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Kinetics of the Alkylation and Acylation of Nickel Dipivaloyimethide

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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 … continued below

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v, 59 pages ; illustrations.

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Johnson, Kenneth Eugene & Hammond, George Simms, 1921-2005 July 1959.

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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.

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v, 59 pages ; illustrations.

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Digitized from microopaque cards.

Work performed under Contract No. W-7405-eng-82.

This report is based on a PhD. thesis by K. E. Johnson submitted July, 1959, to Iowa State University, Ames, Iowa. This work was done under contract with the Atomic Energy Commission.

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  • Report No.: IS-215
  • Grant Number: W-7405-eng-82
  • SuDoc Number: Y 3.At 7:22/IS-215
  • Accession or Local Control No: metadc1201467
  • Archival Resource Key: ark:/67531/metadc1201467

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  • July 1959

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  • Feb. 9, 2020, 2:12 p.m.

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  • April 24, 2020, 1:34 p.m.

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Johnson, Kenneth Eugene & Hammond, George Simms, 1921-2005. Kinetics of the Alkylation and Acylation of Nickel Dipivaloyimethide, report, July 1959; Oak Ridge, Tennessee. (https://digital.library.unt.edu/ark:/67531/metadc1201467/: accessed April 24, 2025), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.

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