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DOI: 10.1055/s-0029-1219202
In situ Formation of NOx and Br Anion for Aerobic Oxidation of Benzylic Alcohols without Transition Metal
Publication History
Publication Date:
15 January 2010 (online)
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Abstract
The reaction of KBrO3 and NH2OH˙HCl in situ generates NOx and Br anion, which combine with 2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO) to construct a NO-activating dioxygen, Br-assisted, TEMPO-catalyzed aerobic oxidation of alcohols. Catalyzed by KBrO/NH2OH˙HCl/TEMPO, various benzylic alcohols can be oxidized quantitatively to their corresponding carbonyl compounds under mild conditions. The easy handling and simple product separation make the process an attractive candidate for the oxidation of alcohols.
Key words
oxidation - alcohols - catalyst - bromate - hydroxylammonium - 2,2,6,6-tetramethylpiperidine-N-oxide
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- Supporting Information
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References and Notes
General Typical
Procedure for the Oxidation
The reaction was carried
out in a 70 mL autoclave, and the general procedure is described
typically with benzyl alcohol as follows: To a reactor were added
benzyl alcohol (2 mL, 19.3 mmol), NH2OH˙HCl
(174.8 mg, 10 mol%), KBrO3 (161.2 mg, 5 mol%),
TEMPO (15.1 mg, 0.5 mol%), and CH2Cl2 (10
mL). The closed autoclave was charged with O2 to 0.3
MPa and warmed to 80 ˚C under stirring. The pressure of
O2 was kept under 0.4 MPa for 2 h. After cooled to r.t.,
20 mL CH2Cl2 were added to the autoclave.
Then the solution was analyzed by gas chromatography, which was
conducted using an Agilent Technologies 6890N Network GC System with
a flame ionization detector and a DB-1 capillary column (30 m × 0.535
mm × 3.0 µm).
General Isolation
Procedure for the Oxidation Product
After GC showed
the reaction to be complete, the reaction mixture was diluted with
CH2Cl2 and transferred into a separation funnel.
The CH2Cl2 solution was washed with 15 mL
of a sat. solution of Na2CO3, followed by
brine. The organic layer was dried over anhyd Na2SO4,
and the solvent was evaporated to yield the product without further purification.