JP2879926B2 - Monoterpene glycoside - Google Patents
Monoterpene glycosideInfo
- Publication number
- JP2879926B2 JP2879926B2 JP2086631A JP8663190A JP2879926B2 JP 2879926 B2 JP2879926 B2 JP 2879926B2 JP 2086631 A JP2086631 A JP 2086631A JP 8663190 A JP8663190 A JP 8663190A JP 2879926 B2 JP2879926 B2 JP 2879926B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- methanol
- chloroform
- formula
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Description
【発明の詳細な説明】 （イ）産業上の利用分野 この発明は、新規モノテルペン配糖体に関する。この
発明の配糖体は、青ジソから単離された新規物質及びそ
れから誘導される化合物である。The present invention relates to a novel monoterpene glycoside. The glycoside of the present invention is a novel substance isolated from blue diso and a compound derived therefrom.
（ロ）従来の技術 青ジソはシソ科（Labiatae）の一年生草本で、茎や葉
等に芳香があり、その葉や花穂は香辛料や交品として利
用される。古くは薬料や漬物として利用されていたこと
が記され（「倭名類衆抄」）、近年広く食用に供されて
いる。青ジソの化学的研究は古くから行われており、主
として精油成分に関する報告が数多く報告されている。
その精油成分としてはペリラアルデヒド、ペリラアルコ
ール、リモネン等が報告されている。(B) Conventional technology Blue jiso is an annual herb of Labiatae, and its stems and leaves have fragrance, and the leaves and spikes are used as spices and replacements. It was noted that it was used as a medicine and pickles in the old days ("Wa-name Zhousho"), and has been widely used for food in recent years. Chemical research on blue diso has been conducted for a long time, and many reports mainly on essential oil components have been reported.
As essential oil components, perilaldehyde, perilla alcohol, limonene and the like have been reported.
これらの精油成分中ことにペリラアルデヒドには鎮静
作用があることが知られている。一方、生姜科生薬の一
成分であるテルピネオールから誘導されたテルピニルテ
トラアセチルグリコシドが、利胆効果を有すると報告さ
れている（特開昭58−183697号公報参照）。It is known that perilaldehyde has a sedative effect especially in these essential oil components. On the other hand, terpinyltetraacetylglycoside derived from terpineol, which is a component of a ginger family herbal medicine, has been reported to have a bile effect (see Japanese Patent Application Laid-Open No. 58-183697).
（ハ）発明が解決しようとする課題 青ジソ中の上記のような精油成分は、揮散しやすく、
薬理活性の発現には、他の成分が関与しているものと考
えられた。(C) Problems to be Solved by the Invention The essential oil components as described above in blue jiso are easy to volatilize,
Other components were considered to be involved in the expression of pharmacological activity.
そこで、青ジソを水溶性有機溶媒であるメタノールで
抽出し、その抽出液をヘキサン、クロロホルムなどの有
機溶媒で処理して得られる水溶性区分から、モノテルペ
ン配糖体を分離しうることを見出し、これをさらに検討
した結果この発明を完成するに至った。Therefore, we have found that monoterpene glycosides can be separated from the water-soluble category obtained by extracting blue diso with methanol, which is a water-soluble organic solvent, and treating the extract with an organic solvent such as hexane and chloroform. As a result of further study, the present invention was completed.
（ニ）課題を解決するための手段 この発明によれば、式（Ｉ）： （式中、Ｒは水素原子またはアシル基を示す） で表されるモノテルペン配糖体が提供される。(D) Means for Solving the Problems According to the present invention, the formula (I): (Wherein, R represents a hydrogen atom or an acyl group).
上記の式（Ｉ）において、Ｒのアシル基とは、炭素数
２〜６の脂肪族カルボン酸から誘導されるアシル基（た
とえば、アセチル、プロピオニル、ブチリルなど）、置
換基を有していてもよい芳香族カルボン酸から誘導され
るアシル基（たとえば、ベンゾイル、フエナシル、ニト
ロベンゾイル、クロルベンゾイル、ジメチルアミノベン
ゾイルなど）が含まれる。好ましいアシル基は、アセチ
ルまたはプロピオニルである。In the above formula (I), the acyl group of R may be an acyl group derived from an aliphatic carboxylic acid having 2 to 6 carbon atoms (for example, acetyl, propionyl, butyryl, etc.), even if it has a substituent. Acyl groups derived from good aromatic carboxylic acids (eg, benzoyl, phenacyl, nitrobenzoyl, chlorobenzoyl, dimethylaminobenzoyl, and the like) are included. Preferred acyl groups are acetyl or propionyl.
式（Ｉ）でＲが全て水素原子の化合物は、青ジソから
抽出分離することができる。Compounds of the formula (I) wherein R is all hydrogen atoms can be extracted and separated from blue diso.
たとえば、青ジソの葉部をそのまま場合により乾燥し
て、水溶性の有機溶媒（たとえばメタノール、エタノー
ルなどの低級アルコール）で、室温〜加温下（たとえば
30〜50℃）で抽出処理を行う。アルコールの使用量は、
生青ジソの葉1Kgに対して５〜20好ましくは10〜20
である。抽出は、通常１〜７日間、好ましくは２〜３日
間漬物で行うのが好ましい。得られた抽出液は、10分の
１ないし100分の１好ましくは50分の１ないし100分の１
の容量まで濃縮する。濃縮は通常60℃以下好ましくは40
〜50℃の範囲で行われる。濃縮後、析出物を濾別し、濾
液に等量の水を加え、低極性溶媒で脂質類を除去する。
低極性溶媒としては、ｎ−ペンタン、ｎ−ヘキサン等が
好ましく、濃縮液と等量で約５回ないしは６回好ましく
はほとんど着色がなくなるまで行うのがよい。次いで残
った水層をやや極性の高い溶媒で抽出する。このときの
溶媒としてはクロロホルムあるいは酢酸エチル等が用い
られ、濃縮液と等量で約５回ないし６回行われる。得ら
れた抽出液を減圧下で濃縮して粗目的画分が得られる。For example, the leaves of blue turquoise may be dried as it is, and then dried with a water-soluble organic solvent (for example, lower alcohols such as methanol and ethanol) at room temperature to under heating (for example,
(30 ~ 50 ° C). The amount of alcohol used is
5-20, preferably 10-20, per 1 Kg of fresh blue jiso leaves
It is. The extraction is preferably carried out with pickles usually for 1 to 7 days, preferably for 2 to 3 days. The extract obtained is 1/10 to 1/100, preferably 1/50 to 1/100.
Concentrate to volume. Concentration is usually 60 ° C. or less, preferably 40
Performed in the range of 〜50 ° C. After concentration, the precipitate is separated by filtration, an equal amount of water is added to the filtrate, and lipids are removed with a low-polar solvent.
As the low-polarity solvent, n-pentane, n-hexane and the like are preferable, and the same amount as the concentrated solution is preferably used about 5 to 6 times, preferably until almost no coloring occurs. The remaining aqueous layer is then extracted with a slightly more polar solvent. Chloroform or ethyl acetate is used as a solvent at this time, and the reaction is performed about 5 to 6 times in the same amount as the concentrated liquid. The obtained extract is concentrated under reduced pressure to obtain a crude target fraction.
この粗目的画分は、常法に従って、分離、精製に付さ
れる。たとえばシリカゲルカラムクロマトグラフィー
（シリカゲル量：粗目的区分に対し20〜50倍好ましくは
20倍、展開溶媒：クロロホルム−メタノール、酢酸エチ
ル−メタノール、クロロホルム−アセトンなど）に付
し、得られる溶離液を高速液体クロマトグラフィーに付
すと、目的とする化合物を単離することができる。This crude target fraction is subjected to separation and purification according to a conventional method. For example, silica gel column chromatography (silica gel amount: 20 to 50 times, preferably
(20 times, developing solvent: chloroform-methanol, ethyl acetate-methanol, chloroform-acetone, etc.) and the resulting eluate is subjected to high performance liquid chromatography to isolate the target compound.
なお上記粗目的画分には、少なくとも４種の配糖体が
含まれることが判明している。この発明の目的物質であ
る式（Ｉ）でＲが全て水素原子の化合物以外に、たとえ
ばオイゲニールグルコピラノシドが含まれている。It has been found that the crude target fraction contains at least four glycosides. For example, eugenyl glucopyranoside is contained in addition to the compound of formula (I) in which R is all hydrogen atoms, which is the target substance of the present invention.
一方、この発明の目的物質でＲがアシル基の化合物
は、次式に従って合成によって製造することもできる。On the other hand, the compound of the present invention in which R is an acyl group can also be produced by synthesis according to the following formula.
（上記式中Ｒ′はアシル基、Ｘはブロム原子のようなハ
ロゲン原子） 上記の反応は、コーニッヒ・クノール法を利用するも
ので、式（II）のペリリルアルコールに炭酸銀の存在下
式（III）の化合物を反応さすことによって行われる。
反応は通常有機溶媒（たとえばエチルエーテル、ジオキ
サンなど）中、室温ないし若干高められた温度で行われ
る。反応後、溶媒を除去し、残渣をたとえばシリカゲル
カラムクロマトグラフィーに付し、その溶離液を濃縮
し、さらに濃縮物を再結晶すると目的物の結晶を得るこ
とができる。 (In the above formula, R 'is an acyl group, X is a halogen atom such as a bromine atom) The above reaction utilizes the Koenig-Knoll method, and is carried out by reacting a perillyl alcohol of the formula (II) with silver carbonate. It is carried out by reacting the compound of (III).
The reaction is usually carried out in an organic solvent (eg, ethyl ether, dioxane, etc.) at room temperature or slightly elevated temperature. After the reaction, the solvent is removed, the residue is subjected to, for example, silica gel column chromatography, the eluate is concentrated, and the concentrate is recrystallized to obtain the desired crystal.
また、式（Ｉ）′の化合物は、アルカリ加水分解に付
すことにより式（Ｉ）のＲが全て水素原子である化合物
に導くことができる。Further, the compound of the formula (I) ′ can be converted to a compound of the formula (I) in which all R are hydrogen atoms by subjecting the compound to alkali hydrolysis.
かくして、青ジソから分離された化合物（式（Ｉ）中
Ｒ＝Ｈ）は、１−ペリリルβ−Ｄ−グルコピラノシドで
ある。この化合物は、上記の合成法によって得ることが
できるが、対応するα−異性体もこの発明に含まれる。
また、式（Ｉ）でＲがアシル基の化合物は一般に上記の
天然物と同じ立体異性体であることが好ましいが、α−
異性体であってもよい。この発明は、β−異性体及びα
−異性体の混合物も含まれる。The compound thus isolated from blue diso (R = H in formula (I)) is 1-perylyl β-D-glucopyranoside. This compound can be obtained by the above synthesis method, but the corresponding α-isomer is also included in the present invention.
In general, the compound of the formula (I) wherein R is an acyl group is preferably the same stereoisomer as the above natural product, but α-
It may be an isomer. The invention relates to the β-isomer and α
-Mixtures of isomers are also included.
この発明の化合物は、着香料として用いることができ
る。たとえば、着香料として菓子類（ガム、アメなど）
に添加すると、口中で分解されて、シソ様の香気を呈す
ることができる。The compound of the present invention can be used as a flavoring agent. For example, confectionery (gum, candy, etc.)
When added to the mouth, it is decomposed in the mouth to give a perilla-like odor.
また、この発明の化合物は、抗菌作用や利胆作用を有
する。この抗菌作用を利用して、工業用の殺菌又は静菌
剤として用いることができる。一方利胆作用を利用して
利胆剤として用いることができる。利胆剤としては、通
常、医薬的に受容な担体または賦形剤と共に投与され
る。投与剤型としては、経口又は非経口の何れであって
もよく錠剤、カプセル剤、粉末剤、注射剤などが含まれ
る。これらの製剤は、常法によって作ることができる。Further, the compound of the present invention has an antibacterial action and a bile action. By utilizing this antibacterial action, it can be used as an industrial bactericidal or bacteriostatic agent. On the other hand, it can be used as a bile drug utilizing a bile effect. Bile agents are usually administered with a pharmaceutically acceptable carrier or excipient. The dosage form may be oral or parenteral, and includes tablets, capsules, powders, injections and the like. These preparations can be prepared by a conventional method.
（ホ）実施例 以下に実施例で本発明をさらに詳しく説明する。しか
しこれらの例は単なる実例であって本発明を限定するも
のではない。以下の参考例、実施例のカラムクロマトグ
ラフィーにおける溶出はTLC（Thin Layer Chromatograp
hy）及び高速液体クロマトグラフィー（High Performan
ce Chromatography）による観察下に行われた。TLCはメ
ルク社製のシリカゲルF254（Art.7715）を用い、展開溶
媒としてはクロロホルム：メタノール（容量比5:1）
を、検出法としてバニリン−硫酸試薬を噴霧後、加熱発
色させた。HPLCはケムコ社製のカラム（Chemcosorb 5−
ODS−H,4.0mm×150mm）を用い、溶離液として水−メタ
ノール（容量比50:50）、流量1.0ml/minで、示差屈折計
を用いて検出した。融点は微量融点測定装置で測定し未
補正である。IRスペクトルは日立製260−10、UVスペク
トルは島津製UV−210A、核磁気共鳴（NMR）スペクトル
は日本電子製JNM−GX−270、高速液体クロマトグラフィ
ーは日立製Ｌ−6200システム、ガスクロマトグラフィー
は島津製GC−9A、施光度はホリバ製SEPA200で測定し
た。NMRスペクトルは全δ値をppmで示した。(E) Examples The present invention will be described in more detail with reference to the following examples. However, these examples are merely illustrative and do not limit the invention. The elution by column chromatography in the following Reference Examples and Examples was performed by TLC (Thin Layer Chromatograp
hy) and high performance liquid chromatography (High Performan)
ce Chromatography). TLC uses silica gel F254 (Art.7715) manufactured by Merck and chloroform: methanol (volume ratio: 5: 1) as a developing solvent.
Was sprayed with a vanillin-sulfuric acid reagent as a detection method and then heated to develop a color. HPLC was performed using a column manufactured by Chemcosorb (Chemcosorb 5-
ODS-H, 4.0 mm x 150 mm), water-methanol (volume ratio 50:50) as eluent, flow rate 1.0 ml / min, and detection was performed using a differential refractometer. The melting point is measured by a micro melting point measuring apparatus and is uncorrected. The IR spectrum is Hitachi 260-10, the UV spectrum is Shimadzu UV-210A, the nuclear magnetic resonance (NMR) spectrum is JEOL's JNM-GX-270, the high performance liquid chromatography is the Hitachi L-6200 system, gas chromatography. Was measured by Shimadzu GC-9A, and the light intensity was measured by Horiba SEPA200. NMR spectra showed all δ values in ppm.
実施例1. 青ジソの葉部（10Kg）にメタノール100を加え、室
温で３日間抽出した。濾過した後、抽出液を得る。この
操作を３回繰り返した後、約100分の１量まで60℃以下
で減圧濃縮し、得られたアルコールエキスをｎ−ヘキサ
ンで脂質類を除去し、次にクロロホルムで抽出し、クロ
ロホルム抽出物を得る。クロロホルム抽出物をシリカゲ
ルカラムクロマトグラフィーにかけ、クロロホルム−メ
タノール混合溶媒で溶出させた。30％メタノールで溶出
する成分を減圧濃縮し、緑褐色油状物質を得た。この成
分を分取用TLCでRf0.3−0.4の画分を集めた後、逆相用
（ケムコソルブ５−ODS−Ｈ）のカラムに通導し、50％
メタノールで溶出し、目的物の溶出部を集め、減圧下に
蒸発乾固させて、ペリリルグルコシド500mgを得た。Example 1. Methanol 100 was added to a leaf portion (10 kg) of blue croaker and extracted at room temperature for 3 days. After filtration, an extract is obtained. After repeating this operation three times, the mixture was concentrated under reduced pressure at a temperature of 60 ° C. or lower to about 1/100 volume, the lipids were removed from the obtained alcohol extract with n-hexane, and then extracted with chloroform. Get. The chloroform extract was subjected to silica gel column chromatography, and eluted with a chloroform-methanol mixed solvent. The component eluted with 30% methanol was concentrated under reduced pressure to obtain a green-brown oily substance. After fractions of Rf 0.3-0.4 were collected by preparative TLC, this component was passed through a column for reverse phase (Chemcosolve 5-ODS-H) to give 50%
Elution was performed with methanol, and the eluted portion of the target substance was collected and evaporated to dryness under reduced pressure to obtain 500 mg of perillyl glucoside.
得られたペリリルグルコシドの物性は次に示す通りで
あった。水、メタノール、エタノール、クロロホルムに
易溶。エチルエーテルに難溶。The physical properties of the obtained perillylglucoside were as follows. Easily soluble in water, methanol, ethanol and chloroform. Poorly soluble in ethyl ether.
実施例２ 7.9gのアセトブロモグルコースと等モルの１−ペリリ
ルアルコール2.74g（0.019mol）をエーテル20mlに溶解
させ、室温で攪拌しながら、Ag2CO33.0gを加え同じ温度
で24時間攪拌する。Ag2CO3を濾過して除去した後、減圧
下で溶媒を留去して粗反応油を得る。この粗反応油をシ
リカゲルカラムクロマトグラフィーにかけ、薄層クロマ
トグラフィーによるスポット（Rf0.3）の確認を指標と
して、ｎ−ヘキサン−酢酸エチル（容量比5:1）で抽出
する成分を集め、減圧下で溶媒を留去して白色結晶を得
た。本品をエーテル−石油エーテルから再結晶して１−
ペリリルグルコシドテトラアセテート1.5gを得た。得ら
れた１−ペリリルグルコシドテトラアセテートの物性は
次に示すとおりであった。 Example 2 A solution of 7.9 g of acetobromoglucose and 2.74 g (0.019 mol) of equimolar 1-perillyl alcohol in 20 ml of ether was added with 3.0 g of Ag 2 CO 3 with stirring at room temperature for 24 hours at the same temperature. Stir. After Ag 2 CO 3 is removed by filtration, the solvent is distilled off under reduced pressure to obtain a crude reaction oil. The crude reaction oil is subjected to silica gel column chromatography, and components extracted with n-hexane-ethyl acetate (volume ratio 5: 1) are collected using the confirmation of a spot (Rf0.3) by thin-layer chromatography as an index, and collected under reduced pressure. The solvent was distilled off to obtain white crystals. This product was recrystallized from ether-petroleum ether to give 1-
1.5 g of perillyl glucoside tetraacetate were obtained. The physical properties of the obtained 1-perylylglucoside tetraacetate were as follows.
1.0gの１−ペリリルグルコシドテトラアセテートをメ
タノール10mlに溶解し、10％KOH水溶液10mlを加え、室
温で５時間攪拌しな。反応液を氷酢酸で中和した後、減
圧下40℃以下でメタノールを留去し、残液をクロロホル
ムで抽出した。クロロホルム層を減圧濃縮して、TLC上
単一の１−ペリリルグルコシドを得た。本品をクロロホ
ルム−エーテルから再結晶し、0.6gの１−ペリリルグル
コシドを得た（収率69％）。 1.0 g of 1-perylylglucoside tetraacetate was dissolved in 10 ml of methanol, 10 ml of a 10% aqueous KOH solution was added, and the mixture was not stirred at room temperature for 5 hours. After the reaction solution was neutralized with glacial acetic acid, methanol was distilled off under reduced pressure at 40 ° C. or lower, and the residue was extracted with chloroform. The chloroform layer was concentrated under reduced pressure to obtain a single 1-perylylglucoside on TLC. This product was recrystallized from chloroform-ether to obtain 0.6 g of 1-perylylglucoside (yield: 69%).
ここで得た１−ペリリルグルコシドの物性値は青ジソ
から単離した化合物のそれと施光度を除いてよく一致し
た。The physical property values of 1-perylylglucoside obtained here agreed well with those of the compound isolated from blue diso except for the degree of light irradiation.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ａ６１Ｋ 31/70 ＡＣＴ Ａ６１Ｋ 31/70 ＡＣＴ ＡＤＺ ＡＤＺ (58)調査した分野(Int.Cl.6，ＤＢ名) C07H 15/18 A61K 31/70 A61K 7/46 411 A01N 43/16 A23G 3/00 A23L 1/221 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (51) Int.Cl. 6 identification code FI A61K 31/70 ACT A61K 31/70 ACT ADZ ADZ (58) Investigation field (Int.Cl. 6 , DB name) C07H 15/18 A61K 31 / 70 A61K 7/46 411 A01N 43/16 A23G 3/00 A23L 1/221 CA (STN) REGISTRY (STN)
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2086631A JP2879926B2 (en) | 1990-03-31 | 1990-03-31 | Monoterpene glycoside |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2086631A JP2879926B2 (en) | 1990-03-31 | 1990-03-31 | Monoterpene glycoside |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03287597A JPH03287597A (en) | 1991-12-18 |
| JP2879926B2 true JP2879926B2 (en) | 1999-04-05 |
Family
ID=13892378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2086631A Expired - Fee Related JP2879926B2 (en) | 1990-03-31 | 1990-03-31 | Monoterpene glycoside |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2879926B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110832A (en) * | 1990-10-09 | 1992-05-05 | Doyle E. Chastain | Using perillyl alcohol to kill bacteria and yeasts |
| WO1996014827A1 (en) | 1994-11-10 | 1996-05-23 | Kanebo, Ltd. | Sustained-release aromatic and method of detecting microorganism by using the same |
-
1990
- 1990-03-31 JP JP2086631A patent/JP2879926B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03287597A (en) | 1991-12-18 |
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