AQUEOUS ORGANIC-CHEMISTRY .1. AQUATHERMOLYSIS - COMPARISON WITH THERMOLYSIS IN THE REACTIVITY OF ALIPHATIC-COMPOUNDS

The first report in this series describes a scoping study on a set of n-C10 aliphatic compounds with structures representative of those found in oil shale kerogens. 1-Decene underwent acid-catalyzed double bond isomerization and dimerization reactions, and 1-decyne was hydrated under aquathermolysis conditions. Acid-catalyzed aldol condensation reactions were observed for 1-decanal and 2-decanone, and the major products were α,β-unsaturated aldehydes and ketones. Decyl decanoate was four times more reactive with water than thermally at 250 °C and readily hydrolyzed to the corresponding carboxylic acid and alcohol. 1-Decanenitrile readily hydrated to 1-nonanecarboxamide, which then underwent further hydrolysis to 1-decanoic acid and ammonium hydroxide. The ammonium hydroxide will autocatalyze the hydrolysis of both the 1-decanenitrile and 1-decanamide. 1-Decylamine was converted thermally to the corresponding decanenitrile, and under aqueous conditions self-condensation took place to provide didecylamine and tridecylamine. The thermolysis of 1-decanethiol was found to be the source for hydrogen sulfide evolution during reaction to form dialkyl sulfides. In simulated maturation environments water can act as an amphoteric catalyst promoting ionic reaction pathways at high temperature for bonds that are not thermally labile. The presence of brine and clay facilitated the observed ionic chemistry and specific acid-catalyzed reactions. Reactivity is also facilitated by autocatalysis by water-soluble products. © 1990, American Chemical Society. All rights reserved.