1-Chloro-3-iodobenzene → Ethyl (3-chlorophenyl)(difluoro)acetate

To a mixture of copper bronze (2.93 g, 46.1 mmol) in DMSO (5.0 mL) was added ethyl bromodifluoroacetate (3.2 mL, 25 mmol) under argon at room temperature (see Sato, K. et al; Chem. Pharm. Bull. 47:1013-1016, 1999). After stirring for 1 h, 1-chloro-3-iodobenzene (2.57 mL, 20.8 mmol) was added under argon at room temperature. After shaking for 3 days, the mixture was diluted with saturated NH4Cl (50 mL) and extracted with ether (25 mL). The biphasic mixture was filtered through a pad of Celite, and the filter cake was washed with ether (25 mL). The organic layer was separated from the filtrate, and the aqueous layer was extracted with ether (25 mL). The combined organic layers were washed with saturated NH4Cl (2×15 mL) and brine (15 mL), dried (Na2SO4), and concentrated to afford the title compound (4.77 g, 97%) as a clear yellow oil. 1H NMR (300 MHz, CDCl3) δ 7.63-7.59 (m, 1H), 7.53-7.45 (m, 2H), 7.43-7.36 (m, 1H), 4.31 (q, J=7.2 Hz, 2H), 1.32 (t, J=7.2 Hz, 3H).

1. stirringAfter shaking for 3 days
2. extractionextracted with ether (25 mL)
3. filtrationThe biphasic mixture was filtered through a pad of Celite
4. washthe filter cake was washed with ether (25 mL)
5. customThe organic layer was separated from the filtrate
6. extractionthe aqueous layer was extracted with ether (25 mL)
7. washThe combined organic layers were washed with saturated NH4Cl (2×15 mL) and brine (15 mL)
8. dry with materialdried (Na2SO4)
9. concentrationconcentrated

ORD record

ord-483aa59640bc445d9a41a152454c96b2

Source dataset

uspto-grants-2009_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07550474B2