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      繡球化學(xué)成分研究

      2014-09-26 02:27賀蘭云黃海疆
      中國當(dāng)代醫(yī)藥 2014年22期
      關(guān)鍵詞:繡球化學(xué)成分

      賀蘭云++黃海疆

      [摘要] 目的 對繡球莖枝水提取物進(jìn)行化學(xué)成分研究。 方法 采用大孔樹脂、硅膠柱色譜、高效制備液相等方法,對繡球莖枝水提取物進(jìn)行化學(xué)成分分離,并通過1H,13C-NMR,MS等波譜方法鑒定化合物的結(jié)構(gòu)。 結(jié)果 分離得到9個(gè)化合物,分別鑒定為馬錢苷元(1),馬錢子苷(2),馬錢苷酸(3),幼枝含斷氧化馬錢子苷(4),四乙酰開聯(lián)番木鱉苷(5),獐牙菜苷(6),阿魏酸(7),對羥基桂皮酸(8),松柏苷(9)。 結(jié)論 化合物均1~6為首次從該植物中分離得到。

      [關(guān)鍵詞] 虎耳草科;繡球;化學(xué)成分;環(huán)烯醚萜

      [中圖分類號] R284 [文獻(xiàn)標(biāo)識碼] A [文章編號] 1674-4721(2014)08(a)-0059-03

      Studies on chemical constituents of Hydrangea macrophylla

      HE Lan-yun HUANG Hai-jiang

      Dongguan National Medicine Group Co. Ltd of Guangdong Province,Dongguan 441900,China

      [Abstract] Objective To study the chemical constituents of Hydrangea macrophylla. Methods Nine compounds were separated and purified by column chromatography over macroporous resin,silica gel and preparative HPLC.Their chemical structures were elucidated by MS,1H and 13C-NMR data. Results Nine compounds were isolated from the leaves of Hydrangea macrophylla and identified as loganetin(1),loganin(2),loganic acid(3),secoxyloganin(4),secologanoside(5),sweroside(6),ferulic acid(7),p-hydroxy cinnamic acid(8) and coniferin(9). Conclusion Compounds 1-6 are isolated from Hydrangea macrophylla for the first time.

      [Key words] Saxifragaceae;Hydrangea macrophylla;Chemical constituents;Iridoids

      繡球(Hydrangea macrophylla)為虎耳草科(Saxifragaceae)繡球?qū)伲℉ydrangea)植物。繡球?qū)僦参锶澜缂s80種,分布于亞洲及拉丁美洲、北美洲,我國有45種。繡球又名八仙花、紫陽花,為繡球?qū)僦械拿耖g常用中藥,分布廣泛,我國各地園林與民間常有栽培[1]。繡球具有清熱解毒抗瘧之功效,主治瘧疾、心熱驚悸、煩躁等。近年來,國內(nèi)外科學(xué)家對該屬植物的活性成分進(jìn)行了較多的研究,發(fā)現(xiàn)繡球中含有大量結(jié)構(gòu)新穎的異香豆素類[2-5]、環(huán)烯醚萜類化合物[6-9],并且具有良好的抗瘧[10-11]、抗過敏[12-13]、抗菌[14]、降血糖等作用[15]。因而,對繡球的化學(xué)成分及其生物活性成分進(jìn)行研究是一項(xiàng)非常有意義的工作,可藉此發(fā)現(xiàn)具有藥理活性的前體化合物用于藥物研制。本研究利用大孔吸附樹脂,硅膠柱色譜,制備液相色譜等分離手段,從繡球莖枝水提物中分離得到了9個(gè)化合物,分別鑒定為馬錢苷元(1),馬錢子苷(2),馬錢苷酸(3),幼枝含斷氧化馬錢子苷(4),四乙酰開聯(lián)番木鱉苷(5),獐牙菜苷(6),阿魏酸(7),對羥基桂皮酸(8),松柏苷(9)。

      1 材料與方法

      1.1 材料

      Bruker DRX-500 MHz磁共振波譜儀(瑞士,TMS為內(nèi)標(biāo));Agilent Technonlgies 6520質(zhì)譜儀(美國安捷倫公司),LABOROTA4000旋轉(zhuǎn)蒸發(fā)儀(德國海道夫公司),Shimadazu LC-6AD制備型高效液相色譜儀(日本島津公司),YMC ODS-A(250×20 mm,5 μm)色譜柱(日本YMC公司)。

      色譜用硅膠(青島海洋化工廠);大孔吸附樹脂D101型(天津海光化工有限公司);提取分離用試劑均為分析純(東莞市東江化學(xué)試劑有限公司);制備HPLC用乙腈為色譜純(美國TEDIA試劑公司),水為重蒸水(自制)。

      繡球莖枝采于2013年采自四川樂山,經(jīng)廣東省東莞國藥集團(tuán)有限公司妮娜副主任藥師鑒定為繡球?qū)僦参锢C球H. macrophylla的莖枝。

      1.2 方法

      以上數(shù)據(jù)與文獻(xiàn)報(bào)道[21]數(shù)據(jù)基本一致,鑒定化合物9為松柏苷。

      3 討論

      環(huán)烯醚萜苷類化合物(馬錢子苷、獐牙菜苷等)為繡球中主要的活性成分和特征成分。近年來研究表明,環(huán)烯醚萜苷類化合物具有抗瘧、降血糖等活性作用,因此有必要對其有效成分進(jìn)行質(zhì)量控制。本文為繡球的進(jìn)一步研究奠定了基礎(chǔ)。

      [參考文獻(xiàn)]

      [1] 江蘇新醫(yī)學(xué)院.中藥大辭典[M].上海:上??茖W(xué)技術(shù)出版社,1985:21.

      [2] Khalil AT,Chang FR,Lee YH,et al.Chemical constituents from the Hydrangea chinensis[J].Arch Pharm Res,2003, 26(1):15.endprint

      [3] Yoshikawa M,Uchida E,Chatani N,et al.Thunberginols A,B,and F,new antiallergic and antimicrobial principles from Hydrangeae dulcisfolium[J].Chem Pharm Bull,1992, 40(11):3121.

      [4] Yoshikawa M,Matsuda H,Shimoda H,et al.Development of bioactive functions in Hydrangeae dulcisfolium[J].Chem Pharm Bull,1996,44(8):1440.

      [5] Yoshikawa M,Uchida E,Chatani N,et al.Thunberginols C,D,and E,new antiallgergic and antimicrobial dihydroisocoumarins from Hydrangea dulicsfolium[J].Chem Pharm Bull,1992,40(12):3352.

      [6] Sakai H,Kakuda R,Yaoita Y,et al.Secoiridoid glycosides from the leaves of Hydrangea macrophylla subsp. Serrate[J].J Nat Med,2007,61(1):226.

      [7] Kikuchi M,Kakuda R,Yaoita Y.Macropyllanosides A-D,secoiridoid glycosides from the leaves of Hydrangea macrophylla subsp. Serrate[J].Heterocycles,2008,76(1):313.

      [8] Uesato S,Hashimoto T,Takeda Y,et al.New secoiridoid glycosides hydrangenosides E,F(xiàn) and G from Hydrangea scandens[J].Chem Pharm Bull,1982,30(11):4222.

      [9] Uesato S,Hashimoto T,Takeda Y,et al.Novel type secoiridoid glycosides,hydrangenosides B,C and G from Hydrangea scandens[J].Chem Pharm Bull,1981,29(11):3421.

      [10] 黃世英,王光添.繡球花抗瘧實(shí)驗(yàn)研究及臨床療效觀察[J].廣西中醫(yī)藥,1988,11(3):44.

      [11] Murakami N,Mostaqul HM,Tamura S,et al.New anti-malarial flavonol glycoside from Hydrangeae dulcisfolium[J].Bioorg Med Chem Lett,2001,11(18):2445.

      [12] Khalifa TI,El-Gindi OD,Ammar HA,et al.Iridoid glycosides and phenolic compounds from Hydrangeae hortensis[J].J Pharm Sci,2001,28(1):221.

      [13] Subha V,Sukumar D.Phytochemical and pharmacological studies on Hydrangeae macrophylla[J].J Indian Chem Soc,2007,84(10):1026.

      [14] Yoshikawa M,Harada E,Naitoh Y,et al.Development of bioactive functions in Hydrangea dulcisfolium[J].Chem Pharm Bull,1994,42(11):2225.

      [15] Zhang HL,Matsuda H,Kumahara A,et al.New type of anti-diabetic compounds from the processed leaves of Hydrangea dulcisfolium[J].Bioorg Med Chem Lett,2007, 17(12):4972.

      [16] Claudia M,Young M,Marcia R,et al.Fungitoxic non-glycosidic iridiods from Alibertia Macrophylia[J].Phytochemistry,1992,31(10):3433.

      [17] Jensen SR,Lyse-petersen SE,Nielsen BJ.Novel 6/5-iridoid glucosides from Dipsacus sylvestris[J].Phytochemistry,1979,18(1):273.

      [18] Xu M,Wang D,Zhang YJ,et al.Iridoidal glucosides from Gentiana rhodantha[J].Nat Prod Res,2008,10(6):491.

      [19] 楊中鐸,李濤,李援朝.萱草根化學(xué)成分的研究[J].中國中藥雜志,2008,33(3):269.

      [20] 蔡金艷,宮立孟,張勇慧,等.金線蓮化學(xué)成分的研究[J].中藥材,2008,31(3):3370.

      [21] Panthama N,Kanokmedhakul S,Kanokmedhakul K.Galloyl and hexa-hydroxydiphenoyl esters of phenylpropanoid glucosides,phenylpropanoids and phenylpropanoid glucosides from rhizome of Balanophora fungosa[J].Chem Pharm Bull,2009,57(12):1352.

      (收稿日期:2014-05-14 本文編輯:郭靜娟)endprint

      [3] Yoshikawa M,Uchida E,Chatani N,et al.Thunberginols A,B,and F,new antiallergic and antimicrobial principles from Hydrangeae dulcisfolium[J].Chem Pharm Bull,1992, 40(11):3121.

      [4] Yoshikawa M,Matsuda H,Shimoda H,et al.Development of bioactive functions in Hydrangeae dulcisfolium[J].Chem Pharm Bull,1996,44(8):1440.

      [5] Yoshikawa M,Uchida E,Chatani N,et al.Thunberginols C,D,and E,new antiallgergic and antimicrobial dihydroisocoumarins from Hydrangea dulicsfolium[J].Chem Pharm Bull,1992,40(12):3352.

      [6] Sakai H,Kakuda R,Yaoita Y,et al.Secoiridoid glycosides from the leaves of Hydrangea macrophylla subsp. Serrate[J].J Nat Med,2007,61(1):226.

      [7] Kikuchi M,Kakuda R,Yaoita Y.Macropyllanosides A-D,secoiridoid glycosides from the leaves of Hydrangea macrophylla subsp. Serrate[J].Heterocycles,2008,76(1):313.

      [8] Uesato S,Hashimoto T,Takeda Y,et al.New secoiridoid glycosides hydrangenosides E,F(xiàn) and G from Hydrangea scandens[J].Chem Pharm Bull,1982,30(11):4222.

      [9] Uesato S,Hashimoto T,Takeda Y,et al.Novel type secoiridoid glycosides,hydrangenosides B,C and G from Hydrangea scandens[J].Chem Pharm Bull,1981,29(11):3421.

      [10] 黃世英,王光添.繡球花抗瘧實(shí)驗(yàn)研究及臨床療效觀察[J].廣西中醫(yī)藥,1988,11(3):44.

      [11] Murakami N,Mostaqul HM,Tamura S,et al.New anti-malarial flavonol glycoside from Hydrangeae dulcisfolium[J].Bioorg Med Chem Lett,2001,11(18):2445.

      [12] Khalifa TI,El-Gindi OD,Ammar HA,et al.Iridoid glycosides and phenolic compounds from Hydrangeae hortensis[J].J Pharm Sci,2001,28(1):221.

      [13] Subha V,Sukumar D.Phytochemical and pharmacological studies on Hydrangeae macrophylla[J].J Indian Chem Soc,2007,84(10):1026.

      [14] Yoshikawa M,Harada E,Naitoh Y,et al.Development of bioactive functions in Hydrangea dulcisfolium[J].Chem Pharm Bull,1994,42(11):2225.

      [15] Zhang HL,Matsuda H,Kumahara A,et al.New type of anti-diabetic compounds from the processed leaves of Hydrangea dulcisfolium[J].Bioorg Med Chem Lett,2007, 17(12):4972.

      [16] Claudia M,Young M,Marcia R,et al.Fungitoxic non-glycosidic iridiods from Alibertia Macrophylia[J].Phytochemistry,1992,31(10):3433.

      [17] Jensen SR,Lyse-petersen SE,Nielsen BJ.Novel 6/5-iridoid glucosides from Dipsacus sylvestris[J].Phytochemistry,1979,18(1):273.

      [18] Xu M,Wang D,Zhang YJ,et al.Iridoidal glucosides from Gentiana rhodantha[J].Nat Prod Res,2008,10(6):491.

      [19] 楊中鐸,李濤,李援朝.萱草根化學(xué)成分的研究[J].中國中藥雜志,2008,33(3):269.

      [20] 蔡金艷,宮立孟,張勇慧,等.金線蓮化學(xué)成分的研究[J].中藥材,2008,31(3):3370.

      [21] Panthama N,Kanokmedhakul S,Kanokmedhakul K.Galloyl and hexa-hydroxydiphenoyl esters of phenylpropanoid glucosides,phenylpropanoids and phenylpropanoid glucosides from rhizome of Balanophora fungosa[J].Chem Pharm Bull,2009,57(12):1352.

      (收稿日期:2014-05-14 本文編輯:郭靜娟)endprint

      [3] Yoshikawa M,Uchida E,Chatani N,et al.Thunberginols A,B,and F,new antiallergic and antimicrobial principles from Hydrangeae dulcisfolium[J].Chem Pharm Bull,1992, 40(11):3121.

      [4] Yoshikawa M,Matsuda H,Shimoda H,et al.Development of bioactive functions in Hydrangeae dulcisfolium[J].Chem Pharm Bull,1996,44(8):1440.

      [5] Yoshikawa M,Uchida E,Chatani N,et al.Thunberginols C,D,and E,new antiallgergic and antimicrobial dihydroisocoumarins from Hydrangea dulicsfolium[J].Chem Pharm Bull,1992,40(12):3352.

      [6] Sakai H,Kakuda R,Yaoita Y,et al.Secoiridoid glycosides from the leaves of Hydrangea macrophylla subsp. Serrate[J].J Nat Med,2007,61(1):226.

      [7] Kikuchi M,Kakuda R,Yaoita Y.Macropyllanosides A-D,secoiridoid glycosides from the leaves of Hydrangea macrophylla subsp. Serrate[J].Heterocycles,2008,76(1):313.

      [8] Uesato S,Hashimoto T,Takeda Y,et al.New secoiridoid glycosides hydrangenosides E,F(xiàn) and G from Hydrangea scandens[J].Chem Pharm Bull,1982,30(11):4222.

      [9] Uesato S,Hashimoto T,Takeda Y,et al.Novel type secoiridoid glycosides,hydrangenosides B,C and G from Hydrangea scandens[J].Chem Pharm Bull,1981,29(11):3421.

      [10] 黃世英,王光添.繡球花抗瘧實(shí)驗(yàn)研究及臨床療效觀察[J].廣西中醫(yī)藥,1988,11(3):44.

      [11] Murakami N,Mostaqul HM,Tamura S,et al.New anti-malarial flavonol glycoside from Hydrangeae dulcisfolium[J].Bioorg Med Chem Lett,2001,11(18):2445.

      [12] Khalifa TI,El-Gindi OD,Ammar HA,et al.Iridoid glycosides and phenolic compounds from Hydrangeae hortensis[J].J Pharm Sci,2001,28(1):221.

      [13] Subha V,Sukumar D.Phytochemical and pharmacological studies on Hydrangeae macrophylla[J].J Indian Chem Soc,2007,84(10):1026.

      [14] Yoshikawa M,Harada E,Naitoh Y,et al.Development of bioactive functions in Hydrangea dulcisfolium[J].Chem Pharm Bull,1994,42(11):2225.

      [15] Zhang HL,Matsuda H,Kumahara A,et al.New type of anti-diabetic compounds from the processed leaves of Hydrangea dulcisfolium[J].Bioorg Med Chem Lett,2007, 17(12):4972.

      [16] Claudia M,Young M,Marcia R,et al.Fungitoxic non-glycosidic iridiods from Alibertia Macrophylia[J].Phytochemistry,1992,31(10):3433.

      [17] Jensen SR,Lyse-petersen SE,Nielsen BJ.Novel 6/5-iridoid glucosides from Dipsacus sylvestris[J].Phytochemistry,1979,18(1):273.

      [18] Xu M,Wang D,Zhang YJ,et al.Iridoidal glucosides from Gentiana rhodantha[J].Nat Prod Res,2008,10(6):491.

      [19] 楊中鐸,李濤,李援朝.萱草根化學(xué)成分的研究[J].中國中藥雜志,2008,33(3):269.

      [20] 蔡金艷,宮立孟,張勇慧,等.金線蓮化學(xué)成分的研究[J].中藥材,2008,31(3):3370.

      [21] Panthama N,Kanokmedhakul S,Kanokmedhakul K.Galloyl and hexa-hydroxydiphenoyl esters of phenylpropanoid glucosides,phenylpropanoids and phenylpropanoid glucosides from rhizome of Balanophora fungosa[J].Chem Pharm Bull,2009,57(12):1352.

      (收稿日期:2014-05-14 本文編輯:郭靜娟)endprint

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