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The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

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John W. Nicholson

School of Natural Science, University of Greenwich, Chatam, Kent ME4 4TB, United Kingdom

Alan D. Wilson

Materials Technology Group, Laboratory of the Government Chemist (Retired), London, United Kingdom

J. Chem. Educ., 2004, 81 (9), p 1362

DOI: 10.1021/ed081p1362

Publication Date (Web): September 1, 2004

Section:

History, Education, and Documentation

Abstract

This article describes the history of the reaction converting carboxylic acids to ketones. The reaction has been rediscovered several times, yet has actually been known for centuries. The best known version of the process is the Dakin–West reaction (1928), which applies to α-amino acids and also involves the simultaneous conversion of the amine group to amido functionality. Unlike other examples, this particular reaction has attracted a reasonable amount of attention and it appears to be better known than the conversion of simple carboxylic acids to ketones. However, this reaction was described as long ago as 1612, when Beguin published an account of it in his book, Tyrocinium Chymicum. Since then, many chemists have rediscovered the reaction, apparently independently. One of the earliest modern accounts was by W. H. Perkin, Sr., in 1886, who made various simple ketones by refluxing the appropriate carboxylic acids with base. However, this work has been largely ignored, including by his son, W. H. Perkin, Jr., who used a more complicated base-catalyzed ketonization to prepare small ring compounds in the early years of the 20th century. Other articles detailing the application of ketonization to organic acids are discussed, including our own work, which employed the process to crosslink carboxylated polymers for possible technical application in coatings. Despite its relative obscurity, the reaction was used by Woodward et al. in the total synthesis of strychnine, reported in 1963, and this is discussed in detail at the end of the article.

Keywords (Audience):

Second-Year Undergraduate

Keywords (Domain):

Organic Chemistry

Keywords (Subject):

Synthesis

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This article has been cited by 2 ACS Journal articles (2 most recent appear below).

Cyanocuprates Convert Carboxylic Acids Directly into Ketones
Douglas T Genna and Gary H. Posner
Organic Letters2011 13 (19), 5358-5361
- Cyanocuprates Convert Carboxylic Acids Directly into Ketones
  Douglas T Genna and Gary H. Posner
  Organic Letters2011 13 (19), 5358-5361
  Carboxylic acids were converted directly in 56–99% yields into methyl, n-butyl, and isopropyl ketones using excess cyanocuprates R2CuLi·LiCN. A substrate with a stereocenter α to the carboxylic acid was converted into ketones with very little loss of ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Dakin−West Synthesis of β-Aryl Ketones
Khanh-Van Tran and David Bickar
The Journal of Organic Chemistry2006 71 (17), 6640-6643
- Dakin−West Synthesis of β-Aryl Ketones
  Khanh-Van Tran and David Bickar
  The Journal of Organic Chemistry2006 71 (17), 6640-6643
  Triethylamine and 1-methylimidazole were found to be selective catalysts for the DakinWest synthesis of diaryl ketones and aryl methyl ketones, respectively. In the 1-methylimidazole-catalyzed reaction, catalysis is due to the simultaneous formation of ...
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