Acetonitrile peroxydisulfate reactions

Oxidation of cyclohexene by peroxydisulfate in the presence of copper(II) salts results in the formation of cyclopentanecarboxaldehyde as the main product in an aqueous acetonitrile solution (equation 261), and 2-cyclohexenyl acetate in an acetic acid solution (equation 262).588,589 Reaction (261) has been interpreted as the formation of a radical cation (186) by oxidation of cyclohexene with S2Og, followed by hydrolysis of (186) to the /3-hydroxy alkyl radical (187), which is oxidized by copper(II) salts to the rearranged aldehydic product (188 equation 263).589... 

Marcoux and Adams have carried out a study of the anodic oxidation of a range of azines in acetonitrile at a platinum electrode.347 With the exception of pyridine which could not be oxidized under these conditions, all the other azines were oxidized in a complicated process in which one electron per molecule was transferred to the electrode. The reaction was investigated in some detail for acridine, and the main product was found to be an acridyl-acridinium perchlorate (perchlorate being supplied by the supporting electrolyte). This result, which is directly comparable with that for pyridine oxidation by peroxydisulfate is persuasive evidence for the mediation of the... 

Recently it has been shown that peroxydisulfate ion or, more correctly, S04 formed by homolytic fission of S2Os-, is a particularly convenient reagent for the oxidation of aromatics (including pyridine, benzene and chlorobenzene) in water or aqueous acetonitrile solutions (Ledwith and Russell, 1974a, b, c). These reactions have mechanistic significance in respect of the more complex oxidations outlined above and may be represented overall as in eqn (42). It is interesting that, generated in this manner, the arene cation... 

Ledwith and Russell (1974b) have found that chlorination of benzene, toluene and other aromatic molecules is easily achieved in aqueous acetonitrile containing sodium peroxydisulfate and copper(II) chloride. Toluene, for example, gives no benzyl chloride but a mixture of chlorotoluenes (58% o-, 4% m-, and 38% p-) consistent with the spin distribution in the toluene cation radical. The amount of copper chloride used can be catalytic provided another source of chloride ion (LiCl) is added. Reaction is attributed to the very fast transfer of chlorine atom from copper(II) chloride to the cation radical (132) the metal halide is thus regarded as a trap for the aromatic cation radical. In the absence of copper(II) chloride, reactions of toluene with peroxydisulfate ion and chloride ion give... 

A study involving the peroxydisulfate oxidation products of the antimalarial drug primaquine (e.g., 6-methoxy-5,8-di-[4-amino-r-methylbuylamino]quinoline, N -tri-[4-amino-l-methylbutyl]amine) utilized a C,g colunrn (A = 254nm) and a 95/30/7/1 water/acetonitrile/methanol/water (IM perchloric acid) mobile phase [1497]. Primaquine dimers were also studied. The study followed the reaction of 250 pg/mL primaquine. All products were easily detectable. 

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