JP3670609B2 - Antioxidants containing soybean saponins derivatives - Google Patents

Description

請求項３に係る発明は、次式５（化５）で示されるソーヤサポゲノールＢと次式６（化６）で示されるグルクロン酸誘導体とを反応させて生成した反応生成物の保護基を脱離することにより得られる３−Ｏ−Ｄ−グルクロノピラノシルソーヤサポゲノールＢを含有することを特徴とする抗酸化剤に関する。
【化５】

【化６】

（尚、式中Ｘは反応性基、Ｙは水酸基の保護基、Ｚはカルボキシル基の保護基である。）
【０００８】
【発明の実施の形態】
以下、本発明に係るダイズサポニン類誘導体を含有する抗酸化剤について説明する。本発明に係る抗酸化剤の有効成分は、３−Ｏ−Ｄ−グルクロノピラノシルソーヤサポゲノールＢである。
３−Ｏ−Ｄ−グルクロノピラノシルソーヤサポゲノールＢには、α体とβ体の二つの異性体が存在し得る。本発明では、α体、β体のいずれも抗酸化剤として用いることができるが、次式７（化７）で示されるβ体を使用することが好ましい。この理由は、α体に比べてβ体の方が、優れた抗酸化性を有するからである。
【０００９】
【化７】

【００１０】
次に、３−Ｏ−Ｄ−グルクロノピラノシルソーヤサポゲノールＢの製造方法の一例を説明する。３−Ｏ−Ｄ−グルクロノピラノシルソーヤサポゲノールＢの製造方法としては、次式８（化８）で示されるソーヤサポゲノールＢに、次式９（化９）で示されるグルクロン酸誘導体を反応させた後に、保護基を除去することにより製造することができる。
【００１１】
【化８】

【００１２】
【化９】

（尚、式中Ｘは反応性基、Ｙは水酸基の保護基、Ｚはカルボキシル基の保護基である。）
【００１３】
尚、式９（化９）中の反応性基（Ｘ）とは、式８（化８）で示されるソーヤサポゲノールＢの水酸基と反応してエーテル結合を生ずることができるものである。具体的には、ハロゲン原子であることが好ましく、臭素原子であることがより好ましい。
【００１４】
式９（化９）中の水酸基の保護基（Ｙ）とは、式９中の水酸基のうち反応に関与する必要がない水酸基を、式８（化８）で示されるソーヤサポゲノールＢ中と反応しないように保護することができるものであれば特に限定されず、一般的に水酸基の保護基として使用されているものであればよい。
具体的には、アシル基、ケイ素含有基を例示することができる。アシル基としては、アセチル基、プロピオニル基のような低級アルカノイル基、ｐ−ブロモフェナシル基、ベンジルオキシカルボニル基のような芳香族アシル基などを例示することができる。
またケイ素含有基としては、トリメチルシリル基、ジメチルメトキシシリル基、トリプトキシシリル基などを例示することができる。
【００１５】
式９（化９）中のカルボキシル基の保護基（Ｚ）とは、一般的にカルボキシル基の保護基として使用されるものであれば特に限定はされない。例えば、エステル又は塩が好ましく用いられ、エステルとしては、メタノール、エタノール、ｔ−ブチルアルコール等の低級アルカノール、ｐ−ニトロベンジルアルコール等の芳香族アルコール、トリメチルシリルクロライド、ジメチルメトキシシリルクロライド等のケイ素化合物、ジエトキシホスホニルクロライド等の燐化合物等で形成されるエステルが好ましい。
また塩としては、ナトリウム、カリウム、銀等の金属塩、トリエチルアミン等のアミン塩などを例示することができる。
【００１６】
また式９（化９）で示されるグルクロン酸誘導体中の保護基（Ｘ，Ｙ，Ｚ）の好ましい組合せとしては、Ｘが臭素原子、Ｙがアセチル基、Ｚがメチル基である。この化合物は、例えば、グルクロン酸を原料として、まず四つの水酸基を三フッ化ホウ素酸エーテル錯塩、過塩素酸のような触媒の存在下、無水酢酸でアセチル化する。次いで、有機溶媒中で、カルボキシル基をジアゾメタンのようなアルキル化剤でメチルエステル化する。得られる１，２，３，４−テトラ−Ｏ−アセチル−Ｄ−グルクロン酸メチルを有機溶媒中で臭化水素のようなハロゲン化剤でブロム化することにより得ることができる。
式８（化８）で示されるソーヤサポゲノールＢは醤油の醗酵過程で生じる油又は搾り粕より比較的容易に得ることができる。
【００１７】
式８（化８）に示されるソーヤサポゲノールＢと、式９（化９）で示されるグルクロン酸誘導体を反応させることにより、ソーヤサポゲノールＢの三位の水酸基に選択的にグルクロン酸誘導体が導入されて次式１０（化１０）に示されるソーヤサポゲノールＢ誘導体が得られる。
【００１８】
【化１０】

【００１９】
上記反応に用いられる有機溶媒は特に限定されないが、ベンゼン、ジオキサン、トルエン、キシレン、クロロホルム、テトラヒドロフラン、塩化メチレン、ジメチルホルムアミドなどの非極性有機溶媒の一種又は二種以上の混合溶媒が好ましく用いられ、ベンゼン、ベンゼンとジオキサンとの混合溶媒がより好ましく用いられる。
反応温度は特に限定されないが、室温から用いられる有機溶媒の沸点程度の温度が好ましい。
【００２０】
また上記反応は無水の状態で行われることが好ましい。特に、保護基（Ｘ及びＹ）が水により脱離するものを使用する場合は、無水状態に維持することが望まれる。無水状態に維持するためには、前記有機溶媒として脱水処理した有機溶媒を使用するとともに、硫酸ナトリウムや硫酸カルシウム等の脱水剤を添加すればよい。
さらに上記反応により生ずる副生成物、例えばハロゲン化水素を受容することができる化合物を添加することもできる。ハロゲン化水素の受容体としては、炭酸銀を例示することができる。炭酸銀は室温で低圧乾燥したものを使用することが好ましい。
【００２１】
こうして得られた式１０（化１０）に示されるソーヤサポゲノールＢ誘導体の保護基（Ｙ及びＺ）を除去することにより、３−Ｏ−Ｄ−グルクロノピラノシルソーヤサポゲノールＢを得ることができる。
保護基の除去は、通常の保護基の除去方法に従って行えばよく、例えば、水酸化ナトリウムや水酸化カリウムの水溶液を使用することにより除去することができる。
【００２２】
尚、上記反応により、ソーヤサポゲノールＢの三位の水酸基において、α体とβ体の二種類の異性体が生成する。本発明ではβ体を選択的に生成することが好ましい。
このために、保護基（Ｙ）としてアセチル基などの低級アルカノイル基を使用することが好ましい。また式１０（化１０）に示されるソーヤサポゲノールＢ誘導体には二つの遊離水酸基が存在するので、一旦これを低級アルカノイル基により保護して精製処理した後に、保護基の脱離を行うことが望まれる。
【００２３】
本発明に係る抗酸化剤には、本発明の効果が損なわれない範囲内であれば、その目的に応じて、食品、化粧品、医薬品、医薬部外品などで用いられている抗酸化剤、例えば、ジブチルヒドロキシトルエン、ブチルヒドロキシアミソール、没食子酸プロピル、没食子酸オクチル、トコフェロール、エリソルビン酸、エリソルビン酸ナトリウム、オルトトリルビグアナイド、チオジプロピオン酸ジラウリル、天然ビタミンＥ、パラヒドロキシアニソール、フィチン酸などを適宜任意に配合することができる。
【００２４】
本発明に係る抗酸化剤は、食品、化粧品、医薬品、医薬部外品などの抗酸化剤として好適に使用することができる。
例えば、コーン油、菜種油、綿実油、大豆油、サフラワー油、ヒマワリ油、ごま油、マーガリン、ショートニング、ドレッシング等の油脂、或いは和菓子、洋菓子、スナック菓子、氷菓、清涼飲料水、嗜好飲料、乳製品、大豆加工食品、レトルト食品、冷凍食品などの各種食品に使用することができる。また、本発明に係る抗酸化剤は、化粧水、乳液、ローション、クリーム、美容液、オイル、パック、リップクリームなどの基礎化粧品、ヘアートニック、ヘアーリキッド等の整髪料、育毛・養毛料等の頭髪化粧品、ファンデーション、口紅、頬紅、アイシャドー、アイライナー、マスカラ、アイブロウライナー等のメークアップ化粧品等に使用することができる。
また、本発明に係る抗酸化剤は、上記した食品、化粧品、医薬品、医薬部外品などの酸化を防止するだけでなく、ヒトの生体内酸化により発生する活性酸素やフリーラジカルを消去または低減することができる。
【００２５】
【実施例】
以下、本発明を実施例に基づき説明するが、本発明はこれらの実施例に何ら限定されるものではない。
＜試験例１：試料の調製＞
１．実施例の試料の調製
Ｄ−グルクロン酸（ナカライ社製）３．０ｇを無水酢酸（２００ｍＬ）−三フッ素化ホウ素エーテル錯体（４ｍＬ）に溶解し、５℃で１２時間攪拌した。これを氷水中にあけて、酢酸エチルで抽出した後、飽和炭酸水素ナトリウム水溶液、飽和食塩水、でそれぞれ三回洗浄し、無水硫酸ナトリウムで乾燥した。無水硫酸ナトリウムを濾別後、酢酸エチルを減圧留去して、残渣をメタノール（５０ｍＬ）に溶解した。ジアゾメタンのエーテル溶液を加えてメチル化後、室温で５時間放置した。溶媒を減圧留去した後、残渣をシリカゲルカラムクロマトグラフィー（シリカゲル（メルク社製、６０〜１２０メッシュ）、展開溶媒（クロロホルム：酢酸エチル＝５０：１））で精製処理して、１，２，３，４−テトラ−Ｏ−アセチル−Ｄ−グルクロン酸メチル（４．７ｇ）を得た。
得られた１，２，３，４−テトラ−Ｏ−アセチル−Ｄ−グルクロン酸メチル（４．０ｇ）をクロロホルム（１００ｍＬ）に溶解し、２５％臭化水素−酢酸溶液（１５０ｍＬ）を加え、室温で１２時間攪拌した。氷水中にあけて、クロロホルムで抽出後、飽和炭酸水素ナトリウム水溶液、飽和食塩水で、それぞれ三回洗浄し、無水硫酸ナトリウムで乾燥した。無水硫酸ナトリウムを濾別後、濾液を減圧留去した後、残渣をシリカゲルカラムクロマトグラフィー（シリカゲル（メルク社製、６０〜１２０メッシュ）、展開溶媒（ベンゼン：アセトン＝３０：１））で精製処理して、２，３，４−トリ−Ｏ−アセチル−１−ブロモ−１−デオキシ−α−Ｄ−グルクロン酸メチル（２．５ｇ）を得た。
次に、ソーヤサポゲノールＢ（１．０ｇ）の乾燥ベンゼン溶液（２５０ｍＬ）に、硫酸カルシウム（５ｇ）、炭酸銀（１．８ｇ）を加えた後、前記２，３，４−トリ−Ｏ−アセチル−１−ブロモ−１−デオキシ−α−Ｄ−グルクロン酸メチル（２．５ｇ）の乾燥ベンゼン溶液（１０ｍＬ）を加え、５時間、加熱還流した。無機物を濾別後、濾液を減圧留去して得られた残渣を無水酢酸（５ｍＬ）−ピリジン（１０ｍＬ）に溶解して、室温で８時間攪拌した。氷水中にあけて酢酸エチルで抽出した後、５％塩酸水溶液、飽和炭酸水素ナトリウム水溶液、飽和食塩水で、それぞれ三回洗浄して、無水硫酸ナトリウムで乾燥した。硫酸ナトリウムを濾別した後、減圧留去して、残渣をシリカゲルカラムクロマトグラフィー（シリカゲル（メルク社製、６０〜１２０メッシュ）、展開溶媒（ベンゼン：アセトン＝５０：１〜１５：１））で精製処理して、３−Ｏ−β−Ｄ−グルクロノピラノシルソーヤサポゲノールＢのペンタ−Ｏ−アセチル−モノメチルエステル（１．０ｇ）を得た。これをメタノール（５０ｍＬ）に溶解した後、１０％水酸化カリウム水溶液（２５ｍＬ）を加えて、６０℃で３時間攪拌した。ダウエックス５０ｗ×８（Ｈ^＋型）で中和して、前記樹脂を濾別後、濾液を減圧留去することで、３−Ｏ−β−Ｄ−グルクロノピラノシルソーヤサポゲノールＢ（０．７ｇ）を得た。これを実施例の試料とした。
【００２６】
２．比較例の試料の調製
ダイズ種子粉末（１００ｇ）を１０Ｌのｎ−ヘキサンで２回、１時間ずつ加熱抽出して脱脂処理した。脱脂処理されたダイズ種子粉末を１０Ｌのメタノールで２回、三時間ずつ加熱抽出した。抽出液を減圧留去した後、残渣を１Ｌの水飽和ｎ−ブタノールを用いて１時間、三回ずつ蒸気浴上で攪拌しながら溶解させた。得られた溶液を３００ｍＬのｎ−ブタノール飽和水を用いて３回洗浄した後、ｎ−ブタノール層を回収した。これを８０℃以下の温度で減圧留去した後、残渣を３００ｍＬのメタノールに溶解して、６Ｌのエーテル中に攪拌しながら滴下した。２４時間静置後、析出物を濾別し、６０℃以下の温度で減圧乾燥して、ダイズサポニン類（２．５ｇ）を得た。得られたダイズサポニン類を比較例１の試料とした。
【００２７】
＜試験例２：抗酸化作用試験＞
上記調製した実施例及び比較例の各試料を使用して抗酸化作用試験を行った。試験方法は、まず、エタノールに上記各試料を溶解して８重量％の濃度となるように調製したエタノール溶液を、リノール酸１０ｇに１重量％添加した。この検液を６０℃の恒温槽に入れ、エアーポンプを用いて連続３時間通気した。その後、クロロホルムを用いてリノール酸を抽出し、そのＰＯＶ（過酸化物価）を常法に従い測定した。尚、対照例として、各試料を添加しない場合も同様に測定を行った。結果を表１に記載する。
【００２８】
【表１】

【００２９】
表１に記載のとおり、本発明に係る抗酸化剤は、優れた抗酸化能を有していることがわかる。また、優れた抗酸化能が報告されているダイズサポニン類と比較しても優れた抗酸化能を有していることが分かる。
【００３０】
以下、本発明に係るダイズサポニン誘導体を含有した抗酸化剤が配合された食品の処方例を示す。尚、配合量は重量％である。
＜処方例１；キャンディー＞
グラニュー糖 ５４．０
水飴 ４２．０
酸味料 ０．８
香料 ０．４
実施例の抗酸化剤 ２．８
合計 １００．０重量％
【００３１】
＜処方例２；清涼飲料水＞
果糖、ブドウ糖、液糖 １４．０
クエン酸 ０．２
香料 ０．１
実施例の抗酸化剤 ３．０
水 残 量
合計 １００．０重量％
【００３２】
＜処方例３；液体シャンプー＞
ポリオキシエチレン（３）ラウリル硫酸
トリエタノールアミン（４０％） ３０．０
ラウリル硫酸トリエタノールアミン（４０％） １５．０
ラウロイルジエタノールアミド ６．０
塩化ナトリウム ０．１
クエン酸 ０．１
実施例の抗酸化剤 ０．０５
香料 適 量
防腐剤 適 量
精製水 残 量
合計 １００．０重量％
【００３３】
【発明の効果】
以上詳述した如く、本発明に係るダイズサポニン誘導体を含有した抗酸化剤は、優れた抗酸化能を有するとともに、安価で容易に入手することができ、しかも安全性が高い、という効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antioxidant containing soybean saponins derivatives. Its purpose is, which has an excellent anti-oxidation ability, inexpensive and readily available, and moreover to provide a highly safe antioxidant.
[0002]
[Prior art]
Many of fats and oils, waxes, surfactants, fragrances, vitamins and the like used as raw materials for foods and cosmetics are gradually oxidized by reacting with oxygen in the air. The oxidation reaction that occurs at normal temperature by contacting with oxygen in the air is called auto-oxidation. Fatty acids such as fats and oils, waxes, surfactants and fragrances, aging of polymer compounds, photobleaching of pigments, and the like are due to auto-oxidation.
[0003]
Antioxidants are blended in foods and cosmetics in order to prevent the above-mentioned oxidation reaction, prevent deterioration of quality, and maintain long-term stability.
Antioxidants used as food additives include erythorbic acid, dibutylhydroxytoluene, tocopherol, propyl gallate and the like.
Antioxidants blended in cosmetics include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, tocopherol and the like.
[0004]
[Problems to be solved by the invention]
On the other hand, Japanese Patent Publication No. 61-8867 describes that soybean saponins contained in soybean seeds have an antioxidant action.
In Japanese Patent Publication No. 61-8867, Soya saponin I, Soya saponin II, Soya saponin III using soya sapogenol B as an aglycon, and Soya saponin A ₁ and Soya saponin A ₂ using soya saponin A as an aglycon are disclosed. Soybean saponins such as saponins have antioxidant activity and can be used as antioxidants for foods, cosmetics, etc. In addition, soyasapogenol B is aglycon compared to soybean saponins using soyasapogenol A as aglycone It is described that the soybean saponins described above have an excellent antioxidant action, particularly under low concentration conditions.
[0005]
However, even if the content of soybean saponins in soybean seeds is large, it is very low, about several percent, and soy saponins with aglycone having soy sapogenol B, which has a superior antioxidant action, The content was as very low as 0.1 to 0.2%.
In addition, when trying to obtain soybean saponins using a soya sapogenol B having an aglycone having a superior action as an aglycon, separation from soybean saponins having an aglycon similar in structure to the soya sapogenol A is very much. It was complicated.
As described above, soybean saponins have an antioxidant effect, but a large amount of soybean seeds is required to obtain a sufficient amount of soybean saponins. In addition, soybean saponins having more excellent effects cannot be easily obtained because the separation operation is complicated.
[0006]
As a result of intensive studies in view of the above circumstances, the present inventors have made soya sapogenol B contained in a large amount in oil-soluble waste such as soy sauce generated in the production process of soybean fermented food. It was found that the soybean saponins derivatives synthesized as above have excellent antioxidant ability, can be easily obtained at low cost, and have high safety, and the present invention has been completed.
[0007]
[Means for Solving the Problems]
That is, the invention according to claim 1 relates to an antioxidant containing 3-OD-glucuronopyranosylsoya sapogenol B.
Invention, the 3-O-D-glucuronolactone pyranosyl Sawyer support gate Knoll B is, 3-O-β-D- glucuronolactone pyranosyl represented by the following formula 4 (of 4) according to claim 2 The antioxidant according to claim 1, which is Soya Sapogenol B.
[ Chemical 4 ]

Invention, protecting groups of the formula 5 (of 5) soya support gate Nord B and equation 6 (of 6) reaction products of a glucuronic acid derivative is generated by reacting represented by represented by the according to claim 3 The present invention relates to an antioxidant characterized by containing 3-OD-glucuronopyranosylsoya sapogenol B obtained by detaching saponin.
[Chemical formula 5 ]

[Chemical 6 ]

(Wherein, X is a reactive group, Y is a protecting group for a hydroxyl group, and Z is a protecting group for a carboxyl group.)
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a description will be given to antioxidants containing soy saponins derivative according to the present invention. The active ingredient of the antioxidant according to the present invention is 3-OD-glucuronopyranosylsoya sapogenol B.
In 3-OD-glucuronopyranosylsoya sapogenol B, there can exist two isomers of α-form and β-form. In the present invention, both α-form and β-form can be used as an antioxidant, but it is preferable to use a β-form represented by the following formula 7 (Chemical Formula 7 ). This is because the β form has superior antioxidant properties compared to the α form.
[0009]
[Chemical 7 ]

[0010]
Next, an example of a method for producing 3-OD-glucuronopyranosylsoya sapogenol B will be described. 3-O-D-As a method for producing glucuronolactone pyranosyl Sawyer support gate Nord B is a soya support gate Nord B represented by the following formula 8 (of 8), glucuronic represented by the following formula 9 (of 9) After reacting the acid derivative, it can be produced by removing the protecting group.
[0011]
[Chemical 8 ]

[0012]
[Chemical 9 ]

(Wherein, X is a reactive group, Y is a protecting group for a hydroxyl group, and Z is a protecting group for a carboxyl group.)
[0013]
Here, the reactive group of the formula 9 (of 9) in (X), is capable of reacting with the hydroxyl groups of Sawyer support gate Nord B represented by the formula 8 (of 8) produce an ether linkage. Specifically, a halogen atom is preferable, and a bromine atom is more preferable.
[0014]
The protecting group for the hydroxyl group of the formula 9 (of 9) in (Y), a hydroxy group need not be involved in the reaction of hydroxyl groups in the formula 9, soya support in gate Nord B represented by the formula 8 (of 8) It is not particularly limited as long as it can be protected so as not to react with N, and any one generally used as a hydroxyl-protecting group may be used.
Specifically, an acyl group and a silicon-containing group can be exemplified. Examples of the acyl group include lower alkanoyl groups such as acetyl group and propionyl group, aromatic acyl groups such as p-bromophenacyl group and benzyloxycarbonyl group.
Examples of the silicon-containing group include a trimethylsilyl group, a dimethylmethoxysilyl group, and a tryptoxysilyl group.
[0015]
The protecting group of the carboxyl group of the formula 9 (of 9) in (Z), generally particularly limited so long as it is used as a protecting group of a carboxyl group is not. For example, esters or salts are preferably used. Examples of the esters include lower alcohols such as methanol, ethanol and t-butyl alcohol, aromatic alcohols such as p-nitrobenzyl alcohol, silicon compounds such as trimethylsilyl chloride and dimethylmethoxysilyl chloride, Esters formed with phosphorus compounds such as diethoxyphosphonyl chloride are preferred.
Examples of the salt include metal salts such as sodium, potassium and silver, and amine salts such as triethylamine.
[0016]
The protecting group in the glucuronic acid derivative of the formula 9 (of 9) (X, Y, Z) as a preferred combination of, X is a bromine atom, Y is an acetyl group, Z is a methyl group. In this compound, for example, glucuronic acid is used as a raw material, and four hydroxyl groups are first acetylated with acetic anhydride in the presence of a catalyst such as boron trifluoride etherate or perchloric acid. The carboxyl group is then methyl esterified with an alkylating agent such as diazomethane in an organic solvent. The resulting methyl 1,2,3,4-tetra-O-acetyl-D-glucuronic acid can be obtained by bromination with a halogenating agent such as hydrogen bromide in an organic solvent.
Sawyer support gate Nord B represented by the formula 8 (of 8) can be obtained relatively easily than oil or lees occurring during the process of fermentation of soy sauce.
[0017]
And Sawyer support gate Nord B shown in Equation 8 (of 8), by reacting a glucuronic acid derivative of the formula 9 (of 9), selectively glucuronic acid to a three-position hydroxyl group of Sawyer support gate Nord B Sawyer support gate Nord B derivative derivative is introduced as shown in the following equation 10 (of 10) is obtained.
[0018]
[Chemical formula 10 ]

[0019]
The organic solvent used in the above reaction is not particularly limited, but one or more mixed solvents of nonpolar organic solvents such as benzene, dioxane, toluene, xylene, chloroform, tetrahydrofuran, methylene chloride, dimethylformamide and the like are preferably used. Benzene or a mixed solvent of benzene and dioxane is more preferably used.
Although reaction temperature is not specifically limited, The temperature about the boiling point of the organic solvent used from room temperature is preferable.
[0020]
The above reaction is preferably carried out in an anhydrous state. In particular, in the case where a protecting group (X and Y) is eliminated by water, it is desirable to maintain an anhydrous state. In order to maintain an anhydrous state, a dehydrated organic solvent may be used as the organic solvent and a dehydrating agent such as sodium sulfate or calcium sulfate may be added.
Further, a by-product generated by the above reaction, for example, a compound capable of accepting hydrogen halide can be added. Examples of the hydrogen halide acceptor include silver carbonate. It is preferable to use silver carbonate that has been dried at low pressure at room temperature.
[0021]
By removing soya support gate Nord B derivatives protecting groups (Y and Z) shown in Equation 10 (of 10) thus obtained, the 3-O-D-glucuronolactone pyranosyl Sawyer support gate Nord B Can be obtained.
The removal of the protecting group may be carried out according to the usual method for removing the protecting group, and for example, it can be removed by using an aqueous solution of sodium hydroxide or potassium hydroxide.
[0022]
The above reaction produces two types of isomers, α-form and β-form, at the hydroxyl group at the 3-position of Soyasapogenol B. In the present invention, it is preferable to selectively produce β-form.
Therefore, it is preferable to use a lower alkanoyl group such as an acetyl group as the protecting group (Y). Since the soya support gate Nord B derivative represented the formula 10 (of 10) there are two free hydroxyl groups, after purification treatment protected by temporarily lower alkanoyl group this that removal of the protecting groups Is desired.
[0023]
In the antioxidant according to the present invention, as long as the effects of the present invention are not impaired, the antioxidant used in foods, cosmetics, pharmaceuticals, quasi drugs, etc., depending on the purpose, For example, dibutylhydroxytoluene, butylhydroxyamisole, propyl gallate, octyl gallate, tocopherol, erythorbic acid, sodium erythorbate, orthotolyl biguanide, dilauryl thiodipropionate, natural vitamin E, parahydroxyanisole, phytic acid, etc. It can mix | blend arbitrarily arbitrarily.
[0024]
The antioxidant according to the present invention can be suitably used as an antioxidant for foods, cosmetics, pharmaceuticals, quasi drugs and the like.
For example, oils such as corn oil, rapeseed oil, cottonseed oil, soybean oil, safflower oil, sunflower oil, sesame oil, margarine, shortening, dressing, or Japanese confectionery, Western confectionery, snack confectionery, ice confectionery, soft drinks, beverages, dairy products, soybeans It can be used for various foods such as processed foods, retort foods, and frozen foods. In addition, the antioxidant according to the present invention includes skin lotions, emulsions, lotions, creams, cosmetics, oils, packs, lip balms, and other basic cosmetics, hair styling products such as hair nicks, hair liquids, hair growth and hair restorations, etc. It can be used for makeup cosmetics such as hair cosmetics, foundations, lipsticks, blushers, eye shadows, eye liners, mascaras, eyebrow liners, and the like.
Further, the antioxidant according to the present invention not only prevents oxidation of the above-mentioned foods, cosmetics, pharmaceuticals, quasi drugs, but also eliminates or reduces active oxygen and free radicals generated by human in vivo oxidation. can do.
[0025]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples at all.
<Test Example 1: Preparation of sample>
1. Example Sample Preparation 3.0 g of D-glucuronic acid (Nacalai) was dissolved in acetic anhydride (200 mL) -boron trifluoride ether complex (4 mL) and stirred at 5 ° C. for 12 hours. This was poured into ice water, extracted with ethyl acetate, washed three times with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure, and the residue was dissolved in methanol (50 mL). After adding methyl ether with diazomethane and leaving it at room temperature for 5 hours. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (silica gel (Merck, 60-120 mesh), developing solvent (chloroform: ethyl acetate = 50: 1)), 1, 2, Methyl 3,4-tetra-O-acetyl-D-glucuronate (4.7 g) was obtained.
The resulting methyl 1,2,3,4-tetra-O-acetyl-D-glucuronate (4.0 g) was dissolved in chloroform (100 mL), and a 25% hydrogen bromide-acetic acid solution (150 mL) was added. Stir at room temperature for 12 hours. The mixture was poured into ice water, extracted with chloroform, washed three times with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. After filtering off anhydrous sodium sulfate, the filtrate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (silica gel (Merck, 60-120 mesh), developing solvent (benzene: acetone = 30: 1)). Thus, methyl 2,3,4-tri-O-acetyl-1-bromo-1-deoxy-α-D-glucuronate (2.5 g) was obtained.
Next, after adding calcium sulfate (5 g) and silver carbonate (1.8 g) to a dry benzene solution (250 mL) of soya sapogenol B (1.0 g), the 2,3,4-tri-O is added. A dry benzene solution (10 mL) of methyl acetyl-1-bromo-1-deoxy-α-D-glucuronate (2.5 g) was added, and the mixture was heated to reflux for 5 hours. The inorganic substance was filtered off, and the filtrate was evaporated under reduced pressure. The resulting residue was dissolved in acetic anhydride (5 mL) -pyridine (10 mL) and stirred at room temperature for 8 hours. After opening in ice water and extracting with ethyl acetate, each was washed three times with 5% hydrochloric acid aqueous solution, saturated sodium hydrogen carbonate aqueous solution and saturated brine, and dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, the residue was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (silica gel (Merck, 60-120 mesh), developing solvent (benzene: acetone = 50: 1-15: 1)). Purification was performed to obtain penta-O-acetyl-monomethyl ester (1.0 g) of 3-O-β-D-glucuronopyranosylsoya sapogenol B. This was dissolved in methanol (50 mL), 10% aqueous potassium hydroxide solution (25 mL) was added, and the mixture was stirred at 60 ° C. for 3 hr. 3-O-β-D-glucuronopyranosylsoyasapogenol B is obtained by neutralizing with Dowex 50w × 8 (H ⁺ type), filtering the resin, and distilling the filtrate under reduced pressure. (0.7 g) was obtained. This was used as a sample of the example.
[0026]
2. Preparation of Sample for Comparative Example Soybean seed powder (100 g) was heat-extracted twice with 10 L of n-hexane for 1 hour, and degreased. The defatted soybean seed powder was extracted by heating twice with 10 L of methanol for 3 hours. After evaporating the extract under reduced pressure, the residue was dissolved in 1 L of water-saturated n-butanol with stirring on a steam bath three times for 1 hour. The obtained solution was washed with 300 mL of n-butanol saturated water three times, and then the n-butanol layer was recovered. After this was distilled off under reduced pressure at a temperature of 80 ° C. or lower, the residue was dissolved in 300 mL of methanol and added dropwise to 6 L of ether while stirring. After standing for 24 hours, the precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 ° C. or lower to obtain soybean saponins (2.5 g). The obtained soybean saponins were used as samples of Comparative Example 1.
[0027]
<Test Example 2: Antioxidation test>
Antioxidation test was conducted using the samples prepared in Examples and Comparative Examples. In the test method, first, 1% by weight of an ethanol solution prepared by dissolving each sample in ethanol to a concentration of 8% by weight was added to 10 g of linoleic acid. This test solution was placed in a constant temperature bath at 60 ° C. and aerated for 3 hours continuously using an air pump. Thereafter, linoleic acid was extracted using chloroform, and its POV (peroxide value) was measured according to a conventional method. As a control example, the same measurement was performed when each sample was not added. The results are listed in Table 1.
[0028]
[Table 1]

[0029]
As shown in Table 1, it can be seen that the antioxidant according to the present invention has excellent antioxidant ability. Moreover, it turns out that it has the antioxidant ability outstanding also compared with the soybean saponins with which the outstanding antioxidant ability was reported.
[0030]
Hereinafter, the formulation example of the foodstuff mix | blended with the antioxidant containing the soybean saponin derivative which concerns on this invention is shown. In addition, a compounding quantity is weight%.
<Prescription Example 1; Candy>
Granulated sugar 54.0
Minamata 42.0
Acidulant 0.8
Fragrance 0.4
Antioxidant of Example 2.8
Total 100.0% by weight
[0031]
<Prescription Example 2: Soft drink>
Fructose, glucose, liquid sugar 14.0
Citric acid 0.2
Fragrance 0.1
Antioxidant of Example 3.0
Residual amount of water
Total 100.0% by weight
[0032]
<Prescription Example 3; Liquid Shampoo>
Polyoxyethylene (3) lauryl sulfate Triethanolamine (40%) 30.0
Lauryl sulfate triethanolamine (40%) 15.0
Lauroyl diethanolamide 6.0
Sodium chloride 0.1
Citric acid 0.1
Antioxidant of Example 0.05
Perfume appropriate amount Preservative appropriate amount
Purified water balance
Total 100.0% by weight
[0033]
【The invention's effect】
As described above in detail, the antioxidant containing the soybean saponin derivative according to the present invention has excellent antioxidant ability, can be easily obtained at low cost, and has the effect of high safety. .

Claims (3)

An antioxidant comprising 3-OD-glucuronopyranosylsoya sapogenol B. The 3-OD-glucuronopyranosyl soya sapogenol B is 3-O-β-D-glucuronopyranosyl soya sapogenol B represented by the following formula 1 (Formula 1) The antioxidant of Claim 1 characterized by these.

It is obtained by removing the protecting group of the reaction product produced by reacting soyasapogenol B represented by the following formula 2 (Chemical formula 2) with the glucuronic acid derivative represented by the following formula 3 (Chemical formula 3). An antioxidant comprising 3-OD-glucuronopyranosylsoya sapogenol B.

(Wherein, X is a reactive group, Y is a protecting group for a hydroxyl group, and Z is a protecting group for a carboxyl group.)