Organic Chemistry by Brown, Iverson, Anslyn, Foote | Mayya's Study Guide | Chapter 18

Updated: Aug 31, 2023

Chapter 18: Functional Derivatives of Carboxylic Acids

Table of Contents:

  1. Structure

  2. Acidity of Amides, Imides, and Sulfonamides

  3. Characteristic Reactions

  4. Reaction with Water: Hydrolysis

  5. Reaction with Alcohols

  6. Reactions with Ammonia and Amines

  7. Reaction of Acid Chlorides with Salts of Carboxylic Acids

  8. Reactions with Organometallic Compounds

  9. Reduction

Structure

carboxylic acid derivatives

Acidity of Amides, Imides, and Sulfonamides

Characteristic Reactions

Under basic conditions, the nucleophile attacks the carbonyl carbon pushing electrons up to the oxygen. Under acidic conditions, oxygen first gets protonated which is followed by the nucleophile attack.

reactivity of carboxylic acid derivatives

Reactions With Water: Hydrolysis

Acid Chloride or Anhydride with H2O = Carboxylic Acid

Reaction of acid chloride or anhydride with water

Mechanism

mechanism for conversion of acid chloride into carboxylic acid

Hydrolysis of Esters

Esters can be converted into carboxylic acids under acidic or basic conditions.

hydrolysis of esters

Mechanisms

Mechanism Of Ester Hydrolysis In Acid

Mechanism Of Ester Hydrolysis In Base

Hydrolysis of Amides

Hydrolysis of Amides

Hydrolysis of Nitriles

Hydrolysis of Nitrile

Reactions With Alcohols

Acid Chloride or Anhydride with Alcohol = Ester

Reaction of acid chloride or anhydride with alcohols

Transesterification

Transesterification

Note: Amides do NOT react with alcohols.

Reactions With Ammonia and Amines

Acid Chloride or Anhydride or Ester with an Amine = Amide

Note: Amides do NOT react with amines.

Reaction of Acid Chlorides with Salts of Carboxylic Acids

Reactions With Organometallic Reagents

Grignard and organolithium reagents react twice with esters or acid chlorides to give tertiary alcohols.

Reactions of Acid Chlorides and Esters With Organometallic Reagents

Ester with Grignard Reagent Mechanism

Ester with Grignard Reagent Mechanism

How to predict the reactants from the product of Ester with Grignard?

Mayya's Trick

If you see the product is a tertiary alcohol with two identical R groups, then it could've come from the reaction of ester or acid chloride with Grignard reagent or organolithium.

To go back:

  1. Break the bonds between COH and two R groups attached to it.

  2. Turn OH into =O and add MgBr or Li to the carbons broken off. Second step is acid/water.

How to predict the reactants from the product of Ester with Grignard?

Reaction of Acid Chlorides with Gilman Reagent (organocuprate)

Reaction of Acid Chlorides with Gilman Reagent

Reduction

Reduction of Acid Chloride, Esters and Carboxylic Acids with LiAlH4

Lithium aluminum hydride can be used to reduce esters, acid chlorides and carboxylic acids to alcohols.

Reduction of acid chlorides, carboxylic acids and esters using LiAlH4

Mechanism of Ester with LiAlH4

Mechanism of Ester with LiAlH4

Reduction of Amides with LiAlH4

Lithium aluminum hydride can be used to reduce amides to amines.

Reduction of Amides with LiAlH4.

Reduction of Nitrile with LiAlH4

Lithium aluminum hydride can be used to reduce nitriles (CN) into amines (CH2NH2).

Reduction of Nitrile with LiAlH4

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