Textbook Question
Draw the mechanism for formation of the two addition products.
2
views
Ch. 10 - Reactions of Alcohols, Ethers, Epoxides, Amines, and Sulfur-Containing Compounds
Bruice8th EditionOrganic ChemistryISBN: 9780135213711
Not the one you use?Change textbookSelect a different textbook
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
All textbooks
Bruice 8th EditionCh. 10 - Reactions of Alcohols, Ethers, Epoxides, Amines, and Sulfur-Containing CompoundsProblem 36a
Bruice 8th EditionCh. 10 - Reactions of Alcohols, Ethers, Epoxides, Amines, and Sulfur-Containing CompoundsProblem 36aChapter 11, Problem 36a
The existence of the NIH shift was established by determining the major product obtained from rearrangement of the following arene oxide, in which a hydrogen has been replaced by a deuterium.
a. What would be the major product if the NIH shift occurs? (Hint: A C—H bond is easier to break than a C—D bond.)
Verified step by step guidance1
Step 1: Analyze the structure of the arene oxide provided in the image. The molecule contains a deuterium (D) atom and a hydrogen (H) atom attached to the same carbon adjacent to the epoxide group. The epoxide group is highly reactive and prone to rearrangement under acidic conditions (HB⁺).
Step 2: Understand the NIH shift mechanism. The NIH shift involves the migration of a hydrogen (or deuterium) atom during the rearrangement of the arene oxide. This occurs due to the breaking of the C-H or C-D bond and subsequent reattachment to a neighboring carbon atom.
Step 3: Consider the bond strength of C-H versus C-D. The C-H bond is easier to break than the C-D bond because the C-D bond is stronger due to the heavier mass of deuterium. This means the hydrogen atom is more likely to migrate during the NIH shift.
Step 4: Predict the rearrangement product. During the NIH shift, the hydrogen atom (H) migrates to the neighboring carbon atom, while the deuterium (D) remains in its original position. This results in the formation of a rearranged product where the hydrogen is now attached to a different carbon.
Step 5: Verify the major product. The major product will have the hydrogen atom relocated to the neighboring carbon, while the deuterium remains unchanged. This rearrangement stabilizes the molecule and completes the NIH shift process.
Verified video answer for a similar problem:
This video solution was recommended by our tutors as helpful for the problem above.
Video duration:
5mWas this helpful?
Key Concepts
Here are the essential concepts you must grasp in order to answer the question correctly.
NIH Shift
The NIH shift refers to a specific rearrangement mechanism in organic chemistry where a hydrogen atom is replaced by a deuterium atom during the reaction. This shift is significant in understanding the behavior of arene oxides, as it illustrates how the stability of intermediates can influence the final product. The NIH shift is particularly relevant when considering the bond strengths of C—H versus C—D bonds, as the latter is generally stronger.
Recommended video:
Guided course
03:43
Alkyl Shift
Arene Oxides
Arene oxides are reactive intermediates formed from the oxidation of aromatic compounds. They are characterized by an epoxide-like structure where an oxygen atom is bonded to a carbon atom in the aromatic ring. Understanding the reactivity of arene oxides is crucial for predicting the outcomes of various organic reactions, including rearrangements like the NIH shift, as they can lead to different products based on the stability of the resulting structures.
Recommended video:
Guided course
03:20Benzylic Oxidation
Isotope Effects
Isotope effects refer to the differences in reaction rates or mechanisms that occur when isotopes of an element are substituted in a molecule. In this context, the presence of deuterium (D) instead of hydrogen (H) affects the bond strength, making C—D bonds stronger and less likely to break compared to C—H bonds. This concept is essential for predicting the major product of the NIH shift, as it influences which bond will break during the rearrangement process.
Recommended video:
Guided course
03:06Understanding the hydrogen isotopes.
Related Practice
Textbook Question
Draw all possible resonance contributors for the two carbocations in the preceding reaction. Use the resonance contributors to explain why 1-naphthol is the major product of the reaction.
6
views
Textbook Question
Explain why the two arene oxides in [PROBLEM 10-38] open in opposite directions.
5
views
Textbook Question
How do the major products obtained from rearrangement of the following arene oxides differ?
1
views
Textbook Question
What stereoisomers are obtained from the reaction of the alkenes in [PROBLEM 10-32] with a peroxyacid followed by reaction with hydroxide ion?
c. cis-2-pentene
d. trans-2-pentene
5
views
Textbook Question
The existence of the NIH shift was established by determining the major product obtained from rearrangement of the following arene oxide, in which a hydrogen has been replaced by a deuterium.
b. What would be the major product if the carbocation forms phenol by losing H+ or D+, rather than by going through the NIH shift?
1
views