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19,
2015
Chapter 18
Lecture Outline
Prepared by Layne A. Morsch
The University of Illinois - Springfield
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Copyright 2011 The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Substituent Effects
Inductive Effects
Resonance Effects
Electron-Withdrawing Resonance Effects
Inductive and Resonance Effects
Inductive Effects
Considering inductive effects only, the NH2 group withdraws
electron density and CH3 donates electron density.
Resonance Effects
Resonance effects are only observed with
substituents containing lone pairs or bonds.
Electron-Withdrawing Resonance
Effects
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Meta DirectorsDeactivators
Nitrobenzene reacts more slowly than benzene in all
substitution reactions.
The electron-withdrawing NO2 group deactivates the benzene
ring to electrophilic attack.
The meta product predominates.
The NO2 group is called a meta director.
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Mechanism of
Activation/Deactivation
To understand how substituents activate or deactivate the ring,
we must consider the first step in electrophilic aromatic
substitution.
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The energy diagrams below illustrate the effect of electronwithdrawing and electron-donating groups on the transition state
energy of the rate-determining step.
Figure 18.6 Energy diagrams comparing the rate of electrophilic substitution of substituted benzenes
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Optional
With the NO2 group (and all meta directors) meta attack occurs
because attack at the ortho and para position gives a
destabilized carbocation intermediate.
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Figure 18.7