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      香港鷹爪花中倍半萜類化學(xué)成分研究

      2017-09-09 20:18:11吳水玲劉艷萍陳光英韓長(zhǎng)日
      中國(guó)中藥雜志 2017年16期
      關(guān)鍵詞:倍半萜化學(xué)成分

      吳水玲 劉艷萍 陳光英 韓長(zhǎng)日

      [摘要]綜合運(yùn)用正相硅膠柱色譜、Sephadex LH20凝膠柱色譜、反相ODS柱色譜以及制備型高效液相色譜等現(xiàn)代色譜分離技術(shù)和方法,對(duì)番荔枝科鷹爪花屬植物香港鷹爪花Artabotrys hongkongensis枝葉中的化學(xué)成分進(jìn)行系統(tǒng)研究。根據(jù)化合物的理化性質(zhì)和波譜數(shù)據(jù),并通過與文獻(xiàn)對(duì)照,鑒定了從香港鷹爪花枝葉的90%乙醇提取物的石油醚萃取部位中分離得到的16個(gè)倍半萜類化合物,分別鑒定為:blumenol A (1),4, 5dihydroblumenol A (2),(6R, 9S)3oxoaionol (3),3hydroxyβionone (4),dehydrovomifoliol (5),(3R, 6R, 7E) 3hydroxy4, 7megastigmadien9one (6),sarmentol F (7),10oxoisodauc3en15oic acid (8),fukinone (9),petasitolone (10),βeudesmol (11),trans3β(1hydroxy1methylethyl) 8aβmethyl5methylenedecalin2one (12),10hydroxyaristolan9one (13),aristol8en1one (14),aristolan9en1one (15),aristolan1, 9diene (16)。該研究首次對(duì)香港鷹爪花的化學(xué)成分進(jìn)行了系統(tǒng)研究,所有分離得到的化合物均為首次從鷹爪花屬植物中分離得到。

      [關(guān)鍵詞]番荔枝科; 鷹爪花屬; 香港鷹爪花; 化學(xué)成分; 倍半萜

      Sesquiterpenes from Artabotrys hongkongensis

      WU Shuiling1, LIU Yanping1, CHEN Guangying1, HAN Changri1, SONG Xiaoping1, ZHONG Xia2*, FU Yanhui1*

      (1 Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education, Hainan Normal University,

      Haikou 571158, China;

      2 College of Pharmacy, Hainan Medical University, Haikou 571199, China)

      [Abstract]The chemical consituents from Artabotrys hongkongensis were separated and purified by column chromatographies with silica gel, Sephadex LH20, ODS and RPHPLC The structures of the isolated compounds were identified on the basis of physicochemical properties and spectroscopic analysis, as well as comparisons with the data reported in the literature As a result, 16 sesquiterpenes were isolated and elucidated as blumenol A (1), 4, 5dihydroblumenol A (2), (6R, 9S)3oxoaionol (3), 3hydroxyβionone (4), dehydrovomifoliol (5), (3R, 6R, 7E) 3hydroxy4, 7megastigmadien9one (6), sarmentol F (7), 10oxoisodauc3en15oic acid (8), fukinone (9), petasitolone (10), βeudesmol (11), trans3β(1hydroxy1methylethyl) 8aβmethyl5methylenedecalin2one (12), 10hydroxyaristolan9one (13), aristol8en1one (14), aristolan9en1one (15), and aristolan1, 9diene (16) This is the first study on the chemical consituents of A hongkongensis, and all compounds were isolated from the genus Artabotrys for the first time

      [Key words]Annonaceae; Artabotrys; Artabotrys hongkongensis; chemical constituents; sesquiterpenes

      番荔枝科 Annonaceae鷹爪花屬Artabotrys植物全世界約有100種,分布于熱帶和亞熱帶地區(qū),分布于我國(guó)的有4種,分布于西南部至東南部[1]。在民間,鷹爪花屬植物作為藥用植物歷史悠久,具有清熱解毒、消炎止痛的功效,常用于治療瘧疾和頭頸部淋巴結(jié)核等?,F(xiàn)代藥理學(xué)研究表明該屬植物具有廣泛的生物活性,如抗腫瘤、抗菌、抗瘧以及殺蟲活性等[26]。香港鷹爪花A hongkongensis為番荔枝科鷹爪花屬植物,主產(chǎn)于我國(guó)海南、廣東、廣西、云南和貴州等地。迄今為止,尚未見到有關(guān)香港鷹爪花中化學(xué)成分及其生物活性的研究報(bào)道,本課題組在前期研究中發(fā)現(xiàn)香港鷹爪花枝葉的乙醇提取物對(duì)A549 (人肺癌細(xì)胞株),LOVO (人腸癌細(xì)胞株),6TCEM (人T 細(xì)胞白血病細(xì)胞株) 以及QGY7703 (人肝癌細(xì)胞株) 等4種人腫瘤細(xì)胞株均有較顯著的體外增殖抑制作用,尤其是對(duì)LOVO和QGY7703的抑制作用最為明顯,其IC50 分別達(dá)到28,52 mg·L-1。為進(jìn)一步開發(fā)利用鷹爪花屬藥用植物資源,闡明其藥效物質(zhì)基礎(chǔ),本研究對(duì)采自海南的香港鷹爪花枝葉的化學(xué)成分進(jìn)行了系統(tǒng)研究。綜合運(yùn)用正相硅膠柱色譜、Sephadex LH20凝膠柱色譜、反相ODS柱色譜以及制備型高效液相色譜等現(xiàn)代色譜分離技術(shù)從香港鷹爪花枝葉的90%乙醇提取物的石油醚萃取部位中分離得到了16個(gè)化合物,通過理化性質(zhì)及光譜學(xué)方法確定了這些化合物的化學(xué)結(jié)構(gòu),分別鑒定為blumenol A (1),4,5dihydroblumenol A (2),(6R,9S)3oxoaionol (3),3hydroxyβionone (4),dehydrovomifoliol (5),(3R,6R,7E) 3hydroxy4,7megastigmadien9one (6),sarmentol F (7),10oxoisodauc3en15oic acid (8),fukinone (9),petasitolone (10),βeudesmol (11),trans3β(1hydroxy1methylethyl)8aβmethyl5methylenedecalin2one (12),10hydroxyaristolan9one (13),aristol8en1one (14),aristolan9en1one (15),aristolan1,9diene (16)。本研究首次對(duì)香港鷹爪花的化學(xué)成分進(jìn)行了系統(tǒng)研究,所有分離得到的化合物均為首次從鷹爪花屬植物中分離得到。endprint

      1材料

      Bruker AV400 型超導(dǎo)核磁共振儀 (德國(guó)布魯克公司);Finnigan LCQ Advantage MAX 質(zhì)譜儀 (美國(guó)熱電公司);Agilent 1200 分析型高效液相色譜儀 (美國(guó)安捷倫科技有限公司);Cosmosil C18分析型色譜柱 (4 6 mm×250 mm,5 μm);Dionex制備型高效液相色譜儀(美國(guó)戴安公司);Cosmosil C18制備型色譜柱 (20 mm×250 mm,5 μm);中低壓制備色譜 (瑞士Buchi公司);薄層硅膠GF254和柱色譜硅膠 (青島海洋化工廠);Sephadex LH20 (Amersham Blosclences公司);ODS 柱色譜材料 (C18,10~40 μm,Merck公司);4001N電子天平 (上海民橋精密科技儀器有限公司);BSZ100自動(dòng)部分收集器 (上海青浦滬西儀器有限公司);紫外分析暗箱YOKOZX (武漢藥科新技術(shù)開發(fā)有限公司);旋轉(zhuǎn)蒸發(fā)儀 (日本EYELA公司 N1001型);所用試劑均為分析純?cè)噭?/p>

      香港鷹爪花葉于2015年8月采集于海南省樂東縣尖峰嶺國(guó)家森林公園,經(jīng)海南師范大學(xué)生命科學(xué)學(xué)院鐘瓊芯教授鑒定為番荔枝科鷹爪花屬植物香港鷹爪花A hongkongensis的枝葉,憑證標(biāo)本 (FU20150801) 保存于海南師范大學(xué)熱帶藥用植物化學(xué)教育部重點(diǎn)實(shí)驗(yàn)室標(biāo)本室。

      2提取與分離

      香港鷹爪花的干燥枝葉126 kg,粉碎后,用90%乙醇冷浸提取3次,每次提取1周,提取液減壓濃縮至無(wú)醇味,得總浸膏12 kg??偨嗉铀鞈遥来畏謩e用石油醚和乙酸乙酯進(jìn)行萃取,回收溶劑后得石油醚萃取部位2826 g和乙酸乙酯萃取部位3527 g。取石油醚萃取部位2800 g加粗硅膠 (100~200目) 拌樣,上樣于硅膠 (200~300目) 色譜柱,以石油醚丙酮 (100∶0~50∶50) 梯度洗脫得到6個(gè)流分 (Fr 1~Fr 6)。Fr 2 (238 g) 經(jīng)硅膠柱色譜分離,用石油醚乙酸乙酯 (90∶10~50∶50) 梯度洗脫,得到6個(gè)亞流分 (Fr 2A~2F)。Fr2B經(jīng)Sephadex LH20 (氯仿甲醇1∶1) 純化,再經(jīng)制備型HPLC (甲醇水80∶20) 分離得到化合物1 (438 mg),6 (223 mg),9 (569 mg);Fr2C用Sephadex LH20 (氯仿甲醇1∶1) 純化,再經(jīng)制備型HPLC (甲醇水 75∶25)制備得到化合物2 (216 mg),8 (128 mg),11 (239 mg)。Fr 3 (326 g) 經(jīng)反相ODS柱色譜分離,甲醇水 (50∶50~100∶0) 梯度洗脫,得到7個(gè)亞流分 (Fr3A~3G)。Fr3B經(jīng)Sephadex LH20 (氯仿甲醇1∶1)純化后,再經(jīng)制備型HPLC (甲醇水75∶25) 制備得到化合物3 (96 mg),10 (548 mg),13 (236 mg);Fr3C經(jīng)硅膠柱色譜分離,用石油醚乙酸乙酯 (90∶10~50∶50) 進(jìn)行梯度洗脫,洗脫流分經(jīng)Sephadex LH20 (氯仿甲醇1∶1) 純化后,再經(jīng)制備型HPLC (甲醇水 70∶30) 分離得到化合物4 (158 mg),12 (1082 mg),15 (687 mg);Fr3D經(jīng)硅膠柱色譜分離,用石油醚乙酸乙酯 (80∶20~50∶50) 進(jìn)行梯度洗脫,洗脫流分經(jīng)Sephadex LH20 (氯仿甲醇1∶1) 純化后,再經(jīng)制備型HPLC (甲醇水 65∶35) 分離得到化合物5 (212 mg),7 (119 mg),14 (339 mg),16 (168 mg)。

      3結(jié)構(gòu)鑒定

      化合物1白色無(wú)定形粉末;C13H20O3,ESIMS m/z 225 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 588 (1H,s,H4),579 (1H,d,J=158,56 Hz,H8),573 (1H,d,J=158 Hz,H7),435 (1H,m,H9),241 (1H,d,J=168 Hz,H2a),216 (1H,d,J=168 Hz,H2β),188 (3H,d,J=12 Hz,H13),125 (3H,d,J=66 Hz,H10),102 (3H,s,H12),096 (3H,s,H11); 13CNMR (CDCl3,100 MHz) δ: 1988 (C3),1640 (C5),1359 (C8),1289 (C7),1268 (C4),792 (C6),679 (C9),499 (C2),414 (C1),242 (C10),239 (C12),229 (C11),193 (C13)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[7],故鑒定化合物1為blumenol A。

      化合物2白色無(wú)定形粉末;C13H22O3,ESIMS m/z 227 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 569 (1H,dd,J=158,56 Hz,H8),558 (1H,d,J=158 Hz,H7),429 (1H,m,H9),272 (1H,d,J=136 Hz,H2a),228 (1H,d,J=128 Hz,H4a),216 (1H,m,H5),208 (1H,d,J=128 Hz,H4β),181 (1H,d,J=136 Hz,H2β),118 (3H,d,J=64 Hz,H10),086 (3H,s,H12),082 (3H,s,H11),076 (3H,d,J=58 Hz,H13); 13CNMR (CDCl3,100 MHz) δ: 2122 (C3),1352 (C8),1313 (C7),767 (C6),679 (C9),513 (C2),449 (C4),424 (C1),363 (C5),248 (C12),242 (C11),236 (C10),158 (C13)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[8],故鑒定化合物2為4,5dihydroblumenol A。endprint

      化合物3白色無(wú)定形粉末;C13H20O2,ESIMS m/z 209 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 591 (1H,s,H4),563 (1H,dd,J=158,63 Hz,H8),552 (1H,dd,J=158,88 Hz,H7),251 (1H,d,J=88 Hz,H6),428 (1H,m,H9),232 (1H,d,J=158 Hz,H2a),202 (1H,d,J=158 Hz,H2β),191 (3H,s,H13),127 (3H,d,J=66 Hz,H10),099 (3H,s,H12),093 (3H,s,H11); 13CNMR (CDCl3,100 MHz) δ: 1996 (C3),1623 (C5),1388 (C8),1267 (C4),1260 (C7),685 (C9),556 (C6),476 (C2),364 (C1),279 (C12),272 (C11),240 (C10),2368 (C13)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[9],故鑒定化合物3為(6R,9S)3oxoaionol。

      化合物4白色無(wú)定形粉末;C13H20O2,ESIMS m/z 209 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 721 (1H,d,J=168 Hz,H7),615 (1H,d,J=168 Hz,H8),406 (1H,m,H3),248 (1H,dd,J=168,80 Hz,H4a),229 (3H,s,H10),208 (1H,dd,J=168,100 Hz,H4β),179 (1H,m,H2a),176 (3H,s,H13),148 (1H,t,J=118 Hz,H2β),109 (3H,s,H12),106 (3H,s,H11); 13CNMR (CDCl3,100 MHz) δ: 1982 (C9),1419 (C7),1353 (C6),1322 (C8),1320 (C5),6432 (C3),481 (C2),423 (C4),365 (C1),299 (C11),282 (C12),273 (C10),212 (C13)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[10],故鑒定化合物4為3hydroxyβionone。

      化合物5無(wú)色油狀物;C13H18O3,ESIMS m/z 223 [M+H]+; 1HNMR (CD3OD,400 MHz) δ: 701 (1H,d,J=158 Hz,H7),628 (1H,d,J=158 Hz,H8),591 (1H,s,H4),266 (1H,d,J=168 Hz,H2α),231 (3H,s,H10),221 (1H,d,J=168 Hz,H2β),183 (3H,s,H11),100 (3H,s,H12),096 (3H,s,H13); 13CNMR (CD3OD,100 MHz) δ: 1982 (C3),1970 (C9),1617 (C5),1469 (C7),1305 (C8),1266 (C4),779 (C6),493 (C2),412 (C1),273 (C10),242 (C12),233 (C13),186 (C11)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[11],故鑒定化合物5為dehydrovomifoliol。

      化合物6白色無(wú)定形粉末;C13H20O2,ESIMS m/z 209 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 656 (1H,dd,J=158,96 Hz,H7),609 (1H,d,J=158 Hz,H8),566 (1H,br t,J=16 Hz,H4),249 (1H,d,J=98 Hz,H6),138 (1H,dd,J=136,68 Hz,H2a),229 (3H,s,H10),186 (1H,dd,J=136,68 Hz,H2β),168 (3H,s,H13),103 (3H,s,H11),089 (3H,s,H12); 13CNMR (CDCl3,100 MHz) δ: 1983 (C9),1474 (C7),1358 (C5),1338 (C8),1259 (C4),659 (C3),546 (C6),439 (C2),342 (C1),296 (C11),275 (C10),250 (C12),229 (C13)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[12],故鑒定化合物6為(3R,6R,7E)3hydroxy4,7megastigmadien9one。

      化合物7白色無(wú)定形粉末;C13H24O2,ESIMS m/z 213 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 545 (1H,dd,J=156,68 Hz,H8),524 (1H,dd,J=156,98 Hz,H7),427 (1H,m,H9),373 (1H,m,H3),198 (1H,m,H2a),179 (1H,m,H4a),170 (1H,m,H4β),146 (1H,m,H5),128 (1H,dd,J=109,98 Hz,H6),124 (3H,d,J=64 Hz,H10),120 (1H,dd,J=124,124 Hz,H2β),088 (3H,s,H12),083 (3H,s,H11),079 (3H,d,J=68 Hz,H13); 13CNMR (CDCl3,100 MHz) δ: 1375 (C8),1307 (C7),692 (C9),670 (C3),572 (C6),505 (C2),449 (C4),349 (C1),313 (C12),310 (C5),239 (C10),216 (C11),214 (C13)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[13],故鑒定化合物7為sarmentol F。

      化合物8無(wú)色油狀物;C15H22O3,ESIMS m/z 251 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 696 (1H,d,J=48 Hz,H4),283 (1H,m,H1a),279 (1H,m,H2a),258 (1H,m,H2β),247 (1H,m,H1β),239 (1H,dd,J=86,48 Hz,H5),214 (1H,m,H8a),185 (1H,m,H7a),179 (1H,m,H6),163 (1H,m,H11),139 (1H,m,H7β),136 (1H,m,H8β),128 (3H,s,H14),092 (3H,d,J=68 Hz,H12),089 (3H,d,J=68 Hz,H13); 13CNMR (CDCl3,100 MHz) δ: 2125 (C10),1690 (C15),1509 (C4),1328 (C3),595 (C9),559 (C6),530 (C5),396 (C1),350 (C8),328 (C11),272 (C7),251 (C14),2300 (C2),218 (C13),200 (C12)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[14],故鑒定化合物8為10oxoisodauc3en15oic acid。endprint

      化合物9無(wú)色油狀物;C15H24O,ESIMS m/z 221 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 259 (1H,d,J=148 Hz,H9a),239 (1H,dd,J=163,108 Hz,H6a),208 (1H,dd,J=163,58 Hz,H6β),186 (1H,d,J=148 Hz,H9β),179 (3H,s,H12),175 (1H,m,H10),165 (3H,s,H13),159 (2H,m,H1),139 (1H,m,H4),138 (2H,m,H2),116 (2H,m,H3),086 (3H,s,H15),075 (3H,d,J=68 Hz,H14); 13CNMR(CDCl3,100 MHz) δ: 2058 (C8),1398 (C7),1309 (C11),441 (C9),413 (C10),406 (C6),367 (C5),323 (C4),299 (C3),269 (C2),225 (C15),215 (C12),215 (C13),205 (C1),161 (C14)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道數(shù)據(jù)對(duì)比[15],故鑒定化合物9為fukinone。

      化合物10白色無(wú)定形粉末;C15H24O2,ESIMS m/z 237 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 669 (1H,s,H6),352 (1H,s,11OH),268 (1H,dd,J=172,126 Hz,H9a),227 (1H,dd,J=172,46 Hz,H9β),205 (1H,m,H10),156 (1H,m,H4),139 (6H,s,H12,13),133~177 (6H,m,H1~3),109 (3H,s,H15),0 89 (3H,d,J=68 Hz,H14); 13CNMR(CDCl3,100 MHz) δ: 2029 (C8),1551 (C6),1412 (C7),720 (C11),409 (C9),396 (C10),388 (C5),360 (C4),304 (C3),296 (C12),294 (C13),269 (C2),209 (C15),206 (C1),159 (C14)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[16],故鑒定化合物10為petasitolone。

      化合物11白色無(wú)定形粉末;C15H28O,ESIMS m/z 225 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 476 (1H,s,H11a),448 (1H,s,H11β),235 (1H,m,H3a),199 (1H,m,H3β),180 (1H,m,H5),167 (2H,m,H2),156 (2H,m,H1),148 (2H,m,H9),139 (1H,m,H7),129 (2H,m,H8),125 (6H,s,H13,14),117 (2H,m,H6),073 (3H,s,H15); 13CNMR (CDCl3,100 MHz) δ: 1513 (C4),1054 (C11),729 (C12),500 (C7),496 (C5),420 (C9),410 (C1),370 (C3),361 (C10),273 (C14),272 (C13),249 (C6),236 (C2),226 (C8),165 (C15)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[17],故鑒定化合物11為βeudesmol。

      化合物12白色無(wú)定形粉末;C15H26O2,ESIMS m/z 239 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 488 (1H,s,H11a),456 (1H,s,H11β),249 (1H,m,H7),239 (1H,m,H3a),238 (1H,m,H5),233 (1H,d,J=99 Hz,H9a),219 (1H,d,J=98 Hz,H9β),208 (1H,m,H6a),206 (1H,m,H3β),1669 (1H,m,H6β),165 (1H,m,H2a),154 (1H,m,H2β),149 (2H,m,H1),130 (3H,s,H14),128 (3H,s,H13),073 (3H,s,H15); 13CNMR (CDCl3,100 MHz) δ: 2148 (C8),1486 (C4),1075 (C11),716 (C12),590 (C7),569 (C9),485 (C5),413 (C1),409 (C10),367 (C3),288 (C13),282 (C6),256 (C14),229 (C2),172 (C15)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[1718],故鑒定化合物12為trans3β(1hydroxy1methylethyl)8aβmethyl5methylenedecalin2one。

      化合物13無(wú)色油狀物;C15H24O2,ESIMS m/z 237 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 310 (1H,dd,J=168,88 Hz,H8β),228 (1H,d,J=168 Hz,H8α),189 (1H,m,H1β),166 (1H,m,H2β),158 (1H,m,H2α),148 (1H,m,H4),140 (1H,m,H1α),122133 (3H,m,H3,H7),119 (3H,s,H15),108 (3H,s,H13),106 (3H,s,H12),096 (3H,d,J=68 Hz,H14),078 (1H,d,J=88 Hz,H6); 13CNMR (CDCl3,100 MHz) δ: 2160 (C9),778 (C10),469 (C5),349 (C4),346 (C8),308 (C13),296 (C1),290 (C3),289 (C6),230 (C7),229 (C2),209 (C11),185 (C15),171 (C14),169 (C12)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[19],故鑒定化合物13為10hydroxyaristolan9one。endprint

      化合物14無(wú)色油狀物;C15H22O,ESIMS m/z 219 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 599 (1H,m,H8),585 (1H,dd,J=98,20 Hz,H9),257 (1H,br s,H10),235 (2H,m,H2),195 (1H,m,H4),192 (1H,m,H3β),170 (1H,m,H3α),122 (1H,dd,J=86,56 Hz,H7),115 (3H,s,H13),103 (3H,d,J=68 Hz,H14),099 (3H,s,H12),081 (1H,d,J=86 Hz,H6),055 (3H,s,H15); 13CNMR (CDCl3,100 MHz) δ: 2100 (C1),1274 (C8),1189 (C9),548 (C10),406 (C2),402 (C4),393 (C5),352 (C6),306 (C13),315 (C3),260 (C11),248 (C7),162 (C12),160 (C15),156 (C14)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[19],故鑒定化合物14為aristol8en1one。

      化合物15無(wú)色油狀物;C15H22O,ESIMS m/z 219 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 639 (1H,m,H9α),256 (1H,m,H 8β),248 (1H,m,H2β),235 (1H,m,H8α),230 (1H,m,H2α),201 (1H,m,H4),174 (2H,m,H3),108 (3H,s,H13),105 (3H,d,J=68 Hz,H14),104 (3H,s,H12),100 (3H,s,H15),088 (1H,m,H7),069 (1H,d,J=96 Hz,H6); 13CNMR (CDCl3,100 MHz) δ: 2019 (C1),1434 (C10),1323 (C9),399 (C2),376 (C5),358 (C4),319 (C6),296 (C13),277 (C3),225 (C15),223 (C8),192 (C7),187 (C11),152 (C14),151 (C12)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[19],故鑒定化合物15為aristolan9en1one 。

      化合物16無(wú)色油狀物;C15H22O,ESIMS m/z 203 [M+H]+; 1HNMR (CDCl3,400 MHz) δ: 528 (1H,m,H9),591 (1H,d,J=96 Hz,H1),256 (1H,dd,J=198,69 Hz,H8β),222 (1H,dd,J=198,52 Hz,H8α),556 (1H,dd,J=96,56 Hz,H2),199 (1H,m,H3β),189 (1H,dd,J=184,112 Hz,H3α),106 (3H,m,H13),102 (3H,m,H12),100 (3H,d,J=69 Hz,H14),097 (3H,s,H15),079 (1H,dd,J=92,69 Hz,H7),068 (1H,d,J=92 Hz,H6); 13CNMR (CDCl3,100 MHz) δ: 1406 (C10),1289 (C1),1253 (C2),1228 (C9),352 (C5),340 (C4),322 (C3),315 (C6),300 (C13),225 (C8),212 (C15),198 (C7),184 (C11),152 (C14),151 (C12)。以上數(shù)據(jù)與文獻(xiàn)中報(bào)道的數(shù)據(jù)對(duì)比[19],故鑒定化合物16為aristolan1,9diene。

      4結(jié)果與討論

      倍半萜類化合物是一類重要的天然化合物類群,骨架類型豐富,生物活性廣泛,尤其是在抗腫瘤活性方面表現(xiàn)尤為突出,是天然抗腫瘤藥物的重要來源之一[2021]。本研究首次從香港鷹爪花中分離得到 16個(gè)倍半萜類化合物,所有化合物均為首次從鷹爪花屬植物中分離得到,有研究報(bào)道其中部分化合物表現(xiàn)出了較為顯著的抗腫瘤活性。以上研究結(jié)果不僅表明香港鷹爪花可以作為倍半萜類化合物的重要來源,而且也說明倍半萜類化合物是香港鷹爪花具有顯著的抗腫瘤活性的重要物質(zhì)基礎(chǔ),可為香港鷹爪花藥用價(jià)值的進(jìn)一步的開發(fā)和利用提供科學(xué)依據(jù)。

      [參考文獻(xiàn)]

      [1]中國(guó)植物志編輯委員會(huì) 中國(guó)植物志. 第30卷第2分冊(cè) [M] 北京: 科學(xué)出版社,1979: 122

      [2]劉艷萍,黃麗剛,汪曉翠,等 毛葉鷹爪花中一個(gè)新穎的裂環(huán)多氧取代環(huán)己烯類化合物 [J] 有機(jī)化學(xué),2015,35(9): 1981

      [3]Singh D K, Basha S A, Sarma B K, et al Antifungal activity of a phytoterpenoid (AOSA) isolated from Artabotrytis odoratissimus on spore germination of some fungi [J] Mycobiology, 2006, 34(3): 120

      [4]Srivastava B, Singh P, Srivastava A K, et al Efficacy of Artabotrys odoratissimus oil as a plant based antimicrobial against storage fungi and a flatoxin B1 secretion [J] Int J Food Sci Technol, 2009, 44(10): 1909

      [5]Tattersfield F, Potter C The insecticidal properties of certain species of Annona and of an Indian strain of Mundulea sericea [J] Ann Appl Biol, 1940, 27(2): 262endprint

      [6]Radloff P D, Philipps J, Nkeyi M, et al Arteflene compared with mefloquine for treating Plasmodium falciparum malaria in children [J] Am J Trop Med Hyg, 1996, 55(3): 259

      [7]Xu X H, Ruan B Q, Jiang S H, et al Megastigmanes and flavonoid glycosides of Equisetum debile [J] Chin J Nat Med, 2005, 3(2): 93

      [8]González A G, Guillermo J A, Ravelo A G, et al 4, 5Dihydroblumenol A, a new norisoprenoid from Perrottetia multiflora [J] J Nat Prod, 1994, 57(3): 400

      [9]Yao D, Jin M, Zhang C, et al Chemical constituents of the leaves of Juglans mandshurica [J] Chem Nat Compd, 2016, 52(1): 93

      [10]DellaGreca M, Marino C D, Zarrelli A, et al Isolation and phytotoxicity of apocarotenoids from Chenopodium album [J] J Nat Prod, 2004, 67(9): 1492

      [11]Hisahiro K, Masaki B, Toru O Two new megastigmanes from the leaves of Cucumis sativus [J] Chem Pharm Bull, 2007, 55(1): 133

      [12]Koichi M, Masao K Norisoprenoids from Viburnum dilatatum [J] Phytochemistry, 1996, 41(5): 1333

      [13]Morikawa T, Zhang Y, Nakamura S, et al Bioactive constituents from Chinese natural medicines

      ⅩⅫ. Absolute structures of new megastigmane glycosides, sedumosides E1, E2, E3, F1, F2, and G, from Sedum sarmentosum (Crassulaceae) [J] Chem Pharm Bull, 2007, 55(3): 435

      [14]Masataka M, Sousuke T, Momoyo I, et al Pyrenes and pyrendiones from Uvaria lucida [J] J Nat Med, 2012, 66(3): 453

      [15]Sato T, Tada M, Takahashi T, et al NMR and CD spectral studies of conformational isomers of isoligularone and fukinone, naturally occurring cisdecalin derivatives [J] Chem Lett, 1977(10): 1191

      [16]Naya K, Yoshimura F, Takagi I The structure of petasitolone, a new constituent of Petasites japonicus [J] Bull Chem Soc Jpn, 1971, 44(11): 3165

      [17]Duan J, Wang L, Qian S, et al A new cytotoxic prenylated dihydrobenzofuran derivative and other chemical constituents from the rhizomes of Atractylodes lancea DC [J] Arch Pharm Res, 2008, 31(8): 965

      [18]Torii S, Inlkuchi T Functionalization of transdecalin IV A stereoselective synthesis of dlβcostol, dlarctiol, and the related eudesmane type sesquiterpenes [J] Chem Soc Jpn, 1980, 53(9): 2642

      [19]Su H, Shi D Y, Li J, et al Sesquiterpenes from Laurencia similis [J] Molecules, 2009, 14(5): 1889

      [20]趙愛華, 魏均嫻 倍半萜類化合物生理活性研究進(jìn)展 [J] 天然產(chǎn)物研究與開發(fā), 1995, 7(4): 65

      [21]湯敏燕, 汪洪武, 孫凌峰 具有抗腫瘤活性的天然萜類化合物 [J] 林產(chǎn)化學(xué)與工業(yè), 1997, 17(2):146

      [責(zé)任編輯丁廣治]endprint

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