JPH0471080B2 - - Google Patents
Info
- Publication number
- JPH0471080B2 JPH0471080B2 JP58155552A JP15555283A JPH0471080B2 JP H0471080 B2 JPH0471080 B2 JP H0471080B2 JP 58155552 A JP58155552 A JP 58155552A JP 15555283 A JP15555283 A JP 15555283A JP H0471080 B2 JPH0471080 B2 JP H0471080B2
- Authority
- JP
- Japan
- Prior art keywords
- glucopyranoside
- water
- acid
- lower alcohol
- lucinoside
- 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 - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 229930182490 saponin Natural products 0.000 claims description 29
- 150000007949 saponins Chemical class 0.000 claims description 29
- 235000017709 saponins Nutrition 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 17
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- 239000000284 extract Substances 0.000 claims description 10
- 150000008505 β-D-glucopyranosides Chemical class 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 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
- 238000000605 extraction Methods 0.000 claims description 5
- 229930182494 ginsenoside Natural products 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 244000280244 Luffa acutangula Species 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 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
- 229940089161 ginsenoside Drugs 0.000 claims 1
- 238000005192 partition Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 84
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 244000302544 Luffa aegyptiaca Species 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 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
- 239000000203 mixture Substances 0.000 description 8
- 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 description 7
- 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 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- YURJSTAIMNSZAE-HHNZYBFYSA-N ginsenoside Rg1 Chemical compound O([C@@](C)(CCC=C(C)C)[C@@H]1[C@@H]2[C@@]([C@@]3(C[C@@H]([C@H]4C(C)(C)[C@@H](O)CC[C@]4(C)[C@H]3C[C@H]2O)O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)C)(C)CC1)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O YURJSTAIMNSZAE-HHNZYBFYSA-N 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YURJSTAIMNSZAE-UHFFFAOYSA-N UNPD89172 Natural products C1CC(C2(CC(C3C(C)(C)C(O)CCC3(C)C2CC2O)OC3C(C(O)C(O)C(CO)O3)O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O YURJSTAIMNSZAE-UHFFFAOYSA-N 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- CBEHEBUBNAGGKC-UHFFFAOYSA-N ginsenoside Rg1 Natural products CC(=CCCC(C)(OC1OC(CO)C(O)C(O)C1O)C2CCC3(C)C2C(O)CC4C5(C)CCC(O)C(C)(C)C5CC(OC6OC(CO)C(O)C(O)C6O)C34C)C CBEHEBUBNAGGKC-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- -1 methanol or ethanol Chemical compound 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
- HPVKSGLGOKNQON-UHFFFAOYSA-N 3-O-(beta-D-galactopyranosyl-(1->3)-beta-D-glucopyranosyl)serjanic acid 28-O-beta-D-glucopyranoside Natural products COC(=O)C1(C)CCC2(CCC3(C)C(=CCC4C5(C)CCC(OC6OC(CO)C(O)C(OC7OC(CO)C(O)C(O)C7O)C6O)C(C)(C)C5CCC34C)C2C1)C(=O)OC8OC(CO)C(O)C(O)C8O HPVKSGLGOKNQON-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
- 101100008049 Caenorhabditis elegans cut-5 gene Proteins 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 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
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000954 anitussive effect Effects 0.000 description 1
- 229940124584 antitussives Drugs 0.000 description 1
- 239000007864 aqueous solution 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
- 239000000356 contaminant Substances 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002934 diuretic Substances 0.000 description 1
- 230000001882 diuretic effect Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000035876 healing Effects 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
- 239000000463 material Substances 0.000 description 1
- 239000000401 methanolic extract 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
- 238000012856 packing Methods 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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002594 sorbent 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)
Description
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。
この発明における“ヘチマ”としては、ウリ科
の植物で学名ルフア・シリンドリカ・ロエム
（Luffa cylindrica Roem.）及びこれと植物学的
に類縁の植物が含まれる。
最近、ヘチマの葉から、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
シドが抽出されたとの報告がある〔Nanking
Institute of Materia Medica（Nanking Peop.
R.China）Chung 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
て研究を行つた結果、９つの新規のサポニン〔ル
シノシド（Lucynocide）Ａ、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Rg1が抽出されこ
の発明に到達した。
この発明の新規のサポニン類は、
一般式（）：
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−ヒドロキシヘデラゲニン
−３−Ｏ−（β−Ｄ−グルコピラノシド）−28−Ｏ
−β−グルコピラノシド、〔ルシノシドＡ
（LA1）〕；
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、具体名がアルジユノール酸−３−Ｏ−
（β−Ｄ−グルコピラノシド）−28−Ｏ−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Ｂ−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−Ｏ−（β−Ｄ−グルコピラノ
シド）−28−Ｏ−β−Ｄ−グルコピラノシド、〔ル
シノシドＣ（LB1）〕；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−３−Ｏ−（β−Ｄ−グルコピラノ
シド）−28−Ｏ−β−Ｄ−グルコピラノシド）−28
−Ｏ−β−Ｄ−グルコピラノシド、〔ルシノシド
Ｄ（LD1）〕；
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−Ｏ−（β−Ｄ−グルコピ
ラノシド）−28−Ｏ−β−Ｄ−グルコピラノシド、
〔ルシノシドＥ（LC2）〕；
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−Ｏ−（β−Ｄ−グルコピラノシド）−28
−Ｏ−β−Ｄ−グルコピラノシド〔ルシノシドＦ
（LD2）〕；
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、
具体名がスマリン酸−３−Ｏ−（β−Ｄ−グルコ
ピラノシド）−28−Ｏ−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−Ｏ−（β−Ｄ−グルコピラノシ
ド）−28−Ｏ−β−Ｄ−グルコピラノシド〔ルシ
ノシドＨ（LD3）〕；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ジユノ
ール酸−３−Ｏ−（β−Ｄ−グルコピラノシド）、
〔ルシノシド（LE1）〕である。
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Rg1は次の方法によつて得ることができ
る。
この発明の方法においては、まず原料のヘチマ
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。
次いで下記のような方法で抽出が行われ粗ヘチ
マサポニンが得られる。
(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
繰り返して行つてもよい。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XAD−２、いずれ
もローム・アンド・ハース社製など）に接着吸
着させる。これらの吸着剤は含有サポニン量の
20〜300倍量、望ましくは40〜150倍量用いられ
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
縮し濃縮物を低級アルコールに溶解しエーテ
ル、ｎ−ヘキサン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ヘチマサポ
ニンが得られる。
(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つてもよ
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、又は脂溶性有機溶媒
（エーテル、ｎ−ヘキサンなど）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
燥して粗ヘチマサポニンが得られる。
上記のようにして得られる粗エチマサポニン
は、前記の新規サポニン物質のルシノシドＡ、
Ｂ、Ｃ、Ｄ、Ｅ、Ｆ、Ｇ、Ｈ及び並びに公知物
質のギンゼノシドReとRg1を含有し、これらの各
成分は次の方法によつて分離される。
すなわち上記の粗ヘチマサポニンを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
クロマトグラフイに付される。例えば分取用C18
充填剤（35〜105μ、日本ウオーターズ製）を充
填したカラムを用い溶出溶媒としては前記のごと
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
させた溶離剤で傾斜溶離するクロマトグラフイで
ある。得られた溶出液を、薄層クロマトグラフイ
〔例えばシリカゲルＧ（西独メルク社）の薄層を用
いてクロロホルム／メタノール／水の65：35：10
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〕に対して次のような七つのフ
ラクシヨンに区分され、これらフラクシヨンは蒸
発乾固される。
フラクシヨン番号 含有サポニン
１ ルシノシドＡ、ギンゼノシドReとRg1
２ ルシノシドＢとＣ
３ ルシノシドＤ
５ ルシノシドＦとＧ
６ ルシノシドＩ
７ ルシノシドＨ
No.１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イに付してギ
ンゼノシドRg1、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イに対してルシノシドＡとギ
ンゼノシドReが分離される。
No.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イに付してル
シノシドＢとルシノシドＣの混合液を得、これを
さらにクロロホルム：メタノール：酢酸エチル：
水（２：２：４：１）で溶離するシリカゲルのカ
ラムクロマトグラフイに付してルシノシドＢとル
シノシドＣが分離される。
No.３、４、６、及び７のフラクシヨンを、いず
れもクロロホルム：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
ラフイに付して、それぞれのフラクシヨンからル
シノシドＤ、ルシノシドＥとルシノシドＦ、ルシ
ノシドＩ、及びルシノシドＨが分離される。
No.５のフラクシヨ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イに付される。得られた溶離
液を例えばヌクレオシル30・C18（30±4μ、西独、
エム・ナーゲル社製）カラム（７mm×61cm）を使
用し移動相としては30％アセトニトリル水溶液を
用いる高速液体クロマトグラフイに付してルシノ
シドＦとルシノシドＧが分離される。
このようにして分離されたサポニンのうちでル
シノシドＡ、Ｂ、Ｃ、Ｄ、Ｅ、Ｆ、Ｇ、Ｈ及びＩ
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。
またこの発明の方法によれば、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ポニン
が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−Ｓ−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Rg1が得られ、極めて有用
な発明である。
次にこの発明を実施例によつて説明する。
実施例 １
() ヘチマからの粗ヘチマサポニンの抽出
下記の二つの方法で粗ヘチマサポニンを抽出
した。
(a) ヘチマ地上部の全草の乾燥物５Kgを１cm大
に切断し、メタノール25ml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300mlを加えて懸濁させ、
この懸濁をアンバーライトXDA21を水を
用いて充填した円柱カラムに注入し、次いで
水を20ml／分の流速で流出液の着色がなくな
るまで流下させた（３）。次にメタノール
３を流速10ml／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15ｇを得
た。この残留物をメタノール50mlに溶解しエ
ーテル500ml中に注入し析出物を濾別した。
この操作を２回繰返し、全折出物を40℃で減
圧乾燥し淡褐色の粗ヘチマサポニン10ｇを得
た。
(b) ヘチマ地上部の全草乾燥物7.3Kgを１cm大
に切断し、メタノール40を加え１時間還流
加熱する。得られた残渣につてい上記の操作
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に懸濁させ
エーテル２を加え振盪分配せしめ、その水
層をとつてさらにエーテル１で振盪分配し
てクロロフイールをエーテル層に移して除い
た。得られた水層部をとつて60℃を超えない
温度で減圧下蒸発乾固し182ｇの褐色残留物
を得た。この残留物を水500mlに溶解し、ｎ
−ブタノール１で２回振盪抽出する。ｎ−
ブタノール層を分離し、水200mlとともに振
盪し、爽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50mlに溶解
し、エーテル500ml中に注入し析出部を濾別
する。この析出物を40℃で減圧乾燥し淡褐色
の粗ヘチマサポニン12.5ｇを得た。
() 粗ヘチマサポニンからの新規ヘチマサポニ
ン及びギンゼノシドReとRg1の分離
粗ヘチマサポニン７ｇを35％メタノール300
mlに溶解し、分取用C18充填剤（逆相用、35〜
105μ日本ウオーターズ社製）140ml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イ〔シリカゲルＧ
（西独メルク社）の薄層、クロロホルム／メタ
ノール／水、65：35：10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ヨンに区分し、各
フラクシヨンを蒸発乾固した。
フラクシヨン番号 含有サポニシ
１ ルシノシドＡ、ギンゼノシドRe及びRg1
２ ルシノシドＢとＣ
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Ｉ
７ ルシノシドＨ
フラクシヨン１（0.35ｇ）とフラクシヨン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25ｇ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。かくしてフラクシヨン１からギンゼノシ
ドRg1（95mg）及びルシノシドＡとギンゼシドRe
の混合物（100mg）を得、またフラクシヨン２か
らルシノシドＢとルシノシドＣの混合物（100mg）
を得た。
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とＣの混合物をそれぞれ、シ
リカゲル（10ｇ、60〜230メツシユ、メルク社製）
のカラムに入れ、そのカラムをそれぞれクロロホ
ルム：メタノール：酢酸エチル：水（２：２：
４：１）で溶出し、ルシノシドＡ（25mg）とギン
ゼノシドRe（50mg）並びにルシノシドＢ（30mg）
とルシノシドＣ（30mg）をそれぞれ得た。
フラクシヨン３（0.35ｇ）、４（１ｇ）、６（0.50
ｇ）及び７（0.30ｇ）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35
ｇ、100ｇ、50ｇ及び30ｇ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、フラクシヨン３からルシノシドＤ
（15mg）、フラクシヨン４からはルシノシドＥ（263
mg）及びルシノシドＦ（415mg）、フラクシヨン６
からはルシノイドＩ（10mg）、並びにフラクシヨン
７からはルシノシドＨ（105mg）をそれぞれ得た。
フラクシヨン５（0.25ｇ）をシリカゲル（25ｇ）
を充填したカラムに入れ、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イ
〔日本ウオーターズ社製ALC／GPC型高速液体ク
ロマトグラフ；カラムはヌクレオシル30・C18（30
±4μ、西独エム・ナーゲル社製）充填（７mmφ
×61cm）；移動相は30％アセトニトリル〕に付し
て、ルシノシドＦ（55mg）とルシノシドＧ（55mg）
とを得た。
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。
This invention relates to novel saponins contained in loofah and a method for producing the same. In the present invention, "loofah" includes plants belonging to the Cucurbitaceae family, scientific name Luffa cylindrica Roem., and plants botanically related thereto. Recently, it has been reported that oleanolic acid, palmitic acid, oleanolic acid-3-glucoside, and oleanolic acid-3-glucosyl-28-diglucoside were extracted from loofah leaves [Nanking
Institute of Materia Medica (Nanking Peop.
R.China) Chung Tsao Yao; 1980, 11(2), 5564
(ch)〕. As a result of researching the ingredients contained in loofah, the inventor of this invention found nine new saponins [Lucynocide A, B, C, D, E,
The present invention was achieved by extracting ginsenosides Re and Rg 1 of known Korean ginseng saponins (referred to as F, G, H, and I). The novel saponins of this invention have the general formula (): R 1 is a hydroxymethyl group, R 2 is a β-D-glucopyranoside group, R 3 is a hydroxy group, and R 4 is a hydrogen atom, and the specific name is 21-β-hydroxyhederagenin-3-O-(β -D-glucopyranoside)-28-O
-β-glucopyranoside, [lucinoside A
(LA 1 )]; R 1 is a hydroxymethyl group, R 2 is a β-D-glucopyranoside group, R 3 is a hydrogen atom, and R 4 is a hydroxy group, and the specific name is aldiunoleic acid-3-O-
(β-D-glucopyranoside)-28-O-β-D glucopyranoside, [Lucinoside B (LB 2 )]; R 1 is a methyl group, R 2 is a BD-glucopyranoside group, R 3
is a hydroxy group and R 4 is a hydrogen atom, and the specific name is macaelic acid-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside, [lucinoside C (LB 1 )]; R 1 is formyl group, R 2 is β-
D-glucopyranoside group, R 3 is a hydrogen atom and R 4
is a hydroxy group, and the specific name is 2-α-hydroxygypsogenin-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside)-28
-O-β-D-glucopyranoside, [Lucinoside D (LD 1 )]; R 1 is a hydroxymethyl group, R 2 is a β-D-glucopyranoside group, R 3 and R 4 are hydrogen atoms, and the specific name is hederagenin. -3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside,
[Lucinoside E (LC 2 )]; R 1 is a formyl group, R 2 is a β-D-glucopyranoside group, R 3 and R 4 are hydrogen atoms, and the specific name is gypsogenin-3-O- (β-D-glucopyranoside) −28
-O-β-D-glucopyranoside [Lucinoside F
(LD 2 )]; R 1 is a methyl group, R 2 is a β-D-glucopyranoside group, R 3 is a hydrogen atom, and R 4 is a hydroxy group,
The specific name is sumaric acid-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside, [lucinoside G (LD 4 )]; R 1 is a methyl group, R 2 is β-D- Glucopyranoside group, and R 3 and R 4 are hydrogen atoms, and the specific name is oleanolic acid-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside [lucinoside H (LD 3 )]; and R 1 is a hydroxymethyl group, R 2 and R 3 are hydrogen atoms, and R 4 is a hydroxy group, and the specific name is aldiunoleic acid-3-O-(β-D-glucopyranoside),
[Rusinoside (LE 1 )]. These new saponins and the known ginsenosides Re and Rg 1 can be obtained by the following method. In the method of the present 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. Next, extraction is performed in the following manner to obtain crude loofah saponin. (a) The raw material is heated under reflux with about 2 to 5 times its weight of water, or a lower alcohol such as methanol or ethanol, or a water-containing lower alcohol, and then filtered 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 is adsorbed using a large network-structured porous cross-linked polystyrene resin adsorbent (e.g. Amberlite).
XAD-1, Amberlite XAD-2, both manufactured by Rohm and Haas, etc.). These adsorbents contain saponin content.
The amount used is 20 to 300 times, preferably 40 to 150 times. Next, wash the resin thoroughly with water, and then wash it with a lower alcohol such as ethanol or methanol.
Elute with water containing about 30% or more lower alcohol, concentrate, dissolve the concentrate in lower alcohol, inject into a fat-soluble organic solvent such as ether or n-hexane, and dry the resulting precipitate under reduced pressure to obtain crude loofah saponin. It will be done. (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 and distributed by adding water and shaking, or distributed in a fat-soluble organic solvent (ether, n-hexane, etc.). The aqueous layer is concentrated, the resulting concentrate is dissolved in n-butanol, water is added, shaken and distributed, the resulting n-butanol is concentrated, and the concentrate is dissolved in lower alcohol. , and injected into a fat-soluble organic solvent such as ether, and the resulting precipitate is dried under reduced pressure to obtain crude loofah saponin. The crude Etima saponin obtained as described above contains the above-mentioned new saponin substance lucinoside A,
It contains B, C, D, E, F, G, H, and the known substances ginsenoside Re and Rg 1 , and each of these components is separated by the following method. That is, the above-mentioned crude loofah saponin 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 preparative C 18
A column packed with a packing material (35 to 105μ, manufactured by Nippon Waters) was used, and the eluent used was the above-mentioned lower alcohol-water mixture whose concentration was varied from 40% lower alcohol to 70% lower alcohol. This is a chromatography with gradient elution. The obtained eluate was subjected to thin-layer chromatography [e.g., using a thin layer of silica gel G (Merck & Co., Ltd., West Germany) and chloroform/methanol/water 65:35:10.
The mixture was developed in the lower layer, sprayed with 30% sulfuric acid, and heated at 105°C for 5 minutes to develop color], which was divided into the following seven fractions, and these fractions were evaporated to dryness. Fraction number Saponin contained 1 Lucinoside A, ginsenoside Re and Rg 1 2 Lucinoside B and C 3 Lucinoside D 5 Lucinoside F and G 6 Lucinoside I 7 Lucinoside H For the No. 1 fraction, first chloroform:methanol:water (20:4: Column chromatography on silica gel eluting with 0.1) gives ginsenoside Rg 1 and a mixture of ginsenoside Re and lucinoside A. The latter mixture was then further mixed with chloroform:methanol:ethyl acetate:
Lucinoside A and ginsenoside Re are separated by column chromatography on silica gel eluting with water (2:2:4:1). Regarding No. 2 fraction, first, it was subjected to column chromatography on silica gel eluting with chloroform:methanol:water (20:4:0.1) to obtain a mixture of lucinoside B and lucinoside C, which was further mixed with chloroform:methanol. :Ethyl acetate:
Lucinoside B and C are separated by column chromatography on silica gel, eluting with water (2:2:4:1). Fractions No. 3, 4, 6, and 7 were all mixed with chloroform:methanol:water (20:4:
By column chromatography on silica gel eluting with 0.1), lucinoside D, lucinoside E, lucinoside F, lucinoside I, and lucinoside H are separated from each fraction. Fraction No. 5 is first chromatographed on silica gel eluting with chloroform:methanol:water (20:4:0.1). The obtained eluent is, for example, Nucleosil 30・C 18 (30±4μ, West Germany,
Lucinoside F and G are separated by high performance liquid chromatography using a column (manufactured by M. Nagel) (7 mm x 61 cm) and a 30% acetonitrile aqueous solution as the mobile phase. Of the saponins thus isolated, lucinosides A, B, C, D, E, F, G, H and I
Both are new substances and have antitussive, diuretic, skin moisturizing,
It is useful because it has a healing effect on burns. As for these saponins, individual saponins or a mixture thereof can be used as an active ingredient. Furthermore, according to the method of this invention, not only the above-mentioned useful new saponins can be obtained from inexpensive raw materials such as loofah, but also 20-S-panaki, which was conventionally thought to be contained only in Korean carrots. Ginsenosides Re and Rg 1 , which are saponins with a satriol skeleton and have cell activating activity, are obtained and are an extremely useful invention. Next, the present invention will be explained with reference to examples. Example 1 () Extraction of crude loofah saponin from loofah Crude loofah saponin was extracted by the following two methods. (a) Cut 5 kg of dried whole Luffa loofah plant into 1 cm pieces, add 25 ml of methanol, and heat under reflux for 1 hour. The above operation is carried out twice more on the obtained residue, all the extracts are combined and filtered, and methanol is distilled off under reduced pressure at a temperature not exceeding 60°C to obtain 75 g of methanol extract. Add 300ml of water to this dry extract and suspend it.
This suspension was injected into a cylindrical column packed with Amberlite XDA21 using water, and then water was allowed to flow down at a flow rate of 20 ml/min until the color of the effluent disappeared (3). Next, methanol 3 was eluted by flowing down at a flow rate of 10 ml/min.
The eluates were combined and methanol was distilled off under reduced pressure at a temperature not exceeding 60°C to obtain 15 g of a greenish brown residue. This residue was dissolved in 50 ml of methanol, poured into 500 ml of ether, and the precipitate was filtered off.
This operation was repeated twice, and the entire precipitate was dried under reduced pressure at 40°C to obtain 10 g of light brown crude loofah saponin. (b) Cut 7.3 kg of dried whole plant of loofah above ground into 1 cm pieces, add 40 g of methanol and heat under reflux for 1 hour. The above operation was carried out twice more on the obtained residue, and all the extracts were combined and filtered, and methanol was distilled off under reduced pressure at a temperature not exceeding 60°C. The obtained residue was suspended in water 1, ether 2 was added, and the suspension was shaken for distribution.The aqueous layer was taken and further shaken and distributed with ether 1, and chlorophyll was transferred to the ether layer and removed. The resulting aqueous layer was removed and evaporated to dryness under reduced pressure at a temperature not exceeding 60°C to obtain 182 g of a brown residue. Dissolve this residue in 500 ml of water and
-Extract by shaking twice with 1 part of butanol. n-
Separate the butanol layer and shake with 200 ml of water to transfer and separate the contaminant sugar into the aqueous layer. n
- Distill the butanol layer under reduced pressure at a temperature not exceeding 60°C, dissolve the residue in 50 ml of methanol, pour into 500 ml of ether and filter off the precipitate. This precipitate was dried under reduced pressure at 40°C to obtain 12.5 g of light brown crude loofah saponin. () Separation of new loofah saponin and ginzenoside Re and Rg 1 from crude loofah saponin 7 g of crude loofah saponin was dissolved in 35% methanol 300 ml.
Dissolve in preparative C 18 sorbent (for reversed phase, 35~
The column was filled with 140 ml of 105μ Nippon Waters Co., Ltd.). This column was subjected to gradient elution using 40% methanol → 70% methanol, and the eluate was subjected to thin layer chromatography [Silica gel G
(Merck & Co., West Germany), developed in a lower layer of chloroform/methanol/water, 65:35:10, sprayed with 30% sulfuric acid, and heated at 105°C for 5 minutes to develop color]. The mixture was divided into two fractions and each fraction was evaporated to dryness. Fraction number Containing saponites 1 Lucinoside A, Ginsenoside Re and Rg 1 2 Lucinoside B and C 3 Lucinoside D 4 Lucinoside E and F 5 Lucinoside F and G 6 Lucinoside I 7 Lucinoside H Fraction 1 (0.35g) and Fraction 2
(0.25 g) was placed in a silica gel column (60 to 230 mesh, column packed with 35 g and 25 g of Merck Co., Ltd., respectively), and the column was subjected to fractional elution with chloroform:methanol:water (20:4:0.1). did. Thus, from fraction 1, ginsenoside Rg 1 (95 mg) and lucinoside A and ginsenoside Re
A mixture (100 mg) of lucinoside B and lucinoside C (100 mg) was obtained from fraction 2.
I got it. Silica gel (10 g, 60-230 mesh, manufactured by Merck & Co.)
of chloroform:methanol:ethyl acetate:water (2:2:
4:1), lucinoside A (25 mg), ginsenoside Re (50 mg) and lucinoside B (30 mg)
and lucinoside C (30 mg) were obtained. Fraction 3 (0.35g), 4 (1g), 6 (0.50
g) and 7 (0.30 g), and 35 g of silica gel (60 to 230 mesh, manufactured by Merck & Co.), respectively.
into columns packed with g, 100g, 50g and 30g,
Chloroform/methanol/water (20:4:0.1)
Fractional elution was carried out, and lucinoside D was extracted from fraction 3.
(15 mg), lucinoside E (263
mg) and lucinoside F (415 mg), fraction 6
Rusinoid I (10 mg) was obtained from fraction 7, and lucinoside H (105 mg) was obtained from fraction 7. Fraction 5 (0.25g) and silica gel (25g)
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 [ALC/GPC type high-performance liquid chromatograph manufactured by Nippon Waters Co., Ltd.] ;Column is Nucleosil 30・C 18 (30
±4μ, made by West German M. Nagel) filling (7mmφ
× 61 cm); mobile phase was 30% acetonitrile], and lucinoside F (55 mg) and lucinoside G (55 mg) were added.
I got this. The physical properties of the saponins that are the subject of this invention are shown in Tables 1, 2, and 3 below.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
（β−Ｄ−グルコピラノシド）−28−Ｏ−β−Ｄ−
グルコピラノシド；アルジユノール酸−３−Ｏ−
（β−Ｄ−グルコピラノシド）−28−Ｏ−β−Ｄ−
グルコピラノシド； マカエリン酸−３−Ｏ−（β−Ｄ−グルコピラ
ノシド）−28−Ｏ−β−Ｄ−グルコピラノシド；
２−α−ヒドロキシギプソゲニン−３−Ｏ（β−
Ｄ−グルコピラノシド）−28−Ｏ−β−Ｄ−グル
コピラノシド； ヘデラゲニン−３−Ｏ−（β−Ｄ−グルコピラ
ノシド）−28−Ｏ−β−Ｄ−グルコピラノシド；
キプソゲニン−３−Ｏ−（β−Ｄ−グルコピラノ
シド）−28−Ｏ−β−Ｄ−グルコピラノシド；マ
スリン酸−３−Ｏ−（β−Ｄ−グルコピラノシド）
−28−Ｏ−β−Ｄ−グルコピラノシド；オレアノ
ール酸−３−Ｏ−（β−Ｄ−グルコピラノシド）−
28−Ｏ−β−Ｄ−グルコピラノシド；及び アルジユノール酸−３−Ｏ−（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（ルフア・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かせずして
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、又は水と脂溶性有機
溶媒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、粗ヘチマサポニン
を得、その粗ヘチマサポ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
ロマトグラフイに付し、得られたフラクシヨン
をさらにシリカゲルカラムクロマトグラフイ及
び／又は逆相シリカゲルの高速液体クロマトグ
ラフイに付して分離・精製することからなる、 21−β−ヒドロキシヘデラゲニン−３−Ｏ−
（β−Ｄ−グルコピラノシド）−28−Ｏ−β−Ｄ
−グルコピラノシド；アルジユノール酸−３−
Ｏ−（β−Ｄ−グルコピラノシド）−28−Ｏ−β
−Ｄ−グルコピラノシド； マカエリン酸−３−Ｏ−（β−Ｄ−グルコピ
ラノシド）−28−Ｏ−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−Ｏ−β−Ｄ
−グルコピラノシド；ヘデラゲニン−３−Ｏ−
（β−Ｄ−グルコピラノシド）−28−Ｏ−β−Ｄ
−グルコピラノシド； ギプソゲニン−３−Ｏ−（β−Ｄ−グルコピ
ラノシド）−28−Ｏ−β−Ｄ−グルコピラノシ
ド；マスリン酸−３−Ｏ−（β−Ｄ−グルコピ
ラノシド）−28−Ｏ−β−Ｄ−グルコピラノシ
ド；オレアノール酸−３−Ｏ−（β−Ｄ−グル
コピラノシド）−28−Ｏ−β−Ｄ−グルコピラ
ノシド；及び アルジユノール酸−３−Ｏ−β−Ｄ−グルコ
ピラノシドを、ギンゼノシドと分離することを
特徴とするサポニン類の製造法。[Claims] 1 21-β-hydroxyhederagenin-3-O-
(β-D-glucopyranoside)-28-O-β-D-
Glucopyranoside; Ardjunolic acid-3-O-
(β-D-glucopyranoside)-28-O-β-D-
Glucopyranoside; macaeric acid-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside;
2-α-hydroxygypsogenin-3-O (β-
D-glucopyranoside)-28-O-β-D-glucopyranoside; hederagenin-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside;
Kypsogenin-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside; Maslinic acid-3-O-(β-D-glucopyranoside)
-28-O-β-D-glucopyranoside; oleanolic acid-3-O-(β-D-glucopyranoside)-
A novel saponin selected from the group consisting of 28-O-β-D-glucopyranoside; and aldiunolic acid-3-O-(β-D-glucopyranoside). The following method can be used without degreasing: (a) extraction with water, lower alcohol or lower alcohol containing water; the concentrate is suspended in water; After contacting with a polystyrene resin adsorbent, it is eluted with a lower alcohol or lower alcohol-containing water, the eluate is concentrated, the concentrate is dissolved in a lower alcohol, and the resulting precipitate is injected into a fat-soluble organic solvent. (b) Extract with water, a lower alcohol, or a water-containing lower alcohol, and partition the concentrate directly between n-butanol and water, or between water and a fat-soluble organic solvent, and extract the aqueous layer. The concentrate obtained by concentrating a portion was partitioned between n-butanol and water, and the n
- drying the butanol part under reduced pressure, dissolving the residue in lower alcohol and injecting it into a fat-soluble organic solvent, drying the generated precipitate under reduced pressure to obtain crude loofah saponin, dissolving the crude loofah saponin in lower alcohol, The solution is subjected to reverse-phase silica gel column chromatography, and the resulting fraction is further subjected to silica gel column chromatography and/or reverse-phase silica gel high-performance liquid chromatography for separation and purification, 21 -β-hydroxyhederagenin-3-O-
(β-D-glucopyranoside)-28-O-β-D
-Glucopyranoside; Ardjunolic acid-3-
O-(β-D-glucopyranoside)-28-O-β
-D-glucopyranoside; Macaelic acid-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside; 2-α-hydroxypsogenin-3-O
(β-D-glucopyranoside)28-O-β-D
-Glucopyranoside; hederagenin-3-O-
(β-D-glucopyranoside)-28-O-β-D
-Glucopyranoside; Gypsogenin-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside; Maslinic acid-3-O-(β-D-glucopyranoside)-28-O-β-D- Glucopyranoside; oleanolic acid-3-O-(β-D-glucopyranoside)-28-O-β-D-glucopyranoside; and aldiunolic acid-3-O-β-D-glucopyranoside are separated from ginsenoside. A method for producing saponins.
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 JPS6048995A (en) | 1985-03-16 |
| JPH0471080B2 true 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) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0627065B2 (en) * | 1985-03-08 | 1994-04-13 | 株式会社資生堂 | External skin preparation |
| WO1999034810A1 (en) * | 1998-01-12 | 1999-07-15 | Her Majesty In Right Of Canada As Represented By The Minister Of Agriculture And Agri-Food Canada | A process for the isolation, recovery and purification of non-polar extractives |
| KR100315097B1 (en) * | 1999-02-09 | 2001-11-26 | 박명규 | Separation Method for Panaxadiol and Panaxatriol Using Benzene Ethylene Resin |
| JP4586178B2 (en) * | 2002-12-12 | 2010-11-24 | 三省製薬株式会社 | External preparation for improving skin damaged by burns |
-
1983
- 1983-08-24 JP JP58155552A patent/JPS6048995A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6048995A (en) | 1985-03-16 |
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