KR0148716B1 - Process for producing beat-b glucoside derivatives - Google Patents

Process for producing beat-b glucoside derivatives

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KR0148716B1
KR0148716B1 KR1019950004796A KR19950004796A KR0148716B1 KR 0148716 B1 KR0148716 B1 KR 0148716B1 KR 1019950004796 A KR1019950004796 A KR 1019950004796A KR 19950004796 A KR19950004796 A KR 19950004796A KR 0148716 B1 KR0148716 B1 KR 0148716B1
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beta
glucoside
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crude
geraniol
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KR960034429A (en
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김영회
김근수
이정일
박준영
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박명규
재단법인한국인삼연초연구원
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/44—Preparation of O-glycosides, e.g. glucosides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01004—Cellulase (3.2.1.4), i.e. endo-1,4-beta-glucanase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01021—Beta-glucosidase (3.2.1.21)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/0104—Alpha-L-rhamnosidase (3.2.1.40)

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Saccharide Compounds (AREA)

Abstract

이 발명은 베타-디-글루코사이드 유도체인 제라닐-베타-디-글루코사이드와 씨트로네릴-베타-디-글루코사이드를 간단한 방법으로 제조하기 위한 것임. 제라닐-베타-디-글루코사이드와 씨트로네릴-베타-디-글루코사이드는 제라니올 또는 씨트로넬롤을 각각 초산완충액과 유기용매의 존재하에 당과 효소 반응시켜 제조함. 당으로는 셀로바이오스가 사용됨.This invention is intended to prepare beta-di-glucoside derivatives geranyl-beta-di-glucoside and cytroneryl-beta-di-glucoside in a simple manner. Geranyl-beta-di-glucoside and cytroneryl-beta-di-glucoside are prepared by enzymatic reaction of sugar with geraniol or citronellol in the presence of acetic acid buffer and organic solvent, respectively. Cellobiose is used as the sugar.

Description

베타-디-글루코사이드 유도체 제조방법Method for preparing beta-di-glucoside derivatives

본 발명은 다음의 화학식(1)로 표시되는 베타-디-글루코사이드 유도체의 제조방법에 관한 것이다.The present invention relates to a method for producing a beta-di-glucoside derivative represented by the following formula (1).

상기 화학식(1)에서, R은 다음의 화학식(2) 또는 화학식(3)으로 표시되는 그룹이다.In the above formula (1), R is a group represented by the following formula (2) or formula (3).

전술한 화학식(1)에서, R이 화학식(2)로 표시되는 제라닐-베타-디-글루코사이드와 R이 화학식(3)으로 표시되는 씨트로네릴-베타-디-글루코사이드는 화장품 및 식품용으로 유용하게 사용되고 있다.In the above formula (1), geranyl-beta-di-glucoside in which R is represented by formula (2) and cytroneryl-beta-di-glucoside in which R is represented by formula (3) are used for cosmetics and foods. It is useful.

진술한 화학식(1)의 베타-디-글루코사이드 유도체들은 이미 알려진 품질이다. (참고문헌 제이. 마제스테릭. 케이. 그르즈노프 및 엔. 루직; 플레이버 앤드 프래그랜스 저어날, 볼륨 4, 169-171(1989) 및 코갈리 엘누어 아메드 아이샤그, 헬무트 요오크 및 미카엘 제페자우에르; 프레세니우스 제트. 아날리티칼 케미스트리, 331-336(1985)The beta-di-glucoside derivatives of the formula (1) mentioned are of known quality. (Ref. J. Majesteric. K. Grzhnov and N. Luzic; Flavor and Fragrance Journal, Volume 4, 169-171 (1989) and Kogali El Noor Ahmed Aishag, Helmut Jook and Mikael Zepezauer; Presenius Jet.Analical Chemistry, 331-336 (1985)

전술한 문헌에 따르면 전술한 화학식(1)의 화합물이 여러 단계의 유기반응을 거쳐 제조할수 있도록 되어 있는데, 전술한 바와 같이 여러 단계의 유기반응을 이용하는 방법은 수율이 적고 각개 반응공정에 고가의 반응시설을 필요로하므로 시설비가 많이 들고 대량 생산에 문제가 있는 것으로 나타났다.According to the above-mentioned literature, the compound of formula (1) described above can be prepared through several stages of organic reactions. As described above, the method of using several stages of organic reactions has a low yield and an expensive reaction in each reaction process. Because of the need for facilities, they are expensive and have problems in mass production.

본 발명자등은 전술한 화학식(1)의 베타-디 글루코사이드 유도체를 간단한 방법에 의하여 염가로 대량 생산할 수 있는 방법을 연구한 결과, 제라니올 또는 세트로네롤을 당류와 효소반응시키면 전술한 화학식(1)의 화합물이 간단하게 고수율로 얻어짐을 알게되어 본 발명을 완성하게 되었다.The present inventors have studied a method for mass production of the beta-diglucoside derivative of formula (1) described above by a simple method at low cost. As a result, enzymatic reaction of geraniol or setroneol with sugars leads to It was found that the compound of 1) was simply obtained in high yield to complete the present invention.

본 발명의 목적은 화학식(1)의 베타-디-글루코사이드 유도체를 간단한 방법에 의하여 고수율로 얻을 수 있는 방법을 제공하기위한 것이다.An object of the present invention is to provide a method for obtaining beta-di-glucoside derivatives of formula (1) in high yield by a simple method.

전술한 본 발명의 목적은 제라니올 또는 씨트로네롤을 당류와 효소반응시키는 본 발명의 방법에 의하여 달성된다.The above object of the present invention is achieved by the method of the present invention in which enzymatic reaction of geraniol or citronerole with a saccharide is carried out.

본 발명의 한 형태는 화학식(4)의 제라니올과 화학식(5)의 씨트로네롤중에서 선택된 화합물을 초산 완충용액 또는 유기용매와 같은 용매의 존재하에 당류와 효소반응시켜 화학식(1)의 베타-디-글루코사이드 유도체를 제조하는 방법으로 구성된다.In one embodiment of the present invention, a compound selected from geraniol of formula (4) and cytronerol of formula (5) is enzymatically reacted with sugars in the presence of a solvent such as acetic acid buffer solution or organic solvent to form beta of formula (1). -Di-glucoside derivatives.

본 발명에 있어서 제라니올 또는 씨트로네롤과 반응하는 당류로는 셀로바이오스가 사용되며, 셀로바이오스의 사용량은 제라니올 또는 씨트로네롤의 중량을 기준으로 1-10배 정도로 사용하는 것이 좋다.Cellulose is used as the sugar that reacts with geraniol or citronerole in the present invention, and the amount of cellobiose is preferably used about 1-10 times based on the weight of geraniol or citronerole.

본 발명에서 초산 완충용액은 유기용매와 함께 사용될 수 있다. 그리고 유기 용매로는 메탄올, 에탄올같은 알코올류, 아세톤같이 케톤류, 아세토니트릴, 디옥산, 디메틸설폭사이드 또는 이들의 혼합물이 사용된다.Acetic acid buffer solution in the present invention can be used with an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone, acetonitrile, dioxane, dimethyl sulfoxide or a mixture thereof are used.

본 발명에 사용되는 효소는 조 셀룰라제, 조 헤미셀룰라제, 조 나린기나제, 조 헤스페리디나제, 조 갈락토시다제, 베타-글루코시다제등이 사용되며, 그 사용량은 당류 10g에 대하여 500 - 1,000 유니트를 사용하는 것이 바람직하다.As the enzyme used in the present invention, crude cellulase, crude hemicellulose, crude naringinase, crude hesperidinase, crude galactosidase, beta-glucosidase, and the like are used. It is preferable to use 500-1,000 units.

이하 본 발명을 실시예의하여 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples.

[실시예 1]Example 1

반응용기에 2.0g의 제라니올, 45ml의 0.1M 초산완충용액 (pH 4.8), 10.0g의 샐로바이오스 및 5ml의 효소용액(650 유니트)을 넣고 20℃에서 72시간 교반시킨 다음, 수조에서 10분간 가열시킨후 여과한다.Into the reaction vessel, 2.0 g of geraniol, 45 ml of 0.1 M acetic acid buffer solution (pH 4.8), 10.0 g of salobiose and 5 ml of enzyme solution (650 units) were added and stirred at 20 ° C. for 72 hours. Heat for minutes and filter.

미반응물은 클로로포름으로 추출하여 제거하고 수충을 수포화 부탄올로 추출하여 농축한다음, 앰버라이트 엑스에이디-2 칼럼을 통과시켜 당을 제거한 뒤 40% 메탄올로 생성물을 용출시키고 실리카겔 칼럼 크로마토그라피(클로로포름-메탄올 혼합용액)로 분리하여 점성을 가진 오일상의 제라닐-베타-디-글루코사이드를 얻었다.The unreacted product was extracted with chloroform and removed, the water worms were extracted with saturated butanol, concentrated, passed through an Amberlite XAD-2 column to remove sugars, and the product was eluted with 40% methanol, followed by silica gel column chromatography (chloroform- Methanol mixture solution) to obtain a viscous oily geranyl-beta-di-glucoside.

[실시예 2]Example 2

2.0g의 씨트로네롤, 40ml의 아세토니트릴, 45ml의 0.1M 초산완충용액(pH 4.8), 10.0g의 셀로바이오스 및 5ml의 효소용액(650 유니트)을 반응용기에 넣어서 20℃에서 72시간 교반시키고 수조에서 10분간 가열시킨 후 여과 한다. 미반응물은 클로로포름으로 추출하여 제거하고 수층을 수포화 부탄올로 추출하여 농축한다음 앰버라이트 엑스에이트-2 칼럼을 통과시켜 당을 제거한 뒤 40%의 메탄올로 생성된을 용출시킨다음, 실리카겔 칼럼 크로마토그라피(클로로포름-메탄올 혼합용액)로 분리하여 점성을 가진 오일상의 씨트로네릴-베타-디-글루코사이드를 얻었다.2.0 g of citronerole, 40 ml of acetonitrile, 45 ml of 0.1 M acetic acid buffer solution (pH 4.8), 10.0 g of cellobiose and 5 ml of enzyme solution (650 units) were added to the reaction vessel and stirred at 20 ° C. for 72 hours. Heat for 10 minutes in a water bath and filter. The unreacted material was extracted with chloroform, removed, the aqueous layer was extracted with saturated butanol, concentrated, and passed through an Amberlite Xate-2 column to remove sugars, followed by elution of the resulting product with 40% methanol, followed by silica gel column chromatography. Separation was carried out with (chloroform-methanol mixed solution) to obtain a viscous oily citronyl-beta-di-glucoside.

Claims (3)

제라니올과 씨트로네롤중에서 선택한 하나의 화합물을 셀로바이오스와를 베타-글루코시다제, 조 셀룰라제, 조 헤미셀룰라제, 조 나린기나제, 조 헤스페리디나제 및 조 칼락토시다제중에서 선택된 효소와 함께 용매중에서 반응시켜 화학식(1)로 표시되는 베타-디-글루코사이드 유도체를 제조하는 방법.One compound selected from geraniol and citronerole is selected from cellobiose and beta-glucosidase, crude cellulase, crude hemicellulose, crude naringinase, crude hesperidinase and crude calactosidase. A method of preparing a beta-di-glucoside derivative represented by the formula (1) by reacting with an enzyme in a solvent. 일반식(1)에서, R은 구조식(2) 또는 (3)으로 표시되는 그롭이다.In formula (1), R is a group represented by formula (2) or (3). 제1항에 있어서 용매가 초산 완충용액, 아세토니트릴, 아세톤, 메탄올, 에탄올, 디옥산, 디메틸설폭사이드 및 이들의 혼합액중에서 선택된 것임을 특징으로 하는 방법.The method of claim 1, wherein the solvent is selected from acetate buffer, acetonitrile, acetone, methanol, ethanol, dioxane, dimethyl sulfoxide and mixtures thereof. 제1항에 있어서, 반응온도가, 10~30℃임을 특징으로 하는 방법.The method of claim 1, wherein the reaction temperature is 10 ~ 30 ℃.
KR1019950004796A 1995-03-09 1995-03-09 Process for producing beat-b glucoside derivatives KR0148716B1 (en)

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