Textbook Question
An aqueous solution of a primary or secondary amine reacts with an acyl chloride to form an amide as the major product. However, if the amine is tertiary, an amide is not formed. What product is formed? Explain.
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Ch. 15 - Reactions of Carboxylic Acids and Carboxylic Acid Derivatives
Bruice8th EditionOrganic ChemistryISBN: 9780135213711
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Table of contents
- Ch. 1 - Remembering General Chemistry: Electronic Structure and Bonding (Part 1)31
- Ch. 1 - Remembering General Chemistry: Electronic Structure and Bonding (Part 2)65
- Ch. 2 - Acids and Bases: Central to Understanding Organic Chemistry84
- Ch. 3 - An Introduction to Organic Compounds:Nomenclature, Physical Properties, and Structure183
- Ch. 4 - Isomers: The Arrangement of Atoms in Space121
- Ch. 5 - Alkenes: Structure, Nomenclature, and an Introduction to Reactivity • Thermodynamics and Kinetics83
- Ch. 6 - The Reactions of Alkenes • The Stereochemistry of Addition Reactions175
- Ch. 7 - The Reactions of Alkynes • An Introduction to Multistep Synthesis119
- Ch. 8 - Delocalized Electrons: Their Effect on Stability, pKa, and the Products of a Reaction • Aromaticity and Electronic Effects: An Introduction to the Reactions of Benzene148
- Ch. 9 - Substitution and Elimination Reactions of Alkyl Halides212
- Ch. 10 - Reactions of Alcohols, Ethers, Epoxides, Amines, and Sulfur-Containing Compounds131
- Ch. 11 - Organometallic Compounds60
- Ch. 12 - Radicals90
- Ch. 13 - Mass Spectrometry; Infrared Spectroscopy; UV/Vis Spectroscopy62
- Ch. 14 - NMR Spectroscopy95
- Ch. 15 - Reactions of Carboxylic Acids and Carboxylic Acid Derivatives123
- Ch. 16 - Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid Derivatives141
- Ch. 17 - Reactions at the Alpha-Carbon101
- Ch. 18 - Reactions of Benzene and Substituted Benzenes144
- Ch. 19 - More About Amines • Reactions of Heterocyclic Compounds49
- Ch. 20 - The Organic Chemistry of Carbohydrates80
- Ch. 21 - Amino Acids, Peptides, and Proteins57
- Ch. 22 - Catalysis in Organic Reactions and in Enzymatic Reactions35
- Ch. 23 - The Organic Chemistry of the Coenzymes—Compounds Derived from Vitamins1
- Ch. 28 - Pericyclic Reactions58
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Bruice 8th EditionCh. 15 - Reactions of Carboxylic Acids and Carboxylic Acid DerivativesProblem 71
Bruice 8th EditionCh. 15 - Reactions of Carboxylic Acids and Carboxylic Acid DerivativesProblem 71Chapter 16, Problem 71
When a student treated butanedioic acid with thionyl chloride, she was surprised to find that the product she obtained was an anhydride rather than an acyl chloride. Propose a mechanism to explain why she obtained an anhydride.
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Identify the reactants and their roles: Butanedioic acid (a dicarboxylic acid) reacts with thionyl chloride (SOCl₂), which is commonly used to convert carboxylic acids into acyl chlorides. However, the presence of two carboxylic acid groups in butanedioic acid allows for additional reactivity.
Understand the initial reaction: Thionyl chloride reacts with one of the carboxylic acid groups in butanedioic acid. This reaction involves the nucleophilic attack of the carboxylic acid oxygen on the sulfur atom of SOCl₂, leading to the formation of an intermediate where the hydroxyl group is replaced by a chlorine atom, forming a monoacyl chloride.
Consider the proximity of the second carboxylic acid group: The second carboxylic acid group in butanedioic acid is in close proximity to the newly formed acyl chloride. This spatial arrangement allows for an intramolecular reaction to occur.
Propose the intramolecular reaction: The lone pair of electrons on the oxygen atom of the second carboxylic acid group attacks the carbonyl carbon of the acyl chloride. This nucleophilic attack leads to the formation of a tetrahedral intermediate, which subsequently eliminates a molecule of HCl to form the cyclic anhydride.
Conclude the mechanism: The final product is a cyclic anhydride, specifically succinic anhydride, due to the intramolecular reaction facilitated by the proximity of the two carboxylic acid groups in butanedioic acid. This explains why the student observed an anhydride instead of an acyl chloride as the product.
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Key Concepts
Here are the essential concepts you must grasp in order to answer the question correctly.
Butanedioic Acid Structure
Butanedioic acid, also known as succinic acid, is a dicarboxylic acid with two carboxyl (-COOH) groups. Its structure allows for the possibility of intramolecular reactions, which can lead to the formation of an anhydride. Understanding the molecular structure is crucial for predicting how it reacts with reagents like thionyl chloride.
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Thionyl Chloride as a Reagent
Thionyl chloride (SOCl2) is commonly used to convert carboxylic acids into acyl chlorides. However, it can also facilitate the formation of anhydrides through a dehydration mechanism. Recognizing the dual role of thionyl chloride helps explain the unexpected formation of an anhydride instead of the anticipated acyl chloride.
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Anhydride Formation Mechanism
The formation of an anhydride from butanedioic acid involves a dehydration reaction where two carboxylic acid molecules lose a water molecule. This process can be catalyzed by thionyl chloride, which promotes the removal of water and allows the carboxyl groups to react with each other, leading to the formation of the anhydride. Understanding this mechanism is key to explaining the student's observation.
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Related Practice
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Phosgene (COCl2) was used as a poison gas in World War I. What product would be formed from the reaction of phosgene with each of the following reagents?
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