Reductive ethylation in ethereal solvents

Organic compounds, in particular anthracene and naphthalene, and two coals have been reductively ethylated in tetrahydrofuran (THF) and diglyme using alkali metals to form anions and ethyl iodide to produce ethylates. Product distributions were sensitive to experimental conditions. The rate of anion formation was controlled by their rate of desorption, probably as contact ion pairs, from the alkali metal surface. The enthalpy of formation of a solvated contact ion pair was ?500 kJ mole-1 mainly due to dipole-solvent interaction. 18-crown-6 ether was used to diagnose that, when treated with potassium in THF, anthracepe gave solvated contact ion pairs and probably di-anions whose reactions were characterized by the formation of ethyldihydroanthracene. Naphthalene under identical conditions gave loosely solvated mono-anions which reacted by electron transfer to give diethyldihydronaphthalene. With other alkali metals anthracene and naphthalene gave similar product distributions. The behaviour of other polynuclear aromatic hydrocarbons and of two coals was classified in the same way. It is suggested that when coals are readily solubilized by reductive alkylation mono-alkyldihydro products will predominate. © 1984. Connecticut State Emergency Response Commission A~KNOWLED~E~E~S The authorsa reg ratefult o N. Owen for hisc onstanth elp. 0. Erbaturh asr eceivedg enerouss upportf rom theB ritish Council and the OverseasD eveIopmentA dministration. The work formsp art of a project,‘ The Chemistryo f Solid Fuels’ supportedb y the SERC.