JP2651525B2 - Swell thiamarin compound - Google Patents
Swell thiamarin compoundInfo
- Publication number
- JP2651525B2 JP2651525B2 JP62231292A JP23129287A JP2651525B2 JP 2651525 B2 JP2651525 B2 JP 2651525B2 JP 62231292 A JP62231292 A JP 62231292A JP 23129287 A JP23129287 A JP 23129287A JP 2651525 B2 JP2651525 B2 JP 2651525B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- ddd
- nmr
- glucose
- observed
- 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
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- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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
るスウエルチアマリンの２−アセチル誘導体に関するも
のである。Description: TECHNICAL FIELD The present invention relates to a 2-acetyl derivative of Swellthiamarin, which is contained as a main component in a gentian plant, green leaf gall.
従来技術 リンドウ科植物の青叶胆（Swertia mileensis）は古
来中国漢方においてウイ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 Jia
shen et al;Zhongcaoyao 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
イ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。Prior art The Gentianaceous plant, Swertia mileensis, has long been considered effective for viral hepatitis in Chinese herbal medicine. However, the chemical components contained in this plant are not clear, and there has been a record that the extract was simply used as a herbal medicine. Yes (Liu Jia
shen et al; Zhongcaoyao 13 , 433-444 (1982)).
Recently, various types of hepatitis have become a problem in connection with blood transfusion and the like, and the emergence of an effective therapeutic or preventive drug especially 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 It is therefore an object of the present invention to elucidate the active ingredient contained in blue leaf gall and find a pharmaceutical use such as an antiviral hepatitis agent.
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はアセチル基） で表されるスウエ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 be separated and purified from blue bile as described below,
And the formula is determined (Wherein, R is an acetyl group).
本発明者らは青叶胆（Swertia mileensis）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 conducted the following experiment in order to clarify the water-soluble chemical components of Swertia mileensis.
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
の他の爽雑物も多量に含まれるため、酢酸エチル可溶部
を分取し、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 ground part of blue bile was pulverized and extracted with ethanol, and an ethanol extract was fractionated. After the solvent is distilled off, the extract is treated with benzene, and the benzene-soluble and insoluble parts (residues)
And divided into. The benzene-insoluble part containing the water-soluble component is
Further, the mixture was partitioned between ethyl acetate and water. Since the aqueous solution also contains a large amount of sugars and other impurities, the ethyl acetate-soluble portion was fractionated and subjected to silica gel column chromatography to fractionate into 34 fractions.
次に、フラクション10〜18とフラクション19〜30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▲〔α〕22 D▼1
29゜（CH3OH）の白色粉末であり、UVλmax（CH3OH）nm
は236（logε4.04）でα，β−不飽和カルボニルの吸収
がみられ、IRスペクトル分析ではIR（ヌジョール）cm-1
が3500−3050,1680,1605で、やはりα，β−不飽和カル
ボニルの存在が示唆され、また水酸基の吸収もみられ
た。1 H−NMR（CD3OD）δは 1:5.72（d,J＝1.5Hz） 3:7.63（ｓ） 6:1.75（ddd,J＝1.42,2.7,1.5Hz） 1.91（ddd,J＝14.2,13.0,5.1Hz） 7:4.34（ddd,J＝10.5,5.1,1.5Hz） 4.76（ddd,J＝10.5,13.0,2.7Hz） 8:5.45（ddd,J＝17.0,9.5,9.3Hz） 9:2.92（dd,J＝9.3,1.5Hz） 10a:5.29（dd,J＝9.5,2.4Hz） 10b:5.36（dd,J＝17.0,2.4Hz） １′:4.64（d,J＝7.8Hz） ２′:3.19（dd,J＝7.8,9.0Hz） ３′:3.25−3.40 ４′:3.25−3.40 ５′:3.25−3.40 ６′:3.67（dd,J＝11.9,5.7Hz） 3.89（dd,J＝11.9,2.0Hz） の値を示し（第１図に化合物の1H−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
フィンプロトン、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−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。Next, the fractions 10 to 18 and the fractions 19 to 30 were repeatedly purified by column chromatography (eluent: chloroform / methanol) using silica gel and Sephadex, respectively, to obtain a compound B having a lower polarity than the former, and a polar compound than the latter. Was isolated. Compound A has a melting point of 113-115 ° C. and an optical rotation of ▲ [α] 22 D ▼ 1
29 ゜ (CH 3 OH) white powder, UVλ max (CH 3 OH) nm
Has an absorption of α, β-unsaturated carbonyl at 236 (logε4.04), and IR spectrum analysis shows an IR (nujol) cm −1
Were 3500-3050, 1680, and 1605, suggesting the presence of α, β-unsaturated carbonyl, and also exhibiting hydroxyl group absorption. 1 H-NMR (CD 3 OD) δ 1: 5.72 (d, J = 1.5 Hz) 3: 7.63 (s) 6: 1.75 (ddd, J = 1.42, 2.7, 1.5 Hz) 1.91 (ddd, J = 14.2, 13.0, 5.1 Hz) 7: 4.34 (ddd , J = 10.5,5.1,1.5Hz) 4.76 (ddd, J = 10.5,13.0,2.7Hz) 8: 5.45 (ddd, J = 17.0,9.5,9.3Hz) 9: 2.92 (dd, J = 9.3,1.5Hz) 10a: 5.29 (dd, J = 9.5, 2.4 Hz) 10b: 5.36 (dd, J = 17.0, 2.4 Hz) 1 ': 4.64 (d, J = 7.8 Hz) 2': 3.19 (dd, J = 7.8, 9.0Hz) 3 ': 3.25-3.40 4': 3.25-3.40 5 ': 3.25-3.40 6': 3.67 (dd, J = 11.9, 5.7Hz) 3.89 (dd, J = 11.9, 2.0Hz) (A part of the 1 H-NMR spectrum of the compound is shown in FIG. 1 ). This compound is a glycoside having one molecule of glucose, and the β-bond was found from the coupling constant of the anomeric proton. Was. Regarding the aglycone portion, signals of a 3-substituted olefin proton and a vinyl group, which were shifted to a low magnetic field by the influence of carbonyl, were observed. Further, signals of acetal protons were observed in addition to the methylene and sugar moieties adjacent to oxygen, suggesting that the present compound was a secoiridoid.
化合物ＡのSIMSスペクトル図（第２図）をみるとm/z3
75に（Ｍ＋Ｈ）＋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/z213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、以上の結果より本化合物はス
ウエルチアマリン（Ｉ）と同定された 化合物Ｂは融点104〜105℃、旋光度▲〔α〕24 D▼−9
2゜（メタノール）の白色粉末で、UVλmax（MeOH）nm23
4（logε3.96）、IR（ヌジョール）cm-1は3500−3150,1
720,1675,1605,1230、1 H−NMR（CD3OD）δは 1:5.65（d,J＝1.5Hz） 3:7.55（ｓ） 6:1.75（ddd,J＝14.2,3.2,1.5Hz） 1.85（ddd,J＝14.2,12.7,5.1Hz） 7:4.33（ddd,J＝10.9,5.1,1.5Hz） 4.74（ddd,J＝10.9,12.7,3.2Hz） 8:5.41（ddd,J＝17.2,7.8,7.6Hz） 9:2.90（ddd,J＝7.6,1.5,1.5Hz） 10a:5.29（ddd,J＝7.8,4.2,1.5Hz） 10b:5.36（dd,J＝17.2,4.2Hz） １′:4.81（d,J＝8.1Hz） ２′:4.68（dd,J＝8.1,9.5Hz） ３′:3.60（dd,J＝9.5,8.6Hz） ４′:3.32−3.43 ５′:3.32−3.43 ６′:3.69（dd,J＝12.0,5.9Hz） 3.91（dd,J＝12.0,1.8Hz） CH3:2.06（ｓ） SIMS:509（Ｍ＋Ｈ＋Ｇ）+,417（Ｍ＋Ｈ）+,375,213,205 （尚、1H−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Ａの類縁体であることが判った。Looking at the SIMS spectrum of compound A (Fig. 2), m / z3
A peak of (M + H) + was observed at 75, indicating that the molecular weight of this compound was 374. At m / z 213, a peak derived from the fragment of the aglycone portion was observed. From this, 195 in which one molecule of water was dehydrated and 177 in which another molecule was dehydrated were observed. Compound B, which was identified as amarin (I), had a melting point of 104-105 ° C and an optical rotation of ▲ [α] 24 D ▼ -9
2 ゜ (methanol) white powder, UVλ max (MeOH) nm23
4 (logε3.96), IR (Nujol) cm -1 is 3500-3150,1
720,1675,1605,1230, 1 H-NMR (CD 3 OD) δ 1: 5.65 (d, J = 1.5 Hz) 3: 7.55 (s) 6: 1.75 (ddd, J = 14.2, 3.2, 1.5 Hz) 1.85 (ddd, J = 14.2, 12.7, 5.1 Hz) 7: 4.33 (ddd , J = 10.9,5.1,1.5Hz) 4.74 (ddd, J = 10.9,12.7,3.2Hz) 8: 5.41 (ddd, J = 17.2,7.8,7.6Hz) 9: 2.90 (ddd, J = 7.6,1.5, 1.5a) 10a: 5.29 (ddd, J = 7.8,4.2,1.5Hz) 10b: 5.36 (dd, J = 17.2,4.2Hz) 1 ': 4.81 (d, J = 8.1Hz) 2': 4.68 (dd, 3 ': 3.60 (dd, J = 9.5, 8.6 Hz) 4': 3.32-3.43 5 ': 3.32-3.43 6': 3.69 (dd, J = 12.0, 5.9 Hz) 3.91 (dd , J = 12.0,1.8Hz) CH3: 2.06 (s) SIMS: 509 (M + H + G) +, 417 (M + H) +, 375,213,205 ( Note that shows a part of 1 H-NMR spectrum in Figure 1 bottom) results As a result, the compound was found to be an analog of compound A.
IRにおいて1720cm-1にエステルの吸収がみられるこ
と、1H−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416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
テートであり、またSIMS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。The absorption of ester at 1720 cm -1 was observed in IR, the signal of the methyl group of acetate was seen at δ2.06 in 1 H-NMR, and the proton at the 2-position of glucose was about 1.5 ppm compared to Compound A. Large, low magnetic field shift,
Since the protons at the 1- and 3-positions are also slightly down-field shifted, the molecular weight is 416 from SIMS, and one more acetyl group than compound A, the present compound is a monoacetate of compound A. From the peak at 205, it was found that an acetyl group was present in the sugar moiety, that is, the acetyl group was bonded to the 2-position of glucose.
尚、化合物ＡおよびＢの13C−NMRデータ A:R＝Ｈ B:R＝COCH3 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、1H
−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。The 13 C-NMR data of Compounds A and B A: R = H B: R = COCH 3 In the compound B, a signal derived from the acetyl group was observed in the compound B, the carbon at the 2-position of glucose was shifted downfield compared to A, and the carbons at the 1- and 3-positions were shifted upfield, and 1 H
-The result of the NMR supports 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〕22 D▼：−120゜（CHCl3） UVλmax（MeOH）nm:234（logε3.96） IR（ヌジョール）cm-1:3500,1750,1705,1610,12201 H−NMR（CDCl3）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＝10.9,10.9,5.4Hz） 8:5.35−5.40 9:2.95（ddd,J＝5.9,2.2,2.2Hz） 10a:5.30−5.35 10b:5.30−5.35 １′:4.84（d,J＝8.1Hz） ２′:5.03（dd,J＝8.1,9.8Hz） ３′:5.28（dd,J＝9.8,9.5Hz） ４′:5.10（dd,J＝9.5,9.5Hz） ５′:3.75（ddd,J＝9.5,4.4,2.2） ６′:4.16（dd,J＝12.5,2.2Hz） 4.31（dd,J＝12.5,4.4Hz） CH3:2.02,2.03,2.05,2.11（ｓ） 各分析データはすべて一致した。When compounds A and B were further acetylated to confirm the structure, ▲ [α] 22 D ▼: -120 ゜ (CHCl 3 ) UVλ max (MeOH) nm: 234 (logε3.96) IR (nujol) cm -1 : 3500,1750,1705,1610,1220 1 H-NMR ( CDCl 3 ) δ: 1: 5.47 (d, J = 1.5 Hz) 3: 7.49 (s) 6: 1.75-1.95 1.75-1.95 7: 4.21-4.34 4.84 (ddd, J = 10.9, 10.9, 5.4 Hz) 8: 5.35-5.40 9: 2.95 (ddd, J = 5.9,2.2,2.2Hz) 10a: 5.30-5.35 10b: 5.30-5.35 1 ': 4.84 (d, J = 8.1Hz) 2': 5.03 (dd, J = 8.1 , 9.8Hz) 3 ': 5.28 (dd, J = 9.8,9.5Hz) 4': 5.10 (dd, J = 9.5,9.5Hz) 5 ': 3.75 (ddd, J = 9.5,4.4,2.2) 6': 4.16 (dd, J = 12.5, 2.2 Hz) 4.31 (dd, J = 12.5, 4.4 Hz) CH3: 2.02, 2.03, 2.05, 2.11 (s) All the analysis data matched.
以上より化合物Ａはスウエルチアマリン（Ｉ）、化合
物Ｂはスウエ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−アセチルスウエルチアマリン（II）
と決定した。As described above, compound A is swertimarin (I), and compound B is 2-acetylswelliamarin (II) in which an acetyl group is bonded to the 2-position of glucose of swertimarin.
It was decided.
上記スウエ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、芳香族炭化水素（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。Swellia marin and its 2-acetyl derivative are water-soluble active ingredients of blue bile, and as described above, a polar solvent (eg, ethanol) extraction of dried ground powder of blue bile, aromatic hydrocarbons (eg, benzene, It is a useful compound that can be isolated with high purity by treatment with toluene), partitioning with ethyl acetate-water and silica gel column chromatography, and is expected to be used as a drug, especially an anti-hepatitis agent.
尚スウエルチアマリンについては例えば特開昭54−26
323号に示されている通り、センブリから抽出され、そ
の構造決定もなされている。また同文献には得られたス
ウエルチアマリンを常法でアセチル化することによりテ
トラアセテートを得ること、およびスウエルチアマリン
ならびにそのテトラアセテートが抗炎症作用を有するこ
とを見いだしたことなどが開示されている。しかしなが
らスウエルチアマリンのグルコースの２位水酸基のみを
アセチル化することは化学技術的に極めて困難である
し、またその様な化合物の存在自体未だ見いだされてい
なかった。本発明者らにより青叶胆からスウエルチアマ
リンのみならずその２−アセチル誘導体が始めて分離さ
れ、構造決定されしかもこれらが医薬用途に有用である
ことが見いだされたものであつて、スウエルチアマリン
２−アセチル誘導体は文献未記載の新規化合物で、しか
も天然物由来の医薬用途に有用な化合物の発見であり、
産業上極めて有意義な発明をなすものである。In addition, for Swell thiamarin, see, for example, JP-A-54-26.
As shown in No. 323, it has been extracted from the assembly and its structure has been determined. In addition, the same document discloses that tetraacetate is obtained by acetylating the obtained swerthiamarin by a conventional method, and that it has been found that swerthiamarin and its tetraacetate have an anti-inflammatory effect. I have. However, it is extremely difficult to acetylate only the hydroxyl group at the 2-position of glucose of Swelliamarine, and the existence of such a compound has not yet been found. The present inventors have found that not only Swelliamarin but also a 2-acetyl derivative thereof have been separated from Aoba Gall and its structure has been determined, and that they have been found to be useful for pharmaceutical applications. The 2-acetyl derivative is a novel compound that has not been described in the literature, and is a discovery of a compound derived from a natural product and useful for pharmaceutical use.
This is an invention that is extremely significant in industry.
第１図は本発明にかかるスウエルチアマリン化合物Ａお
よびＢの1H−NMRスペクトル、第２図はスウエルチアマ
リンのSIMSスペクトル図。FIG. 1 is a 1 H-NMR spectrum of the swertiamarin compounds A and B according to the present invention, and FIG. 2 is a SIMS spectrum diagram of the swertiamarin.
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 JPH01230593A (en) | 1989-09-14 |
| JP2651525B2 true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532156B (en) * | 2010-12-15 | 2013-11-06 | 中国科学院昆明植物研究所 | Swerilactones H-K, 1-4 and medicinal composition and application thereof |
| CN115463056B (en) * | 2021-06-11 | 2023-09-29 | 云南英格生物技术有限公司 | Herba Swertiae Mileensis extract and preparation method and application 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01230593A (en) | 1989-09-14 |
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