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Mechanistic and synthetic aspects of the anodic oxidation of substituted benzenes

Mechanistic and synthetic aspects of the anodic oxidation of substituted benzenes
Mechanistic and synthetic aspects of the anodic oxidation of substituted benzenes

The mechanisms of the anodic oxidation of a series of alkylbenzenes and alkoxybenzenes in dry acetonitrile are discussed. Electrochemical techniquen, assisted by analysis of the products, were used to determine the mechanisms. Modulated Specular Reflectance Spectroscopy was used to identify the major intermediates formed during the oxidation of the aromatic compounds. 

An ECE type of mechanism is proposed for the oxidation of both, the alkylbenzenes and the alkoxybenzenes, ltexaethylbenzene and 1,4-Dimethoxybenzene are taken as examples to explain the mechanisms for the oxidation of alkyl and alkoxybenzenes, respectively. Reversible oxidation waves were observed in dry acetonitrile for either hexaethyl benzene and 1,4-dimethoxybenzene. All the other compounds oxidized irreversibly under the same conditions. 

Decay of the cation radical of the alkylbenzenes occurs due to a side chain proton loss, whilst radical cation from the alkoxybenzenes are attacked on the aromatic ring by the acetonitrile. In all cases, the formation of a nitrilium ion is suggested. 

For many of the compounds it was found that preparative electrolyses at constant potential were unsuccessful due to electrode fouling and very poor yields of products. A method of pulsed electrolysis was developed which, in conjunction with the presence of a cationic exchange resin, enabled a high yield of product to be obtained in a relatively clean reaction. This technique greatly extends the utility of the electrochemical method for the functionalization of aromatic compounds.

University of Southampton
Márquez, Olga Pérez de
fbca2b0d-c4c3-4421-9eeb-f2b632ec28e1
Márquez, Olga Pérez de
fbca2b0d-c4c3-4421-9eeb-f2b632ec28e1
Bewick, Alan
89ccb493-55f6-4284-b67b-833ec9e48283

Márquez, Olga Pérez de (1981) Mechanistic and synthetic aspects of the anodic oxidation of substituted benzenes. University of Southampton, Doctoral Thesis, 221pp.

Record type: Thesis (Doctoral)

Abstract

The mechanisms of the anodic oxidation of a series of alkylbenzenes and alkoxybenzenes in dry acetonitrile are discussed. Electrochemical techniquen, assisted by analysis of the products, were used to determine the mechanisms. Modulated Specular Reflectance Spectroscopy was used to identify the major intermediates formed during the oxidation of the aromatic compounds. 

An ECE type of mechanism is proposed for the oxidation of both, the alkylbenzenes and the alkoxybenzenes, ltexaethylbenzene and 1,4-Dimethoxybenzene are taken as examples to explain the mechanisms for the oxidation of alkyl and alkoxybenzenes, respectively. Reversible oxidation waves were observed in dry acetonitrile for either hexaethyl benzene and 1,4-dimethoxybenzene. All the other compounds oxidized irreversibly under the same conditions. 

Decay of the cation radical of the alkylbenzenes occurs due to a side chain proton loss, whilst radical cation from the alkoxybenzenes are attacked on the aromatic ring by the acetonitrile. In all cases, the formation of a nitrilium ion is suggested. 

For many of the compounds it was found that preparative electrolyses at constant potential were unsuccessful due to electrode fouling and very poor yields of products. A method of pulsed electrolysis was developed which, in conjunction with the presence of a cationic exchange resin, enabled a high yield of product to be obtained in a relatively clean reaction. This technique greatly extends the utility of the electrochemical method for the functionalization of aromatic compounds.

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Márquez 1981 Thesis - Version of Record
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Published date: 1981

Identifiers

Local EPrints ID: 459604
URI: http://eprints.soton.ac.uk/id/eprint/459604
PURE UUID: 0f8739e9-89ed-41c5-80e2-e7d232d180c5

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Date deposited: 04 Jul 2022 17:14
Last modified: 23 Jan 2023 18:05

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Contributors

Author: Olga Pérez de Márquez
Thesis advisor: Alan Bewick

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