AQUEOUS HIGH-TEMPERATURE CHEMISTRY OF CARBOCYCLES AND HETEROCYCLES .1. INTRODUCTION AND REACTION OF 3-PYRIDYLMETHANOL, PYRIDINE-3-CARBOXALDEHYDE, AND PYRIDINE-3-CARBOXYLIC ACID

A standard set of conditions for the study of the aquathermolysis of carbo- and heterocyclic compounds are defined. Pyridine and 3-methylpyridine are stable at 250 °C, but pyridine-3-carboxylic acid, pyridine-3-carboxaldehyde, and 3-pyridylmethanol all undergo cleavage to form pyridine with the release of CO2, HCO2H, and HCHO, respectively. These 3-substituted pyridines also all undergo reduction by HCO2H and/or HCHO to give finally 3-methylpyridine. 3-Pyridylmethanol disproportionates to the aldehyde and 3-methylpyridine, and the aldehyde and methanol subsequently undergo an aldol-type condensation to afford bis(3-pyridyl)methane and 1, 2-(bis-3-pyridyl)ethane after further transformations. The aqueous geochemical implications of this chemistry to maturation of source rock kerogens are discussed. © 1990, American Chemical Society. All rights reserved.