Textbook Question
Draw structures for A-D for each of the following:
b.
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Ch. 16 - Reactions of Aldehydes and Ketones • More Reactions of 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. 16 - Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid DerivativesProblem 80
Bruice 8th EditionCh. 16 - Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid DerivativesProblem 80Chapter 17, Problem 80
Propose a mechanism to explain how dimethyl sulfoxide and oxalyl chloride react to form the dimethylchlorosulfonium ion used as the oxidizing agent in the Swern oxidation.
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Step 1: Begin by recognizing that dimethyl sulfoxide (DMSO) acts as a nucleophile due to the lone pair on the sulfur atom. Oxalyl chloride, a reactive electrophile, reacts with DMSO by allowing the sulfur atom to attack one of the carbonyl carbons of oxalyl chloride, leading to the formation of a tetrahedral intermediate.
Step 2: The tetrahedral intermediate collapses, expelling a molecule of carbon dioxide (CO₂) and a molecule of carbon monoxide (CO). This results in the formation of a chlorodimethylsulfonium ion, where the sulfur atom is now positively charged and bonded to a chlorine atom.
Step 3: The chlorodimethylsulfonium ion is highly electrophilic and serves as the oxidizing agent in the Swern oxidation. It reacts with the alcohol substrate (e.g., propan-2-ol) by facilitating the formation of an alkoxysulfonium intermediate.
Step 4: Triethylamine, a base, is introduced to deprotonate the alkoxysulfonium intermediate, leading to the formation of a ketone (e.g., acetone) and dimethyl sulfide as the final products.
Step 5: The overall reaction mechanism highlights the role of dimethyl sulfoxide and oxalyl chloride in generating the reactive chlorodimethylsulfonium ion, which is essential for the oxidation of alcohols to carbonyl compounds in the Swern oxidation.
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Key Concepts
Here are the essential concepts you must grasp in order to answer the question correctly.
Swern Oxidation
Swern oxidation is a method for converting alcohols into carbonyl compounds using dimethyl sulfoxide (DMSO) and an activating agent, typically oxalyl chloride. The process involves the formation of a chlorosulfide intermediate, which subsequently reacts with the alcohol to yield the desired carbonyl compound. This reaction is notable for its mild conditions and high selectivity.
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Strong oxidizing agents
Dimethyl Sulfoxide (DMSO)
Dimethyl sulfoxide is a polar aprotic solvent widely used in organic synthesis. It acts as a reagent in various reactions, including the Swern oxidation, where it facilitates the formation of reactive intermediates. DMSO can stabilize positive charges, making it effective in promoting nucleophilic attacks and enhancing reaction rates.
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Chlorodimethylsulfonium Ion
The chlorodimethylsulfonium ion is a key intermediate in the Swern oxidation mechanism. It is formed when DMSO reacts with oxalyl chloride, resulting in a sulfonium ion that can act as an electrophile. This ion is crucial for the subsequent reaction with alcohols, leading to the formation of the oxidizing agent, dimethylchlorosulfonium, which facilitates the oxidation process.
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Related Practice
Textbook Question
A compound gives the following IR spectrum. Upon reaction with sodium borohydride followed by acidification, it forms the product with the 1H NMR spectrum shown below. Identify the starting material and the product.
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Textbook Question
Propose a mechanism for each of the following reactions:
a.
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Textbook Question
Propose a mechanism for each of the following reactions:
b.
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Textbook Question
a. Propose a mechanism for the following reaction:
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Textbook Question
Unlike a phosphonium ylide that reacts with an aldehyde or a ketone to form an alkene, a sulfonium ylide reacts with an aldehyde or a ketone to form an epoxide. Explain why one ylide forms an alkene, whereas the other forms an epoxide.
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