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Title: Carbon-hydrogen vs. carbon-carbon bond cleavage of 1,2-diarylethane radical cations in acetonitrile-water

Abstract

Radical cations of 1,2-diarylethanes and 1-phenyl-2-arylethanes (Ar = phenyl, p-tolyl, p-anisyl) were generated in acidic 70% acetonitrile-water by Cu/sup 2 +/-catalyzed peroxydisulfate oxidation. The radical cations fragment mainly by loss of benzylic protons (C-H cleavage) rather than by alkyl C-C bond cleavage. The 1,2-diarylethanol products undergo further selective oxidation to aryl aldehydes and arylmethanols via rapid equilibration of diarylethane and diarylethanol radical cations. The radical cation of 2,3-dimethyl-2,3-diphenylbutane fragments efficiently by C-C cleavage, forming cumyl radical and cumyl cation. Oxidations of bibenzyl-bicumyl mixtures show selective oxidation of bicumyl dependent on total substrate concentration, providing evidence of equilibrating radical cations and showing that bicumyl fragments faster than bibenzyl loses protons. The effects of reaction conditions and substrate structure on reactivity are discussed.

Authors:
;
Publication Date:
Research Org.:
Battelle Pacific Northwest Labs., Richland, WA
OSTI Identifier:
6636945
Resource Type:
Journal Article
Journal Name:
J. Org. Chem.; (United States)
Additional Journal Information:
Journal Volume: 49:9
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER COMPOUNDS; CATALYTIC EFFECTS; PEROXIDES; OXIDATION; RADICALS; SYNTHESIS; SULFATES; CATALYSIS; CATIONS; ETHANE; EXPERIMENTAL DATA; NITRILES; WATER; ALKANES; CHARGED PARTICLES; CHEMICAL REACTIONS; DATA; HYDROCARBONS; HYDROGEN COMPOUNDS; INFORMATION; IONS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; SULFUR COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Camaioni, D M, and Franz, J A. Carbon-hydrogen vs. carbon-carbon bond cleavage of 1,2-diarylethane radical cations in acetonitrile-water. United States: N. p., 1984. Web. doi:10.1021/jo00183a023.
Camaioni, D M, & Franz, J A. Carbon-hydrogen vs. carbon-carbon bond cleavage of 1,2-diarylethane radical cations in acetonitrile-water. United States. https://doi.org/10.1021/jo00183a023
Camaioni, D M, and Franz, J A. 1984. "Carbon-hydrogen vs. carbon-carbon bond cleavage of 1,2-diarylethane radical cations in acetonitrile-water". United States. https://doi.org/10.1021/jo00183a023.
@article{osti_6636945,
title = {Carbon-hydrogen vs. carbon-carbon bond cleavage of 1,2-diarylethane radical cations in acetonitrile-water},
author = {Camaioni, D M and Franz, J A},
abstractNote = {Radical cations of 1,2-diarylethanes and 1-phenyl-2-arylethanes (Ar = phenyl, p-tolyl, p-anisyl) were generated in acidic 70% acetonitrile-water by Cu/sup 2 +/-catalyzed peroxydisulfate oxidation. The radical cations fragment mainly by loss of benzylic protons (C-H cleavage) rather than by alkyl C-C bond cleavage. The 1,2-diarylethanol products undergo further selective oxidation to aryl aldehydes and arylmethanols via rapid equilibration of diarylethane and diarylethanol radical cations. The radical cation of 2,3-dimethyl-2,3-diphenylbutane fragments efficiently by C-C cleavage, forming cumyl radical and cumyl cation. Oxidations of bibenzyl-bicumyl mixtures show selective oxidation of bicumyl dependent on total substrate concentration, providing evidence of equilibrating radical cations and showing that bicumyl fragments faster than bibenzyl loses protons. The effects of reaction conditions and substrate structure on reactivity are discussed.},
doi = {10.1021/jo00183a023},
url = {https://www.osti.gov/biblio/6636945}, journal = {J. Org. Chem.; (United States)},
number = ,
volume = 49:9,
place = {United States},
year = {Fri May 04 00:00:00 EDT 1984},
month = {Fri May 04 00:00:00 EDT 1984}
}