Stoichiometry nitrogen oxide production

In contrast to a straightforward and predictable decomposition pattern of photolysis with >400 nm light, irradiation of nitrosamides under nitrogen or helium with a Pyrex filter (>280 nm) is complicated by the formation of oxidized products derived from substrate and solvent, as shown in Table I, such as nitrates XXXIII-XXXV and nitro compound XXXVI, at the expense of the yields of C-nitroso compounds (19,20). Subsequently, it is established that secondary photoreactions occur in which the C-nitroso dimer XIX ( max 280-300 nm) is photolysed to give nitrate XXXIII and N-hexylacetamide in a 1 3 ratio (21). The stoichiometry indicates the disproportionation of C-nitroso monomer XVIII to the redox products. The reaction is believed to occur by a primary photodissociation of XVIII to the C-radical and nitric oxide followed by addition of two nitric oxides on XVIII and rearrangement-decomposition as shown below in analogy... 

The oxidation of ammonia to the various end products listed in Table 7-9 requires different amounts of chlorine per unit amount of ammonia-nitrogen oxidized. These "CI2 reduced to NH3-N oxidized" ratios are given in Table 7-9 for each possible end product on both a molar and a weight basis. These ratios are calculated from the pertinent redox reaction stoichiometry. For example, the two most common end products of... 

Agrawal and Mushran studied the kinetics of the silver ion-catalysed oxidation of acetamide. The stoichiometry is uncertain, but acetic acid and nitrogen are the main products. The rate is approximately first-order with respect to both peroxodisulphate and silver ions, and is almost independent of the substrate concentration. No definite conclusions regarding the mechanism can be drawn, but the kinetics suggest a chain process. Agrawal et report similar results for the oxidation of formamide. 

On the other hand, a very unique redox system involving Cu(l)/Cu(II)/Cu(III) oxidation states was reported by Ribas, Stahl, and coworkers [79-81]. They extensively studied the reactivity of the triazamacrocyclic ligand with Cu(II) and successfully characterized C-H activated Ar-Cu(Ill) and Cu(I) complexes. The careful investigation of the reaction stoichiometry revealed that 0.5 eq of Ar-Cu(III) and 0.5 eq of Ar-Cu(I) are formed from 1.0 eq of Cu(II), thus suggesting an disproportionation of Cu(II) into Cuflll) and Cu(I) during the C-H activation event (Eq. 46). Upon treatment of the isolated Ar-Cu(III) complex with MeOH as an oxygen nucleophile, the C-H alkoxylated product and Cu(l) salt are obtained quantitatively (Eq. 47). A similar C-N bond formation occurs when NH pyridone is used as a nitrogen nucleophile. 

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