Peroxide oxidants, amine oxidation

Organomineral hydroperoxides have been prepared from hydrogen peroxide and organomineral haUdes, hydroxides, oxides, peroxides, and amines (10,33). If HX is an acid, ammonia is used to prevent acidic decomposition. 

Owiag to the lower basicity of the parent amines, aromatic amine oxides cannot be formed directiy by hydrogen peroxide oxidation. These compounds may be obtained by oxidation of the corresponding amine with a peracid perbenzoic, monoperphthaUc, and monopermaleic acids have been employed. 

CH—NHOH) to oxime (C=NOH) and ultimately to the nitroalkane (CH—NO2). Hydrogen peroxide generates amine oxides from tertiary cycloaUphatic... 

Peroxides oxidize TPDD to Wurster s blue, a product with a semiquinone diimine structure [1]. Similarly Wurster s blue is also produced from TPDD by reaction with halogen-containing substances produced by the reaction of aromatic amines and triazines with chlorine gas. 

Oxidation of thiophene with Fenton-like reagents produces 2-hydroxythiophene of which the 2(570 One isomer is the most stable (Eq. 1) <96JCR(S)242>. In contrast, methyltrioxorhenium (Vn) catalyzed hydrogen peroxide oxidation of thiophene and its derivatives forms first the sulfoxide and ultimately the sulfone derivatives <96107211>. Anodic oxidation of aminated dibenzothiophene produces stable radical cation salts <96BSF597>. Reduction of dihalothiophene at carbon cathodes produces the first example of an electrochemical halogen dance reaction (Eq. 2) <96JOC8074>. 

Direct oxidation of primary amines with peroxide oxidants does not provide appreciable yield of hydroxylamines. As was mentioned above, oxidation of secondary amines usually proceeds smoothly giving moderate to good yields of iV,iV-disubstituted hydroxylamines. Oxidation of sterically hindered secondary amines such as 125 (equation 88) can also be done with peracids . Further oxidation of the resulting Af,A-disubstituted hydroxylamines 126 with an excess of m-chloroperbenzoic acid is known to end up with the corresponding nitroxyl radicals of type 127 (equation 88) ° although the reaction can be stopped at the hydroxylamine stage. 

Dimethyldioxirane was reported to provide superior yields of hydroxylamines in comparison to other peroxide oxidizing agents. This reaction worked well on polyfunctional amines such as O-protected aminosaccarides 140 (equation 94), yet it was found to be substrate-sensitive and failed to provide hydroxylamines in several cases . 

Hoffman and coworkers have extensively studied the reactions between amines and sulfonyl peroxides. When primary amines reacted with arylsulfonyl peroxides at —78 °C in ethyl acetate, A-alkyl-O-arylsulfonyl hydroxylamine derivatives were obtained (equation 8), whereas when various primary and secondary amines reacted with sulfonyl peroxides, oxidative deamination was observed. ... 

Hydroperoxides and peroxides oxidize primary and secondary aliphatic amines to imines. Thus f-butyl hydroperoxide oxidizes 4-methyl-2-pentyl-amine to 2-(4-methylpentylidene)-4-methyl-2-pentylamine in 66% yield [29]. Di-r-butyl peroxide reacts in a similar manner [29]. However, this reaction is... 

Compositions and functions of typical commercial products in the 2-alkyl-l-(2-hydroxyethyl)-2-imidazolines series are given in Table 29. 2-Alkyl-l-(2-hydroxyethyl)-2-imidazolines are used in hydrocarbon and aqueous systems as antistatic agents, corrosion inhibitors, detergents, emulsifiers, softeners, and viscosity builders. They are prepared by heating the salt of a carboxylic acid with (2-hydroxyethyl)ethylenediamine at 150—160°C to form a substituted amide 1 mol water is eliminated to form the substituted imidazoline with further heating at 180—200°C. Substituted imidazolines yield three series of cationic surfactants by ethoxylation to form more hydrophilic products quatemization with benzyl chloride, dimethyl sulfate, and other alkyl halides and oxidation with hydrogen peroxide to amine oxides. 

Oxidation of sec-amines to nitrones. In the presence of this tungstate, hydrogen peroxide oxidizes secondary amines to nitrones.1... 

Hydroxylamines are commonly postulated as intermediates in diese oxidations, but dey are rarely isolated or detected. Two examples of reactions in which products at the hydroxylamine oxidation level can be isolated bodi involve peroxides. Oxidation of alkylamines (2 R = Bu, Me and niCH2) with arenesul-fonyl peroxides bearing an electron-wididrawing group gave die arenesulfonyloxyamines in good yields (Scheme 6). A similar reaction of primary amines wi dibenzoyl peroxide gave benzoyloxyamines. ... 

Dibenzoyl peroxide oxidizes morpholine, piperidine and other simple secondary amines in good yield to the corresponding benzoyloxyamines these compounds can then be hydrolyzed in basic conditions to the free hydroxylamines. An analogous reaction t es place between secondary amines and bis(diphe-nylphosphinyl) peroxide for example, diethylamine is converted into the hydroxylamine derivative Et2NOFOPh2 (97%) by this reagent. The products are easily hydrolyzed to the free hydroxylamines, and they can also be used as aminating agents. 

Tertiary amines are also used in the manufacture of amine oxides by the oxidation with hydrogen peroxide. The amine oxides are used in cosmetic preparations for its good foaming properties and mildness to the skin. Another raw material used in the cosmetic industry is the betaines produced by the reaction of a tertiary fatty amine with sodium chloroacetate. The betaines exhibit good foam stability over a wide range of pH, are insensitive to water hardness, and are mild to the skin (33). 

Drugs that are susceptible to oxidation of carbon-hydrogen bonds include ethers (which oxidise to form highly explosive peroxides), aliphatic amines (which oxidise at the a hydrogen atom) and aldehydes (which are easily oxidised to carboxylic acids and peroxy acids). Examples of these reactions are shown in Figure 8.6. 

This procedure has been applied to the determination of organic peroxides hydroxyl amine chromium(VI) cerium(IV) molybdenum(VI) nitrate, chlorate, and perchlorate ions and numerous other oxidants (see, for example. Problems 20-37 and 20-39). 

Peroxides [1] e.g. hydrogen peroxide, per acids, diacylperoxides, hydroperoxides, ketone peroxides [1] Under the influence of peroxides aromatic amines (color developer 3) react with phenols to yield quinone imines [1]. Oxidizing agent Aromatic amine -l- 1-Naohthol Quinone imine dyestuff. 

Fig. 6 Allylic and benzylic C-H amination promoted by peroxide oxidants...

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