Carbon-hydrogen vs. carbon-carbon bond cleavage of 1,2-diarylethane radical cations in acetonitrile-water
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.
- Research Organization:
- Battelle Pacific Northwest Labs., Richland, WA
- OSTI ID:
- 6636945
- Journal Information:
- J. Org. Chem.; (United States), Vol. 49:9
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
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)