反应详情

Synthesis of pentachlorophenyl (E)-3-[4-[bis(4-fluorobenzoyloxymethoxyphosphinyl)difluoromethyl]phenyl]-but-2-enoate (6b1 R1=4-Fluorobenzoyloxymethyl) NaOH (80 mg, 2.0 mmol) in 2 mL of H2O was added dropwise to a stirred suspension of pentachlorophenyl (E)-3-(4-phosphonyldifluoromethyphenyl) but-2-enoate (500 mg, 0.92 mmol) in 5 mL of H2O. When the mixture became clear (pH˜9), AgNO3 (510 mg, 3.0 mmol) was added. After 2 h at 4° C. the gray precipitate was collected by filtration, dried over P2O5 in vacuo, and pulverized in a mortar and pestle. The powder (400 mg) was suspended in dry toluene (10 mL) and iodomethyl 4-fluorobenzoate (290 mg, 1.03 mmol) was added and stirred for 48 h at room temperature. After filtration the solvent was removed in vacuo and the crude product was purified by silica gel column chromatography eluting with 30% EtOAc-hexanes to give colorless oil. Yield 290 mg, (61%). 1H NMR (300 MHz, CDCl3): δ 2.49 (s, 3H), 5.87 (m, 4H), 6.3 (s, 1H), 7.01 (m, 4H), 7.45 (d, J=8.4 Hz, 2H), 7.54 (d, J=8.4 Hz, 2H), 7.94 (m, 4H). 13C NMR (75 MHz, CDCl3): δ 18.3, 82.5, 82.8, 115.0, 115.7, 116.1, 124.5, 126.7, 127.9, 131.4, 132.0, 132.7, 132.9, 144.2, 161.6, 163.6, 164.7, 168.1. HRMS (M+H) calc, 844.9272; found, 844.9278.

1. additionwas added
2. filtrationAfter 2 h at 4° C. the gray precipitate was collected by filtration
3. dry with materialdried over P2O5 in vacuo
4. filtrationAfter filtration the solvent
5. customwas removed in vacuo
6. customthe crude product was purified by silica gel column chromatography
7. washeluting with 30% EtOAc-hexanes
8. customto give colorless oil