Potassium Carbonate → tert-Butyl 4-(3,3,3-trifluoroprop-1-en-2-yl)phenylcarbamate

To a mixture of tert-butyl 4-bromophenylcarbamate (1.67 g, 6.14 mmol), potassium carbonate (3.38 g, 24.46 mmol), and tetrakis(triphenylphosphine)palladium (365 mg, 0.316 mmol), was added 4,4,6-trimethyl-2-(3,3,3-trifluoroprop-1-en-2-yl)-1,3,2-dioxaborinane (1.64 g, 7.39 mmol), and degassed 1,2-dimethoxyethane (40 mL) and water (20 mL). The mixture for refluxed for 2 hours, cooled to ambient temperature, added more of 4,4,6-trimethyl-2-(3,3,3-trifluoroprop-1-en-2-yl)-1,3,2-dioxaborinane (475 mg, 2.14 mmol) and tetrakis(triphenylphosphine)palladium-(189 mg, 0.164 mmol), and refluxed for 5 hours. The reaction mixture was cooled to room temperature, filtered, diluted with water (200 mL), extracted twice with ethyl acetate (200 mL), washed with brine, dried (Na2SO4) and concentrated to an orange oil. The residue was purified by silica gel chromatography (AnaLogix® SF25-40G; 50 micron silica; eluted with 0-15% ethyl acetate in hexane at 30 mL/min) to provide the title compound (1.223 g, 4.26 mmol, 69.4% yield) as a yellow solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 9.53 (s, 1H), 7.52 (d, J=8.8, 2H), 7.40 (d, J=8.4, 2H), 6.03-5.99 (m, 1H), 5.97-5.94 (m, 1H), 1.48 (s, 9H); MS (DCI/NH3) m/e 305 (M+NH4)+.

1. customdegassed 1,2-dimethoxyethane (40 mL) and water (20 mL)
2. temperatureThe mixture for refluxed for 2 hours
3. temperaturerefluxed for 5 hours
4. temperatureThe reaction mixture was cooled to room temperature
5. filtrationfiltered
6. additiondiluted with water (200 mL)
7. extractionextracted twice with ethyl acetate (200 mL)
8. washwashed with brine
9. dry with materialdried (Na2SO4)
10. concentrationconcentrated to an orange oil
11. customThe residue was purified by silica gel chromatography (AnaLogix® SF25-40G; 50 micron silica; eluted with 0-15% ethyl acetate in hexane at 30 mL/min)

ORD 기록

ord-f3209763d32641529df0eaa50ca3ca31

출처 데이터셋

uspto-grants-2012_12

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US08338603B2