Ouyang Ming'an Wang Hanqing Yang Chongren 欧阳明安，华侨大学化学系(泉州 362011) 中草药 1999 0 30 12
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Ouyang Ming'an
( Department ofChemistry, Huaqiao University, Quanzhou, Fujian 362011 )
Yang Chongren
( Kunming Institute ofBotany, Chinese Academy of Sciences, Kunming )
Wang Hanqing
( Lanzhou Institute ofChemical Physics, Chinese Academy of Sciences, Lanzhou ) Abstract Six new oleanane-type saponins,arilloside A-F ( Ⅰ～Ⅵ ), along with a known saponin, polygalasaponin ⅩⅩⅩⅤ ( Ⅶ ), were isolated from the root of Polygala arillataBuch.-Ham.. The structures of these new compounds were elucidated as 3-O- β -D-glucopyranosyl presenegenin28-O- β -D-xylopyranosyl(1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3, 4-di-O-acetyl)- β -D-fucopyranoside( Ⅰ ); 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)- β -D-fucopyranoside( Ⅱ ); 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3,4-di-O-acetyl)- β -D-fucopyranoside( Ⅲ ); 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- [β -D-galactopyranosyl (1 → 4) ] - β -D- β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)- β -D-fucopyranoside( Ⅳ ); 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- [β -D-galactopyranosyl (1 → 4) ] - β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3-O-acetyl)- β -D-fucopyranoside( Ⅴ ) and 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- [β -D-galactopyranosyl (1 → 4) ] - β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3,4-di-O-acetyl)- β -D-fucopyranoside( Ⅵ ) on the basis of spectroscopic and chemical methods.
Key words Polygala arillata Buch.-Ham. Polygalaceae triterpenoid presenegenin oleananetype saponin 摘 要 中药黄花远志Polygala arillata Buch.-Ham.远志科远志属植物，为落叶灌木或小乔木，分布于西南、华东、陕西、湖北等地。其根具有祛风除湿，补虚消肿，调经活血等功效。我们对采自云南省文山县黄花远志的皂苷成分进行了研究，从甲醇提取物中分得7个单体三萜皂苷，经波谱和文献分析确定了它们的结构，其中有6个新三萜皂苷并命名为arillosideA～F。
关键词 黄花远志 三萜皂苷 arilloside A～F Introduction Polygalaarillata Buch.-Ham.is a Chinese medicinal plant, the root of which was used as a tonic,anticoagulant or for the treatment of hepatitis 〔 1 ， 2 〕 . Six new triterpenoid saponins christened as arilloside A ～ F( Ⅰ～Ⅵ )and one known saponin, polygalasaponin ⅩⅩⅩⅤ ( Ⅶ ) were isolated from its root. The last of which, Ⅶ has been previously isolatedfrom P.fallax Hemsl. 〔 3 〕 . Inthis paper, we wish to present the structure elucidation of arilloside A ～ F( Ⅰ～Ⅵ ). Results and Discussion A crudesaponin fraction of the metha-nol extract of the root of P.arillata Buch.-Ham.wassubjected to pass through a porous polymer gel (D101 ) column and the adsorbedmaterials were eluted successively with 30% aq. MeOH and MeOH. The methanol eluate wasrepeatedly chromatographed on silica gel RP-8 to give saponins ( Ⅰ～Ⅶ ). On alkaline hydrolysis, saponins Ⅰ～Ⅶ afforded tenuifolin ( Ⅰ a ) 〔 4 〕 ， the 3-O- β -D-glucopyranoside of presenegenin. Therefore, it wasjustifiable to claim that these saponins Ⅰ～Ⅶ (Fig.1) were analogs of presenegenin glycosides. Fig 1 Chemical structure of Ⅰ～Ⅶ , Ia and HMBC Correlation of Arilloside E ( Ⅴ ) ArillosideA ( Ⅰ ) showed a [ M-H ]- ion peak at m/z 1 187 in the negative FAB-MS and combinedwith DEPT spectrum to give the molecular formula C57 H72 O27 .On acid hydrolysis, Ⅰ affordedglucose, fucose, rhamnose and xylose as its sugar moieties. On alkaline hydrolysis, Ⅰ gave a presenegenin 3-O- β -D-glucopyranoside, tenuif-olin.The 1 HNMR spectrum exhibited the presence of five single methyl signals ( δ 0.76, 0.88, 1.05, 1.51 and 1.89),a tri-substituted olefinic proton [δ 5.71 (t-like) ] in the aglycone moiety and four anomeric protons [δ 5.00 (d, J ＝ 6.8 Hz), 5.05 (d, J ＝ 7.1 Hz), 5.68 (br s) and 6.13 (d,J ＝ 8.0 Hz) ] . The 13 CNMR spectrumsuggested the presence of a carboxyl signal ( δ 182.7), three ester carbonyl signals ( δ 170.2, 170.9 and 176.4) and fouranomeric carbon signals ( δ 94.3, 102.0, 105.2 and 107.2). By comparison of the carbon NMR data of compound Ⅰ with that of polygalasaponin ⅩⅩⅧ〔 5 〕 , compound Ⅰ was found to contain two acetylgroups than polygalasaponin ⅩⅩⅧ . The ester carbonyl signals at δ 170.2 and 170.9 attaching to the positions C-3 and C-4 offucose unit showed the HMBC correlation between the ester carbonyl signal ( δ 170.2) and H-3 ( δ 5.55) of fucose, and the estercarbonyl signal ( δ 170.9)and H-4 ( δ 5.55) of fucose. The proton signals of H-3, H-4 were overlapped and assigned by its TOCSY and HMQCspectra. Thus, the structure of arilloside A was elucidated as 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3,4-di-O-acetyl)- β -D-fucopyranoside.
Arilloside B ( Ⅱ ) showed a [ M-H ] - ion peak at m/z 1235 in the negative FAB-MS,suggesting the molecular formula C58 H76 O29 , combined withthe DEPT spectrum. Compound Ⅱ afforded glucose, fucose, rhamnose, xylose as the sugar components on acidhydrolysis. In the NMR spectra, Ⅱ showed five anomeric proton and carbon signals [δ c 94.9/ δ H 6.00(d, J ＝ 7.9 Hz); δ c 101.1/ δ H 6.45 (br s); δ c 105.3/ δ H 5.01 (d, J ＝ 7.0 Hz); δ c 105.9/ δ H 5.12 (d, J ＝ 6.5 Hz) and δ c 106.8/ δ H 5.02 (d, J ＝ 7.2 Hz) ] . The sugar proton and carbon signals in the NMR spectrumwere assigned by HMQC, TOCSY, 1 H-1 H COSY and HMBC spectra (see Table1). In the HMBC spectrum, long range coupling were observed between the anomeric protonsignal at δ 5.01 (H-1of Glc) and the carbon signal at δ 86.4 due to C-3 of the aglycone; between the anomericproton signal at δ 6.00(H-1 of Fuc) and the carbon signal at δ 176.7 due to C-28 of the aglycone; between the anomericproton signal at δ 6.45(H-1 of Rha) and the carbon signal at δ 73.5 due to C-2 of the fucose; between the anomeric protonsignal at δ 5.02 [ H-1 of Xy1 (inn.) ] and the carbon signal at δ 85.4 due to C-4 of the rhamnose;between the anomeric proton signal at δ 5.12 [ H-1 of Xyl (ter.) ] and the carbon signal at δ 87.8 due to C-3 of the xylose (inn.). From theseevidences, the structure of arilloside B was elucidated as 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)- β -D-fucopyranoside.
Arilloside C ( Ⅲ ) showed a [ M-H ] - ion peak at m/z 1319 in the negative FAB-MS,combined with the DEPT spectrum, its molecular formula was deduced to be C62 H80 O31 .The 1 HNMR spectrum suggesting the presence of two acetyl methyl proton signals( δ 2.00 and 2.02) andfive anomeric proton signal [δ 5.05 (d, J ＝ 7.0 Hz); 5.10 (d, J ＝ 7.1 Hz); 5.18 (d, J ＝ 6.7 Hz); 5.69 (br s) and δ 6.17 (d, J ＝ 7.9 Hz) ] . On acid hydrolysis, compound Ⅲ afforded glucose, fucose, rhamnose and xylose. Thepositions of the acetyl groups were that of C-3, C-4 of the fucose moiety by comparing itsNMR data with those of compounds Ⅰ and Ⅱ . The data of the HMBC spectrum enable us to identify thestructure of Ⅲ as3-O- β -D-glucopyranosylpresenegenin 28-O- β -D-xylopranosyl(1 → 3)- β -D-xylopyrano-syl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3, 4-di-O-acetyl)- β -D-fucopyranoside.
Arilloside D ( Ⅳ ) showed six anomeric protonsignals in the 1 HNMR spectrum at δ 4.85, (d, J ＝ 7.0 Hz), 4.91 (d, J ＝ 7.0 Hz), 4.95 (d, J ＝ 6.7 Hz), 5.16 (d, J ＝ 7.9 Hz) and 6.39 (br s). By 13 CNMR spectrumcombined with HMQC spectrum, the carbon signal positions and chemical shifts of the sixanomeric carbon signals were assigned at δ 103.0, 106.2, 105.0, 105.4, 94.7 and 100.9, respectively.On acid hydrolysis, compound Ⅳ afforded glucose, fucose, rhamnose, xylose and galactose as sugar moieties. Itsmolecular ior was revealed m/z 1 397 [ M-H ]- in the negative FAB-MS and main fragment ions 1 265, 1355, 941 and 679. Sugar linkages were decided by the HMBC spectrum. The HMBC correlationwere observed between the following carbons and protons in the sugar moiety of Ⅳ : C-3 and H-1 of Glc; C-28 andH-1 of Fuc; C-2 of Fuc and H-1 of Rha; C-4 of Rha and H-1 of Xyl (inn.); C-3 of xyl (inn.)and H-1 of Xyl (ter.); C-4 of Xyl (inn.) and H-1 of Gal. Based on these evidences, thestructure of arilloside D was elucidated as 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- [β -D-galactopyranosyl (1 → 4) ] - β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)- β -D-fucopyranoside.
Arilloside E ( Ⅴ ) afforded glucose, fucose,rhamnose, xylose and galactose on acid hydrolysis. Its molecular formula is C66 H88 O35 from the negative FAB-MS and DEPT spectrum. The 1 H, 13 CNMR spectra of Ⅴ exhibited an acetyl signal at δ H 1.92, δ c 171.0 and six anomeric protonand carbon signals at δ 4.85 (d, J ＝ 6.1Hz), 4.93 (d, J ＝ 6.3Hz), 4.98 (d, J ＝ 6.7Hz), 5.14 (d, J ＝ 6.4Hz), 6.01 (d, J ＝ 7.9Hz) and 6.32 (br s); 103.0, 106.2, 105.1, 105.2, 94.5 and 101.5, respectively. The protonand carbon chemical shifts of Ⅴ were similar to those of Ⅳ except for the signals due to fucose moiety. The signal δ 3.93 (H-4 of Fuc) in Ⅳ was changed to δ 5.48 in Ⅴ , and HMBC correlation was observed between the carbonylcarbon δ 171.0 and H-4( δ 5.48) of fucosemoiety. Therefore, arilloside E was elucidated as 3-O- β -D-glucopyranosyl presenegenin 28-O- β -D-xylopyranosyl (1 → 3)- [β -D-galactopyranosyl (1 → 4) ] - β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3-O-acetyl)- β -D-fucopyranoside.
Arilloside F ( Ⅵ ) showed its [ M-H ] - ion peak at m/z 1481 in the negative FAB-MS.The 1 H,13 CNMR spectra exhibited two acetyl signals δ H 2.01, 202/ δ c 170.2, 170.9 and six anomericproton and carbon signals at δ 4.90 (d, J ＝ 7.0Hz); 4.97 (d, J ＝ 6.4Hz); 5.00 (d, J ＝ 7.07Hz), 5.27 (d, J ＝ 7.1Hz), 5.69 (br s) and 6.14 (d, J ＝ 7.8 Hz); 103.3, 106.1, 105.3, 105.5, 102.1 and 94.3,respectively. On acid hydrolysis, compound Ⅵ afforded glucose, fucose, rhamnose, xylose and galactoseas sugar moieties. The positions of the acetyl groups were at C-3, C-4 of fucose moiety bycomparison of the NMR data with those of compounds Ⅰ , Ⅲ , Ⅴ (see Table 1.). The HMBC correlation of Ⅵ enable us to identify thestructure of Ⅵ as3-O- β -D-glucopyranosylpresenegenin 28-O- β -D-xylopyranosyl(1 → 3)- [β -D-galactopyranosyl (1 → 4) ] - β -D-xylopyranosyl (1 → 4)- α -L-rhamnopyranosyl (1 → 2)-(3,4-di-O-acetyl)- β -D-fucopyranoside. Experimental Generalprocedure: 1 H,13 CNMR spectra were obtained with Bruker AM-400,DRX-500 spectrometer; FAB mass spectrum were taken on VG Autospec 3000 systemspectrometer; chromatographic materials used was RP-8(40 ～ 60 μ m, Merck), silica gel (160 ～ 200 mesh and 10 ～ 40 μ m); spots were detected by spraying with 5% H2 SO4 followed by heating.
Extraction andisolation ： Polygalaarillata Buch.-Ham. was collected in Wenshan, Yunnan province, China in July 1996 andvoucher specimen was deposited in the Herbarium of Kunming Institute of Botany, ChineseAcademy of Sciences. The dried root (2 kg) was extracted with 70% MeOH. The extract (150g) was passed through a porous polymer gel (D101 ) column. After the contents ofthe adsorbed materials were eluted with MeOH. The MeOH eluate (45 g) was chromatographedon silica gel with CHCl3 -MeOH-H2 O (7 ∶ 3 ∶ 0.5) to give ten fractions. Fr.V ～ Fr.X were repeatedly by chromatographed RP-8 gel column(eluting with MeOH-H2 O/5 ∶ 5 ～ 7 ∶ 3) ， and finally purified on silica gel (10 ～ 40 m) with CHCl3 -MeOH-H2 O(8 ∶ 2 ∶ 0.5 ～ 7 ∶ 3 ∶ 0.5) to give: Ⅰ (70 mg), Ⅱ (60 mg), Ⅲ (43 mg), Ⅳ (205 mg), Ⅴ (170 mg), Ⅵ (200 mg) and Ⅶ (87 mg).
Arilloside A,C57 H72 O27 ,1 HNMR: δ 0.76 (3 H, s, H-29), 0.88 (3 H,s, H-30), 1.05 (3 H, s, H-26), 1.51 (3 H, s, H-25), 1.89 (3 H, s, H-24), 3.79 (1 H, H-27),4.05 (1 H, H-27), 4.70 (H-2), 4.59 (H-3), 5.71 (H-12), 2.01 (3 H, Ac), 2.02 (3 H, Ac),5.00 (1 H, d, J ＝ 6.8Hz, H-1 of Glc), 5.05 (1 H, d, J ＝ 7.1 Hz, H-1 of Xyl), 5.68 (1 H, br s, H-1 of Rha), 1.70 (3H, d, J ＝ 4.5 Hz, H-6of Rha), 6.13 (1 H, d, J ＝ 8.0 Hz, H-1 of Fuc), 1.16 (3 H, d, J ＝ 4.7 Hz, H-6 of Fuc); FAB-MS m/z:1 187 [ M-H ] - , 1 025 [ M-H-162 ] - , 893 [ M-H-162-132 ] - , 747 [ M-H-162-132-146 ] - , 679 [ M-H-132-146×2 ] - , 13 CNMR data see Table 1.
Arilloside B, C58 H76 O29 ,1 HNMR: δ 0.76 (3 H, s, H-29),0.85 (3 H, s, H-30), 1.10 (3 H, s, H-26), 1.52 (3 H, s, H-25), 1.90 (3 H, s, H-24), 3.80(1 H, H-27), 4.10 (1 H, H-27), 4.63 (H-2), 4.51 (H-3), 5.79 (H-12), 5.01 (1 H, d, J ＝ 7.2 Hz, H-1 of Glc), 5.02 (1 H,d, J ＝ 7.1 Hz, H-1 ofXyl (inn.) ] , 5.12 [ 1 H, d,J ＝ 6.2 Hz, H-1 of Xyl (ter.) ] , 6.00 (1 H, d, J ＝ 7.9 Hz, H-1 of Fuc), 1.47 (3 H, d, J ＝ 4.6 Hz, H-6 of Fuc), 6.45 (1 H, br s, H-1 of Rha), 1.63 (3H, d, J ＝ 4.4 Hz, H-6of Rha); FAB-MS m/z:1 235 [ M-H ] - ,1 103 [ M-H-132 ] - , 1 073 [ M-H-162 ] - , 971 [ M-H-132 × 2 ] - , 679 [ M-H-132 × 2-146 × 2 ] - , 13 CNMR data see Table 1. Table 1 13 CNMR chemical shifts of compounds Ⅰ～Ⅶ (pyridine-d5 ) | Algycone | Ⅰ | Ⅱ | Ⅲ | Ⅳ | Ⅴ | Ⅵ | Ⅶ | | 1 | 44.4 | 44.1 | 44.3 | 44.2 | 44.1 | 44.2 | 44.3 | | 2 | 70.5 | 70.4 | 70.3 | 70.3 | 70.4 | 70.2 | 70.3 | | 3 | 86.5 | 86.4 | 86.1 | 86.6 | 86.9 | 86.7 | 87.2 | | 4 | 53.2 | 52.8 | 52.9 | 53.0 | 53.1 | 53.1 | 53.4 | | 5 | 52.5 | 52.2 | 52.5 | 52.3 | 52.2 | 52.2 | 52.5 | | 6 | 21.5 | 21.4 | 21.4 | 21.4 | 21.4 | 21.5 | 21.2 | | 7 | 33.9 | 33.6 | 33.6 | 32.2 | 32.3 | 32.3 | 33.6 | | 8 | 41.2 | 41.3 | 41.2 | 41.0 | 41.0 | 41.2 | 41.1 | | 9 | 49.4 | 49.2 | 49.4 | 49.2 | 49.2 | 49.2 | 49.3 | | 10 | 37.1 | 37.1 | 37.1 | 36.8 | 36.9 | 37.1 | 37.1 | | 11 | 23.7 | 23.6 | 23.0 | 23.3 | 23.3 | 23.4 | 23.4 | | 12 | 128.0 | 127.9 | 127.9 | 127.8 | 127.9 | 128.0 | 128.2 | | 13 | 139.1 | 139.1 | 139.0 | 138.9 | 138.8 | 139.0 | 138.8 | | 14 | 47.2 | 47.1 | 47.1 | 46.9 | 47.0 | 47.2 | 47.2 | | 15 | 24.8 | 24.3 | 24.6 | 24.5 | 24.4 | 24.4 | 24.6 | | 16 | 24.6 | 24.2 | 24.0 | 24.3 | 24.2 | 24.2 | 24.2 | | 17 | 48.2 | 48.2 | 48.1 | 48.1 | 48.1 | 48.1 | 48.2 | | 18 | 41.7 | 42.1 | 42.0 | 41.9 | 42.0 | 41.9 | 41.8 | | 19 | 45.5 | 45.2 | 45.5 | 45.2 | 45.2 | 45.1 | 45.9 | | 20 | 30.6 | 30.9 | 30.8 | 30.6 | 30.6 | 30.6 | 30.7 | | 21 | 34.0 | 33.8 | 33.9 | 33.8 | 33.8 | 33.7 | 34.0 | | 22 | 32.5 | 32.2 | 32.3 | 32.2 | 32.1 | 32.2 | 32.5 | | 23 | 182.7 | 182.1 | 182.0 | 183.0 | 182.9 | 182.4 | 182.5 | | 24 | 14.6 | 14.4 | 14.3 | 14.2 | 14.4 | 14.4 | 14.9 | | 25 | 17.6 | 17.6 | 17.5 | 17.4 | 17.4 | 17.6 | 17.6 | | 26 | 18.9 | 18.9 | 18.9 | 19.0 | 18.7 | 18.9 | 18.9 | | 27 | 64.5 | 64.2 | 64.5 | 64.2 | 64.1 | 64.2 | 64.3 | | 28 | 176.4 | 176.7 | 176.4 | 176.5 | 176.5 | 176.5 | 176.5 | | 29 | 33.2 | 33.2 | 33.1 | 32.9 | 32.9 | 33.2 | 33.1 | | 30 | 24.0 | 24.0 | 24.0 | 23.7 | 23.7 | 24.0 | 23.8 | | C-3-Glc | | | | | | | | | 1 | 105.2 | 105.3 | 105.2 | 105.0 | 105.1 | 105.3 | 105.2 | | 2 | 75.3 | 75.4 | 75.3 | 75.1 | 75.1 | 75.2 | 75.3 | | 3 | 78.0 | 78.2 | 78.3 | 77.8 | 77.9 | 78.2 | 77.6 | | 4 | 71.6 | 71.6 | 71.7 | 71.3 | 71.3 | 71.4 | 71.6 | | 5 | 78.2 | 78.3 | 78.3 | 77.9 | 78.4 | 78.2 | 77.8 | | 6 | 62.7 | 62.7 | 62.8 | 62.4 | 62.4 | 62.7 | 62.5 | | C-28-Fuc | | | | | | | | | 1 | 94.3 | 94.9 | 94.3 | 94.7 | 94.5 | 94.3 | 94.1 | | 2 | 72.7 | 73.5 | 73.0 | 73.2 | 72.4 | 72.4 | 72.5 | | 3 | 74.9 | 76.9 | 74.5 | 76.7 | 74.3 | 74.8 | 74.9 | | 4 | 70.8 | 73.3 | 71.4 | 73.1 | 74.7 | 71.1 | 71.3 | | 5 | 70.1 | 72.5 | 70.1 | 72.3 | 70.5 | 70.4 | 70.1 | | 6 | 16.2 | 17.6 | 16.1 | 16.8 | 16.4 | 16.2 | 16.3 | | Ac at C-3 | 20.5 | | 20.4 | | | 20.5 | 20.3 | | 170.2 | | 170.1 | | | 170.2 | 170.2 | | Ac at C-4 | 20.8 | | 20.6 | | 20.6 | 20.7 | 20.7 | | 170.9 | | 170.8 | | 171.0 | 170.9 | 170.8 | | Rha | | | | | | | | | 1 | 102.0 | 101.1 | 102.0 | 100.9 | 101.5 | 102.1 | 102.2 | | 2 | 71.5 | 71.8 | 72.4 | 71.6 | 71.6 | 71.6 | 71.5 | | 3 | 71.6 | 72.5 | 72.9 | 72.4 | 71.3 | 71.2 | 71.8 | | 4 | 84.5 | 85.4 | 84.4 | 85.2 | 85.1 | 84.3 | 84.6 | | 5 | 69.0 | 68.0 | 69.0 | 67.7 | 68.0 | 68.9 | 68.9 | | 6 | 18.6 | 18.5 | 18.6 | 18.2 | 18.4 | 18.7 | 18.7 | | Xyl | | inn. | inn. | inn. | inn. | inn. | | 1 | 107.2 | 106.8 | 106.6 | 106.2 | 106.2 | 106.1 | 106.7 | | 2 | 76.0 | 75.4 | 76.2 | 75.8 | 75.8 | 75.8 | 75.3 | | 3 | 78.6 | 87.8 | 87.3 | 84.1 | 84.6 | 85.3 | 76.7 | | 4 | 77.1 | 70.7 | 71.3 | 71.1 | 70.9 | 71.4 | 77.5 | | 5 | 67.4 | 67.3 | 67.6 | 65.4 | 66.1 | 66.2 | 64.9 | | Gal | | | | | | | | | 1 | | | | 103.0 | 103.0 | 103.0 | 103.8 | | 2 | | | | 70.0 | 70.0 | 71.4 | 71.9 | | 3 | | | | 74.4 | 74.4 | 74.8 | 75.0 | | 4 | | | | 69.9 | 69.7 | 69.9 | 70.2 | | 5 | | | | 77.3 | 77.6 | 77.5 | 77.1 | | 6 | | | | 62.1 | 62.1 | 62.3 | 62.1 | | Xyl | | ter. | ter. | ter. | ter. | ter. | | | 1 | | 105.9 | 105.8 | 105.4 | 105.2 | 105.5 | | | 2 | | 75.3 | 74.9 | 74.8 | 74.8 | 74.8 | | | 3 | | 78.0 | 78.1 | 77.1 | 77.2 | 77.6 | | | 4 | | 68.9 | 70.3 | 69.9 | 70.0 | 70.1 | | | 5 | | 67.0 | 67.0 | 66.7 | 66.7 | 67.0 | | Arilloside C, C62 H80 O31 ,1 HNMR: δ 0.77(3H, s, H-29), 0.90 (3 H, s, H-30), 1.09 (3 H, s, H-26), 1.61 (3 H, s, H-25), 1.95 (3 H, s,H-24), 3.76 (1 H, H-27), 4.00 (1 H, H-27), 4.70 (H-2), 3.59 (H-3), 5.78 (H-12), 2.01 (3 H,Ac), 2.02 (3 H, Ac), 5.05 [ 1 H, d, J ＝ 7.0Hz, H-1 of Glc ] , 5.10 [ 1 H, d, J ＝ 7.1 Hz, H-1 of Xyl (inn.) ] , 5.18 [ 1 H, d, J ＝ 6.7 Hz, H-1 of Xyl (ter.) ] , 5.69 (1 H, br s, H-1 of Rha), 1.70 (3 H, d, J ＝ 4.6 Hz, H-6 of Rha), 6.17 (1 H,d, J ＝ 7.9 Hz, H-1 of Fuc), 1.19 (3 H, d, J ＝ 4.5Hz, H-6 of Fuc); FAB-MS m/z: 1 319 [ M-H ] - , 1 187 [ M-H-132 ] - , 1 025 [ M-H-132-162 ] - , 893 [ M-H-162-132 × 2 ] - .
Arilloside D, C64 H86 O34 ,1 HNMR: δ 0.76(3H, s, H-29), 0.83 (3 H, s, H-30), 1.07 (3 H, s, H-26), 1.48 (3 H, s, H-25), 1.86 (3 H, s,H-24), 3.77 (1 H, H-27), 4.08 (1 H, H-27), 4.62 (H-2), 4.47 (H-3), 5.48 (H-12), 4.85 (1 H,d, J ＝ 7.0 Hz, H-1 ofGal), 4.91 [ 1 H, d, J ＝ 7.0 Hz, H-1 of Xyl(inn.) ] , 4.95 (1 H, d, J ＝ 6.7 Hz, H-1 of Glc), 5.16 [ 1 H, d, J ＝ 6.5 Hz, H-1 of Xyl (ter.) ] , 5.97 [ 1 H, d, J ＝ 7.9 Hz, H-1 of Fuc ] , 1.44 (3 H, d, J ＝ 4.5 Hz, H-6 of Fuc), 6.39 (1 H, br s, H-1 of Rha), 1.56 (3H, d, J ＝ 4.3 Hz, H-6of Rha), FAB-MS m/z: 1 397 [ M-H ] - ,1 266 [ M-H-132 ] - , 1 235 [ M-H-162 ] - , 941 [ M-H-162 × 2-132 ] - , 679 [ M-H-162-132 × 2-146 × 2 ] - , 13 CNMR data see Table 1.
Arilloside E, C66 H88 O35 ,1 HNMR: δ 0.75(3H, s, H-29), 0.82 (3 H, s, H-30), 1.06 (3 H, s, H-26), 1.47 (3 H, s, H-25), 1.85 (3 H, s,H-24), 3.76 (1 H, H-27), 4.06 (1 H, H-27), 4.60 (H-2), 4.48 (H-3), 5.61 (H-12), 1.92 (3 H,s, Ac), 4.85 (1 H, d, J ＝ 6.1 Hz, H-1 of Gal), 4.93 [ 1 H, d, J ＝ 6.3 Hz, H-1 of Xyl (inn.) ] , 4.98 (1 H, d, J ＝ 6.7 Hz, H-1 of Glc), 5.14 [ 1 H, d, J ＝ 6.4 Hz, H-1 of Xyl (ter.) ] , 6.01 [ 1 H, d, J ＝ 7.9 Hz, H-1 of Fuc ] , 1.20 (3 H, d, J ＝ 5.7 Hz, H-6 of Fuc), 6.32 (1 H, br s, H-1 of Rha), 1.68 (3H, d, J ＝ 5.0 Hz, H-6of Rha), FAB-MS m/z: 1 439 [ M-H ] - ,1 307 [ M-H-132 ] - ， 1 277 [ M-H-162 ] - , 1 145 [ M-H-162-132 ] - ， 679 [ M-H-162-132×2-146×2-42 ] - , 13 CNMR data see Table 1.
Arilloside F, C68 H89 O36 ,1 HNMR: δ 0.78(3H, s, H-29), 0.89 (3 H, s, H-30), 1.08 (3 H, s, H-26), 1.54 (3 H, s, H-25), 1.92 (3 H, s,H-24), 3.80 (1 H, H-27), 4.06 (1 H, H-27), 4.50 (H-2), 4.55 (H-3), 5.79 (H-12), 2.01 (3 H,s, Ac), 2.02 (3 H, s, Ac), 4.90 (1 H, d, J ＝ 7.0 Hz, H-1 of Gal), 4.97 [ 1 H, d, J ＝ 6.4 Hz, H-1 of Xyl (inn.) ] , 5.00 [ 1 H, d, J ＝ 7.0 Hz, H-1 of Glc ] , 5.27 [ 1 H, d, J ＝ 7.1 Hz, H-1 of Xyl (ter.) ] , 6.14 [ 1 H, d, J ＝ 7.8 Hz, H-1 of Fuc ] , 1.18 (3 H, d, J ＝ 5.5 Hz, H-6 of Fuc), 5.69 (1 H, br s, H-1 of Rha), 1.64 (3H, d, J ＝ 4.5 Hz, H-6of Rha); FAB-MS m/z: 1 481 [ M-H ] - ,1 349 [ M-H-132 ] - , 1 319 [ M-H-162 ] - , 1 187 [ M-H-162-132 ] - ， 1 025 [ M-H-162×2-132 ] - , 679 [ M-H-162-132×2-146×2-42×2 ] - ， 13 CNMR data see Table 1.
Alkalinehydrolysis of Ⅰ～Ⅵ .Eachcompound (3 mg) except for compound Ⅳ . As an example, Ⅳ (50 mg) was treated with 5% NaOH (10 mL) for 6 h at 50 ℃ and the reaction mixture wasadded to 0.5 mol/L HCl to pH ＝ 7.0 . The hydrolysate was passed through porous MCI gel column and washed withwater, the adsorbed materials was eluted with aq. MeOH. The methanol eluate (20 mg)obtained, proved to be tenuifolin, with NMR data as follows: δ c:180.6 (C-23), 180.2 (C-28), 139.6 (C-13), 127.7 (C-12),86.0 (C-3), 70.2 (C-2), 64.6 (C-27), 52.9 (C-4), 52.5 (C-5), 49.2 (C-9), 48.1 (C-17), 46.5(C-14), 45.6 (C-19), 44.2 (C-1), 41.6 (C-18), 40.9 (C-8), 37.1 (C-10), 34.2 (C-21), 33.5(C-7), 33.2 (C-29), 33.1 (C-22), 31.0 (C-30), 24.6 (C-15), 24.1 (C-16), 24.0 (C-30), 23.8(C-11),
21.3 (C-6), 18.8 (C-26), 17.3 (C-25), 14.2 (C-24), Glu δ c:105.4 (C-1), 75.3 (C-2), 78.4 (C-3), 71.7 (C-4), 78.4(C-5), 62.5 (C-6); 1 HNMR: δ 0.85 (3 H, s, H-29), 0.99 (3 H, s, H-30), 1.04 (3 H, s,H-26), 1.51 (3 H, s, H-25), 1.97 (3 H, s, H-24), 3.36 (1 H, dd, J ＝ 4, 14 Hz, H-18), 4.61 (1 H, d, J ＝ 2.9 Hz, H-3), 4.71 (1 H, m, H-2), 4.48 [ H-3), 5.85 (1 H, t-like, H-12),5.08 (1 H d, J ＝ 7.8Hz, H-1 of Glu); FAB-MS m/z: 679 [ M-H ] - , 517 [ M-H ] - . Compounds Ⅰ～Ⅲ and Ⅴ～Ⅵ gave the same product, tenuifolin on alkaline hydrolysisas proved by comparing with TLC.
Acid hydrolysisof Ⅰ～Ⅵ . Eachsaponin (3 mg) in 1 mL MeOH was refluxed in 10 mL 4 mol/L HCl for 10 h. The hydrolysatewas extracted with AcOEt. The aqueous layer was then adjusted to pH 7 with NaHCO3 .After evaporating to dryness, the mixture sugars were extracted with pyridine from theresidue and analyzed by TLC using the authentic sugar (D-glucose, D-fucose, D-xylose andD-galactose) on silica gel with CHCl3 -MeOH-H2 O(7 ∶ 3 ∶ 0.5); sugar detected with 4% α -naphthol-EtOH-5% H2 SO4 .
The anomericconfigurations of glucose, fucose, xylose and galactose in these saponins were alldetermined to be β andthat of rhamnose was determined to be α (JH1-H2 < 2 Hz) from the JH1-H2 value of the anomericproton signals.
Acknowledgments-theauthors are grat-eful to Chinese Postdoctoral Fund for financial support. Reference 1 Jiang Su Medicinal College. Dictionary of Chinese CrudeDrug. Shanghai:Shanghai Scientific Technologic Publisher, 1977:2071
2 Mao S L, et al.Acta Pharmaceutica Sinica, 1996, 31:118
3 Zhang D M, et al.Chem Pharm Bull, 1996, 44:2092
4 Yoshikawa M, et al.Chem Pharm Bull, 1995, 43:2115
5 Zhang D M, et al.Chem Pharm Bull, 1996, 44:810 Recieved in 1999-01-29
(Ouyang Ming'an Wang Hanqing Yang Chongren)
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