Metal catalysis in oxidation by peroxides. 31. The hydroxylation of benzene by VO(O sub 2 )(PIC)(H sub 2 O) sub 2 : Mechanistic and synthetic aspects

Journal Article · Fri Sep 01 04:00:00 EDT 1989 · Journal of Organic Chemistry; (USA)

DOI:https://doi.org/10.1021/jo00279a027· OSTI ID:7071514

Bonchio, M; Conte, V; Di Furia, F; Modena, G ^[1]

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1. Centro Meccanismi di Reazioni Organiche del CNR, Padova (Italy)

The oxidation of benzene to phenol by the vanadium(V) peroxo complex VO(O{sub 2})(PIC)(H{sub 2}O){sub 2} (1) has been investigated in various solvents and in the presence of both one-electron donors and radical traps. The hypothesis is advanced that the active oxidizing species is a vanadium complex resulting from the monoreduction of 1, i.e., formally a radical-anion derivative. Such a process readily occurs in noncoordinating solvents (CH{sub 3}NO{sub 2}, C{sub 6}H{sub 6}, and also CH{sub 3}CN) whereas it is almost suppressed in coordinating ones (CH{sub 3}OH and DMF). The PIC ligand plays a role, likely in stabilizing the active species, which, however, may be formed also from simple peroxo complexes such as VO(O{sub 2})(OR). As far as the synthetic applications of 1 are concerned, preliminary data indicate that by running the oxidation in a two-phase system the main drawback of the process, i.e., the fast decomposition of the oxidant, may be, at least in part, overcome.

• OSTI ID: 7071514
• Journal Information: Journal of Organic Chemistry; (USA), Journal Name: Journal of Organic Chemistry; (USA) Vol. 54:18; ISSN JOCEA; ISSN 0022-3263
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AROMATICS
BENZENE
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
ELEMENTS
EXPERIMENTAL DATA
HYDROCARBONS
HYDROXYLATION
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
METALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PEROXIDES
TRANSITION ELEMENT COMPOUNDS
VANADIUM COMPOUNDS
VANADIUM OXIDES