Dimethylformamide → Ethyl 2-(5-amino-2-cyano-4-fluorophenyl)acetate

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Reaktionsgleichung

[NH2:1][C:2]1[C:3]([F:15])=[CH:4][C:5](Br)=[C:6]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:7]=1.[CH3:16][N:17](C=O)C>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:1][C:2]1[C:3]([F:15])=[CH:4][C:5]([C:16]#[N:17])=[C:6]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:7]=1

Komponenten

Reaktionsbedingungen

Temperatur: 100 °C

Versuchsvorschrift

A solution of Example C5 (3 g, 10.9 mmol) in DMF (50 mL) was treated with ZnCN2 (1.7 g, 16.4 mmol) and Pd(PPh3)4 (1.26 g, 1.09 mmol), sparged with N2 and heated at 100° C. for 12 h. The mixture was cooled to RT, treated with water and extracted with EtOAc (3×). The combined organics were washed with brine (3×), dried over Na2SO4, concentrated to dryness and purified via silica gel chromatography (EtOAc/pet ether) to afford ethyl 2-(5-amino-2-cyano-4-fluorophenyl)acetate (600 mg, 25% yield). 1H NMR (400 MHz, CDCl3): δ 7.19 (d, J=2.4 Hz, 1H), 6.67 (d, J=8.4 Hz, 1H), 4.13-4.11 (q, J=6.8 Hz, 2H), 3.66 (s, 2H), 1.23-1.19 (t, J=6.8 Hz, 3H).

Aufarbeitung

customsparged with N2
temperatureThe mixture was cooled to RT
additiontreated with water
extractionextracted with EtOAc (3×)
washThe combined organics were washed with brine (3×)
dry with materialdried over Na2SO4
concentrationconcentrated to dryness
custompurified via silica gel chromatography (EtOAc/pet ether)

Quellen und Nachweise

ORD-Eintrag: ord-b3af355249e345a2b718928e1461f443
Quelldatensatz: uspto-grants-2013_06
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US08461179B1

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