Textbook Question
For each horizontal row of substituted benzenes, indicate
c. the one that yields the highest percentage of meta product in an electrophilic aromatic substitution reaction.
19. Reactions of Aromatics: EAS and Beyond
Electron Withdrawing Groups
Problem 31
Textbook Question
Substitution at the benzylic position of the molecules shown was observed to occur at different rates. Explain this observation.
Verified step by step guidance1
Identify the benzylic position in the molecules. The benzylic position is the carbon atom directly attached to a benzene ring. This position is often reactive due to the resonance stabilization provided by the benzene ring.
Analyze the substituents on the benzene ring and the benzylic carbon. Substituents can influence the reactivity of the benzylic position through electronic effects (inductive or resonance effects). Electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) play a key role here.
Consider the stability of the intermediate formed during the substitution reaction. For example, in an SN1 reaction, the formation of a benzylic carbocation intermediate is stabilized by resonance with the benzene ring. Substituents that stabilize or destabilize this intermediate will affect the reaction rate.
Evaluate steric effects. Bulky substituents near the benzylic position can hinder the approach of the nucleophile, slowing down the reaction. Conversely, less steric hindrance allows for faster substitution.
Compare the molecules based on the above factors (electronic effects, intermediate stability, and steric effects) to explain why substitution occurs at different rates. For example, a molecule with an electron-donating group at the para position may stabilize the benzylic carbocation more effectively, leading to a faster reaction rate.
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Key Concepts
Here are the essential concepts you must grasp in order to answer the question correctly.
Benzylic Position
The benzylic position refers to the carbon atom directly attached to a benzene ring. This position is significant in organic chemistry because it often exhibits unique reactivity due to the resonance stabilization provided by the aromatic system. Substitutions at this position can be influenced by the electronic effects of substituents on the benzene ring, affecting the rate of reaction.
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Reactions at Benzylic Positions Concept 1
Substitution Reactions
Substitution reactions involve the replacement of one atom or group in a molecule with another. In the context of benzylic substitution, these reactions can occur via mechanisms such as nucleophilic substitution (SN1 or SN2) or electrophilic substitution. The rate of substitution can vary based on factors like sterics, electronics, and the nature of the leaving group.
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01:34Recognizing Substitution Reactions.
Resonance and Stability
Resonance is a concept that describes the delocalization of electrons in a molecule, which can stabilize certain intermediates during chemical reactions. In benzylic substitution, the stability of the carbocation intermediate formed during the reaction can significantly influence the reaction rate. More stable intermediates lead to faster reactions, explaining the observed differences in substitution rates.
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03:43The radical stability trend.
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