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岩芋中的一个新苯丙素苷(英文)
发布时间:2018-04-21浏览次数:246返回列表

岩芋中的一个新苯丙素苷+

唐贵华,王跃虎,龙春林

(1中国科学院昆明植物研究所,云南昆明650204;2中国科学院研究生院,北京100049)

摘要:从岩芋(Rem usatia vivipara)干燥的球茎中分离得到10个化合物,其中一个为新的苯丙素苷,经波谱学分析及酸水解的方法确定该新化合物的结构为Caffeyl alcohol-3- 0 - p-D-glucopyranoside。已知化合物包括3个苯丙素类(松柏苷,caffeyl alcohol和松柏醇),3个新木脂素[11,7,9,9´-tetrahydroxy-3,3 7dimethoxy-8- 0 -l: neolign-7´-ene,(7R,8S) △7 3,3´-dimethoxy-l,7,9,9Ltetrahydroxy-8- 0 -l´-neolignan-7- 0 - p-D-glucopyranoside,以及dehydrodiconiferyl alcohoi-i-p-D-glucosidel, 1个酰胺[(2E,4E) - N -isobutyl-2, l-decadienamide],1个甾体皂苷(methyl proto-taccaoside)和1个三萜皂苷(saxifragifolin B)。所有化合物均为首次从岩芋属植物中分离得到。

关键词:岩芋;天南星科;苯丙素苷

中图分类号:Q 916

文献标识码:A

文章编号:0253-2.

一01-087-01

A New Phenylpropanoid Glucoside from

Remusatia vivipara (Araceae)

TANG Gui-Hual,p, WANG Yue-Hul, LONG Chun-Linixx

(1 Kunming Institute of Botanv,Chinese Academy of Sciences,Kunming 650204, China;

2 Graduate UniversitV of Chinese Academy of Sciences, Beijing 100049, China)

Abstract:A new phenylpropanoid glucoside, caffeyl alcohol-3- 0 -p-D-glucopyranoside, together with nineknown compounds, was isolated from the dry corms of Remusatia vivipara Schott. The structure of the newcompound was determined by the spectroscopic method and acidic hydrolysis. The known compounds included three phenylpropanoids (coniferin, caffeyl alcohol and coniferyl alcohol), three neolignans[11, 7, 9, 9´tetrahydroxy-3, 3´-dimethoxy-8-0 -l´-neolign-7´-ene,(7R,8S) 厶7 3,3´-dimethoxy-l,7,9,9´-tetrahydroxy-8- 0 -l´-neolignan-7- 0 - p-D-glucopyranoside, and dehydrodiconiferyl alcohol-l-,B-D-glucoside], an amide[(2 E,ⅡE) - N -isobutyl-2, l-decadienamidel,a steroid saponin (methyl proto-taccaoside) and a triterpenoidsaponin (saxifragifolin B).All compounds were isolated from the genus Remusatia for the first time.

Key words: Remusatia vivipara; Araceae; phenylpropanoid glucoside

Remusatia vivipara (Lodd. ) Schott (Arace-ae) is a perennial herb mainly epiphytic on rocksand cliff-ledges in the subtropical forests of Asiasuch as SW China, Sri Lanka, Nepal, India,Myanmar, Thailand, Vietnam and Indonesia,and Cameroon in West Africa (11, 1979). Itscorms are strongly poisonous but used externallyto treat breast mastitis, abscesses, acariasis andso on ( Health Bureau of Yunnan Province,1973). Up to now, the chemical constituents ofthe plant have not been reported yet. So a phy-tochemical investigation of the R. vivipara wascarried out, which led to the isolation of a newphenylpropanoid glucoside (1) from the corms,together with nine known compounds: coniferin (2) (Sugiyama et a. , 1993) , caffeyl alcohol (3)(Quideau and Ralph, 1992), coniferyl alcohol (4)(Quideau and Ralph, 1992), 4, 7, 9, 9´-tetra-hydroxy-3, 3´-dimethoxy-8- O -4´-neolign-7´-ene (5)(Lourith et a., 2005), (7R . 85) -A7´-3, 3´-dimethoxy-4, 7, 9, 9´-tetrahydroxy-8- O -4: ne-olignan-7-0. -[3-D-glucopyranoside (6) (Ma eta., 2008) , dehydrodiconiferyl alcohol-4-[3-D-gluco-side (7) (Ye et a., 2004), (2E, 4E) -N-isobutyl-2, 4-decadienamide (8) (Yasuda et a.,1981) , methyl proto-taccaoside (9) (Idaka et a.,1991) and saxifragifolin B (10) (Waltho et a.,1986). The structure elucidation of the new com-pound is reported.

Results and Discussion

Compound l was obtained as white amor-phous powder. Negative HRESIMS analysis ofthe compound exhibited a quasimolcular ion peakat mz 327.1083 [M-Hl (calcd, 327.1079),corresponding to the molecular formula Ci.,- Hp。Os for l. Its IR spectrum showed absorptionbands for hydroxy groups (3441 cm.l) and aphenyl ring (1631 cm.l, 1611 cm.l and 1515cm.l). In the 13C NMR spectrum of l (Table1), 15 carbon signals including two oxygenatedmethylenes [8c 63. 8 (C-9), 62. 4 (C-6´)l, tenmethines [ 8 c 131. 5 (C-7) , 127. 5 (C-8) , 123. 4(C-6), 117. 0 (C-5), 116. 5 (C-2), 104. 4 (C-11) , 78. 4 ( C-5´) , 77. 6 ( C-3´), 74. 9 ( C-2) ,71. 4 (C-4´)] and three quaternary carbons [ 8 c148. 1 (C-4), 146. 9 (C-3), 130. 8 (C-l)] wereobserved. The lH NMR spectrum of l (Table1) displayed signals for an ABX benzene ring [8H 7. 31 (1H, d, J =1. 6 Hz, H-2), 6. 95 (1H,dd, J =8. 2, 1. 6 Hz, H-6) and 6. 77 (1H, d, ]=8.2 Hz, H-5)l, a trans-allylic moiety [8 H6. 48 (1H, d, J =15. 9 Hz, H-7), 6. 20 (1H,dt, J =15. 9, 6. 0 Hz, H-8) and 4. 18 (2H, dd,J = 6. 0, 1. 1 Hz, H-9)l. In addition, its lHNMR spectrum showed an anomeric proton sig-nal at 8 4. 75 (1H, d, J =7. 1 Hz, H-l), indi-cating the presence of a sugar moiety in l. Acidhydrolysis of l yielded a D-glucose and deter-mined by TLC and its optical rotation ( [ a l3= +50. 3 (c 0. 055, Hp 0》. The coupling con-stant (J =7.1 Hz) of H-l and H-2´ deducedthe glucose to be a [3-anomeric configuration.

In the HMBC spectrum ( Fig. 1 ), H-7showed correlations to C-2 and C-6, and H-8showed to C-l, meanwhile H-2 and H-6 alsoshowed correlations to C-l. These correlationsindicated that the propenol moiety was placed atC-l. The assignments of C-3 and C-4 were as-certained by the HMBC correlation from H-5 toC-l and C-3, H-6 to C-2 and C-4, H-2 to C-4and C-6. The linkage of the [3-D-glucose substit-uent to C-3 was established by the correlationfrom H-l to C-3. Therefore, 1 was elucidatedas caffeyl alcohol-3- O -[3-D-glucopyranoside.

Experimental

General MCl gel CHP 20P (75-150 )um, MitsubishiChemical Corporation, Tokyo), silica gel G (300-100mesh, Qingdao Makall Group Co. , I,td) ? Cis silica gel(10-75 )um, Fuji Silysia Chemical I,td. ) , silica gel H (10-10 )um), and Sephadex I,H-20 (GE Healthcare Bio-Xciences AB) were used for column chromatography, andsilica gel GF.:, ( Qingdao) , for preparative TI.C as pro-coated plates. The TI,C spots were visualized under UVlight and by dipping int0 5% Hz SO, in alcohol, followedby heating. Semipreparative HPI,C was carried out on anAgilent 1200 series pump equipped with a diode array de-tector and a Zorbax SB-Cis column (5. 0 )um, 49. 11 X 250mm). 1D and 2D NMR spectra were obtained on BRUK-ER AM-IOO and DRX-500 spectrometers with TMS as in-ternal standard. MS analyses were performed on a VGAuto Spec-3000 mass spectrometer. Optical rotationswere measured with a HoribasePA-300 polarimeter. UVspectra were determined on a Shimadzu double-beam210Aspectrometer. 1R spectra were measured on a Bio-RadFTS-135 infrared spectrophotometer with KBr disks.

Plant material The corms of R. vivipara were col-lected in October 2008 from I.uxi City, Yunnan Province,People´s Republic of China and identified by Dr. HuGuang-Wan (Kunming Institute of Botany, Chinese A-cademy of Sciences). A voucher specimen (No. I,X005)was deposited at the I,aboratory of Ethnobotany, Kun-ming Institute of Botany. Extraction and isolation The air-dried, powderedcorms of R. vivipara (1. 0 kg) was exhaustively extractedwith 95% EtOH (3 times) and then with MeOH (twice)under reflux. The crude extract (68 g) was suspended inHz and then partitioned successively with EtOAe and n-BuOH to obtain two fractions: EtOAe (A, 13 g) , and n-BuOH (B, 6 g). Fr. B was subjected to column chroma-tography over MCl gel CHP 20P with MeOH-Hz O (agradient elution of increasing concentration) and gainedfive fractions (Bi-Bs). Each fraction was further purifiedby repeated column chromatography (Cis silica gel, Seph-adex I,H-20, silica gel) and then semipreparative HPI,Cto obtain compounds. From Fr. B, , compounds l (11. 2mg) and 2 (6.1 mg) were obtained. Fr. Bz gave com-pound 6 (11. 3 mg). Fr. B, afforded compounds 9 (30. 7mg) and 10 (15. 2 mg). Fr. A was subjected to reversed-phase column chromatography over Cis silica gel elutingwith a gradient of increasing MeOH in Hz O (5%-95%)and obtained five fractions ( Ai-As ). Subsequently, Fr.A. and A, were chromatographed on Sephadex I.H-20 col-umn. repeated silica gel column and then followed bysemipreparative HPI,C, to give compounds 3 ( 7. 5 mg) ,4 (11. 6 mg), 5 (5. 6 mg), and 7 (11. 0 mg) from Fr. Azand 8 (3. 5 mg) from Fr. Ai.

Acid hydrolysis of l: A solution of l (11. 0 mg) in 2mol.l.´l HCI (2 ml) was heated at 900C for l h. After e-vaporating the acidic solution, the reaction mixture wassubjected to column chromatography over silica gel(CHCI: -MeOH-Hz O, 3 : 1 : 0. 05) to yield a D-glucose(1.1 mg), which was detected by TI,C comparing withthe authentic sample and its optical rotation, [ a l~)´ s +50. 3 ( c 0. 055, Hz.

Caffeyl alcohol-3- O - p-D-glucopyranoside ( 1) : Whiteamorphous powder; [ a- -35. 2 ( c 0. 125, MeOH) ; UV(MeOH) 1 W.H (log ~ ) 263 (3. 51) nm; 1R u Kl,´:CITI´l :3111? 1631, 1610, 1515, 1283 ? 1071 ; 1H and isC NMR(see Table l); ESIMS mz 363 [M +CIl´, 327 [M -Hl- ; HRESIMS mz 327.1083 [M-Hl- (calcd for CisHii,Os , 327. 1079).

Caffeyl alcohol ( 3): White amorphous powder(MeOH); 1H NMR (CD3 0D, 100 MHz) 8H: 6.86(1H, d , J =1. 7 Hz, H-2) ? 6. 68 (1H, d , J = 8.1Hz, H-5), 6. 71 (1H, dd , J = 8. 1, 1. 7 Hz, H-6),6.12 (1H, d , J =15. 8 Hz, H-7), 6.10 (1H, dt , J=15. 8, 6. 0 Hz, H-8), 11. 16 (2H, dd , J = 6. 0, 1. 3Hz, H-9); ESIMS mz 165 [M-Hl´. This compoundwas determined according to its MS spectrum and bycomparing its lH NMR data with compounds l and 4. lts1H NMR data were reported for the first time.Acknowledgment: We thank Mr. Zhang Jia-Xian, in LuxiCity of Yunnan Province, for his help to collect the plantmaterial.

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