Arylamines oxidation potential

Trifluoroacetic acid (CF3CO3H) sits between peroxyacetic acid and peroxydisulfuric acid in oxidizing potential. Anhydrous solutions of peroxytrifluoroacetic acid in methylene chloride can be prepared by the addition of 90 %+ hydrogen peroxide to a solution of trifluoroacetic anhydride in methylene chloride containing a trace of sulfuric acid. Solutions of peroxytrifluoroacetic acid prepared from less concentrated hydrogen peroxide solution or trifluoroacetic acid are less reactive to arylamines. 

Heteroatom (O and N) attachment to the C8-site of dG to form 8-oxo-dG and C8-arylamine adducts lowers the oxidation potential relative to dG. The oxidation potential of 8-oxo-dG is 0.74 V versus NHE. Consequently, 8-oxo-dG can act as a deep radical cation trap within duplex DNA. Depending on the DNA sequence, an 8-oxo-dG lesion will be the preferential site of further oxidation and will protect isolated Gs and GG steps from oxidation the oxidation of 8-oxo-dG by G(—H) occurs with a rate of 4.6 x 10 /M/s. Thus, there is speculation that GC-rich domains outside the coding regions of genes serve to protect the genome from mutagenesis by oxidation. ... 

There has been a review of the effects of high pressure on the substitution reactions of amines with haloaromatic compounds, including polyhalobenzenes.17 Nucleophilic substitutions by amines often proceed readily in dimethyl sulfoxide (DMSO). The pAa values, in DMSO, have been reported for some ammonium ions derived from amines widely used as nucleophiles in, S Ar reactions.18 Correlations have been established19 between the oxidation potentials and the basicities of some arylamine and diarylamine anions and the rate constants for their reactions with aryl halides in DMSO. 

As noted for heteroatom attachment in 8-oxo-dG and C8-arylamine adducts, attachment of the Ph moiety to the C-8 site of dG enhances the one-electron donor characteristics of the purine nucleoside. The redox properties of 8-/>-X-Ph-dG (X = OH, OCH3, CH3, H, CN, CHO) adducts have been studied by cyclic voltammetry in anhydrous DMF. The C8-aryl adducts exhibited irreversible one-electron oxidation peaks with half-peak potentials ( p/2) ranging from 0.85 V versus saturated calomel electrode (SCE) for 8-/>-PhOH-dG (X = OH) up to 1.11 V/SCE for 8- -CHO-Ph-dG. All adducts were oxidized more readily than dG, which gave p/2= 1.14 V/SCE in DMF (Table 2). 

The iodine oxidative closure of iron tricarbonyl complex 299 (R = H and Me), itself prepared by the reaction of an arylamine with the tricarbonyl-(cyclohexadienyl)iron cation, may have potential as a method. ... 

Arylamines display electronic properties that are favorable for materials science. In particular, arylamines are readily oxidized to the aminium form, and this leads to conductivity in polyanilines, hole-transport properties in triarylamines, stable polyradicals with low energy or ground-state, high-spin structures, and the potential to conduct electrochemical sensing. The high yields of the palladium-catalyzed formation of di- and triarylamines has allowed for ready access to these materials as both small molecules and discrete oligomeric or polymeric macromolecules. 

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