Methyl acetoacetate → Methyl 4-(2-ethoxy-2-oxoethyl)-3-methylbenzoate

HRID 410040Notes

Reaction equation

Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12].O=C(C)[CH2:15][C:16]([O:18][CH3:19])=[O:17].[O-]P([O-])([O-])=O.[K+].[K+].[K+].[C:29](P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1C)(C)(C)C>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:19]([O:18][C:16](=[O:17])[CH2:15][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12])[CH3:29]

Participants

Conditions

Temperature: 110 °C

Procedure

Methyl 4-bromo-3-methylbenzoate (1.5 g, 6.55 mmol), methyl 3-oxobutanoate (0.99 g, 8.51 mmol) and K3PO4 (4.17 g, 19.6 mmol) were mixed with Pd(OAc)2 (15 mg) and di-tert-butyl(2′-methyl-[1,1′-biphenyl]-2-yl)phosphine (39 mg), and diluted with toluene (25 ml). The resultant mixture was simply degassed via vacuum and charged with argon. Then it was heated at 90° C. for 24 h and at 110° C. for 5 hours. After aqueous work-up with EtOAc, the desired product-methyl 4-(2-ethoxy-2-oxoethyl)-3-methylbenzoate was isolated by column chromatography, eluting with EtOAc/Hexane (1/3), as oil (366 mg, 25%).

Workup

customThe resultant mixture was simply degassed via vacuum
additioncharged with argon

Sources & evidence

ORD record: ord-93ba0c47540f48edadf95ec8a84d9366
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08759548B2

Reaction notes

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