Butyl hydroperoxide tertiary

Verhoeff, J., "Explosion Hazards of Tertiary Butyl Hydroperoxide (TBHP)," Inst. Chem. Eng. Symposium Series, 68 (1981). 

We have prepared a series of copolymers under the conditions shown in Table 2. The monomer feed was always a 50 50 ratio of chloroprene to sulfur dioxide. Copolymerizations were carried out in bulk at temperatures from -78 to 100°. Initiators were tertiary butyl hydroperoxide at low temperatures, where it forms a redox system with the SO2 and is more effective than one might otherwise expect. Silver nitrate was used at 0° and 25°, azoiso-butyronitrile at 40° and 60°, and azodicyclohexanecarbonitrile... 

PhI02 is rather bulky and plugs the pores, thus preventing further access of reactants to the active sites [49-50,63-64]. Therefore turn-overs are quite low when PhIO is used as oxidant. For the oxidation of methyl cyclohexane on TMPcY [49-50,63-64] and of cyclohexane on Fet.BuPcY [67] turn-overs are 5.6 and 7.6 respectively. It should be noted that the reported turn-overs for oxidations with PhIO correspond to conversions of less than 1 substrate molecule per two supercages, or to total conversions of less than 0.1 %. Therefore the observed activities and selectivities may be influenced by sorption effects. Furthermore iodosobenzene is a rather expensive oxidant and not practical to use because of its low solubility in solvents. Therefore some researchers tend to use other oxidantia such as air [65,66] and tertiary butyl hydroperoxide (t-ButOOH) [57]. In the oxidation of n-octane with t-ButOOH turn-overs as high as 6000 have been reported [57]. 

The activity of titanium based catalysts for the oxidation of organic compounds is well known. Wulff et al. in 1971 [1] patented for Shell Oil a process for the selective epoxidation of propylene with hydroperoxides like ethylbenzene hydroperoxide (EBH) or tertiary-butyl hydroperoxide (TBH) with the use of a catalyst made of Ti02 deposited on high surface area Si02. A Shell Oil plant for the production of 130,000 tons/y of propylene oxide at Moerdijk, Holland, is based on this technology. 

Delta-1,8-Terpodiene Teriary Butyl Alcohol Tertiary Butyl Hydroperoxide 2,4,5-T(Esters)... 

In the present work, the construction of a mimic of cytochrome P-450 is attempted by in situ synthesis of iron-phthallocyanines in the supercages of zeolite Y and in the channels of VPI-5. Its catalytic activity and selectivity is tested in the oxyfunctionalization of n-alkanes with tertiary butyl hydroperoxide. 

Perkins MJ (1996) A radical reappraisal of Gif reactions. Chem Soc Rev 25 229-236 Phulkar S, Rao BSM, Schuchmann H-P, von Sonntag C (1990) Radiolysis of tertiary butyl hydroperoxide in aqueous solution. Reductive cleavage by the solvated electron, the hydrogen atom, and, in particular, the superoxide radical anion. Z Naturforsch 45b 1425-1432 Pimblott SM, LaVerne JA (1997) Stochastic simulation of the electron radiolysis of water and aqueous solutions. J Phys Chem A 101 5828-5838... 

A homogeneous catalytic process, developed by Oxirane, uses a molybdenum catalyst that epoxidizes propylene by transferring an oxygen atom from tertiary butyl hydroperoxide. This is shown by 8.28. The hydroperoxide is obtained by the auto-oxidation of isobutane. The co-product of propylene oxide, /-butanol, finds use as an antiknock gasoline additive. It is also used in the synthesis of methyl /-butyl ether, another important gasoline additive. The over-... 

An alternatives to the use of the ethylbenzene hydroperoxide is tertiary-butyl hydroperoxide obtained from isobutane and dioxygen. The product alcohol is converted with methanol to MTBE (methyl tertiary butylether). 

Macroporous glycidyl methacrylate-ethylene glycol dimethacrylate (GMA-EGDM) copolymer beads were synthesised and characterised for pore volume and surface area. These reactive copolymers were derivatised with 2-picolyl amine and coordinated with chromium and vanadium ions. The peroxocomplexes of these supported metal complexes were generated by the addition of hydrogen peroxide / tertiary butyl hydroperoxide(tert. -BHP) and shown to catalyse a variety of oxidation reactions. 

Finally, reactivity degree four (4) chemicals, the most dangerous group, are materials which are easily capable of detonation at normal temperatures, or may undergo explosive decomposition or reaction under normal conditions. Dibenzoyl peroxide, picric acid, tertiary butyl hydroperoxide, ethyl nitrite, and trinitrobenzene are representative of degree four (4) chemicals. 

A general synthesis for all diastereomeric L-hexoses, as an example for monosaccharides that often do not occur in the chiral pool, has been worked out. The epoxidation of allylic alcohols with tertiary butyl hydroperoxide in presence of titanyl tartaric ester catalysts converts the carbon-carbon double bond stereose-lectively to a diol and is thus ideally suited for the preparation of carbohydrates. The procedure is particularly useful as a repetitive two-carbon homologiza-tion in total syntheses of higher monosaccharides and other poly hydroxy compounds. It starts with a Wittig reaction of a benzylated a-hydroxy aldehyde with (triphenylphosphoran-ylidene)acetaldehyde to produce the olefinic double bond needed for epoxidation. Reduction with sodium-borohydride... 

Isobutane reacts with high purity oxygen noncatalytically at about 300°F and 500 psig in accordance with Eq. (13) to form tertiary butyl hydroperoxide (TBHP). A small amount of tertiary butyl alcohol is also formed by the reaction of isobutane with oxygen, as shown in Eq. (14). The TBHP then reacts with propylene in the presence of a molybdenum catalyst, as shown in Eq. (15), at about 250°F and 600 psig to yield propylene oxide and tertiary butyl alcohol as a by-product. 

A simplified flow sheet of the isobutane peroxidation process is shown in Figure 6 [10]. Isobutane and high purity oxygen are reacted in the oxidation reactor at approximately 250°F and 500 psig. This reaction proceeds without catalyst in a mixture of water and tertiary butyl alcohol. It is highly exothermic and in order to maintain a relatively constant reactor temperature the heat of reaction is removed by vaporization and condensation of the TBA and water mixture. Isobutane is separated from tertiary butyl hydroperoxide and recycled to the oxidation reactor. 

The bottoms product from the isobutane separation is a mixture of tertiary butyl alcohol and tertiary butyl hydroperoxide. This mixture enters the epoxidation reactor where it reacts with propylene to form propylene oxide. The catalyst is either molybdenum based as in the process developed by Halcon and practiced by ARCO or TiOj on silica in the Shell process. 

The structure and behavior of methyl radicals on surfaces was compared with that in aqueous solution. Methyl radicals were produced and characterized by EPR in a fast-mixing flow system of Ti(III) with tertiary butyl hydroperoxide.(133) As a side investigation, the reaction of methyl radicals with oxygen dissolved in water was monitored not only by EPR but by chemiluminescence using an electronic image intensifier.(134)... 

Vinyl acetate is polymerized in dispersion form using various initiators. Exanples of ionic initiators commonly used for free-radical emulsion polymerizations are ammonium, sodium or potassium persulfate. Topical nonionic hydrophobic initiators include 2,2 -azobis(isobutyronitrile) (AIBN) and benzoyl peroxide. Water-soluble nonionic initiators such as tertiary-butyl hydroperoxide are also employed. The initiator 4,4 -azobis(4-cyanovaleric acid) in its acid state is oil soluble, while neutralization causes it to become water soluble providing for further diversity in initiators. 

The above initiators are thermal initiators that require heat to produce radicals. Redox systems offer further degrees of freedom in that they allow free-radical polymerizations without the use of significant quantities of heat Tertiary-butyl hydroperoxide/sodium formaldehyde sulfoxylate or potassium persulfate/sodhim... 

This example involves the manufacture of 100 million pounds per year of di-tertiary-butyl peroxide (DTBP) by the catalytic reaction of tertiary-butyl hydroperoxide (TBHP) with excess tertiary-butyl alcohol (TEA) at 170°F and 15 psia according to the reaction... 

In natural product synthesis it is sometimes important to eliminate selenoxide oxidatively to form the corresponding olefin. Alumina in combination with tertiary-butyl hydroperoxide in THF offers much improved yields in comparison to conventional methods [77]. Lebar et al. report the application of this reagent in the synthesis of primary allylic alcohols (e.g. equation 4.13) [78]. 

When tertiary-butyl hydroperoxide and selenium dioxide are adsorbed together on silica gel they produce a reagent which selectively oxidises a methyl group to an allylic alcohol without oxidation of other functional... 

SCHEME 3. OXIDATIVE EPOXIDATION REACTIONS OE DIVINYLDIMETHYLSILOXANES IN THE PRESENCE OE TERTIARY-BUTYL HYDROPEROXIDE. 

FIGURE 1 Dependence of the yield of compound I on the time in oxidative epoxidation reactions of tetramethyldivinyldisiloxane by tertiary-butyl hydroperoxide in various solvents, at 1 2.5 molar ratio of siloxane oxidizer. 

It has been reported that the CN group of 4-(methylthio)benzonitrile is quantitatively and selectively oxidised to amide by tertiary butyl hydroperoxide (TBHP) in strong alkaline aqueous medium in presence of cetyltrimethyl ammonium sulfate [(CTA)2SOJ (Scheme 89). TBHP does not oxidise the CN group at pH 7 (even at 100 °C), however in the absence of (CTA)2SO, only the methylsulfenyl group is oxidised to methylsulfinyl. But under basic conditions, TBHP converts both groups into amide and sulfonyl groups respectively (Scheme 89). 

Tertiary Butyl Hydroperoxide Tert-Butyl Tetramethylolmethane Pentaerythritol... 

One of the ways that aqueous emulsion polymerization processes can be classified is on the basis of the types of the initiators also referred to as catalysts. In one type of polymerization system, an organic peroxide, preferably water-soluble, is used. The organic peroxides include cumene hydroperoxide, diisopropyl benzene hydroperoxide, triisopropyl benzene hydroperoxide, and tertiary butyl hydroperoxide. A second type of emulsion polymerization employs an inorganic peroxide. Suitable compounds include perborates, persulfates, perphosphates, percarbonates, barium peroxide, zinc peroxide, and hydrogen peroxide. Specific examples of inorganic peroxides are ammonium persulfate and sodium perphosphate. 

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