反应详情

A solution of 13 (1.02 g, 4.06 mmol, 10 equiv) in CH3CN (3.5 mL 1.16M) was treated with triphenylphosphine (1.17 g, 4.47 mmol, 1.1 equiv) and stirred at reflux for 10 h. Additional triphenylphosphine (0.532 g, 2.03 mmol, 0.5 equiv) was added to the reaction mixture and stirring was continued at reflux for 5 h. The reaction mixture was concentrated under reduced pressure and washed repeatedly with Et2O (5×10 mL washes). The remaining residue was then solubilized in the minimum volume of CH2Cl2 and concentrated under reduced pressure to afford 14 as a colorless foam (1.90 g, 2.08 g theoretical, 91.3%): 1H NMR (CDCl3, 250 MHz) δ7.82-7.51 (m, 15H, ArH), 3.70-3.46 (m, 5H, CH3OC(O)R and CH2PPh3), 2.13 (t, 2H, J=7.4 Hz, CH2C(O)OCH3), 1.62-1.02 (m, 12H, alkyl protons); FABHRMS (NBA) m/e 433.2312 (C28H34BrO2P--Br- requires 433.2296).

1. temperatureat reflux for 10 h
2. stirringstirring
3. temperatureat reflux for 5 h
4. concentrationThe reaction mixture was concentrated under reduced pressure
5. washwashed repeatedly with Et2O (5×10 mL washes)
6. concentrationconcentrated under reduced pressure