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78.1,77.0,61.1),Rha C-1~C-6(102.6,72.4,72.6,73.8, 81.1,72.8,69.8,18.4),Rib C-1~C-5(104.5,72.4,69.7,
[28]
70.2,18.5)。对比参考文献波谱数据 ,鉴定该化合物 69.0,65.1),GlcⅠ C-1~C-6(95.5,73.8,78.7,70.7,77.8,
为刺五加皂苷C3。 69.1),Glc Ⅱ C-1~C-6(104.6,75.2,76.5,78.1,77.1,
化 合 物 13:白 色 无 定 形 粉 末 。 ESI-MS 显 示 m/z 61.2),28-O-Rha C-1~C-6(102.6,72.4,72.5,73.9,70.1,
-
[24]
1 219 [M-H] ,综合其1D-NMR数据分析,推测其分子 18.3)。对比参考文献波谱数据 ,鉴定该化合物为
1
式为 C59H96O26。 H-NMR(500 MHz,C5D5N)显示 7 个甲 huzhangoside D。
基质子信号:δ H 0.84,0.85,0.85,1.01,1.06,1.18,1.19 化 合 物 15:白 色 无 定 形 粉 末 。 ESI-MS 显 示 m/z
-
(each 3H,s,CH3 );5 个糖端基质子信号:δ H 4.90(1H,d, 1 219 [M-H] ,综合其1D-NMR数据分析,推测其分子
J=6.2 Hz,Ara H-1),5.15(1H,d,J=7.9 Hz,3-O-Glc 式为 C59H96O26。 H-NMR(500 MHz,C5D5N)显示 6 个甲
1
H-1),5.82(1H,br s,Rha H-1),6.21(1H,d,J=8.1 Hz, 基质子信号:δ H 0.81,0.85,0.95,1.05,1.12,1.16(each
GlcⅠ H-1)和4.92(1H,d,J= 7.8 Hz,GlcⅡ H-1);Rha的 3H,s,CH3 );5 个糖端基质子信号:δ H 5.09(1H,d,J=6.4
甲基质子信号:δH 1.68(3H,d,J=6.2 Hz);苷元部分特征 Hz,Ara H-1),6.25(1H,s,3-O-Rha H-1),5.85(1H,br s,
质子信号:δ H 3.15(1H,m,H-18),5.38(1H,br s,H-12)。 28-O-Rha H-1),6.32(1H,d,J=8.2 Hz,Glc Ⅰ H-1)和
13 C-NMR(125 MHz,C5D5N)中δ C:38.7(C-1),26.4(C-2), 4.97(1H,d,J=7.9 Hz,GlcⅡ H-1);3-O-Rha 的甲基质子
88.7(C-3),39.4(C-4),55.7(C-5),18.5(C-6),33.1(C-7), 信号:δH 1.62(3H,d,J=6.2 Hz);28-O-Rha的甲基质子信
39.8(C-8),48.0(C-9),36.9(C-10),23.7(C-11),122.8 号:δ H 1.69(3H,d,J=6.2 Hz);苷元部分特征质子信号:
(C-12),144.0(C-13),42.0(C-14),28.1(C-15),23.3 δ H 3.12(1H,dd,J=3.6、13.7 Hz,H-18),5.34(1H,br s,
(C-16),47.0(C-17),41.6(C-18),46.2(C-19),30.7 H-12)。 C-NMR(125 MHz,C5D5N)中δ C:39.1(C-1),
13
(C-20),33.9(C-21),32.5(C-22),28.1(C-23),16.8 26.2(C-2),81.1(C-3),43.5(C-4),47.8(C-5),18.2(C-6),
(C-24),15.5(C-25),17.4(C-26),26.0(C-27),176.4 32.7(C-7),40.0(C-8),48.2(C-9),36.8(C-10),23.8
(C-28),33.1(C-29),23.6(C-30),Ara C-1~C-5(104.7, (C-11),122.9(C-12),144.1(C-13),42.2(C-14),28.4
80.9,73.4,68.2,64.9),3-O-Glc C-1~C-6(105.9,76.3, (C-15),23.3(C-16),47.1(C-17),41.7(C-18),46.1
78.2,71.5,78.0,62.5),GlcⅠ C-1~C-6(95.6,73.8,78.6, (C-19),30.7(C-20),33.9(C-21),32.5(C-22),63.9
70.8,78.0,69.1),Glc Ⅱ C-1~C-6(104.8,75.3,76.4, (C-23),13.8(C-24),16.2(C-25),17.4(C-26),26.0
78.2,77.1,61.2),Rha C-1~C-6(102.7,72.5,72.7,73.9, (C-27),176.5(C-28),33.1(C-29),23.6(C-30),Ara
70.2,18.5)。对比参考文献波谱数据 ,鉴定该化合物 C-1~C-5(104.3,75.6,74.7,69.3,65.7),3-O-Rha C-1~
[29]
为刺五加皂苷A1。 C-6(101.7,72.3,72.5,74.1,69.7,18.5),GlcⅠ C-1~C-6
化 合 物 14:白 色 无 定 形 粉 末 。 ESI-MS 显 示 m/z (95.6,73.9,78.7,70.8,77.9,69.2),Glc Ⅱ C-1~C-6
1 351 [M-H] ,综合其1D-NMR数据分析,推测其分子 (104.8,75.3,76.5,78.2,77.1,61.2),28-O-Rha C-1~C-6
-
1
式为 C64H104O30。 H-NMR(500 MHz,C5D5N)显示 6 个甲 (102.7,72.5,72.7,74.0,70.3,18.5)。对比参考文献波谱
基质子信号:δ H 0.83,0.86,0.97,1.02,1.10,1.13(each 数据 ,鉴定该化合物为刺楸皂苷B。
[30]
3H,s,CH3 );6 个糖端基质子信号:δ H 4.94(1H,d,J=7.0 化 合 物 16:白 色 无 定 形 粉 末 。 ESI-MS 显 示 m/z
Hz,Ara H-1),5.95(1H,d,J=4.6 Hz,Rib H-1),6.31(1H, 1 389 [M+Na] ,综合其 1D-NMR 数据分析,推测其分子
+
s,3-O-Rha H-1),5.81(1H,br s,28-O-Rha H-1),6.21 式为 C65H106O30。 H-NMR(500 MHz,C5D5N)显示 7 个甲
1
(1H,d,J=8.0 Hz,GlcⅠ H-1)和 4.97(1H,d,J=7.9 Hz, 基质子信号:δ H 0.87,1.08,1.09,1.15,1.22(each 3H,s,
GlcⅡ H-1);3-O-Rha 的甲基质子信号:δ H 1.67(3H,d, CH3 ),0.86(6H,s,2×CH3 );6 个糖端基质子信号:δ H 4.75
J=6.2 Hz);28-O-Rha 的甲基质子信号:δ H 1.68(3H,d, (1H,d,J=6.2 Hz,Ara H-1),5.15(1H,d,J=7.9 Hz,
J=6.1 Hz);苷元部分特征质子信号:δ H 3.22(1H,dd,J= 3-O-Glc H-1),6.17(1H,s,3-O-Rha H-1),5.85(1H,br s,
3.8、13.7 Hz,H-18),5.41(1H,br s,H-12)。 C-NMR 28-O-Rha H-1),6.28(1H,d,J=8.2 Hz,GlcⅠ H-1),GlcⅡ
13
(125 MHz,C5D5N)中 δ C:39.0(C-1),26.2(C-2),81.0 H-1(overlapped);3-O-Rha的甲基质子信号:δ H 1.62(3H,
(C-3),43.5(C-4),47.7(C-5),18.1(C-6),32.7(C-7),39.9 d,J=6.2 Hz);28-O-Rha的甲基质子信号:δH 1.66(3H,d,
(C-8),48.1(C-9),36.8(C-10),23.8(C-11),122.8 J=6.1 Hz);苷元部分特征质子信号:δ H 3.16(1H,dd,J=
(C-12),144.0(C-13),42.1(C-14),28.3(C-15),23.3 4.0、11.5 Hz,H-18),5.39(1H,br s,H-12)。 C-NMR
13
(C-16),47.1(C-17),41.6(C-18),46.1(C-19),30.7 (125 MHz,C5D5N)中 δ C:38.8(C-1),26.5(C-2),88.6
(C-20),33.9(C-21),32.4(C-22),63.9(C-23),13.9 (C-3),39.4(C-4),55.8(C-5),18.5(C-6),33.0(C-7),39.7
(C-24),16.1(C-25),17.5(C-26),26.1(C-27),176.5 (C-8),47.9(C-9),36.9(C-10),23.8(C-11),122.8
(C-28),33.2(C-29),23.7(C-30),Ara C-1~C-5(104.6, (C-12),144.0(C-13),42.0(C-14),28.1(C-15),23.3
75.3,75.0,69.7,66.4),3-O-Rha C-1~C-6(101.2,71.9, (C-16),47.0(C-17),41.5(C-18),46.1(C-19),30.7
·608 · China Pharmacy 2022 Vol. 33 No. 5 中国药房 2022年第33卷第5期