Nitrogen-containing compound oxidations

Nitrobenzene chloride, sulfonylperoxy radical reactions, 1035, 1036 2-Nitrobenzenesulfinylperoxy intermediate, superoxide reactions, 1034 Nitrogen-containing compound oxidation bis(trimethylsilyl) peroxide reactions, 802-3, 804 dioxiranes, 1151-5 primary aromatic amines, 1151 A-oxidation, 531-8, 539 Nitrohpids, hpid hydroperoxides, 952-4 Nitronate ions, dioxirane oxidation, 1152-3 Nitrosation, malondialdehyde, 667 Nitroso compounds, spin trapping, 664 Nitrotyrosine, peroxynitiite determination, 740-1... 

Urea (24), amino acids (25), and creatinine (26) are also decomposed during superchlorination or shock treatment, with formation of N2 and other oxidation products. However, the process is slower than with ammonium ion (see Chloramines and BROMAMINEs). Urea is the principal nitrogen-containing compound in swimming pools. Since it is an amide, it reacts slowly with chlorine, yielding N2, NCl, and NO/ (27). 

As expected from the Lewis acidity of Ti4+, the titanosilicates strongly adsorb and oxidize basic nitrogen-containing compounds with a lone pair of electrons localized on the N atom. By contrast, nitrogen oxides (NOx) and nitro compounds... 

Since the methoxyl group attached to the carbon adjacent to nitrogen can be readily replaced by various carbon nucleophiles, a-methoxylated carbamates are useful intermediates for the syntheses of nitrogen-containing compounds. The electrochemical oxidation of silyl-substituted carbamates provides a highly regioselective route to these useful compounds. 

Nitrogen compounds are also effective as nucleophiles in the anodic oxidation of silyl-substituted ethers. The electrochemical oxidation in the presence of a carbamate or a sulfonamide in dry THF or dichloromethane results in the selective cleavage of the C-Si bond and the introduction of the nitrogen nucleophile at the carbon (Scheme 21) [55]. Since a-methoxycarbamates are useful intermediates in the synthesis of nitrogen-containing compounds [44], this reaction provides useful access to such compounds. Cyclic silyl-substkuted ethers such as 2-silyltetrahydrofurans are also effective for the introduction of nitrogen nucleophiles. The anodic oxidation in the presence of a carbamate or a... 

The only cationic surfactant (Fig. 23) found in any quantity in the environment is ditallow dimethylammonium chloride (DTDMAC), which is mainly the quaternary ammonium salt distearyldimethylammonium chloride (DSDMAC). The organic chemistry and characterization of cationic surfactants has been reported and reviewed [330 - 332 ]. The different types of cationic surfactants are fatty acid amides [333], amidoamine [334], imidazoline [335], petroleum feed stock derived surfactants [336], nitrile-derived surfactants [337], aromatic and cyclic surfactants [338], non-nitrogen containing compounds [339], polymeric cationic surfactants [340], and amine oxides [341]. 

Finally, it is important to note that many of the anodic reactions discussed above cannot be duplicated with traditional chemical oxidants. For this reason, the anodic oxidation of nitrogen-containing compounds represents a powerful class of reactions that has the potential to open up entirely new synthetic pathways to complex molecules. From the work already accomplished, it is clear that employing such an approach is both feasible and beneficial, and that the ability to selectively oxidize amines and amides is a valuable tool for any synthetic chemist to have at their disposal. 

Figure 8.13 The central role of transdeamination in metabolism of amino adds and further metabolism of the oxoacids in the liver. The box contains the reactions for conversion of the amino acids to their respective oxoacids. Processes are as follows (1) digestion of protein in the intestine and absorption of resultant amino acids, (2) degradation of endogenous protein to amino acids (primarily but not exclusively muscle protein), (3) protein synthesis, (4) conversion of amino acid to other nitrogen-containing compounds (see Table 8.4), (5) oxidation to CO2, (6) conversion to glucose via gluconeogenesis, (7) conversion to fat.

Sulfur- and nitrogen-containing compounds will produce their corresponding oxides and should not be incinerated without considering their effects on air quality. Halogenated hydrocarbons not only may affect air quality but also may corrode the incinerator. Also, organo-metallic compounds containing cadmium, mercury, and so on, are not recommended for incineration because of the potential for air and solid waste contamination. 

Electrochemically generated nickel(lll) oxide is approximated as NiO(OH). Analytical figures obtained for the chemically prepared oxide approximate to NiO(OH).H20. The material behaves as a radical source and the initial step in the oxidation of alkanols is radical attack with removal of the a-hydrogen atom. This is followed by an electron transfer from the carbon radical so generated, see Scheme 8.4 [54], The same process also attacks aldehydes in the gem-diol form. The nickel oxide electrode also attacks nitrogen-containing compounds (p. 281). 

Molybdenum(VI) oxide is used in catalyst compositions to carry out desulfurization of petroleum feedstocks and to remove nitrogen-containing compounds from petroleum fractions. Other uses of this oxide include preparation of various molybdate salts and as reagents for chemical analyses. 

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