JPH0428358B2 - - Google Patents
Info
- Publication number
- JPH0428358B2 JPH0428358B2 JP56212393A JP21239381A JPH0428358B2 JP H0428358 B2 JPH0428358 B2 JP H0428358B2 JP 56212393 A JP56212393 A JP 56212393A JP 21239381 A JP21239381 A JP 21239381A JP H0428358 B2 JPH0428358 B2 JP H0428358B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- cyclopentenone
- allyl
- hydroxy
- reaction
- 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 - Lifetime
Links
- 108090000371 Esterases Proteins 0.000 claims description 6
- 210000004185 liver Anatomy 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OOJIJAGFQCKGCL-UHFFFAOYSA-N 5-methylcyclopent-2-en-1-one Chemical compound CC1CC=CC1=O OOJIJAGFQCKGCL-UHFFFAOYSA-N 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HNNRFEWGWVQYNP-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-prop-2-enylcyclopent-2-en-1-one Chemical compound CC1(O)C=CC(=O)C1CC=C HNNRFEWGWVQYNP-UHFFFAOYSA-N 0.000 description 1
- POXLZMAYYAQOLM-UHFFFAOYSA-N 4-methylcyclopent-2-en-1-one Chemical compound CC1CC(=O)C=C1 POXLZMAYYAQOLM-UHFFFAOYSA-N 0.000 description 1
- HHRWLPSFRHWAPU-UHFFFAOYSA-N 5-hydroxy-4-methylcyclopent-2-en-1-one Chemical compound CC1C=CC(=O)C1O HHRWLPSFRHWAPU-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は光学活性な（−）−２−アリル−３
−ヒドロキシ−３−メチル−４−シクロペンテノ
ンの製造方法に関する。
（−）−２−アリル−３−ヒドロキシ−３−
メチル−４−シクロペンテノンは本発明者らによ
つて初めて合成された新規化合物であつて、該化
合物はそれ自身農薬およびその中間体として有用
であるばかりでなく、香料や医薬品の中間体とし
ても有用であり、たとえば該化合物を転位させる
ことによりＳ（＋）−アレスロロンとすることがで
き、この化合物はピレスロイド中間体として極め
て価値ある化合物である。
本発明の（−）−２−アリル−３−ヒドロキ
シ−３−メチル−４−シクロペンテノンは、
式（Ｉ）
で示されるｄ−３−アセトキシ−２−アリル−
３−メチル−４−シクロペンテノンに豚肝臓エス
テラーゼ（PorcineLiver Esterase）を作用させ
て加水分解することにより製造することができ
る。
本発明において、原料として用いられる式
（Ｉ）で示されるアセテートは、たとえば以下に
示す方法により容易に合成することができる。
ｄ−３−アセトキシ−２−アリル−３−メチ
ル−４−シクロペンテノンの加水分解反応は、豚
肝臓エステラーゼとともにPH６〜９の緩衝溶液
中、反応温度約20〜40℃、反応時間約10〜40時間
の条件で激しく攪拌することにより行われる。
かかる加水分解反応において、豚肝臓エステラ
ーゼの使用量は原料アセテートに対して通常0.5
〜30重量％であり、また加水分解反応における原
料アセテートの濃度は通常１〜30重量％である。
この加水分解反応は、光学収率のうえから原料
アセテートの反応率が50％未満で終了することが
好ましい。
反応終了後、加水分解反応液をたとえばメチル
イソブチルケトン、酢酸エチル、エチルエーテ
ル、ジクロルメタン等の溶媒により、（−）−
２−アリル−３−ヒドロキシ−３−メチル−４−
シクロペンテノンおよび未反応の２−アリル−３
−アセトキシ−３−メチル−４−シクロペンテノ
ンを抽出し、得られた有機層から溶媒を留去した
のち、濃陥残渣をカラムクロマトグラフイーで処
理することにより、目的とする（−）−２−ア
リル−３−ヒドロキシ−３−メチル−４−シクロ
ペンテノンを混合物から単離することができる。
以下、実施例により本発明を説明する。
実施例
ｄ−３−アセトキシ−２−アリル−３−メチ
ル−４−シクロペンテノン1g、Porcine Liver
Esterase（シグマ社製）150mgおよび３，2M硫酸
アンモニウム水溶液（PH８）30mlを混合し、20℃
にて20時間激しく攪拌する。反応終了後水30mlを
加えメチルイソブチルケトン50mlにて３回抽出す
る。得られた有機層から溶媒を留去し、濃縮残渣
を酢酸エチルエステル：トルエン＝３：５の混合
液にてカラムクロマト精製し、（−）−２−ア
リル−３−ヒドロキシ−３−メチル−４−シクロ
ペンテノン0.368gを得た。
収率47％
n20 D 1.4983
α〕20 D−23.9°（Ｃ＝１，CHC3）
上記化合物を転位して得られたアレスロロンの
光学純度は98％であつた。
（光学純度の分析方法 Agric，Biol.Chem.，
41，（10）2003〜2006（1977））
dl−３−アセトキシ−２−アリル−３−メチル
−４−シクロペンテノン２ｇ、Porcine Liver
Esterase（シグマ社製）80mg、0.1Mリン酸バツフ
アー水溶液（PH７）90mlおよびメタノール10mlを
混合し、30〜35℃にて20時間激しく攪拌する。反
応終了後、メチルイソブチルケトン50mlにて４回
抽出する。以下、実施例１に準じて後処理、精製
して（−）−２−アリル−３−ヒドロキシ−３
−メチル−４−シクロペンテノン0.76ｇを得た。
収率 48.5％
α〕20 D−21.8°（Ｃ＝１，CHC3）
また、このものを転位して得たアレスロロンの
光学純度は96％であつた。 DETAILED DESCRIPTION OF THE INVENTION The present invention provides optically active (-)-2-allyl-3
-Relating to a method for producing hydroxy-3-methyl-4-cyclopentenone. (-)-2-allyl-3-hydroxy-3-
Methyl-4-cyclopentenone is a new compound synthesized for the first time by the present inventors, and the compound itself is not only useful as a pesticide and its intermediate, but also as an intermediate for fragrances and pharmaceuticals. For example, the compound can be rearranged to give S(+)-allethrone, which is an extremely valuable compound as a pyrethroid intermediate. The (-)-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone of the present invention has the formula (I) d-3-acetoxy-2-allyl-
It can be produced by hydrolyzing 3-methyl-4-cyclopentenone with porcine liver esterase. In the present invention, the acetate represented by formula (I) used as a raw material can be easily synthesized, for example, by the method shown below. The hydrolysis reaction of d-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone is carried out together with pig liver esterase in a buffer solution with a pH of 6 to 9, at a reaction temperature of approximately 20 to 40°C, and a reaction time of approximately 10 to 40°C. This is done by vigorous stirring under conditions of 40 hours. In such hydrolysis reactions, the amount of pig liver esterase used is usually 0.5 to the raw material acetate.
30% by weight, and the concentration of raw acetate in the hydrolysis reaction is usually 1 to 30% by weight. This hydrolysis reaction is preferably completed when the reaction rate of the raw material acetate is less than 50% from the viewpoint of optical yield. After the reaction is completed, the hydrolysis reaction solution is diluted with (-)- by a solvent such as methyl isobutyl ketone, ethyl acetate, ethyl ether, dichloromethane, etc.
2-allyl-3-hydroxy-3-methyl-4-
Cyclopentenone and unreacted 2-allyl-3
-Acetoxy-3-methyl-4-cyclopentenone is extracted, the solvent is distilled off from the obtained organic layer, and the concentrated residue is treated with column chromatography to obtain the desired (-)- 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone can be isolated from the mixture. The present invention will be explained below with reference to Examples. Example d-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone 1 g, Porcine Liver
Mix 150 mg of Esterase (manufactured by Sigma) and 30 ml of 3,2M ammonium sulfate aqueous solution (PH8), and
Stir vigorously for 20 hours. After the reaction is complete, add 30 ml of water and extract three times with 50 ml of methyl isobutyl ketone. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography using a mixture of ethyl acetate and toluene = 3:5 to obtain (-)-2-allyl-3-hydroxy-3-methyl- 0.368 g of 4-cyclopentenone was obtained. Yield: 47% n 20 D 1.4983 α] 20 D −23.9° (C=1, CHC 3 ) The optical purity of arethrolone obtained by rearranging the above compound was 98%. (Analysis method of optical purity Agric, Biol.Chem.,
41, (10) 2003-2006 (1977)) dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone 2g, Porcine Liver
80 mg of Esterase (manufactured by Sigma), 90 ml of 0.1 M phosphate buffer aqueous solution (PH7) and 10 ml of methanol are mixed and stirred vigorously at 30 to 35°C for 20 hours. After the reaction is complete, extract 4 times with 50 ml of methyl isobutyl ketone. Hereinafter, according to Example 1, after treatment and purification, (-)-2-allyl-3-hydroxy-3
0.76 g of -methyl-4-cyclopentenone was obtained. Yield 48.5% α] 20 D −21.8° (C=1, CHC 3 ) Furthermore, the optical purity of arethrolone obtained by rearrangement of this product was 96%.
Claims (1)
チル−４−シクロペンテノンに豚肝臓エステラー
ゼを作用させて加水分解することを特徴とする
（−）−２−アリル−３−ヒドロキシ−３−メチル
−４−シクロペンテノンの製造方法。1 (-)-2-allyl-3-hydroxy-3-, characterized in that d-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone is hydrolyzed by the action of pig liver esterase. Method for producing methyl-4-cyclopentenone.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21239381A JPS58111690A (en) | 1981-12-25 | 1981-12-25 | L(-)-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone and its preparation |
| DE8282110716T DE3265658D1 (en) | 1981-11-19 | 1982-11-19 | 4-cyclopentenones and their production |
| EP82110716A EP0080671B1 (en) | 1981-11-19 | 1982-11-19 | 4-cyclopentenones and their production |
| US06/443,017 US4511655A (en) | 1981-11-19 | 1982-11-19 | Process for producing 4-cyclopentenones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21239381A JPS58111690A (en) | 1981-12-25 | 1981-12-25 | L(-)-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58111690A JPS58111690A (en) | 1983-07-02 |
| JPH0428358B2 true JPH0428358B2 (en) | 1992-05-14 |
Family
ID=16621836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21239381A Granted JPS58111690A (en) | 1981-11-19 | 1981-12-25 | L(-)-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58111690A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0115860B1 (en) * | 1983-02-03 | 1988-10-12 | Sumitomo Chemical Company, Limited | Optically active 4-hydroxy-2-cyclopentenones, and their production |
| JPS6420091A (en) * | 1987-07-13 | 1989-01-24 | Sumitomo Chemical Co | Biochemical production of (r)-4-hydroxy-2-cyclopentenone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55160740A (en) * | 1979-05-31 | 1980-12-13 | Sumitomo Chem Co Ltd | Preparation of cyclopentenolone |
| JPS5626832A (en) * | 1979-08-14 | 1981-03-16 | Sumitomo Chem Co Ltd | Preparation of cyclopentenolone |
-
1981
- 1981-12-25 JP JP21239381A patent/JPS58111690A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55160740A (en) * | 1979-05-31 | 1980-12-13 | Sumitomo Chem Co Ltd | Preparation of cyclopentenolone |
| JPS5626832A (en) * | 1979-08-14 | 1981-03-16 | Sumitomo Chem Co Ltd | Preparation of cyclopentenolone |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58111690A (en) | 1983-07-02 |
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