在25 mL的干燥二氯甲烷中溶解139 mg二氫卟吩醇7 (0.239 mmol), 在氮氣保護下, 迅速加入20 mg N-甲基嗎啉氧化物(N-MMO)并避光攪拌15 min, 再小量分批加入30 mg高釕酸四丙基銨(TPAP), 攪拌6 h后反應結束.加入20 mL水, 靜置過夜后分出水層, 水層用二氯甲烷萃取(15 mL×3), 合并有機層并用無水硫酸鈉干燥.除去溶劑, 剩余物經硅膠柱層析分離[洗脫劑: V(石油醚):V(乙酸乙酯)＝3:1], 得78 mg黃紅色固體8 (0.134 mmol), 產率為56%. mp. 203~206 ℃; UV-vis (CH2Cl2)λmax [ε/(L?mol－1?cm－1)]: 412 (1.38×105), 509 (2.02×104), 536 (2.81×104), 610 (3.06×104), 669 (5.78×104) nm; 1H NMR (CDCl3) δ: 0.04 (br s, 1H, NH), 0.88 (br s, 1H, NH), 1.42 (d, J＝7.0 Hz, 3H, 18-CH3), 1.63 (t, J＝7.6 Hz, 3H, 3a-CH3), 1.66 (t, J＝7.6 Hz, 3H, 8a-CH3), 2.27~2.34 (m, 2H, 17a+17bH), 2.42~2.50 (m, 1H, 17a+17b-H), 2.57~2.65 (m, 1H, 17a+17b-H), 3.55 (q, J＝7.6 Hz, 2H, 8a-H), 3.74 (q, J＝7.5 Hz, 2H, 3a-H), 3.27, 3.45, 3.54, 3.63 (each s, each 3H, CH3+OCH3), 4.03 (dd, J＝9.2, 3.2 Hz, 1H, 17-H), 4.98 (d, J＝20.0 Hz, 1H, 132-H), 5.05 (d, J＝20.0 Hz, 1H, 132-H), 5.18 (q, J＝7.0 Hz, 1H, 18-H), 9.21, 9.27 (each s, each 1H, meso-H), 11.80(s, 1H, 20-CHO); IR (KBr) v: 3465 (N—H), 2920 (C—H), 1742, 1697 (C＝O), 1604 (C＝C), 1502 (chlorin skeleton), 1457, 1388, 1264, 1198, 1083, 1043 cm－1; EI-MS m/z: 579.4 (M+H+). Anal. calcd for C35H38N4O4: C 72.64, H 6.62, N 9.68; found C 72.81, H 6.76, N 9.60.
化學慧定制合成事業部
