Reaction Steps
Triphenylphosphine (1.98 g, 7.55 mmol), CCl4 (2.18 mL, 22.62 mmol), and dry CH2Cl2 (13.7 mL) were added to 2-(4-benzyloxy-2-nitrophenyl)ethanol (1.03 g, 3.77 mmol) in a round bottom flask. A red solution with pink precipitate formed, but dissolved after 30 min. The solution was allowed to stir overnight under positive pressure of nitrogen. The solution was checked by TLC (20% ethyl acetate/petroleum ether) and then concentrated using a rotoevaporator. The brown oily residue was purified using silica gel column chromatography and a 10% ethyl acetate, 5% CHCl3, and 85% petroleum ether solvent system. 2-(4-Benzyloxy-2-nitrophenyl)ethyl chloride was isolated as a thick yellowish oil which solidified upon standing in the refrigerator (1.06 g, 3.64 mmol, 97% yield). Mp 38-40° C.; TLC (20% ethyl acetate/hexane) Rf=0.53; 1H-NMR (500 MHz, CDCl3) 7.51 (d, 2.5, 1H), 7.33 (m, 5H), 7.23 (d, 8.5, 1H), 7.10 (dd, 2.5, 8.5, 1H), 5.02 (s, 2H), 3.70 (t, 7.0, 2H), 3.20 (t, 7.0, 2H); 13C-NMR (125 MHz, CDCl3) 158.1, 149.5, 135.7, 143.0, 128.7, 128.4, 127.5, 125.1, 120.4, 110.7, 70.6, 44.0, 35.8; IR (neat) 3092, 3038, 2962, 2919, 2865, 1618, 1570, 1532, 1499, 1451, 1343, 1294, 1197, 1160, 1062, 1019, 906, 847, 809, 739, 696, 652; EI-MS m/z (relative intensity) 291 (M+, 10); isotope pattern of M+ and M++2 agrees with the presence of one chlorine atom. Accurate mass (EI-MS) for C15H1435ClNO3: calcd. 291.0662, obsd. 291.0667.
