Page 156 - 《广西植物》2023年第6期
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1 1 4 2 广 西 植 物 43 卷
(Agl C ̄5)ꎬ 114.9 ( Caf C ̄8″)ꎬ 113.8 ( Caf C ̄2″)ꎬ pedicularioside Mꎮ
102.5 (Glu C ̄1′)ꎬ 101.5 ( Rha C ̄1‴)ꎬ 79.3 ( Glu 化合物 15 黄绿色固体ꎬ分子式为 C H O ꎮ
35 46 20
+ 1
C ̄3′)ꎬ 74.7 ( Glu C ̄5′)ꎬ 74.7 ( Glu C ̄2′)ꎬ 71.9 ESI ̄MS m / z: 809. 26 [ M + Na] ꎮ H ̄NMR ( 500
(Rha C ̄4‴)ꎬ 70. 8 ( Rha C ̄2‴)ꎬ 70. 6 ( Rha C ̄ MHzꎬ DMSO ̄d ) δ : 7.47 (1Hꎬ dꎬ J = 15.8 Hzꎬ
6 H
3‴)ꎬ 70. 5 ( Agl C ̄8)ꎬ 69. 4 ( Rha C ̄5‴)ꎬ 69. 0 Caf H ̄7″)ꎬ 7.03 (1Hꎬ dꎬ J = 2.1 Hzꎬ Caf H ̄2″)ꎬ
(Glu C ̄4′)ꎬ 61. 0 ( Glu C ̄6′)ꎬ 35. 2 ( Agl C ̄7)ꎬ 6.98 (1Hꎬ ddꎬ J = 8.3ꎬ 2.1 Hzꎬ Caf H ̄6″)ꎬ 6.76
18.4 ( Rha C ̄6‴)ꎮ 以上数据与文 献 ( Lan et al.ꎬ (1Hꎬ dꎬ J = 8.1 Hzꎬ Caf H ̄5″)ꎬ 6.71 ~ 6.68 (2Hꎬ
2018)报道的毛蕊花苷( acteoside) 的数据基本一 mꎬ Agl H ̄2 / 5)ꎬ 6.58 (1Hꎬ ddꎬ J = 8.0ꎬ 2.0 Hzꎬ
致ꎬ 故鉴定化合物 13 为毛蕊花苷(acteoside)ꎮ Agl H ̄6)ꎬ 6.20 (1Hꎬ dꎬ J = 15.9 Hzꎬ Caf H ̄8″)ꎬ
化合物 14 黄色固体ꎬ分子式为 C H O ꎮ 5.02 (1Hꎬ dꎬ J = 1.5 Hzꎬ Rha H ̄1‴)ꎬ 4.76 (1Hꎬ
35 46 19
+ 1
ESI ̄MS m / z: 793. 26 [ M + Na] ꎮ H ̄NMR ( 600 dꎬ J = 2.8 Hzꎬ Api H ̄1 ‴′)ꎬ 4.68 (1Hꎬ tꎬ J = 9.7
MHzꎬ DMSO ̄d ) δ : 7.54 (1Hꎬ dꎬ J = 15.8 Hzꎬ Hzꎬ Glu H ̄4′)ꎬ 4.42 (1Hꎬ dꎬ J = 7.8 Hzꎬ Glu H ̄
6 H
Acyl H ̄7″)ꎬ 7.29 ( 1Hꎬ dꎬ J = 2. 0 Hzꎬ Acyl H ̄ 1′)ꎬ 4.25 (1Hꎬ ddꎬ J = 7.8ꎬ 3.9 Hzꎬ Agl H ̄7)ꎬ
2″)ꎬ 7.09 (1Hꎬ ddꎬ J = 8.3ꎬ 2.0 Hzꎬ Acyl H ̄6″)ꎬ 3.79 (1Hꎬ dꎬ J = 9.3 Hzꎬ Agl H ̄8a)ꎬ 3.72 ~ 3.57
6.79 (1Hꎬ dꎬ J = 8.1 Hzꎬ Acyl H ̄5″)ꎬ 6.59 (2Hꎬ (7Hꎬ mꎬ Glu H ̄3′ / 5′ꎬ Api H ̄2 ‴′ / 3 ‴′ / 4 ‴′ꎬ Rha
mꎬ Agl H ̄2 / 5)ꎬ 6.50 (1Hꎬ ddꎬ J = 8.1ꎬ 2.1 Hzꎬ H ̄2‴)ꎬ 3.57 ~ 3.46 (2Hꎬ mꎬ Agl H ̄8bꎬ Glu H ̄6′
Agl H ̄6)ꎬ 6. 41 ( 1Hꎬ dꎬ J = 15. 9 Hzꎬ Acyl H ̄ a)ꎬ 3.36 ~ 3.17 (6Hꎬ mꎬ Api H ̄5 ‴′ꎬ Glu H ̄2′ / 6′ꎬ
8″)ꎬ 5.03 (1Hꎬ dꎬ J = 1.7 Hzꎬ Rha H ̄1‴)ꎬ 4.78 Rha H ̄3‴/ 5‴)ꎬ 3. 13 ( 3Hꎬ dꎬ J = 6. 1 Hzꎬ 7 ̄
(1Hꎬ dꎬ J = 2.9 Hzꎬ Api H ̄1 ‴′)ꎬ 4.64 (1Hꎬ tꎬ OCH )ꎬ 3.09 (1Hꎬ dꎬ J = 9.4 Hzꎬ Rha H ̄4‴)ꎬ
3
13
J = 9. 7 Hzꎬ Glu H ̄4′)ꎬ 4. 38 ( 1Hꎬ dꎬ J = 7. 9 0.96 (3Hꎬ dꎬ J = 6.2 Hzꎬ Rha H ̄6‴)ꎮ C ̄NMR
Hzꎬ Glu H ̄1′)ꎬ 3.80 (3Hꎬ sꎬ 3″ ̄OCH )ꎬ 3.76 ~ (125 MHzꎬ DMSO ̄d ) δ : 165. 7 ( Caf C ̄9″)ꎬ
3 6 C
3.63 (7Hꎬ mꎬ Glu H ̄3′ / 5′ꎬ Api H ̄2 ‴′ / 3 ‴′ / 4 ‴′ꎬ 148.5 (Caf C ̄4″)ꎬ 145.8 ( Caf C ̄7″)ꎬ 145.6 ( Caf
Rha H ̄2‴)ꎬ 3. 57 ~ 3. 48 ( 2Hꎬ mꎬ Agl H ̄8 )ꎬ C ̄3″)ꎬ 145.2 (Agl C ̄4)ꎬ 145.0 (Agl C ̄3)ꎬ 129.7
3.32 ~ 3.18 (6Hꎬ mꎬ Api H ̄5‴′ꎬ Glu H ̄2′ / 6′ꎬ Rha (Agl C ̄1)ꎬ 125.5 ( Caf C ̄1″)ꎬ 121.4 ( Caf C ̄6″)ꎬ
H ̄3″ / 5‴) ꎬ 3.10 (1Hꎬ tꎬ J = 9.4 Hzꎬ Rha H ̄4‴)ꎬ 118.1 ( Agl C ̄6)ꎬ 115.8 ( Caf C ̄5″)ꎬ 115.4 ( Agl
2.80 ~ 2.65 (2Hꎬ mꎬ Agl H ̄7)ꎬ 0.98 (3Hꎬ dꎬ J = C ̄5)ꎬ 114.8 (Caf C ̄2″)ꎬ 114.0 ( Agl C ̄2)ꎬ 113.4
13
6.2 Hzꎬ Rha H ̄6‴)ꎮ C ̄NMR (150 MHzꎬ DMSO ̄ (Caf C ̄8″)ꎬ 109. 1 ( Api C ̄1 ‴′)ꎬ 102. 8 ( Glc C ̄
d ) δ : 166. 3 ( Acyl C ̄9″)ꎬ 150. 0 ( Acyl C ̄3″)ꎬ 1′)ꎬ 101. 2 ( Rha C ̄1‴)ꎬ 82. 2 ( Agl C ̄7)ꎬ 78. 9
6 C
148.4 ( Acyl C ̄4″)ꎬ 146. 2 ( Acyl C ̄7″)ꎬ 145. 5 (Glc C ̄3′)ꎬ 78. 8 ( Api C ̄3 ‴′)ꎬ 75. 9 ( Api C ̄
(Agl C ̄3)ꎬ 144.0 ( Agl C ̄4)ꎬ 129.6 ( Agl C ̄1)ꎬ 2 ‴′)ꎬ 74. 3 ( Glc C ̄2′)ꎬ 73. 7 ( Agl C ̄8)ꎬ 73. 4
126.0 ( Acyl C ̄1″)ꎬ 123. 7 ( Acyl C ̄6″)ꎬ 120. 0 ( Api C ̄4 ‴′)ꎬ 72.7 (Glc C ̄5′)ꎬ 71.6 (Rha C ̄4‴)ꎬ
(Agl C ̄6)ꎬ 116.8 ( Agl C ̄2)ꎬ 116.0 ( Agl C ̄5)ꎬ 70.5 (Rha C ̄5‴)ꎬ 70.4 (Rha C ̄3‴)ꎬ 69.3 (Glc C ̄
115.7 ( Acyl C ̄8″)ꎬ 114. 3 ( Acyl C ̄5″)ꎬ 111. 5 4′)ꎬ 68. 7 ( Rha C ̄5‴)ꎬ 67. 0 ( Glc C ̄6′)ꎬ 63. 2
(Acyl C ̄2″)ꎬ 109.6 ( Api C ̄1 ‴′)ꎬ 102.7 ( Glu C ̄ (Api C ̄5 ‴′)ꎬ 56.0 (7 ̄OCH )ꎬ 18.1 ( Rha C ̄6‴)ꎮ
3
1′)ꎬ 101.7 ( Rha C ̄1‴)ꎬ 79.3 ( Glu C ̄3′ꎬ Api C ̄ 分析质谱和 NMR 数据ꎬ发现化合物 15 与连翘酯
3‴′)ꎬ 76.4 ( Api C ̄2 ‴′)ꎬ 74.8 ( Glu C ̄2′)ꎬ 73.9 苷 B 的结构相近( Wang et al.ꎬ 2005) ꎬ主要区别
( Api C ̄4 ‴′)ꎬ 73.3 (Glu C ̄5′)ꎬ 72.1 (Rha C ̄4‴)ꎬ 在于化 合 物 15 多 了 1 个 甲 氧 基 结 构 片 段 信 号
71.0 (Rha C ̄2‴)ꎬ 70.8 (Rha C ̄3‴)ꎬ 70.8 (Agl C ̄ [ δ 3.13 (3Hꎬ dꎬ J = 6.1 Hzꎬ7 ̄OCH ) ꎬδ 56.0
C
3
H
8)ꎬ 69. 9 ( Glu C ̄4′)ꎬ 69. 2 ( Rha C ̄5‴)ꎬ 67. 6 (7 ̄OCH ) ] ꎬ以及由甲氧基引起的 C ̄7 位次甲基
3
(Glu C ̄6′)ꎬ 63.6 (Api C ̄5 ‴′)ꎬ 56.1 (3″ ̄OCH )ꎬ CH 的化学位移向低场位移的信号 δ 73.4 ( Agl
C
3
35.5 (Agl C ̄7)ꎬ 18.6 (Rha C ̄6‴)ꎮ 以上数据与文 C ̄8) ꎬ82.2 ( Agl C ̄7) ꎬ129.7 ( Agl C ̄1) ꎬ HMBC
献(Jia & Gaoꎬ 1993)报道的 pedicularioside M 的数 谱上 可 观 测 δ 3. 13 ( 3Hꎬ dꎬ J = 6. 1 Hzꎬ 7 ̄
H
据 基 本 一 致ꎬ 故 鉴 定 化 合 物 14 为 OCH ) 与 δ 82.2( Agl C ̄7 ) 远程相关的信号ꎬ进
3
C