THE REACTIONS OF UNACTIVATED ARYL HALIDES WITH SODIUM METHOXIDE IN HMPA; SYNTHESIS OF PHENOLS, ANISOLES, AND METHOXYPHENOLS

Article abstract of DOI:10.1016/S0040-4020(01)97647-1

Sodium methoxide reacts with dichlorobenzenes in HMPA to give the chloroanisoles as a result of a S_NAr process.Excess MeONa then effects the demethylation of the ethers to give the chlorophenols via an S_N2 reaction.With tri- and tetrachlorobenzenes the initially formed chloroanisoles can be dealkylated to chlorophenols or can suffer further substitution to give the chlorodimethoxybenzenes; these react with excess MeONa to give the chloromethoxyphenols.The results obtained with the various isomers of the di-, tri-, and tetrachlorobenzenes are presented and discussed on the basis of the electronic effects of the substituents.