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6 期 马文杰等: 全缘叶紫珠化学成分研究 1 1 4 1
MHzꎬ DMSO ̄d ) δ : 7.54 (1Hꎬ dꎬ J = 15.8 Hzꎬ 6)ꎬ 6.30 (1Hꎬ dꎬ J = 15.9 Hzꎬ Caf H ̄8″)ꎬ 5.20
6 H
Acyl H ̄7″)ꎬ 7.29 ( 1Hꎬ dꎬ J = 2. 0 Hzꎬ Acyl H ̄ (1Hꎬ dꎬ J = 1.7 Hzꎬ Rha H ̄1‴)ꎬ 4.51 (1Hꎬ ddꎬ
2″)ꎬ 7.09 (1Hꎬ ddꎬ J = 8.2ꎬ 2.0 Hzꎬ Acyl H ̄6″)ꎬ J = 11.9ꎬ 2.2 Hzꎬ Glu H ̄6a′)ꎬ 4.39 ~ 4.36 (1Hꎬ
6.79 (1Hꎬ dꎬ J = 8.1 Hzꎬ Acyl H ̄5″)ꎬ 6.70 (2Hꎬ mꎬ Glu H ̄6b′)ꎬ 4.34 (1Hꎬ dꎬ J = 7.9 Hzꎬ Glu H ̄
dꎬ J = 8.1 Hzꎬ Agl H ̄2 / 5)ꎬ 6.58 (1Hꎬ ddꎬ J = 1′)ꎬ 4. 04 ~ 3. 93 ( 3Hꎬ mꎬ Agl H ̄8bꎬ Rha H ̄2‴/
8.1ꎬ 2.1 Hzꎬ Agl H ̄6)ꎬ 6.42 (1Hꎬ dꎬ J = 15.9 4‴)ꎬ 3.75 ~ 3.69 (2Hꎬ mꎬ Agl H ̄8aꎬ Rha H ̄3‴)ꎬ
Hzꎬ Acyl H ̄8″)ꎬ 5.03 (1Hꎬ dꎬ J = 1.7 Hzꎬ Rha 3. 58 ~ 3. 55 ( 1Hꎬ mꎬ Glu H ̄5′)ꎬ 3. 54 ( 1Hꎬ dꎬ
H ̄1‴)ꎬ 4.76 (1Hꎬ dꎬ J = 2.9 Hzꎬ Api H ̄1 ‴′)ꎬ J = 8.9 Hzꎬ Glu H ̄3′)ꎬ 3.42 (1Hꎬ mꎬ Glu H ̄4′)ꎬ
4.68 (1Hꎬ tꎬ J = 9.7 Hzꎬ Glu H ̄4′)ꎬ 4.42 (1Hꎬ 3.35 ~ 3.30 (1Hꎬ mꎬ Glu H ̄2′)ꎬ 2.83 ~ 2.73 (2Hꎬ
dꎬ J = 7. 9 Hzꎬ Glu H ̄1′)ꎬ 4. 25 ( 1Hꎬ ddꎬ J = mꎬ Agl H ̄7)ꎬ 1.26 (3Hꎬ dꎬ J = 6.2 Hzꎬ Rha H ̄
13
7.9ꎬ 3.8 Hzꎬ Agl H ̄7)ꎬ 3.80 (3Hꎬ sꎬ 3″ ̄OCH )ꎬ 6‴)ꎮ C ̄NMR ( 150 MHzꎬ DMSO ̄d ) δ : 169. 2
3 6 C
3.78 (1Hꎬ sꎬ Agl H ̄8a)ꎬ 3.69 (3Hꎬ mꎬ Glu H ̄5′ꎬ (Caf C ̄9″)ꎬ 149.5 (Caf C ̄4″)ꎬ 147.2 (Caf C ̄7″)ꎬ
Rha H ̄2‴ꎬ Api H ̄2 ‴′)ꎬ 3.62 (3Hꎬ mꎬ Api H ̄3 ‴′ / 146.7 ( Caf C ̄3″)ꎬ 146.0 ( Agl C ̄3)ꎬ 144.6 ( Agl
4 ‴′)ꎬ 3.57 ~ 3.48 (3Hꎬ mꎬ Agl H ̄8bꎬ Glu H ̄2′ / C ̄4)ꎬ 131.4 (Agl C ̄1)ꎬ 127.6 ( Caf C ̄1″)ꎬ 123.2
3′)ꎬ 3.40 ~ 3.30 (2Hꎬ mꎬ Glu H ̄6′ꎬ Rha H ̄5‴)ꎬ (Caf C ̄6″)ꎬ 121.3 ( Agl C ̄6)ꎬ 117.1 ( Agl C ̄2)ꎬ
3.26 (3Hꎬ mꎬ Rha H ̄3‴ꎬ Api H ̄5 ‴′)ꎬ 3.13 (3Hꎬ 116.5 ( Agl C ̄5)ꎬ 116.4 ( Caf C ̄5″)ꎬ 115.1 ( Caf
sꎬ7 ̄OCH )ꎬ 3. 09 ( 1Hꎬ dꎬ J = 9. 4 Hzꎬ Rha H ̄ C ̄2″)ꎬ 114. 8 ( Caf C ̄8″)ꎬ 104. 3 ( Glu C ̄1′)ꎬ
3
13
4‴)ꎬ 0.98 (3Hꎬ dꎬ J = 6.2 Hzꎬ Rha H ̄6‴)ꎮ C ̄ 102.6 ( Rha C ̄1‴)ꎬ 83.9 ( Glu C ̄3′)ꎬ 75.6 ( Glu
NMR ( 150 MHzꎬ DMSO ̄d ) δ : 165. 8 ( Acyl C ̄ C ̄2′)ꎬ 75.3 ( Glu C ̄5′)ꎬ 73.9 ( Rha C ̄4‴)ꎬ 72.4
6 C
9″)ꎬ 149. 5 ( Acyl C ̄3″)ꎬ 147. 9 ( Acyl C ̄4″)ꎬ (Agl C ̄8)ꎬ 72.3 ( Rha C ̄3‴)ꎬ 72.2 ( Rha C ̄2‴)ꎬ
145.8 (Agl C ̄4)ꎬ 145.2 ( Acyl C ̄7″)ꎬ 145.0 ( Agl 70.3 (Glu C ̄4′)ꎬ 70.0 (Rha C ̄5‴)ꎬ 64.6 ( Glu C ̄
C ̄3)ꎬ 129.7 (Agl C ̄1)ꎬ 125.5 (Acyl C ̄1″)ꎬ 123.3 6′)ꎬ 36.6 (Agl C ̄7)ꎬ 17.9 ( Rha C ̄6‴)ꎮ 以上数
(Acyl C ̄6″)ꎬ 118.1 ( Agl C ̄6)ꎬ 115.5 ( Agl C ̄5ꎬ 据与文献(Saimaru & Oriharaꎬ 2010)报道的异毛蕊
Acyl C ̄5″)ꎬ 114.1 (Agl C ̄2)ꎬ 113.9 (Acyl C ̄8″)ꎬ 花苷 ( isoacteoside) 的数据基本一致ꎬ故鉴定化合
111.1 ( Acyl C ̄2″)ꎬ 109. 1 ( Api C ̄1 ‴′)ꎬ 102. 8 物 12 为异毛蕊花苷(isoacteoside)ꎮ
(Glu C ̄1′)ꎬ 101.3 (Rha C ̄1‴)ꎬ 82.3 ( Agl C ̄7)ꎬ 化合物 13 橙红色膏体ꎬ分子式为 C H O ꎮ
29 36 15
+ 1
78.9 (Api C ̄3 ‴′)ꎬ 78.8 (Glu C ̄3′)ꎬ 75.9 (Api C ̄ ESI ̄MS m / z: 647. 21 [ M + Na] ꎮ H ̄NMR ( 600
2 ‴′)ꎬ 74. 3 ( Glu C ̄2′)ꎬ 73. 7 ( Agl C ̄8)ꎬ 73. 4 MHzꎬ DMSO ̄d ) δ : 7.46 (1Hꎬ dꎬ J = 15.8 Hzꎬ
6 H
( Api C ̄4 ‴′)ꎬ 72.8 (Glu C ̄5′)ꎬ 71.7 (Rha C ̄4‴)ꎬ Caf H ̄7″)ꎬ 7.03 (1Hꎬ dꎬ J = 2.0 Hzꎬ Caf H ̄2″)ꎬ
70.5 (Rha C ̄2‴)ꎬ 70.4 (Rha C ̄3‴)ꎬ 69.3 (Glu C ̄ 6.97 (1Hꎬ ddꎬ J = 8.2ꎬ 2.1 Hzꎬ Caf H ̄6″)ꎬ 6.76
4′)ꎬ 68. 8 ( Rha C ̄5‴)ꎬ 67. 1 ( Glu C ̄6′)ꎬ 63. 2 (1Hꎬ dꎬ J = 8.1 Hzꎬ Caf H ̄5″)ꎬ 6.65 ~ 6.61 (2Hꎬ
(Api C ̄5 ‴′)ꎬ 56.0 (7 ̄OCH )ꎬ 55.6 (3″ ̄OCH )ꎬ mꎬ Agl H ̄2 / 5)ꎬ 6.49 (1Hꎬ ddꎬ J = 8.1ꎬ 2.1 Hzꎬ
3 3
18.1 ( Rha C ̄6‴)ꎮ 以 上 数 据 与 文 献 ( Xu et al.ꎬ Agl H ̄6)ꎬ 6.20 (1Hꎬ dꎬ J = 15.9 Hzꎬ Caf H ̄8″)ꎬ
2019)报道的 nepetifosides D 的数据基本一致ꎬ故 4.72 (1Hꎬ mꎬ Glu H ̄4′)ꎬ 4.35 (1Hꎬ dꎬ J = 7.9
鉴定化合物 11 为 nepetifosides Dꎮ Hzꎬ Glu H ̄1′)ꎬ 3.88 (1Hꎬ ddꎬ J = 9.2ꎬ 6.4 Hzꎬ
化合物 12 橙红色膏体ꎬ分子式为 C H O ꎮ Rha H ̄2‴)ꎬ 3.72 ~ 3.07 (10Hꎬ mꎬ Agl H ̄8ꎬ Rha /
29 36 15
+ 1
ESI ̄MS m / z: 647. 21 [ M + Na] ꎮ H ̄NMR ( 600 Glu ̄H)ꎬ 2. 76 ~ 2. 63 ( 2Hꎬ mꎬ Agl H ̄7)ꎬ 0. 96
13
MHzꎬ CD OD) δ : 7. 57 ( 1Hꎬ dꎬ J = 15. 8 Hzꎬ (3Hꎬ dꎬ J = 6.1 Hzꎬ Rha H ̄6‴)ꎮ C ̄NMR (150
3 H
Caf H ̄7″)ꎬ 7.05 (1Hꎬ dꎬ J = 2.1 Hzꎬ Caf H ̄2″)ꎬ MHzꎬ DMSO ̄d ) δ : 166. 0 ( Caf C ̄9″)ꎬ 148. 8
6 C
6.89 (1Hꎬ ddꎬ J = 8.2ꎬ 2.1 Hzꎬ Caf H ̄6″)ꎬ 6.78 (Caf C ̄3″)ꎬ 145.8 ( Caf C ̄7″)ꎬ 145.2 ( Agl C ̄3ꎬ
(1Hꎬ dꎬ J = 8.2 Hzꎬ Caf H ̄5″)ꎬ 6. 69 ( 1Hꎬ dꎬ Caf C ̄4″)ꎬ 143. 8 ( Agl C ̄4)ꎬ 129. 4 ( Agl C ̄1)ꎬ
J = 2.0 Hzꎬ Agl H ̄2)ꎬ 6.65 (1Hꎬ dꎬ J = 8.0 Hzꎬ 125.7 (Caf C ̄1″)ꎬ 121.7 ( Caf C ̄6″)ꎬ 119.8 ( Agl
Agl H ̄5)ꎬ 6.54 (1Hꎬ ddꎬ J = 8.0ꎬ 2.0 Hzꎬ Agl H ̄ C ̄6)ꎬ 116.5 (Caf C ̄5″)ꎬ 116.0 ( Agl C ̄2)ꎬ 115.7