曾广方, 周炳南, 赵志远. 中药黄酮类的研究 Ⅹ.海州常山成分的研究新黄酮甙海常素的分离及其化学结构J. 药学学报, 1963, 10(8): 480-488.
引用本文: 曾广方, 周炳南, 赵志远. 中药黄酮类的研究 Ⅹ.海州常山成分的研究新黄酮甙海常素的分离及其化学结构J. 药学学报, 1963, 10(8): 480-488.
TSENG KWONG-fong, CHOU PING-NAN AND CHAO TSE-YUA, . STUDIES ON THE FLAVONOIDS PRESENT IN CHINESE DRUGS X. A NEW FLAVONOID GLYCOSIDE, CLERODENDRIN, FROM CLERODENDRON TRICHOTOMUM THUMB.J. Acta Pharmaceutica Sinica, 1963, 10(8): 480-488.
Citation: TSENG KWONG-fong, CHOU PING-NAN AND CHAO TSE-YUA, . STUDIES ON THE FLAVONOIDS PRESENT IN CHINESE DRUGS X. A NEW FLAVONOID GLYCOSIDE, CLERODENDRIN, FROM CLERODENDRON TRICHOTOMUM THUMB.J. Acta Pharmaceutica Sinica, 1963, 10(8): 480-488.

中药黄酮类的研究 Ⅹ.海州常山成分的研究新黄酮甙海常素的分离及其化学结构

STUDIES ON THE FLAVONOIDS PRESENT IN CHINESE DRUGS X. A NEW FLAVONOID GLYCOSIDE, CLERODENDRIN, FROM CLERODENDRON TRICHOTOMUM THUMB.

  • 摘要: 海州常山(Clerodendron trichotomum Thumb.)为馬鞭草科(Verbenaceae)植物,其叶有降低血压作用.作者等从叶中分离出一种新黄酮甙結晶,命名为海常素(clerodendrin),分子式C27H26O17·3(1/2)H2O,熔点215℃(分解),不含甲氧基;从物理化學性貭知属于黄酮甙类.水解后,得甙元分子式C15H16O5·(1/2)H2O,熔点347℃(分解),并得三乙酰化物,分子式C21H16O8,熔点182℃;这二化合物証明为洋芹子素(apigenin)及其乙酰化物.所接糖証明为葡萄糖醛酸.从甲酯的制备及水解后甙元的定量測定,知其含有二分子葡萄糖醛酸,并經証实均連接在7位上.海常素的結构应为(Ⅰ)式.此外还分得熔点为220℃及235℃的二种結晶,前者經鉴定为中肌醇;后者为生物碱,但因量少未进行鉴定.

     

    Abstract: The Chinese drug Hai-Chou-Chang-Shan (Clerodendron tnchotomum Thumb.) belongs to family Verbenaceae which has been used as a sedative and antihypertensive drug. From the aqueous extract of its leaves, we have succeeded in isolating three crystalline components. The component (Ⅰ) was obtained in light yellow needles, C27H26O17·3(1/2)H2O, m.p. 215℃ (decomp.), yield 0.5%. Its U.V. absorption showes λmax 270, 341 mμ, I.R. spectrum vCO 1660 cm-1, vCOOH 1730 cm-1. It gave positive reactions with ferric chloride, Mg+HCl, and ZrOCl2. It is soluble in diluted solution of sodium bicarbonate and sodium hydroxide in yellow colour, slightly soluble in methanol, ethanol and 60% acetic acid but insoluble in ether and other organic solvents. From its physical and chemical properties, it has been shown to be a new flavonoid compound, and, therefore, it is named clerodendrin. On hydrolysis with hydrochloric acid, the clerodendrin gave an aglycone, light yellowish needle crystals and a sugar portion. The aglycone has a m.p. 347℃ (decomp.) and a triacetate, m.p. 182℃ was obtained. The aglycone was lastly identified as apigenin and no depression of melting point was observed when mixed with an authentic sample. By paper partition chromatography and colour test, it shows that the sugar part of clerodendrin is glucuronic acid. When clerodendrin was esterified with methanol, a dimethylester m.p. 170℃ was obtained, the clerodendrin, therefore, must carry two carboxyl groups. We also further determined the glucuronic acid quantitatively by acid hydrolysis, and two moles were found. In order to ascertain the position of glucuronic acid, the clerodendrin was methylated with dia2omethane then hydrolyzed a known compound, acacetin, was obtained. From the positive test of ZrOCl2 which demonstrates that the 5-position in clerodendrin is free, so that it is conclusive that the glucuronic acid must link in the 7-position. Therefore, the structure of clerodendrin has been confirmed to be apigenin-7-diglucuronide. The component (Ⅱ) was obtained in colourless crystals, m.p. 221℃, sweet taste; its acetate melted at 215-216℃. All of these properties were comformed to mesoinositol and its acetate, and no depression of melting point was observed when both were mixed with authentic samples respectively. The component (Ⅲ) is an alkaloid. It was obtained in colourless needles, m.p. 235℃, and gave positively with most alkaloid reagent, but its yield was too low for detail investigation.

     

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