Ketone synthesis by Gilman and van Ess

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The ketone synthesis by Gilman and van Ess is a name reaction in organic chemistry , which was named after Henry Gilman (1893-1986) and Paul R. van Ess and published in 1933. The reaction is a method of converting a carboxylic acid into a ketone .

Overview reaction

The carboxylic acid is converted to a ketone by reaction with a lithium alkyl compound and subsequent hydrolysis :

Overview of the ketone synthesis by Gilman and van Ess

mechanism

In the first step, the carboxylic acid reacts with a lithium alkyl compound , the carboxylic acid being deprotonated and the oxygen atom of the alcohol group attacking the lithium atom . Then another lithium alkyl compound is added, the lithium atom attaching to the oxygen atom of the carbonyl group . The alcoholate is protonated and hydrolyzed . In the last step, water is split off and a ketone is formed .

Mechanism of ketone synthesis by Gilman and van Ess

literature

  • Alfred Hassner, C. Stumer: Organic Syntheses Based on Name Reactions (=  Tetrahedron organic chemistry series . Volume 22 ). Elsevier, 2002, ISBN 978-0-08-043259-5 , pp. 130 ( limited preview in Google Book search).

Individual evidence

  1. ^ Henry Gilman, Paul R. van Ess: The Preparation of Ketones by the Carbonation of Organolithium Compounds In: Journal of the American Chemical Society . 55, No. 3, 1933, pp. 1258-1261, doi: 10.1021 / ja01330a070 .