国产绿奇楠沉香的化学成分研究
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摘要
为了解国产绿‘奇楠’沉香的化学成分,采用色谱和波谱方法从其乙醚和乙醇提取物中分离鉴定了7个化合物,分别鉴定为顺式-7-羟基菖蒲烯(1),(5R,6R,7S,8R)-2-(苯乙基)-6,7,8-三羟基-5,6,7,8-四氢-5-[2-(2-苯乙基)色酮基-6-氧代]色酮(2), 1-羟基-1,5-二苯基戊-3-酮(3),丁香树脂酚葡萄糖苷(4),(3β)-齐墩果-12-烯-3,23-二醇(5),β-谷甾醇(6)和棕榈酸-α-单甘油酯(7)。化合物1、3～5和7均为首次从沉香中分离得到,其中化合物1表现出非常甜的芳香气味。乙酰胆碱酯酶体外抑制活性测试结果表明,50μmol L~(–1)的化合物1对乙酰胆碱酯酶抑制率为(49.9±1.4)%。
To understand the chemical constituents of Chinese agarwood "Qi-Nan", seven compounds were isolated by various column chromatographic methods. On the basis of spectral data, they were identified as cis-7-hydroxycalamenene(1),(5 R,6 R,7 S,8 R)-2-(phenylethyl)-6,7,8-trihydroxy-5,6,7,8-tetrahydro-5-[2-(2-phenylethyl)chromonyl-6-oxy]chromone(2), 1-hydroxy-1,5-diphenylpentan-3-one(3), syringaresinol-glycoside(4),(3β)-olean-12-ene-3,23-diol(5), β-sitosterol(6) and hexadecanoic acid, 2,3-dihydroxypropyl ester(7). Compounds 1,3-5, and 7 were isolated from agarwood for the first time, and compound 1 showed a very sweet aromatic odor.Compound 1 showed acetylcholinesterase(AChE) inhibitory activity with the inhibition rate of(49.9 ±1.4)% at the concentration of 50 μmol L~(–1).
To understand the chemical constituents of Chinese agarwood "Qi-Nan", seven compounds were isolated by various column chromatographic methods. On the basis of spectral data, they were identified as cis-7-hydroxycalamenene(1),(5 R,6 R,7 S,8 R)-2-(phenylethyl)-6,7,8-trihydroxy-5,6,7,8-tetrahydro-5-[2-(2-phenylethyl)chromonyl-6-oxy]chromone(2), 1-hydroxy-1,5-diphenylpentan-3-one(3), syringaresinol-glycoside(4),(3β)-olean-12-ene-3,23-diol(5), β-sitosterol(6) and hexadecanoic acid, 2,3-dihydroxypropyl ester(7). Compounds 1,3-5, and 7 were isolated from agarwood for the first time, and compound 1 showed a very sweet aromatic odor.Compound 1 showed acetylcholinesterase(AChE) inhibitory activity with the inhibition rate of(49.9 ±1.4)% at the concentration of 50 μmol L~(–1).
引文
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[26]UEDA J Y,IMAMURA L,TEZUKA Y,et al.New sesquiterpene from Vietnamese agarwood and its induction effect on brain-derived neurotrophic factor mRNA expression in vitro[J].Bioorg Med Chem,2006,14(10):3571?3574.doi:10.1016/j.bmc.2006.01.023.
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[31]IWAGOE K,KONISHI T,KIYOSAWA S,et al.The structures of AH10 and AH11,nobel bi-phenylethylchromones from agalwood[J].Chem Pharm Bull,1986,34(11):4889?4891.
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[35]LI W,CAI C H,DONG W H,et al.2-(2-Phenylethyl)chromone derivatives from Chinese agarwood induced by artificial holing[J].Fitoterapia,2014,98:117-123.doi:10.1016/j.fitote.2014.07.011.
[36]LI W,MEI W L,ZUO W J,et al.Advances in chemical constituents and biological activities from Aquilaria sinensis[J].J Trop Subtrop Bot,2014,22(2):201-212.doi:10.3969/j.issn.1005-3395.2014.02.015.李薇,梅文莉,左文健,等.白木香的化学成分与生物活性研究进展[J].热带亚热带植物学报,2014,22(2):201-212.doi:10.3969/j.issn.1005-3395.2014.02.015.
[2]YAMAGATA E,YONEDA K.Pharmacognostical studies on the crude drug of agarwood(VI):On“Kanankoh”[J].Nat Med,1987,41(2):142-146.
[3]NAKANISHI T,INADA A,NISHI M,et al.A new and a known derivatives of 2-(2-phenylethyl)chromone from a kind of agarwood(“Kanankoh,”in Japanese)originating from Aquilaria agallocha[J].JNat Prod,1986,49(6):1106-1108.doi:10.1021/np50048a024.
[4]ISHIHARA M,TSUNEYA T,UNEYAMA K.Fragrant sesquiterpenes from agarwood[J].Phytochemistry,1993,33(5):1147-1155.doi:10.1016/0031-9422(93)85039-T.
[5]XIE Z W.Discussion on Varieties of Chinese Medicinal Herb,Vol.2[M].Shanghai:Shanghai Science and Technology Press,1984.谢宗万.中药材品种论述,中册[M].上海:上海科学技术出版社,1984.
[6]YANG D L,MEI W L,ZENG Y B,et al.2-(2-Phenylethyl)chromone derivatives in Chinese agarwood“Qi-Nan”from Aquilaria sinensis[J].Planta Med,2013,79(14):1329-1334.doi:10.1055/s-0033-1350647.
[7]DAI H F.Research Progress of Agarwood[M].Beijing:Science Press,2017.戴好富.沉香的现代研究[M].北京:科学出版社,2017.
[8]YANG D L,MEI W L,YANG J L,et al.GC-MS analysis of the fragrant sesquiterpenes and 2-(2-phenylethyl)chromone derivatives in four types of agarwood“Qi-Nan”[J].Chin J Trop Crops,2014,35(6):1235-1243.doi:10.3969/j.issn.1000-2561.2014.06.033.杨德兰,梅文莉,杨锦玲,等.GC-MS分析4种奇楠沉香中致香的倍半萜和2-(2-苯乙基)色酮类成分[J].热带作物学报,2014,35(6):1235-1243.doi:10.3969/j.issn.1000-2561.2014.06.033.
[9]FU L G.Red Book of Chinese Plant:Rare and Endangered Plants[M].Beijing:Science Press,1992:670.傅立国.中国植物红皮书--稀有濒危植物[M].北京:科学出版社,1992:670.
[10]YANG D L,WANG H,GUO Z K,et al.A new 2-(2-phenylethyl)chromone derivative in Chinese agarwood‘Qi-Nan’from Aquilaria sinensis[J].J Asian Nat Prod Res,2014,16(7):770-776.doi:10.1080/10286020.2014.896342.
[11]YANG D L,WANG H,GUO Z K,et al.Fragrant agarofuran and eremophilane sesquiterpenes in agarwood‘Qi-Nan’from Aquilaria sinensis[J].Phytochem Lett,2014,8:121-125.doi:10.1016/j.phytol.2014.03.003.
[12]YANG D L,LI W,DONG W H,et al.Five new 5,11-epoxyguaiane sesquiterpenes in agarwood“Qi-Nan”from Aquilaria sinensis[J].Fitoterapia,2016,112:191-196.doi:10.1016/j.fitote.2016.05.014.
[13]SHAO H,MEI W L,KONG F D,et al.A new 2-(2-phenylethyl)chromone glycoside in Chinese agarwood“Qi-Nan”from Aquilaria sinensis[J].J Asian Nat Prod Res,2017,19(1):42?46.doi:10.1080/10286020.2016.1187602.
[14]ELLMAN G L,COURTNEY K D,ANDRES V Jr,et al.A new and rapid colorimetric determination of acetylcholinesterase activity[J].Biochem Pharmacol,1961,7(2):91-95.doi:10.1016/0006-2952(61)90145-9.
[15]DAVILA-HUERTA G,HAMADA H,DAVIS G D,et al.Cadinane-type sesquiterpenes induced in Gossypium cotyledons by bacterial inoculation[J].Phytochemistry,1995,39(3):531-536.doi:10.1016/0031-9422(94)00958-V.
[16]IWAGOE K,KAKAE T,KONISHI T,et al.Studies on the agalwood(Jinko):VIII.Structures of bi-phenylethylchromone derivatives[J].Chem Pharm Bull,1989,37(1):124-128.
[17]NIWA M,JIANG P F,HIRATA Y.Constituents of Wikstroemia sikokiana:II.Absolute configurations of 1,5-diphenylpentane-1,3-diols[J].Chem Pharm Bull,1987,35(1):108-111.
[18]KOBAYASHI H,KARASAWA H,MIYASE T,et al.Studies on the constituents of Cistanchis herba:V.Isolation and structures of two new phenylpropanoid glycosides,cistanosides E and F[J].Chem Pharm Bull,1985,32:1452-1457.
[19]SONG Z H,MO S H,CHEN Y,et al.Studies on chemical constituents of Cistanche tubulosa(Schenk)R.Wight[J].China J Chin Mat Med,2000,25(12):728-730.宋志宏,莫少红,陈燕,等.管花肉苁蓉化学成分的研究[J].中国中药杂志,2000,25(12):728-730.
[20]WANG K W,SUN H X,WU B,et al.Two novel olean triterpenoids from Celastrus hypoleucus[J].Helv Chim Acta,2005,88(5):990-995.doi:10.1002/hlca.200590094.
[21]CUI Y L,MU Q,HU C Q.Studies on the chemical constituents of Caragana rosea[J].Chin Pharm J,2004,39(3):173-175.doi:10.3321/j.issn:1001-2494.2004.03.005.崔益冷,穆青,胡昌奇.红花锦鸡儿化学成分的研究[J].中国药学杂志,2004,39(3):173-175.doi:10.3321/j.issn:1001-2494.2004.03.005.
[22]LU L M,SONG S J,WU Y,et al.Study on the chemical constituents of the ovum oil of Rana temporaria chensinensis David(II)[J].JShenyang Pharm Univ,2002,19(1):25-26.doi:10.3969/j.issn.1006-2858.2002.01.007.卢立明,宋少江,武勇,等.哈士蟆卵油化学成分研究(II)[J].沈阳药科大学学报,2002,19(1):25-26.doi:10.3969/j.issn.1006-2858.2002.01.007.
[23]ISHIHARA M,TSUNEYA T,SHIGA M,et al.Three sesquiterpenes from agarwood[J].Phytochemistry,1991,30(2):563-566.doi:10.1016/0031-9422(91)83727-3.
[24]ISHIHARA M,TSUNEYA T,UNEYAMA K.Guaiane sesquiterpenes from agarwood[J].Phytochemistry,1991,30(10):3343-3347.doi:10.1016/0031-9422(91)83206-Z.
[25]HASHIMOTO K,NAKAHARA S,INOUE T,et al.A new chromone from agarwood and pyrolysis products of chromone derivatives[J].Chem Pharm Bull,1985,33(11):5088?5091.
[26]UEDA J Y,IMAMURA L,TEZUKA Y,et al.New sesquiterpene from Vietnamese agarwood and its induction effect on brain-derived neurotrophic factor mRNA expression in vitro[J].Bioorg Med Chem,2006,14(10):3571?3574.doi:10.1016/j.bmc.2006.01.023.
[27]YANG Y,CHEN H Q,KONG F D,et al.Dimeric sesquiterpenoid-4H-chromone derivatives from agarwood of Aquilaria crassna and their cytotoxicity[J].Phytochemistry,2018,145:207?213.doi:10.1016/j.phytochem.2017.08.007.
[28]YANG Y,MEI W L,KONG F D,et al.Four new bi-2-(2-phenylethyl)chromone derivatives of agarwood from Aquilaria crassna[J].Fitoterapia,2017,119:20?25.doi:10.1016/j.fitote.2017.03.008.
[29]XIANG P,MEI W L,CHEN H Q,et al.Four new biphenylethylchromones from artificial agarwood[J].Fitoterapia,2017,120:61?66.doi:10.1016/j.fitote.2017.05.012.
[30]HUO H X,ZHU Z X,SONG Y L,et al.Anti-inflammatory dimeric2-(2-phenylethyl)chromones from the resinous wood of Aquilaria sinensis[J].J Nat Prod,2018,81(3):543?553.doi:10.1021/acs.jnat prod.7b00919.
[31]IWAGOE K,KONISHI T,KIYOSAWA S,et al.The structures of AH10 and AH11,nobel bi-phenylethylchromones from agalwood[J].Chem Pharm Bull,1986,34(11):4889?4891.
[32]IWAGOE K,KODAMA S,KONISHI T,et al.The structures of AH15and AH18,new bi-and tri-phenylethylchromones from agalwood[J].Chem Pharm Bull,1987,35(11):4680?4682.
[33]KONISHI T,IWAGOE K,KIYOSAWA S,et al.Tri-2-(2-phenylethyl)chromones from agalwood[J].Phytochemistry,1989,28(12):3548-3550.doi:10.1016/0031-9422(89)80391-7.
[34]PENG Y J,HUANG C S,LIU H X,et al.Recent advances in the structure and biological activity of 1,5-dihpenylpentadions[J].Nat Prod Res Dev,2009,21(6):1069-1075,1079.doi:10.3969/j.issn.1001-6880.2009.06.041.彭艳君,黄初升,刘红星,等.1,5-二芳基戊烷类化合物生物活性与结构关系的研究进展[J].天然产物研究与开发,2009,21(6):1069-1075,1079.doi:10.3969/j.issn.1001-6880.2009.06.041.
[35]LI W,CAI C H,DONG W H,et al.2-(2-Phenylethyl)chromone derivatives from Chinese agarwood induced by artificial holing[J].Fitoterapia,2014,98:117-123.doi:10.1016/j.fitote.2014.07.011.
[36]LI W,MEI W L,ZUO W J,et al.Advances in chemical constituents and biological activities from Aquilaria sinensis[J].J Trop Subtrop Bot,2014,22(2):201-212.doi:10.3969/j.issn.1005-3395.2014.02.015.李薇,梅文莉,左文健,等.白木香的化学成分与生物活性研究进展[J].热带亚热带植物学报,2014,22(2):201-212.doi:10.3969/j.issn.1005-3395.2014.02.015.