王麗萍　付文衛(wèi)　譚紅勝　張　洪　徐宏喜

(1 上海中醫(yī)藥大學(xué)中藥學(xué)院，上海，201203； 2 中藥創(chuàng)新藥物研發(fā)上海高校工程研究中心，上海，201203)

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王麗萍1,2付文衛(wèi)1,2譚紅勝1,2張洪1,2徐宏喜1,2

(1 上海中醫(yī)藥大學(xué)中藥學(xué)院，上海，201203； 2 中藥創(chuàng)新藥物研發(fā)上海高校工程研究中心，上海，201203)

1　中國(guó)藤黃屬植物中酮類(lèi)化合物的分布

2　藤黃屬植物中酮類(lèi)化合物的結(jié)構(gòu)與分類(lèi)

表1　中國(guó)藤黃屬植物中的酮類(lèi)化合物的分布

表1　中國(guó)藤黃屬植物中的酮類(lèi)化合物的分布(續(xù))

表1　中國(guó)藤黃屬植物中的酮類(lèi)化合物的分布(續(xù))

表1　中國(guó)藤黃屬植物中的酮類(lèi)化合物的分布(續(xù))

表1　中國(guó)藤黃屬植物中的酮類(lèi)化合物的分布(續(xù))

表1　中國(guó)藤黃屬植物中的酮類(lèi)化合物的分布(續(xù))

表1　中國(guó)藤黃屬植物中的酮類(lèi)化合物的分布(續(xù))

圖1　酮類(lèi)化合物的基本母核

圖2　典型的二氧化取代的酮類(lèi)化合物

圖3　典型的三氧化取代的酮類(lèi)化合物

圖4　典型的四氧化取代的酮類(lèi)化合物

圖5　典型的五氧化取代的酮類(lèi)化合物

圖6　典型的二氧化取代的異戊烯基酮類(lèi)化合物

圖7　典型的單異戊烯基取代的三氧化酮類(lèi)化合物

圖8　典型的二異戊烯基取代的三氧化酮類(lèi)化合物

圖9　典型的含有C10取代三氧化酮類(lèi)化合物

圖10　典型的單異戊烯基取代的四氧化酮類(lèi)化合物

圖11　典型的二異戊烯基取代的四氧化酮類(lèi)化合物

圖12　典型的三異戊烯基取代的四氧化酮類(lèi)化合物

圖13　典型的含有C10取代的四氧化酮

圖14　典型的五氧化取代異戊烯基酮類(lèi)化合物

圖15　典型的二氫及四氫酮類(lèi)化合物

圖16　典型的四氫籠狀酮類(lèi)化合物

圖17　典型的六氫酮類(lèi)化合物

圖18　典型的酮二聚體類(lèi)化合物

3　酮類(lèi)化合物波譜學(xué)特征[111]

3.3核磁共振氫譜[112]

3)甲氧基：甲氧基上的質(zhì)子通常為3個(gè)質(zhì)子的單峰，其化學(xué)位移多在δH3.7～3.8 ppm左右。

圖19　常見(jiàn)異戊烯基上氫的化學(xué)位移值

3.4核磁共振碳譜[112]

圖20　不同類(lèi)型異戊烯基上碳的化學(xué)位移值

4　提取與分離方法[1]

4)乙醇等有機(jī)溶劑提取法、HSCCC法分離純化[115]：取干燥藤黃樹(shù)脂2 kg，95%乙醇室溫浸提5 d(4 L×5)，浸提液減壓濃縮得浸膏1 428 g。在TBE-1000A高速逆流色譜儀上采用n-hexane-ethyl acetate-methanol-water(7∶3∶8∶2，v/v/v/v)溶劑系統(tǒng)，溶劑系統(tǒng)的有機(jī)相中加入0.1 % trifluoroacetic acid，水相中加入0.03 % triethylamine，取3.157 g浸膏以30 mL的上相和10 mL下相的混合溶劑溶解上樣，經(jīng)一次分離，可得到1.134 g的 gambogic acid和180.5 mg的gambogenic acid，將其中的混合物進(jìn)一步在TBE-300B的高速逆流色譜儀上分離，分別以n-hexane-ethyl acetate-methanol-water(5∶5∶10∶5，v/v/v/v)和n-hexane-methyl tert-butyl ether-acetonitrile-water(8∶2∶6∶4，v/v/v/v)為溶劑系統(tǒng)可以進(jìn)一步分離得到11.6 mg的isogambogenic acid和10.4 mg的β-morellic acid。

6　結(jié)語(yǔ)

圖21　藤黃屬植物中酮類(lèi)化合物可能的生物合成途經(jīng)

圖22　藤黃屬植物中籠狀酮類(lèi)化合物可能的生物合成途經(jīng)

隨著現(xiàn)代分析方法的發(fā)展和應(yīng)用，我們課題組基于LC-MS的高效、快速分離分析方法也以用于中國(guó)藤黃屬植物的化學(xué)成分研究，尤其是針對(duì)廣西藤黃Garciniakwangsiensis及紅萼藤黃Garciniarubrisepala等前期研究較少的中國(guó)藤黃屬植物，以期發(fā)現(xiàn)更多結(jié)構(gòu)新穎、活性強(qiáng)、不良反應(yīng)小的先導(dǎo)化合物。同時(shí)，進(jìn)一步進(jìn)行結(jié)構(gòu)修飾和優(yōu)化等方面的研究工作，針對(duì)性地開(kāi)展這些化合物的構(gòu)-效關(guān)系及作用靶點(diǎn)研究，為新藥開(kāi)發(fā)奠定基礎(chǔ)。

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(2016-07-05收稿責(zé)任編輯：洪志強(qiáng))

Chemistry of Xanthones Isolated from Garcinia Species in China

Wang Liping1,2，F(xiàn)u Wenwei1,2，Tan Hongsheng1,2，Zhang Hong1,2，Xu Hongxi1,2

(1SchoolofPharmacy，ShanghaiUniversityofTraditionalChineseMedicine，Shanghai201203，China; 2EngineeringResearchCenterofShanghaiCollegesforTCMNewDrugDiscovery，Shanghai201203，China)

Xanthones are one of the biggest classes of natural compounds in Garcinia species with various biological activities and are subdivided according to the degree of oxygenation and different substituted positions.This review focuses on the distribution，isolation，structural classification，spectral characteristics and biosynthesis pathway of xanthones isolated from Garcinia species in China.

Garcinia species; Xanthone; Structural classification; Spectral characteristics; Biosynthesis pathway

國(guó)家自然科學(xué)基金重點(diǎn)項(xiàng)目(編號(hào)：81130069)；國(guó)家自然科學(xué)基金面上項(xiàng)目(編號(hào)：81173485)

王麗萍(1991.04—)，女，碩士研究生，研究方向：中藥活性成分研究，E-mail：maxine_wlp0411@163.com

徐宏喜(1961.07—)，男，博士，教授，院長(zhǎng)，研究方向：中藥活性成分及藥理作用機(jī)制研究，E-mail：xuhongxi88@gmail.com

R284.1;R284.2

A doi：10.3969/j.issn.1673-7202.2016.07.004