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Pinane hydroperoxide (commonly pinanyl hydroperoxide, 2-pinane hydroperoxide; CAS RN 28324-52-9) is an organic hydroperoxide derived from the autoxidation/oxidation of pinane (and related pinene precursors).
It functions as a convenient laboratory and industrial oxidant and as a radical source/initiator for polymerization and organic transformations.
CAS Registry Number: 28324-52-9
SYNONYMS
pinanyl hydroperoxide, 2-pinane hydroperoxide, 2-pinanyl hydroperoxide,
Pinane hydroperoxide is a bicyclic terpene-derived hydroperoxide built on the pinane skeleton (related to the pinene family).
The bicyclo[3.1.1]heptane skeleton bears methyl substituents (typical 2,6,6-trimethyl substitution pattern) and a hydroperoxy (–OOH) functional group attached at the 2-position (the "pinanyl" position).
The result is a secondary hydroperoxide center on a strained, bridged bicyclic framework.
The ring system imparts conformational rigidity and steric shielding to the hydroperoxide group, which influences both thermal stability and reactivity (steric hindrance can slow some bimolecular decomposition pathways but the O–O bond remains kinetically labile).
Stereochemistry: multiple stereoisomers are possible depending on which face of the ring the hydroperoxy substituent resides (endo/exo; cis/trans relationships).
Literature preparations often isolate a predominant isomer (commonly cis- or trans-2-pinanyl hydroperoxide depending on precursor and oxidation conditions). Early synthetic reports and characterization (NMR/X-ray for related derivatives) document stereochemical assignments; analytical spectra (¹H, ¹³C NMR, IR, MS) are used to verify configuration.
Physical properties (typical, vendor-specified)
Vendor technical data sheets (TDS) and catalogs typically report a set of practical properties (note: exact values vary with grade/purity):
Appearance: colorless to pale yellow liquid.
Typical active oxygen content (as hydroperoxide): ~4.7–5.2% (depends on concentration/specification).
Hydroperoxide content (wt% of product): many technical grades list 50–55% "content" (this often reflects the % active hydroperoxide in a marketed formulation).
Always review the supplier SDS/TDS for exact numbers.
Boiling/melting point: Not commonly used because thermal decomposition of organic peroxides precedes normal boiling; therefore decomposition onset (temperature at which exotherm occurs) is a more relevant practical metric. Decomposition kinetics (see Section 7) are often measured instead.
Note: Hydroperoxides often have limited stable physical property tables because their permitted storage/transport is constrained by peroxide hazard regulations; vendors therefore provide handling and decomposition data rather than classical boiling points.
Occurrence and industrial availability
Pinane hydroperoxide is manufactured commercially (multiple suppliers in China, Japan, Europe) and marketed for industrial uses (polymerization initiator, curing/oxidation agent).
It is obtained mainly through controlled oxidation/autoxidation of pinane or via oxidation of pinane precursors such as α- or β-pinene followed by hydrogenation/isomerization steps in some routes. Marketed product names include GLIDOX grades and generic "pinanyl hydroperoxide" materials from peroxide suppliers. Technical datasheets list packaging in IBCs (e.g., 1000 L) and typical assay specifications.
Synthesis and formation routes
Autoxidation of pinane/pinene pathway (industrial and laboratory)
The most common production route is the selective oxidation (autoxidation or catalytic oxidation) of the pinane/pinene series using molecular oxygen (air or O₂) under controlled conditions.
Radical chain autoxidation of the hydrocarbon feedstock yields hydroperoxide intermediates; these can be isolated or further processed.
Reaction conditions (temperature, solvent, pressure, catalysts such as transition metal complexes, radical initiators, and inhibitors) dictate regioselectivity (2- vs 1-position) and stereochemistry. Several kinetic studies investigate the oxygenation of pinane to 2-pinane hydroperoxide and provide rate laws and activation parameters (temperature/pressure conditions reported in the 353–373 K range under several atm O₂).
Catalytic oxidation routes
Metal-catalyzed oxidation (e.g., supported metal or metal-porphyrin catalysts) can increase selectivity to the desired hydroperoxide.
Literature examples describe oxidations over encaged metal catalysts and metalloporphyrin systems yielding pinane (or p-menthane) hydroperoxides with varying selectivity; these methods are useful when optimizing for downstream chemical conversions (e.g., to linalool or pinanol).
Laboratory synthetic notes
Classic preparative methods in the literature describe the formation of cis-1-pinane-2-hydroperoxide from β-pinene (via epoxidation/acid rearrangement series) or from direct autoxidation followed by separation/purification.
Hydrogenation of pinane hydroperoxide gives the corresponding alcohol (pinanol), and this is used in preparative sequences; hydrogenation kinetics under Pd/C catalysts have been characterized.
SAFETY INFORMATION ABOUT PINANE HYDROPEROXIDE
First aid measures:
Description of first aid measures:
General advice:
Consult a physician.
Show this safety data sheet to the doctor in attendance.
Move out of dangerous area:
If inhaled:
If breathed in, move person into fresh air.
If not breathing, give artificial respiration.
Consult a physician.
In case of skin contact:
Take off contaminated clothing and shoes immediately.
Wash off with soap and plenty of water.
Consult a physician.
In case of eye contact:
Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
Continue rinsing eyes during transport to hospital.
If swallowed:
Do NOT induce vomiting.
Never give anything by mouth to an unconscious person.
Rinse mouth with water.
Consult a physician.
Firefighting measures:
Extinguishing media:
Suitable extinguishing media:
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
Carbon oxides, Nitrogen oxides (NOx), Hydrogen chloride gas
Advice for firefighters:
Wear self-contained breathing apparatus for firefighting if necessary.
Accidental release measures:
Personal precautions, protective equipment and emergency procedures
Use personal protective equipment.
Avoid breathing vapours, mist or gas.
Evacuate personnel to safe areas.
Environmental precautions:
Prevent further leakage or spillage if safe to do so.
Do not let product enter drains.
Discharge into the environment must be avoided.
Methods and materials for containment and cleaning up:
Soak up with inert absorbent material and dispose of as hazardous waste.
Keep in suitable, closed containers for disposal.
Handling and storage:
Precautions for safe handling:
Avoid inhalation of vapour or mist.
Conditions for safe storage, including any incompatibilities:
Keep container tightly closed in a dry and well-ventilated place.
Containers which are opened must be carefully resealed and kept upright to prevent leakage.
Storage class (TRGS 510): 8A: Combustible, corrosive hazardous materials
Exposure controls/personal protection:
Control parameters:
Components with workplace control parameters
Contains no substances with occupational exposure limit values.
Exposure controls:
Appropriate engineering controls:
Handle in accordance with good industrial hygiene and safety practice.
Wash hands before breaks and at the end of workday.
Personal protective equipment:
Eye/face protection:
Tightly fitting safety goggles.
Faceshield (8-inch minimum).
Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).
Skin protection:
Handle with gloves.
Gloves must be inspected prior to use.
Use proper glove
removal technique (without touching glove's outer surface) to avoid skin contact with this product.
Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
Full contact:
Material: Nitrile rubber
Minimum layer thickness: 0.11 mm
Break through time: 480 min
Material tested:Dermatril (KCL 740 / Aldrich Z677272, Size M)
Splash contact
Material: Nitrile rubber
Minimum layer thickness: 0.11 mm
Break through time: 480 min
Material tested:Dermatril (KCL 740 / Aldrich Z677272, Size M)
It should not be construed as offering an approval for any specific use scenario.
Body Protection:
Complete suit protecting against chemicals, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection:
Where risk assessment shows air-purifying respirators are appropriate use a fullface respirator with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup to engineering controls.
If the respirator is the sole means of protection, use a full-face supplied air respirator.
Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).
Control of environmental exposure
Prevent further leakage or spillage if safe to do so.
Do not let product enter drains.
Discharge into the environment must be avoided.
Stability and reactivity:
Chemical stability:
Stable under recommended storage conditions.
Incompatible materials:
Strong oxidizing agents:
Hazardous decomposition products:
Hazardous decomposition products formed under fire conditions.
Carbon oxides, Nitrogen oxides (NOx), Hydrogen chloride gas.
Disposal considerations:
Waste treatment methods:
Product:
Offer surplus and non-recyclable solutions to a licensed disposal company.
Contact a licensed professional waste disposal service to dispose of this material.
Contaminated packaging:
Dispose of as unused product
