將248 mg (0.409 mmol)化合物1a溶解于25 mL二氯甲烷中, 加入由氫氧化鉀飽和的5 mL甲醇溶液, 室溫攪拌1.5 h, 加入20 mL水, 攪拌下滴加濃鹽酸調節pH至3.加入30 mL二氯甲烷分出有機層, 水相用二氯甲烷萃取(40 mL×2), 合并有機層, 水洗兩次后用無水硫酸鈉干燥, 減壓除盡溶劑, 用少量2 mL二氯甲烷將固體混合物溶解, 移至含有1.5 mL羥乙胺的20 ml干燥的甲苯中, 攪拌回流8 h, 減壓除去反應溶劑, 將所得粗產物13重新溶解在20 mL四氫呋喃中, 將反應體系溫度降低至0 ℃, 加入氫氧化鋰溶液(400 mg LiOH溶解在20 mL甲醇和5 mL水中), 室溫攪拌6 h, 用25%的硫酸溶液調至pH值為2, 用CH2Cl2萃取反應液(15 mL×3), 合并有機層, 水洗后用無水硫酸鈉干燥, 減壓濃縮, 剩余物用硅膠柱層析[洗脫劑: V(石油醚):V(乙酸乙酯)＝3:1]分離, 得73 mg黃綠色固體14 (0.115 mmol).產率28%. m.p. 225~228 ℃; UV-vis (CH2Cl2) λmax [ε/(L?mol－1?cm－1)]: 382 (5.23×104), 422 (1.03×103), 508 (9.22×102), 548 (5.15×103), 715 (9.02×103) nm; 1H NMR (400 MHz, CDCl3) δ: 0.73 (br s, 1H, NH), 0.80 (br s, 1H, NH), 1.54 (t, J＝7.6 Hz, 3H, 8a-CH3), 1.62 (d, J＝7.2 Hz, 3H, 18-CH3), 1.78~1.98 (m, 1H, 17a+17b-H), 2.27~2.46 (m, 2H, 17a+17b-H), 2.61~2.69 (m, 1H, 17a+17b-H), 2.91, 3.13, 3.54 (each s, each 3H, CH3+OCH3), 3.43 (q, J＝7.6 Hz, 2H, 8a-H), 4.07~4.13 (m, 3H, CH2OH+18-H), 4.67 (t, J＝5.0 Hz, 2H, NCH2), 5.03 (dd, J＝8.9, 2.0 Hz, 1H, 18-H), 4.75 (dd, J＝9.0, 3.0 Hz, 1H, 17-H), 6.09 (d, J＝11. 6 Hz, 1H, cis-3b-H), 6.16 (d, J＝17.8 Hz, 1H, trans-3b-H), 7.63 (dd, J＝17.8, 11.6 Hz, 3a-H), 8.13, 8.76, 10.18 (each s, each 1H, meso-H), 11.73 (s, 1H, 12-CHO); 13C NMR (CDCl3)δ: 196.3, 173.8, 171.7, 159.6, 150.7, 148.9, 146.7, 144.8, 144.6, 139.6, 138.9, 135.6, 134.0, 132.6, 131.8, 131.7, 118.9, 118.0, 106.0, 104.9, 96.8, 51.8, 51.6, 49.4, 49.6, 30.9, 29.8, 29.7, 22.1, 20.5, 19.3, 16.9, 16.3, 15.9, 15.4, 11.4; IR (KBr) v: 3454 (N—H), 2956 (C—H), 1741, 1706 (C＝O), 1604 (C＝C), 1523 (chlo in skeleton), 1463, 1365, 1229, 1032, 989 cm－1; EI-MS m/z: 636.2 (M+H+). Anal. calcd for C36H37N5O6: C 68.02, H 5.87, N 11.02; found C 68.21, H 6.01, N 11.09.
化學慧定制合成事業部
