石炭モデル化合物の還元と還元アルキル化反応 Ｉ ２環と３環芳香族化合物の還元と還元メチル化反応

Abstract

In order to elucidate the coal solubilization mechanism by reductive alkylation, six coal-related polyaromatic compounds (PAHs) were treated in M/THF/CH3I and M/NH3-THF/CH3I systems (M: Li, Na and K). In the K/THF system, acenaphthylene and anthracene, which posess high electron affinities, form dianions readily whilst naphthalene, acenaphthene and phenanthrene formed almost dianions after 72hr.The reduction and reductive methylation products were analyzed by GC and GC-MS in detail. Protons and methyl groups occupied positions of highest electron density in the dianions as calculated by HMO theory. The reaction in liquid ammonia was more reactive than in THF. Product distributions were characteristic of PAHs. The products were typed into reduction, reductive methylation, methylation, reductive dimerization and other compounds. The conversion in the K/THF/CH3I system increased in the order of acenaphthylene, acenaphthene, fluorene>anthracene>naphthalene>phenanthrene and in the K/NH3-THF/CH3I system the conversion was almost 100% except phenanthrene. The study of changing the concentration of PAHs and the kind of metals showed potassium as superior reducing metal for PAHs conversion.