JPS6059220B2 - Method for producing optically active 3-bromobutanoic acid - Google Patents
Method for producing optically active 3-bromobutanoic acidInfo
- Publication number
- JPS6059220B2 JPS6059220B2 JP24116683A JP24116683A JPS6059220B2 JP S6059220 B2 JPS6059220 B2 JP S6059220B2 JP 24116683 A JP24116683 A JP 24116683A JP 24116683 A JP24116683 A JP 24116683A JP S6059220 B2 JPS6059220 B2 JP S6059220B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- cyclodextrin
- acid
- bromobutanoic acid
- producing optically
- 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
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、光学活性な３−ブロモブタン酸の新規な製
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 optically active 3-bromobutanoic acid.
３−ブロモブタン酸は、非天然のアミノ酸、β−メチ
ルーβ−アラニン合成の中間体としても有用である。3-bromobutanoic acid is also useful as an intermediate in the synthesis of the unnatural amino acid, β-methyl-β-alanine.
後者の中間体としては、特に光学活性な３−ブロモブタ
ン酸の合成が望まれていた。 炭素−炭素２重結合を持
つ不飽和化合物に対する臭化水素の付加は、不飽和化合
物を適当な溶媒中に溶解した後、臭化水素ガスを吹きこ
んで得られる１本化学会、実験化学講座２０、ｐ１９３
）。 例えば、臭化アルカリから１、２−ジプロムブロ
パンが得られているが、このような反応によつては光学
活性な臭化水素化物を得ることはできない。 そこで、
本発明者らは、光学活性な３−ブロモブタン酸を高い不
整収率で得るために、種々研究を重ねた結果、本発明を
成すに至つた。As the latter intermediate, it has been particularly desired to synthesize optically active 3-bromobutanoic acid. Addition of hydrogen bromide to an unsaturated compound having a carbon-carbon double bond can be obtained by dissolving the unsaturated compound in a suitable solvent and then blowing hydrogen bromide gas into it. 20, p193
). For example, 1,2-dipromobropane has been obtained from alkali bromide, but optically active hydrobromide cannot be obtained by such a reaction. Therefore,
The present inventors have conducted various studies in order to obtain optically active 3-bromobutanoic acid in a high asymmetric yield, and as a result, they have accomplished the present invention.
すなわち、本発明は、クロトン酸をサイクロデキスト
リンに包接させた後、固体のまま臭化水素ガスを作用さ
せ、その後包接体から臭化水素化物を抽出することによ
り、光学活性なＳ−（＋）一３−ブロモブタン酸を高収
率、かつ高不整収率で得る方法を提供するものである。That is, in the present invention, after crotonic acid is included in cyclodextrin, hydrogen bromide gas is applied to it while it is solid, and then hydrobromide is extracted from the clathrate, thereby producing optically active S-( +) Provides a method for obtaining 1-3-bromobutanoic acid in high yield and highly asymmetric yield.
本発明に用いられるサイクロデキストリンは、デンプ
ンあるいはデキストリンに特殊な微生物あるいは酸素を
作用させて得られる環状デキストリンであり、その特徴
は、ドーナツ状の分子構造を有し、その内部に直径約６
〜１０への空洞を有することである。サイクロデキスト
リンには、ｄ−グルコースの構成単位の数の違いにより
、α−サイクロデキストリン、β−サイクロデキストリ
ンおよびγ−サイクロデキストリンの３種が現在単離さ
れているが、本発明では、これらの中のα−サイクロデ
キストリンとβ−サイクロデキストリンとを用いる事が
できる。 包接に際しては、溶液法が適している。The cyclodextrin used in the present invention is a cyclic dextrin obtained by the action of special microorganisms or oxygen on starch or dextrin, and its characteristic is that it has a donut-shaped molecular structure, with an inner diameter of approximately 6 mm.
~10 to have cavities. Currently, three types of cyclodextrin have been isolated, α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, depending on the number of constituent units of d-glucose. α-cyclodextrin and β-cyclodextrin can be used. A solution method is suitable for inclusion.
すなわち、サイクロデキストリンの飽和水溶液に、クロ
トン酸を加え、３紛〜１時間、好ましくは１〜４時間攪
拌して、包接化合物を沈澱として得る。包接化合物は、
真空乾燥し、得られた粉末はクロトン酸特有の臭は消失
しているが、粉末をジメチルスルホキシトー山に溶解し
てＨ核磁気共鳴を測定すると、クロトン酸由来のシグナ
ルが観測されるし、ジエチルエーテルで粉末を処理する
と再びクロトン酸臭がすることから、粉末にクロトン酸
が包接されていることは明らかてある。 このようにし
て得られたクロトン酸包接化合物を減圧下で充分に乾燥
した後、光をしや断して粉末のまま臭化水素ガスを吹き
こみ室温で溶媒〜５０時間、好ましくは１０〜２時間反
応させる。That is, crotonic acid is added to a saturated aqueous solution of cyclodextrin and stirred for 3 to 1 hour, preferably 1 to 4 hours, to obtain the clathrate compound as a precipitate. The clathrate compound is
The odor characteristic of crotonic acid has disappeared from the powder obtained after vacuum drying, but when the powder is dissolved in dimethyl sulfoxytose and H nuclear magnetic resonance is measured, a signal derived from crotonic acid is observed. When the powder is treated with diethyl ether, the odor of crotonic acid reappears, so it is clear that the powder contains crotonic acid. After thoroughly drying the crotonic acid clathrate compound obtained in this way under reduced pressure, the light is cut off and hydrogen bromide gas is blown into the powdered form at room temperature for 50 hours, preferably 10 hours. Let react for 2 hours.
この際特に必要な事は、包接化合物を充分に乾燥するこ
とと、乾燥した塩素ガスを用いる事である。もし、両者
あるいはどちらかがしめつていると、複反応が起り化学
収率ばかりか、光学収率も低下する。次に実施例により
本発明とさらに詳細に説明する。What is particularly necessary at this time is to sufficiently dry the clathrate compound and to use dry chlorine gas. If either or both of them are tightened, a double reaction will occur and not only the chemical yield but also the optical yield will decrease. Next, the present invention will be explained in more detail with reference to Examples.
実施例１
α−サイクロデキストリン２００ｙを１６００ｍ１の精
製水に入れて攪拌しつつ、約８Ｃ）Ｃに加熱する。Example 1 200 y of α-cyclodextrin is added to 1600 ml of purified water and heated to about 8 C) while stirring.
得られた溶液にクロトン酸２０Ｖを加えて約３時間５０
℃に加熱しつつ攪拌した後、放冷し生じた沈澱をろ過し
包接化合物を得る。この包接化合物を２（代）一昼夜真
空乾燥した。この包接化合物を密閉容器内に入れ、光を
当てすに室温で２叫間、臭化水素ガスにさらした後、未
反応臭化水素ガスを真空下に除去した。このようにして
得られた包接体は、以下のようにして光学活性な３−ブ
ロモブタン酸のサイクロデキストリン包接体であること
が確認された。Add 20V of crotonic acid to the resulting solution and leave for about 3 hours.
After stirring while heating to °C, the mixture is allowed to cool and the resulting precipitate is filtered to obtain the clathrate compound. This clathrate compound was vacuum-dried overnight for two generations. This clathrate compound was placed in a sealed container and exposed to hydrogen bromide gas at room temperature for 2 hours under light, and then unreacted hydrogen bromide gas was removed under vacuum. The clathrate thus obtained was confirmed to be an optically active cyclodextrin clathrate of 3-bromobutanoic acid as described below.
この包接体からエチルエーテルで反応した臭化水素化物
を抽出し、シリカゲルカラムと１，２ージクロロエタン
でクロマト分離して、３−ブロモブタン酸を得た。収率
２９％、ジエチルエーテル中濃度１．２２（ｙ／１００
ｍ１）て測定した〔α〕自ま＋５．０で、文献値〔Ｌ．
Ｊ．ＡｒＫｌｒｅｗｓ，Ｊ．Ｅ．Ｈａｒｄｗｉｃｋｅ，
Ｊ．Ａｍｅｒ．Ｃｈｅｍ．ＳＯｎ．，７４，３５８２（
１９５２））との比較より光学収率は、ほぼ２９％であ
つた。元素分析値Hydrobromide reacted with ethyl ether was extracted from this clathrate, and chromatographically separated using a silica gel column and 1,2-dichloroethane to obtain 3-bromobutanoic acid. Yield 29%, concentration in diethyl ether 1.22 (y/100
m1) was measured with [α] +5.0, which was the literature value [L.
J. ArKlrews, J. E. Hardwicke,
J. Amer. Chem. SOn. ,74,3582(
The optical yield was approximately 29% when compared with 1952)). Elemental analysis value
Claims (1)
、臭化水素と接触させることを特徴とする光学活性な３
−ブロモブタン酸の製造方法。1 Optically active 3 characterized by including crotonic acid in cyclodextrin and then contacting it with hydrogen bromide
- A method for producing bromobutanoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24116683A JPS6059220B2 (en) | 1983-12-20 | 1983-12-20 | Method for producing optically active 3-bromobutanoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24116683A JPS6059220B2 (en) | 1983-12-20 | 1983-12-20 | Method for producing optically active 3-bromobutanoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60130545A JPS60130545A (en) | 1985-07-12 |
| JPS6059220B2 true JPS6059220B2 (en) | 1985-12-24 |
Family
ID=17070232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24116683A Expired JPS6059220B2 (en) | 1983-12-20 | 1983-12-20 | Method for producing optically active 3-bromobutanoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6059220B2 (en) |
-
1983
- 1983-12-20 JP JP24116683A patent/JPS6059220B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60130545A (en) | 1985-07-12 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |