JPS5843792A - Preparation of aliphatic or alicyclic glycoside using-enzyme - Google Patents
Preparation of aliphatic or alicyclic glycoside using-enzymeInfo
- Publication number
- JPS5843792A JPS5843792A JP56143023A JP14302381A JPS5843792A JP S5843792 A JPS5843792 A JP S5843792A JP 56143023 A JP56143023 A JP 56143023A JP 14302381 A JP14302381 A JP 14302381A JP S5843792 A JPS5843792 A JP S5843792A
- Authority
- JP
- Japan
- Prior art keywords
- organic solvent
- beta
- alpha
- alicyclic
- enzyme
- 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
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 10
- -1 alicyclic glycoside Chemical class 0.000 title claims description 13
- 229930182470 glycoside Natural products 0.000 title claims description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 102000004190 Enzymes Human genes 0.000 claims description 10
- 108090000790 Enzymes Proteins 0.000 claims description 10
- 239000002612 dispersion medium Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 101000874334 Dalbergia nigrescens Isoflavonoid 7-O-beta-apiosyl-glucoside beta-glycosidase Proteins 0.000 abstract description 7
- 101000757733 Enterococcus faecalis (strain ATCC 700802 / V583) Autolysin Proteins 0.000 abstract description 7
- 101000757734 Mycolicibacterium phlei 38 kDa autolysin Proteins 0.000 abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- 241000228212 Aspergillus Species 0.000 abstract 1
- NEZJDVYDSZTRFS-YBXAARCKSA-N Phenylgalactoside Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1 NEZJDVYDSZTRFS-YBXAARCKSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000008363 phosphate buffer Substances 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- 240000006439 Aspergillus oryzae Species 0.000 description 2
- 235000002247 Aspergillus oryzae Nutrition 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 102000005744 Glycoside Hydrolases Human genes 0.000 description 2
- 108010031186 Glycoside Hydrolases Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002338 glycosides Chemical class 0.000 description 2
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- XIVUBGOYMBSEMA-UHFFFAOYSA-N 1,4-dioxane;methylsulfinylmethane Chemical compound CS(C)=O.C1COCCO1 XIVUBGOYMBSEMA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WDJUZGPOPHTGOT-OAXVISGBSA-N Digitoxin Natural products O([C@H]1[C@@H](C)O[C@@H](O[C@@H]2C[C@@H]3[C@@](C)([C@@H]4[C@H]([C@]5(O)[C@@](C)([C@H](C6=CC(=O)OC6)CC5)CC4)CC3)CC2)C[C@H]1O)[C@H]1O[C@@H](C)[C@H](O[C@H]2O[C@@H](C)[C@@H](O)[C@@H](O)C2)[C@@H](O)C1 WDJUZGPOPHTGOT-OAXVISGBSA-N 0.000 description 1
- 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 1
- 101150030330 MAJIN gene Proteins 0.000 description 1
- NEZJDVYDSZTRFS-RMPHRYRLSA-N Phenyl beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1 NEZJDVYDSZTRFS-RMPHRYRLSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-FPRJBGLDSA-N beta-D-galactose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-FPRJBGLDSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WDJUZGPOPHTGOT-XUDUSOBPSA-N digitoxin Chemical compound C1[C@H](O)[C@H](O)[C@@H](C)O[C@H]1O[C@@H]1[C@@H](C)O[C@@H](O[C@@H]2[C@H](O[C@@H](O[C@@H]3C[C@@H]4[C@]([C@@H]5[C@H]([C@]6(CC[C@@H]([C@@]6(C)CC5)C=5COC(=O)C=5)O)CC4)(C)CC3)C[C@@H]2O)C)C[C@@H]1O WDJUZGPOPHTGOT-XUDUSOBPSA-N 0.000 description 1
- 229960000648 digitoxin Drugs 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 150000008195 galaktosides Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000013595 glycosylation Effects 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- HEGSGKPQLMEBJL-RKQHYHRCSA-N octyl beta-D-glucopyranoside Chemical compound CCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HEGSGKPQLMEBJL-RKQHYHRCSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000008136 β-glycosides Chemical class 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
【発明の詳細な説明】
本発明社酵素による脂肪族あるいは脂環族グリコシドの
新規な製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing aliphatic or alicyclic glycosides using an enzyme.
医薬品の中ではジグトキシン（ａｉｇｔｏｘｉｎ）のよ
うな配糖体が重要な地位を占めて−るが１これらの化学
合成は、反応の選択性、立体特異性の低さ、反応の煩雑
さなどから困難なことが多い〇一方１ダリコシダーゼを
用−、アリールグリコシドとアルキルアルコールとの間
Ｋ）ランスグリコシデージ冒ンを行なわせる方法社１、
反応が選択的、立体特異的且つ１段階の反応であるので
、極めて好まし−ものである◎しかし高級アルキルアル
コールは、水に難溶なものが多く、十分な基質濃度が得
られない０又１これを克服するために有機溶媒を使用し
て溶解度を上げると酵素が失活し１高収率に目的配糖体
を得ることが困難であった〇本発明者らは１原理的には
化学合成法よシ優れている酵素法のこれらの欠点を克服
すべく鋭意研究を進めた結果１高濃度の有機溶媒中で安
定なα−および／ｌた祉β−グリコシダーゼを用−るこ
とｋより１本発明を完成するに至った。すなわち１濃度
の有機溶媒中で安定なａ−および／またはβ−グリコシ
ダーゼの存在下に％ａ−および／また紘β−アリールグ
リフシトと置換または未置換の脂肪族あるーは脂環族ア
ルコールとを反応させることを特徴とする酵素による脂
肪族あるい轄脂環族グリコシドの製造方法である。Glycosides such as digitoxin (aigtoxin) occupy an important position in pharmaceuticals, but their chemical synthesis is difficult due to low reaction selectivity, low stereospecificity, and complicated reactions. 〇 On the other hand, using dalicosidase, between an aryl glycoside and an alkyl alcohol.
This is extremely preferable because the reaction is selective, stereospecific, and a one-step reaction. However, many higher alkyl alcohols are sparingly soluble in water, making it impossible to obtain a sufficient substrate concentration. 1 In order to overcome this problem, using an organic solvent to increase the solubility deactivates the enzyme and 1 makes it difficult to obtain the target glycoside in high yield. As a result of intensive research to overcome these drawbacks of the enzymatic method, which is superior to the chemical synthesis method, we found that 1. The use of α- and β-glycosidase, which is stable in highly concentrated organic solvents. As a result, we have completed the present invention. That is, in the presence of stable a- and/or β-glycosidase in an organic solvent at a concentration of 1% a- and/or β-aryl glyphsite and a substituted or unsubstituted aliphatic or alicyclic alcohol. This is a method for producing an aliphatic or alicyclic glycoside using an enzyme, which is characterized by reacting the following.
本発明で杜高濃度の有機溶媒中で安定なａ−および／ｌ
ｔたはβ−グリコシダーゼを用いることにより有機溶媒
を含有する水浴液中または水相と有機溶媒相とから−な
る媒体中で反応を行なうことができ、水に難溶なアルフ
ールのグリフシトが得ら、れる。また酵素を用いること
によって目的物が高収率に得られ仝。さらに目的−とす
る纜−グリフシト又はβ−グリコシドを選択的に製造す
ることができる。また水単独の反応系の場合に比較して
、本発明の有機溶媒を用いる反応系では好ましい温度依
存性が得られる。In the present invention, a- and /l-stable in highly concentrated organic solvents
By using t- or β-glycosidase, the reaction can be carried out in a water bath solution containing an organic solvent or in a medium consisting of an aqueous phase and an organic solvent phase, and glyphsites of alfur, which are sparingly soluble in water, can be obtained. , will be. Furthermore, by using enzymes, the target product can be obtained in high yield. Furthermore, it is possible to selectively produce the desired glyphsites or β-glycosides. Furthermore, compared to a reaction system using only water, the reaction system using the organic solvent of the present invention provides preferable temperature dependence.
本発明に用−るａ、β−グリコシダーゼとしては、有機
溶媒に安定なものであれば−かなる起源のものでも良い
が、工業的応用″置針る点から微生物起源のものが好ま
しくアスペルギルスオリゼー（ムａｐｅｒｇｉ１１ｕｉ
ｏｒｙｉａｅ ） ｓクルイベａｖイ七スラ 、ク
イチス（Ｋｌｕｙｙ＠ｒｏｍｙｏｅｓ Ｌａｏｔｉｓ）
などのα−１β−グリコシダーゼなどが挙げられる。The a,β-glycosidase used in the present invention may be of any origin as long as it is stable in organic solvents, but from the standpoint of industrial application, those of microbial origin are preferred. muapergi11ui
oryiae) s Kluyybe av Ichisura, Kluyy (Kluyy@romyoes Laotis)
Examples include α-1β-glycosidase such as.
本−発明に用いる有機溶媒に安定なａ−、β−グリコシ
ダーゼと杜、有機溶媒濃度５０％の水溶液あるい祉分散
媒体中で相対活性３０％以上を示すものである（水溶媒
の同条件下での酵素活性を１００％とする）。The a-, β-glycosidase used in the present invention is stable in organic solvents and exhibits a relative activity of 30% or more in an aqueous solution or dispersion medium with an organic solvent concentration of 50% (under the same conditions in an aqueous solvent). (The enzyme activity at 100% is taken as 100%).
本発明に用いる有機溶媒としては、アセトフェノン、ア
ニソール１クロルベンゼン、四塩化炭素にトロベンゼン
１プ四ビオフェノン、ヘキサン、ベンゼン、アセトニト
リル、アセトン１．ジオキサン−ジメチルスルホキシド
、ジメチルホルムアミド、グリフホルム、酢酸エチルエ
ステルなどを用いる。又１本発明に用−るアルコールそ
のものを溶媒成分とすることもできる。The organic solvents used in the present invention include acetophenone, anisole, chlorobenzene, carbon tetrachloride, trobenzene, tetrabiophenone, hexane, benzene, acetonitrile, and acetone. Dioxane-dimethyl sulfoxide, dimethylformamide, glyphform, acetic acid ethyl ester, etc. are used. Furthermore, the alcohol itself used in the present invention can also be used as a solvent component.
高濃度の有機溶媒を含有する水溶液とは１有機溶媒をｓ
Ｏ〜−０％・好ましくは３０−５０％を含む溶液をいう
。An aqueous solution containing a high concentration of organic solvent means 1 s of organic solvent.
It refers to a solution containing 0 to -0%, preferably 30-50%.
また水相と有機溶媒相とからなる分散媒体としては１水
相と有機溶媒相との混合比（Ｖ／Ｖ ）が工：１０〜１
０：１であるものが好まし−。In addition, as a dispersion medium consisting of an aqueous phase and an organic solvent phase, the mixing ratio (V/V) of the aqueous phase and the organic solvent phase is approximately 10 to 1.
Preferably, the ratio is 0:1.
本発明に用いるα−９β−アリールグリフシトとは置換
屯しくけ未置換のアリール基と糖類との結合体である。The α-9β-arylglyphsite used in the present invention is a combination of a substituted and unsubstituted aryl group and a saccharide.
置換屯しくけ未置換のアリール基トシては１例えばフエ
ニ／’ １） Ａｔ ４ ｋ 、ｐ −二）田７エエル
、ｐ−ハｐゲン化フェニル、ナフチル基などが挙けられ
る。Examples of substituted and unsubstituted aryl groups include phenyl, phenyl, phenyl, phenyl, naphthyl, and the like.
糖類として轄グルフース、ガラクトースなどの単糖類、
！ルトース、ラクトース、ゲンチオビオースなどの三糖
のはか一オリゴ類など°が挙げられるＯ
具体的には、フェニル−％−ｖ−ガラクトシド、Ｐ−、
ｐ
フェニル−’１４−Ｄ−グルフシド、トルイル−幾−Ｄ
−ガラクトシドなどが挙けられる。Monosaccharides such as glucose and galactose,
! Specific examples include phenyl-%-v-galactoside, P-,
p phenyl-'14-D-glufside, toluyl-14-D
- Examples include galactoside.
本発明に用いる置換ま念は未置換の脂肪族あるいは脂環
族アルコールと祉炭素原子数１−４６の第１級、第８級
あるいは第３級アルコールであり、ｔた％ノブリコール
あるい祉８価以上のフル：Ｉ −ルトシて祉、メタノー
ル１エタノール、シクロヘキサノール、インプルパノー
ル、オクタツール、エチレングリコール、エチレングリ
コールモノアルキルエーテ〃、グリ七ロール、サリシル
アルコ−＃ ｓ ヘンシルフルコール等を挙けることが
できるＯ
本発明方法において、ａ−および／ｌたはβ−アリール
グリコシドと置換また祉未置換の脂肪族あるい社脂環族
アルコールとの反応割合は、アリールグリコシ下１当量
に対してアルコール１当量以上であることが好ましい。The substituted alcohol used in the present invention is an unsubstituted aliphatic or alicyclic alcohol and a primary, octadic or tertiary alcohol having 1 to 46 carbon atoms; Fluids with a valence of 8 or higher: I-rutocytyl alcohol, methanol 1 ethanol, cyclohexanol, inpulpanol, octatool, ethylene glycol, ethylene glycol monoalkyl ether, gly7ol, salicyl alcohol, etc. In the method of the present invention, the reaction ratio of the a- and /l or β-aryl glycoside with the substituted or unsubstituted aliphatic or alicyclic alcohol is 1 equivalent of the aryl glycoside. It is preferable that the amount of alcohol is 1 equivalent or more.
また反応の田社通常３〜９０間で選択するが１アスペル
ギルスオリゼーのグリコシダーゼを用−る場合にはｐＨ
ｓ附近、タルイペロマイ七スラクチスの酵素を用いる場
合にはｐＨ７附近が好ましい。In addition, the reaction temperature is usually selected between 3 and 90, but when using Aspergillus oryzae glycosidase, the pH
In the case of using the enzyme of Taluperomy hepta-slactis, the pH is preferably around 7.
反応時間−は通常５−ｓｏｏ分であり、反応温度は通常
４〜５０℃である。The reaction time is usually 5-soo minutes, and the reaction temperature is usually 4 to 50°C.
本発明方法により得られる脂肪族ある―は脂環 □族グ
リコシＹは医薬品などの用途に利用される。The aliphatic and alicyclic □ group glycosylation Y obtained by the method of the present invention is used for pharmaceuticals and the like.
以下１本発明を実施例により具体的に゛説明する。The present invention will be specifically explained below using examples.
実施例 Ｌ
７エエルーβ−Ｄ−ガラクトシド及ヒシクロヘキサノー
ルよりシクνヘキシルーβ−Ｄ−ガラクトシドの合成◇
フェニル−β−ｐ−ガラクトシド２５．６岬（０，１ミ
リモル）とシクロヘキサノール０．６５ｍ ） ０．Ｉ
Ｍリン酸緩衝液（ｐｉ（ｓ、ｏ ） ｏ、４−とアセ
トニトリルｏ、ｓ−の混液に溶解し１これに、アスペル
ギ〃スオリゼのβ−ガラ表トシダーゼ（真人製５ａｏ６
ｏνｔ）ｌ、５ｖ＋＋１を０．１−の上記リン酸緩衝液
に溶解したものを加え、４℃でＳ時間反応させた。これ
に％０４工Ｍ炭酸ナトリウム液１−を加えて酵素を失活
させたのち、メタノ−／Ｉ／ｇ、ａ−を加え、酵素を沈
殿させた。４℃でｌＦ！＃間放置後遠心分離し、酵素を
除いた上清を、高速液体り四マドグラフィーにかけ、生
成物の分離定量を行なった。シクロへキシル−β−Ｄ−
ガラクトシドは、４０％の収率で得られたＯ
実施例 ２
フェニル−β−Ｄ−グルコシド及び凰−オクタト・
ノールより司−オクチル−β−ｐ−グルコシドの合成。Example L 7 Synthesis of hexyl β-D-galactoside from β-D-galactoside and hiscyclohexanol ◇ 25.6 caps (0.1 mmol) of phenyl-β-p-galactoside and 0.65 m of cyclohexanol) 0. I
Dissolve in a mixture of M phosphate buffer (pi(s,o) o,4- and acetonitrile o,s-1) and add Aspergillus oryzae β-gala tosidase (Majin 5ao6) to this solution.
ovt)l, 5v++1 dissolved in 0.1- of the above phosphate buffer was added, and the mixture was reacted at 4°C for S hours. After adding %04M sodium carbonate solution 1- to this to inactivate the enzyme, methanol/I/g, a- was added to precipitate the enzyme. lF at 4℃! After standing for a period of time, the mixture was centrifuged, and the supernatant from which the enzyme was removed was subjected to high-performance liquid chromatography to separate and quantify the product. cyclohexyl-β-D-
Galactoside was obtained in a yield of 40%. Example 2 Synthesis of octyl-β-p-glucoside from phenyl-β-D-glucoside and 凰-octato-nol.
０、Ｉ Ｍリン酸緩衝液Ｓ田７，０ １０−に７二二Ｑ
、３Ｂ？、タルイペｐマイセスラクチスのグリコシダー
ゼ（合同酒精） ｏ、ｓｏｔを溶解するＯ一方に）ロベ
ンゼンマ０−に！−オクタツール１．ｓｏｗ ヲ泪かし
、二液を合したのち、スターラーを用い１ｓｓ’ｃで１
．！ｉ時間激しく攪拌したＯ冷却後１日塩化炭素及び水
各１１ Ｉｌｌを加え遠心分離し亀二相を完全に分離し
た０水相をとり、メタノール３３ｓｊを加え１室温に１
時間放置し１紳素を沈殿させ、遠心分離して除いた。上
清の溶媒をロータリーエバポレーターで除いたのち、残
渣をりＨｌｅｇ ＄ Ａ’ Ａ−メタノール−水−１０
：４：ｌ（容量比）の下層にて抽出し、これを、シリカ
ゲルカラム（１０〇−）にかけた０同じ溶媒で溶出し、
−一オクチルグルコシド相当分画をｐ−タリーエバポレ
ーターｋかけ、溶媒を留去した。得られたｎ−オクチル
４ｌ−Ｄ−グＡ／＝ｔシト−１４８８１で収率ｆ１．＋
、１％であった。0, IM phosphate buffer S 7,0 10-722Q
, 3B? , Taruipe p. Myces lactis glycosidase ( joint spirits ) o, dissolves sot O on the other hand ) Lobenzenma 0- to! - Octatool 1. Sow sow, combine the two liquids, and stir with a stirrer to 1ss'c.
．． ! Stir vigorously for i hours. After cooling, add 11 liters each of carbon chloride and water, centrifuge, and completely separate the two phases. Take the aqueous phase, add 33sj of methanol, and bring to room temperature.
The mixture was allowed to stand for a period of time to precipitate 1 chloride, which was removed by centrifugation. After removing the supernatant solvent using a rotary evaporator, the residue was poured into Hleg $ A' A-methanol-water-10
:4:l (volume ratio) was extracted in the lower layer, and this was eluted with the same solvent applied to a silica gel column (100-).
The fraction corresponding to -1 octyl glucoside was subjected to a p-tally evaporator k, and the solvent was distilled off. The obtained n-octyl 4l-D-guA/=tcyto-14881 with a yield f1. +
, 1%.
特許出願人 東洋紡績株式金社Patent applicant: Toyobo Co., Ltd. Kinsha
Claims (1)
溶媒相とからなる分散媒体中で、高濃度の、有機溶媒中
で安定なａ−および／またはβ−グリコシダーゼの存在
下に１α−および／ｌたはβ−アリールグリコシドと置
換また捻未置換の脂肪族あるい紘脂環族アルコールとを
反応させることを特徴とする酵素による脂肪族あるいは
脂環族グリコシドの製造方法ＯIn an aqueous solution containing a high concentration of organic solvent or in a dispersion medium consisting of an aqueous phase and an organic solvent phase, 1α- and A method for producing an aliphatic or alicyclic glycoside using an enzyme, which is characterized by reacting a /l or β-aryl glycoside with a substituted or unsubstituted aliphatic or alicyclic alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56143023A JPS5928400B2 (en) | 1981-09-09 | 1981-09-09 | Method for producing aliphatic or alicyclic glycosides using enzymes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56143023A JPS5928400B2 (en) | 1981-09-09 | 1981-09-09 | Method for producing aliphatic or alicyclic glycosides using enzymes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5843792A true JPS5843792A (en) | 1983-03-14 |
| JPS5928400B2 JPS5928400B2 (en) | 1984-07-12 |
Family
ID=15329114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56143023A Expired JPS5928400B2 (en) | 1981-09-09 | 1981-09-09 | Method for producing aliphatic or alicyclic glycosides using enzymes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5928400B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996011281A1 (en) * | 1994-10-09 | 1996-04-18 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Process for the preparation of long-chain alkyl glycosides |
| US6037151A (en) * | 1994-10-09 | 2000-03-14 | Yissum Research Development Company Of The Hebrew | Process for the preparation of long-chain alkyl glycosides |
-
1981
- 1981-09-09 JP JP56143023A patent/JPS5928400B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996011281A1 (en) * | 1994-10-09 | 1996-04-18 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Process for the preparation of long-chain alkyl glycosides |
| US6037151A (en) * | 1994-10-09 | 2000-03-14 | Yissum Research Development Company Of The Hebrew | Process for the preparation of long-chain alkyl glycosides |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5928400B2 (en) | 1984-07-12 |
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