Alcohols, reaction with hydrogen peroxide

Materials. Chemically pure solvents and reagent grade ceric ammonium nitrate were used as received. Cumene hydroperoxide was purified via the sodium salt. Lucidol tert-butyl hydroperoxide was purified by low temperature crystallization. Tetralin hydroperoxide, cyclohexenyl hydroperoxide, and 2-phenylbutyl-2-hydroperoxide were prepared by hydrocarbon oxidation and purified by the usual means. 1,1-Diphenyl-ethyl hydroperoxide and triphenylmethyl hydroperoxide were prepared from the alcohols by the acid-catalyzed reaction with hydrogen peroxide (10). 

Explosive reaction with nitric acid at 75°C. Reaction with hydrogen peroxide + nitric acid forms an explosive peroxide. To fight fire, use alcohol foam, dry chemical, or CO2. When heated to decomposition it emits acrid smoke and irritating fumes. See also KETONES and CYCLOHEXANE. 

Hydration of attenic nitriles. 4,4-Dialkyl-substitutcd allenic nitriles (1) are converted into allenic amides (2) in 60 70% yield by reaction with hydrogen peroxide in alcoholic sodium hydroxide. 

A new process for the synthesis of glycerine is based on this direct oxidation process for acrolein. Reaction of acrolein with isopropanol gives allyl alcohol and acetone as products. Hydroxylation of allyl alcohol by reaction with hydrogen peroxide, obtained from liquid-phase oxidation of isopropanol, is made to yield glycerine as a product. ... 

Similar TS-1 films have been applied for phenol hydroxyl-ation reaction to dihydroxybenzenes (hydroquinone and catechol) [354] and catalytic oxidation of styrene to benzaldehyde and phenylacetaldehyde [355] with hydrogen peroxide as oxidant in batch-type membrane reactors. The dihydroxybenzenes and phenylacetaldehyde selectivity values increased with in-framework Ti content. In order to reduce the TS-1 membrane costs, Chen et al. [356] have successMly synthesized TS-1 on mullite tubes by replacing TPAOH with TPABr/EtjNH system (4% of the initial cost). The catalytic activity was tested in the probe reaction of isopropyl alcohol oxidation with hydrogen peroxide under pervaporation condition at 60°C. In general, future work on TS-1 film catalysts is required to improve mass transfer resistances and reaction conversion without compromising selectivity. 

The reaction of boronic esters with (dihalomethyl)lithium is particularly well suited to the building of asymmetric structures in which there are no functional substituents. At the end of the synthesis, the boronic ester group can be replaced by reaction with hydrogen peroxide to form the corresponding asymmetric secondary alcohol [11,12, 29]. 

Petoxycatboxyhc acids have been obtained from the hydrolysis of stable o2onides with catboxyhc acids, pethydtolysis of acyhinida2ohdes, reaction of ketenes with hydrogen peroxide, electrochemical oxidation of alcohols and catboxyhc acids, and oxidation of catboxyhc acids with oxygen in the presence of o2one (181). 

This reaction provides a wide variety of products since decomposition of the deuterated alkylborane intermediate (164) can be achieved with hydrogen peroxide to yield labeled alcohols (165), with hydroxylamine-O-sulfonic acid leading to deuterated amines (166), as well as with boiling propionic acid or propionic acid-OD, to form mono- (167) or dideuterio (168) hydrocarbons, respectively. Furthermore, if a monodeuterium label at the sterically more accessible position (170) is sufficient, the use of expensive metal deute-... 

Deuterioboration of 5a-cholest-2-ene (171), followed by oxidation of the alkylborane intermediate with hydrogen peroxide in the presence of sodium hydroxide, illustrates the application of this method for the preparation of c/5-deuterium labeled alcohols.(For the preparation of tra 5 -deuterium labeled alcohols see section VII-A.) The predominant reaction product is 2a-di-5a-cholestan-3a-ol (172, 1.03 D/mole) which is accompanied by 3a-di-5a-cholestan-2a-ol (173) and other minor products." ... 

Heteropoly acids can be synergistically combined with phase-transfer catalysis in the so-called Ishii-Venturello chemistry for oxidation reactions such as oxidation of alcohols, allyl alcohols, alkenes, alkynes, P-unsaturated acids, vic-diols, phenol, and amines with hydrogen peroxide (Mizuno et al., 1994). Recent examples include the epoxidations of alkyl undecylenates (Yadav and Satoskar, 1997) and. styrene (Yadav and Pujari, 2000). 

The reaction of hydrogen peroxide with an alcohol in the presence of sulphuric acid gives rise to the corresponding hydroperoxide ... 

In the M. capsulatus (Bath) system, all three components are necessary to obtain turnover with NADH as the reductant (57). With the M. trichosporium OB3b system, protein B is apparently not required (27). Instead, in this latter system, protein B increases the initial rates of the catalytic hydroxylation reaction (27). Catalysis can be achieved by means of a shunt pathway with hydrogen peroxide and Hox alone from both organisms (58-60). The efficiency of the shunt pathway, however, varies significantly. With M. trichosporium OB3b, alcohol yields greater than those obtained with the completely reconstituted system have been observed (58). Furthermore, upon addition of protein... 

The experimental data on the reactions of ketyl radicals with hydrogen and benzoyl peroxides were analyzed within the framework of IPM [68]. The elementary step was treated as a reaction with the dissociation of the O—H bond of the ketyl radical and formation of the same bond in acid (from acyl peroxide), alcohol (from alkyl peroxide), and water (from hydrogen peroxide). The hydroperoxyl radical also possesses the reducing activity and reacts with hydrogen peroxide by the reaction... 

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