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N-丁基20-(2’-甲酰乙烯基)红紫素-18二酰亚胺甲酯(6) 的合成2017-09-12

将0.4 mL三氯氧磷滴加到由0.4 mL 3, 3-二甲氨基丙烯醛和4 mL二氯甲烷组成的混合溶液, 在0 ℃下搅拌15 min.然后在相同温度下, 搅拌加入到已经预冷至-5 ℃的含有128 mg锌配合物5(0.184 mmol)的20 mL二氯甲烷中.撤去冰水浴, 室温搅拌18 h.搅拌下加入120 mL饱和碳酸氢钠水溶液, 室温搅拌过夜, 用二氯甲烷萃取反应液(30 mL×3), 合并有机层并水洗两次, 无水硫酸钠干燥后用重氮甲烷进行甲基化处理, 减压除去溶剂, 将所得固体混合物用硅胶柱层析分离[洗脱剂: V(石油醚):V(乙酸乙酯)=3:1], 得75 mg红色固体6 (0.108 mmol), 产率59%. m.p. 206~209 ℃; UV-vis (CH2Cl2)λmax [ε/(L•mol-1•cm-1)]: 367 (5.93×103), 420 (1.12×104), 532 (9.41×102), 570 (5.08×103), 735 (9.45×103) nm; 1H NMR (CDCl3) δ: -0.02 (br s, 1H, NH), 0.60 (br s, 1H, NH), 0.88 (t, J=6.6 Hz, N-C-C-C-CH3), 1.30 (t, J=7.6 Hz, 3H, 8a-CH3), 1.63 (d, J=7.2 Hz, 3H, 18-CH3), 1.18~1.78 (m, 4H, NC-CH2CH2-C), 1.98~2.20 (m, 2H, 17a+17b-H), 2.27~2.50 (m, 1H, 17a+17b-H), 2.76~2.87 (m, 1H, 17a+17b-H), 2.98, 3.09, 3.62, 3.72 (each s, each 3H, CH3+OCH3), 3.56 (q, J=7.6 Hz, 2H, 8a-H), 4.34 (t, J=6.6 Hz, 2H, NCH2-), 4.61 (q, J=7.2 Hz, 1H, 18-H), 5.11 (dd, J=8.8, 2.7 Hz, 1H, 17-H), 6.12 (d, J=17.8 Hz, 1H, trans-3b-H), 6.16 (d, J=11.5 Hz, 1H, cis-3b-H), 6.19 (dd, J=15.7, 7.7 Hz, 1H, 20b-H), 7.71 (dd, J=17.8, 11.5 Hz, 1H, 3a-H), 8.93 (d, J=15.7 Hz, 1H, 20a-H), 9.30, 9.36 (each s, each 1H, meso-H), 10.11 (d, J=7.7 Hz, 20b-CHO); 13C NMR (CDCl3) δ: 201.1, 174.4, 172.8, 166.0, 161.7, 154.0, 151.3, 146.7, 144.7, 143.6, 140.7, 139.6, 137.1, 136.2, 135.7, 133.8, 131.0, 130.7, 130.2, 129.9, 123.2, 106.6, 106, 1, 101.8, 94.0, 52.6, 52.2, 49.8, 31.7, 31.2, 31.0, 30.7, 30.6, 26.1, 24.4, 24.3, 20.0, 18.2, 12.9, 12.8, .11.8; IR (KBr) v: 3346 (N—H), 2960 (C—H), 1738, 1704 (C=O), 1664 (C=C), 1542 (chlorin skeleton), 1458, 1365, 1174, 1068, 981 cm-1; EI-MS m/z: 688.2 (M+H+). Anal. calcd for C41H45N5O5: C 71.59, H 6.59, N 10.18; found C 71.61, H 6.44, N 9.99.

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