Aqueous hydrogen peroxide

The alkene is allowed to react at low temperatures with a mixture of aqueous hydrogen peroxide, base, and a co-solvent to give a low conversion of the alkene (29). These conditions permit reaction of the water-insoluble alkene and minimise the subsequent ionic reactions of the epoxide product. Phase-transfer techniques have been employed (30). A variation of this scheme using a peroxycarbimic acid has been reported (31). 

The perfluoroalkane sulfonic acids were fkst reported ki 1954. Trifluoromethanesulfonic acid was obtained by the oxidation of bis(ttifluoromethyl thio) mercury with aqueous hydrogen peroxide (1). The preparation of a series of perfluoroalkanesulfonic acids derived from electrochemical fluotination (ECF) of alkane sulfonyl haUdes was also disclosed ki the same year (2). The synthetic operations employed when the perfluoroalkanesulfonic acid is derived from electrochemical fluotination, which is the best method of preparation, are shown ki equations 1—3. 

Table 2. Physical Properties of Aqueous Hydrogen Peroxide...

The decomposition of aqueous hydrogen peroxide is minimized by various purification steps during manufacture, use of clean passive equipment, control of contaminants, and the addition of stabilizers. The decomposition is zero-order with respect to hydrogen peroxide concentration. 

In Du Pont patents (116) the catalyst is prepared by spray-drying a mixture of colloidal siUca or other carriers and Pt/Pd salts. Aqueous hydrogen peroxide solutions up to 20 wt % ate reported for reaction conditions of 10—17°C and 13.7 MPa (140 kg/cm ) with 60—70% of the hydrogen feed selectively forming hydrogen peroxide. 

Aqueous hydrogen peroxide is sold in grades ranging from 3 to 86 wt %, most often containing 35, 50, and 70 wt % H2O2. In the United States, the only use for 86% H2O2 (ca 1994) is for attitude (flight path behavior) control of space craft, etc. This minor amount is imported. 

In spite of widespread usage of these compounds, the stmctures of only the calcium, barium, and strontium compounds are reasonably weU-estabhshed. The materials are generally made by trituratiag the oxides, or hydroxides, with aqueous hydrogen peroxide and dryiag the soHd products. The commercial products are typically mixtures of the peroxides with varyiag amounts of hydroxides, oxides, carbonates, hydrates, and peroxohydrates. 

Arsenic Peroxides. Arsenic peroxides have not been isolated however, elemental arsenic, and a great variety of arsenic compounds, have been found to be effective catalysts ia the epoxidation of olefins by aqueous hydrogen peroxide. Transient peroxoarsenic compounds are beheved to be iavolved ia these systems. Compounds that act as effective epoxidation catalysts iaclude arsenic trioxide, arsenic pentoxide, arsenious acid, arsenic acid, arsenic trichloride, arsenic oxychloride, triphenyl arsiae, phenylarsonic acid, and the arsenates of sodium, ammonium, and bismuth (56). To avoid having to dispose of the toxic residues of these reactions, the arsenic can be immobi1i2ed on a polystyrene resia (57). 

Peroxohydrates are usually made by simple crystallization from solutions of salts or other compounds in aqueous hydrogen peroxide. They are fairly stable under ambient conditions, but traces of transition metals catalyze the Hberation of oxygen from the hydrogen peroxide. Early work on peroxohydrates has been reviewed (92). 

When dissolved ia water, the solution is identical with that obtained by dissolving sodium carbonate ia aqueous hydrogen peroxide. There is some evidence for the presence of the traces of tme peroxocarbonate anion, HCO , ia these solutions (95). If the peroxohydrate is heated for about an hour at 100°C and then allowed to cool to room temperature, some decomposition occurs and the product effervesces when placed ia water. Electron spia resonance experiments (64) iadicate that free radicals are present ia this partially decomposed material, but the nature of these radicals is obscure. 

Ammonium carbonate peroxohydrate, (NH 2 02 H2O2, first reported in 1980 (31), is crystalli2ed from a solution of ammonium hydrogen carbonate in aqueous hydrogen peroxide. The vibrational spectmm confirms the presence of molecular hydrogen peroxide. The compound is unstable and unlikely to find commercial appHcation. 

Obsolete uses of urea peroxohydrate, as a convenient source of aqueous hydrogen peroxide, include the chemical deburring of metals, as a topical disinfectant and mouth wash, and as a hairdresser s bleach. In the 1990s the compound has been studied as a laboratory oxidant in organic chemistry (99,100). It effects epoxidation, the Baeyer-Villiger reaction, oxidation of aromatic amines to nitro compounds, and the conversion of sodium and nitrogen compounds to S—O and N—O compounds. 

The AFO reaction has seen very few variations since it was first reported in 1934. However, the most significant modification was reported in 1958 by Ozawa and further elaborated by Smith and others. Prior to this modification the intermediate chalcones were purified and then subjected to hydrogen peroxide in a basic medium. With the modification, the chalcone was generated in situ, from an aldehyde and a hydroxyacetophenone, and then allowed to react with aqueous hydrogen peroxide in the presence of sodium hydroxide to deliver the flavonol. Smith and coworkers conducted a limited study to examine the scope and limitations of this modification.Flavonols were delivered in 51-67% however, no flavonols were isolated with highly reactive aldehydes such as p-nitrobenzaldehyde and when 2-hydroxy-4-methoxyacetophenone was used. 

In the preparation of quinoxaline N-oxides, it is advantageous to use peracetic acid rather than aqueous hydrogen peroxide as the... 

Reaction of 2,3-diphenylquinoxaline with excess of aqueous hydrogen peroxide in acetic acid gives, in addition to the expected 1,4-dioxide, A A" -dibenzoyl o-phenylenediamineA ... 

When an alkene reacts with BH3 in THF solution, rapid addition to the double bond occurs three times and a tricilkylborcme, R3B, is formed. For example, 1 molar equivalent of BH3 adds to 3 molar equivalents of cyclohexene to yield tricyclohexylborane. When tricvclohexylborane is then treated with aqueous hydrogen peroxide (H2C>2) in basic solution, an oxidation takes place. The three C-B bonds are broken, -OH groups bond to the three carbons, and 3 equivalents of cyclohexanol are produced. The net effect of the... 

Treatment of an or.jS-unsaturated ketone with basic aqueous hydrogen peroxide yields an epoxy ketone. The reaction is specific to unsatnrated ketones isolated alkene double bonds do not react. Propose a mechanism. 

Epoxidation systems based on molybdenum and tungsten catalysts have been extensively studied for more than 40 years. The typical catalysts - MoVI-oxo or WVI-oxo species - do, however, behave rather differently, depending on whether anionic or neutral complexes are employed. Whereas the anionic catalysts, especially the use of tungstates under phase-transfer conditions, are able to activate aqueous hydrogen peroxide efficiently for the formation of epoxides, neutral molybdenum or tungsten complexes do react with hydrogen peroxide, but better selectivities are often achieved with organic hydroperoxides (e.g., TBHP) as terminal oxidants [44, 45],... 

In a recent screening of different metal salts, Lane and Burgess found that simple manganese(n) and (in) salts catalyzed the formation of epoxides in DMF or t-BuOH in the presence of aqueous hydrogen peroxide (Scheme 6.7) [68]. It was further established that the addition of bicarbonate was of importance for the epoxidation reaction. 

The second major discovery regarding the use of MTO as an epoxidation catalyst came in 1996, when Sharpless and coworkers reported on the use of substoichio-metric amounts of pyridine as a co-catalyst in the system [103]. A change of solvent from tert-butanol to dichloromethane and the introduction of 12 mol% of pyridine even allowed the synthesis of very sensitive epoxides with aqueous hydrogen peroxide as the terminal oxidant. A significant rate acceleration was also observed for the epoxidation reaction performed in the presence of pyridine. This discovery was the first example of an efficient MTO-based system for epoxidation under neutral to basic conditions. Under these conditions the detrimental acid-induced decomposition of the epoxide is effectively avoided. With this novel system, a variety of... 

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