JPH045438B2 - - Google Patents
Info
- Publication number
- JPH045438B2 JPH045438B2 JP24578483A JP24578483A JPH045438B2 JP H045438 B2 JPH045438 B2 JP H045438B2 JP 24578483 A JP24578483 A JP 24578483A JP 24578483 A JP24578483 A JP 24578483A JP H045438 B2 JPH045438 B2 JP H045438B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- formula
- bacterial cells
- carboxylic acid
- group
- 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
- 150000002148 esters Chemical class 0.000 claims description 17
- 230000001580 bacterial effect Effects 0.000 claims description 15
- 244000005700 microbiome Species 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 241000589158 Agrobacterium Species 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- ODXYWRPJDYJIPT-UHFFFAOYSA-N methyl beta-(acetylthio)isobutyrate Chemical compound COC(=O)C(C)CSC(C)=O ODXYWRPJDYJIPT-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VFVHNRJEYQGRGE-UHFFFAOYSA-N 3-acetylsulfanyl-2-methylpropanoic acid Chemical compound OC(=O)C(C)CSC(C)=O VFVHNRJEYQGRGE-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- 241000589155 Agrobacterium tumefaciens Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 L-form carboxylic acid esters Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- ZERPWJMPLLLIIK-UHFFFAOYSA-N methyl 3-benzoylsulfanyl-2-methylpropanoate Chemical compound COC(=O)C(C)CSC(=O)C1=CC=CC=C1 ZERPWJMPLLLIIK-UHFFFAOYSA-N 0.000 description 1
- BECGSBWTFYFALC-UHFFFAOYSA-N methyl 4-acetylsulfanyl-2-methylbutanoate Chemical compound COC(=O)C(C)CCSC(C)=O BECGSBWTFYFALC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Description
【発明の詳細な説明】
本発明は、一般式
（式中R1はアルキル基、アラル基又はアリール
基、R2はアルキル基、ｎは１又は２を示す）で
表わされる光学活性カルボン酸及びその対掌体エ
ステルの製造法に関する。
式のカルボン酸及びその対掌体エステルは光
学活性を有する種々の生理活性物質を合成するた
めの原料として利用されている。従来、式の光
学活性カルボン酸の製造法としては、あらかじめ
有機合成的にラセミ体のカルボン酸を合成したの
ち、光学分割剤を用いて分割する方法、すなわち
物理化学的に一方の光学活性体とその対掌体とに
分別する方法が知られている（特開昭55−118455
号、同56−81557号、同57−188563号、ヨーロツ
パ特許公開第79200477号各明細書参照）。一方、
光学活性カルボン酸エステルはカルボン酸を分割
したのち、エステル化反応を行ない、光学活性エ
ステルに導く方法などがとられている。しかしこ
れらの方法では、高価な分割剤が多量に必要とさ
れること、この分割剤が不純物として製品中に混
入しやすいこと、分割工程が複雑であることなど
の欠点があり、工業的な製法としては必ずしも満
足できるものではない。
本発明者らは、Ｄ体又はＬ体のカルボン酸エス
テルの混合物を不斉加水分解する方法に関して鋭
意研究を行つた結果、アグロバクテリウム属の微
生物を用いることにより、式の光学活性カルボ
ン酸及びその対掌体エステルを効率よく製造でき
ることを見い出した。
本発明は、一般式
（式中R3はアルキル基を示し、R1、R2及びｎは
前記の意味を有する）で表わされるエステルに、
エステル結合を不斉加水分解する能力を有するア
グロバクテリウム属に属する微生物の培養液、菌
体又は菌体処理物を作用させることを特徴とす
る、一般式
（式中R1、R2及びｎは前記の意味を有する）で
表わされる光学活性カルボン酸及びその対掌体エ
ステルの製造法である。
式及び式の化合物の置換基R1のためのア
ルキル基としては例えばメチル基、エチル基な
ど、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エニル基が挙げられ
る。
本発明に用いられるエステル（）としては、
例えばＳ−アセチル−β−メルカプトイソ酪酸メ
チル、Ｓ−アセチル−γ−メルカプト−α−メチ
ル−ｎ−酪酸メチル、Ｓ−ベンゾイル−β−メル
カプトイソ酪酸メチル、Ｓ−フエニルアセチル−
β−メルカプトイソ酪酸メチルなどが挙げられ
る。
本発明に用いられるアグロバクテリウム属の微
生物は、前記の化合物のエステル結合を不斉加水
分解する能力を有する微生物であつて、例えばア
グロバクテリウム・ラジオバクター
（Agrobacterium radiobacter）などの微生物が
挙げられる。これらの微生物はこれを含む培養
液、分離した菌体又は菌体処理物として用いられ
る。
これらの微生物の培養は、通常は液体培養で行
われるが、固体培養によつても行うことができ
る。培地としては、微生物が通常資化しうる炭素
源、窒素源、ビタミン、ミネラルなどの成分を適
宜配合したものが用いられる。微生物の加水分解
能を向上させるため、培地にエステルを少量添加
することが好ましい。培養は微生物が生育可能で
ある温度及びPHで行われるが、通常50℃以下の温
度で、PH２〜11の範囲で行われる。微生物の生育
を促進させるために通気撹拌を行つてもよい。
加水分解反応を行うに際しては、培養の開始時
又は途中で培地にエステル（）を添加してもよ
く、あらかじめ微生物を培養したのち培養液にエ
ステル（）を添加してもよい。また増殖した微
生物の菌体を遠心分離等により採取し、これをエ
ステルを含む反応媒体に加えてもよい。この場合
菌体は取り扱い上の便宜から、乾燥菌体例えば凍
結乾燥菌体、噴霧乾燥菌体又は有機溶媒例えばア
セトン、トルエン等で処理した菌体、あるいは菌
体破壊物、菌体抽出物等の菌体処理物を用いるこ
ともできる。反応媒体としては例えばイオン交換
水又は緩衝液が用いられる。反応媒体又は培養液
中のエステルの濃度は0.01〜50重量％が好まし
い。エステルは水に懸濁した状態で加えることも
できる。メタノール、アセトンなどの有機溶媒を
反応液に加えてエステルの溶解性を向上させるこ
ともできる。反応液のPHは２〜11、好ましくは５
〜８の範囲である。反応が進行するに伴い生成し
たカルボン酸により反応液のPHが低下してくる
が、この場合は適当な中和剤で最適PHに維持する
ことが好ましい。反応温度は５〜50℃が好まし
い。
反応液又は培養液からの生成物の分離精製は通
常の方法例えば抽出、再結晶、カラムクロマトグ
ラフイ等により行うことができる。
下記実施例中の％は重量％を意味する。
実施例 １
アグロバクテリウム・ラジオパクターIFO
12607（Agrobacterium radiobacter）を肉エキス
1.0％、NaCl 0.5％及びペプトン1.0％から成る液
体培地（PH 7.2）100mlに植菌し、30℃１日間振
盪培養を行つた。培養終了後、培養液を遠心分離
し、得られた菌体の全量をイオン交換水で洗浄し
たのち、Ｍ／10燐酸緩衝液（PH 7.0）50mlに懸
濁した。この菌体懸濁液に（±）−Ｓ−アセチル
−β−メルカプトイソ酪酸メチル2.5mlを加え、
30℃で48時間振盪して反応させた。
この時のＳ−アセチル−β−メルカプトイソ酪
酸メチルの分解率は49％であつた。反応液をPH
7.0に調整し、Ｓ−アセチル−β−メルカプトイ
ソ酪酸メチルを酢酸エチルで抽出した。次いで水
層のPHを硫酸で2.0に下げたのち、水層中のＳ−
アセチル−β−メルカプトイソ酪酸を酢酸エチル
で抽出した。抽出液に無水硫酸ナトリウムを加え
て脱水処理したのち、溶媒を蒸発除去した。抽出
されたＳ−アセチル−β−メルカプトイソ酪酸及
びＳ−アセチル−β−メルカプトイソ酪酸メチル
の比旋光度をユニオン技研社製旋光度計
（PM101型）で測定した。結果を表１に示す。
これから、光学活性カルボン酸とその対掌体エ
ステルが生成していることが判る。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula The present invention relates to a method for producing an optically active carboxylic acid represented by the formula (wherein R 1 is an alkyl group, an aral group, or an aryl group, R 2 is an alkyl group, and n is 1 or 2) and its enantiomer ester. Carboxylic acids of the formula and their enantiomers are used as raw materials for synthesizing various physiologically active substances with optical activity. Conventionally, the method for producing the optically active carboxylic acid of the formula is to first synthesize a racemic carboxylic acid by organic synthesis and then resolve it using an optical resolving agent. A method of separating the enantiomers is known (Japanese Unexamined Patent Publication No. 118455-1989).
No. 56-81557, No. 57-188563, and European Patent Publication No. 79200477). on the other hand,
Optically active carboxylic acid esters are obtained by splitting the carboxylic acid and then performing an esterification reaction to produce optically active esters. However, these methods have drawbacks such as the need for a large amount of expensive resolving agent, the ease with which this resolving agent is mixed into the product as an impurity, and the complexity of the resolving process, making industrial production methods difficult. This is not necessarily satisfactory. The present inventors conducted intensive research on a method for asymmetrically hydrolyzing a mixture of D- or L-form carboxylic acid esters, and found that by using microorganisms of the genus Agrobacterium, optically active carboxylic acids of the formula We have discovered that the enantiomer ester can be produced efficiently. The present invention is based on the general formula (In the formula, R 3 represents an alkyl group, and R 1 , R 2 and n have the above-mentioned meanings.)
A general formula characterized by the action of a culture solution, bacterial cells, or treated bacterial cells of a microorganism belonging to the genus Agrobacterium that has the ability to asymmetrically hydrolyze ester bonds. This is a method for producing an optically active carboxylic acid represented by the formula (wherein R 1 , R 2 and n have the above-mentioned meanings) and its enantiomer ester. Examples of the alkyl group for the substituent R 1 of the formula and the compound of the formula include methyl group, ethyl group, etc., examples of the aralkyl group include benzyl group, and examples of the aryl group include phenyl group. As the ester () used in the present invention,
For example, methyl S-acetyl-β-mercaptoisobutyrate, methyl S-acetyl-γ-mercapto-α-methyl-n-butyrate, methyl S-benzoyl-β-mercaptoisobutyrate, S-phenylacetyl-
Examples include methyl β-mercaptoisobutyrate. The microorganism of the genus Agrobacterium used in the present invention is a microorganism that has the ability to asymmetrically hydrolyze the ester bond of the above-mentioned compound, and examples thereof include microorganisms such as Agrobacterium radiobacter. . These microorganisms are used as a culture solution containing them, isolated bacterial cells, or treated bacterial cells. Cultivation of these microorganisms is usually carried out in liquid culture, but it can also be carried out in solid culture. As a medium, one containing appropriately blended components such as a carbon source, nitrogen source, vitamins, and minerals that can be normally assimilated by microorganisms is used. In order to improve the hydrolytic ability of microorganisms, it is preferable to add a small amount of ester to the medium. Cultivation is carried out at a temperature and pH at which microorganisms can grow, but it is usually carried out at a temperature of 50°C or less and a pH range of 2 to 11. Aeration and stirring may be performed to promote the growth of microorganisms. When carrying out the hydrolysis reaction, the ester (2) may be added to the medium at the beginning or during the culture, or the ester (2) may be added to the culture solution after culturing the microorganism in advance. Alternatively, the cells of the grown microorganism may be collected by centrifugation or the like and added to the reaction medium containing the ester. In this case, for convenience of handling, the bacterial cells are dried, such as freeze-dried bacterial cells, spray-dried bacterial cells, bacterial cells treated with organic solvents such as acetone, toluene, etc., or bacterial cell destruction materials, bacterial cell extracts, etc. A processed product of bacterial cells can also be used. For example, ion-exchanged water or a buffer solution is used as the reaction medium. The concentration of ester in the reaction medium or culture solution is preferably 0.01 to 50% by weight. The ester can also be added in suspension in water. The solubility of the ester can also be improved by adding an organic solvent such as methanol or acetone to the reaction solution. The pH of the reaction solution is 2 to 11, preferably 5.
It is in the range of ~8. As the reaction progresses, the pH of the reaction solution decreases due to the generated carboxylic acid, but in this case it is preferable to maintain the pH at an optimum level using a suitable neutralizing agent. The reaction temperature is preferably 5 to 50°C. Separation and purification of the product from the reaction solution or culture solution can be carried out by conventional methods such as extraction, recrystallization, column chromatography, etc. In the following examples, % means weight %. Example 1 Agrobacterium radiopacter IFO
12607 (Agrobacterium radiobacter) as meat extract
1.0%, NaCl 0.5%, and peptone 1.0% (PH 7.2) (100 ml) was inoculated, and cultured with shaking at 30°C for 1 day. After the culture was completed, the culture solution was centrifuged, and the entire amount of the obtained bacterial cells was washed with ion-exchanged water, and then suspended in 50 ml of M/10 phosphate buffer (PH 7.0). Add 2.5 ml of methyl (±)-S-acetyl-β-mercaptoisobutyrate to this bacterial cell suspension,
The reaction was performed by shaking at 30°C for 48 hours. The decomposition rate of methyl S-acetyl-β-mercaptoisobutyrate at this time was 49%. PH of reaction solution
7.0, and methyl S-acetyl-β-mercaptoisobutyrate was extracted with ethyl acetate. Next, after lowering the pH of the aqueous layer to 2.0 with sulfuric acid, the S-
Acetyl-β-mercaptoisobutyric acid was extracted with ethyl acetate. The extract was dehydrated by adding anhydrous sodium sulfate, and then the solvent was removed by evaporation. The specific optical rotation of the extracted S-acetyl-β-mercaptoisobutyric acid and methyl S-acetyl-β-mercaptoisobutyrate was measured using a polarimeter (model PM101, manufactured by Union Giken Co., Ltd.). The results are shown in Table 1. It is clear from this that an optically active carboxylic acid and its enantiomer ester are produced. 【table】
Claims (1)
ール基、R2及びR3はアルキル基、ｎは１又は２
を示す）で表されるエステルに、エステル結合を
不斉加水分解する能力を有するアグロバクテリウ
ム属に属する微生物の培養液、菌体又は菌体処理
物を作用させることを特徴とする、一般式 （式中、R2及びｎは前記の意味を有する）で表
される光学活性カルボン酸及びその対掌体エステ
ルの製造法。[Claims] 1. General formula (In the formula, R 1 is an alkyl group, an aralkyl group, or an aryl group, R 2 and R 3 are an alkyl group, and n is 1 or 2
A general formula characterized in that a culture solution, bacterial cells, or treated bacterial cells of a microorganism belonging to the genus Agrobacterium that has the ability to asymmetrically hydrolyze an ester bond are allowed to act on an ester represented by A method for producing an optically active carboxylic acid represented by the formula (wherein R 2 and n have the above-mentioned meanings) and its enantiomer ester.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24578483A JPS60141297A (en) | 1983-12-28 | 1983-12-28 | Production of optically active carboxylic acid and its antipode ester |
| EP84304238A EP0130752B1 (en) | 1983-07-04 | 1984-06-22 | Process for preparing optically active carboxylic acids and antipode esters thereof |
| US06/627,093 US4629701A (en) | 1983-07-04 | 1984-07-02 | Process for preparing optically active carboxylic acids and antipode esters thereof |
| DE19843424440 DE3424440A1 (en) | 1983-07-04 | 1984-07-03 | METHOD FOR PRODUCING OPTICALLY ACTIVE CARBONIC ACIDS AND THEIR ESTERS IN THE FORM OF THE OPTICAL ANTIPODES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24578483A JPS60141297A (en) | 1983-12-28 | 1983-12-28 | Production of optically active carboxylic acid and its antipode ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60141297A JPS60141297A (en) | 1985-07-26 |
| JPH045438B2 true JPH045438B2 (en) | 1992-01-31 |
Family
ID=17138773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24578483A Granted JPS60141297A (en) | 1983-07-04 | 1983-12-28 | Production of optically active carboxylic acid and its antipode ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60141297A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63245694A (en) * | 1986-11-13 | 1988-10-12 | Showa Shell Sekiyu Kk | Production of optically active sulfur-containing carboxylic acid and antipodal ester thereof |
-
1983
- 1983-12-28 JP JP24578483A patent/JPS60141297A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60141297A (en) | 1985-07-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |