80-15-9

Basic information

• Product Name: Cumyl hydroperoxide
• Synonyms: TRIGONOX K-80;1-Methyl-1-phenylethyl hydroperoxide;3(2h)isoxazolone,5-(aminomethyl)-;7-Cumyl hydroperoxide;7-cumylhydroperoxide;7-Hydroperoxykumen;alpha,alpha-dimethylbenzyl-hydroperoxid;alpha-Cumene hydroperoxide
• CAS NO: 80-15-9
• Molecular Formula: C₉H₁₂O₂
• Molecular Weight: 152.19
• EINECS: 201-254-7
• Product Categories: Organic Peroxide;Synthetic Organic Chemistry;additives
• Mol File: 80-15-9.mol

Chemical Properties

• Melting Point: -30 °C
• Boiling Point: 100-101 °C8 mm Hg(lit.)
• Flash Point: 192 °C
• Appearance: colourless liquid
• Density: 1.05 g/mL at 25 °C(lit.)
• Vapor Density: 5.4 (vs air)
• Vapor Pressure: <0.03 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.5230
• Storage Temp.: 2-8°C
• PKA: pK1:12.60 (25°C)
• Water Solubility: Slightly soluble
• Stability: Stable. combustible. Strong oxidizer. Incompatible with a variety of organic materials, reacting vigorously or violently with ac
• BRN: 1908117
• CAS DataBase Reference: Cumyl hydroperoxide(CAS DataBase Reference)
• NIST Chemistry Reference: Cumyl hydroperoxide(80-15-9)
• EPA Substance Registry System: Cumyl hydroperoxide(80-15-9)

Safety Data

• Hazard Codes: O,T,N
• Statements: 7-21/22-23-34-48/20/22-51/53-66-65-10-37
• Safety Statements: 14-3/7-36/37/39-45-50-61-14A-26-62-47-7
• RIDADR: UN 3109 5.2
• WGK Germany: 3
• RTECS: MX2450000
• TSCA: Yes
• HazardClass: 5.2
• PackingGroup: II
• Hazardous Substances Data: 80-15-9(Hazardous Substances Data)

Usage

Uses

Used in Chemical Production:
Cumyl hydroperoxide is used as a raw material for the production of acetone and phenol, which are important building blocks in the chemical industry.
Used in Polymerization Catalysts:
Cumyl hydroperoxide is used as a polymerization catalyst, particularly in redox systems, to facilitate rapid polymerization.
Used in Organic Synthesis:
Cumyl hydroperoxide is used in organic syntheses, including the preparation of polystyrene nanocapsules, methylstyrene, acetophenone, and cumyl alcohol.
Used in Curing Agents:
Cumyl hydroperoxide is used as a curing agent for polyester resins, promoting the hardening and cross-linking of the polymer.
Used in Oxidation Reactions:
Cumyl hydroperoxide is used as an oxidizer in organic chemical reactions, enabling the conversion of various organic compounds.
Used in Initiating Radical Polymerization:
Cumyl hydroperoxide is used as an initiator for radical polymerization, particularly for acrylate and methacrylate monomers, to initiate the polymerization process.
Used in Epoxidation Reactions:
Cumyl hydroperoxide is used as an epoxidation reagent for allylic alcohols and fatty acid esters, promoting the formation of epoxides.
Used in Research:
Cumyl hydroperoxide is used in research studies to investigate the mechanism of NADPH-dependent lipid peroxidation, providing insights into oxidative processes in biological systems.
Used in the Cumene Process:
Cumyl hydroperoxide is employed as an intermediate in the cumene process for developing phenol and acetone from benzene and propene, contributing to the production of these valuable chemicals.

Air & Water Reactions

Slightly soluble in water and oxidized in air at approximately 130°C.

Reactivity Profile

Cumyl hydroperoxide is a strong oxidizing agent. May react explosively upon contact with reducing reagents Violent reaction occurs upon contact with copper, copper alloys, lead alloys, and mineral acids. Contact with charcoal powder gives a strong exothermic reaction. Decomposes explosively with sodium iodide [Chem. Eng. News, 1990, 68(6), 2]. Can be exploded by shock or heat [Sax, 2 ed., 1965, p. 643]. May ignite organic materials.

Hazard

Toxic by inhalation and skin absorption. Strong oxidizing agent; may ignite organic materials.

Health Hazard

Cumene hydroperoxide is a mild to moderateskin irritant on rabbits. Subcutaneousapplication exhibited a strong delayed reactionwith symptoms of erythema and edema(Floyd and Stockinger 1958). Strong solutionscan irritate the eyes severely, affectingthe cornea and iris.Its toxicity is comparable to that of tertbutylhydroperoxide. The toxic routes areingestion and inhalation. The acute toxicitysymptoms in rats and mice were muscleweakness, shivering, and prostration.Oral administration of 400 mg/kg resulted inexcessive urinary bleeding in rats.LD50 value, oral (rats): 382 mg/kgLD50 value, intraperitoneal (rats): 95 mg/kgAlthough cumene hydroperoxide is toxic,its pretreatment may be effective against thetoxicity of hydrogen peroxide. In humans, itstoxicity is low.Cumene hydroperoxide is mutagenic andtumorigenic (NIOSH 1986). It may causetumors at the site of application. In mice,skin and blood tumors have been observed.Its cancer-causing effects on humans are notknown.

Health Hazard

Inhalation of vapor causes headache and burning throat. Liquid causes severe irritation of eyes; on skin, causes burning, throbbing sensation, irritation, and blisters. Ingestion causes irritation of mouth and stomach.

Fire Hazard

Flammable; highly reactive and oxidizing. Flash point 79°C (174.2°F); vapor density 5.2 (air= 1); autoignition temperature not reported; self-accelerating decomposition temperature 93°C (199.4°F). When exposed to heat or flame, it may ignite and/or explode. A 91–95% concentration of cumene hydroperoxide decomposes violently at 150°C (302°F) (NFPA 1986). Duswalt and Hood (1990) reported violent decomposition when this compound mixed accidentally with a 2-propanol solution of sodium iodide. It forms an explosive mixture with air. The explosive concentration range is not reported. Hazardous when mixed with easily oxidizable compounds. Fire-extinguishing agent: water from a sprinkler or fog nozzle from an explosion-resistant location.

Flammability and Explosibility

Nonflammable

Potential Exposure

Cumene hydroperoxide is used as polymerization initiator, curing agent for unsaturated polyester resins and cross-linking agent; as an intermediate in the process for making phenol plus acetone from cumene.

storage

Cumene hydroperoxide is stored in a cool,dry and well-ventilated area isolated fromother chemicals. It should be protectedagainst physical damage. It may be shippedin wooden boxes with inside glass or earthenwarecontainers or in 55-gallon metal drums.

Shipping

UN3109 Organic peroxide type F, liquid, Hazard Class: 5.2; Labels: 5.2-Organic peroxide, Technical Name Required.

Purification Methods

Purify the hydroperoxide by adding 100mL of 70% material slowly and with agitation to 300mL of 25% NaOH in water, keeping the temperature below 30o. The resulting crystals of the sodium salt are filtered off, washed twice with 25 mL portions of *benzene, then stirred with 100mL of *benzene for 20minutes. After filtering off the crystals and repeating the washing, they are suspended in 100mL of distilled water and the pH is adjusted to 7.5 by addition of 4M HCl. The free hydroperoxide is extracted into two 20mL portions of n-hexane, and the solvent is evaporated under vacuum at room temperature, the last traces being removed at 40-50o/1mm [Fordham & Williams Canad J Res 27B 943 1949]. Petroleum ether, but not diethyl ether, can be used instead of *benzene, and powdered solid CO2 can replace the 4M HCl. [Beilstein 6 IV 3221.] The material is potentially EXPLOSIVE.

Incompatibilities

The pure material is reported to explode on heating at elevated temperatures (various values given are 50°, 109, 150°C) or in strong sunlight. The substance is a strong oxidizer; reacts violently with combustible and reducing agents, causing fire and explosion hazard. Contact with metallic salts of cobalt, copper or lead alloys; mineral acids; bases; and amines may lead to violent decomposition. Vapor forms an explosive mixture with air. May accumulate static electrical charges, and may cause ignition of its vapors.

InChI:InChI=1/C9H12.H2O2/c1-8(2)9-6-4-3-5-7-9;1-2/h3-8H,1-2H3;1-2H

Upstream product

• 67-56-1 methanol 
• 98-82-8 Isopropylbenzene 
• 934-53-2 cumenyl chloride 
• 617-94-7 1-methyl-1-phenylethyl alcohol 
• 7175-54-4 cumyl peroxy radical 
• 3468-83-5 3-acetyl-2,5,6,7,8-pentahydroxy-1,4-naphthoquinone 
• 1143-11-9 2,3,5,6,8-pentahydroxynaphthalene-1,4-dione 
• 3718-80-7 2-acetyl-3,5,6,8-tetrahydroxy-1,4-naphthoquinone (Spinochrome A) 
• 1471-96-1 echinochrome A 
• 476-37-9 2,3,5,6,7,8-hexahydroxynaphthalene-1,4-dione, 
• 127092-00-6 4-methoxybicumene 
• 54234-35-4 [1-(1-Methoxy-1-methyl-ethylperoxy)-1-methyl-ethyl]-benzene 
• 82951-48-2 cumene hydrotrioxide 
• 7074-00-2 peroxybenzoic acid phenylisopropyl ester 

Downstream Products

• 101356-68-7 1-[(1-methyl-1-phenyl-ethyl)-peroxymethyl]-piperidine 
• 34236-39-0 cumyl peracetate 
• 34557-54-5 methane 
• 617-94-7 1-methyl-1-phenylethyl alcohol 
• 67-64-1 acetone 
• 108-95-2 phenol 
• 31710-39-1 2,2'-Di-tert-butyl-5,5'-dimethyl-4,4'-sulfinyl-di-phenol 
• 18057-16-4 trimethylsilyl(cumyl) peroxide 
• 98-86-2 acetophenone 
• 96217-08-2 (1-methyl-1-phenyl-ethyl)-trityl peroxide 
• 104583-62-2 2,5,2',5'-Tetramethyl-4,4'-sulfinyl-di-phenol 
• 599-64-4 p-cumylphenol 
• 80-43-3 bis(1-methyl-1-phenylethyl)peroxide 
• 79707-64-5 2,6-di-tert-butyl-4-methyl-4-(α-cumyl)peroxy-2,5-cyclohexadiene-1-one 

Relevant articles and documents

Insights into the mechanism of cumene peroxidation using supported gold and silver nanoparticles

Due to the considerable industrial implications, an in-depth study of cumene peroxidation using supported gold and silver nanoparticles was carried out to gain more insight into the mechanism of this reaction. Supported gold nanoparticles were found to ef

The Initiation Properties of 2-Cyano-2-propyl Hydroperoxide in Oxidation Processes

The initiating ability of 2-cyano-2-propyl hydroperoxide in the oxidation reaction of cumene by molecular oxygen has been investigated and compared with the initiating ability of cumene hydroperoxide. - Keywords: Autoxidation; Cumene; Initiation ability;

Oxidation of cumene in the presence of high concentrations of ascorbic acid

Initiated oxidation of cumene by oxygen in the presence of ascorbic acid was studied.

Aerobic oxidation of cumene to cumene hydroperoxide catalyzed by metalloporphyrins

A protocol for the aerobic oxidation of cumene to cumene hydroperoxide (CHP) catalyzed by metalloporphyrins is reported herein. Typically, the reaction was performed in an intermittent mode under an atmospheric pressure of air and below 130°C. Several imp

A highly efficient transformation from cumene to cumyl hydroperoxide via catalytic aerobic oxidation at room temperature and investigations into solvent effects, reaction networks and mechanisms

Cumyl hydroperoxide (CHP) is an important intermediate for the production of phenol/acetone, but suffers from severe reaction conditions and a low yield industrially. Here, an efficient transformation from cumene to CHP was developed. Different solvents were modulated for cumene oxidation catalyzed by NHPI/Co, and reaction network and mechanisms were investigated methodically. Hexafluoroisopropanol (HFIP) markedly promoted the transformation from cumene to CHP compared to other solvents at room temperature. A cumene conversion high up to 64.3% were observed with a selectivity to CHP of 71.7%. The solvent HFIP exhibited a significant promotion on cumene oxidation due to its contribution to the enhancement of the concentration of PINO radicals. Moreover, cumyl, cumyl oxyl and methyl radicals were captured by TEMPO and analyzed by HRMS, and the reaction paths and mechanisms from cumene to products were inferred. The preparation method discovered in this work may open an access to the production of CHP.

LIGHT INDUCED CATALYTIC C-H OXYGENATION OF ALKANES

A method of oxygenating a benzylic C-H bond is provided. The method comprises light induced activation of an initiator and subsequent reaction with oxygen, resulting in the formation of free radicals. Subsequently, free radicals catalyze the reaction of the benzylic C-H bond with oxygen, thereby forming an oxygenated compound.

A new highly active La2O3-CuO-MgO catalyst for the synthesis of cumyl peroxide by catalytic oxidation

In this study, different magnesium, copper, lanthanide single metal, and composite multimetal oxide catalysts were preparedviathe coprecipitation route for the aerobic oxidation of cumene into cumene hydroperoxide. All catalysts were characterized using several analytical techniques, including XRD, SEM, EDS, FT-IR, BET, CO2-TPD, XPS, and TG-DTG. La2O3-CuO-MgO shows higher oxidation activity and yield than other catalysts. The results of XRD and SEM studies show that the copper and magnesium particles in the catalyst are smaller in size and have a distribution over a larger area due to the introduction of the lanthanum element. The CO2-TPD results confirmed that the catalyst has more alkali density and alkali strength, which can excite active sites and prevent the decomposition of cumene hydroperoxide. XPS results show that due to the promotional effect of La2O3, there are more lattice and active oxygen species in the catalyst, which can effectively utilize the lattice defects under the strong interaction between metal oxides for rapid adsorption and activation, thus improving the oxidation performance. Besides, La2O3-CuO-MgO exhibits good stability and crystalline structure due to its high oxygen mobility inhibiting coking during the cycle stability test. Finally, the possible reaction pathway and promotional mechanism on La2O3-CuO-MgO in cumene oxidation are proposed. We expect this study to shed more light on the nature of the surface-active site(s) of La2O3-CuO-MgO catalyst for cumene oxidation and the development of heterogeneous catalysts with high activity in a wide range of applications.

Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes

Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, CoIII(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R′H) at ambient conditions (CoIII(qpy)OOR + R′H → CoII(qpy) + R′?+ ROOH). The resulting alkyl radical (R′?) reacts rapidly with O2to form alkylperoxy radical (R′OO?), which is efficiently scavenged by CoII(qpy) to give CoIII(qpy)OOR′ (CoII(qpy) + R′OO?→ CoIII(qpy)OOR′). This unique reactivity enables CoIII(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R′H + O2→ R′OOH) under 1 atm air and at room temperature.

Low-temperature oxidation of isopropylbenzene mediated by the system of NHPI, Fe(acac)3 and 1,10-phenanthroline

Highly efficient oxidation of isopropylbenzene mediated by the system of NHPI/Fe(acac)3/Phen has been carried out at temperature as low as 60 °C. Significant improvement of catalysis by NHPI was associated with an enhanced oxidizing ability of Fe(III) tandem with Phen, which caused the intense generation of PINO. Furthermore, NMR observations revealed formation of a hydrogen-bonded NHPI-Phen adduct soluble in acetonitrile and isopropylbenzene. Based on this phenomenon, the system was applicable for the oxidation of solvent-free isopropylbenzene. The promise of the system of NHPI/Fe(acac)3/Phen for the selective synthesis of isopropylbenzene hydroperoxide was demonstrated by oxidation at a low content of Fe(acac)3.

The influence of Fe(III) acetylacetonate and o-phenanthroline towards improvement of NHPI-catalyzed cumene oxidation

Cumene hydroperoxide (CHP) is the most important product or intermediate in the oxidative processing of cumene. In the present study, cooperative action of NHPI catalyst with Fe(acac)3/Phen additives in oxidation of cumene has been described in terms of oxidation rate and selectivity for products, notably CHP, under variable conditions. The oxidation characteristics were influenced by promoting additives, the main function of which was to generate an active PINO radical. An abundance of the additives might enhance the non-selective conversion of intermediates and decomposition of CHP, which led to a decrease in CHP selectivity. The addition of 0.0003 mol% Fe(acac)3 was sufficient to initiate NHPI catalyzed fast cumene oxidation and very selective CHP production at 50 °°C. Phen showed an impressive multifaceted effect, as the increase in its amount initially lowered the CHP selectivity and then increased to 95% with a large excess of Phen over Fe(acac)3. That was due to the different ability of iron complexes of various compositions to react to NHPI and to CHP. UV-VIZ spectroscopy and DFT calculation was used to elucidate assistance of Phen in reduction of Fe(acac)3 with NHPI and creation of FeII/FeIII –Phen2or3 complexes as reversible single-electron carriers upon catalysis by NHPI. In addition, the selective formation of CHP contributes to the resistance of NHPI to degradation during catalysis.