Video Experimental Relacionado

Updated: Apr 27, 2026

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

Conocimientos mecánicos sobre la oxidación de fenoles sustituidos a través de la abstracción de átomos de hidrógeno

Jung Yoon Lee¹, Ryan L Peterson, Kei Ohkubo

¹Department of Chemistry, Johns Hopkins University , Baltimore, Maryland 21218, United States.

Journal of the American Chemical Society

|June 24, 2014

Resumen

Este estudio sintetizó un nuevo complejo cobre-superoxo para investigar la reactividad del adducto cobre-I) -O2 en la oxidación del fenol. Los hallazgos revelan un mecanismo que involucra la transferencia de átomos de hidrógeno y la transferencia parcial de carga, lo que lleva a los productos de benzoquinona.

Área de la Ciencia:

Química bioorgánica Química bioorgánica.
Química organometálica Química orgánica de los metales.
La catálisis por oxidación.

Sus antecedentes:

Los adductos de cobre-oxígeno son cruciales en los sistemas biológicos y la catálisis.
Comprender su reactividad proporciona información sobre los mecanismos de oxidación.
Los complejos de cobre-superoxo son intermediarios clave en estos procesos.

Objetivo del estudio:

Para sintetizar y caracterizar un nuevo complejo cuprico-superoxo.
Para dilucidar el mecanismo de las reacciones de oxidación-oxigenación del fenol mediadas por este complejo.
Para investigar el papel de la transferencia de átomos de hidrógeno (HAT) y la transferencia de carga en la vía de reacción.

Principales métodos:

Síntesis y caracterización de un nuevo complejo cobre-superoxo utilizando espectroscopias UV-vis, de resonancia Raman y EPR.
Estudios cinéticos que incluyen 2,6-di-tert-butilfenoles para-sustituidos (p-X-DTBPs).
Mediciones del efecto del isótopo cinético del deuterio y experimentos de etiquetado con (18) O.

Principales resultados:

El complejo de cobre-superoxo sintetizado reacciona con p-X-DTBPs para producir 2,6-di-tert-butil-1,4-benzoquinona (DTBQ).
Los datos cinéticos indican un paso de transferencia de átomo de hidrógeno (HAT) que limita la velocidad con transferencia parcial de carga.
El análisis del producto y el etiquetado con (18) O revelan vías distintas para diferentes sustitutos de sustrato, incluida la escisión O-O y la hidrólisis.

Conclusiones:

El estudio proporciona conocimientos mecanicistas sobre la reactividad del adducto cobre-oxígeno.
La reacción procede a través de HAT, seguido de acoplamiento radical y posterior oxidación.
Los hallazgos contribuyen a la comprensión de las reacciones de oxidación catalizadas por el cobre y la activación del oxígeno.

Más Videos Relacionados

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Published on: June 20, 2014

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Published on: April 10, 2015

Videos de Conceptos Relacionados

Oxidation of Phenols to Quinones

Oxidation of Phenols to Quinones

In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.

Oxidation of Alcohols

Oxidation of Alcohols

In this lesson, the oxidation of alcohols is discussed in depth. The various reagents used for oxidation of primary and secondary alcohols are detailed, and their mechanism of action is provided.
The process of oxidation in a chemical reaction is observed in any of the three forms:

Reactions at the Benzylic Position: Oxidation and Reduction

Reactions at the Benzylic Position: Oxidation and Reduction

The benzylic position describes the position of a carbon atom attached directly to a benzene ring. Benzene by itself does not undergo oxidation. In contrast, the benzylic carbon is quite reactive in the presence of strong oxidizing agents such as KMnO4 or H2CrO4. Therefore, alkylbenzenes are readily oxidized to benzoic acid, irrespective of the type of alkyl groups.

Benzene to Phenol via Cumene: Hock Process

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...

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.