AQUEOUS HIGH-TEMPERATURE CHEMISTRY OF CARBOCYCLES AND HETEROCYCLES .7. MONOSUBSTITUTED BENZENES WITH 2 CARBON-ATOM SIDE-CHAINS OXYGENATED AT THE ALPHA-POSITION AND BETA-POSITION

The aquathermolysis of monosubstituted benzenes with two carbon atom side chains oxygenated at both the α- and β-positions was studied. All the model compounds showed high reactivity in both water and cyclohexane. The α-keto and α-hydroxy acids showed mainly decarbonylation and decarboxylation reactions; loss of formic acid was also observed. For the acids, the α-keto aldehyde, and for the glycol disproportionation products are key intermediates for condensation and cyclization products. Mechanistic pathways are suggested in Schemes I-V for the formation of all products. A section tying together the reactivity trends and implications noted in the monosubstituted benzene series (parts 2 and 5-7) is included at the end of this paper. © 1990, American Chemical Society. All rights reserved.