Aqueous high-temperature chemistry of carbo- and heterocycles. 12. Benzonitriles and pyridinecarbonitriles, benzamides and pyridinecarboxamides, and benzylamines and pyridylamines

Nitrile reaction in high‐temperature water: Kinetics and mechanism

“…Most studies have focused attention on the overall destruction efficiencies, with less analysis of the underlying reaction pathways and quantitative kinetics. More specific study of nitriles in a hydrothermal environment is limited to the work by Katritzky and coworkers on benzonitrile and pyridinecarbonitriles (Katritzky et al, 1990). Two-phase benzonitrile hydrolysis at 250°C yielded the amide and carboxylic acid with some degree of decarboxylation of the acid.…”

Microwave‐Assisted Organic Synthesis in Near‐Critical Water at 300 °C –A Proof‐of‐Concept Study

“…The hydrolysis of benzamide (Scheme ) under NCW conditions has been investigated on several occasions, most notably by the groups of Katritzky22 and Vogel 23. Katritzky and co‐workers22 studied this hydrolysis with conventional thermal heating, both in superheated cyclohexane and in NCW. In cyclohexane at 250 °C after 5 d, 74 % of the starting benzamide, 22 % of benzonitrile by‐product, and only 4 % of the desired benzoic acid were isolated.…”

Hydrothermal Liquefaction to Convert Biomass into Crude Oil

“…Benzonitriles, pyridinecarbonitriles, benzamides, and pyridinecarboxamides are almost unaffected by thermolysis, but are rapidly hydrolyzed in water at 250 ° C to the corresponding ammonium carboxylates (the nitriles via the amides). The ammonia formed autocatalyzes these hydrolysates and the subsequent decarboxylations (Katritzky et al 1990 ). In the formation and depolymerization of resource materials, autocatalysis appears to be a major mechanistic pathway.…”