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

HRID 1525355

Reaktionsgleichung

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]

Komponenten

Reaktionsbedingungen

Temperatur: 100 °C

Versuchsvorschrift

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)+. Intermediate 4: A solution of Intermediate 4A (0.048 g, 0.171 mmol) in 50% TFA/DCM (2 mL) was stirred at rt. After 1 h, the reaction was concentrated to give Intermediate 4 (0.038 g, 100% yield) as a yellow solid. The material was carried onto the next step without further purification. MS (ESI) m/z: 225.1 (M+H)+.

Aufarbeitung

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

Quellen und Nachweise

ORD-Eintrag: ord-a7bd80ae2a0148ca945ecd7f166cd470
Quelldatensatz: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US09079929B2

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