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α-Oxidation of Ketone; 1-(4-methoxyphenyl)-3-oxobutan-2-yl benzoate

SyntheticPage 912
Submitted Dec 16, 2019, published Jan 14, 2020
Yoichiro Hirose (yoichiro.hirose@tcichemicals.com), Yuta Yamamoto (yuta.yamamoto@tcichemicals.com), Yuko Konishi (yuko.konishi@tcichemicals.com)


			Reaction Scheme: α-Oxidation of Ketone

Chemicals Used

4-(4-Methoxyphenyl)-2-butanone (TCI)
o-Benzoyl-N-methylhydroxylamine Hydrochloride (TCI)

Procedure

To a solution of 4-(4-methoxyphenyl)-2-butanone (0.679 mL, 4.0 mmol) in DMSO (10 mL) was added o-benzoyl-N-methylhydroxylamine hydrochloride (884 mg, 4.5 mmol) and the mixture was stirred at 50°C for 12 hours. Deionized water (100 mL) was added to the reaction mixture. After being stirred for 10 minutes, the mixture was extracted with ethyl acetate (100 mL) and the separated organic layer was washed with 2M hydrochloric acid (100 mL), saturated aqueous sodium bicarbonate solution (100 mL) and brine (100 mL), dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the residue was purified by column chromatography (3:97–30:70 ethyl acetate / hexane on SiO2), giving slightly yellow oil (0.90 g, 75%).

Author's Comments

This procedure is a practical way to introduce benzoyl oxy group at α position of ketones. By hydrolysis of obtained benzoate α-hydroxy ketones are easily prepared.

Data

1H NMR (400 MHz, CDCl3); δ 2.09 (s, 3H), 3.14 (ddd, 2H, J = 14.8, 5.2, 2.4 Hz), 3.76 (s, 3H), 5.37 (dd, 1H, J = 5.2, 2.8 Hz), 6.82 (td, 2H, J = 8.8, 2.6 Hz), 7.17 (td, 2H, J = 8.8, 2.6 Hz), 7.44 (tt, 2H, J = 7.6, 1.6 Hz), 7.57 (tt, 1H, J = 7.2, 2.0 Hz), 8.02 (dd, 2H, J = 7.2, 1.6 Hz)


Lead Reference

Org. Lett., Vol. 7, No. 25, 2005, 5729-5732.

Supplementary Information

1H NMR.pdf (1H NMR.pdf)

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Get structure file (.cdx, .sk2, .mol)

Keywords: ketones, oxidation

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