Arylamines oxidative dealkylation

According to the proposed mechanism, the superoxo derivative of LCo(salen), where L is the N-bonded Ar-NH-CH -Pr ligand, abstracts an 

H-atom from a free amine to give either the amino radical 43 or the a-aralkylamino radical 44. Further oxidation and hydrolysis afford the observed products [60]. 

The Fe(TPP)Cl/02/ system, containing the added reducing agent catalyzes the oxidative dealkylation of tertiary amines 45 

N-Dimethylaniline is oxidized by molecular presence of iron salts and complexes like FeCl 

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Carcinogenic aminoazo dyes were previously found to increase the latent period of linoleate peroxidation and that DAB was a more effective antioxidant than MAB (13). Furthermore, as autoxidation of the linoleic acid proceeded, N-demethylation of DAB and MAB occurred. Demethylation of DAB also occurred in vitro when DAB is dissolved in cottonseed oil and mixed with ground brown rice (14). Our results clearly indicate that a linoleic acid hydroperoxide-hematin system readily N-demethylates DAB to MAB and MAB to AB. Previously, it was found that in this system, HCHO formation by N-demethylation of DAB was faster than that obtained with MAB (15). Similar results are now reported during the H202 peroxidase catalyzed oxidation of DAB and MAB. Peroxidase and H2O2 have previously been reported to catalyze the N-dealkylation of other arylamines (16, 17). 

In addition to direct oxygenation, e.g. by aryl hydrocarbon hydroxylase, oxidative N- or 0-dealkylation is another process catalyzed by components of the Cytochrome P-450 System (mixed-function oxidases). Reduction also occurs in this system NADPH-cytochrome P-450 reductase has an activity similar to microsomal nitroreductase, i.e. transformation of aronaatic nitro compounds into the corresponding arylamines takes place. The oxidation may be followed by other enzymic reactions, e.g. epoxides are hydrated to vicinal diols by microsomal epoxide hydratase or they are coupled with glutathione by glutathione-S-epoxide transferase. 

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