Hydrogen peroxide-acetonitrile

HOMOCONJUGATE ADDITION, 66 Homo-Michael acceptor, 69 Hydrogen peroxide-acetonitrile, 63 4-Hydroxy-2-butanone, 93... 

EPOXIDATION OF OLEFINS BY HYDROGEN PEROXIDE-ACETONITRILE cw-CYCLOOCTENE OXIDE... 

Triacetonamine and 2,2,6,6-tetramethyl-4-piperidinol are oxidized by the hydrogen peroxide-sodium carbonate system very selectively, giving practically a quantitative yield (45). For amine oxidation, the hydrogen peroxide-acetonitrile system is often effective enough (46,47), while for hindered piperidine oxidation, peracids can be also used. 

Hydrogen peroxide acetonitrile Azoxy compounds from amines... 

Hydrogen peroxide acetonitrile Azines from 0x0 compds. 

Nitroso compounds are formed selectively via the oxidation of a primary aromatic amine with Caro s acid [7722-86-3] (H2SO ) or Oxone (Du Pont trademark) monopersulfate compound (2KHSO KHSO K SO aniline black [13007-86-8] is obtained if the oxidation is carried out with salts of persulfiiric acid (31). Oxidation of aromatic amines to nitro compounds can be carried out with peroxytrifluoroacetic acid (32). Hydrogen peroxide with acetonitrile converts aniline in a methanol solution to azoxybenzene [495-48-7] (33), perborate in glacial acetic acid yields azobenzene [103-33-3] (34). 

Tetracyanoethylene oxide [3189-43-3] (8), oxiranetetracarbonitnle, is the most notable member of the class of oxacyanocarbons (57). It is made by treating TCNE with hydrogen peroxide in acetonitrile. In reactions unprecedented for olefin oxides, it adds to olefins to form 2,2,5,5-tetracyanotetrahydrofuran [3041-31-4] in the case of ethylene, acetylenes, and aromatic hydrocarbons via cleavage of the ring C—C bond. The benzene adduct (9) is 3t ,7t -dihydro-l,l,3,3-phthalantetracarbonitrile [3041-36-9], C22HgN O. 

This type of amination by an oxaziridine is assumed to be the key step of a novel process for hydrazine manufacture, in the course of which butanone in solution with ammonia is reacted with hydrogen peroxide and acetonitrile. The smooth formation of oxaziridines from Schiff bases and hydrogen peroxide-nitrile mixtures is as well known as NH transfer from an oxaziridine like (300), suggesting the intermediacy of (300) as the N—N forming agent (72TL633). 

If a dilute solution of hydrogen peroxide in dry acetonitrile is added to a solution of a sulphoxide and an iron(II) salt in dry acetonitrile then the sulphone is produced in quantitative yield34. This latter reaction works equally well for aliphatic and aromatic sulphoxides and is thought to involve oxygen transfer by the reaction of a ferryl ion with the sulphoxide, as shown in equation (12). 

Iron(III) salts also activate the oxidation of sulphoxides by hydrogen peroxide in dry acetonitrile although the yields are typically lower than for the iron(II) system35. With iron(III) salts the hydrogen peroxide seems to be activated by direct complexation between the metal ion and the peroxide moiety. 

The performance of various solvents can be explained with the help of the role of these solvents in the reaction. These solvents help in keeping teth benzene and hydrogen peroxide in one phase. This helps in the easy transport of both the reactants to the active sites of the catalyst. The acetonitrile, and acetone adsorption data on these catalysts (Fig. 6), suggests that acetonitrile has a greater affinity to the catalytic surface than acetone. There by acetonitrile is more effective in transporting the reactants to the catalyst active sites. At the same time, they also help the products in desorbing and vacating the active sites. 

In addition, also nonheme iron catalysts containing BPMEN 1 and TPA 2 as ligands are known to activate hydrogen peroxide for the epoxidation of olefins (Scheme 1) [20-26]. More recently, especially Que and coworkers were able to improve the catalyst productivity to nearly quantitative conversion of the alkene by using an acetonitrile/acetic acid solution [27-29]. The carboxylic acid is required to increase the efficiency of the reaction and the epoxide/diol product ratio. The competitive dihydroxylation reaction suggested the participation of different active species in these oxidations (Scheme 2). 

Two reagents were investigated as less expensive replacements for MCPBA in the epoxidation of VII (a) 30% hydrogen peroxide in acetic acid at 90-100°C (b) 30% hydrogen peroxide and acetonitrile in ethanol in the presence of potassium bicarbonate (19,20). The first reaction gave a mixture of VIII and an unidentified product. 

The extremely violent interaction of phosphorus(V) oxide and cone, hydrogen peroxide to give peroxomonophosphoric acid may be moderated by using acetonitrile as a diluent. 

Anhydrous peroxytrifluoroacetic acid is not easy to handle, but the procedure has recently been revised.121 Namely, reaction of urea-hydrogen peroxide complex (UHP) with tri-fluoroacetic anhydride in acetonitrile at 0 °C gives solutions of peroxytrifluoroacetic acid, which oxidize aldoximes to nitroalkanes in good yields (Eqs. 2.58 and 2.59). Ketoximes fail to react under these conditions, the parent ketone being recovered. 

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