Tributylamine → (E)-tert-butyl 3-(2-acetyl-5-chlorophenyl)acrylate

HRID 515757

Reaction equation

Br[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9](=[O:11])[CH3:10].C(N(CCCC)CCCC)CCC.[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])(=[O:28])[CH:26]=[CH2:27]>CN(C=O)C.[Pd].CC([O-])=O.CC([O-])=O.[Pd+2]>[C:9]([C:3]1[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=1/[CH:27]=[CH:26]/[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])(=[O:11])[CH3:10]

Participants

Conditions

Temperature: 100 °C

Procedure

To a degassed solution of 1-(2-bromo-4-chlorophenyl)ethanone (1.0 g, 4.28 mmol), tributylamine (2.041 mL, 8.57 mmol), and tert-butyl acrylate (1.255 mL, 8.57 mmol) in DMF (10 mL) was added palladium on carbon (0.456 g, 0.428 mmol) and Pd(OAc)2 (0.096 g, 0.428 mmol). The reaction mixture was warmed to 100° C. After 16 h, the reaction was cooled to rt. The reaction was filtered and the solid was rinsed with DMF. The filtrate was diluted with EtOAc, washed with H2O (2×), brine, dried over Na2SO4, filtered and concentrated. Purification by normal phase chromatography afforded Intermediate 4A (0.760 g, 63%), as a brown oil. MS (ESI) m/z: 225.0 (M-C4H8+H)+.

Workup

temperaturethe reaction was cooled to rt
filtrationThe reaction was filtered
washthe solid was rinsed with DMF
additionThe filtrate was diluted with EtOAc
washwashed with H2O (2×), brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated
customPurification by normal phase chromatography

Sources & evidence

ORD record: ord-e6109ceab95f42b99835a4e040a87c59
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09108951B2

Linked notes

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