Ethyl bromodifluoroacetate → Ethyl 2-(4-bromo-2,6-dimethylphenyl)-2,2-difluoroacetate

HRID 708804

Reaktionsgleichung

[Br:1][C:2]1[CH:3]=[C:4]([CH3:10])[C:5](I)=[C:6]([CH3:8])[CH:7]=1.Br[C:12]([F:19])([F:18])[C:13]([O:15][CH2:16][CH3:17])=[O:14]>CS(C)=O.[Cu]>[Br:1][C:2]1[CH:3]=[C:4]([CH3:10])[C:5]([C:12]([F:19])([F:18])[C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:6]([CH3:8])[CH:7]=1

Komponenten

Reaktionsbedingungen

Temperatur: 60 °C

Versuchsvorschrift

To a degassed solution of 5-bromo-2-iodo-1,3-dimethylbenzene (3.9 g, 12.54 mmol) and ethyl 2-bromo-2,2-difluoroacetate (3.22 ml, 25.08 mmol) in DMSO (30 ml) was added copper (3.19 g, 50.2 mmol). The reaction mixture was stirred at 60° C. for 3 h, then cooled to r.t. and filtered. The filtrate was diluted with EtOAc and water, extracted with EtOAc (3×). The combined organic layer was washed with brine, dried with MgSO4, filtered and concentrated. The crude product was purified by flash chromatography to give Intermediate 7A (3.4 g, 11.07 mmol, 88% yield) as a colorless oil. 1H NMR (400 MHz, chloroform-d) δ ppm 1.32 (t, J=7.03 Hz, 3H) 2.44 (t, J=4.17 Hz, 6H) 4.32 (q, J=7.18 Hz, 2H) 7.23 (s, 2H). 19F NMR (376 MHz, chloroform-d) δ ppm −95.28 (br. s., 2F).

Aufarbeitung

temperaturecooled to r.t.
filtrationfiltered
additionThe filtrate was diluted with EtOAc and water
extractionextracted with EtOAc (3×)
washThe combined organic layer was washed with brine
dry with materialdried with MgSO4
filtrationfiltered
concentrationconcentrated
customThe crude product was purified by flash chromatography

Quellen und Nachweise

ORD-Eintrag: ord-43108a86b60045159095cf0762cf1d8c
Quelldatensatz: uspto-grants-2015_11
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US09174974B2

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