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 widely
used in a variety of oxidation processes.
Chemical Properties
tert-Butyl hydroperoxide (TBHP) is a water-white liquid
commonly commercially available as a 70% solution in
water; 80% solutions are also available. It is used to initiate
polymerization reactions and in organic syntheses to introduce peroxy groups into the molecule. TBHP vapor can
burn in the absence of air and may be flammable at either
elevated temperature or at reduced pressure. Fine mist/spray
may be combustible at temperatures below the normal flash
point. When evaporated, the residual liquid will concentrate
TBHP content and may reach an explosive concentration
(＞90%). Closed containers may generate internal pressure
through the degradation of TBHP to oxygen . TBHP is a
highly reactive product. The three types of significant physical
hazards are flammability, thermal, and decomposition
due to contamination.
To minimize these hazards, avoid exposure to heat, fire, or
any condition that will concentrate the liquid material. Store
away from heat, sparks, open flames, foreign contaminants,
combustibles, and reducing agents. Inspect containers frequently
to identify bulges or leaks (7a, 125).
Uses
Different sources of media describe the Uses of 75-91-2 differently. You can refer to the following data:
1. TBHP is an intermediate in the production of propylene
oxide and t-butyl alcohol from isobutane and propylene. It is
primarily used as an initiator and finishing catalyst in the
solution and emulsion polymerization methods for polystyrene
and polyacrylates. Other uses are for the polymerization
of vinyl chloride and vinyl acetate and as an oxidation
and sulfonation catalyst in bleaching and deodorizing operations.
It is a strong oxidant and reacts violently with
combustible and reducing materials, and metallic and sulfur
compounds.
2. tert-Butyl hydroperoxide is used as an initiator for radical polymerization and in various oxidation process 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.
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.
Definition
ChEBI: Tert-butyl hydroperoxide is an alkyl hydroperoxide in which the alkyl group is tert-butyl. It is widely used in a variety of oxidation processes. It has a role as an antibacterial agent and an oxidising agent.
General Description
Watery odorless colorless liquid. Floats and mixes slowly with water.
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
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.
Waste liquid treatment process in TPO production process and device thereof
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Paragraph 0148-0169, (2021/03/31)
The invention relates to a waste liquid treatment process and device in a TPO production process, in particular to a waste liquid treatment process and device based on oxidant cyclic utilization in the TPO production process. The method comprises the following steps: mixing the synthetic waste liquid with sulfuric acid and water, carrying out esterification reaction to obtain a material phase, further carrying out mixing reaction on the material phase and hydrogen peroxide, carrying out liquid separation to obtain a tert-butyl hydroperoxide phase, and carrying out alkali washing to obtain tert-butyl hydroperoxide; tert-butyl hydroperoxide can return to a TPO synthesis section to be used as an oxidizing agent for preparing TPO; by adopting the process, the problem of high treatment cost ofthe synthetic waste liquid in the TPO production process is solved; and through the waste liquid treatment process, the resource utilization of the synthetic waste liquid is realized, the raw materialpurchasing and process production costs of the TPO production process are greatly reduced, and the economic value is obvious.
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.
