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14.11 : Acid Halides to Esters: Alcoholysis

Alcoholysis is a nucleophilic acyl substitution reaction in which an alcohol functions as a nucleophile. Acid halides react with alcohol to produce esters. The mechanism proceeds in three steps:

  1. First, the alcohol acts as a nucleophile and attacks the acyl carbon to form a tetrahedral intermediate.
  2. Next, the carbonyl re-forms with the loss of a chloride ion.
  3. Lastly, the positively charged intermediate loses a proton to give an ester as the final product along with H3O+, making HCl an overall byproduct of the reaction.

Figure1

Pyridine is used as a base to neutralize the acidic reaction mixture.

Alcoholysis of sulfonyl chlorides follows a similar pattern and forms sulfonic acid esters.

Figure2

Tags
AlcoholysisNucleophilic Acyl SubstitutionAcid HalidesEstersTetrahedral IntermediateCarbonylChloride IonProtonPyridineSulfonyl ChloridesSulfonic Acid Esters

From Chapter 14:

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14.11 : Acid Halides to Esters: Alcoholysis

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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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14.12 : Acid Halides to Amides: Aminolysis

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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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