternative to heavy metal oxidants.
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Epoxidation Agent: For selective conversion of alkenes to epoxides.
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Intermediate: Key raw material in the Halcon process for producing propylene oxide.
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Other Applications:
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Bleaching and Deodorizing agent.
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Oxidant in Advanced Oxidation Processes (AOPs) for wastewater treatment.
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Research Tool: Used in biochemistry and cell biology as a direct-acting oxidative stress-inducing agent to study mechanisms like Ca²⁺-dependent signal transduction.
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Regulated Uses: Listed as a Food Contact Substance (FCS) for use in adhesives and coatings (21 CFR 175.105, 176.170).
Chemical and Physical Properties
Molecular & Basic Physical Properties:
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Molecular Formula: C₄H₁₀O₂ | Molecular Weight: 90.12 g/mol
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Appearance: Colorless to pale yellow liquid. Described as "watery," odorless, or having a pungent odor.
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Density: ~0.88-0.90 g/cm³ at 20°C (less dense than water).
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Melting Point: -8 °C to -3 °C
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Boiling Point/Decomposition: Decomposes at ~89 °C (at atmospheric pressure). BP reported as 35-40 °C at reduced pressure (20-23 mmHg).
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Solubility: Miscible or slowly mixes with water. Soluble in common organic solvents (ethanol, diethyl ether, chloroform).
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Refractive Index: ~1.4015 at 20°C
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pKa: ~12.8 at 20°C
Chemical & Reactivity Properties:
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Core Structure: Contains a weak peroxy bond (-O-O-) which is key to its reactivity and thermal instability.
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Thermal Stability:
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Autoignition Temperature: ~238 °C
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Self-Accelerating Decomposition Temperature (SADT): ~80-90 °C.
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Half-life Temperatures (in chlorobenzene): 10 h @ 164 °C; 1 h @ 185 °C; 1 min @ 207 °C.
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Reactivity: A strong oxidizing agent. Decomposition is accelerated by heat, acids, bases, and metal ions (Cu, Co, Mn). Decomposition products include tert-butanol, acetone, and methane.
Spectroscopic Identifiers:
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CAS Registry Number: 75-91-2
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InChIKey: CIHOLLKRGTVIJN-UHFFFAOYSA-N
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Canonical SMILES: CC(C)(C)OO
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Other IDs: EC 200-915-7, UNII 955VYL842B, ChEBI CHEBI:64090, DTXSID9024693.
Safety and Handling
Hazard Classification (GHS):
TBHP is classified as a hazardous substance with multiple dangers. Common hazard statements include:
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Physical Hazards: Flammable liquid and vapor (H226); Heating may cause a fire (H242).
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Health Hazards: Toxic if swallowed/inhaled (H301/H330); Causes severe skin burns and eye damage (H314); May cause an allergic skin reaction (H317); Suspected of causing genetic defects (H341).
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Environmental Hazard: Toxic to aquatic life with long-lasting effects (H411).
Key Hazardous Properties:
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Flammability: Flash point between 26-43 °C (closed cup). Vapor density (~2-3.1 relative to air) means vapors can sink and accumulate.
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Reactivity: An organic peroxide and strong oxidizer. Incompatible with reducing agents, strong acids/bases, and metals. Can undergo violent exothermic decomposition.
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Toxicity: Irritant and corrosive. Animal studies show it is toxic via oral, dermal, and inhalation routes. It is metabolized in vivo to methyl radicals, leading to oxidative stress and DNA damage (e.g., 8-methylguanine formation).
Safe Handling and Storage:
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Storage: Store in a cool (≤ 30 °C), well-ventilated area away from heat, sparks, and sunlight. Use non-metallic containers and ensure compatibility of seals/gaskets.
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Handling: Use personal protective equipment (PPE) including chemical-resistant gloves, goggles, and face shield. Implement engineering controls to prevent vapor inhalation.
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Transport: Classified as UN 3105 (Organic peroxide type D, liquid) or similar (e.g., UN 3103, 3109 depending on concentration and formulation). Requires "Oxidizer" and "Flammable Liquid" labels.
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Spill & Fire Response: For spills, contain and absorb with inert material. For fires, use water spray, fog, alcohol-resistant foam, or dry chemical powder. Do not use direct water jet on burning material. Cool exposed containers with water from a safe distance.
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First Aid: Skin/eye contact: Irrigate with copious amounts of water for at least 15 minutes. Seek immediate medical attention. Inhalation: Move to fresh air.
Waste Disposal: Must be treated as hazardous waste. Often recommended to be carefully destroyed by controlled reaction with a reducing agent (e.g., sodium sulfite) before disposal via incineration.