JPH046360B2 - - Google Patents
Info
- Publication number
- JPH046360B2 JPH046360B2 JP885682A JP885682A JPH046360B2 JP H046360 B2 JPH046360 B2 JP H046360B2 JP 885682 A JP885682 A JP 885682A JP 885682 A JP885682 A JP 885682A JP H046360 B2 JPH046360 B2 JP H046360B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- carboxylic acid
- acid compound
- compound represented
- culture
- 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
- -1 carboxylic acid compound Chemical class 0.000 claims description 12
- 244000005700 microbiome Species 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 6
- 238000012258 culturing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000007858 starting material Substances 0.000 description 8
- 241000461774 Gloeosporium Species 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical compound OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001888 Peptone Substances 0.000 description 3
- 108010080698 Peptones Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000019319 peptone Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- OVSKIKFHRZPJSS-DOMIDYPGSA-N 2-(2,4-dichlorophenoxy)acetic acid Chemical compound OC(=O)[14CH2]OC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-DOMIDYPGSA-N 0.000 description 1
- PCCMNBRZMKANQD-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)ethanol Chemical compound OCCOC1=CC=C(Cl)C=C1Cl PCCMNBRZMKANQD-UHFFFAOYSA-N 0.000 description 1
- LOJHHQNEBFCTQK-UHFFFAOYSA-N 2-phenoxypropan-1-ol Chemical compound OCC(C)OC1=CC=CC=C1 LOJHHQNEBFCTQK-UHFFFAOYSA-N 0.000 description 1
- 241000152100 Colletotrichum horii Species 0.000 description 1
- 244000205754 Colocasia esculenta Species 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 238000009629 microbiological culture Methods 0.000 description 1
- 229940111688 monobasic potassium phosphate Drugs 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical group [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Description
本発明は、不整炭素を有するカルボン酸化合物
のラセミ体をグロエオスポリウム属に属する微生
物と共に培養するか、その微生物の培養物又はそ
の処理物を作用せしめ、光学活性を有するアルコ
ール化合物の製法、および／又は光学活性を有す
るカルボン酸化合物の製法に関する。
先に本発明者らの１人、仲嶋らは不整炭素を有
しないカルボン酸化合物、例えば２，４−ジクロ
ロフエノキシ酢酸を微生物の培養物により２（２，
４−ジクロロフエノキシ）エタノールに変換する
ことを見出した。〔ケミカル・フアーマシユーテ
イカル・ブルテイン21（３）671〜673頁（1973年）
参照〕
本発明者らは、これらの知見から、鋭意研究を
重ねた結果、不整炭素を有するカルボン酸化合物
のラセミ体を出発物質として用い、グロエオスポ
リウム属に属する微生物と共に培養するか、その
微生物の培養物又はその処理物を作用せしめて、
光学活性を有するアルコール化合物に変換される
ことを、更に光学活性を有するカルボン酸化合物
が得られることを見出し、本発明に至つた。
本発明に用いられる出発物質は、一般式
（式中、Ｘは置換されていてもよい環式構造を有
する基、R1は低級アルキル基を示す。）で表され
るカルボン酸化合物のラセミ体であり、式中のＸ
の置換されていてもよい環式構造を有する基とし
ては、例えば、
The present invention provides a method for producing an optically active alcohol compound by culturing a racemic form of a carboxylic acid compound having an asymmetric carbon with a microorganism belonging to the genus Gloeosporium, or acting on a culture of the microorganism or a treated product thereof; and/or a method for producing a carboxylic acid compound having optical activity. One of the present inventors, Nakajima et al., previously reported that a carboxylic acid compound having no asymmetric carbon, such as 2,4-dichlorophenoxyacetic acid, was prepared by microbial culture using 2 (2,
4-dichlorophenoxy) ethanol. [Chemical Pharmaceutical Bulletin 21 (3) pp. 671-673 (1973)
Reference] Based on these findings, the present inventors have conducted intensive research, and as a result, the present inventors have found that using a racemic form of a carboxylic acid compound having an asymmetric carbon as a starting material, culturing it together with a microorganism belonging to the genus Gloeosporium, or culturing it with a microorganism belonging to the genus Gloeosporium. By allowing a culture of microorganisms or a processed product thereof to act,
The present inventors have discovered that it can be converted into an optically active alcohol compound, and that an optically active carboxylic acid compound can also be obtained, leading to the present invention. The starting materials used in the present invention have the general formula (In the formula, X is a group having an optionally substituted cyclic structure, and R 1 is a lower alkyl group.)
As the group having an optionally substituted cyclic structure, for example,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
の構造を有する基などがあげられるが、特にこれ
らの基のみに限定されるものではない。
反応に用いられる微生物としては、例えばグロ
エオスポリウム（Gloeosporium）属に属するグ
ロエオスポリウム・オリバラム・アルム
（Gloeosporium olivarum Alm）（香川大学農学
部植物病学研究室より入手）、グロエオスポリウ
ム・カキ（Gloeosporium kaki）（財団法人発酵
研究所より入手、IFO6445）などがあげられる。
本発明を実施するにはグロエオスポリウム属に
属する微生物を、任意の出発物質を加えた適宜な
培地にて、静置あるいは振とう培養を行い、一定
時間培養し反応させたのち、培養液を菌体と濾液
に分離する。この反応は微生物の培養液やその処
理物中に出発物質を加えて静置又は振とうして反
応させてもよい。
次いで濾液に、抽出・精製操作を加え、目的の
物質を得ることができる。例えば、濾液のPHをア
ルカリ性に調整したのち、エーテル等の有機溶媒
にて抽出する。抽出液を洗浄後、減圧濃縮、クロ
マトグラフイ等の操作により、目的の光学活性を
有するアルコール化合物を得ることができる。
一方、有機溶媒による抽出後の濾液残査のPHを
酸性に調整したのち、エーテル等の有機溶媒にて
抽出する。抽出液を洗浄後、減圧濃縮、クロマト
グラフイ等の操作により、目的の光学活性を有す
るカルボン酸化合物を得ることができる。
なお、出発物質や目的物質の物性により、抽
出、分離、精製等の条件を適宜変えることが好ま
しい。
本発明にて得た光学活性を有する物質は除草
剤、殺虫剤等として有用である。
実施例 １
ペプトン90ｇ、硫酸マグネシウム７水物3.6ｇ、
第１リン酸カリウム9.0ｇ、シユクロース450ｇの
組成を有するペプトン培地９に出発物質とし
て、２−フエノキシ−プロピオン酸4.25ｇを加え
た後、PH5.5に調整し、グレオスポリウム・オリ
バラム・アルムを接種後、２容のジヤーフアメ
ンターに分注した後、27〜28℃、５日間通気撹拌
培養する。通気量は、1.2／分、ペラ回転数は
450r.p.m.とする。
培養終了後、この培養反応液を吸引濾過により
菌体と濾液とに分離する。
次いで、濾液を10％水酸化カリウムにてPH9.2
に調整したのち、エーテル３にて抽出を行う。
このエーテル抽出液を飽和食塩水にて洗液が中性
になるまで洗浄を繰り返した後、芒硝にて乾燥を
行う。次いでエーテル抽出液を減圧濃縮し、この
濃縮液をシリカゲルカラムクロマトグラフイーに
てクロロホルムを用い展開し、その溶出液を減圧
乾固し、光学活性を有する２−フエノキシ−プロ
パノール0.8ｇを得た。
比旋光度：〔α〕25 D＋13.7゜（c0.00876、メタノー
ル）
なお、本物質の赤外吸収スペクトル、核磁気共
鳴スペクトル、マススペクトルは別に調製した２
−フエノキシ−プロパノールのラセミ体と一致し
た。
一方、エーテル抽出した残査を塩酸にてPH1.5
と調整した後、エーテル３にて更に抽出を行
い、この抽出液を飽和食塩水にて洗浄した後、芒
硝にて乾燥を行う。次いで減圧濃縮し、この濃縮
液をシリカゲルカラムクロマトグラフイーにてク
ロロホルムを用いて展開し、その溶出液を減圧乾
固し、光学活性を有する２−フエノキシ−プロピ
オン酸１ｇを得た。
比旋光度：〔α〕25 D＋16.9゜（C0.025、アセトン）
なお、本物質の赤外吸収スペクトル、核磁気共
鳴スペクトルおよびマススペクトルは、出発物質
の２−フエノキシ−プロピオン酸（ラセミ体）と
一致した。
実施例 ２
実施例１と同様にペプトン培地に種々の出発物
質を加え下記の条件にて反応を試み目的物質を得
た。Examples include groups having the structure of [Formula], but the group is not particularly limited to these groups. Examples of microorganisms used in the reaction include Gloeosporium olivarum Alm, which belongs to the genus Gloeosporium (obtained from the Plant Pathology Laboratory, Faculty of Agriculture, Kagawa University), Examples include oysters (Gloeosporium kaki) (obtained from Fermentation Research Institute, IFO6445). To carry out the present invention, microorganisms belonging to the genus Gloeosporium are cultured either statically or with shaking in an appropriate medium containing an arbitrary starting material, and after culturing and reacting for a certain period of time, the culture solution Separate into bacterial cells and filtrate. This reaction may be carried out by adding a starting material to a culture solution of microorganisms or a processed product thereof, and allowing the mixture to stand or be shaken. Next, the filtrate can be subjected to extraction and purification operations to obtain the desired substance. For example, after adjusting the pH of the filtrate to alkaline, it is extracted with an organic solvent such as ether. After washing the extract, an alcohol compound having the desired optical activity can be obtained by vacuum concentration, chromatography, or other operations. On the other hand, after the pH of the filtrate residue after extraction with an organic solvent is adjusted to acidic, it is extracted with an organic solvent such as ether. After washing the extract, a carboxylic acid compound having the desired optical activity can be obtained by vacuum concentration, chromatography, and other operations. Note that it is preferable to change the conditions for extraction, separation, purification, etc. as appropriate depending on the physical properties of the starting material and target material. The optically active substance obtained in the present invention is useful as a herbicide, insecticide, etc. Example 1 90 g of peptone, 3.6 g of magnesium sulfate heptahydrate,
After adding 4.25 g of 2-phenoxy-propionic acid as a starting material to peptone medium 9 having the composition of monobasic potassium phosphate 9.0 g and sucrose 450 g, the pH was adjusted to 5.5, and after inoculation with Gleosporium olivarum arum. After dispensing the mixture into 2-volume jar fermenters, the mixture was cultured with aeration at 27-28°C for 5 days. Airflow rate is 1.2/min, propeller rotation speed is
450rpm. After completion of the culture, the culture reaction solution is separated into bacterial cells and a filtrate by suction filtration. Next, the filtrate was adjusted to pH 9.2 with 10% potassium hydroxide.
After adjusting to , extract with ether 3.
This ether extract was washed repeatedly with saturated brine until the washings became neutral, and then dried with Glauber's salt. Next, the ether extract was concentrated under reduced pressure, and this concentrated liquid was developed using chloroform in silica gel column chromatography, and the eluate was dried under reduced pressure to obtain 0.8 g of optically active 2-phenoxy-propanol. Specific optical rotation: [α] 25 D +13.7° (c0.00876, methanol) The infrared absorption spectrum, nuclear magnetic resonance spectrum, and mass spectrum of this substance were prepared separately.
It was consistent with the racemic form of -phenoxy-propanol. On the other hand, the residue extracted with ether was diluted with hydrochloric acid to pH 1.5.
After this adjustment, extraction is further performed with ether 3, and this extract is washed with saturated saline, and then dried with Glauber's salt. Next, the concentrate was concentrated under reduced pressure, and this concentrated solution was developed using chloroform in silica gel column chromatography, and the eluate was dried under reduced pressure to obtain 1 g of optically active 2-phenoxy-propionic acid. Specific rotation: [α] 25 D +16.9° (C0.025, acetone) The infrared absorption spectrum, nuclear magnetic resonance spectrum, and mass spectrum of this substance are based on the starting material 2-phenoxy-propionic acid (racemic body). Example 2 In the same manner as in Example 1, various starting materials were added to a peptone medium and reactions were attempted under the following conditions to obtain the target substance.
【表】【table】
【表】
なお、各生成物質の赤外吸収スペクトル、核磁
気共鳴スペクトルおよびマススペクトルは、各生
成物質に対応するラセミ体のものと一致した。[Table] The infrared absorption spectrum, nuclear magnetic resonance spectrum, and mass spectrum of each product substance were consistent with those of the racemate corresponding to each product substance.
Claims (1)
する基、R1は低級アルキル基を示す。）で表され
るカルボン酸化合物のラセミ体を、グロエオスポ
リウム属に属する微生物と共に培養するか、その
微生物の培養物又はその処理物を作用せしめ、光
学活性を有する一般式 （式中、ＸおよびR1は前記と同じく意味する。）
で表されるアルコール化合物の製法、および／又
は、光学活性を有する一般式 （式中、ＸおよびR1は前記と同じく意味する。）
で表されるカルボン酸化合物の製法。[Claims] 1. General formula (In the formula, X is a group having an optionally substituted cyclic structure, and R 1 is a lower alkyl group.) A racemic form of a carboxylic acid compound represented by A general formula that has optical activity by culturing or acting on a culture of the microorganism or a processed product thereof. (In the formula, X and R 1 have the same meanings as above.)
A method for producing an alcohol compound represented by and/or a general formula having optical activity (In the formula, X and R 1 have the same meanings as above.)
A method for producing a carboxylic acid compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP885682A JPS58126792A (en) | 1982-01-25 | 1982-01-25 | Preparation of optically active substance by microorganism |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP885682A JPS58126792A (en) | 1982-01-25 | 1982-01-25 | Preparation of optically active substance by microorganism |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58126792A JPS58126792A (en) | 1983-07-28 |
| JPH046360B2 true JPH046360B2 (en) | 1992-02-05 |
Family
ID=11704362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP885682A Granted JPS58126792A (en) | 1982-01-25 | 1982-01-25 | Preparation of optically active substance by microorganism |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58126792A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568641A (en) * | 1983-07-27 | 1986-02-04 | Imperial Chemical Industries Plc | Process for producing optically active aryloxypropionic acids and derivatives thereof |
| JPS615795A (en) * | 1984-06-21 | 1986-01-11 | Kaken Pharmaceut Co Ltd | Production of optically active substance by means of microorganism |
-
1982
- 1982-01-25 JP JP885682A patent/JPS58126792A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58126792A (en) | 1983-07-28 |
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