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18.24 : Benzene to Phenol via Cumene: Hock Process

The synthesis of phenol from benzene via cumene and cumene hydroperoxide is called the Hock process. First, a Friedel–Crafts alkylation reaction of benzene with propene gives cumene. Then cumene forms cumene hydroperoxide via a radical chain reaction. In the chain initiation step, the benzylic hydrogen is abstracted to give a benzylic radical. In the chain propagation step, the benzylic radical reacts with an oxygen diradical to form a cumene hydroperoxide radical. The cumene hydroperoxide radical reacts with anothercumene molecule to yield cumene hydroperoxide, regenerating the benzylic radical. In the subsequent protonation step, cumene hydroperoxide gives an oxonium ion. Further, a hydrolytic rearrangement migrates the phenyl group to oxygen (with the loss of water) to yield the carbocation. Finally, the addition of water and a subsequent rearrangement involving a proton shift gives phenol as theproduct.

Tags
BenzenePhenolCumeneHock ProcessFriedel Crafts AlkylationCumene HydroperoxideRadical Chain ReactionBenzylic RadicalOxygen DiradicalOxonium IonHydrolytic RearrangementCarbocationProton Shift

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18.24 : Benzene to Phenol via Cumene: Hock Process

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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–Crafts Alkylation of Benzene

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18.10 : Electrophilic Aromatic Substitution: Friedel–Crafts Acylation of Benzene

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18.11 : Limitations of Friedel–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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18.14 : <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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