JPS6048995A - Novel saponin and its preparation - Google Patents
Novel saponin and its preparationInfo
- Publication number
- JPS6048995A JPS6048995A JP58155552A JP15555283A JPS6048995A JP S6048995 A JPS6048995 A JP S6048995A JP 58155552 A JP58155552 A JP 58155552A JP 15555283 A JP15555283 A JP 15555283A JP S6048995 A JPS6048995 A JP S6048995A
- Authority
- JP
- Japan
- Prior art keywords
- glucopyranoside
- water
- lower alcohol
- lucinoside
- concentrate
- 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.)
- Granted
Links
- 229930182490 saponin Natural products 0.000 title claims description 21
- 150000007949 saponins Chemical class 0.000 title claims description 21
- 239000001397 quillaja saponaria molina bark Substances 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims abstract description 18
- 239000012141 concentrate Substances 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 3
- 235000017709 saponins Nutrition 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 244000280244 Luffa acutangula Species 0.000 claims description 17
- 239000000284 extract Substances 0.000 claims description 9
- 150000008505 β-D-glucopyranosides Chemical class 0.000 claims description 9
- PWAOOJDMFUQOKB-WCZZMFLVSA-N ginsenoside Re Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](O[C@@H]2[C@H]3C(C)(C)[C@@H](O)CC[C@]3(C)[C@@H]3[C@@]([C@@]4(CC[C@@H]([C@H]4[C@H](O)C3)[C@](C)(CCC=C(C)C)O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C)(C)C2)O[C@H](CO)[C@@H](O)[C@@H]1O PWAOOJDMFUQOKB-WCZZMFLVSA-N 0.000 claims description 8
- AOGZLQUEBLOQCI-UHFFFAOYSA-N ginsenoside-Re Natural products CC1OC(OCC2OC(OC3CC4(C)C(CC(O)C5C(CCC45C)C(C)(CCC=C(C)C)OC6OC(CO)C(O)C(O)C6O)C7(C)CCC(O)C(C)(C)C37)C(O)C(O)C2O)C(O)C(O)C1O AOGZLQUEBLOQCI-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- GXWUEMSASMVWKO-GNLHUFSQSA-N (4as,6ar,6as,6br,10s,12ar,14br)-10-[(2s,3r,4s,5s)-4,5-dihydroxy-3-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]oxy-2,2,6a,6b,9,9,12a-heptamethyl-1,3,4,5,6,6a,7,8,8a,10,11,12,13,14b-tetradecahydropicene-4a-carboxylic acid Chemical compound O([C@@H]1[C@@H](O)[C@@H](O)CO[C@H]1O[C@H]1CC[C@]2(C)[C@H]3CC=C4[C@@]([C@@]3(CCC2C1(C)C)C)(C)CC[C@]1(CCC(C[C@@H]14)(C)C)C(O)=O)[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O GXWUEMSASMVWKO-GNLHUFSQSA-N 0.000 claims description 5
- 229930182494 ginsenoside Natural products 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 229940089161 ginsenoside Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- MDZKJHQSJHYOHJ-LLICELPBSA-N maslinic acid Chemical compound C1[C@@H](O)[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CCC(C)(C)C[C@H]5C4=CC[C@@H]3[C@]21C MDZKJHQSJHYOHJ-LLICELPBSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000000954 anitussive effect Effects 0.000 abstract description 2
- 229940124584 antitussives Drugs 0.000 abstract description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002934 diuretic Substances 0.000 abstract description 2
- 230000001882 diuretic effect Effects 0.000 abstract description 2
- 244000302544 Luffa aegyptiaca Species 0.000 abstract 2
- 239000004909 Moisturizer Substances 0.000 abstract 1
- 206010053615 Thermal burn Diseases 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000001333 moisturizer Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 81
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DBERHVIZRVGDFO-UHFFFAOYSA-N Acetoxyacetone Chemical compound CC(=O)COC(C)=O DBERHVIZRVGDFO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- -1 ethanol or methanol Chemical compound 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- RYVMUASDIZQXAA-UHFFFAOYSA-N pyranoside Natural products O1C2(OCC(C)C(OC3C(C(O)C(O)C(CO)O3)O)C2)C(C)C(C2(CCC3C4(C)CC5O)C)C1CC2C3CC=C4CC5OC(C(C1O)O)OC(CO)C1OC(C1OC2C(C(OC3C(C(O)C(O)C(CO)O3)O)C(O)C(CO)O2)O)OC(CO)C(O)C1OC1OCC(O)C(O)C1O RYVMUASDIZQXAA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- NTWLPZMPTFQYQI-UHFFFAOYSA-N (3alpha)-olean-12-ene-3,23-diol Natural products C1CC(O)C(C)(CO)C2CCC3(C)C4(C)CCC5(C)CCC(C)(C)CC5C4=CCC3C21C NTWLPZMPTFQYQI-UHFFFAOYSA-N 0.000 description 1
- DLNAGMLXUYEHQS-UHFFFAOYSA-N 3-O-beta-D-glucopyranosylserjanic acid Natural products COC(=O)C1(C)CCC2(CCC3(C)C(=CCC4C5(C)CCC(OC6OC(CO)C(O)C(O)C6O)C(C)(C)C5CCC34C)C2C1)C(=O)O DLNAGMLXUYEHQS-UHFFFAOYSA-N 0.000 description 1
- MIJYXULNPSFWEK-GTOFXWBISA-N 3beta-hydroxyolean-12-en-28-oic acid Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CCC(C)(C)C[C@H]5C4=CC[C@@H]3[C@]21C MIJYXULNPSFWEK-GTOFXWBISA-N 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- JKLISIRFYWXLQG-UHFFFAOYSA-N Epioleonolsaeure Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CCC5(C(O)=O)CCC(C)(C)CC5C4CCC3C21C JKLISIRFYWXLQG-UHFFFAOYSA-N 0.000 description 1
- GCGBHJLBFAPRDB-UHFFFAOYSA-N Hederagenin Natural products CC1(C)CCC2(CCC3(C)C4CCC5C(C)(CO)C(O)CCC5(C)C4CC=C3C2C1)C(=O)O GCGBHJLBFAPRDB-UHFFFAOYSA-N 0.000 description 1
- YBRJHZPWOMJYKQ-UHFFFAOYSA-N Oleanolic acid Natural products CC1(C)CC2C3=CCC4C5(C)CCC(O)C(C)(C)C5CCC4(C)C3(C)CCC2(C1)C(=O)O YBRJHZPWOMJYKQ-UHFFFAOYSA-N 0.000 description 1
- MIJYXULNPSFWEK-UHFFFAOYSA-N Oleanolinsaeure Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CCC5(C(O)=O)CCC(C)(C)CC5C4=CCC3C21C MIJYXULNPSFWEK-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 240000004371 Panax ginseng Species 0.000 description 1
- 235000002789 Panax ginseng Nutrition 0.000 description 1
- GCGBHJLBFAPRDB-KCVAUKQGSA-N Scutellaric acid Natural products CC1(C)CC[C@@]2(CC[C@@]3(C)[C@@H]4CC[C@H]5[C@@](C)(CO)[C@H](O)CC[C@]5(C)[C@H]4CC=C3[C@@H]2C1)C(=O)O GCGBHJLBFAPRDB-KCVAUKQGSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- KVMXBSSOCCPAOR-UHFFFAOYSA-N ginsenoside ra1 Chemical compound C1CC(C2(CCC3C(C)(C)C(OC4C(C(O)C(O)C(CO)O4)OC4C(C(O)C(O)C(CO)O4)O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC(C(C(O)C1O)O)OC1COC(C(C1O)O)OCC1OC1OCC(O)C(O)C1O KVMXBSSOCCPAOR-UHFFFAOYSA-N 0.000 description 1
- YLOTVUIQEWTDME-UHFFFAOYSA-N ginsenoside-Ra1 Natural products CC(=CCCC(C)(OC1OC(COC2OCC(OC3OCC(O)C(O)C3O)C(O)C2O)C(O)C(O)C1O)C4CCC5(C)C4C(O)CC6C7(C)CCC(OC8C(O)C(O)C(CO)OC8OC9OC(CO)C(O)C(O)C9O)C(C)(C)C7CCC56C)C YLOTVUIQEWTDME-UHFFFAOYSA-N 0.000 description 1
- PGOYMURMZNDHNS-MYPRUECHSA-N hederagenin Chemical group C1C[C@H](O)[C@@](C)(CO)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CCC(C)(C)C[C@H]5C4=CC[C@@H]3[C@]21C PGOYMURMZNDHNS-MYPRUECHSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229940100243 oleanolic acid Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- HZLWUYJLOIAQFC-UHFFFAOYSA-N prosapogenin PS-A Natural products C12CC(C)(C)CCC2(C(O)=O)CCC(C2(CCC3C4(C)C)C)(C)C1=CCC2C3(C)CCC4OC1OCC(O)C(O)C1O HZLWUYJLOIAQFC-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
Description
【発明の詳細な説明】
この発明はヘチマに含有される新規サポニン類とその製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel saponins contained in loofah and a method for producing the same.
この発明における゛ヘチマ″としては、ウリ科３−
の植物で学名ルファ・シリンドリカ・ロエム（１−ｕｆ
ｆａ ｃｙｌｉｎｄｒｉｃａ Ｒｏｅｎ＋ 、 ）及び
これと植物学的に類縁の植物が含まれる。The "loofah" in this invention is a plant belonging to the Cucurbitaceae family, scientific name Rufa cylindrica loem (1-uf
fa cylindrica Roen+) and plants botanically related thereto.
最近、ヘチマの菓から、オレアノール酸、パルミチン酸
、オレアノール酸−３−グルコシド及びオレアノール酸
−３−グルコシル−２８−ジグルコシドが抽出されたど
の報告がある（ Ｎ ａｎｋｉｎｇＩ ｎ５ｊｆｊＬＩ
ｊｅ ｏｒ Ｍ ａｉｅｒ ｆａ Ｍｅｄｌｃａ （１
’Ｊ ａｎｋｉｎｇＰｅｏｐ 、 Ｒ，Ｃｈｉｎａ）
Ｃｈｕｎｏ Ｔｓａｏ Ｙａｏ； １９８０゜１１ （
２） 、 ５５６４ （ｃｈ） ）。Recently, there has been a report that oleanolic acid, palmitic acid, oleanolic acid-3-glucoside, and oleanolic acid-3-glucosyl-28-diglucoside were extracted from loofah confectionery.
je or Maier fa Medlca (1
'JankingPeop, R, China)
Chuno Tsao Yao; 1980゜11 (
2), 5564 (ch)).
この発明の発明者は、ヘチマの含有成分について研究を
行ったｌｉｉ！ｉ果、９つの新規のサポニン〔ルシノシ
ド（１−ｕｃｙｎｏｃｉｄｅ ）Δ、Ｂ、Ｃ，Ｄ、、Ｅ
。The inventor of this invention conducted research on the ingredients contained in loofah! i fruit, nine new saponins [1-ucynocide Δ, B, C, D, , E
.
Ｆ、Ｇ、Ｈ及びＩと呼称）と、公知の朝鮮ニンジンサポ
ニンのギンゼノシドＲｅとＲＯ＋が抽出されこの発明に
到達した。This invention was achieved by extracting ginsenosides Re and RO+ of known Korean ginseng saponins (referred to as F, G, H, and I).
この発明の新規のサポニン類は、
４−
一般式（Ｉ）：
で表され、
Ｒ１がヒドロキシメチル基、Ｒ２がβ−Ｄ−グルコピラ
ノシド基、Ｒ３がヒドロキシ基及びＲ４が水素原子で具
体名が２１−β−ヒドロキシへデラゲニン−３−０−（
β−Ｄ−グルコピラノシド）−２８−０−β−グルコピ
ラノシド、（ルシノシドＡ（ＬＡ＋））：
Ｒ１がヒドロキシメチル基、Ｒ２がβ−Ｄ−グルコピラ
ノシド基、Ｒ３が水素原子及びＲ４がヒドロキシ基で、
具体名がアルシュノール′Ｍ−３−０−（β−Ｄ−グル
コピラノシド）−２８−０−β−Ｄグルコピラノシド、
（ルシノシドＢ（ＬＢ２））；Ｒ１がメチル基、Ｒ２が
β−Ｄ−グルコピラノシド基、Ｒ３がヒドロキシ基及び
Ｒ４が水素原子で、具体名がマカエリン酸−３−０−（
β−Ｄ−グルコピラノシド）−２８−０−β−Ｄ−グル
コピラノシド、〔ルシノシドＣ（ＬＢ＋ ））：Ｒ１が
ホルミル基 Ｒ２がβ−Ｄ−グルコピラノシド基、Ｒ３
が水素原子及びＲ４がヒドロキシ基で、具体名が２−α
−ヒドロキシギプソゲニンー３−〇−（β−Ｄ−グルコ
ピラノシド）−２８−Ｑ−β−り一グルコビラノシド）
−２８−Ｑ−β−Ｄ−１ルコビラノシド、（ルシノシド
Ｄ（１−Ｄ＋））：Ｒ１がヒドロキシメチル基、Ｒ２が
β−Ｄ−グルコピラノシド基、Ｒ３とＲ４とが水素原子
で、具体名がヘデラゲニン−３−０−（β−Ｄ−グルコ
ピラノシド）−２８−０−β−Ｄ−グル］ピラノシド、
〔ルシノシドＥ （１−０２） ） ：Ｒ１がホルミル
基、Ｒ２がβ−Ｄ−グルコピラノシド基、Ｒ３とＲ４が
水素原子で具体名がギプソゲニン−３−０−（β−Ｄ−
グル］ピラノシド）−２８−０−β−Ｄ−グルコピラノ
シド〔ルシノシドＦ （Ｉ−Ｄ２） ） ：
Ｒ１がメチル基、Ｒ２がβ−Ｄ−グルコピラノシド基、
Ｒ３が水素原子及びＲ４がヒドロキシ基で、具体名がス
マツジｌ’１ｌｔ−３−０−（β−Ｄ−グルコピラノシ
ド）−２８−Ｑ−β−Ｄ−グルコピラノシド、〔ルシノ
シドＧ（ＬＤ４））：
Ｒ１がメチル基、Ｒ２がβ−Ｄ−グルコピラノシド基、
及びＲ３とＲ４とが水素原子で具体名がオレアノール酸
−３−０−（β−Ｄ−グルコピラノシド）−２８−Ｑ−
β−Ｄ−グルコピラノシド〔ルシノシドＨ（ＬＤａ））
：及び
Ｒ１がヒドロキシメチル基、Ｒ２とＲ３とが水素原子及
びＲ４がヒドロキシ基で具体名がアルシュノール酸−３
−０−（β−Ｄ−グルコピラノシド）、（ルシノシドＩ
（ＬＥ＋））である。The novel saponins of this invention are represented by 4-general formula (I): where R1 is a hydroxymethyl group, R2 is a β-D-glucopyranoside group, R3 is a hydroxy group, and R4 is a hydrogen atom, and the specific name is 21 -β-hydroxyhederagenin-3-0-(
β-D-glucopyranoside) -28-0-β-glucopyranoside, (Lucinoside A (LA+)): R1 is a hydroxymethyl group, R2 is a β-D-glucopyranoside group, R3 is a hydrogen atom and R4 is a hydroxy group,
The specific name is Alshnol'M-3-0-(β-D-glucopyranoside)-28-0-β-D glucopyranoside,
(Rusinoside B (LB2)); R1 is a methyl group, R2 is a β-D-glucopyranoside group, R3 is a hydroxy group, and R4 is a hydrogen atom, and the specific name is macaeriic acid-3-0-(
β-D-glucopyranoside) -28-0-β-D-glucopyranoside, [lucinoside C(LB+)): R1 is formyl group, R2 is β-D-glucopyranoside group, R3
is a hydrogen atom and R4 is a hydroxy group, and the specific name is 2-α
-Hydroxygypsogenin-3-〇-(β-D-glucopyranoside)-28-Q-β-ri-glucobyranoside)
-28-Q-β-D-1 Lucobyranoside, (Lucinoside D(1-D+)): R1 is a hydroxymethyl group, R2 is a β-D-glucopyranoside group, R3 and R4 are hydrogen atoms, and the specific name is hederagenin. -3-0-(β-D-glucopyranoside)-28-0-β-D-glu]pyranoside,
[Rusinoside E (1-02)): R1 is a formyl group, R2 is a β-D-glucopyranoside group, R3 and R4 are hydrogen atoms, and the specific name is gipsogenin-3-0-(β-D-
[glu]pyranoside)-28-0-β-D-glucopyranoside [lucinoside F (I-D2)): R1 is a methyl group, R2 is a β-D-glucopyranoside group,
R3 is a hydrogen atom and R4 is a hydroxy group, and the specific name is Sumatsuji l'1lt-3-0-(β-D-glucopyranoside)-28-Q-β-D-glucopyranoside, [Rusinoside G (LD4)): R1 is a methyl group, R2 is a β-D-glucopyranoside group,
and R3 and R4 are hydrogen atoms, and the specific name is oleanolic acid-3-0-(β-D-glucopyranoside)-28-Q-
β-D-glucopyranoside [Lucinoside H (LDa)]
: and R1 is a hydroxymethyl group, R2 and R3 are hydrogen atoms, and R4 is a hydroxy group, and the specific name is alshnolic acid-3
-0-(β-D-glucopyranoside), (Rusinoside I
(LE+)).
これらの新規のサポニン並びに公知のギンゼノシドＲｅ
とＲσ１は次の方法によって得ることができる。These new saponins as well as the known ginsenoside Re
and Rσ1 can be obtained by the following method.
この発明の方法においては、まず原料のヘチマ７−
の地上部もしくは地下部を脱脂処理しないか、あるいは
ベンゼンやｎ−ヘキサンのような通常の脂溶性有機溶媒
を用いて脱脂処理後抽出が行われる。In the method of this invention, the above-ground or underground parts of the raw material loofah are either not degreased or extracted after degreasing using a common fat-soluble organic solvent such as benzene or n-hexane. .
次いで下記のような方法で抽出が行われ粗へチマサボニ
ンが得られる。Next, extraction is performed in the following manner to obtain crude hechima sabonin.
（ａ）原料をその約２〜５倍重量の水またはメタノール
、エタノールのごとき低級アルコールまたは含水低級ア
ルコールと共に加熱還流し濾過して抽出液を得る。この
抽出操作は必要に応じて繰り返して行ってもよい。抽出
液を合して濃縮しその濃縮物を水に懸濁させる。得られ
た懸濁液を巨大網状構造で多孔性の架橋されたポリスチ
レン系樹脂吸着剤（例えばアンバーライトＸＡＤ−１，
アンバーライトＸＡ［）−２，いずれもローム・アンド
・ハース社製など）に接触吸着させる。これらの吸着剤
は含有サポニンｍの２０〜３００倍量、望ましくは４０
〜１５０（８ｆｆｉ用いられる。次いで水で樹脂をよく
洗い、次いでエタノールやメタノールのような低級アル
コールや、約３０％以上の低級アルコール含有水で溶離
し濃縮しその濃縮物を低級アル８−
コールに溶解しエーテル、ｎ−ヘキサンなどの脂溶性有
機Ｓ＊に注入し生成した析出物を減圧乾燥して粗へチマ
サポニンが得られる。(a) The raw material is heated under reflux and filtered with water or a lower alcohol such as methanol or ethanol or a water-containing lower alcohol in an amount of about 2 to 5 times its weight to obtain an extract. This extraction operation may be repeated as necessary. The extracts are combined and concentrated and the concentrate is suspended in water. The resulting suspension was treated with a porous cross-linked polystyrene resin adsorbent with a large network structure (e.g. Amberlite XAD-1,
Amberlite These adsorbents are used in an amount of 20 to 300 times the content of saponin m, preferably 40
~150 (8ffi) is used.Then, the resin is thoroughly washed with water, and then eluted and concentrated with a lower alcohol such as ethanol or methanol, or water containing about 30% or more lower alcohol, and the concentrate is converted into lower alcohol 8-alcohol. Crude loofah saponin is obtained by dissolving and injecting into a fat-soluble organic S* such as ether or n-hexane, and drying the resulting precipitate under reduced pressure.
（ｂ ）原料をその約２〜５倍重量の水またはメタノー
ルのごとき低級アルコール又は含水メタノール、含水エ
タノールのごとき含水低級アルコールと共に加熱し、濾
過して抽出液を得る。この抽出操作は必要に応じて繰り
返し行ってもよい。この抽出液を合して濃縮し、その濃
縮物を、そのままｎ−ブタノールに溶解して水を加えて
振盪して分配するか、又は水と脂溶性有機溶媒（エーテ
ル、ｎ−へキサンなど）に分配しその水層部を濃縮して
得られた濃縮物をｎ−ブタノールに溶解し水を加えて振
盪して分配し、得られたｎ−ブタノール部を濃縮し、そ
の濃縮物を低級アルコールに溶解し、エーテルなどの脂
溶性有機溶媒に注入し、生成した析出物を減圧乾燥して
粗へチマサボニンが得られる。(b) The raw material is heated with about 2 to 5 times its weight of water or a lower alcohol such as methanol, or a water-containing lower alcohol such as water-containing methanol or water-containing ethanol, and filtered to obtain an extract. This extraction operation may be repeated as necessary. The extracts are combined and concentrated, and the concentrate is either directly dissolved in n-butanol, added with water and shaken, and distributed, or mixed with water and a fat-soluble organic solvent (ether, n-hexane, etc.). Dissolve the concentrate in n-butanol, add water, shake and distribute, concentrate the obtained n-butanol, and dissolve the concentrate in lower alcohol. The crude loofah sabonin is obtained by dissolving it in water, injecting it into a fat-soluble organic solvent such as ether, and drying the resulting precipitate under reduced pressure.
上記のようにして得られる粗へチマサボニンは、前記の
新規サポニン物質のルシノシドＡ、Ｂ、Ｃ。The crude loofah sabonin obtained as described above contains lucinosides A, B, and C of the above-mentioned novel saponin substances.
Ｄ、Ｅ、Ｆ、Ｇ、Ｉ−１及び■並びに公知物質のギンゼ
ノシドＲｅとＲｏｌを含有し、これらの各成分は次の方
法によって分離される。It contains D, E, F, G, I-1 and (2) as well as the known substances ginsenoside Re and Rol, and each of these components is separated by the following method.
すなわち−上記の粗へチマサボニンを３〜７倍重量のメ
タノール、エタノールのごとき低級アルコールに溶解し
、その溶液は逆相シリカゲルカラムクロマトグラフィに
付される。例えば分収用Ｃ１９充填剤（３５〜１０５μ
１日本つΔ−ターズ製）を充填したカラムを用い溶出溶
媒どしては前記のごとき低級アルコール−水の混合物の
４０％低級アルコールから７０％低級アルコールへと順
に濃度を変化させた溶前剤で傾斜溶離するクロマトグラ
フィである。得られた溶出液を、薄層クロマトグラフィ
〔例えばシリカゲルＧ（西独メルク礼）の薄層を用いて
クロロホルム／メタノール／水の（ｉ５ ： ３５ ：
１０混合物の下層で展開し３０％硫酸を噴霧し１０５℃
で５分加熱して発色）に付して次のような七つのフラク
ションに区分され、これらフラクションは蒸発乾固され
る。That is, - the above-mentioned crude loofah sabonin is dissolved in a lower alcohol such as methanol or ethanol in an amount of 3 to 7 times its weight, and the solution is subjected to reverse phase silica gel column chromatography. For example, C19 packing material for separation (35-105μ
Using a column packed with 100% Δ-Tars (manufactured by Japan), the elution solvent was a solvent pre-solvent whose concentration was varied from 40% lower alcohol to 70% lower alcohol from the lower alcohol-water mixture described above. Chromatography with gradient elution. The obtained eluate was subjected to thin-layer chromatography [e.g., chloroform/methanol/water (i5: 35:
10 Developed in the lower layer of the mixture, sprayed with 30% sulfuric acid, and heated to 105°C.
The mixture was heated for 5 minutes to develop color) and divided into the following seven fractions, and these fractions were evaporated to dryness.
フラクション番号 含有サポニン
１ ルシノシドＡ、ギンゼノ
シドＲｅとＲＣｌ＋
２ ルシノシドＢと０
３ ルシノシドＤ
５ ルシノシドＦと０
６ ルシノシドＩ
７ ルシノシドトＩ
Ｍ１フラクションについては、まずクロロホルム：メタ
ノール：水（２０： ４ ： ０．１＞で溶離するシリ
カゲルのカラムクロマトグラフィに付してギンゼノシド
Ｒａ１、及びギンゼノシドＲｅとルシノシドＡの混合液
が得られる。次いで後者の混合液をさらにクロロホルム
：メタノール：酢酸エチル：水（２： ２ ： ４ ：
１ ）で溶離するシリカゲルのカラムクロマトグラフ
ィに付してルシノシドへとギンゼノシドＲｅが分離され
る。Fraction number Saponin contained 1 Lucinoside A, Ginzenoside Re and RCl+ 2 Lucinoside B and 0 3 Lucinoside D 5 Lucinoside F and 0 6 Lucinoside I 7 Lucinoside I For the M1 fraction, first chloroform: methanol: water (20: 4: 0.1 Column chromatography on silica gel eluting with > yields ginsenoside Ra1 and a mixture of ginsenoside Re and lucinoside A. The latter mixture is then further diluted with chloroform:methanol:ethyl acetate:water (2:2:4:
Ginsenoside Re is separated into lucinoside by column chromatography on silica gel eluting with 1).
Ｎｔｌ、 ２フラクシヨンについては、まずクロロホル
ム：メタノール：水（２０： ４ ： ０．１）で溶離
するシリカゲルのカラムクロマトグラフィに付してル１
１ −
ジノシトＢとルシノシドＣの混合液を１５１、これをさ
らにクロロホルム：メタノール：酢酸エチル：水（２：
２：／ｌ：１）で溶離するシリカゲルのカラムクロマト
グラフィに付してルシノシドＢとルシノシドＣが分離さ
れる。For the Ntl, 2 fraction, the 1.
1 - A mixed solution of dinoside B and lucinoside C was added to 151, and this was further mixed with chloroform:methanol:ethyl acetate:water (2:
Lucinoside B and C are separated by column chromatography on silica gel, eluting with 2:/l:1).
陽３．４．６、及び７のフラクションを、いずれもクロ
ロボルム：メタノール：水（２０：４：０．１）で溶離
するシリカゲルのカラムクロマトグラフィに付して、そ
れぞれのフラクションからルシノシドＤ１ルシノシドＥ
とルシノシドＦ１ルシノシド■、及びルシノシド１」が
分離される。Fractions 3.4.6 and 7 were subjected to column chromatography on silica gel eluting with chloroborum:methanol:water (20:4:0.1) to extract lucinoside D1 and lucinoside E from each fraction.
, lucinoside F1, lucinoside ■, and lucinoside 1'' are separated.
ｆＶ＆１１．５のフラクションはまずクロロホルム：メ
タノール：水（２０： ４ ： ０．１）で溶離するシ
リカゲルのクロマトグラフィに付される。得られた溶離
液を例えばヌクレオシル３Ｏ−Ｃ１０（３０±４μ、西
独、エム・ナーグル社製）カラム（７ｍｍＸ ６１ｃ＋
ｎ ）を使用し移動相としては３０％アセトニ］〜リル
水溶液を用いる高速液体クロマトグラフィに付してルシ
ノシドＦとルシノシドＧが分離される。The fV&11.5 fraction is first chromatographed on silica gel eluting with chloroform:methanol:water (20:4:0.1). The obtained eluate was applied to, for example, a Nucleosil 3O-C10 (30±4μ, manufactured by M Nagl, West Germany) column (7 mm x 61c+).
Lucinoside F and Lucinoside G are separated by high performance liquid chromatography using a 30% acetonyl acetate solution as a mobile phase.
このようにして分離されたサポニンのうちでル１２−
ジノシトＡ、Ｂ、Ｃ，Ｄ、Ｅ、Ｆ、Ｇ、Ｈ及び■はいず
れも新規物質であり、鎮咳、利尿、潤肌、火傷部回復作
用などを有し有用である。そしてこれらのサポニンは個
々のサポニンもしくはその混合物を有効成分として使用
することができる。Among the saponins isolated in this way, 12-dinocyto A, B, C, D, E, F, G, H and ■ are all new substances, and have antitussive, diuretic, moisturizing skin, and recovery from burns. It is useful because of its effects. As for these saponins, individual saponins or a mixture thereof can be used as an active ingredient.
またこの発明の方法にＪ：れば、ヘチマのような安価な
原料から上記のような有用な新規サボニンカ得られるだ
けでなく、従来朝鮮ニンジンにのみ含有されているとさ
れていた２０−８−パナキサトリオール骨格のサポニン
で細胞賦活活性を有し有用なギンゼノシドＲｅとＲ（Ｉ
ｔが得られ、極めて有用な発明である。In addition, by using the method of the present invention, not only can useful new saponins as described above be obtained from inexpensive raw materials such as loofah, but also 20-8- Useful ginsenosides Re and R (I
This is an extremely useful invention.
次にこの発明を実施例によって説明する。Next, the invention will be explained by way of examples.
実施例１
（ｉ ）ヘチマからの粗へチマサボニンの抽出下記の二
つの方法で粗へチマサポニンを抽出した。Example 1 (i) Extraction of crude loofah saponin from loofah. Crude loofah saponin was extracted by the following two methods.
（ａ ）ヘチマ地上部の全草の乾燥物５ ｋ（ｌを１ω
大に切断し、メタノール２５１！を加えて１時間還流加
熱する。得られた残渣について上記の操作をさらに２回
行ない、全抽出液を合して濾過し、減圧下６０℃を超え
ない温度でメタノールを留去しメタノールエキス７５ｇ
を得る。この乾燥エキスに水３００ ｘｌを加えて懸濁
させ、この懸濁液をアンバーライトＸＤＡ２１Ｑを水を
用いて充填した円柱カラムに注入し、次いで水を２０ｙ
ｉｌ１分の流速で流出液の着色がなくなるまで流下させ
た（３ｇ）。次にメタノール３Ωを流速１０ｙ１／分で
流下させて溶離した。溶出液を合し、減圧下６０℃を超
えない温度メタノールを留去し緑褐色の残留物１５０を
得た。(a) The dry matter of the entire above-ground part of the loofah plant is 5k (l is 1ω
Cut into large pieces, methanol 251! and heated under reflux for 1 hour. The above operation was performed twice more on the obtained residue, all extracts were combined and filtered, and methanol was distilled off under reduced pressure at a temperature not exceeding 60°C to obtain 75 g of methanol extract.
get. Add 300 xl of water to this dry extract to suspend it, inject this suspension into a cylindrical column filled with Amberlite XDA21Q using water, and then add 20xl of water.
The solution was allowed to flow down at a flow rate of 1 minute until the color of the effluent disappeared (3 g). Next, methanol (3Ω) was allowed to flow down at a flow rate of 10y1/min for elution. The eluates were combined and the methanol was distilled off under reduced pressure at a temperature not exceeding 60°C to obtain a greenish brown residue 150.
この残留物をメタノール５０ ｘｌに溶解しエーテル５
００ ｍｌ中に注入し析出物を濾別した。この操作を２
回繰返し、全析出物を４０℃で減圧乾燥し淡褐色の粗へ
ヂマサボニン１０ｇを得た。This residue was dissolved in 50 xl of methanol and 5 ml of ether.
00 ml, and the precipitate was filtered off. This operation 2
The whole precipitate was dried under reduced pressure at 40°C several times to obtain 10 g of light brown crude Hejima sabonin.
（ｂ ）ヘチマ地」一部の全草乾燥物７ 、３ ｋ（］
を１印大に切断し、メタノール４０Ｑを加え１時間還流
加熱する。得られた残漬にってい上記の操作をさらに２
回行い、全抽出液を合して濾過し減圧下６０℃を超えな
い温度でメタノールを留去した。得られた残留物を水１
Ｑに懸濁させエーテル２Ｑを加え振盪分配せしめ、その
水層をとってさらにエーテル１Ｑで振盪分配してクロロ
フィールをエーテル層に移して除いた。得られた水層部
をとって６０℃を超えない温度で減圧不蒸発乾固し１８
２ｇの褐色残留物を得た。この残留物を水５００ ｘｉ
に溶解し、ｎ −ブタノール１Ｑで２回振盪抽出する。(b) Loofah ground” Some whole plant dried matter 7,3k (]
Cut into 1-mark size pieces, add methanol 40Q, and heat under reflux for 1 hour. Repeat the above operation two more times with the resulting residue.
All extracts were combined and filtered, and methanol was distilled off under reduced pressure at a temperature not exceeding 60°C. The resulting residue was mixed with 1 part of water.
The suspension was suspended in Ether 2Q, shaken and distributed, and the aqueous layer was taken and further shaken and distributed with Ether 1Q to remove chlorophyll by transfer to the ether layer. The resulting aqueous layer was taken and dried under reduced pressure without evaporation at a temperature not exceeding 60°C.
2 g of brown residue were obtained. Add this residue to 500 xi of water.
and shake-extracted twice with 1Q of n-butanol.
ｎ−ブタノール層を分離し、水２００厭とともに振盪し
、夾雑する糖を水層に移行分離する。ｎ−ブタノール層
を６０℃を超えない温度で減圧蒸留し、その残留物をメ
タノール５０ ｍｌに溶解し、エーテル５００厭中に注
入し析出物を濾別する。この析出物を４０℃で減圧乾燥
し淡褐色の粗へヂマサポニン１２．５（Ｉを得た。The n-butanol layer is separated and shaken with 200 g of water to transfer and separate contaminating sugars to the aqueous layer. The n-butanol layer is distilled under reduced pressure at a temperature not exceeding 60 DEG C., and the residue is dissolved in 50 ml of methanol, poured into 500 ml of ether, and the precipitate is filtered off. This precipitate was dried under reduced pressure at 40°C to obtain light brown crude Hejima saponin 12.5 (I).
粗へチマサポニン７ｇを３５％メタノール３００１に溶
解し、分取用Ｃ１９充填剤（逆相用、３５〜１０５μ日
本ウォーターズ社製） １４０１１ｉを充填したカラム
に通導した。このカラムを４０％メタノール→７０％メ
タノールを用いて傾斜溶離し、その溶出液を薄層クロマ
トグラフィ（シリカゲルＧ（西独１５−
メルク社）の薄層、クロロボルム／メタノール／水、６
５：３５：１０の下層で展開し３０％硫酸を噴霧し１０
５℃で５分加熱して発色〕に付して次のような七つの７
ラクシヨンに区分し、各フラクションを蒸発乾固した。7 g of crude loofah saponin was dissolved in 35% methanol 3001, and the solution was passed through a column packed with preparative C19 packing material (for reverse phase, 35-105μ, manufactured by Nippon Waters Co., Ltd.) 14011i. This column was subjected to gradient elution using 40% methanol → 70% methanol, and the eluate was subjected to thin layer chromatography (thin layer of silica gel G (15-Merck AG, West Germany), chloroborum/methanol/water, 6
Developed in the lower layer of 5:35:10 and sprayed with 30% sulfuric acid.
Heat for 5 minutes at 5°C to develop color] to form the following seven 7s.
The mixture was divided into fractions and each fraction was evaporated to dryness.
（以下余白、次頁に続く。）
＝１６−
フラクション番号 含有サポニン
１ ルシノシドＡ、ギンゼノ
シドＲｅ及びＲｏｔ
２ ルシノシドＢと０
３ ルシノシドＤ
４ ルシノシドＥとＦ
５ ルシノシドＦとＧ
６ ルシノシド■
７ ルシノシドＨ
フラクション１ （０，３５Ｇ）とフラクション２（０
，２５ｇ）とをシリカゲルのカラム（６０〜２３０メツ
シユ、メルク社製をそれぞれ３５ｇと２５（ｌ充填した
カラム）に入れ、そのカラムをそれぞれクロロホルム：
メタノール：水（２０： ４ ： ０，１）で分画溶離
した。かくしてフラクション１からギンゼノシドＲＯ１
（９５ｍ Ｑ ＞及びルシノシドＡとギンゼノシドＲｅ
の混合物（１００ｍｇ）を得、またフラクション２から
ルシノシドＢとルシノシドＣ（７）混合物（１００ｍΩ
）を得た。(Continued in the margin below) = 16- Fraction number Containing saponin 1 Lucinoside A, ginzenoside Re and Rot 2 Lucinoside B and 0 3 Lucinoside D 4 Lucinoside E and F 5 Lucinoside F and G 6 Lucinoside ■ 7 Lucinoside H Fraction 1 (0,35G) and fraction 2 (0
, 25 g) were placed in a silica gel column (60-230 mesh, manufactured by Merck & Co., Ltd., packed with 35 g and 25 (L), respectively), and the columns were filled with chloroform:
Fractional elution was performed with methanol:water (20:4:0.1). Thus from fraction 1 ginsenoside RO1
(95m Q > and lucinoside A and ginsenoside Re
A mixture (100 mg) of lucinoside B and lucinoside C (7) was obtained from fraction 2 (100 mΩ
) was obtained.
上記のルシノシドＡとギンゼノシドＲｅとの混合物とル
シノシドＢどＣの混合物をそれぞれ、シリカゲル（１０
ｇ、 ６０〜２３０メツシユ、メルり社！１１）のカラ
ムに入れ、そのカラムをそれぞれクロロボルム：メタノ
ール：酢酸エチル：水（２：２＋４：１）で溶出し、ル
シノシドＡ（２５ｍａ）とギンゼノシドＲｅ （５０ｍ
ａ ）並びにルシノシドＢ（３０＋１１０）とルシノ
シドＣ（３０＋ｎ Ｏ）をそれぞれ得た。The mixture of lucinoside A and ginzenoside Re and the mixture of lucinoside B and C were each mixed with silica gel (10
g, 60-230 meshes, Merurisha! 11), and the columns were eluted with chloroborum:methanol:ethyl acetate:water (2:2+4:1), and lucinoside A (25ma) and ginsenoside Re (50ma) were added to the column.
a ) and lucinoside B (30+110) and lucinoside C (30+n O) were obtained, respectively.
フラクション３ （０，３５（＋） 、４ （ｌａ ）
、６（０，５０１Ｊ）及び７ （０，３０ＣＩ）のそれ
ぞれを、シリカゲル（６０〜２３０メツシユ、メルク社
製）をそれぞれ３５Ｇ 、 １００ＣＩ、 ５０（＋及
び３０（ｌ充填したカラムに入れ、クロロホルム・メタ
ノール・水（２０：４：０．１）で分画溶離し、フラク
ション３からルシノシドＤ （１５＋１１（Ｊ） 、フ
ラクション４からはルシノシドＥ （２６３＋１１（］
）及びルシノシドＦ （４１５ｍａ ） 、フラクシ
ョン６からはルシノシドＩ（１０１１１ｇ）、並びにフ
ラクション７からはルシノシド１」（１０５１１１＜１
）をそれぞれ得た。Fraction 3 (0,35(+), 4 (la)
, 6 (0,501 J) and 7 (0,30 CI) were placed in columns filled with silica gel (60-230 mesh, manufactured by Merck & Co., Ltd.) at 35 G, 100 CI, 50 (+ and 30 (L), respectively, and chloroform. Fractional elution with methanol/water (20:4:0.1) yields lucinoside D (15+11(J)) from fraction 3 and lucinoside E (263+11(J) from fraction 4).
) and lucinoside F (415 ma), from fraction 6 lucinoside I (10111 g), and from fraction 7 lucinoside 1''(105111<1
) were obtained respectively.
フラクション５ （０，２５０）をシリカゲル（２５（
１）を充１眞したカラムに入れ、そのカラムをクロロホ
ルム：メタノール：水（２０： ４ ： ０．１）の下
層で溶出し、その濃縮物を高速液体クロマトグラフィ〔
日本ウォーターズ社製ＡＬＣ／ＧＰＣ型高速液体りロマ
トグラフ二カラムはヌクレオシル３０・Ｃ，９（３０±
４μ、西独エム・ナーゲル社製）充填（７ｍｍφ×６１
の）；移動相は３０％アセトニトリル）に付して、ルシ
ノシドＦ（５５ｎ＋ｇ）とルシノシドＧ（５５ｍｇ）と
を得た。Fraction 5 (0,250) was dissolved in silica gel (25 (
1) was placed in a column filled with 1), the column was eluted with the lower layer of chloroform:methanol:water (20:4:0.1), and the concentrate was subjected to high performance liquid chromatography [
Nippon Waters ALC/GPC type high performance liquid chromatograph two columns are Nucleosil 30・C,9 (30±
4μ, made by West German M. Nagel) filling (7mmφ x 61
); mobile phase was 30% acetonitrile) to obtain lucinoside F (55n+g) and lucinoside G (55 mg).
なおこの発明の対象であるサポニン類の物性は次の第１
，２及び３表に示すとおりである。The physical properties of the saponins that are the subject of this invention are as follows:
, as shown in Tables 2 and 3.
（以下余白、次頁に続く。） 特開昭ＧＯ−４８９９５（７） （４）−〇閃− ｑり （） 凶−〇工一 鼎 ４２ ηｏｏ−Φ寸Φ囚トロわ■ＱＮ寸■Ｑ(Margin below, continued on next page.) Tokukai Sho GO-48995 (7) (4) -〇Flash- qri () Evil-〇Koichi Ding 42 ηoo-Φ size Φ prisoner ■QN size■Q
Claims (1)
−Ｄ−グルコピラノシド）−２８−Ｑ−β−Ｄ−グルコ
ピラノシド：アルジュノールｆｆ−３−０−（β−Ｄ−
グルコピラノシド）−２８−Ｑ−β−Ｄ−グルコピラノ
シド； マカエリンＦＩＱ−３−０−（β−Ｄ−グルコピラノシ
ド）−２８−Ｑ−β−Ｄ−グルコピラノシド；２−α−
ヒドロキシギプソゲニン−３−０−（β−Ｄ−グルコピ
ラノシド）−２８−０−β−Ｄ−グルコピラノシド； ヘデラゲニン−３−０−（β−Ｄ−グルコピラノシド）
−２８−Ｑ−β−Ｄ−グルコピラノシド；キプソゲニン
−３−０−（β−Ｄ−グルコピラノシド）−２８−Ｑ−
〇−〇−グルコピラノシド；マスリン酸−３−０−（β
−Ｄ−グルコピラノシド）−２８−０−β−Ｄ−グルコ
ピラノシド：オレアノール酸−３−０−（β−Ｄ−グル
コピラノシド）−２８−Ｑ−β−Ｄ−グルコピラノシド
；及び アルシュノールＭ−３−〇−β−Ｄ−グルコピラノシド
からなる群より選択される新規サポニン。 ２、ヘチマ（ルファ・シリンドリカ、ロエム）の地上部
もしくは地下部を脱脂処理するがせずして下記方法： （ａ ）水、低級アルコールまたは含水低級アルコール
にて抽出し、その濃縮物を水中に懸濁させその懸濁液を
巨大網状構造で多孔性の架橋されたポリスチレン系樹脂
吸着剤と接触させた後、低級アルコールまたは低級アル
コール含有水で溶離し、その溶出液を濃縮し、その濃縮
物を低級アルコールに溶解し脂溶性有機溶媒に注入し生
成した析出物を減圧乾燥するか、または （ｂ ）水、低級アルコールまたは含水低級アルコール
で抽出し、その濃縮物を、そのままｎ−ブタノールと水
に分配するか、又は水ど脂溶性有機溶媒に分配しその水
居部を濃縮して得られた濃縮物をｎ−ブタノールと水に
分配して、そのｎ−ブタノール部を減圧乾燥し、残留物
を低級アルコールに溶解し脂溶性有機溶媒に注入し生成
した析出物を減圧乾燥して、粗へヂマサボニンを得、そ
の粗へチマサボニンを低級アルコールに溶解し、その溶
液を逆相シリカゲルカラムクロマトグラフィに付し、得
られたフラクションをさらにシリカゲルカラムクロマト
グラフィ及び／又は逆相シリカゲルの高速液体クロマト
グラフィに付して分離・精製することからなる、 ２１−β−ヒドロキシへデラゲニン−３−０−（β−Ｄ
−グルコピラノシド）−２８−Ｑ−β−Ｄ−グルコピラ
ノシド；アルシュノールＩＱ−３−０−（β−Ｄ−グル
コピラノシド）−２８−Ｑ−β−Ｄ−グルコビラノシド
； マカエリンｌ−３−０−（β−Ｄ−グルコピラノシド）
−２８−０−β−Ｄ−グルコピラノシド；２−α−ヒド
ロキシプソゲニン−３＝Ｏ−（β−Ｄ−グルコピラノシ
ド）−２８−０−β−Ｄ−グルコピラノシド；ヘデラゲ
ニン−３−０−（β−Ｄ−グルコピラノシド）−２８−
０−β−Ｄ−グルコピラノシド； ギブソゲニン−３−０−（β−Ｄ−グルコピラノシド）
−２８−０−β−Ｄ−グルコピラノシド；マスリン酸−
３−０−（β−Ｄ−グルコピラノシド）−２８−Ｑ−β
−Ｄ−グルコピラノシド；オレアノール酸−３−０−（
β−Ｄ−グルコピラノシド）−２８−０−β−Ｄ−グル
コピラノシド；及び アルシュノールＭ−３−０−β−Ｄ−グルコピラノシド
；並びにギンゼノシドＲｅ及びギンゼノシドＲ（１＋を
得ることを特徴とするサポニン類の製造法。1.21-β-hydroxyhederagenin-3-〇-(β
-D-glucopyranoside) -28-Q-β-D-glucopyranoside: Arjunol ff-3-0-(β-D-
macaerin FIQ-3-0-(β-D-glucopyranoside)-28-Q-β-D-glucopyranoside; 2-α-
Hydroxygypsogenin-3-0-(β-D-glucopyranoside)-28-0-β-D-glucopyranoside; Hederagenin-3-0-(β-D-glucopyranoside)
-28-Q-β-D-glucopyranoside; Kypsogenin-3-0-(β-D-glucopyranoside)-28-Q-
〇-〇-glucopyranoside; maslinic acid-3-0-(β
-D-glucopyranoside)-28-0-β-D-glucopyranoside: Oleanolic acid-3-0-(β-D-glucopyranoside)-28-Q-β-D-glucopyranoside; and Alshnol M-3-〇- A novel saponin selected from the group consisting of β-D-glucopyranoside. 2. The above-ground or underground parts of loofah (Rufa cylindrica, loem) are degreased, but the following method: (a) Extract with water, lower alcohol, or water-containing lower alcohol, and add the concentrate to water. After suspending and contacting the suspension with a porous cross-linked polystyrene resin adsorbent with a large network structure, it is eluted with a lower alcohol or lower alcohol-containing water, and the eluate is concentrated to form a concentrate. Dissolve it in a lower alcohol and inject it into a fat-soluble organic solvent and dry the resulting precipitate under reduced pressure, or (b) extract it with water, a lower alcohol, or a water-containing lower alcohol, and add the concentrate directly to n-butanol and water. Alternatively, the concentrate obtained by partitioning into water or a fat-soluble organic solvent and concentrating the water portion is distributed between n-butanol and water, and the n-butanol portion is dried under reduced pressure to remove the remaining The product was dissolved in a lower alcohol and poured into a fat-soluble organic solvent, and the resulting precipitate was dried under reduced pressure to obtain crude Hejima sabonin.The crude Hejima sabonin was dissolved in a lower alcohol, and the solution was subjected to reverse-phase silica gel column chromatography. 21-β-hydroxyhederagenin-3-0-(β-D
-glucopyranoside)-28-Q-β-D-glucopyranoside; alshnol IQ-3-0-(β-D-glucopyranoside)-28-Q-β-D-glucopyranoside; macaerin l-3-0-(β- D-glucopyranoside)
-28-0-β-D-glucopyranoside; 2-α-hydroxypsogenin-3=O-(β-D-glucopyranoside) -28-0-β-D-glucopyranoside; hederagenin-3-0-(β- D-glucopyranoside)-28-
0-β-D-glucopyranoside; Gibsogenin-3-0-(β-D-glucopyranoside)
-28-0-β-D-glucopyranoside; maslinic acid-
3-0-(β-D-glucopyranoside)-28-Q-β
-D-glucopyranoside; oleanolic acid-3-0-(
β-D-glucopyranoside)-28-0-β-D-glucopyranoside; and Alshnol M-3-0-β-D-glucopyranoside; and ginsenoside Re and ginsenoside R (saponins characterized by obtaining 1+) Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58155552A JPS6048995A (en) | 1983-08-24 | 1983-08-24 | Novel saponin and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58155552A JPS6048995A (en) | 1983-08-24 | 1983-08-24 | Novel saponin and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6048995A true JPS6048995A (en) | 1985-03-16 |
| JPH0471080B2 JPH0471080B2 (en) | 1992-11-12 |
Family
ID=15608555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58155552A Granted JPS6048995A (en) | 1983-08-24 | 1983-08-24 | Novel saponin and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6048995A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61205203A (en) * | 1985-03-08 | 1986-09-11 | Shiseido Co Ltd | External preparation for skin |
| KR100315097B1 (en) * | 1999-02-09 | 2001-11-26 | 박명규 | Separation Method for Panaxadiol and Panaxatriol Using Benzene Ethylene Resin |
| JP2002500088A (en) * | 1998-01-12 | 2002-01-08 | ハー マジェスティ イン ライト オブ カナダ アズ リプレゼンティッド バイ ザ ミニスター オブ アグリカルチャー アンド アグリ−フード カナダ | Methods for isolation, recovery and purification of non-polar extracts |
| JP2004189676A (en) * | 2002-12-12 | 2004-07-08 | Sansho Seiyaku Co Ltd | External preparation for ameliorating damaged skin |
-
1983
- 1983-08-24 JP JP58155552A patent/JPS6048995A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61205203A (en) * | 1985-03-08 | 1986-09-11 | Shiseido Co Ltd | External preparation for skin |
| JP2002500088A (en) * | 1998-01-12 | 2002-01-08 | ハー マジェスティ イン ライト オブ カナダ アズ リプレゼンティッド バイ ザ ミニスター オブ アグリカルチャー アンド アグリ−フード カナダ | Methods for isolation, recovery and purification of non-polar extracts |
| KR100315097B1 (en) * | 1999-02-09 | 2001-11-26 | 박명규 | Separation Method for Panaxadiol and Panaxatriol Using Benzene Ethylene Resin |
| JP2004189676A (en) * | 2002-12-12 | 2004-07-08 | Sansho Seiyaku Co Ltd | External preparation for ameliorating damaged skin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471080B2 (en) | 1992-11-12 |
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