ORTHO-SUBSTITUTED CHLOROBENZENES RELATED TO METAMECONINE

Chlorinated derivatives of metameconine were formed for the first time. Partial demethylation of the derivatives with sulphuric acid occurred in highly selective fashion at the methoxyl ortho to the halogen, without regard to the relative position of the carbonyl group which is known to be highly directive for demethylations in the absence of halogen. The phenolic products of the demethylations are needed for the synthesis of sterically hindered diphenyl ethers. They showed a type of intermolecular hydrogen bonding in the crystal which was markedly subject to steric interference by the halogen atoms.