86% |
In toluene; at 20℃; for 12h; |
Example 2: Synthesis of Compound IB; (2-Bromomethyl-phenyl)-methanol (0.25g, 1.24 mmol) wasdissolved in toluene (10cm3), and added dropwise to astirred suspension oftetrakis(triphenylphosphine)palladium(O) (1.43g, 1.24mmol) in toluene (60cm3) . The suspension was degassed andpurged with N2. The mixture was stirred at roomtemperature for 12 hours, and then filtered. The solidproduct was washed with diethyl ether (3 x 20cm3) anddried in vacua to give compound IB as an amorphous, off-white solid (605mg, 86%), this was then recrystallisedfrom dichloromethane and petroleum ether to give yellowcubes, mp 168-171 C (decomp.) (Found: C, 54.96; H,4.28%; C26H24BrOPPd requires C, 54.81; H, 4.28%); NMRassignments made by HMQC, NOE, DEPT, 8H [CDC13] 2.80 (2H,d, 3JH-ia,ib-31p = 2.5 Hz), 4.55 (bs, 2H, H-4), 6.15 (1H, d, Jk-7,8 = 7.68 Hz, H-7), 7.0 (m, 3H, H-8 or 9 or 10), 7.40-7.55 (m, 6H, PPh3), 7.60-7.70, (m, 9H, PPh3) ; 5C [CDC13]30.91 (C-l), 64.18 (C-4), 124.89 (C-8 or 9'or 10), 127.65(C-7), 127.75, (C-8 or 9 or 10), 128.39 (PPh3-C) , 128.54(PPh3-C) , 128.64, (C-8 or 9 or 10), 130.41, (PPh3-C) ,131.0 (PPh3-ipso 4C) , 134.26 (PPh3-C) , 134.47 (PPh3-C) ,138.9 (C-2 or C-3), 141.05 (C-2 / C-3); 8P [CDC13] 42.61(s) ; m/z Electrospray (2M - 79Br)*+, 1058 (47%) C26H24BrOPPdrequires 568; X-ray data, (C-l-Pd, 2.066A) , (O-Pd, 2.124A) ,(P-Pd, 2.194A), (Cl-Pd, 2.5055A) . |