AQUEOUS-ORGANIC CHEMISTRY .6. REACTIVITY OF HYDROXYNAPHTHALENES

Hydroxyaromatics are abundant in lignite and subbituminous coals. Clea vage of ethers in coals generates additional hydroxyaromatics. Reducti on of the carbonyl intermediates of these hydroxyaromatics in 15% form ic acid or 15% sodium formate provides hydrogenated species which can act as hydrogen donors during coal liquefaction. At 315-degrees-C over a period of 3 days, 1- and 2-hydroxynaphthalenes showed little change under simple thermolytic or aquathermolytic conditions. These compoun ds underwent reduction to a small extent on aquathermolysis in 15% for mic acid and to a larger extent in 15% sodium formate. 1,2-, 1,3-, 1,4 -, and 2,3-Dihydroxynaphthalenes were all highly reactive at 315-degre es-C in all four systems (cyclohexane, water, 15% formic acid, and 15% HCO2Na). The major products resulted from dehydroxylation or decarbon ylation followed by ring opening, and self-condensation. In the presen ce of reducing agents (HCO2H or HCO2Na), large amounts of indane, tetr alin, naphthalene, and methylated hydroxynaphthalenes resulted. 1,4-Di methoxynaphthalene underwent ether cleavage and was transformed into v arious mono- and dihydroxynaphthalenes. Some of the hydroxynaphthalene products had been C-methylated. In the presence of HCO2Na, large amou nts of reduction products were obtained.