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14.12 : Acid Halides to Amides: Aminolysis

Aminolysis is a nucleophilic acyl substitution reaction, where ammonia or amines act as nucleophiles to give the substitution product. Acid halides react with ammonia, primary amines, and secondary amines to yield primary, secondary, and tertiary amides, respectively.

In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride ion. In the last step, the amide nitrogen is deprotonated by another equivalent of the amine to give the final substitution product.

Figure1

If the amine is expensive, the reaction is performed with one equivalent of the amine and a second equivalent of an inexpensive base like triethylamine, pyridine, or sodium hydroxide.

Tags
Acid HalidesAminolysisNucleophilic Acyl SubstitutionAmmoniaAminesPrimary AmidesSecondary AmidesTertiary AmidesTetrahedral IntermediateChloride IonDeprotonationTriethylaminePyridineSodium Hydroxide

From Chapter 14:

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14.12 : Acid Halides to Amides: Aminolysis

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14.1 : Carboxylic Acid Derivatives: Overview

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14.2 : Nomenclature of Carboxylic Acid Derivatives: Acid Halides, Esters, and Acid Anhydrides

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14.3 : Nomenclature of Carboxylic Acid Derivatives: Amides and Nitriles

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14.4 : Structures of Carboxylic Acid Derivatives

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14.5 : Physical Properties of Carboxylic Acid Derivatives

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14.6 : Acidity and Basicity of Carboxylic Acid Derivatives

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14.7 : Spectroscopy of Carboxylic Acid Derivatives

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14.8 : Relative Reactivity of Carboxylic Acid Derivatives

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14.9 : Nucleophilic Acyl Substitution of Carboxylic Acid Derivatives

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14.10 : Acid Halides to Carboxylic Acids: Hydrolysis

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14.11 : Acid Halides to Esters: Alcoholysis

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14.13 : Acid Halides to Alcohols: LiAlH<sub>4</sub> Reduction

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14.14 : Acid Halides to Alcohols: Grignard Reaction

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14.15 : Acid Halides to Ketones: Gilman Reagent

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