JP2876162B2 - ω-Hydroxyalkyl-β-galactoside compound and method for producing the same - Google Patents
ω-Hydroxyalkyl-β-galactoside compound and method for producing the sameInfo
- Publication number
- JP2876162B2 JP2876162B2 JP2274339A JP27433990A JP2876162B2 JP 2876162 B2 JP2876162 B2 JP 2876162B2 JP 2274339 A JP2274339 A JP 2274339A JP 27433990 A JP27433990 A JP 27433990A JP 2876162 B2 JP2876162 B2 JP 2876162B2
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- JP
- Japan
- Prior art keywords
- formula
- galactoside
- hydroxyalkyl
- compound
- present
- 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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- Saccharide Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、ω−ヒドロキシアルキル−β−ガラクトシ
ド化合物に関するものである。The present invention relates to an ω-hydroxyalkyl-β-galactoside compound.
近年、アルキルグリコシドが低刺激性、低毒性生分解
性という特徴を持つ天然由来の非イオン界面活性剤とし
て注目されているが、本発明の化合物は新規なアルキル
グリコシドの１種であり、同様な用途において特異な性
能を発揮するものと期待されている。In recent years, alkyl glycosides have attracted attention as naturally occurring nonionic surfactants having characteristics of low irritation and low toxicity and biodegradability. However, the compounds of the present invention are one type of novel alkyl glycosides, and It is expected to exhibit unique performance in applications.
［従来の技術］ アルキルグリコシドの合成には様々な方法が報告され
ているが、代表的なものはデンプンの加水分解物あるい
は精製グルコースを糖源とし、アルコールと酸触媒の存
在下に直接反応させるフィッシャー法である。しかし、
この方法は生成物が反応中に着色し易く、また立体配置
の異なる副生物が生成する等の欠点を有している。ま
た、アルキルグリコシド自体の性質としても溶解度が低
すぎることや洗浄力の点で十分満足できるものではな
い。[Prior art] Various methods have been reported for the synthesis of alkyl glycosides, but a typical one is to directly react with an alcohol and an acid catalyst in the presence of a hydrolyzate of starch or purified glucose as a sugar source. Fisher method. But,
This method has disadvantages such as that the product is liable to be colored during the reaction and that by-products having different configurations are formed. In addition, the properties of the alkyl glycoside itself are not sufficiently satisfactory in terms of too low solubility and detergency.
［発明が解決しようとする課題］ 本発明の目的は、新規なアルキルグリコシドとしてω
−ヒドロキシアルキル−β−ガラクトシド化合物および
酵素によるその製造方法を提供することである。[Problems to be Solved by the Invention] An object of the present invention is to provide a novel alkyl glycoside as ω
-Hydroxyalkyl-β-galactoside compounds and their production by enzymes.
［課題を解決するための手段］ すなわち本発明は、一般式（Ｉ） （式中、ｎは８ないし12の整数を表す。） でしめされるω−ヒドロキシアルキル−β−ガラクトシ
ド化合物、および 一般式（II） （式中、Ｒはアルキル基、アリル基及び糖残基から選ば
れる１種を表す。） で示されるガラクトース誘導体をリン酸緩衝液と有機溶
媒の混合液中で、β−ガラクトシダーゼの存在下、一般
式（III） HO−CnH2n−OH （III） （式中、ｎは８ないし12の整数を表す。） で示されるα，ω−長鎖ジオールと反応させることを特
徴とする一般式（Ｉ） （式中、ｎは前記に同じ。） で示されるω−ヒドロキシアルキル−β−ガラクトシド
化合物の製造方法である。[Means for Solving the Problems] That is, the present invention provides a compound represented by the general formula (I): (In the formula, n represents an integer of 8 to 12.) An ω-hydroxyalkyl-β-galactoside compound represented by the following general formula (II): (In the formula, R represents one selected from an alkyl group, an allyl group, and a sugar residue.) A galactose derivative represented by the following formula is prepared in a mixture of a phosphate buffer and an organic solvent in the presence of β-galactosidase. formula (III) (wherein, n represents. an integer of 8 to 12) HO-C n H 2n -OH (III) represented by alpha, generally characterized by reacting an ω- long chain diol Formula (I) (Wherein, n is the same as described above.) A method for producing an ω-hydroxyalkyl-β-galactoside compound represented by the following formula:
本発明の一般式（Ｉ）で示されるω−ヒドロキシアル
キル−β−ガラクトシド化合物は、末端に水酸基を持つ
炭素数８ないし12のアルキル基を有することを特徴とす
るグリコシドである。その構造上の特徴により、本化合
物は水への溶解性が良く、界面化学的な性質を有し、か
つ優れた生分解性を有していることなどの点で従来より
も優れている。The ω-hydroxyalkyl-β-galactoside compound represented by the general formula (I) of the present invention is a glycoside characterized by having an alkyl group having 8 to 12 carbon atoms having a hydroxyl group at a terminal. Due to its structural characteristics, the present compound is superior to conventional compounds in that it has good solubility in water, has surface chemistry, and has excellent biodegradability.
次に本発明の製造方法についてであるが、本発明の方
法は、β−ガラクトシダーゼを用いる糖転移反応を応用
したものである。以下に製造方法の詳細を述べるが、本
発明の化合物はこの製造方法に限定されず、製造するこ
とができる。Next, regarding the production method of the present invention, the method of the present invention is an application of a glycosyl transfer reaction using β-galactosidase. The details of the production method are described below, but the compound of the present invention is not limited to this production method and can be produced.
本発明の製造方法で使用される出発物質は、一般式
（II）で示されるガラクトース誘導体であれば何れでも
使用できる。具体的に列挙すれば、メチルガラクトシ
ド、エチルガラクトシド、フェニリガラクトシド、ニト
ロフェニルガラクトシド、ラクトース、ガラクトース、
ガラクタン加水分解物等が挙げられる。出発物質は市販
品がそのまま使用可能で場合によっては、精製処理を行
っても良い。As a starting material used in the production method of the present invention, any galactose derivative represented by the general formula (II) can be used. Specifically, methyl galactoside, ethyl galactoside, phenyligalactoside, nitrophenyl galactoside, lactose, galactose,
Galactan hydrolyzate and the like. As a starting material, a commercially available product can be used as it is, and in some cases, a purification treatment may be performed.
本発明の製造方法で使用されるもう一方の出発物質の
一般式（II）で示されるα，ω−長鎖ジオールは、具体
的に列挙すれば、1,8−オクタンジオール、２−エチル
−1,6−ヘキサンジオール、1,9−ノナンジオール,1,10
−デカンジオール,1,11−ウンデカンジオール、1,12−
ドデカンジオール等が挙げられる。The α, ω-long-chain diol represented by the general formula (II), which is the other starting material used in the production method of the present invention, is specifically listed as 1,8-octanediol, 2-ethyl-diol. 1,6-hexanediol, 1,9-nonanediol, 1,10
-Decanediol, 1,11-undecanediol, 1,12-
Dodecanediol and the like.
本発明の製造方法で使用される酵素は、β−ガラクト
シダーゼであり、例えば、アスペルギルス・オリゼ起源
のβ−ガラクトシダーゼ、エシェリヒア・コリー起源の
β−ガラクトシダーゼ、サッカロミセス・フラギラス起
源のβ−ガラクトシダーゼ等が使用できる。The enzyme used in the production method of the present invention is β-galactosidase, for example, β-galactosidase derived from Aspergillus oryzae, β-galactosidase derived from Escherichia coli, β-galactosidase derived from Saccharomyces fragilis, and the like. .
本発明の製造方法では、溶媒としてリン酸緩衝液（pH
＝6.38）と有機溶媒の混合溶液が使用される。有機溶媒
は酵素活性に悪影響を及ぼさず、かつ反応物を溶解する
ものであれば何れでも使用できる。特にアセトニトリ
ル、アセトン、1,4−ジオキサン等は好ましい有機溶媒
である。リン酸緩衝液と有機溶媒の混合比は、反応物に
応じて適宜選択されるが、通常4:1ないし2:3が好まし
い。In the production method of the present invention, a phosphate buffer (pH
= 6.38) and an organic solvent. Any organic solvent can be used as long as it does not adversely affect the enzyme activity and dissolves the reaction product. Particularly, acetonitrile, acetone, 1,4-dioxane and the like are preferred organic solvents. The mixing ratio between the phosphate buffer and the organic solvent is appropriately selected depending on the reaction product, but is usually preferably from 4: 1 to 2: 3.
本発明の製造方法の実施態様を述べれば、リン酸緩衝
液と有機溶媒の混合溶液にガラクトース誘導体とその約
10倍モル量のα，ω−ジオールを溶解し、β−ガラクト
シダーゼは、0.05ないし3mg protein/ml濃度になるよう
に添加して30℃で数時間ないし数十時間穏やかに撹拌し
て反応させる。加熱して反応を停止させた後、生成物の
単離は液体カラムクロマトなどの通常の方法によって行
うことができる。According to an embodiment of the production method of the present invention, a galactose derivative and its approx.
A 10-fold molar amount of α, ω-diol is dissolved, β-galactosidase is added to a concentration of 0.05 to 3 mg protein / ml, and the mixture is gently stirred at 30 ° C. for several hours to tens of hours to react. After stopping the reaction by heating, the product can be isolated by a conventional method such as liquid column chromatography.
以下、実施例により本発明を更に具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
実施例 １ ｏ−ニトロフェニルグリコシド（以下ONPGと略称す）
12.5mg（10-2mol/L）及び1,8−オクタンジオール584.8m
g（10-1mol/L）をソレンセンのリン酸緩衝液（M/15,pH
6.38）7mlとアセトン2mlの混合溶液に溶解させ、β−Ｄ
−ガラクトシダーゼ（E.coli）240units（0.8mg）を溶
解したリン酸緩衝液1mlを加えて30℃で30分間撹拌する
ことにより反応を行った。反応終了後エバポレーターで
溶液を濃縮し、析出する1,8−オクタンジオールを濾別
した。濾液にアセトンを加え副生するアセトン不溶のガ
ラクトースを濾別し、アセトン溶液からの再結晶により
８−ヒドロキシオクチルβ−Ｄ−ガラクトシドを純粋に
得た。この収率は92.3％であった。分析の結果は下記の
通りであった。Example 1 o-nitrophenyl glycoside (hereinafter abbreviated as ONPG)
12.5 mg (10 -2 mol / L) and 1,8-octanediol 584.8m
g (10 -1 mol / L) in phosphate buffer of Sorensen (M / 15, pH
6.38) Dissolve in a mixed solution of 7 ml and acetone 2 ml, and add β-D
-A reaction was carried out by adding 1 ml of a phosphate buffer in which 240 units (0.8 mg) of galactosidase (E. coli) was dissolved and stirring at 30 ° C for 30 minutes. After completion of the reaction, the solution was concentrated using an evaporator, and the precipitated 1,8-octanediol was separated by filtration. Acetone was added to the filtrate, and acetone-insoluble galactose produced as a by-product was filtered off, and 8-hydroxyoctyl β-D-galactoside was obtained pure by recrystallization from the acetone solution. The yield was 92.3%. The results of the analysis were as follows.
・融点 123−124℃ ・比旋光度 ▲［α］26 D▼ −17.1（Ｃ＝1,MeOH） ・元素分析 Ｃ Ｈ 実験値 54.68 ％ 8.89％ 計算値 54.53 ％ 9.15％ IR、Ｈ−NMR、Ｃ−NMRの結果については第１図、第２
図及び第３図に示す。-Melting point 123-124 ° C-Specific rotation ▲ [α] 26 D ▼-17.1 (C = 1, MeOH)-Elemental analysis CH Experimental value 54.68% 8.89% Calculated value 54.53% 9.15% IR, H-NMR, C 1 and 2 for the NMR results.
This is shown in the figure and FIG.
実施例 ２ ラクトース144.1mg（10-2mol/L）及び1,8−オクタン
ジオール584.8mg（10-1mol/L）をソレンセルのリン酸緩
衝液（M/15,pH6.38）7mlとアセトン2mlの混合溶液に溶
解させ、β−Ｄ−ガラクトシダーゼ（E.coli）479units
（1.2mg）を溶解したリン酸緩衝液1mlを加えて30℃で８
時間撹拌することにより反応を行った。実施例１と同様
な操作により８−ヒドロキシオクチルβ−Ｄ−ガラクト
シドを純粋に得た。収率49.6％であった。Example 2 Lactose 144.1mg (10 -2 mol / L) and 1,8-octanediol 584.8mg (10 -1 mol / L) phosphate buffer Sorenseru (M / 15, pH6.38) 7ml and acetone Dissolved in 2 ml of the mixed solution, and β-D-galactosidase (E. coli) 479 units
(1.2 mg) in 1 ml of phosphate buffer, and
The reaction was performed by stirring for hours. By the same operation as in Example 1, 8-hydroxyoctyl β-D-galactoside was obtained purely. The yield was 49.6%.
実施例 ３ ONPG 120.5mg（10-2mol/L）及び1,10−デカンジオー
ル697.1mg（10-1mol/L）をソレンセンのリン酸緩衝液
（M/15,pH6.38）3mlとアセトン6mlの混合溶液に溶解さ
せ、β−Ｄ−ガラクトシダーゼ（E.coli）240units（0.
8mg）を溶解したリン酸緩衝液1mlを加えて30℃で３時間
撹拌することにより反応を行った。実施例１と同様な操
作により10−ヒドロキシデシルβ−Ｄ−ガラクトシドを
純粋に得た。収率77.8％であった。Example 3 ONPG 120.5mg (10 -2 mol / L) and 1,10-decanediol 697.1mg (10 -1 mol / L) phosphate buffer Sorensen (M / 15, pH6.38) 3ml of acetone After dissolving in 6 ml of the mixed solution, β-D-galactosidase (E. coli) 240 units (0.
The reaction was carried out by adding 1 ml of a phosphate buffer in which 8 mg) was dissolved and stirring at 30 ° C. for 3 hours. By the same operation as in Example 1, 10-hydroxydecyl β-D-galactoside was purely obtained. The yield was 77.8%.
・融点 134−135℃ ・比旋光度 ▲［α］25 D▼ −15.3（Ｃ＝1,MeOH） ・元素分析 Ｃ Ｈ 実験値 57.10 ％ 9.17％ 計算値 57.12 ％ 9.59％ IR、Ｈ−NMR、Ｃ−NMRの結果については第４図、第５
図及び第６図に示す。・ Melting point 134-135 ° C. ・ Specific optical rotation ▲ [α] 25 D ▼ -15.3 (C = 1, MeOH) ・ Elemental analysis CH Experimental value 57.10% 9.17% Calculated value 57.12% 9.59% IR, H-NMR, C FIGS. 4 and 5 show the results of NMR.
FIG. 6 and FIG.
［発明の効果］ 本発明により新規なアルキルグリコシドとして溶解性
や生分解性に富むω−ヒドロキシアルキルβ−ガラクト
シドが提供され、洗浄剤等への応用が期待される。[Effects of the Invention] The present invention provides ω-hydroxyalkyl β-galactoside which is highly soluble and biodegradable as a novel alkyl glycoside, and is expected to be applied to detergents and the like.
第１〜３図は、実施例１で得られた８−ヒドロキシオク
チルβ−Ｄ−ガラクトシドのIR、Ｈ−NMR、Ｃ−NMRスペ
クトルを示す。第４〜６図も同様に、10−ヒドロキシデ
シルβ−Ｄ−ガラクトシドのIR、Ｈ−NMR、Ｃ−NMRスペ
クトルを示す。1 to 3 show IR, H-NMR and C-NMR spectra of 8-hydroxyoctyl β-D-galactoside obtained in Example 1. 4 to 6 also show IR, H-NMR and C-NMR spectra of 10-hydroxydecyl β-D-galactoside.
Claims (2)
ド化合物。1. The compound of the general formula (I) (In the formula, n represents an integer of 8 to 12.) An ω-hydroxyalkyl-β-galactoside compound represented by the formula:
れる１種を表す。） で示されるガラクトース誘導体をリン酸緩衝液と有機溶
媒の混合液中で、β−ガラクトシダーゼの存在下、一般
式（III） HO−CnH2n−OH （III） （式中、ｎは８ないし12の整数を表す。） で示されるα，ω−長鎖ジオールと反応させることを特
徴とする一般式（Ｉ） （式中、ｎは前記に同じ。） で示されるω−ヒドロキシアルキル−β−ガラクトシド
化合物の製造方法。2. A compound of the general formula (II) (In the formula, R represents one selected from an alkyl group, an allyl group, and a sugar residue.) A galactose derivative represented by the following formula is prepared in a mixture of a phosphate buffer and an organic solvent in the presence of β-galactosidase. formula (III) (wherein, n represents. an integer of 8 to 12) HO-C n H 2n -OH (III) represented by alpha, generally characterized by reacting an ω- long chain diol Formula (I) (In the formula, n is the same as above.) A method for producing an ω-hydroxyalkyl-β-galactoside compound represented by the following formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2274339A JP2876162B2 (en) | 1990-10-12 | 1990-10-12 | ω-Hydroxyalkyl-β-galactoside compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2274339A JP2876162B2 (en) | 1990-10-12 | 1990-10-12 | ω-Hydroxyalkyl-β-galactoside compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04149190A JPH04149190A (en) | 1992-05-22 |
| JP2876162B2 true JP2876162B2 (en) | 1999-03-31 |
Family
ID=17540280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2274339A Expired - Fee Related JP2876162B2 (en) | 1990-10-12 | 1990-10-12 | ω-Hydroxyalkyl-β-galactoside compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2876162B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2831539B1 (en) * | 2001-10-25 | 2005-02-11 | Seppic Sa | USE OF ALKYLPOLYGLYCOSIDES AS EMULSIFYING AGENTS FOR THE PREPARATION OF OIL-IN-WATER EMULSION CONTAINING MINERAL FILLERS OR PIGMENTS, AND OIL-IN-WATER EMULSIONS CONTAINING SUCH ALKYLPOLYGLYCOSIDES |
-
1990
- 1990-10-12 JP JP2274339A patent/JP2876162B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04149190A (en) | 1992-05-22 |
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