Aromatic Radical Nucleophilic Substitution Reactions Initiated by Sodium Amalgam in Liquid Ammonia

Article abstract of DOI:10.1021/jo00014a030

Neither 1-chloronaphthalene nor 2-chloroquinoline reacted with Ph2P^- ions in liquid ammonia.However, in the presence of sodium amalgam , reaction did occur, and the substitution products 1-naphthyldiphenylphosphine and 2-quinolinyldiphenylphosphine (isolated as the P-oxides), respectively, were obtained in good yield. p-Bromoanisole reacted with Na(Hg) amalgam in the presence of Ph2C^- ions in liquid ammonia to give anisole as the only product, but when benzonitrile was used as a redox catalyst, a good yield of the substitution product p-anisyldiphenylphosphine (isolated as the P-oxide) was obtained.It is believed that Na(Hg) amalgam initiated these S_RN1 reactions.Preparative-scale reactions gave good yields of the substitution products.