SRN1 reactions electrochemical induction

Alkoxide or aryloxide anions are also reputed to be inactive in SRN1 reactions. There is, however, one example of such a reaction at an sp3 carbon the nitro-derivative of 4-nitrocumyl reacts with phenoxide and 1-methyl-2-naphthoxide ions yielding the corresponding ethers (Kornblum et al., 1967). A similar reaction has been reported for halobenzenes in t-butyl alcohol upon stimulation by sodium amalgam (Rajan and Sridaran, 1977). This reaction could not, however, be reproduced (Rossi and Pierini, 1980) and other attempts to make phenoxide ions react at sp2 carbons have been equally unsuccessful (Ciminale et al., 1978 Rossi and Bunnett, 1973 Semmelhack and Bargar, 1980). It has been found, more recently, that phenoxide ions react with a series of aryl halides under electrochemical induction, but that the coupling occurs at the p- or o-phenolic carbon rather than at the phenolic oxygen (Alam et al., 1988 Amatore et al., 1988). This is... 

Electrochemical induction of the reaction (Pinson and Saveant, 1974), as shown to occur in a number of cases with aromatic and heteroaromatic substrates (Saveant, 1980a, 1986, 1988), also provides evidence for the SRN1 mechanism. The electrochemical approach allows, in addition, a quantitative analysis of the mechanism and reactivity problems and will be described in this connection in the next subsection. 

Fig. 17 Indirect electrochemical induction of SRN1 reactions. Cyclic voltammetry of (a) 4-cyanopyridine (2.2 mM) in the absence (—) and presence (—) of 8.9 mM 2-chlorobenzonitrile (b) 4-cyanopyridine (6.6 mM) in the presence of 8.9 mM 2-chloro-benzonitrile and 35mM PhS. (Adapted from Amatore et al., 1984b.)...

On the other hand, analysis of the cyclic voltammetric data pertaining to the direct and indirect electrochemical induction of SRN1 reactions by means... 

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