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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 : Espectroscopía de RMN de derivados del benceno

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18.2 : Reacciones en la posición bencílica: oxidación y reducción

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18.3 : Reacciones en la posición bencílica: halogenación

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18.4 : Sustitución aromática electrofílica: descripción general

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18.5 : Sustitución aromática electrofílica: cloración y bromación del benceno

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18.6 : Sustitución aromática electrofílica: fluoración y yodación del benceno

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18.7 : Sustitución aromática electrofílica: nitración del benceno

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18.8 : Sustitución aromática electrofílica: sulfonación del benceno

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18.9 : Sustitución aromática electrofílica: Friedel-Crafts alquilación de benceno

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18.10 : Sustitución aromática electrofílica: acilación de benceno de Friedel-Crafts

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18.11 : Limitaciones de las reacciones de Friedel-Crafts

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18.12 : Efecto Directivo de los Sustituyentes: Grupos Orto-Para-Directores

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18.13 : Efecto Directivo de los Sustituyentes: Grupos Meta-Directores

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18.14 : Activadores orto-para-direccionamientos: –CH3, –OH, –⁠NH2, –OCH3

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