Benzoic Acid → Methyl 4-(3-methoxyphenyl)-4-oxobutanoate

HRID 1972241Notes

Reaction equation

[CH:1](=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][CH3:9])[CH:3]=1.[C:11]([O:15][CH3:16])(=[O:14])[CH:12]=[CH2:13].NC1C(C)=CC=CN=1.C(O)(=O)C1C=CC=CC=1>C(OCC)C.[Cl-].[Na+].O.O>[CH3:9][O:8][C:4]1[CH:3]=[C:2]([C:1](=[O:10])[CH2:13][CH2:12][C:11]([O:15][CH3:16])=[O:14])[CH:7]=[CH:6][CH:5]=1

Participants

Conditions

Temperature: 130 °C

Procedure

A screw-capped tube equipped with a magnetic stir bar is charged with m-anisaldehyde (3.04 mL, 25 mmol), methyl acrylate (4.50 mL, 50 mmol), (PPh3)3RhCl (1.16 g, 1.25 mmol), 2-amino-3-picoline (1.06 mL, 10 mmol), and benzoic acid (702 mg, 5 mmol). The reaction mixture is stirred at 130° C. for 3 days. After cooling to room temperature, the resulting mixture is dissolved in diethyl ether and ished with water and brine. The organic phase is then dried over Na2SO4 and concentrated. The residue is then purified on silica gel (10-30% ethyl acetate in hexane) to give methyl 4-(3-methoxyphenyl)-4-oxobutanoate (5.02 g, 90%) as a clear reddish brown oil. 1H NMR (CDCl3, 400 MHz) δ 7.57 (d, J=9.5 Hz, 1H), 7.51 (dd, J=3.0, 2.0 Hz, 1H), 7.38 (t, J=10.0 Hz, 1H), 7.12 (ddd, J=10.5, 3.5, 1.0 Hz, 1H), 3.85 (s, 3H), 3.71 (s, 3H), 3.32 (t, J=8.5 Hz, 2H), 2.77 (t, J=8.5 Hz, 2H).

Workup

customA screw-capped tube equipped with a magnetic stir bar
temperatureAfter cooling to room temperature
dry with materialThe organic phase is then dried over Na2SO4
concentrationconcentrated
customThe residue is then purified on silica gel (10-30% ethyl acetate in hexane)

Sources & evidence

ORD record: ord-3563887740284f07bfbf8d4d8f82395f
Source dataset: uspto-grants-2013_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08431607B2

Reaction notes

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