Textbook Question
Predict the major products of the following base-catalyzed aldol condensations with dehydration.
(a) benzophenone (PhCOPh) + propionaldehyde
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Ch. 22 - Condensations and Alpha Substitutions of Carbonyl Compounds
Wade9th EditionOrganic ChemistryISBN: 9780135213728
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Table of contents
- Ch.1 - Structure and Bonding107
- Ch. 2 - Acids and Bases; Functional Groups115
- Ch.3 - Structure and Stereochemistry of Alkanes100
- Ch.4 - The Study of Chemical Reactions99
- Ch.5 - Stereochemistry93
- Ch.6 - Alkyl Halides; Nucleophilic Substitution118
- Ch. 7 - Structure and Synthesis of Alkenes; Elimination158
- Ch.8 - Reactions of Alkenes171
- Ch.9 - Alkynes91
- Ch.10 - Structure and Synthesis of Alcohols143
- Ch.11 - Reactions of Alcohols104
- Ch. 12 - Infrared Spectroscopy and Mass Spectrometry22
- Ch. 13 - Nuclear Magnetic Resonance Spectroscopy45
- Ch. 14 - Ethers, Epoxides, and Thioethers72
- Ch. 15 - Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy89
- Ch. 16 - Aromatic Compounds74
- Ch. 17 - Reactions of Aromatic Compounds126
- Ch. 18 - Ketones and Aldehydes193
- Ch. 19 - Amines129
- Ch. 20 - Carboxylic Acids77
- Ch. 21 - Carboxylic Acid Derivatives141
- Ch. 22 - Condensations and Alpha Substitutions of Carbonyl Compounds175
- Ch. 23 - Carbohydrates and Nucleic Acids93
- Ch. 24 - Amino Acids, Peptides, and Proteins54
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Wade 9th EditionCh. 22 - Condensations and Alpha Substitutions of Carbonyl CompoundsProblem 30
Wade 9th EditionCh. 22 - Condensations and Alpha Substitutions of Carbonyl CompoundsProblem 30Chapter 22, Problem 30
Show how octane-2,7-dione might cyclize to a cycloheptenone. Explain why ring closure to the cycloheptenone is not favored.
Verified step by step guidance1
Step 1: Begin by identifying the functional groups in octane-2,7-dione. This molecule contains two ketone groups located at positions 2 and 7 on the octane chain. These ketones can participate in intramolecular aldol condensation, which is a common mechanism for cyclization.
Step 2: Analyze the mechanism for cyclization. The first step involves the enolate formation at one of the ketone groups. The ketone at position 2 can form an enolate ion by deprotonation of the alpha-hydrogen using a base. Represent this enolate formation using the formula: .
Step 3: The enolate ion formed at position 2 can attack the carbonyl carbon of the ketone at position 7. This nucleophilic attack leads to the formation of a new C-C bond, resulting in a seven-membered ring intermediate. Represent the cyclization step using curved arrows to show the movement of electrons.
Step 4: After the ring closure, the intermediate undergoes protonation and dehydration to form the final product, cycloheptenone. The dehydration step involves the elimination of water, which creates the double bond in the cycloheptenone structure. Represent the final structure as: .
Step 5: Explain why the ring closure to cycloheptenone is not favored. Seven-membered rings are less stable due to increased ring strain compared to six-membered rings. Additionally, the transition state for forming a seven-membered ring is higher in energy, making the reaction kinetically less favorable. This is why cyclization to smaller rings, such as five- or six-membered rings, is typically preferred in organic reactions.
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Key Concepts
Here are the essential concepts you must grasp in order to answer the question correctly.
Cyclization Reactions
Cyclization reactions involve the formation of a cyclic compound from a linear precursor. In the case of octane-2,7-dione, the molecule can undergo intramolecular reactions where functional groups react to form a ring structure. Understanding the mechanisms of cyclization, including the role of nucleophiles and electrophiles, is crucial for predicting the formation of cycloheptenone.
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Stability of Cyclic Compounds
The stability of cyclic compounds is influenced by factors such as ring strain, torsional strain, and angle strain. Cycloheptenone, being a seven-membered ring, may experience significant strain due to its non-ideal bond angles and steric interactions. This strain can make the formation of cycloheptenone less favorable compared to other possible products or conformations.
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Thermodynamics of Ring Closure
The thermodynamics of ring closure involves evaluating the energy changes associated with forming a cyclic structure. Factors such as enthalpy and entropy play a critical role in determining whether a cyclization reaction is favorable. In the case of octane-2,7-dione, unfavorable enthalpic contributions from strain and steric hindrance may outweigh any entropic benefits, leading to a disfavoring of cycloheptenone formation.
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Related Practice
Textbook Question
Show how each compound can be dissected into reagents joined by an aldol condensation, then decide whether the necessary aldol condensation is feasible.
(a)
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Textbook Question
Propose mechanisms for the following base-catalyzed condensations, with dehydration.
(b) benzaldehyde with propionaldehyde
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Textbook Question
When cyclodecane-1,6-dione is treated with sodium carbonate, the product gives a UV spectrum similar to that of 1-acetyl-2-methylcyclopentene. Propose a structure for the product, and give a mechanism for its formation.
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Textbook Question
Show how each compound can be dissected into reagents joined by an aldol condensation, then decide whether the necessary aldol condensation is feasible.
(b)
746
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Textbook Question
Predict the major products of the following base-catalyzed aldol condensations with dehydration.
(b) 2,2-dimethylpropanal + acetophenone
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