Methanol → 3-(4-Formyl-3,5-dimethylphenyl)-acrylic acid methyl ester

HRID 1513269Notes

Reaction equation

N[C:2]1[CH:9]=[C:8]([CH3:10])[C:5]([CH:6]=[O:7])=[C:4]([CH3:11])[CH:3]=1.N([O-])=O.[Na+].CO.[C:18]([O:22][CH3:23])(=[O:21])[CH:19]=[CH2:20]>[H+].[B-](F)(F)(F)F.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:23][O:22][C:18](=[O:21])[CH:19]=[CH:20][C:2]1[CH:9]=[C:8]([CH3:10])[C:5]([CH:6]=[O:7])=[C:4]([CH3:11])[CH:3]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a suspension of 4-amino-2,6-dimethylbenzaldehyde (1.0 g., 6.71 mmol) in enough 42% HBF4 to be stirred at 0° C. was added a solution of NaNO2 (463 mg, 6.71 mmol) in water (5 mL) slowly. After 30 min at 0° C., MeOH (20 mL) was added followed by Pd(OAc)2 (229 mg) and methyl acrylate (1155 mg, 13.42 mmol). The reaction mixture was heated at 80° C. for 30 min then the suspension was filtered through Celite and washed with CH2Cl2. The filtrate was extracted with CH2Cl2 and the organic layer was washed with water, brine, dried with MgSO4, and filtered. The solvent was removed under reduced pressure and the residue was purified by flash chromatography (heptane/EtOAc=10:1 to 5:1) to give the title compound. MS: m/z 219 (M+1).

Workup

temperatureThe reaction mixture was heated at 80° C. for 30 min
filtrationthe suspension was filtered through Celite
washwashed with CH2Cl2
extractionThe filtrate was extracted with CH2Cl2
washthe organic layer was washed with water, brine
dry with materialdried with MgSO4
filtrationfiltered
customThe solvent was removed under reduced pressure
customthe residue was purified by flash chromatography (heptane/EtOAc=10:1 to 5:1)

Sources & evidence

ORD record: ord-820b9d1cf5c84c139bb6bc5c4bf6102c
Source dataset: uspto-grants-2012_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08217065B2

Reaction notes

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