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Kinetics of the Alkylation and Acylation of Nickel Dipivaloyimethide (open access)

Kinetics of the Alkylation and Acylation of Nickel Dipivaloyimethide

Abstract: A study was made of the reactions of nickel dipivaloyimethide with the following reagents: tirphenylmethyl chloride, benzoyl chloride, [rho]-chloro and [rho]-methyl benzoyl chloride. Infrared spectra of the easily hydrolyzed product of tritylation seem to indicate that enol ether, the product of O-alkylation, is formed. the acyl halides reactor to give the triketones. the latter have been characterized by spectra and C, H, analysis. the kinetics of all the reactions studied were found to settle down to a second order rate law after a fast initial reaction. These reactions are catalyzed by an impurity in the acyl chloride. Then benzoyl chloride with a different purity was used, the second order rate constant for the benzoylation of nickel DPM ranged from 0.02-0.20. The air oxidation of nickel dipivaloymethide was found to compete with the acylations under the conditions of these studies. An investigation of the phenomenon showed that nickel pivalate is the major product. Pivalic acid was also detected in the product mixture. This oxidation takes place in chlorobenzene and in aromatic hydrocarbons. It occurs in 1201 when small amount on benzoyl chlorides are present.
Date: July 1959
Creator: Johnson, Kenneth Eugene & Hammond, George Simms, 1921-2005
System: The UNT Digital Library