牡丹皮化学成分研究(2)
化合物2:C23H28O12, MW: 496; 白色无定形粉末,易溶于水和含水的甲醇、丙酮;1H-NMR (400 MHz, CD3OD+H2O),(ppm): 1.55 (3H, s, H-10), 2.01 (1H, d, J=12.1 Hz, H-3), 2.38 (1H, d, J=12.1 Hz, H-3), 2.15 (1H, d, J=10.6 Hz, H-6), 2.77 (1H, d, J=6.0 Hz, H-5), 2.67 (1H, dd, J=6.6 Hz, 10.6 Hz, H-6), 4.94 (1H, d, J=12 Hz, H-8), 5.06 (1H, overlapped), 5.60 (1H, s, H-9), 7.05 (2H, dd, J=8.8, 1.9 Hz, H-5”, 3”), 8.11 (2H, dd, J=1.9, 8.8 Hz, H-2”, 4”), 4.70 (1H, d, J=7.8 Hz, H-1’), 4.06 (1H, d, J=12 Hz, H-6’), 3.81 (1H, dd, J=12.0, 6.1 Hz, H-6’), 3.4-3.6 (4H, H-2’, 3’, 4’, 5’, overlapped). 与文献oxypaeoniflorin数据一致[2,3]。
, 百拇医药
化合物3:C23H38O13, MW: 522; 白色无定形粉末,易溶于水和含水的甲醇和丙酮; 1H-NMR (400 MHz, CD3OD+H2O),(ppm): 1.31 (3H, s, H-10), 1.74 (1H, d, J=12.1 Hz, H-3), 1.91 (1H, d, J=12.1 Hz, H-3), 1.77 (1H, d, J=10.6 Hz, H-6), 2.53 (1H, d, J=6.0 Hz, H-5), 2.45 (1H, dd, J=6.6, 10.6 Hz, H-6), 3.16 (1H, d, J=12.0 Hz, H-8), 3.26 (1H, overlapped, H-1), 5.36 (1H, s, H-9), 6.81 (1H, d, J=8.0 Hz, H-5”), 7.52 (1H, dd, J=8.0, 1.9 Hz, H-6”), 7.54 (1H, d, J=1.9 Hz, H-2”), 4.49 (1H, d, J=7.8 Hz, H-1’), 3.78 (1H, d, J=12 Hz, H-6’), 3.55 (1H, dd, J=12 Hz, J=6.1 Hz, H-6’), 3.2-3.4 (4H, H-2’, 3’, 4’, 5’, m). 与文献mudanpioside A数据[2]一致。
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化合物4:C9H12O6N2, MW: 244; 白色粉末,易于水,甲醇, 1H-NMR (400 MHz, D2O)(ppm): 7.88 (1H, d, J=8.0 Hz, H-6), 5.91 (1H, d, J=4.2 Hz, H-1’), 5.90 (1H, d, J=8.1 Hz, H-5), 4.37 (1H, dd, J=4.1, 5.3 Hz, H-4’), 4.24 (1H, dd, J=5.3 Hz, 10.1 Hz, H-2’), 4.15 (1H, d, J=4.1 Hz, H-3’), 3.95 (1H, d, J=12.8, 2.0 Hz, H-5’), 3.82 (1H, dd, J=8.5, 0.6 Hz, H-5’); 13C-NMR (100 MHz, D2O),ppm,154.4 (C-2), 168.9 (C-4), 105.0 (C-5), 144.5 (C-6), 92.1 (C-1’), 72.1 (C-2’), 76.3 (C-3’), 86.9 (C-4’), 63.4 (C-5’). 与文献尿嘧啶核苷数据一致[4]。
, 百拇医药
化合物5:C10H14O5N2, MW: 242; 无色针状晶体,溶于水,含水的甲醇和丙酮, 1H-NMR (400 MHz, D2O),(ppm): 7.66 (1H, s, H-6), 6.28 (1H, t, J=6.7 Hz, H-1’), 4.48 (1H, m, H-3’), 4.03 (1H, m, H-4’), 3.86 (1H, dd, J=12.5, 3.2 Hz, H-5’), 3.78 (1H, dd, J=12.5, 4.9 Hz, H-5’), 2.38 (2H, m, H-2’), 1.90 (3H, s, CH3-5). 与文献胸腺嘧啶脱氧核苷数据一致[4]。
化合物6:C9H10O3, MW: 166; 白色针状晶体,常温下易升华,溶于水,易溶于甲醇、丙酮。1H-NMR (400 MHz, D2O),(ppm): 2.73 (3H, s, H-8), 4.02 (3H, s, H-9), 6.60 (1H, d, J=2.5 Hz, H-3), 6.67 (1H, dd, J=2.5, 8.9 Hz, H-5), 7.97 (1H, d, J=8.9 Hz, H-6). 与文献丹皮酚数据一致[3]。
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化合物7:C11H12O2N2, MW: 204; 白色无定形粉末,易溶于水,甲醇,1H-NMR (400 MHz, CD3OD+D2O),(ppm): 7.70 (1H, d, J=7.9 Hz, H-4), 7.47 (1H, d, J=8.1 Hz, H-7), 7.27 (1H, s, H-2), 7.15 (1H, dd, J=8.1, 7.1 Hz, H-6), 7.06 (1H, dd, J=7.9, 7.1 Hz, H-5), 3.62 (1H, dd, J=9.1, 3.9 Hz, H-11), 3.40 (1H, dd, J=15.1, 3.9 Hz, H-10), 3.06 (1H, dd, J=15.1, 9.1 Hz, H-10). 与文献色氨酸数据[5]一致.
化合物8:C7H6O5, MW: 170, 白色针状结晶,溶于水,易溶于甲醇,丙酮;1H-NMR (400M, CD3COCD3),(ppm): 7.16 (2H, s, H-2, 6). TLC检测与标准品相同。与文献没食子酸数据[6]一致。
, 百拇医药
参考文献
[1] 国家中医药管理局,《中华本草》编委会,中华本草,上海科学技术出版社,1999,1:53.
[2] Lin H-C, Ding H-Y., Wu T-S., Wu P-L. Monoterpene glycosides from Paeonia suffruticosa[J]. Phytochemistry,1996,41:237-242.
[3] Kitagawa, I, Yoshikawa, M, Tsunage, K, & Tani, TStudies on moutan cortex II. On the chemical constituents[J]. Shoyakugaku Zasshi,1979,33:171-177.
[4] Jones, AJ, Grant, D M, Winkley M W,& Robins R K.Carbon-13 magnetic resonance. XVII. Pyrimidine and purine nucleosides[J]. Journal of American Chemical Society,1970,92:4079-4087.
[5] Fitzgerald, J S.The major alkaloid of Pultenase altissima: Nb ,Nb-Dimethyl-l-t ryptophan methyl ester[J]. Australian Journal of Chemistry,1963,16:246-249.
[6] 李勇军, 何 讯, 刘丽娜,等. 红草化学成分的研究[J]. 中国中药杂志, 2005, 30(6): 444., http://www.100md.com(于兆海)
, 百拇医药
化合物3:C23H38O13, MW: 522; 白色无定形粉末,易溶于水和含水的甲醇和丙酮; 1H-NMR (400 MHz, CD3OD+H2O),(ppm): 1.31 (3H, s, H-10), 1.74 (1H, d, J=12.1 Hz, H-3), 1.91 (1H, d, J=12.1 Hz, H-3), 1.77 (1H, d, J=10.6 Hz, H-6), 2.53 (1H, d, J=6.0 Hz, H-5), 2.45 (1H, dd, J=6.6, 10.6 Hz, H-6), 3.16 (1H, d, J=12.0 Hz, H-8), 3.26 (1H, overlapped, H-1), 5.36 (1H, s, H-9), 6.81 (1H, d, J=8.0 Hz, H-5”), 7.52 (1H, dd, J=8.0, 1.9 Hz, H-6”), 7.54 (1H, d, J=1.9 Hz, H-2”), 4.49 (1H, d, J=7.8 Hz, H-1’), 3.78 (1H, d, J=12 Hz, H-6’), 3.55 (1H, dd, J=12 Hz, J=6.1 Hz, H-6’), 3.2-3.4 (4H, H-2’, 3’, 4’, 5’, m). 与文献mudanpioside A数据[2]一致。
, 百拇医药
化合物4:C9H12O6N2, MW: 244; 白色粉末,易于水,甲醇, 1H-NMR (400 MHz, D2O)(ppm): 7.88 (1H, d, J=8.0 Hz, H-6), 5.91 (1H, d, J=4.2 Hz, H-1’), 5.90 (1H, d, J=8.1 Hz, H-5), 4.37 (1H, dd, J=4.1, 5.3 Hz, H-4’), 4.24 (1H, dd, J=5.3 Hz, 10.1 Hz, H-2’), 4.15 (1H, d, J=4.1 Hz, H-3’), 3.95 (1H, d, J=12.8, 2.0 Hz, H-5’), 3.82 (1H, dd, J=8.5, 0.6 Hz, H-5’); 13C-NMR (100 MHz, D2O),ppm,154.4 (C-2), 168.9 (C-4), 105.0 (C-5), 144.5 (C-6), 92.1 (C-1’), 72.1 (C-2’), 76.3 (C-3’), 86.9 (C-4’), 63.4 (C-5’). 与文献尿嘧啶核苷数据一致[4]。
, 百拇医药
化合物5:C10H14O5N2, MW: 242; 无色针状晶体,溶于水,含水的甲醇和丙酮, 1H-NMR (400 MHz, D2O),(ppm): 7.66 (1H, s, H-6), 6.28 (1H, t, J=6.7 Hz, H-1’), 4.48 (1H, m, H-3’), 4.03 (1H, m, H-4’), 3.86 (1H, dd, J=12.5, 3.2 Hz, H-5’), 3.78 (1H, dd, J=12.5, 4.9 Hz, H-5’), 2.38 (2H, m, H-2’), 1.90 (3H, s, CH3-5). 与文献胸腺嘧啶脱氧核苷数据一致[4]。
化合物6:C9H10O3, MW: 166; 白色针状晶体,常温下易升华,溶于水,易溶于甲醇、丙酮。1H-NMR (400 MHz, D2O),(ppm): 2.73 (3H, s, H-8), 4.02 (3H, s, H-9), 6.60 (1H, d, J=2.5 Hz, H-3), 6.67 (1H, dd, J=2.5, 8.9 Hz, H-5), 7.97 (1H, d, J=8.9 Hz, H-6). 与文献丹皮酚数据一致[3]。
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化合物7:C11H12O2N2, MW: 204; 白色无定形粉末,易溶于水,甲醇,1H-NMR (400 MHz, CD3OD+D2O),(ppm): 7.70 (1H, d, J=7.9 Hz, H-4), 7.47 (1H, d, J=8.1 Hz, H-7), 7.27 (1H, s, H-2), 7.15 (1H, dd, J=8.1, 7.1 Hz, H-6), 7.06 (1H, dd, J=7.9, 7.1 Hz, H-5), 3.62 (1H, dd, J=9.1, 3.9 Hz, H-11), 3.40 (1H, dd, J=15.1, 3.9 Hz, H-10), 3.06 (1H, dd, J=15.1, 9.1 Hz, H-10). 与文献色氨酸数据[5]一致.
化合物8:C7H6O5, MW: 170, 白色针状结晶,溶于水,易溶于甲醇,丙酮;1H-NMR (400M, CD3COCD3),(ppm): 7.16 (2H, s, H-2, 6). TLC检测与标准品相同。与文献没食子酸数据[6]一致。
, 百拇医药
参考文献
[1] 国家中医药管理局,《中华本草》编委会,中华本草,上海科学技术出版社,1999,1:53.
[2] Lin H-C, Ding H-Y., Wu T-S., Wu P-L. Monoterpene glycosides from Paeonia suffruticosa[J]. Phytochemistry,1996,41:237-242.
[3] Kitagawa, I, Yoshikawa, M, Tsunage, K, & Tani, TStudies on moutan cortex II. On the chemical constituents[J]. Shoyakugaku Zasshi,1979,33:171-177.
[4] Jones, AJ, Grant, D M, Winkley M W,& Robins R K.Carbon-13 magnetic resonance. XVII. Pyrimidine and purine nucleosides[J]. Journal of American Chemical Society,1970,92:4079-4087.
[5] Fitzgerald, J S.The major alkaloid of Pultenase altissima: Nb ,Nb-Dimethyl-l-t ryptophan methyl ester[J]. Australian Journal of Chemistry,1963,16:246-249.
[6] 李勇军, 何 讯, 刘丽娜,等. 红草化学成分的研究[J]. 中国中药杂志, 2005, 30(6): 444., http://www.100md.com(于兆海)