JPH01230593A - Swertiamarin - Google Patents
SwertiamarinInfo
- Publication number
- JPH01230593A JPH01230593A JP23129287A JP23129287A JPH01230593A JP H01230593 A JPH01230593 A JP H01230593A JP 23129287 A JP23129287 A JP 23129287A JP 23129287 A JP23129287 A JP 23129287A JP H01230593 A JPH01230593 A JP H01230593A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- ddd
- benzene
- swertiamarin
- ethyl acetate
- 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
- HEYZWPRKKUGDCR-WRMJXEAJSA-N Swertiamarin Natural products O([C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1)[C@H]1[C@@H](C=C)[C@@]2(O)C(C(=O)OCC2)=CO1 HEYZWPRKKUGDCR-WRMJXEAJSA-N 0.000 title description 10
- HEYZWPRKKUGDCR-QBXMEVCASA-N Swertiamarin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@H](C=C)[C@]2(O)CCOC(=O)C2=CO1 HEYZWPRKKUGDCR-QBXMEVCASA-N 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000284 extract Substances 0.000 abstract description 3
- 238000010898 silica gel chromatography Methods 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 abstract description 2
- 229920005654 Sephadex Polymers 0.000 abstract description 2
- 239000012507 Sephadex™ Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004440 column chromatography Methods 0.000 abstract description 2
- 239000000741 silica gel Substances 0.000 abstract description 2
- 229910002027 silica gel Inorganic materials 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 241000096270 Swertia leducii Species 0.000 abstract 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229940126062 Compound A Drugs 0.000 description 6
- 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 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 241001071804 Gentianaceae Species 0.000 description 3
- 206010019799 Hepatitis viral Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- -1 swertiamarin compound Chemical class 0.000 description 3
- 201000001862 viral hepatitis Diseases 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 2
- TWCMVXMQHSVIOJ-UHFFFAOYSA-N Aglycone of yadanzioside D Natural products COC(=O)C12OCC34C(CC5C(=CC(O)C(O)C5(C)C3C(O)C1O)C)OC(=O)C(OC(=O)C)C24 TWCMVXMQHSVIOJ-UHFFFAOYSA-N 0.000 description 2
- PLMKQQMDOMTZGG-UHFFFAOYSA-N Astrantiagenin E-methylester Natural products CC12CCC(O)C(C)(CO)C1CCC1(C)C2CC=C2C3CC(C)(C)CCC3(C(=O)OC)CCC21C PLMKQQMDOMTZGG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 208000006454 hepatitis Diseases 0.000 description 2
- 241000411851 herbal medicine Species 0.000 description 2
- PFOARMALXZGCHY-UHFFFAOYSA-N homoegonol Natural products C1=C(OC)C(OC)=CC=C1C1=CC2=CC(CCCO)=CC(OC)=C2O1 PFOARMALXZGCHY-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001530209 Swertia Species 0.000 description 1
- 150000001241 acetals Chemical group 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000469 ethanolic extract Substances 0.000 description 1
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 231100000283 hepatitis Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
技 術 分 野
本発明はリンドウ科植物青叶胆に主成分として含まれる
スウェルチアマリンならびにその２−アセチル誘導体に
関するものである。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to swertiamarin and its 2-acetyl derivatives, which are contained as a main component in the Gentianaceae plant, Gentianaceae.
従・来 技 術
リンドウ科植物の青叶胆（Ｓｗｅｒ口ａ ｍ１ｌｅｅｎ
ｓｉｓ）は古来中国漢方においてウィルス性肝炎に有効
とされているが、この植物に含まれる化学成分は明らか
でなく単にエキスを漢方薬として使用してきた記録があ
る（Ｌｉｕ Ｊｉａｓｈｅｎ ｅｔ ａｌ；Ｚｈｏｎｇ
ｃａｏｙａ。Traditional and previous technology Gentianaceae plant green leaves (swermouth a m1leen)
sis) has been said to be effective against viral hepatitis in ancient Chinese herbal medicine, but the chemical components contained in this plant are not clear, and there is a record that the extract was simply used as a herbal medicine (Liu Jiashen et al; Zhong
caoya.
１３、 ４３３〜４４４ （１９８２＞） 、近時、輸
血などに関連し各種肝炎が問題となり、特にウィルス性
肝炎の有効な治療薬ないしは予防薬の出現が待たれてい
る。13, 433-444 (1982>) Recently, various types of hepatitis related to blood transfusions have become a problem, and the emergence of effective therapeutic or preventive drugs for viral hepatitis has been awaited.
発明が解決しようとする問題点
そこで青叶胆に含まれる有効成分を解明し、抗ウイルス
肝炎剤などの医薬用途を見出すことが本発明目的である
。Problems to be Solved by the Invention Therefore, it is an object of the present invention to elucidate the active ingredients contained in Ao-Kan-Gi and find out its medicinal uses such as anti-viral hepatitis agents.
問題点を解決するための手段
本発明目的は、後述の如く青叶胆から分離精製され、且
つ構造決定された
式
（式中、Ｒは水素またはアセチル基）
で表されるスウェルチアマリン化合物により達成せられ
る。Means for Solving the Problems The object of the present invention is to obtain a swertiamarin compound, which is isolated and purified from Aokikan gall and whose structure has been determined as described below, and is represented by the formula (wherein R is hydrogen or an acetyl group). It can be achieved.
本発明者らは青叶胆（Ｓｗｅｒｔｉａ ｍ１ｌｅｅｎｓ
ｉｓ）の水溶性化学成分を明らかにする目的で下記の実
験を行った。The present inventors have discovered that Swertia m1leens
The following experiment was conducted for the purpose of clarifying the water-soluble chemical components of is).
実施例
先ず青叶胆の乾燥地上部を粉砕後エタノールで抽出し、
エタノール抽出液を分取した。溶剤留去後、抽出物をベ
ンゼンで処理し、ベンゼン可溶部と不溶部（゛残渣）と
に分けた。水溶性成分の含まれるベンゼン不溶部を、さ
らに酢酸エチルと水で分配した。水溶液には糖類、その
他の吏雑物も多量に含まれるため、酢酸エチル可溶部を
分収し、シリカゲルカラムクロマトグラフィを実施して
３４のフラクションに分画した。Example: First, the dried above-ground parts of Aokawa gall were crushed and extracted with ethanol.
The ethanol extract was separated. After the solvent was distilled off, the extract was treated with benzene and separated into a benzene-soluble portion and an insoluble portion (residue). The benzene-insoluble portion containing water-soluble components was further partitioned between ethyl acetate and water. Since the aqueous solution contained a large amount of sugars and other impurities, the ethyl acetate soluble portion was collected and fractionated into 34 fractions by silica gel column chromatography.
次に、フラクションｌＯ〜ｌ♂とフラクション１９〜３
０とについてそれぞれシリカゲル、セファデックスを用
いたカラムクロマトグラフィ（溶離液クロロホルム・メ
タノール）により繰り返し精製を行い、前者より極性の
低い化合物Ｂを、また後者より極性の高い化合物Ａを単
離した。化合物Ａは融点１１３〜１１５℃、旋光度Ｃ（
Ｚ）Ｄ−＋２９°（ＣＩ１３Ｈ）の白色粉末であり、Ｕ
ＶλｓａＸ（ＣＪＯＩＩ）ｎｍは２３６（ｌｏｇε４．
０４＞でα、β−不飽和不飽和ニルボニルがみられ、Ｉ
Ｒスペクトル分析ではＩＲ＜ｌジヲール）ｃｍ’が３５
００−３０５０．１６８０．１６０５で、やはりα、β
−不飽和不飽和ニルボニルが示唆され、また水酸基の吸
収もみられた。Next, fractions lO~l♂ and fractions 19~3
0 and 0 were repeatedly purified by column chromatography (eluent: chloroform/methanol) using silica gel and Sephadex, respectively, to isolate Compound B, which is less polar than the former, and Compound A, which is more polar than the latter. Compound A has a melting point of 113-115°C and an optical rotation of C (
Z) D-+29° (CI13H) white powder, U
VλsaX (CJOII) nm is 236 (logε4.
04>, α, β-unsaturated unsaturated nylbonyl was observed, and I
In R spectrum analysis, IR<l diol) cm' is 35
00-3050.1680.1605, also α, β
-Unsaturated unsaturated nylbonyl was suggested, and absorption of hydroxyl groups was also observed.
’１１−ＮＭＲ（ＣＤ３０Ｄ ）δは
１： ５．７２ （ｄ、Ｊ・１．５１１ｚ）３：
７．６３ （ｓ）
６： １．７５ （ｄｄｄ、Ｊ＝１４．２，２．７
，１．５Ｈｚ）１．９１ （ｄｄｄ、Ｊ＝１４．２．
１３．０，５．１Ｈｚ）７： ４ｊ４ （ｄｄｄ、
Ｊ＝ＩＯ，５，５，１，１，５Ｈｚ）４．７６ （ｄ
ｄｄ、Ｊ＝ＩＯ，５，１３，０，２，７Ｈｚ＞８：
５．４５ （ｄｄｄ、 Ｊ＝Ｉ７．０． ９．５．
９ｊｊｌｚ）９： ２．９２ （ｄｄ、Ｊ＝９ｊ
、１．５Ｈｚ）１０ａ： ５．２９ （ｄｄ、、Ｌ
９．５，２．４Ｈｚ）１０ｂ： ５ｊ６ （ｄｄ、
Ｊ＝１７．０，２．４Ｈｚ）ｌ”： ４．６４ （
ｄ、Ｊ＝７．８Ｈｚ）２’： ３．ＩＱ （ｄｄ、
Ｊ＝７．８，９．０Ｈｚ）３″： ３．２５−３．４
０
４’： ３．２５−３．４０
５’： ３．２５−３．４０
６’： ３．６７ （ｄｄ、Ｊ＝１１．９，５．７
Ｈｚ）３．８９ （ｄｄ、Ｊ＝Ｉ１．９．２．０Ｈｚ
）の値を示しく第１図に化合物の’Ｈ−ＮＭＲスペクト
ルの一部を示す）、本化合物はグルコース１分子を有す
る配糖体であり、アノメリックプロトンのカップリング
定数よりβ−結合していることが判った。アグリコン部
分についてはカルボニルの影響で低磁場シフトした３置
換オレフインプロトン、ビニル基のシグナルが認められ
た。さらに酸素に隣接するメチレン、糖部分以外にアセ
タールのプロトンのシグナルがみられることから本化合
物はセコイリドイドと推定できた。'11-NMR (CD30D) δ is 1: 5.72 (d, J・1.511z) 3:
7.63 (s) 6: 1.75 (ddd, J=14.2, 2.7
, 1.5Hz) 1.91 (ddd, J=14.2.
13.0, 5.1Hz) 7: 4j4 (ddd,
J=IO, 5, 5, 1, 1, 5Hz) 4.76 (d
dd, J=IO, 5, 13, 0, 2, 7Hz>8:
5.45 (ddd, J=I7.0.9.5.
9jjlz) 9: 2.92 (dd, J=9j
, 1.5Hz) 10a: 5.29 (dd, ,L
9.5, 2.4Hz) 10b: 5j6 (dd,
J=17.0, 2.4Hz)l”: 4.64 (
d, J=7.8Hz)2': 3. IQ (dd,
J=7.8, 9.0Hz) 3″: 3.25-3.4
0 4': 3.25-3.40 5': 3.25-3.40 6': 3.67 (dd, J=11.9, 5.7
Hz) 3.89 (dd, J=I1.9.2.0Hz
Figure 1 shows a part of the 'H-NMR spectrum of the compound).This compound is a glycoside with one molecule of glucose, and the coupling constant of anomeric proton indicates that it is β-bonded. It turns out that there is. Regarding the aglycone moiety, signals of a trisubstituted olefin proton and vinyl group shifted down the magnetic field due to the influence of carbonyl were observed. Furthermore, since signals of acetal protons were observed in methylene adjacent to oxygen and in addition to sugar moieties, this compound was presumed to be a secoiridoid.
化合′ＰＩＩＪＡのＳＩＭＳスペクトル図（第２図）を
みるとＩＩｌ／ｚ ３７５に（Ｍ＋ｔｌ）のピークが認
められ、本化合物の分子量が３７４であることが判った
。ｍ／ｚ ２１３にはアグリコン部分のフラグメントに
由来するピークが認められ、これより１分子の水が脱水
した１９５、さらにもう１分子脱水した １７７のピー
クがみられ、以上の結果より木１ヒ合物はスウェルチア
マリン（Ｉ）と同定された
化合物Ｂは融点１０４〜１０５℃、旋光度〔α〕Ｄ−９
２”（メタノール）の白色粉末で、ＵＶλ、、、（Ｍｅ
ｏｌｌ）ｎ＋ｎ２３４（Ｉｏｇε ３．Ｑ６） 、
ＩＲ（ヌジタール）ｃｍ’ は３５００−３１５０
゜１７２０、１６７５． ＋６０５．１２３０、’Ｈ−
ＮＭＲ（ＣＤ、０口）δ は
Ｉ： ５．６５ （ｄ、 Ｊ＝１．５１１ｚ）３
：、７．５５ （５）
６： １．７５ （ｄｄｄ、Ｊ＝Ｉ４．２，３．２
． １．５１１ｚ）１．８５ （ｄｄｄ、Ｊ＝１４．
２． １２．７．５．１ｔｌｚ）７： ４．３３
（ｄｄｄ、Ｊ＝ＩＯ，９，５，１，１，５１１ｚ）４．
７４ （ｄｄｄ、Ｊ＝ＩＯ，９，１２，７，３，２Ｈ
ｚ）８： ５．４１ （ｄｄｄ、Ｊ＝１７．２，７
．♂、 ７ 、６ ｔｌ ｚ ）９： ２．９０
（ｄｄｄ、Ｊ＝７．６，１．５，１．５Ｈｚ）１０ａ
： ５．２９ （ｄｄｄ、、Ｌ７．８，４．２．
１．５Ｈｚ）１０ｂ： ５ｊ６ （ｄｄ、Ｊ＝１７
．２，４．２Ｈｚ）１’： ４．８１ （ｄ、Ｊ＝
８．ｌｌ１ｚ）２°： ４．６８ （ｄｄ、Ｊ＝８
．１．９．５Ｈｚ）３’： ３．６０ （ｄｄ、Ｊ
：９．５，８．６ｆｌｚ）４’： ３１２−３．４３
５’： ３．３２−３．４３
６’： ３．６９ （ｄｄ、Ｊ＝Ｉ２．０，５．９
１１ｚ）３．９１ （ｄｄ、Ｊ＝１２．０． １．８
１１ｚ）ＣＨ３： ２．０６ （ｓ）
ＳＩＭＳ ：
５０９ （Ｍ＋）ｌ＋Ｇ）□ 、 ４１７ （＋
Ｌ＋Ｈ）＋、 ３７５． ２１３． ２０５（尚、’
ＩＩ−ＮＭＲスペクトルの一部を第１図下段に示す）
の結果から、化合物への類縁体であることが判った。Looking at the SIMS spectrum diagram (Figure 2) of compound 'PIIJA, a (M+tl) peak was observed at IIl/z 375, indicating that the molecular weight of this compound was 374. At m/z 213, a peak derived from a fragment of the aglycone moiety was observed, and from this, a peak of 195, where one molecule of water was dehydrated, and a peak of 177, where one molecule of water was dehydrated, were found. Compound B, which was identified as swertiamarin (I), has a melting point of 104-105°C and an optical rotation [α]D-9.
2” (methanol) white powder with UV λ, (Me
oll)n+n234(Iogε 3.Q6),
IR (nugital) cm' is 3500-3150
゜1720, 1675. +605.1230,'H-
NMR (CD, 0 ports) δ is I: 5.65 (d, J=1.511z)3
:, 7.55 (5) 6: 1.75 (ddd, J=I4.2, 3.2
．． 1.511z) 1.85 (ddd, J=14.
2. 12.7.5.1tlz) 7: 4.33
(ddd, J=IO, 9,5,1,1,511z)4.
74 (ddd, J=IO, 9, 12, 7, 3, 2H
z) 8: 5.41 (ddd, J=17.2,7
．． ♂, 7, 6 tl z) 9: 2.90
(ddd, J=7.6, 1.5, 1.5Hz) 10a
: 5.29 (ddd,, L7.8, 4.2.
1.5Hz) 10b: 5j6 (dd, J=17
．． 2,4.2Hz) 1': 4.81 (d, J=
8. ll1z) 2°: 4.68 (dd, J=8
．． 1.9.5Hz) 3': 3.60 (dd, J
:9.5,8.6flz) 4': 312-3.43 5': 3.32-3.43 6': 3.69 (dd, J=I2.0,5.9
11z) 3.91 (dd, J=12.0. 1.8
11z) CH3: 2.06 (s) SIMS: 509 (M+)l+G)□, 417 (+
L+H)+, 375. 213. 205 (also, '
A portion of the II-NMR spectrum is shown in the lower part of Figure 1), which revealed that it was an analogue of the compound.
ＩＲにおいて１７２０ｃｍ１’にエステルの吸収がみら
れること、’ＩＩ−ＮＭＲでδ２．０６にアセテートの
メチル基のシグナルがみられること、化合物Ａに比しグ
ルコースの２位のプロトンが約１．５ｐｐｍと大きく、
低磁場シフトしており、１位および３位のプロトンも若
干低磁場シフトしていること、ＳＩＭＳから分子量が４
１６で、化合物Ａよりアセチル基１個分多いことから、
本化合物は化合物Ａのモノアセテ−１・であり、またＳ
ＩＭＳで２０５にピークがみられることから、アセチル
基が糖部分に存在すること、すなわちグルコースの２位
に結合していることが判った。Ester absorption is seen at 1720 cm1' in IR, a signal of the methyl group of acetate is seen at δ2.06 in 'II-NMR, and the proton at the 2-position of glucose is approximately 1.5 ppm compared to Compound A. big,
The protons at the 1st and 3rd positions are also slightly shifted down the magnetic field, and SIMS shows that the molecular weight is 4.
16, which has one more acetyl group than compound A,
This compound is monoacetate-1 of compound A, and S
Since a peak was observed at 205 in IMS, it was found that the acetyl group was present in the sugar moiety, that is, it was bonded to the 2-position of glucose.
尚、化合物ＡおよびＢの１３Ｃ−ＮＭＲデータ＾ ：
Ｒ＝Ｈ
Ｂ ： Ｒ＝ＣＯＣＩ＋。In addition, 13C-NMR data of compounds A and B:
R=HB: R=COCI+.
八 Ｂ
１ ９９．１ ９
９．６３ １５４．７
１５３．２４ １０９．０
１１０．４５ ６４．４
６４．２６ ３３．
７ ３３．４７ ６
５．９ ６６、ＩＡ
１３３．８ １３３．３９
５１．９ ５２．２１０
１２１．２ １２１．
４１’ １００．２
９８．８２’ ？４．５
７５．３３’ ？？、９
７５．１４° ７１．５
７１．４５’ ？８．６
７８．７６° ６２．６
６２．５６０ １６８．０
！６７．８をみても、化合物Ｂではアセチ
ル基に由来するシグナルがみられ、グルコースの２位の
炭素がＡに比し低磁場シフトし、１位、３位の炭素が高
磁場シフトしていて、’Ｉｔ−ＮＭＲの結果と共にアセ
チル基がグルコースの２位に結合していることを支持し
ている。Eight B 1 99.1 9
9.63 154.7
153.24 109.0
110.45 64.4
64.26 33.
7 33.47 6
5.9 66, IA
133.8 133.39
51.9 52.210
121.2 121.
41' 100.2
98.82'? 4.5
75.33'? ? ,9
75.14° 71.5
71.45'? 8.6
78.76° 62.6
62.560 168.0
! 67.8, a signal derived from the acetyl group is seen in compound B, and the carbon at the 2nd position of glucose has shifted down the magnetic field compared to A, and the carbons at the 1st and 3rd positions have shifted up the magnetic field. , 'It-NMR results support that the acetyl group is bonded to the 2-position of glucose.
さらに構造を確認するため化合物ＡおよびＢを夫々アセ
チル化したところ、下記の如く〔α） ｏ ：
１２０° （ＣＨＣＩｓ）ＵＶλｗａｘ（ＭｅＯＨ）ｎ
ｍ ： ２３４（ｌｏ（ε３．９Ｇ）−１。In order to further confirm the structure, compounds A and B were each acetylated, and as shown below [α) o:
120° (CHCIs)UVλwax(MeOH)n
m: 234(lo(ε3.9G)-1.
［ＲＤジｙ４）ｃｏ＋ 、 ３５１１０． １７
５０． １７０５． １６１０． １２２０’ｌｉＮＭ
Ｒ（ＣＤＣｌ２）δ ：
１： ５．４７ （ｄ、Ｊ＝１．５Ｈｚ）３：
７．４９ （ｓ）
６： １．７５−１．９５
１．７５−１．９５
７： ４．２１−４．３４
４．８４ （ｄｄｄ、Ｊ＝１０．９．ｌｏ、９． ５
．４１１ｚ）８： ５ｊ５−５．４０
９： ２．９５ （ｄｄｄ、Ｊ＝５．９，２．２，
２．２）１ｚ）１０ａ： ５ｊＯ−５１５
１０ｂ： ５．３Ｏ−５ｊ５
１°： ４１４ （ｄ、Ｊ＝８．１）１ｚ）２’：
５．０３ （ｄｄ、Ｊ＝８．１，９．８１１ｚ）
３°： ５．２８ （ｄｄ、Ｊ・９．８．９．５Ｈ
ｚ）４°： ５．１０ （ｄｄ、Ｊ＝Ｑ、５．９．
５Ｈｚ）５″： ３．７５ （ｄｄｄ、Ｊ＝９．５
，４．４，２．２）６°： ４．１６ （ｄｄ、Ｊ
＝１２．５．２．２１１ｚ）４．３１ （ｄｄ、
Ｊ＝１２．５． ４．４Ｈｚ＞Ｃｌｌ３： ２．０２
，２．０３，２．０５，２．１１ （ｓ）各分析デー
タはすべて一致した。[RDjiy4)co+, 35110. 17
50. 1705. 1610. 1220'liNM
R(CDCl2)δ: 1: 5.47 (d, J=1.5Hz) 3:
7.49 (s) 6: 1.75-1.95 1.75-1.95 7: 4.21-4.34 4.84 (ddd, J=10.9.lo, 9.5
．． 411z) 8: 5j5-5.40 9: 2.95 (ddd, J=5.9, 2.2,
2.2) 1z) 10a: 5jO-515 10b: 5.3O-5j5 1°: 414 (d, J=8.1) 1z) 2':
5.03 (dd, J=8.1, 9.811z)
3°: 5.28 (dd, J・9.8.9.5H
z) 4°: 5.10 (dd, J=Q, 5.9.
5Hz) 5″: 3.75 (ddd, J=9.5
, 4.4, 2.2) 6°: 4.16 (dd, J
=12.5.2.211z)4.31 (dd,
J=12.5. 4.4Hz>Cll3: 2.02
, 2.03, 2.05, 2.11 (s) All analytical data were consistent.
以上より化合物Ａはスウェルチアマリン（Ｉ）化合￥Ｉ
ＩＩＪＢはスウェルチアマリンのグルコースの２位にア
セチル基が結合した２−アセチルスウェルチアマリン（
Ｉ［）と決定した。From the above, compound A is a swertiamarin (I) compound￥I
IIJB is 2-acetyl swertiamarin (2-acetyl swertiamarin), which has an acetyl group attached to the 2-position of glucose in swertiamarin.
It was determined that I[).
本発明にかかるスウェルチアマリンならびにその２−ア
セチル誘導体は青叶胆の水溶性有効成分であり、上記の
如く青叶胆の乾燥地上部粉末の極性溶剤（例えばエタノ
ール）抽出、芳香族炭１ヒ水素（例えばベンゼン、トル
エン）処理、酢酸エチル−水による分配ならびにシリカ
ゲルカラムクロマトグラフィにより高純度に単離せられ
るものであって、医薬、就中抗肝炎剤としての用途が期
待される有用な化合物である。Swertiamarin and its 2-acetyl derivatives according to the present invention are water-soluble active ingredients of Ao-kanji. It can be isolated with high purity by hydrogen treatment (e.g. benzene, toluene), ethyl acetate-water partitioning, and silica gel column chromatography, and is a useful compound expected to be used as a medicine, especially as an anti-hepatitis agent. .
第１図は本発明にかかるスウェルチアマリン化合物Ａお
よびＢの’Ｈ−ＮＭＲスペクトル、第２図はスウェルチ
アマリンのＳＩＭＳスペクトル図。
特許出願代理人FIG. 1 is a 'H-NMR spectrum of swertiamarin compounds A and B according to the present invention, and FIG. 2 is a SIMS spectrum diagram of swertiamarin. patent application agent
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62231292A JP2651525B2 (en) | 1987-09-16 | 1987-09-16 | Swell thiamarin compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62231292A JP2651525B2 (en) | 1987-09-16 | 1987-09-16 | Swell thiamarin compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01230593A true JPH01230593A (en) | 1989-09-14 |
| JP2651525B2 JP2651525B2 (en) | 1997-09-10 |
Family
ID=16921320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62231292A Expired - Lifetime JP2651525B2 (en) | 1987-09-16 | 1987-09-16 | Swell thiamarin compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2651525B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532156A (en) * | 2010-12-15 | 2012-07-04 | 中国科学院昆明植物研究所 | Swerilactones H-K, 1-4 and medicinal composition and application thereof |
| WO2022257932A1 (en) * | 2021-06-11 | 2022-12-15 | 云南英格生物技术有限公司 | Swertiae mileensis herba extract, and preparation method therefor and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5426323A (en) * | 1977-07-26 | 1979-02-27 | Koshiro Chiyuuji Shiyouten Kk | Antiinflammatory agent |
-
1987
- 1987-09-16 JP JP62231292A patent/JP2651525B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5426323A (en) * | 1977-07-26 | 1979-02-27 | Koshiro Chiyuuji Shiyouten Kk | Antiinflammatory agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532156A (en) * | 2010-12-15 | 2012-07-04 | 中国科学院昆明植物研究所 | Swerilactones H-K, 1-4 and medicinal composition and application thereof |
| WO2022257932A1 (en) * | 2021-06-11 | 2022-12-15 | 云南英格生物技术有限公司 | Swertiae mileensis herba extract, and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2651525B2 (en) | 1997-09-10 |
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