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13.17 : Loss of Carboxy Group as CO2: Decarboxylation of Malonic Acid Derivatives

Just like β-keto acids—which upon thermal decarboxylation form ketones—β-dicarboxylic acids undergo decarboxylation to generate monocarboxylic acids with the liberation of carbon dioxide.

Figure1

The mechanism initiates with an internal electronic redistribution, resulting in a cyclic six-membered transition state. This is followed by a C–C bond cleavage to produce an enol by releasing carbon dioxide gas. Next, the enol rapidly tautomerizes under the acidic conditionsto yield a more stable monocarboxylic acid.

Figure2

In malonic ester synthesis, the key step is the decarboxylation of malonic acid, wherein alkyl halides are converted to monocarboxylic acids.

Figure3

Tags
DecarboxylationMalonic Acid DerivativesCarbon Dioxide LiberationKeto AcidsDicarboxylic AcidsMonocarboxylic AcidsCyclic Transition StateC C Bond CleavageEnol FormationTautomerizationAcidic ConditionsMalonic Ester SynthesisAlkyl Halides

From Chapter 13:

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13.17 : Loss of Carboxy Group as CO2: Decarboxylation of Malonic Acid Derivatives

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13.1 : IUPAC Nomenclature of Carboxylic Acids

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13.2 : Physical Properties of Carboxylic Acids

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13.3 : Acidity of Carboxylic Acids

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13.4 : Substituent Effects on Acidity of Carboxylic Acids

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13.5 : IR and UV–Vis Spectroscopy of Carboxylic Acids

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13.6 : NMR and Mass Spectroscopy of Carboxylic Acids

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13.7 : Preparation of Carboxylic Acids: Overview

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13.8 : Preparation of Carboxylic Acids: Hydrolysis of Nitriles

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13.9 : Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents

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13.10 : Reactions of Carboxylic Acids: Introduction

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13.11 : Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview

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13.12 : Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism

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13.13 : Carboxylic Acids to Methylesters: Alkylation using Diazomethane

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13.14 : Carboxylic Acids to Acid Chlorides

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