Tertiary butyl hydrogen peroxide

When tertiary butyl hydrogen peroxide (TBHP) was used alone as the radical initiator, no grafting of methylmethacrylate (MMA) onto wool was observed. However, TBHP in conjunction with mineral acids, such as H2SO4, HNO3, or HCIO4 afforded good results [26]. Protonation of TBHP by the acid aided in the dissociation of TBHP to yield free radicals, which initiated grafting reaction. 

Similarly CrAPO-5, derived from isomorphous replacement of A1 by Cr in AlPO-5, was shown to be an active and selective catalyst for the oxidation of secondary alcohols [191]. For example, carveol was chemoselectively oxidised by tertiary butyl hydrogen peroxide (TBHP) at the alcohol group (94% selectivity at 62% conversion) rather than at the carbon-carbon double bond. The initial assumption that Cr coordinated tetrahedrally in the lattice is the active species was later revoked and it seems now that Cr " is present as an octahedral species associated with the framework [192]. 

For oxidative epoxidation of divinyldimethylsiloxanes as oxidizers, tertiary-butyl hydro peroxide and hydrogen peroxide have been used by us for the first time. The reaction was carried out in the presence of molybdenum containing catal) ts at the ratio of siloxane peroxide 1 1, 1 2 and 1 2.5. The oxidative epoxidation of divinykiloxanes in the presence of tertiary-butyl hydro peroxide proceeds according to the following (Scheme 3) [27] ... 

Influence of the solvents, catalysts, reaction temperatures and comparative oxidizing ability of tertiary-butyl hydro peroxide, hydrogen peroxide on the yield of compounds I and II has been investigated and obtained results are presented in Tables 1 and 2. 

At comparison of oxidative epoxidation abilities of tertiary-butyl hydro peroxide and hydrogen peroxide (at the presence of the same catalyst) appeared, that oxidizing ability of tertiary-butyl hydro peroxide is higher, than hydrogen peroxide (see the yields of diepoxy derivatives). 

So the oxidative epoxidation of 1.1.3.3-tetramethyl-l,3-divinyldisiloxane and 1.1.3.3.5.5-hexamethyl-1.5-divinyltrisiloxane by tertiary-butyl hydro peroxide and hydrogen hydro peroxide at the presence of mol5d deniim catalysts in the medium of various organic solvents and ratio of initial compounds has been investigated and optimal conditions of the reaction has been established. 

Tertiary butyl alcohol (900 ml., 702 g., 9.47 moles) is dissolved in a solution prepared by mixing 28 ml. (0.50 mole) of concentrated sulfuric acid with 1.5 1. of water in a 5-1. round-bottomed flask (Note 1) equipped with a thermometer, stirrer, gas inlet tube, and two addition burets. One buret is charged with 86 ml. (1 mole) of 11.6iH hydrogen peroxide (Note 2), and the other with a solution of 278 g. (1 mole) of ferrous sulfate pentahydrate and 55.5 ml. (1 mole) of concentrated sulfuric acid in 570 ml. of water (Note 3). The reaction flask is swept out with nitrogen and cooled to 10° by means of an ice bath. Stirring is commenced and the two solutions are added simultaneously and equivalently over a period of 20 minutes. The temperature is held below 20°. 

Inclusion in the reaction of a cooxidant serves to return the osmium to the osmium tetroxide level of oxidation and allows for the use of osmium in catalytic amounts. Various cooxidants have been used for this purpose historically, the application of sodium or potassium chlorate in this regard was first reported by Hofmann [7]. Milas and co-workers [8,9] introduced the use of hydrogen peroxide in f-butyl alcohol as an alternative to the metal chlorates. Although catalytic cis dihydroxylation by using perchlorates or hydrogen peroxide usually gives good yields of diols, it is difficult to avoid overoxidation, which with some types of olefins becomes a serious limitation to the method. Superior cooxidants that minimize overoxidation are alkaline t-butylhydroperoxide, introduced by Sharpless and Akashi [10], and tertiary amine oxides such as A - rn e t h y I rn o r p h o I i n e - A - o x i d e (NMO), introduced by VanRheenen, Kelly, and Cha (the Upjohn process) [11], A new, important addition to this list of cooxidants is potassium ferricyanide, introduced by Minato, Yamamoto, and Tsuji in 1990 [12]. 

Aqueous or alcohol solutions of amine oxides are normally obtained by oxidizing tertiary amines with either hydrogen peroxide or a peracid.4 For example, N,N-dimethyldodecyl-amine oxide has been prepared by treating N,N-dimethyl-dodecylamine with aqueous hydrogen peroxide.5 The procedure illustrated in this preparation permits the oxidation of tertiary amines with /-butyl hydroperoxide in organic solvents under relatively anhydrous conditions.6 In this procedure the reaction time is short and the method is as convenient as the use of aqueous hydrogen peroxide or a peracid as the oxidant. Furthermore, isolation of the anhydrous amine oxide is often relatively simple. 

Tertiary alkylamines can be converted into the corresponding N-oxides with hydrogen peroxide or with peroxy acids." r-Butyl hydroperoxide has also been used in the presence of a catalyst such as VO(acac)2. Sharpless and coworkers have carried out the oxidative kinetic resolution of several p-hy-droxy tertiary amines such as (41) with r-butyl hydroperoxide, titanium(rv) isoprcqtoxide and (-i-)-diiso-propyl tartrate, the titanium(rv) tartrate ratio being ateut 2 1." After 60% conversion, one enantiomer was selectively oxidized, and the other enantiomer could be recovered in good optical purity (Scheme... 

Hydroxylation by hydrogen peroxide in t-butyl alcohol solution is catalyzed by osmium tetroxide. The catalyst is volatile and dangerous to handle but is conveniently used in a solution of the tertiary alcohol. The yields of diols are usually low (30-60%), and the process has not been adapted to large-scale preparations. In contrast to hydroxylation by performic acid, this procedure leads to cis addition of the two hydroxyl groups to the double bond. An extensive study of other catalysts has been made. Some catalysts, e.g., selenium dioxide and pertungstic acid, catalyze addition in the trans direction. Hydroxylation of cyclopentadiene takes place in the 1,4-positions to give 2-cyclopenten-l,4-diol. ... 

Tertiary alcohols are resistant to oxidation. rcr -Butyl alcohol is frequently used as a solvent in oxidations. However, some tertiary alcohols are converted into tertiary hydroperoxides on treatment with hydrogen peroxide in sulfuric acid [177, 179]. Dimethylphenylcarbinol added to a mixture of 87% hydrogen peroxide and sulfuric acid at a temperature below 0 °C gives a 94% yield of cumyl hydroperoxide after 3.5 h [777]. Similarly, acetylenic alcohols with the tertiary hydroxyl group adjacent to the triple bonds are converted into the corresponding hydroperoxides in high yields [179] (equation 272). 

The method described is essentially that of Swem, Billen, Findley, and Scanlan. /mM5-l,2-Cyclohexanediol also has been prepared by hydrolysis of cyclohexene oxide. j-l,2-Cydo-hexanediol has been prepared by the reaction of cyclohexene with hydrogen peroxide in tertiary butyl alcohol with osmium tetroxide as a catalyst. Hydrogenation of catechol over Raney nickel catalyst at 150° gives a mixture (m.p. 73-77°) of cis- and trans-1,2-cyclohexanediols. ... 

Red cell GSPHx-1 and plasma GSPHx-3 are assayed by enzymatic methods using a variety of peroxide substrates, with tertiary-butyl peroxide being a commonly used substrate since it is not as affected by catalase as is hydrogen peroxide. The values obtained are dependent on the substrate used and the reaction conditions. During selenium supple-... 

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. 

Benzoxazoles have also been aminated with secondary or primary aliphatic amines (1 equiv.) in the presence of catalytic amount of iodine (5 mol%), aqueous f-butyl hydroperoxide (1 equiv.), and acetic acid (1.1 equiv.) at ambient temperature for 12 h [102]. Authors believe that protonation of benzoxazole results in the formation of equilibrium amount of the salt 69, which adds alkylamine to form 2-aminobenoxazoline 70 (Scheme 46). Interaction of 70 with iodine generates 2-amino-3-iodobenzoxazoline 68, which eliminates HI to give the amination product. The reaction cycle is maintained due to oxidation of iodide ions with t-BuOOH. It is important to note that this envirorunentally benign method produces tertiary butanol and water as by-products. Use of iV-iodosuccinimide catalyst in combination with aqueous hydrogen peroxide in acetonitrile solution allows to reduce the reaction time to 4 h [103]. Benzothiazole under the same conditions remaines unchanged. 

Batch Di (3-pentyl) Malate Process Acetaldehyde from Acetic Acid Ethylene by Oxidative Dehydrogenation of Ethane Butadiene to n-Butvraldehvde and n-Butanol Methacrylic Acid to Methylmethacrylate Coproduction of Ethylene and Acetic Acid from Ethane Methylmethacrylate from Propyne Mixed-Cd Byproduct Upgrade Hydrogen Peroxide Manufacture Di-tertiary-butyl-peroxide Manufacture Vinyl Acetate Process PM Acetate Manufacture Propoxylated Ethylenediamine Petroleum Products... 

The reaction is carried out by adding alkyl halide to the white gel of lithium 9,9-di- -butyl-9-borabicyclo[3.3.1]nonanate suspended in hexane, and the reaction is quenched with alkaline hydrogen peroxide. The results are summarized in Table 25.10 [23]. Tertiary alkylhalides are smoothly converted to the corresponding alkanes, whereas primary and secondary halides are inert under the reaction conditions. 

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. 

Li and coworkers published addition reactions of ethers, sulfides, or tertiary amines 40 to p-dicarbonyl compounds 39 (Fig. 8) [96]. Fe2(CO)9 proved to be the catalyst of choice and di-tert-butyl peroxide the optimal oxidant. a-Functionalized p-dicarbonyl compounds 41 were isolated in 52-98% yield. Although the details of the catalytic cycle remain unclear, it seems to be likely that the peroxide is reductively cleaved by the Fe(0) catalyst leading to an Fe(I) complex and a ferf-butoxyl radical, which abstracts the a-hydrogen atom of 40. Addition of the resulting radical to the free enol form of 39 or the corresponding iron enolate of 39 may subsequently occur. It remains unclear, however, whether the main catalytic reaction proceeds on an Fe(0)-Fe(I) oxidation stage or whether further oxidation of initially formed Fe(I) rather leads to an Fe(II) catalyst. This cannot be excluded,... 

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