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多穗金粟兰中一个新的酚苷(英文)
发布时间:2018-04-21浏览次数:267返回列表

多穗金粟兰中一个新的酚苷+

冉新辉1,2,倪 伟z,魏 刚s,陈昌祥z,刘海洋 (1广州中医药大学第一临床医学院,广东广州510405;2中国科学院昆明植物研究所植物化学与西部植物资源

持续利用国家重点实验室,云南昆明650204;3广州中医药大学新药研究中心,广东广州510006)

摘要:从多穗金粟兰(Chloranthus multistachys)全株的甲醇提取物中分离得到1个新的酚苷,通过波谱技术鉴定其结构为丁香酸 -。-I,鼠李吡喃糖苷(1)。同时还首次从该植物中分离得到两个已知倍半萜内酯和一个已知木脂素:1 p,二羟基5a,8p-=氢7(11)Z桉叶烯8,12内酯(2), ip, la二羟基5a,8p-=氢7(11)}桉叶烯8,12内酯(3),(一)(7S,8R)-dihydrodehydrodiconifery alcohol (4)。

关键词:多穗金粟兰;金粟兰科;酚苷;倍半萜内酯

中图分类号:Q 916

文献标识码:A

文章编号:0253-2´

01-083-01

A New Phenolic Glycoside from Chloranthus

multistach ys( Chloranthaceae)

RAN Xin-Huil´p, NI Weip, WEI Gang´3, CHEN Chang-XiangP, LIU Hai-YangP

(1 The First Affiliated Hospital of Guangzhou UniversitY of Traditional Chinese Medicine,Guangzhou 510405, China;

2 State Kev Laborarorv of Phvrochemistrv and Plant Resources in West China,Kunming Institute of Botanv,

Chinese Academv of Sciences, Kunming 650204, China;3 Research Center of New Drug,

Guangzhou UniversitY of Traditional Chinese Medicine, Guangzhou 510006, China)

Abstract:A new phenolic glycoside, named syringic acid-l-O-a -I,-rhamnopyranoside (1), together withthree known compounds were isolated from the MeOH extract of the whole plants of Chloranthus multistachyS. Their structures were elucidated on the basis of extensive spectroscopic. To the best of our knowledge,the three known compounds,1,Ⅱp-dihydroxy-s,8p(H)-eudesm-7 (11)Z-en-8 12-olide (2),1,iadihydroxy-5a,8p(H)-eudesm-7 (11) 2-en-8, 12-olide (3), and(一)(7S,8R)-dihydrodehydrodiconiferyalcohol (4) were all isolated from this plant for the first time.

Key words: Chloranthus multistachys;Chloranthaceae; Phenolic glycoside; Sesquiterpene lactones

The plants of genus Chloranthus (Chloran-thaceae) , comprising 15 species, are mainly distrib-uted in the east of Asia (Zhou, 1993). Most ofthese plants have been using as important medicinalherbs for the treatment of tumors, theumatisms,and emmeniopathy in traditional Chinese medicine(Jiangsu New Medical College, 1977). Previousphytochemical investigation on this genus revealedthe presence of monoterpenoids, sesquiterpenoids,bisesquiterpenoids, diterpenoids, ligans, and fla-vone glycosides (Wu et a., 2007; Yang andYue, 2006; Yang et a., 2007; 2008; Wang eta., 2008; Xu et a., 2007; 11 et a., 2008).Chloranthus multistachys is a perennial herbwhich mainly distributes over the south of Chinaand its roots has been used to treat bone fracturein China as folk medicine (Editorial Committeeof the Administration Bureau of TranditionalChinese Medicine, 1998). One sesquiterpenoid,three bisesquiterpenoids, and nine ent-kauranediterpenoids have been isolated from this plant(Yang and Yue, 2006; 2008). As a part of oursystematic research works on the genus (Tenget a., 2009), the chemical constituents ofC. multistachys were investigated and a newphenolic glycoside, syringic acid-4- O - a -L-rh-amnopyranoside (1) was obtained, along withthree known compounds, ip, 4p-dihydroxy-5a . 8p ( H )-eudesm-7 (11) 2-en-8, 12-olide(2) (Yang et a., 2007), ip, 4a-dihydroxy-5a . 8p ( H )-eudesm-7 (11) 2-en-8, 12-olide(3) (Yang et a., 2007), and ( - )-(75 ,8R )-dihydrodehydrodiconifery alcohol (4) (Zhu eta., 2008) (Fig. 1). In this paper, we report theisolation and structural elucidation of the newphenolic glycoside.Results and Discussion

Compound l was isolated as an amorphouspowder and showed the molecular formula Ci.,-Hi0 00, with 6 degrees of unsatuation, by thenegative HR-ESI-MS at mz 343. 1040 [M-Hl-.The IR spectrum displayed peaks indicatinghydroxygen groups (3422 cm.l), benzene rings(1592, 1502, 1460 cm.l), and carboxyl groups(1700 cm.l). UV absorptions at kr117ix211, 254nm suggested that l had an excellent conjugatedsystem. Analysis of the "3C-NMR and DEPTspectra (Table l) of l indicated one carbonyl ( 8c 169. 6, s), two methoxyls ( 8c 56. 5, q), twospP methines ( 8c 107. 7, d), and four spP qua-ternary carbons [ 8c 128. 0 (s) , 154. 4 (X 2, s) ,139.7 (s)l, which showed the presence of sy-ringic acid moiety in this compound (Shao eta., 2008). The signals at 8H 5. 33 (d, H-l),4. 14 (m, H-2), 3. 89 (m, H-3), 3. 44 (m, H-4´) , 4. 25 (m, H-5) , 1. 20 (d, H-6) in theIH-NMR spectrum and signals at 8c 103. 3 (d, C-11), 71. 9 (d, C-2), 72.1 (d, C-3´), 73. 6 (d,C-4´), 71.2 (d, C-5´), 17.8 (q, C-6´) in the"3C-NMR spectrum (Table l) of l showed a L-thamnose in this compound. The anomeric con-figuration of the thamnopyranosyl was deter-mined as a -oriented on the ground the chemicalshift values of the C-3´ ( 8c 72. 1) and C-5´ ( 8c71. 2) to those of the corresponding carbons ofmethyl a-and p-rhamnopyranoside (Kasai eta., 1979). The L-rhamnose was linked to C-4by the HMBC correlation from H-l to C-4 asshown in Fig. 2. based on above mentioned evi-dence, the structure of l was identified to be sy-ringic acid -4- O - a -L-rhamnopyranoside.Experimental General experimental procedures Optical rotationwere taken on a HoribaseAP-300 polarimeter. UV spec-tra were obtained on a Shimadzu UV-2IOIPC spectropho-tometer. 1R spectra were measured with a Bio-Rad FTS-135 spectrometer with KBr pellets. FAB mass spectrawere obtained on a VG Auto spec-3000 spectrometer andhigh-resolution ESl mass spectra were recorded on an AP1Qstar Pulsar I.CT instrument. NMR spectra weremeasured in CDs D and recorded on a Bruker AM-IOO ora DRX-500 NMR spectrometer with TMS as an internalstandard. Separation and purification were performed bycolumn chromatography on silica gel (200 - 300 mesh,Qingdao Marine Chemical Inc. , Qingdao, People´ s Re-public of China) , RP-18 ( Merck) and Sephadex I,H-20(Amersham Biosciences, Sweden). Fractions were moni-tored by TI,C, and spots were visualized by heating silicagel plates sprayed with 10% H.SO, in EtOH.

Plant material The whole plants Chloranthus mul-tistachys was collected in August 2007 from Xinning, HunanProvince, P. R. China, and identified by Dr. En-De I.iu ofKunming Institute of Botany. A voucher specimen (No.HYOO01) was deposited at the State Key I,aboratory of Phy-tochemistry and Plant Resources in West China.

Extraction and isolation Dried and powered wholeplants of C. multistachys (20 kg) were extracted threetimes with CHs H under reflux. The filtrate was evapo-rated under reduced pressure to give a residue, which wassuspended into water and partitioned with EtOAc. TheEtOAe portion (1300 g) was subjected to column chro-matography over silica gel eluted with petroleum ether-Me:] C (1 : 0

1 : 1) to give fraction Fr. 1- 7. Fr. 3 (50g) was repeatedly separated on silica gel, Rp-18, andSephadex I,H-20 (MeOH) column chromatography to af-ford 2 (19 mg) , 3 (110 mg) , and 4 (30 mg). Fr. 6 (15 g)was chromatographed on silica gel column eluting withCHCls-MeOH (30 : 1 1 : 1) and Rp-18 column elutingwith a MeOH-H2 0 gradient system (20%+60%), fur-ther purified on Sephadex I,H-20 using MeOH as solventto yield l (15 mg).

syringic acid-4- O - a -L-rhamnopyranoside ( 1) : CinHii)O9 , yellow amorphous powder. [ alj = - 81. 20。( c = 0. 12, MeOH). lR \)K": CITI´1 : 3122, 2936, 2851 1700, 1592, 1553, 1502, 1160, 1393, 1129. UV (CH,OH) Amax (log e ): 211 (11. 38), 251 (3. 89) nm. IH-NMR and ´sC-NMR: see Table l. Negative FAB-MS m厂z (%): 313 [M-ll- (83) 325 [M-18l- (100) , 197 [M-H -116l- (13) ; HR-ESl-MS mz : 313.1010 [M-ll-(calcd for Ci.j His Og cald. 313. 1029).

ip, 4p-dihydroxy-5a , 8p ( H ) -eudesm-7 (11)2-en-8, 12-olide (2): Ci.j Hz:] Oi, white powder. IH-NMR (500 MHz, CD3 0D): 8H 11. 91 (1H, m. H-8),3. 21 (1H, dd, J =3. 8, 11. 9 Hz, H-l) 2. 92 (1H, dd,J = 3. 5, 111. 1 Hz, H-6a ) 2. 61 (1H, dd, J = 6. 311. 8 Hz, H-9 p ) , 2. 51 (1H, t, J =13. 6 Hz, H-6 p ) ,1. 90 (1H, m. H-2 p), 1. 81 (3H, m. H-13), 1. 72(1H, m. H-3 p ) , 1. 55 (1H, m. H-2 a ) 1. 16 (1H,m. H-3 a ) 1. 23 (3H, s. H-15) 1. 20 (3H, s H-ll) 1. 16 (1H, dd, J =3. 5, 13.1 Hz, H-5) 0. 89 (1H, t,J =11. 7 Hz, H-9a ); ´sC-NMR (125 MHz, CD3 0D):ac: 79. 1 (d, C-l), 27. 2 (t, C-2) 110. 1 (t, C-3) 71. 6(s, C-I) , 52. 6 (d, C-5) 21. 0 (t, C-6) 166. 11 (s, C-7) , 80. 11 ( d, C-8 ) 17. 2 ( t, C-9 ) 111. 5 ( s, C-10 ) ,120. 3 (s, C-ll) 177. 3 (s, C-12), 8. 0 (q, C-13), 13. 11(q, C-ll) , 29. 7 (q, C-15).

ip , 4a -dihydroxy-5a , 8p ( H ) -eudesm-7 (11)2-en-8, 12-olide (3): Cis H22 O1 white powder. 1H-NMR (500 MHz, CDs OD) : 8H 11. 66 (1H, dd, J =6. 3,10. 11 Hz, H-8) 3. 15 (1H, dd, J =11. 3, 11. 3 Hz, H-1), 2. 96 (1H, dd, J = 3. 3, 13. 9 Hz, H-6a), 2. 55(1H, dd, J =6. 2, 11. 9 Hz, H-9p), 2. 12 (1H, m. H-6p), 1. 71 (1H, m. H-3a ) 1. 68 (3H, s. H-13) 1. 57 (2H,m H-2) 1. 18 (1H,m H-3 a ) 1. 19 (1H,dd, J = 13. 2, 3.11 Hz, H-5), 1. 07 (3H, s. H-15),0. 91 (3H, s. H-ll) 0. 80 (1H, t, J =11. 7 Hz, H-9a); isC-NMR (125 MHz, CDs OD) : 8 c´ 77. 3 (d, C-l),27. 7 (t, C-2) 110. 1 (t, C-3) 71. 9 (s, C-l), 53. 0 (d,C-5) 22. 11 (t, C-6 ) 163. 7 (s, C-7) , 78. 11 (d, C-8 ) 16. 8 (t, C-9) 39. 9 (s, C-10) , 119. 11 (s, C-ll) 175. 7(s, C-12) 7. 6 (q, C-13), 13. 0 (q, C-ll), 21. 6 (q, C-15).

(-) - (7S , 8R ) -dihydrodehydrodiconifery alcohol(4): Czo H:l, Oei, colorless oil. IH-NMR (CDs OD, 100MHz): 8H 6. 91 (1H, d, J =1. 8, H-2) 6. 82 (1H, dd,J =1. 8, 8.1 Hz, H-6), 6. 78 (1H, s), 6. 75 (1H, s.H-2´), 6. 72 (1H, s H-6´), 5. 19 (1H, d, J =6. 3 Hz,H-7) 3. 81 (3H, s. OCH: ), 3. 80 (3H, s. OCHs ),3. 75 (1H, m. H-9), 3. 56 (2H, t, J =6. 5 Hz, H-9´),3. 16 (1H, m. H-8) 2. 62 (2H, t, J =7. 11 Hz, H-7´),1. 83 (2H, m. H-8´) ; ´3C_NMR (CDs OD, 100 MHz) :ac 131. 8 (C-l), 110. 5 (C-2) 117. 5 (C-3) 115. 2 (C-l) , 116. 1 ( C-5 ) 119. 7 (C-6) 89. 0 ( C-7) , 55. 11 ( C-8) 61. 9 (C-9) 136. 9 (C-l´) , 1111. 0 (C-2´) , 115. 2 (C-3´) , 119. 1 ( C-l´) , 129. 8 ( C-5´) , 117. 9 ( C-6´) , 35. 8(C-7´), 32. 9 (C-8´), 62. 2 (C-9´), 56. 3 56. 7 (3, 3´-

Acknowledgements: The authors are grateful to the mem-bers of the analytical group of the State Key I,aboratory ofPhytochemistry and Plant Resources in West China, Kun-ming Institute of Botany, Chinese Academy of Sciencesfor all of the spectral measurements.

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