JPH05219970A - Production of organic acid ester - Google Patents
Production of organic acid esterInfo
- Publication number
- JPH05219970A JPH05219970A JP2382892A JP2382892A JPH05219970A JP H05219970 A JPH05219970 A JP H05219970A JP 2382892 A JP2382892 A JP 2382892A JP 2382892 A JP2382892 A JP 2382892A JP H05219970 A JPH05219970 A JP H05219970A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- ester
- organic acid
- erythorbic
- 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.)
- Pending
Links
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は酵素のエステル化反応及
びエステル交換反応を利用した、アスコルビン酸又はエ
リソルビン酸の有機酸エステルの製造法に関する。アス
コルビン酸又はエリソルビン酸は強い還元能を有するた
め、一般に酸化防止剤として食品、化粧品等の添加物と
して多方面で利用されている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organic acid ester of ascorbic acid or erythorbic acid by utilizing an esterification reaction and a transesterification reaction of an enzyme. Since ascorbic acid or erythorbic acid has a strong reducing ability, it is generally used as an antioxidant in various fields as an additive for foods, cosmetics and the like.
【０００２】しかし、これら化合物は難脂溶性であるた
め、特に高脂肪含有食品であるナッツ類、ポテトチッ
プ、マヨネーズ、マーガリン及びフライ加工スナック食
品等の酸化防止には、脂溶性の高いアスコルビン酸の有
機酸エステル（例えば、パルミチン酸、ミリスチン酸、
又はステアリン酸のエステル等）が用いられている。ア
スコルビン酸の有機酸エステルのあるものの塩は食品系
における界面活性剤として、また、果物、生花等の褐変
防止剤として有用である。However, since these compounds are sparingly fat-soluble, in order to prevent oxidation of nuts, potato chips, mayonnaise, margarine, and fried snack foods, which are high-fat foods, ascorbic acid, which is highly fat-soluble, is used. Organic acid esters (eg, palmitic acid, myristic acid,
Or stearic acid ester, etc.) is used. Salts of some organic acid esters of ascorbic acid are useful as surfactants in food systems and as browning inhibitors for fruits and fresh flowers.
【０００３】[0003]
【従来の技術】これらのアスコルビン酸又はエリソルビ
ン酸の有機酸エステルの製造法は、例えば、フッ化水素
を溶媒及び触媒としたアスコルビン酸−６−パルミチン
酸エステルの製造法（特開昭５４−８８２６１号）、ま
た、９６％以上の濃硫酸を溶媒及び触媒とする製造法
（特開昭５９−１７００８６号）が知られている。最
近、酵素を用いて穏和な条件でアスコルビン酸又はエリ
ソルビン酸の有機酸エステルを製造する方法が提案され
ている（特開平３−１１７４９５号）。2. Description of the Related Art A method for producing these organic acid esters of ascorbic acid or erythorbic acid is, for example, a method for producing ascorbic acid-6-palmitic acid ester using hydrogen fluoride as a solvent and a catalyst (JP-A-54-88261). No.), and a production method using 96% or more concentrated sulfuric acid as a solvent and a catalyst (JP-A-59-170086). Recently, a method of producing an organic acid ester of ascorbic acid or erythorbic acid using an enzyme under mild conditions has been proposed (JP-A-3-117495).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、フッ化
水素あるいは濃硫酸を用いる方法は酸の強い腐食性の
為、装置材質の制限及び取扱の困難さがある。また、酵
素を用いてアスコルビン酸又はエリソルビン酸と有機酸
からエステルを製造する方法は、その生成速度の低い事
が難点であった。However, the method of using hydrogen fluoride or concentrated sulfuric acid has a strong corrosive property of acid, so that the material of the device is limited and the handling is difficult. Further, the method of producing an ester from ascorbic acid or erythorbic acid and an organic acid using an enzyme has a drawback that the production rate is low.
【０００５】[0005]
【課題を解決するための手段】そこで、本発明者らは酵
素を用いたアスコルビン酸又はエリソルビン酸の有機酸
エステル合成反応において、低級カルボン酸のエノール
エステル存在下に反応を行うと、生成速度を向上させ得
る事を発見し本発明を完成させた。即ち、本発明はアス
コルビン酸又はエリソルビン酸と一般式（Ｉ） Ｒ1 ＣＯＯＲ2 …（Ｉ） （式中Ｒ1 は炭素数４以上のアルキル基、炭素数２以上
のアルケニル基、アラルキル基、又はアリール基、Ｒ2
は水素、メチル基、エチル基又はプロピル基を表す）で
示される有機酸又はそのエステルとを有機溶媒中でリパ
ーゼの存在下に反応させ一般式（II）又は (III)SUMMARY OF THE INVENTION Therefore, the inventors of the present invention, in the reaction of synthesizing an organic acid ester of ascorbic acid or erythorbic acid using an enzyme, when the reaction is carried out in the presence of an enol ester of a lower carboxylic acid, the production rate is increased. The present invention was completed by discovering that it can be improved. That is, the present invention relates to ascorbic acid or erythorbic acid and general formula (I) R 1 COOR 2 ... (I) (wherein R 1 is an alkyl group having 4 or more carbon atoms, an alkenyl group having 2 or more carbon atoms, or an aralkyl group, or Aryl group, R 2
Represents a hydrogen, a methyl group, an ethyl group or a propyl group) and is reacted with an organic acid represented by the general formula (II) or (III) in the presence of a lipase in an organic solvent.
【０００６】[0006]
【化３】 [Chemical 3]
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】（式中Ｒ1 は前記と同義である。）で示さ
れるアスコルビン酸又はエリソルビン酸の有機酸エステ
ルを合成する時に一般式（IV） Ｒ3 ＣＯＯＣ（−Ｒ4 ）＝ＣＨ2 …（IV） （式中Ｒ3 は炭素数１〜３のアルキル基、Ｒ4 は水素又
はメチル基を表す）で示される低級カルボン酸のエノー
ルエステル存在下に行う事を特徴とする有機酸エステル
の製造法である。When synthesizing an organic acid ester of ascorbic acid or erythorbic acid represented by the formula (wherein R 1 has the same meaning as described above), R 3 COOC (-R 4 ) = CH 2 ( IV) Production of an organic acid ester characterized by being carried out in the presence of an enol ester of a lower carboxylic acid represented by the formula (wherein R 3 represents an alkyl group having 1 to 3 carbon atoms and R 4 represents hydrogen or a methyl group) Is the law.
【０００９】上記Ｒ1 としては、例えばブチル基（炭素
数＝４）、ペンチル基（炭素数＝５）等の低級アルキル
基からドデシル基（炭素数＝１２）、ペンタドデシル基
（炭素数＝１５）、ヘキサデシル基（炭素数＝１７）等
の高級アルキル基である。また、不飽和結合を有するア
ルケニル基は、エチレン基（炭素数＝２）、プロピレン
基（炭素数＝３）等の低級アルケニル基からノナデカペ
ンタエニル基（炭素数＝１９）、ヘンイコサンヘキサエ
ニル基（炭素数＝２１）等の高級アルケニル基である。
アラルキル基としては、例えばベンジル基、アリール基
としては例えばフェニル基が挙げられる。Ｒ2 は、水
素、メチル基、エチル基、又はプロピル基を表す。一般
式（Ｉ）の化合物としてはステアリン酸、パルミチン酸
又はその低級エステルが好ましい。Examples of R 1 include lower alkyl groups such as butyl group (carbon number = 4), pentyl group (carbon number = 5) to dodecyl group (carbon number = 12), pentadodecyl group (carbon number = 15). ), A hexadecyl group (having 17 carbon atoms), and the like. In addition, the alkenyl group having an unsaturated bond may be a lower alkenyl group such as an ethylene group (carbon number = 2) or a propylene group (carbon number = 3), a nonadecapentaenyl group (carbon number = 19), or a henicoshexahexa group. It is a higher alkenyl group such as an enyl group (carbon number = 21).
Examples of the aralkyl group include a benzyl group, and examples of the aryl group include a phenyl group. R 2 represents hydrogen, a methyl group, an ethyl group, or a propyl group. As the compound of the general formula (I), stearic acid, palmitic acid or a lower ester thereof is preferable.
【００１０】本発明において反応は、アスコルビン酸又
はエリソルビン酸、一般式（Ｉ）の有機酸又はそのエス
テル、及び一般式（IV）の低級カルボン酸のエノールエ
ステルを同時に加える方法、またこれらを順序を問わず
逐次加えて行う方法のいずれでも行う事が出来る。In the present invention, the reaction is carried out by simultaneously adding ascorbic acid or erythorbic acid, an organic acid of the general formula (I) or an ester thereof, and an enol ester of a lower carboxylic acid of the general formula (IV), and the order of adding them. Regardless of the method of adding sequentially, it can be performed.
【００１１】本発明において用いる低級カルボン酸のエ
ノールエステルの具体例としては酢酸ビニル、酢酸イソ
プロペニル、プロピオン酸ビニルを挙げることができ
る。これらは、アスコルビン酸又はエリソルビン酸に対
して０．１〜１．２当量用いるのが適当であり、好まし
くは０．５〜１．０当量である。Specific examples of the enol ester of a lower carboxylic acid used in the present invention include vinyl acetate, isopropenyl acetate and vinyl propionate. These are appropriately used in an amount of 0.1 to 1.2 equivalents, preferably 0.5 to 1.0 equivalents, with respect to ascorbic acid or erythorbic acid.
【００１２】本発明においてエステル合成を行わせる反
応は溶液状又は懸濁液状にて行う事が必要であり、一般
式（Ｉ）の化合物として高級有機酸類を用いる場合は、
これらが液状でないので有機溶媒を添加して溶液状又は
スラリー状で反応させる事が出来る。有機溶媒として
は、アセトン、第３級ブタノール、エチルエーテル、テ
トラヒドロフラン、ジオキサン、ヘキサン、ベンゼン等
を用いる事が出来る。In the present invention, the reaction for carrying out the ester synthesis needs to be carried out in the form of a solution or suspension. When a higher organic acid is used as the compound of the general formula (I),
Since these are not liquid, it is possible to react them in the form of a solution or slurry by adding an organic solvent. As the organic solvent, acetone, tertiary butanol, ethyl ether, tetrahydrofuran, dioxane, hexane, benzene or the like can be used.
【００１３】反応方法としては、固定化した酵素や微生
物を充填したカラムに反応媒体を少量ずつ流す事によっ
て行う事もできる。反応温度は１０〜９０℃であり、よ
り好ましくは２０〜７０℃である。As a reaction method, the reaction medium can be flown little by little through a column packed with immobilized enzymes or microorganisms. The reaction temperature is 10 to 90 ° C, more preferably 20 to 70 ° C.
【００１４】本発明の方法において用いられるリパーゼ
は、エステル合成及びエステル交換活性を持つものであ
れば、動物、微生物のいずれによって生産されたもので
もよく、例えばシュードモナス属、カンジダ属などの微
生物由来のリバーゼのほか、高等動物由来の膵臓リパー
ゼなどが挙げられる。これらのリパーゼは、市販品であ
っても、また粗製、精製品いずれも使用できる。また、
リパーゼは乾燥させたものをそのまま使用する事もでき
るが、不溶性担体に固定化して使用する事が出来る。さ
らに、本発明においてリパーゼは１種類のものをそのま
ま使用する事も出来るが、２種類以上のものを混合して
使用する事も出来る。The lipase used in the method of the present invention may be produced by any of animals and microorganisms, as long as it has ester synthesis and transesterification activity. For example, lipase derived from microorganisms such as Pseudomonas sp. And Candida sp. Besides revertase, pancreatic lipase derived from higher animals can be mentioned. These lipases may be commercially available products, or may be crude or purified products. Also,
Although the dried lipase can be used as it is, it can be immobilized on an insoluble carrier before use. Further, in the present invention, one kind of lipase can be used as it is, but two or more kinds of lipase can be mixed and used.
【００１５】[0015]
【実施例】以下、実施例及び比較例により本発明の詳細
を説明する。The details of the present invention will be described below with reference to Examples and Comparative Examples.
【００１６】実施例１ 第３級ブタノール４０mlにアスコルビン酸４ｇを懸濁
し、リポザイムＩＭ２０（ノボ社製；イオン交換樹脂に
リパーゼを固着したもの）４ｇ、ステアリン酸６．５
ｇ、及び酢酸ビニル２ｇを添加し、４０℃で２４時間反
応させた。反応後、リポザイムＩＭ２０を沈降分離し、
上澄３０mlを抜液し、溶液中のアスコルビン酸−６−ス
テアレートの濃度を測定したところ、１．１９％であっ
た。Example 1 4 g of ascorbic acid was suspended in 40 ml of tertiary butanol, and lipozyme IM20 (manufactured by Novo Co .; ion-exchange resin with lipase fixed) 4 g, stearic acid 6.5.
g and 2 g of vinyl acetate were added, and the mixture was reacted at 40 ° C. for 24 hours. After the reaction, the lipozyme IM20 was separated by sedimentation,
When 30 ml of the supernatant was drained and the concentration of ascorbic acid-6-stearate in the solution was measured, it was 1.19%.
【００１７】比較例１ 実施例１と同様に操作し、ただし酢酸ビニルを加えずに
４０℃で２４時間反応を行い、反応後、リポザイムＩＭ
２０を沈降分離し、上澄３０mlを抜液し、溶液中のアス
コルビン酸−６−ステアレートの濃度を測定したとこ
ろ、０．６４％であった。Comparative Example 1 The same operation as in Example 1 was carried out, except that the reaction was carried out at 40 ° C. for 24 hours without adding vinyl acetate, and after the reaction, Lipozyme IM
20 was separated by sedimentation, 30 ml of the supernatant was drained, and the concentration of ascorbic acid-6-stearate in the solution was measured and found to be 0.64%.
【００１８】実施例２ 実施例１においてステアリン酸６．５ｇをパルミチン酸
５．３ｇに換えた他は同様にして反応させた。反応後、
リポザイムＩＭ２０を沈降分離し、上澄３０mlを抜液
し、溶液中のアスコルビン酸−６−パルミテートの濃度
を測定したところ、１．３９％であった。Example 2 A reaction was carried out in the same manner as in Example 1 except that 6.5 g of stearic acid was replaced with 5.3 g of palmitic acid. After the reaction
Lipozyme IM20 was separated by sedimentation, 30 ml of the supernatant was drained, and the concentration of ascorbic acid-6-palmitate in the solution was measured and found to be 1.39%.
【００１９】比較例２ 実施例２と同様に操作し、ただし酢酸ビニルを加えずに
反応した。実施例２と同様に操作した上澄液中のアスコ
ルビン酸−６−パルミテートの濃度は０．７３％であっ
た。Comparative Example 2 The procedure of Example 2 was repeated except that vinyl acetate was not added. The concentration of ascorbic acid-6-palmitate in the supernatant liquid operated in the same manner as in Example 2 was 0.73%.
【００２０】実施例３ 実施例１においてステアリン酸６．５ｇの代りにステア
リン酸メチル６．８ｇを用いて同様に反応したところ、
アスコルビン酸−６−ステアレートの濃度は０．９６％
であった。Example 3 In the same manner as in Example 1, except that 6.5 g of stearic acid was used and 6.8 g of methyl stearate was used, the same reaction was carried out.
The concentration of ascorbic acid-6-stearate is 0.96%
Met.
【００２１】比較例３ 酢酸ビニルを加えなかったことを除いて実施例３と同様
に反応させたところアスコルビン酸−６−ステアレート
の濃度は０．４５％であった。Comparative Example 3 The reaction was carried out in the same manner as in Example 3 except that vinyl acetate was not added, and the concentration of ascorbic acid-6-stearate was 0.45%.
【００２２】[0022]
【発明の効果】本発明は、リパーゼのエステル合成能に
よりアスコルビン酸あるいはエリソルビン酸を低級カル
ボン酸のエノールエステルでアシル化し、つづいて、リ
パーゼのエステル交換能による有機酸又はエステルとの
エステル交換反応でエステルを合成する事で、アスコル
ビン酸又はエリソルビン酸と有機酸との直接エステル化
の速度を上回り、生産性を著しく向上させる事ができ
る。INDUSTRIAL APPLICABILITY According to the present invention, ascorbic acid or erythorbic acid is acylated with an enol ester of a lower carboxylic acid by the ester-synthesizing ability of lipase, and then transesterification reaction with an organic acid or ester is carried out by the transesterifying ability of lipase. By synthesizing the ester, the rate of direct esterification of ascorbic acid or erythorbic acid with the organic acid can be exceeded, and the productivity can be remarkably improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 崎前 明宏 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Sakimae 20-1 Miyukicho, Otake-shi, Hiroshima Mitsubishi Rayon Co., Ltd. Central Research Laboratory
Claims (1)
般式（Ｉ） Ｒ1 ＣＯＯＲ2 …（Ｉ） （式中Ｒ1 は炭素数４以上のアルキル基、炭素数２以上
のアルケニル基、アラルキル基、又はアリール基、Ｒ2
は水素、メチル基、エチル基又はプロピル基を表す）で
示される有機酸又はエステルとを有機溶媒中でリパーゼ
の存在下に反応させ一般式（II）又は (III) 【化１】 【化２】 （式中、Ｒ1 は前記と同じ意味を有する）で示されるア
スコルビン酸又はエリソルビン酸の有機酸エステルを合
成する時に一般式（IV） Ｒ3 ＣＯＯＣ（−Ｒ4 ）＝ＣＨ2 …（IV） （式中Ｒ3 は炭素数１〜３のアルキル基、Ｒ4 は水素又
はメチル基を表す）で示される低級カルボン酸のエノー
ルエステル存在下に行う事を特徴とする有機酸エステル
の製造法。1. Ascorbic acid or erythorbic acid and general formula (I) R 1 COOR 2 ... (I) (wherein R 1 is an alkyl group having 4 or more carbon atoms, an alkenyl group having 2 or more carbon atoms, or an aralkyl group, or Aryl group, R 2
Represents hydrogen, a methyl group, an ethyl group or a propyl group) and is reacted with an organic acid or ester represented by the general formula (II) or (III) in an organic solvent in the presence of lipase. [Chemical 2] (Wherein R 1 has the same meaning as described above) when synthesizing an organic acid ester of ascorbic acid or erythorbic acid represented by the general formula (IV) R 3 COOC (-R 4 ) = CH 2 ... (IV) (Wherein R 3 represents an alkyl group having 1 to 3 carbon atoms and R 4 represents hydrogen or a methyl group), and the process is carried out in the presence of an enol ester of a lower carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2382892A JPH05219970A (en) | 1992-02-10 | 1992-02-10 | Production of organic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2382892A JPH05219970A (en) | 1992-02-10 | 1992-02-10 | Production of organic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05219970A true JPH05219970A (en) | 1993-08-31 |
Family
ID=12121238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2382892A Pending JPH05219970A (en) | 1992-02-10 | 1992-02-10 | Production of organic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05219970A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0675120A3 (en) * | 1994-03-01 | 1998-07-08 | Scotia Holdings Plc | Use of ascorbyl-gamma-linolenate or a ascorbyl-dihomo-gamma-linolenate for the treatment of asthma, cancer, cardiovascular and inflammatory disorders |
| WO2003025194A1 (en) * | 2001-09-12 | 2003-03-27 | Mitsubishi Rayon Co., Ltd. | Process for producing monomer |
| WO2015041385A1 (en) * | 2013-09-23 | 2015-03-26 | 주식회사 두산에코비즈넷 | Incubator having ultraviolet lamp |
-
1992
- 1992-02-10 JP JP2382892A patent/JPH05219970A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0675120A3 (en) * | 1994-03-01 | 1998-07-08 | Scotia Holdings Plc | Use of ascorbyl-gamma-linolenate or a ascorbyl-dihomo-gamma-linolenate for the treatment of asthma, cancer, cardiovascular and inflammatory disorders |
| US5847000A (en) * | 1994-03-01 | 1998-12-08 | Scotia Holdings Plc | Fatty acid derivatives |
| WO2003025194A1 (en) * | 2001-09-12 | 2003-03-27 | Mitsubishi Rayon Co., Ltd. | Process for producing monomer |
| US7125692B2 (en) | 2001-09-12 | 2006-10-24 | Mitsubishi Rayon Co., Ltd. | Process for producing monomer |
| WO2015041385A1 (en) * | 2013-09-23 | 2015-03-26 | 주식회사 두산에코비즈넷 | Incubator having ultraviolet lamp |
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