JPH05331157A - Ascorbic acid ester - Google Patents
Ascorbic acid esterInfo
- Publication number
- JPH05331157A JPH05331157A JP4133572A JP13357292A JPH05331157A JP H05331157 A JPH05331157 A JP H05331157A JP 4133572 A JP4133572 A JP 4133572A JP 13357292 A JP13357292 A JP 13357292A JP H05331157 A JPH05331157 A JP H05331157A
- Authority
- JP
- Japan
- Prior art keywords
- ascorbic acid
- compound
- lipase
- formula
- acid ester
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規なアスコルビン酸エ
ステルに関する。FIELD OF THE INVENTION The present invention relates to a novel ascorbic acid ester.
【０００２】[0002]
【従来の技術】アスコルビン酸と脂肪族カルボン酸のエ
ステル例えばアスコルビン酸パルミテートは特開昭５４
−８８２６１号公報などに記載されているがアスコルビ
ン酸（メタ）アクリル酸エステルに関しては従来知られ
ていない。2. Description of the Related Art Esters of ascorbic acid and aliphatic carboxylic acids such as ascorbic acid palmitate are disclosed in JP-A-54.
However, ascorbic acid (meth) acrylic acid ester has not been known so far.
【０００３】[0003]
【発明が解決しようとする課題】還元能と重合性を有す
る新規なアスコルビン酸（メタ）アクリル酸エステルを
提供する。PROBLEM TO BE SOLVED BY THE INVENTION A novel ascorbic acid (meth) acrylic acid ester having reducing ability and polymerizability is provided.
【０００４】[0004]
【課題を解決するための手段】本発明は下記の一般式
（１）で表わされるアスコルビン酸エステルである。The present invention is an ascorbic acid ester represented by the following general formula (1).
【０００５】[0005]
【化２】 [Chemical 2]
【０００６】（式中Ｒ1 は水素又はメチル基を示す。）
本発明の上記一般式（１）で表わされるアスコルビン酸
エステルは、還元能を有すると共に、重合性官能基を有
するので、単独で、あるいは他の重合性化合物と共重合
させ、親水性高分子あるいは還元能のある高分子として
有用である。以下、上記一般式（１）で表わされる本発
明のアスコルビン酸エステルの製造方法につき説明す
る。本発明化合物は例えば下記に示す各種の方法により
製造される。(In the formula, R 1 represents hydrogen or a methyl group.)
Since the ascorbic acid ester represented by the above general formula (1) of the present invention has a reducing ability and a polymerizable functional group, it may be used alone or in copolymerization with another polymerizable compound to obtain a hydrophilic polymer or It is useful as a polymer with reducing ability. Hereinafter, the method for producing the ascorbic acid ester of the present invention represented by the above general formula (1) will be described. The compound of the present invention is produced, for example, by various methods shown below.
【０００７】（製造法Ａ） 一般式（２）(Production Method A) General Formula (2)
【０００８】[0008]
【化３】 [Chemical 3]
【０００９】〔式中、Ｒ1 、Ｒ2 は各々独立に水素又は
メチル基を示す。〕で表わされる（メタ）アクリル酸エ
ノールエステルと、アスコルビン酸を有機溶媒中リパー
ゼの存在下に反応させる。この方法は酵素の選択的な反
応性を利用するもので温和な条件下で反応できるので有
利である。反応溶媒としては、ピリジン、ｔ−ブタノー
ル、テトラヒドロフラン、ジオキサン、ｔ−アミルアル
コールなどがあげられるが、この他にもアスコルビン酸
の溶解度が大きいものであれば使用できる。リパーゼは
エステル交換反応の能力のあるものであれば、いずれで
も使用できるが、シュードモナス属（天野製薬、リパー
ゼＰＳ）、ムコール属（天野製薬、リパーゼＭ１０）、
アスペルギラス属（天野製薬、リパーゼアマノＡ６）、
リゾポス属（大阪細菌研究所，リパーゼダイケン１０
０）、キャンディダ属（シグマ、リパーゼタイプVII ）
などの微生物由来のものや、パンクレアチンなどの動物
由来のものなどを例示できる。[In the formula, R 1 and R 2 each independently represent hydrogen or a methyl group. ] The (meth) acrylic acid enol ester represented by the following formula is reacted with ascorbic acid in the presence of lipase in an organic solvent. This method utilizes the selective reactivity of the enzyme and is advantageous because it can react under mild conditions. Examples of the reaction solvent include pyridine, t-butanol, tetrahydrofuran, dioxane, t-amyl alcohol, and the like. In addition to these, any solvent having a high solubility of ascorbic acid can be used. Any lipase can be used as long as it has the ability of transesterification, but Pseudomonas sp. (Amano Pharmaceutical Co., Lipase PS), Mucor sp. (Amano Pharmaceutical Co., Lipase M10),
Aspergillus (Amano Pharmaceutical Co., Lipase Amano A6),
Rhizopos (Osaka Bacterial Research Institute, Lipase Daiken 10
0), Candida (sigma, lipase type VII)
Examples thereof include those derived from microorganisms such as, and those derived from animals such as pancreatin.
【００１０】リパーゼのエステル交換能を発揮させるた
めには酵素の三次元構造を発現もしくは維持するために
微量の水が必要であるため、市販リパーゼの使用に際し
てはバッファー液で処理するなどして活性を賦括してか
ら処理することが好ましい。またリパーゼ又はリパーゼ
源を不溶性担体に固定化して利用することも可能であ
る。リパーゼを使用する場合の反応温度は３０℃から６
０℃であり、反応時間は１０〜５０時間が好ましい。In order to exert the transesterification ability of lipase, a trace amount of water is required to express or maintain the three-dimensional structure of the enzyme. Therefore, when using commercially available lipase, it is necessary to treat it with a buffer solution to activate it. It is preferable that the treatment is carried out after the treatment. It is also possible to immobilize a lipase or a lipase source on an insoluble carrier before use. The reaction temperature when using lipase is from 30 ° C to 6 ° C.
It is 0 ° C., and the reaction time is preferably 10 to 50 hours.
【００１１】化合物（２）はアスコルビン酸に対して当
量用いる事ができるが、反応の効率を考えると、５％〜
２０％過剰に用いるのが良い。反応終了後酵素を分離
し、反応液を濃縮し、得られた粗製物を再結晶する事に
より精製する。以上の合成の詳細は実施例において記述
する。The compound (2) can be used in an equivalent amount with respect to ascorbic acid.
It is better to use an excess of 20%. After completion of the reaction, the enzyme is separated, the reaction solution is concentrated, and the obtained crude product is recrystallized for purification. Details of the above synthesis will be described in Examples.
【００１２】（製造法Ｂ） 一般式（３）(Production Method B) General Formula (3)
【００１３】[0013]
【化４】 [Chemical 4]
【００１４】〔式中、Ｒ1 は前記に同じ〕とアスコルビ
ン酸とを反応させる。上記反応は溶媒中、−１０〜２０
℃、好ましくは０〜１０℃、反応時間５〜４０時間で行
なわれる。化合物（３）は、アスコルビン酸に対して過
剰量用いるのが、反応効率から好ましいが、化合物
（３）は反応性が大きいので、二級水酸基への反応も若
干進行し、反応選択率が低下する可能性がある。従っ
て、化合物（３）を当量もしくは１〜１０％少なめに添
加する方が好ましい。反応中、塩化水素が発生するが、
これをトラップする目的で塩基性化合物、例えばアルカ
リ、アミンなどを加えることができる。しかし、アスコ
ルビン酸がこれらの添加により酸化されやすくなるの
で、添加しなくともよい。溶媒としては水、テトラヒド
ロフラン、ジオキサン、ジメチルホルムアミド、ジメチ
ルスルホキシド、アセトン、クロロホルムなど及びこれ
らの溶媒の混合溶媒を使用できる。[Wherein R 1 is the same as above] is reacted with ascorbic acid. The above reaction is carried out in a solvent at -10 to 20.
C., preferably 0-10.degree. C., and a reaction time of 5-40 hours. It is preferable to use an excessive amount of the compound (3) with respect to ascorbic acid from the viewpoint of reaction efficiency. However, since the compound (3) has a high reactivity, the reaction to the secondary hydroxyl group also slightly progresses and the reaction selectivity decreases. there's a possibility that. Therefore, it is preferable to add the compound (3) in an equivalent amount or 1 to 10% less. Hydrogen chloride is generated during the reaction,
A basic compound such as an alkali or an amine can be added for the purpose of trapping this. However, since ascorbic acid is easily oxidized by the addition of these, it is not necessary to add it. As the solvent, water, tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide, acetone, chloroform and the like and mixed solvents of these solvents can be used.
【００１５】（製造法Ｃ） 一般式（４）(Production Method C) General Formula (4)
【００１６】[0016]
【化５】 [Chemical 5]
【００１７】（式中、Ｒ1 は前記と同じ）製造法Ｂの化
合物（３）の代りに化合物（４）を用いる他は製造法Ｂ
と全く同様に行なうことができる。ただし、反応の進行
を早めるため塩基性縮合剤例えばピリジン、ピコリン、
Ｎ，Ｎ−ジメチルアミノピリジン、トリエチルアミンな
どの添加が好ましい。上記製造法Ｂ，Ｃによって得られ
る本発明化合物は反応終了後通常の分離方法に従って単
離できる。(Wherein R 1 is the same as above) except that the compound (4) is used instead of the compound (3) of the manufacturing method B.
You can do exactly the same as. However, in order to accelerate the reaction, basic condensing agents such as pyridine, picoline,
Addition of N, N-dimethylaminopyridine, triethylamine and the like is preferable. The compound of the present invention obtained by the above production methods B and C can be isolated by a usual separation method after the reaction is completed.
【００１８】[0018]
【実施例】次に本発明を更に説明するため、本発明の化
合物の製造例を実施例としてあげる。EXAMPLES Next, in order to further explain the present invention, production examples of the compounds of the present invention will be given as Examples.
【００１９】実施例１ アスコルビン酸メタアクリル酸エステルの合成 リパーゼＰＳ（天野製薬）１ｇをｐＨ７．０、１／２０
Ｍリン酸バッファー２５ｍｌに溶解し、大豆レシチン
０．８ｇを加え攪拌する。これにケイソウ土１０ｇを加
えてさらに攪拌したのち４０℃で減圧濃縮した。これを
さらに４０℃で減圧乾燥して固定化リパーゼＰＳ１１．
８ｇを調製した。この固定化リパーゼＰＳから４ｇをと
り、あらかじめ４０℃でアスコルビン酸４ｇを脱水ｔ−
ブタノール４０ｍｌに溶解した溶液に添加し、さらにメ
タクリル酸ビニルエステル２．７ｇ（１．０５当量）を
加え４０℃で２４時間反応させる。反応液をＨＰＬＣで
分析すると反応率は９５％であった。固定化リパーゼＰ
Ｓを濾別し、反応液を濃縮した。得られた粗生成物をア
セトン／ベンゼン混合溶媒にて再結晶をくり返すと、
２．３ｇのアスコルビン酸メタクリル酸エステルが得ら
れた。 Example 1 Synthesis of ascorbic acid methacrylic acid ester 1 g of lipase PS (Amano Pharmaceutical Co., Ltd.) was added at pH 7.0 and 1/20.
Dissolve in 25 ml of M phosphate buffer, add 0.8 g of soybean lecithin, and stir. To this, 10 g of diatomaceous earth was added, further stirred, and then concentrated under reduced pressure at 40 ° C. This was further dried under reduced pressure at 40 ° C. and immobilized lipase PS11.
8 g was prepared. 4 g of this immobilized lipase PS was taken and 40 g of ascorbic acid was dehydrated at 40 ° C. in advance.
It is added to a solution dissolved in 40 ml of butanol, 2.7 g (1.05 equivalent) of vinyl methacrylate is further added, and the mixture is reacted at 40 ° C. for 24 hours. When the reaction solution was analyzed by HPLC, the reaction rate was 95%. Immobilized lipase P
S was filtered off and the reaction solution was concentrated. When the obtained crude product was repeatedly recrystallized with an acetone / benzene mixed solvent,
2.3 g of ascorbic acid methacrylic acid ester was obtained.
【００２０】ｍｐ．１５３−１５６℃，Ｍ+ ＝２４４．
０５８３（Ｃ10Ｈ12Ｏ7 ）1 Ｈ−ＮＭＲ（ＣＤ3 ＣＮ）；δ １．９２（３Ｈ，
ｓ），４．１２（１Ｈ，ｍ），４．２４（２Ｈ，ｍ），
４．７７（１Ｈ，ｄ，Ｊ＝１．６Ｈｚ），５．６５（１
Ｈ，ｄ，Ｊ＝１．６Ｈｚ），６．１３（１Ｈ，ｄ，Ｊ＝
１．６Ｈｚ），13 Ｃ−ＮＭＲ（ＣＤ3 ＣＮ）；δ １６．５４，６３．
８０，６５．７２，７４．２８，１１７．９８，１２
４．５９，１３５．３０，１４９．５３，１６５．８
１，１６８．７１Mp. 153-156 ° C, M + = 244.
0583 (C 10 H 12 O 7 ) 1 H-NMR (CD 3 CN); δ 1.92 (3H,
s), 4.12 (1H, m), 4.24 (2H, m),
4.77 (1H, d, J = 1.6Hz), 5.65 (1
H, d, J = 1.6 Hz), 6.13 (1H, d, J =
1.6 Hz), 13 C-NMR (CD 3 CN); δ 16.54, 63.
80, 65.72, 74.28, 117.98, 12
4.59, 135.30, 149.53, 165.8
1,168.71
【００２１】実施例２ アスコルビン酸アクリル酸エステルの合成 実施例１におけるメタクリル酸ビニルエステルの代りに
アクリル酸ビニルエステルを使用した以外は全く同様に
反応、精製を行なって１．８ｇのアスコルビン酸アクリ
ル酸エステルを得た。 Example 2 Synthesis of Ascorbic Acid Acrylic Acid Ester 1.8 g of ascorbic acid acrylic acid was prepared by the same reaction and purification as in Example 1 except that vinyl acrylate was used instead of vinyl methacrylate. The ester was obtained.
【００２２】ｍｐ．１５３−１６２℃，Ｍ+ ＝２３０．
０４１７（Ｃ9 Ｈ10Ｏ7 ）1 Ｈ−ＮＭＲ（アセトン−ｄ6 ）；δ ４．２４（１
Ｈ，ｍ），４．３３（２Ｈ，ｍ），４．８４（１Ｈ，
ｄ，Ｊ＝１．６Ｈｚ），５．９３（１Ｈ，ｄｄ，Ｊ＝
１．６，１０．８Ｈｚ），６．１９（１Ｈ，ｄｄ，Ｊ＝
１０．８，１７．２Ｈｚ），６．４１（１Ｈ，ｄｄ，Ｊ
＝１．６，１７．６Ｈｚ）Mp. 153-162 ° C, M + = 230.
0417 (C 9 H 10 O 7 ) 1 H-NMR (acetone-d 6 ); δ 4.24 (1
H, m), 4.33 (2H, m), 4.84 (1H,
d, J = 1.6 Hz), 5.93 (1H, dd, J =
1.6, 10.8 Hz), 6.19 (1H, dd, J =
10.8, 17.2Hz), 6.41 (1H, dd, J
= 1.6, 17.6 Hz)
【００２３】実施例３ アスコルビン酸メタクリル酸エステルの合成 アスコルビン酸３．５ｇを脱水テトラヒドロフラン３０
ｍｌに溶解し、脱水トリエチルアミン１ｇを加え氷水で
冷却する。メタクリル酸クロリド１ｇ（０．９５当量）
を滴下し、滴下終了後室温で５時間攪拌の後、反応液を
４０℃にて減圧乾固する。得られた粗製物にアセトン／
ベンゼン混合溶媒を加え加熱し、不溶物を熱時ろ過で除
く。ろ液を冷却して０．８ｇのアスコルビン酸メタアク
リル酸エステルが得られた。 Example 3 Synthesis of Ascorbic Acid Methacrylic Acid Ester 3.5 g of ascorbic acid was added to dehydrated tetrahydrofuran 30
Dissolve in ml, add 1 g of dehydrated triethylamine and cool with ice water. Methacrylic acid chloride 1g (0.95 equivalent)
Is added dropwise, and after completion of the addition, the mixture is stirred at room temperature for 5 hours, and then the reaction solution is dried under reduced pressure at 40 ° C. Acetone /
Add benzene mixed solvent and heat to remove insoluble matter by filtration while hot. The filtrate was cooled and 0.8 g of ascorbic acid methacrylic acid ester was obtained.
【００２４】実施例４ アスコルビン酸アクリル酸エステルの合成 実施例３のメタクリル酸クロリドの代りにアクリル酸無
水物を使用した以外は全く同様に反応させ、反応液を処
理して０．６ｇのアスコルビン酸アクリル酸エステルを
得た。 Example 4 Synthesis of Ascorbic Acid Acrylate Ester The reaction was carried out in the same manner except that acrylic acid anhydride was used in place of the methacrylic acid chloride of Example 3, and the reaction solution was treated to give 0.6 g of ascorbic acid. Acrylic ester was obtained.
【００２５】[0025]
【発明の効果】新規な重合性のアスコルビン酸エステル
が得られる。The novel polymerizable ascorbic acid ester can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 (Ｃ１２Ｐ 17/04 Ｃ１２Ｒ 1:66） (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 (51) Int.Cl. 5 Identification number Reference number within the agency FI technical display location (C12P 17/04 C12R 1:66) (72) Inventor Akihiro Sakimae 20 Miyukicho, Otake City, Hiroshima Prefecture No. 1 Mitsubishi Rayon Co., Ltd. Central Research Laboratory
Claims (1)
アスコルビン酸エステル。1. The following formula (1): (In the formula, R 1 represents hydrogen or a methyl group.) An ascorbic acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4133572A JPH05331157A (en) | 1992-05-26 | 1992-05-26 | Ascorbic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4133572A JPH05331157A (en) | 1992-05-26 | 1992-05-26 | Ascorbic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05331157A true JPH05331157A (en) | 1993-12-14 |
Family
ID=15107948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4133572A Pending JPH05331157A (en) | 1992-05-26 | 1992-05-26 | Ascorbic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05331157A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073372A (en) * | 2001-08-30 | 2003-03-12 | Manac Inc | Method for producing phenylethynyl phthalic anhydride derivative |
| WO2021049472A1 (en) * | 2019-09-10 | 2021-03-18 | 学校法人 関西大学 | Compound, resin, composition, resist film, pattern forming method, underlayer film, and optical article |
-
1992
- 1992-05-26 JP JP4133572A patent/JPH05331157A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073372A (en) * | 2001-08-30 | 2003-03-12 | Manac Inc | Method for producing phenylethynyl phthalic anhydride derivative |
| WO2021049472A1 (en) * | 2019-09-10 | 2021-03-18 | 学校法人 関西大学 | Compound, resin, composition, resist film, pattern forming method, underlayer film, and optical article |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH1081648A (en) | Enantiomerangereicherte malonic acid monoester alphamonosubstituted with tertiary hydrocarbon group or its salt and its production | |
| US5614643A (en) | Process for the enzymatic production of isomerically pure isosorbide-2 and 5-monoesters as well as their conversion into isosorbide-2- and 5-nitrate | |
| JPH05331157A (en) | Ascorbic acid ester | |
| JPH06740B2 (en) | Process for producing optically active carboxylic acid amide | |
| AU670088B2 (en) | Enzymatic process to separate racemic mixtures of delta valerolactones | |
| EP0239122B1 (en) | Process for the enzymatic resolution of racemic 2-amino-1-alkanols | |
| JPH06256278A (en) | Optically active alpha-carbamoylalkanoic acid derivative and its production | |
| JP3098332B2 (en) | Enzymatic preparation of isomeric pure isosorbide-2- and -5-monoesters and their conversion to isosorbide-2- and -5-nitrate | |
| JP2002171994A (en) | Method for producing optically active tetrahydrofuran-2-carboxylic acid or its antipode ester | |
| JP3072150B2 (en) | Method for producing optically active [3] (1,1 ') ferrocenophanes | |
| JP2655893B2 (en) | Method for synthesizing optically active β-halolactic acid or glycidyl acid | |
| JP3090286B2 (en) | Method for producing carboxyalkyl acrylate and method for producing methoxycarbonylalkyl acrylate used in this method | |
| JPH08332095A (en) | Production of indenol | |
| EP0472336A1 (en) | Process for preparing optically active 3-hydroxybutane derivatives | |
| JPS62205797A (en) | Production of optically active compound | |
| JPH0191789A (en) | Production of optically active beta-substituted glutaric acid monoester | |
| JP2639651B2 (en) | Process for producing optically active carboxylic acid and its enantiomer ester | |
| JP3046383B2 (en) | Method for producing optically active indolehydroxy acids | |
| JPH08119958A (en) | Production of optically active chroman compound | |
| JPS60130539A (en) | Preparation of optically active styrene halohydrin | |
| JPH10210997A (en) | Production of optically active 3-quinacridinol | |
| JP2899404B2 (en) | Process for producing (R) -2-hydroxy-4-phenylbutyric acid | |
| JPH0573396B2 (en) | ||
| JP3438389B2 (en) | Method for selective esterification of phenol derivative having alcoholic hydroxyl group using lipase | |
| JPH0475589A (en) | Production of optically active norbornene derivative |