Journal of the American Chemical Society p. 2799 - 2805 (1984)
Update date:2022-08-11
Topics:
Koppang, Miles D.
Woolsey, Neil F.
Bartak, Duane E.
The radical anions of three isomers of cyanoanisole have been electrochemically generated and subsequently shown to react by at least three different reaction pathways in dry N,N-dimethylformamide (DMF).The o-cyanoanisole radical anion (Epc = -2.3 V vs.SCE) dimerizes (k2 = 3.2*102 M-1 s-1) to form an intermediate dimeric dianion.The dianion, which can be oxidized (Epa = -1.1 V vs.SCE), undergoes a slow intramolecular disproportionation reaction to form o-cyanophenoxide ion, methide ion, and unreduced substrate (k3 = 1.9*10-2 s-1).Subsequent protonation results in the formation of methane and p-cyanophenol in an overall two-electron process.The m-cyanoanisole radical anion (Epc = -2.3 V vs.SCE) is very stable (t1/2 > 103 s) under anhydrous DMF conditions.Overall, slow carbon-carbon bond cleavage with loss of cyanide occurs competitively with β-carbon-oxygen bond cleavage to produce anisole and m-cyanophenol, respectively.The final products of the reduction of p-cyanoanisole are p-cyanophenol and methane; however, the radical anion of p-cyanoanisole (Epc = -2.5 V vs.SCE) undergoes a relatively rapid unimolecular fragmentation reaction (k1 = 7 s-1).The initial products of the fragmentation are p-cyanophenoxide ion and the methyl radical, which is reduced further to methide ion.Hydrogen atom abstraction reactions by the methyl radical can also occur in the bulk solution to produce methane.
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