CN1081192C - 一种鞘类脂糖苷化合物及其提取方法 - Google Patents
一种鞘类脂糖苷化合物及其提取方法 Download PDFInfo
- Publication number
- CN1081192C CN1081192C CN99116047A CN99116047A CN1081192C CN 1081192 C CN1081192 C CN 1081192C CN 99116047 A CN99116047 A CN 99116047A CN 99116047 A CN99116047 A CN 99116047A CN 1081192 C CN1081192 C CN 1081192C
- Authority
- CN
- China
- Prior art keywords
- compound
- extracted
- column chromatography
- sphingolipid
- south china
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 Sphingolipid glycoside compound Chemical class 0.000 title claims abstract description 10
- 229930182470 glycoside Natural products 0.000 title claims abstract description 8
- 238000000605 extraction Methods 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004440 column chromatography Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 241000796400 Iotrochota Species 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000741 silica gel Substances 0.000 abstract description 4
- 229910002027 silica gel Inorganic materials 0.000 abstract description 4
- 229930014626 natural product Natural products 0.000 abstract description 3
- 229930184667 Iotroridoside Natural products 0.000 abstract description 2
- 229940038384 octadecane Drugs 0.000 abstract description 2
- 210000004881 tumor cell Anatomy 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 2
- ASFAFOSQXBRFMV-LJQANCHMSA-N 3-n-(2-benzyl-1,3-dihydroxypropan-2-yl)-1-n-[(1r)-1-(4-fluorophenyl)ethyl]-5-[methyl(methylsulfonyl)amino]benzene-1,3-dicarboxamide Chemical compound N([C@H](C)C=1C=CC(F)=CC=1)C(=O)C(C=1)=CC(N(C)S(C)(=O)=O)=CC=1C(=O)NC(CO)(CO)CC1=CC=CC=C1 ASFAFOSQXBRFMV-LJQANCHMSA-N 0.000 abstract 1
- 229920005654 Sephadex Polymers 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000012634 fragment Substances 0.000 abstract 1
- ZDLBWMYNYNATIW-UHFFFAOYSA-N tetracos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCC=C ZDLBWMYNYNATIW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 5
- 235000014347 soups Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 241000243142 Porifera Species 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000001551 total correlation spectroscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 3
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 3
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 3
- 238000003929 heteronuclear multiple quantum coherence Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003334 secondary amides Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XAFPURGXVZDMJH-LLVAEMQGSA-N CCCCCCCCCCCCCC[C@@H](O)[C@@H](O)[C@@H](N)CO.CCCCCCCCCCCCCC[C@@H](O)[C@@H](O)[C@@H](N)CO Chemical group CCCCCCCCCCCCCC[C@@H](O)[C@@H](O)[C@@H](N)CO.CCCCCCCCCCCCCC[C@@H](O)[C@@H](O)[C@@H](N)CO XAFPURGXVZDMJH-LLVAEMQGSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Abstract
本发明涉及一种从中国南海海绵Iotrochota ridley中提取、分离的新鞘类脂糖苷化合物。本发明所述化合物的化学名为:1-(β-D-吡喃葡糖氧基)-3,4-二羟基-2-[(4’Z)-2’-羟基二十四碳烯酰胺基-4’]-十八烷。命名为:Iotroridoside A,其化学结构式如下:该化合物是以工业乙醇从中国南海海绵Iotrochota ridley中提取、浓缩,并以正丁醇等溶剂萃取,经硅胶柱层析和适当溶剂淋洗,再以葡聚糖凝胶柱层析得白色粉状物。该化合物具有新型骨架结构,即其支链二十四碳烯酰胺基具有独特的双键片段,这是以往所获得的此类天然产物所没有的。同时该化合物还具有极强的肿瘤细胞毒活性。因此,具有良好的应用前景。
Description
本发明涉及一种从中国南海海绵Iotrochota ridley中分离、提取的新鞘类脂糖苷化合物。
海绵是一种低等的多细胞动物,种类繁多,分布极广,以海产为主。自七十年代以来,人们已从海绵中发现了许多结构独特的萜类、生物碱、大环内酯和糖苷等化合物。近几年来,由于有效成分的分离、纯化技术的显著改进,尤其是600兆核磁共振仪等现代先进分析仪器的出现以及各种二维谱技术的迅猛发展,使海洋天然产物中的一些结构较复杂的化合物,特别是鞘类脂糖苷化合物的结构鉴定工作在九十年代才取得一些重要进展。经药理试验表明,鞘类脂糖苷化合物大多具有抗真菌和抗肿瘤等生理活性。因而,它们是一类具有广阔应用前景的天然产物。本发明所涉及的化合物经IR、EIMS、FABMS、1HNMR、13CNMR、GCOSY、TOCSY、HMQC和HMBC等现代物理手段和化学方法确定结构如下:
该化合物的化学名称为::1-(B-D-吡喃葡糖氧基)-3,4-二羟基-2-[(4′Z)-2′-羟基二十四碳烯酰胺基-4′]-十八烷。命名为:Iotroridoside A,其物理常数如下:
vKBr max(cm-1):3363,2919,2850,2287,1629,1536,1465,1376,1168,1035,898,721,605;δ1H(C3D5N,TMS)ppm:8.54(1H,d,J=9Hz,NH),5.90(1H,dt,J=10.2,7.2Hz,H4’),5.60(1H,dt,J=10.8,7.2Hz,H5’),5.24(1H,m,H2),4.93(1H,d,J=8.4Hz,H1”),4.68(1H,dd,J=10.2,4.2Hz,H1a),4.62(1H,m,H2’),4.50(1H,dd,J=10.8,4.2Hz,H1b),4.45(1H,dd,J=12,2.4Hz,H6”a),4.31(1H,dd,J=12,5.4Hz,H6”b),4.27(1H,dd,J=12,4.8Hz,H3),4.19(1H,m,H4”),4.16(1H,m,H4),4.15(1H,m,H3”),3.97(1H,m,H2”),3.84(1H,m,H5”),3.00(1H,m,H3’a),2.82(1H,m,H3’b),2.22(1H,m,H5a),2.17(2H,m,H6’),1.88(2H,m,H5b,H6a),1.66(1H,m,H6b),1.42(2H,m,H7),1.35(2H,m,H7’),1.34~1.20(26CH2),1.25(H17,H23’),1.24(H16,H22’),0.86(6H,t,J=6.6Hz,18-CH3,24’-CH3);δ13C(C5D5N,TMS)ppm:174.98(Cl’),132.39(C5’),126.27(C4’),105.53(C1”),78.52(C3”),78.43(C5”),75.85(C3),75.13(C2”),72.57(C4”),72.48(C2’),71.51(C4),70.42(C1),72.57(C4”),72.48(C2’),71.51(C4),70.42(C1),62.65(C6”),51.80(C2),34.22(C5),33.56(C3’),32.14(C16,C22’),30.37~29.90(23CH2),29.70(C7),27.90(C6’),26.54(C6),22.94(C17,C23’),14.28(C18,C24’);FABMS得分子量843,EIMS(m/z):568,490,458,406,370,356,328,307,265,225,179,145,123,111,97,83,70(100%),57,55,43
该化合物的提取方法如下:以中国南海海绵为原料,将晒干的海绵用酒精浸泡、抽提,将抽提物浓缩至浆状物,然后将其分散在适量的水中,再以等量的乙酸乙酯和正丁醇依次萃取,将所获得的正丁醇可溶物进行三次硅胶柱层析和两次葡聚糖凝胶LH-20柱层析得白色粉状物,即该化合物。
生理活性试验表明,该化合物对小鼠L1210白血病细胞的细胞毒作用EC50值为80ng/ml。
本发明所述的化合物,不但具有新型双键片段的酰胺骨架结构,而且具有极强的肿瘤细胞的细胞毒活性。因此,本发明所涉及的新化合物具有十分重要的理论价值和应用价值。
实施例:一、分离提纯:
中国南海海绵Iotrochota ridley,晒干(2.2g)切碎后用95%工业酒精(5kg)于室温下浸泡提取三次,合并提取物并减压浓缩至浆状物,将此浆状物均匀分散于500ml水中,分别用等量的乙酸乙酯和正丁醇萃取三次,正丁醇萃取物经减压浓缩得黑色浆状物23g。
上述浆状物经硅胶(150g,Merk 70~230目)柱层析(φ=4.6×35cm),以500ml不同比例的氯仿-甲醇(100%,90%,85%,80%,70%)梯度洗脱,获得A、B、C、D、E五个初组分。C组分(1g)经两次硅胶(80g,30g,青岛海洋化工分厂,300~400目)柱层析(φ2.4×48,φ1.6×48,洗脱剂:90%氯仿-甲醇)得粗产物45mg。将此粗产物再经二次葡聚糖凝胶LH-20(30%氯仿-甲醇)柱层析,得白色粉状物29.6mg。二、结构鉴定1.红外3363cm-1处的宽峰说明分子含羟基,1629、1536cm-1等处的中等偏弱吸收峰显示分子可能含仲酰胺片段。2.1HNMR、13CNMR(C5D5N,ppm)显示分子含有一根邻二取代双键(δH5.90,dt,J=10.2,7.2Hz,δC126.7和δH5.60,dt,J=10.8,7.2Hz,δC132.39),因两烯氢间的偶合常数小于12Hz,故双键的立体构型为顺式。另有10个连氧或氮的亚甲基(或次甲基)及两个甲基(δH0.86,6H,t,J=6.6Hz,δC14.28)。δH4.93(1H,d,J=8.4Hz)以及δC105.53是特征的葡萄糖异头碳氢信号,暗示分子可能含葡糖环。δH8.54(1H,d,J=9Hz,NH)以及δC174.98(酰胺羰基)指明分子含有一个仲酰胺片段,恰与红外提供的信息吻合。另外,δH1.34~1.20,δC30.37~29.90都有一个巨大的亚甲基信号峰,说明分子含一根或一根以上的长脂肪链。3.GCOSY同核相关谱显示分子有三个偶合体系:①从异头氢(1″)出发找偶合点可连接出一个六元糖环结构(1″→6″),再由HMQC异核相关谱可找出其相应的δC值(105.53,75.13,78.52,72.57,78.43和62.65ppm),将其δC值与文献值对照,可知是β-D-吡哺葡糖环。②从仲酰胺氢出发可推导出一个植物鞘氨醇(phytosphingosine)片段(1→6),同样可由HMQC定出相应的δC值。③从双键氢(4′,5′)出发可推出一不饱和脂肪长链(1′→mCH2),其中有一连氧亚甲基,可能与酰胺羰基相连。HMBC指出,NH与C=O、C=O与H2′有2JCH远程偶合,C1与H1″有3JCH远程偶合,由此可将三个偶合体系连成一片,得到如下初步结构:
上述结构与文献报导的一些鞘类脂糖苷化合物类似,但结构上又有独特的地方,即4′位有双键,这是以前所没出现过的,因此是新化合物。该化合物的TOCSY、HMBC等相关谱则进一步证实了这一结构,见表1。表1 IotroridosideA的δ1H,δ13C,TOCSY和HMBC数据表
4.根据FABMS得分子量843,推算出m+n=25,同时由1HNMR的氢积分面积也可推得m+n=25,但m,n仍需进一步确定。我们应用如下化学方法解决了这一问题。5.取样品5mg,在6.5ml82%的甲醇水溶液(含1NHCl)中进行酸解反应。常压下85℃左右回流12小时。产物用石油醚萃取三次(5ml×3),合并石油醚层,用去离子水洗二遍,Na2SO4干燥,过夜。浓缩石油醚溶液,得产物3.5mg。TLC显示此产物仍混有少量反应物,因此再对产物进行硅胶(10克,青岛海洋化工分厂,300~400目)柱层析(φ1.2×43,洗脱剂:80%石油醚-乙酸乙酯)得纯产物2.0mg。作EIMS,得数据如下:396(M+),378(M-H2O),337(M-COOCH3),304,139,125,111,103(γ裂解),90(100%,β裂解),83,69,57,55,43。由该质谱数据及实施例二(3)中所提供的信息综合推得水解产物的结构式如下:6.因n=15,则m=25-15=10,由此我们便可确定该化合物的结构式如下:
序号 | δ1H,ppm | δ13C,ppm | 1H-1HGCOSY | TOCSY | HMBC |
1a | 4.68 | 70.42 | 1b,2 | 1b,2,3,NH | 3,1″ |
1b | 4.50 | 1a,2 | 1a,2,3,NH | ||
2 | 5.24 | 51.80 | 1,3,NH | 1,3,NH,4 | 1,3 |
3 | 4.27 | 75.85 | 2,4 | 1,2,4,5,6 | 4 |
4 | 4.16 | 71.51 | 3,5 | 2,3,5,6,7,(CH2)n | 4,3 |
5a | 2.22 | 34.22 | 5b,4,6 | 3,4,5b,6,7,(CH2)n | 3 |
5b | 1.88 | 5a,4,6 | 3,4,5a,6,7,(CH2)n |
6a | 1.88 | 26.54 | 6b,5,7 | 3,4,5,6b,7,(CH2)n | |
6b | 1.66 | 6a,5,7 | 3,4,5,6a,7,(CH2)n | ||
16 | 1.24 | 32.14 | 17,18 | ||
17 | 1.25 | 22.94 | 18 | ||
18 | 0.86 | 14.28 | 16,17 | ||
1′ | / | 174.98 | / | / | NH,2′ |
2′ | 4.62 | 72.48 | 3′ | 3′,4′,5′ | 3′ |
3′a | 3.00 | 33.56 | 3′b,2′,4′ | 2′,3′b,4′,5′,6′ | 5′ |
3′b | 2.82 | 3′a,2′,4′ | 2,3′a,4′,5′,6′ | ||
4′ | 5.90 | 126.27 | 3′,5′,6′ | 2′,3′,5′,6′,7′,(CH2)n | 3′,6′ |
5′ | 5.60 | 132.39 | 4′,6′ | 2′,3′,4′,6′,7′,(CH2)n | 3′,6′ |
6′ | 2.17 | 27.90 | 5′,7′ | 3′,4′,5′,7′,(CH2)n | 4′,7′ |
22′ | 1.24 | 32.14 | 23′,24′ | ||
23′ | 1.25 | 22.94 | 24′ | ||
24′ | 0.86 | 14.28 | 22′,23′ | ||
1″ | 4.93 | 105.53 | 2″ | 2″,3″,4″,5″ | 2″,1 |
2″ | 3.97 | 75.13 | 1″,3″ | 1″,3″,4″,5″,6″ | 3″ |
3″ | 4.15 | 78.52 | 2″,4″ | 1″,2″,4″,5″,6″ | 2″,4″ |
4″ | 4.19 | 72.57 | 3″,5″ | 1″,2″,3″,5″,6″ | 6″ |
5″ | 3.84 | 78.43 | 4″,6″ | 1″,2″,3″,4″,6″ | 4″ |
6″a | 4.45 | 62.65 | 6″b,5″ | 2″,3″,4″,5″,6″b | |
6″b | 4.31 | 6″a,5″ | 2″,3″,4″,5″,6″a | ||
NH | 8.54 | / | 2 | 1,2,3,4 | / |
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN99116047A CN1081192C (zh) | 1999-02-03 | 1999-02-03 | 一种鞘类脂糖苷化合物及其提取方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN99116047A CN1081192C (zh) | 1999-02-03 | 1999-02-03 | 一种鞘类脂糖苷化合物及其提取方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1224724A CN1224724A (zh) | 1999-08-04 |
CN1081192C true CN1081192C (zh) | 2002-03-20 |
Family
ID=5278898
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN99116047A Expired - Fee Related CN1081192C (zh) | 1999-02-03 | 1999-02-03 | 一种鞘类脂糖苷化合物及其提取方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1081192C (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10231300A (ja) * | 1997-02-20 | 1998-09-02 | Toyobo Co Ltd | 新規なセリン誘導体の配糖体 |
-
1999
- 1999-02-03 CN CN99116047A patent/CN1081192C/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10231300A (ja) * | 1997-02-20 | 1998-09-02 | Toyobo Co Ltd | 新規なセリン誘導体の配糖体 |
Also Published As
Publication number | Publication date |
---|---|
CN1224724A (zh) | 1999-08-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Endo et al. | The constituents of Gardenia jasminoides geniposide and genipin-gentiobioside | |
Roy et al. | Synthesis of “Sugar‐Rods” with Phytohemagglutinin Cross‐Linking Properties by Using the Palladium‐Catalyzed Sonogashira Reaction | |
Yosioka et al. | Soil bacterial hydrolysis leading to genuine aglycone. V. on ginsenosides-Rb1, Rb2, and Rc of the ginseng root saponins | |
Wang et al. | Enhanced recovery of antitumor ganoderic acid T from Ganoderma lucidum mycelia by novel chemical conversion strategy | |
KITAGAWA et al. | Saponin and sapogenol. XXXII. Chemical constituents of the seeds of Vigna angularis (Willd.) Ohwi et Ohashi.(2). Azukisaponins I, II, III, and IV | |
Tabata et al. | Structure elucidation of roselipins, inhibitors of diacylglycerol acyltransferase produced by gliodadium roseum KF-1040 | |
AU688177B2 (en) | Eleutherobin and analogs thereof | |
KR100293968B1 (ko) | 20(에스)-진세노사이드알에이취투의제조방법 | |
Zhu et al. | Synthesis of 3-O-(β-d-xylopyranosyl-(1→ 2)-β-d-glucopyranosyl)-3′-O-(β-d-glucopyranosyl) tamarixetin, the putative structure of aescuflavoside A from the seeds of Aesculus chinensis | |
Řezanka et al. | N-acylated bacteriohopanehexol-mannosamides from the thermophilic bacterium Alicyclobacillus acidoterrestris | |
FUJIMOTO et al. | New Toxic Metabolites from a Mushroom, Hebeloma vinosophyllum. I.: Structures of hebevinosides I, II, III, IV, and V | |
CN113603730A (zh) | 硼酸三酯为糖受体选择性合成氧糖苷或2-脱氧糖的方法 | |
Giang et al. | ent-pimarane-type diterpenoids from Siegesbeckia orientalis L. | |
CN1081192C (zh) | 一种鞘类脂糖苷化合物及其提取方法 | |
Rahman et al. | New withanolides from Withania coagulans | |
Palter et al. | A bitter principle of safflower; Matairesinol monoglucoside | |
Yamada et al. | Isolation and structure of a monomethylated ganglioside possessing neuritogenic activity from the ovary of the sea urchin Diadema setosum | |
NAGAO et al. | Studies on the constituents of Thladiantha dubia BUNGE. I.: The structures of dubiosides A, B and C, the quillaic acid glucuronide saponins isolated from the tuber | |
CN108586559B (zh) | 一种羊毛甾烷型三萜类化合物及其制备方法和用途 | |
CUI et al. | Triterpene glycosides from the bark of Robinia pseudo-acacia L. II | |
CN104387426A (zh) | 一种区域选择性合成6-o-丙烯酰基糖类衍生物的方法 | |
Zong et al. | Total synthesis of ipomoeassin F and its analogs for biomedical research | |
Kanchanapoom et al. | Pregnane and pregnane glycosides from the Malagasy plant, Cynanchum aphyllum | |
Kawano et al. | Biologically active glycosides from asteroidea, XVII. Glycosphingolipids from the starfish Acanthaster planci, 3. Isolation and structure of two new ceramide lactosides | |
Bhandari et al. | A triterpenoid saponin from Polycarpone loeflingiae |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |