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N-丁基红紫素-18二酰亚胺甲酯锌配合物(5) 的合成2017-09-12

将248 mg (0.409 mmol)脱镁叶绿酸甲酯-a (1a)溶解于25 mL二氯甲烷中, 加入由氢氧化钾饱和的5 mL甲醇溶液, 室温搅拌1.5 h, 加入20 mL水, 搅拌下滴加浓盐酸调节pH值约至2.加入30 mL二氯甲烷分出有机层, 水相用二氯甲烷萃取(40 mL×2), 合并有机层, 水洗两次后用无水硫酸钠干燥, 减压除尽溶剂, 用少量二氯甲烷将固体混合物溶解, 移至含有1.5 mL正丁胺和1 g研细的醋酸锌的20 mL干燥的吡啶中, 搅拌回流8 h.减压除去反应溶剂, 先后加入30 mL二氯甲烷和60 mL水进行分层.分出有机相并水洗两次, 干燥后用重氮甲烷进行甲基化, 减压除去溶剂, 将所得固体混合物经硅胶柱层析分离[洗脱剂: V(石油醚):V(乙酸乙酯)=3:1], 得194 mg绿色固体5 (0.278 mmol), 产率68%. m.p. 201~203 ℃; UV-vis (CH2Cl2)λmax [ε/(L• mol-1•cm-1)]: 418 (5.23×103), 483 (1.07×104), 513 (9.42×102), 551 (5.01×103), 709 (9.34×103) nm; 1H NMR (CDCl3) δ: 0.92 (t, J=6.6 Hz, 3H, N-C-C-C-CH3), 1.33 (t, J=7.6 Hz, 3H, 8a-CH3), 1.53 (d, J=7.2 Hz, 3H, 18-CH3), 1.24~1.64 (m, 4H, NC-CH2CH2-C), 1.88~2.01 (m, 2H, 17a+17b-H), 2.08~2.31 (m, 1H, 17a+17b-H), 2.52~2.73 (m, 1H, 17a+17b-H), 2.97, 3.00, 3.51, 3.61 (each s, each 3H, CH3+OCH3), 3.46 (q, J=7.6 Hz, 2H, 8a-H), 4.07 (q, J=7.2 Hz, 1H, 18-H), 4.27 (t, J=6.6 Hz, 2H, NCH2), 4.77 (dd, J=8.4, 3.0 Hz, 1H, 17-H), 5.95 (d, J=11.6 Hz, 1H, cis-3b-H), 5.97 (d, J=17.8 Hz, 1H, trans-3b-H), 7.60 (dd, J=17.8, 11.6 Hz, 3a-H), 7.93, 8.80, 9.04 (each s, 2H, meso-H); 13C NMR (CDCl3) δ: 175.1, 164.7, 156.0, 152.3, 150.7, 147.0, 144.0, 142.2, 141.3, 140.6, 140.2, 136.6, 136.2, 135.9, 134.7, 130.3, 129.9, 128.1, 124.9, 122.5, 113.9, 112.4, 109.9, 104.6, 101.3, 93.8, 52.7, 52.5, 49.8, 32.1, 30.7, 30.6, 24.5, 20.0, 18.2, 12.8, 12.3, 11.9; IR (KBr) v: 3410 (N—H), 2929 (C—H), 1726, 1690 (C=O), 1647 (C=C), 1551 (chlorin skeleton), 1437, 1380, 1271, 1141, 1070 cm-1; EI-MS m/z: 698.5 (M+H+). Anal. calcd for C38H41N5O4Zn: C 65.47, H 5.93, N 10.05; found C 65.51, H 6.09, N 10.19.

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