75-91-2 Usage
Chemical Description
Tert-butyl hydroperoxide and dibenzoyl peroxide are organic peroxides that are commonly used as radical initiators in organic synthesis.
Description
tert-Butyl hydroperoxide (TBHP) is an organic peroxide that is widely used in a variety of oxidation processes.
Uses
Used in Chemical Production:
TBHP is used as an intermediate in the production of propylene oxide and t-butyl alcohol from isobutane and propylene.
Used in Polymerization Processes:
TBHP is used as an initiator and finishing catalyst in the solution and emulsion polymerization methods for polystyrene and polyacrylates.
Used in Plastics Industry:
TBHP is used for the polymerization of vinyl chloride and vinyl acetate.
Used in Bleaching and Deodorizing Operations:
TBHP is used as an oxidation and sulfonation catalyst in bleaching and deodorizing operations.
Used in Organic Synthesis:
TBHP is used as an initiator for radical polymerization and in various oxidation processes such as Sharpless epoxidation. It is involved in osmium catalyzed vicinal hydroxylation of olefins under alkaline conditions. Furthermore, it is used in catalytic asymmetric oxidation of sulfides to sulfoxides using binaphthol as a chiral auxiliary and in the oxidation of dibenzothiophenes. It plays an important role for the introduction of peroxy groups in organic synthesis.
Used in Safety Precautions:
Production Methods
TBHP is produced by the liquid-phase reaction of isobutane
and molecular oxygen or by mixing equimolar amounts of
t-butyl alcohol and 30–50% hydrogen peroxide. TBHP can
also be prepared from t-butyl alcohol and 30% hydrogen
peroxide in the presence of sulfuric acid or by oxidation of
tert-butylmagnesium chloride. The manufacturing process of
TBHP is in a closed system.
Air & Water Reactions
Water soluble.
Reactivity Profile
Most alkyl monohydroperoxides are liquid. The explosivity of the lower members (e.g., methyl hydroperoxide, or possibly, traces of the dialkyl peroxides) decreasing with increasing chain length and branching [Bretherick 2nd ed. 1979 p. 10]. Though relatively stable, explosions have been caused by distillation to dryness [Milas, JACS 1946, 68, 205] or attempted distillation at atmospheric pressure [Castrantas 1965 p. 15].
Hazard
Moderate fire risk. Oxidizer.
Health Hazard
tert-Butyl hydroperoxide is a strong irritant.Floyd and Stockinger (1958) observed thatdirect cutaneous application in rats did notcause immediate discomfort, but the delayedaction was severe. The symptoms were erythemaand edema within 2–3 days. Exposureto 500 mg in 24 hours produced asevere effect on rabbit skin, while a rinse of150 mg/min was severe to eyes.It is moderately toxic; the effects aresomewhat similar to those of MEK peroxide.Symptoms from oral administration in ratswere weakness, shivering, and prostration.LD50 value, intraperitoneal (rats): 87 mg/kgLD50 value, oral (rats): 406 mg/kg.
Flammability and Explosibility
tert-Butyl hydroperoxide is a flammable liquid and a highly reactive oxidizing agent.
Pure TBHP is shock sensitive and may explode on heating. Carbon dioxide or dry
chemical extinguishers should be used for fires involving tert-butyl hydroperoxide.
Safety Profile
Moderately toxic by
ingestion and inhalation. A severe skin and
eye irritant. Mutation data reported. At
highest dosage levels, symptoms noted were
severe depression, incoordmation, and
cyanosis. Death was due to respiratory
arrest. Very dangerous fire hazard when
exposed to heat or flame, or by spontaneous
chemical reaction such as with reducing
materials. Moderately explosive; may
explode during distillation. Violent reaction
with traces of acid. Concentrated solutions
may ignite spontaneously on contact with
molecular sieve. Mixtures with transition
metal salts may react vigorously and release
oxygen. Forms an unstable solution with
1,2-dichloroethane. To fight fire, use alcohol
foam, CO2, dry chemical. When heated to
decomposition it emits acrid smoke and
fumes. See also PEROXIDES, ORGANIC.
Carcinogenicity
A study performed to evaluate
the carcinogenicity of TBHP found it was not carcinogenic
when applied to the skin of mice at 16.6% of the peroxide 6
times a week for 45 weeks. However, if its application was
preceded by 0.05 mg of 4-nitroquinoline-1-oxide as a 0.25%
solution in benzene applied 20 times over 7 weeks followed
by TBHP (16.6% in benzene), then malignant skin tumors
appeared between days 390 and 405 of the experiment .
This supports the theory that peroxides are not complete
carcinogens, but may act as promoters . The effects of
TBHP on promotable and nonpromotable mouse epidermal
cell culture lines were reported by Muehlematter et al. .
storage
tert-butyl hydroperoxide should be stored in the dark at room temperature
(do not refrigerate) separately from oxidizable compounds, flammable substances,
and acids. Reactions involving this substance should be carried out behind a safety
shield.
Toxicity evaluation
TBHP accelerates oxidation of glutathione and decreases the
metabolism of sodium hexobarbital in rat livers and is a strong
oxidation agent.
Incompatibilities
tert-Butyl hydroperoxide and concentrated aqueous solutions of TBHP react
violently with traces of acid and the salts of certain metals, including, in particular,
manganese, iron, and cobalt. Mixing anhydrous tert-butyl hydroperoxide with
organic and readily oxidized substances can cause ignition and explosion. TBHP can
initiate polymerization of certain olefins.
Waste Disposal
Excess tert-butyl hydroperoxide and waste material containing this substance should be placed in an
appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines.
Check Digit Verification of cas no
The CAS Registry Mumber 75-91-2 includes 5 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 2 digits, 7 and 5 respectively; the second part has 2 digits, 9 and 1 respectively.
Calculate Digit Verification of CAS Registry Number 75-91:
(4*7)+(3*5)+(2*9)+(1*1)=62
62 % 10 = 2
So 75-91-2 is a valid CAS Registry Number.
InChI:InChI=1/C4H10O2/c1-4(2,3)6-5/h5H,1-3H3
75-91-2Relevant articles and documents
Synthesis and purification method of high-purity tert-butyl peroxy-2-ethylhexyl carbonate
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Paragraph 0020; 0029-0031; 0034-0036; 0039-0041; 0044-0046, (2021/02/10)
The invention belongs to the fields of peroxidation, organic synthesis and peroxide purification, and particularly relates to a synthesis and purification method of tert-butyl peroxy-2-ethylhexyl carbonate, which comprises the steps of peroxidation reaction, substitution synthesis reaction, peroxide purification and the like. According to the method, the discharge of the waste liquid and the treatment cost of subsequent waste liquid are reduced, the reaction conditions are easy to control, the product yield is high, and the product purity is high and can reach 99% or above.
Selective Functionalization of Hydrocarbons Using a ppm Bioinspired Molecular Tweezer via Proton-Coupled Electron Transfer
Chen, Hongyu,Wang, Lingling,Xu, Sheng,Liu, Xiaohui,He, Qian,Song, Lijuan,Ji, Hongbing
, p. 6810 - 6815 (2021/06/28)
An expanded porphyrin-biscopper hexaphyrin was introduced as a bioinspired molecular tweezer to co-catalyze functionalization of C(sp3)-H bonds. Theoretical and experimental investigations suggested that the biscopper hexaphyrin served as a molecular tweezer to mimic the enzymatic orientation/proximity effect, efficiently activating the N-hydroxyphthalimide (NHPI) via light-free proton-coupled electron transfer (PCET), at an exceptionally low catalyst loading of 10 mol ppm. The resulting N-oxyl radical (PINO) was versatile for chemoselective C-H oxidation and amination of hydrocarbons.
PROCESS AND SYSTEM TO MAKE SUBSTITUTED LACTONES
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Paragraph 0052-0053, (2021/02/05)
A process for oxidizing iso-butane with oxygen to produce t-butyl hydroperoxide and t-butyl alcohol; dehydrating at least a portion of the t-butyl alcohol to produce di-tert-butyl ether and isobutylene; epoxidizing at least a portion of the isobutylene with the t-butyl hydroperoxide to produce isobutylene oxide and t-butyl alcohol; and carbonylating at least a portion of the isobutylene oxide with carbon monoxide to produce pivalolactone.