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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
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