Single electron transfer mechanism of oxidative dechlorination of 4-chloroanisole on copper(II)-smectite

Journal Article · Sun Nov 01 00:00:00 EST 1987 · Environ. Sci. Technol.; (United States)

DOI:https://doi.org/10.1021/es00164a014· OSTI ID:5090125

Govindaraj, N; Mortland, M M; Boyd, S A

4-Chloroanisole was found to react with Cu(II)-smectite forming a blue clay-organic complex. The presence of radical cation intermediates in the complex was confirmed by electron spin resonance and infrared spectroscopy. The radical cation intermediates were formed via an initial one electron oxidation of 4-chloroanisole by Cu(II)-smectite. Coupling of the radical cation of 4-chloroanisole (I) with a neutral 4-chloroanisole molecule gave a biphenyl radical cation (VI). Single electron transfer from the dimerized radical cation (VI) to Cu(II)-smectite resulted in the formation of a nonradical dication biphenyl intermediate (V). Reaction of the blue clay-organic complex with methanol resulted in the formation of the final dechlorinated dimeric product, viz., 4,4'-dimethoxybiphenyl. Chloride ion was recovered form the methanol extract. It is suggested that Cu(II)-smectite may be a useful catalyst in the oxidative polymerization and dechlorination of chlorinated aromatic toxicants. The products of these reactions should be significantly less toxic than the parent compounds. 15 references, 4 figures, 2 tables.

• Research Organization: Michigan State Univ., East Lansing (USA)
• OSTI ID: 5090125
• Journal Information: Environ. Sci. Technol.; (United States), Vol. 21:11
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
ANISOLE
DECHLORINATION
POLYMERIZATION
AROMATICS
CATALYSTS
CATIONS
COMPLEXES
COPPER
ELECTRON SPIN RESONANCE
ELECTRON TRANSFER
INFRARED SPECTRA
RADICALS
SMECTITE
ALUMINIUM COMPOUNDS
ALUMINIUM SILICATES
CHARGED PARTICLES
CHEMICAL REACTIONS
CLAYS
DEHALOGENATION
ELEMENTS
ETHERS
IONS
MAGNETIC RESONANCE
METALS
MINERALS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
RESONANCE
SILICATE MINERALS
SILICATES
SILICON COMPOUNDS
SPECTRA
TRANSITION ELEMENTS
510200* - Environment
Terrestrial- Chemicals Monitoring & Transport- (-1989)