Hydrogen peroxide primary amines

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). 

One of the exciting results to come out of heterogeneous catalysis research since the early 1980s is the discovery and development of catalysts that employ hydrogen peroxide to selectively oxidize organic compounds at low temperatures in the liquid phase. These catalysts are based on titanium, and the important discovery was a way to isolate titanium in framework locations of the inner cavities of zeolites (molecular sieves). Thus, mild oxidations may be run in water or water-soluble solvents. Practicing organic chemists now have a way to catalytically oxidize benzene to phenols alkanes to alcohols and ketones primary alcohols to aldehydes, acids, esters, and acetals secondary alcohols to ketones primary amines to oximes secondary amines to hydroxyl-amines and tertiary amines to amine oxides. 

Amines are another important group of analytes. Mellbin and Smith [72] compared three different fluorescent reagents, dansyl chloride, 4-chloro-7-nitrobenzo-1,2,5-oxadiazole, and o-phthaldialdehyde, for derivatization of alkylamines. The dansyl tag was found to be the most effective. Hamachi et al. [73] described the application of an HPLC-POCL method for determination of a fluorescent derivative of the synthetic peptide ebiratide. Another comparative study was done by Kwakman et al. [74], where naphthalene-2,3-dialdehyde and anthracene-2,3-dial-dehyde were evaluated as precolumn labeling agents for primary amines. The anthracene-2,3-dialdehyde derivatives were not stable, especially in the presence of hydrogen peroxide, and the POCL detection of these derivatives was therefore... 

The oxidation of primary and secondary alcohols in the presence of 1-naphthylamine, 2-naphthylamine, or phenyl-1-naphthylamine is characterized by the high values of the inhibition coefficient / > 10 [1-7], Alkylperoxyl, a-ketoperoxyl radicals, and (3-hydroxyperoxyl radicals, like the peroxyl radicals derived from tertiary alcohols, appeared to be incapable of reducing the aminyl radicals formed from aromatic amines. For example, when the oxidation of tert-butanol is inhibited by 1-naphthylamine, the coefficient /is equal to 2, which coincides with the value found in the inhibited oxidation of alkanes [3], However, the addition of hydrogen peroxide to the tert-butanol getting oxidized helps to perform the cyclic chain termination mechanism (1-naphthylamine as the inhibitor, T = 393 K, cumyl peroxide as initiator, p02 = 98 kPa [8]). This is due to the participation of the formed hydroperoxyl radical in the chain termination ... 

In contrast to the flavin-dependent monoamine oxidases, SSAO/VAP-1 has evolved to hydroxylate a tyrosine residue in the active site which is further oxidized to the quinone state by oxygen in the presence of copper ion releasing hydrogen peroxide [28-30]. The primary amine in the substrate (R-NH2, Scheme 1) forms a Schiff-base with the quinone carbonyl group, which through a series of steps ultimately releases the aldehyde product. 

With concentrated mineral acids azobenzene gives red salts, as may be shown by pouring hydrochloric acid on it. Addition of hydrogen leads to the re-formation of the hydrazo-compound. Oxygen is added on and the azoxy-compound formed by the action of hydrogen peroxide or nitric acid. The synthesis of asymmetrical aromatic azo-compounds from nitroso-compounds and primary amines was discussed above. 

Anilines are converted into nitrosoarenes ArNO by the action of hydrogen peroxide in the presence of [Mo(0)(02)2(H20) (HMPA)]224, whereas catalysis of the reaction by titanium silicate and zeolites results in the formation of azoxybenzenes ArN (0)=NAr225. Azo compounds ArN=NAr are formed in 42-99% yields by the phase-transfer assisted potassium permanganate oxidation of primary aromatic amines in aqueous benzene containing a little tetrabutylammonium bromide226. The reaction of arylamines with chromyl chloride gives solid adducts which, on hydrolysis, yield mixtures of azo compounds, p-benzoquinone and p-benzoquinone anils 234227. 

Copper-containing amine oxidases (non-blue copper proteins) catalyze the oxidative deamination of primary amines to the corresponding aldehydes with the release of ammonia and concomitant reduction of oxygen to hydrogen peroxide. They typically use a quinone redox cofactor [topaquinone (TPQ)], which is bound covalently in the active site, and are thought to form a Cu(I)-TPQ semi-quinone radical intermediate during the redox reaction [13]. 

The effect of oxygen and hydrogen peroxide on the reaction of carbonyl sulfide on primary amines is discussed in Section 3. 

The reaction appears to be applicable to a wide range of aromatic starting materials, exceptions being aromatic aldehydes and aromatic primary amines [96]. In effect, the aromatic compound to be converted is stirred with an aqueous solution of hydroxylamine hydrochloride in the presence of metallic ions such as copper ions [95-97] or complex ions such as the pentacyanoam-mine ferrate(II) ion [98]. The mixture is then treated with 30% hydrogen peroxide and a highly colored complex of the nitrosophenol forms. Presumably, the free nitrosophenol may be isolated by treatment of the complex with an acid (Eq. 50). 

Addition of an oxygen atom from hydrogen peroxide or a peroxyacid to a primary or secondary amine might be expected to yield an amine oxide-type... 

AMI and PM3 calculations reveal that epoxidations by DMDO and TFDO involve peroxide-bond cr at a very early stage and that TFDO is the most reactive dioxirane as the CF3 group in it stabilizes this cr level. In accord with previous calculations a spiro transition state is predicted. Furthermore, allene is predicted to be less reactive than alkenes toward epoxidation by DMDO.192 DFT calculations on the oxidation of primary amines by dimethyldioxirane predict a late transition state with a barrier of 17.7 kcal mol-1 which is drastically lowered by hydrogen bonding to the O—O bond to just 1.3 kcal mol-1 in protic solvents.193... 

The use of chemiluminescence reactions for the detection of metal ions by liquid chromatography was recently reported [59,60]. The detectors made use of the chemiluminescence produced in the reaction between luminol and hydrogen peroxide which is catalyzed by transition metals. The column effluent was mixed with the reagents in order to yield the chemiluminescence. The reaction was fast and was carried out at room temperature. By varying the pH of the buffer, selectivity towards certain metals was also achieved. For example, at pH 10-11 nickel could be analyzed but lead and aluminium were inactive at pH 13-14, the converse was true [59]. Aminco-Bowman has marketed a liquid chromatographic system in which amino acids and amines are analyzed by means of the fluorescence produced on reaction with the reagent fluorescamine. Fluorescamine does not fluoresce, but it does react with primary amino groups to produce fluorescent derivatives. The reaction is instantaneous and may be carried out at room temperature, usually at pH 9. This detection system promises to be far more sensitive than the ninhydrin detection system and is much more easily adapted to HPLC. 

Monoamine oxidases catalyze oxidative deamination of many primary, secondary, and tertiary amines. They have a wide tissue distribution including brain, liver, and intestine. A variety of endogenous amines, such as catecholamines, and pharmacological substances are metabolized. The products of primary amines are the corresponding aldehydes, ammonia, and hydrogen peroxide. 

Lysyl oxidase contains a single Type 2 copper center (see Copper Proteins with Type 2 Sites) at the active site, bound by three histidine residues. The metal ion appears not to be redox active during turnover, and the oxidation chemistry is instead performed by a covalently attached cofactor, lysine tyrosyl quinone, derived from a tyrosine residue in the protein (vide infra. Section 3.1). The overall reaction involves oxidation of the primary amine group of a peptide-bound lysine residue, reduction of dioxygen to hydrogen peroxide, and release of ammonium ion (equation 4). 

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