AQUEOUS HIGH-TEMPERATURE CHEMISTRY OF CARBOCYCLE AND HETEROCYCLE .30.AQUATHERMOLYSIS OF PHENYL-SUBSTITUTED HYDROXYQUINOLINES

A range of phenylquinolones and hydroxy-substituted phenylquinolines w as synthesized and subjected to aquathermolysis in water alone, in 15% aqueous formic acid, and in 15% aqueous sodium formate at 315 and 460 degrees C. Thermal controls were obtained using cyclohexane as solven t. It was thought that the hydroxy substituent might provide a ''handl e'' of activation for subsequent ring opening, denitrogenation, and po ssible biaryl cleavage pathways. At 350 degrees C all substrates tende d to give mainly quinolines via deoxygenation as the main pathway. At 460 degrees C all substrates gave complex product slates with some rin g opening to lower molecular weight products. Some denitrogenation was observed via ring opening and further reaction. Decarbonylation to yi eld indoles was also noted as a competing reaction pathway to quinolin e ring opening. The indoles subsequently underwent ring opening reacti ons.