Benzyl hydroperoxides

An analogous study of benzyl hydroperoxide indicates a rate law at 25 °C of... 

Irradiation of toluene in the presence of chlorine yielded benzyl hydroperoxide, benzaldehyde, peroxybenzoic acid, carbon monoxide, carbon dioxide, and other unidentified products (Hanst and Gay, 1983). The photooxidation of toluene in the presence of nitrogen oxides (NO and NO2) yielded small amounts of formaldehyde and traces of acetaldehyde or other low molecular weight carbonyls (Altshuller et al, 1970). Other photooxidation products not previously mentioned include phenol, phthalaldehydes, and benzoyl alcohol (Altshuller, 1983). A carbon dioxide yield of 8.4% was achieved when toluene adsorbed on silica gel was irradiated with light X >290 nm) for 17 h (Freitag et ah, 1985). 

Benzol hjthiophene, see Naphthalene 1,2,3-Benzotriazin-4 (3/J -one, see Azinnhos-methyl Benzotriazole, see Tetrachloroethylene Benzyl alcohol, see Benzo[a]anthracene, Benzyl butyl phthalate. Benzyl chloride, Permethrin. o-Xylene, m-Xylene, p-Xylene. Toluene 0-Benzyl alcohol, see o-Xylene m-Benzyl alcohol, see m-Xylene p-Benzyl alcohol, see p-Xylene 10-Benzyl-10-hydroanthracen-9-one, see Benzo [ a] anthracene Benzyl hydroperoxide, see Toluene Benzyl nitrate, see Toluene Benzylsuccinic acid, see Toluene... 

Q -(4-Bromophenylazo)benzyl hydroperoxide, 3606 Q -(4-Bromophenylazo)phenylethyl a-hydroperoxide, 3648... 

Benzyl hydroperoxides lO-Hydroperoxy-9-anthrone (Z)-l,2-di-9-anthrylethene-l,2-diyl acetal (PEPDOD) 1.445 1.357 a 81... 

Toluene is, in low conversion, oxidized, with air, in the liquid phase to benzyl hydroperoxide, which yields mainly benzyl alcohol and some benzaldehyde upon hydrolysis, for example, in the presence of a cobalt salt. Benzyl alcohol thus obtained requires a more thorough purification for use in perfumes and flavors. 

The ready formation of benzylic hydroperoxides is used in industrial oxidations, as in the synthesis of propylene oxide and phenol (see Sections 9.5.2 and 9.5.4, respectively). In contrast with autoxidation of alkenes, where various secondary processes may follow, autoxidation of arenes is less complicated. Chain termination of 99 may lead to an alcohol and aldehyde [Eq. (9.151)], and the rapid autoxidation of the latter may produce the corresponding carboxylic acid [Eq. (9.152)] ... 

Metal ions [Co(III), Mn(m), Cu(II)] have a pronounced effect on the rate and product distribution of autoxidation. In the presence of metal ions, secondary transformations become dominant and selectivity in the formation of benzylic hydroperoxide 100 decreases. 

X,Y- Xylyl) Ethanol. (CH3)2C6H3CH2CH2 OH, C10H14b mw 150.24 OB to COa -276.89%. A violent expln occurs if this compd is added to 90% hydrogen peroxide, and the mixt is then acidified with coned sulfuric add. See also in Vol 5, D1328-R under a, a - Dimethyl-benzyl Hydroperoxide... ... 

Bromophenylazo)-2-propyl hydroperoxide, 3150 a-(4-Bromophenylazo)benzyl hydroperoxide, 3600 a-(4-Bromophenylazo)phenylethyl a-hydroperoxide, 3641 1,2-Dihydroperoxy-1,2-bis(benzeneazo)cyclohexane, 3756 a-Phenylazo-4-bromobenzyl hydroperoxide, 3601 a-Phenylazo-4-fluorobenzyl hydroperoxide, 3602 a-Phenylazobenzyl hydroperoxide, 3603 1-Phenylazocyclohexyl hydroperoxide, 3533 3,3,5-Triphenyl-4,4-dimethyl-5-hydroperoxy-4,5-dihydro(3H)pyrazole, 3835... 

Other Organic Compounds aniline hydrochloride benzyl hydroperoxide butyl chloride dicyclohexyl peroxide diethyl sulfide methyl iodide 2-naphthoyl bromide sodium S-phenyl thiosulfite fert-butyl fluoride... 

Aniline hydrochloride Benzyl hydroperoxide Butyl chloride Dicyclohexyl peroxide Diethyl sulfide Methyl iodide 2-Naphthoyl bromide Sodium S-phenyl thiosulfite ferf-Butyl fluoride... 

For example, a series of alkylaromatics afforded the corresponding aralkyl ketones in high selectivities with TBHP in the presence of CrAPO-5 (3 m %) at 80 °C (Table 5). TBHP could be replaced by Oj but this required neutralization of Bronsted acid sites on the CrAPO-5, by ion-exchange, in order to avoid acid-catalyzed decomposition of the benzylic hydroperoxide to the eorresponding phenol, which inhibits the autoxidation. The addition of a small amount of TBHP to initiate the reaction also had a beneficial effect. 

Toluene reacts slowly with O2 at T below 450 K to give benzyl hydroperoxide, benzyl alcohol, benzaldehyde, and dibenzyl peroxide by a free-radical chain process ... 

Air oxidation of toluene in the presence of transition metal ions in their lower oxidation state gives benzoic acid. Initiation is achieved by a redox reaction between benzyl hydroperoxide and the metal ion. In addition, if all the metal ion is not associated with hydroperoxide, initiation can occur via reaction of the higher valency state of the metal ion with toluene ... 

Autoxidation of o-, m-, and p-xylenes at long chain lengths gives 0-, m-, and p-methyl-substituted benzyl hydroperoxides. Rates of autoxidation are more than twice the rate of autoxidation of toluene and depend on the position of the substituent. ... 

By rapid reduction of one enantiomeric series of benzylic hydroperoxides, [2.2]para-cyclophane-based diphosphine 5 kinetically resolves those active compounds. ... 

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