The Suzuki–Miyaura cross-coupling reaction using heterogeneous Pd/C has a homogeneous component. The soluble palladium concentration increases during the reaction reaching a maximum at ca. 90% conversion before falling to <4 ppm.
The reactions of acrylonitrile, crotonitrile, propionitrile, and a small set of related reaction products were investigated in high-temperature water. Hydrolysis of the cyano group yielded the corresponding amides, which underwent similar hydrolysis to yield the carboxylic acids. The conversion of acrylonitrile was more rapid than that of its saturated analogue propionitrile, as the unsaturated site of acrylonitrile provided a facile pathway for the formation of alcohols, amines, and ethers. Carbon-carbon bond cleavage pathways involving the hydration of the olefin moiety were also observed for acrylonitrile.
The reaction pathways, kinetics and mechanisms underlying the hydrolysis of aliphatic and aromatic nitriles in high-temperature water (HTW) were investigated. The reaction products were the associated amides and carboxylic acids. Autocatalytic kinetics were observed and confirmed by experiment and analysis of the physical chemistry of the HTW reaction environment. A model incorporating two autocatalytic steps captured the observed kinetics well, and the associated optimized rate constants highlighted the key differences in the reaction chemistry of aliphatic and aromatic nitriles. The rate behavior of nitrile hydrolysis at these conditions has tangible consequences regarding optimal processing strategies.