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18.14 : orthopara-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

All ortho–para directors, excludinghalogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding intermediates through resonance effects via pi-donation. As a result, the energy of the transition state is lowered for ortho and para intermediates, leading to an accelerated reaction.

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Ortho para directing ActivatorsCH3OHNH2OCH3Electron donatingElectrophilic SubstitutionNitrationAnisoleBenzeneResonance StabilizationTransition State

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18.14 : <em>ortho</em>&ndash;<em>para</em>-Directing Activators: &ndash;CH<sub>3</sub>, &ndash;OH, &ndash;&NoBreak;NH<sub>2</sub>, &ndash;OCH<sub>3</sub>

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18.1 : NMR Spectroscopy of Benzene Derivatives

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18.2 : Reactions at the Benzylic Position: Oxidation and Reduction

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18.3 : Reactions at the Benzylic Position: Halogenation

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18.4 : Electrophilic Aromatic Substitution: Overview

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18.5 : Electrophilic Aromatic Substitution: Chlorination and Bromination of Benzene

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18.6 : Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

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18.7 : Electrophilic Aromatic Substitution: Nitration of Benzene

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18.8 : Electrophilic Aromatic Substitution: Sulfonation of Benzene

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18.9 : Electrophilic Aromatic Substitution: Friedel&ndash;Crafts Alkylation of Benzene

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18.10 : Electrophilic Aromatic Substitution: Friedel&ndash;Crafts Acylation of Benzene

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18.11 : Limitations of Friedel&ndash;Crafts Reactions

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18.12 : Directing Effect of Substituents: <em>ortho</em>&ndash;<em>para</em>-Directing Groups

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18.13 : Directing Effect of Substituents: <em>meta</em>-Directing Groups

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18.15 : <em>ortho</em>&ndash;<em>para</em>-Directing Deactivators: Halogens

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