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Chapter 14

Carboxylic Acid Derivatives

Carboxylic Acid Derivatives: Overview
Carboxylic Acid Derivatives: Overview
Carboxylic acid derivatives are formed by replacing the hydroxyl group of carboxylic acids with a different functional group. The most common carboxylic ...
Nomenclature of Carboxylic Acid Derivatives: Acid Halides, Esters, and Acid Anhydrides
Nomenclature of Carboxylic Acid Derivatives: Acid Halides, Esters, and Acid Anhydrides
Naming Acid Halides The IUPAC and common names of acid halides are derived from the corresponding carboxylic acids, by changing “ic acid” to ...
Nomenclature of Carboxylic Acid Derivatives: Amides and Nitriles
Nomenclature of Carboxylic Acid Derivatives: Amides and Nitriles
Naming Amides The IUPAC and common names of amides are derived from the parent carboxylic acid, by replacing the suffix “oic acid” and ...
Structures of Carboxylic Acid Derivatives
Structures of Carboxylic Acid Derivatives
Structure of Carboxylic Acid Derivatives Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or ...
Physical Properties of Carboxylic Acid Derivatives
Physical Properties of Carboxylic Acid Derivatives
Intermolecular forces dictate several physical properties such as boiling points, melting points, solubilities, and so forth. They are classified into ...
Acidity and Basicity of Carboxylic Acid Derivatives
Acidity and Basicity of Carboxylic Acid Derivatives
Carboxylic acids are the strongest among organic acids, as they readily lose the hydroxyl proton to form a resonance-stabilized carboxylate ion. In ...
Spectroscopy of Carboxylic Acid Derivatives
Spectroscopy of Carboxylic Acid Derivatives
Infrared spectroscopy is primarily used to determine the types of bonds and functional groups. In carboxylic acid derivatives, a typical carbonyl bond ...
Relative Reactivity of Carboxylic Acid Derivatives
Relative Reactivity of Carboxylic Acid Derivatives
Carboxylic acid derivatives such as acid halides, anhydrides, esters, and amides undergo nucleophilic acyl substitution reactions with varying degrees of ...
Nucleophilic Acyl Substitution of Carboxylic Acid Derivatives
Nucleophilic Acyl Substitution of Carboxylic Acid Derivatives
Nucleophilic acyl substitution is an important class of substitution reactions involving a nucleophile and an acyl compound, such as carboxylic acids and ...
Acid Halides to Carboxylic Acids: Hydrolysis
Acid Halides to Carboxylic Acids: Hydrolysis
Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction ...
Acid Halides to Esters: Alcoholysis
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 ...
Acid Halides to Amides: Aminolysis
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 ...
Acid Halides to Alcohols: LiAlH<sub>4</sub> Reduction
Acid Halides to Alcohols: LiAlH4 Reduction
Acid halides are reduced to alcohols in the presence of a strong reducing agent like lithium aluminum hydride. The mechanism proceeds in three steps. ...
Acid Halides to Alcohols: Grignard Reaction
Acid Halides to Alcohols: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert acid halides to tertiary alcohols. The reaction requires two equivalents of the ...
Acid Halides to Ketones: Gilman Reagent
Acid Halides to Ketones: Gilman Reagent
Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at ...
Preparation of Acid Anhydrides
Preparation of Acid Anhydrides
One of the methods for preparing symmetrical or unsymmetrical acid anhydrides involves the treatment of acid chlorides with the sodium salt of carboxylic ...
Reactions of Acid Anhydrides
Reactions of Acid Anhydrides
The reactions of acid anhydrides are analogous to the reactions of acid chlorides and proceed via a nucleophilic acyl substitution. They only differ in ...
Esters to Carboxylic Acids: Saponification
Esters to Carboxylic Acids: Saponification
Esters can be hydrolyzed to carboxylic acids under acidic or basic conditions. Base-promoted hydrolysis of esters is a nucleophilic acyl substitution ...
Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
Hydrolysis of esters under acidic conditions proceeds through a nucleophilic acyl substitution. In the presence of excess water, the reaction proceeds in ...
Esters to Alcohols: Hydride Reductions
Esters to Alcohols: Hydride Reductions
Esters are reduced to primary alcohols when treated with a strong reducing agent like lithium aluminum hydride. The reaction requires two equivalents of ...
Esters to Alcohols: Grignard Reaction
Esters to Alcohols: Grignard Reaction
The reaction of an ester with a Grignard reagent, followed by hydrolysis of the magnesium alkoxide salt in aqueous acid, yields a tertiary alcohol. In the ...
Preparation of Amides
Preparation of Amides
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC). The ...
Amides to Carboxylic Acids: Hydrolysis
Amides to Carboxylic Acids: Hydrolysis
Amides can undergo either acid-catalyzed hydrolysis or base-promoted hydrolysis through a typical nucleophilic acyl substitution. Each hydrolysis requires ...
Amides to Amines: LiAlH<sub>4</sub> Reduction
Amides to Amines: LiAlH4 Reduction
Amide reduction with strong reducing agents like lithium aluminum hydride proceeds through a nucleophilic acyl substitution to form amines. Primary, ...
Preparation of Nitriles
Preparation of Nitriles
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or ...
Nitriles to Carboxylic Acids: Hydrolysis
Nitriles to Carboxylic Acids: Hydrolysis
Nitriles undergo acid-catalyzed hydrolysis or base-catalyzed hydrolysis to form a carboxylic acid. These reactions proceed via an amide intermediate. The ...
Nitriles to Ketones: Grignard Reaction
Nitriles to Ketones: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles ...
Nitriles to Amines: LiAlH<sub>4</sub> Reduction
Nitriles to Amines: LiAlH4 Reduction
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. ...
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