JP2571950B2 - Cyclopentenone derivatives and their production - Google Patents
Cyclopentenone derivatives and their productionInfo
- Publication number
- JP2571950B2 JP2571950B2 JP63057961A JP5796188A JP2571950B2 JP 2571950 B2 JP2571950 B2 JP 2571950B2 JP 63057961 A JP63057961 A JP 63057961A JP 5796188 A JP5796188 A JP 5796188A JP 2571950 B2 JP2571950 B2 JP 2571950B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- structural formula
- acetoxy
- cyclopentenone
- represented
- 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 - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】 本発明は、構造式（Ｉ） （式中、Ｒは水素またはアセチル基を、Ｒ′は炭素数
１〜２のアルキル基またはベンジル基を表す） で示されるシクロペンテノン誘導体及びその製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound represented by the structural formula (I) Wherein R represents hydrogen or an acetyl group, and R ′ represents an alkyl group or benzyl group having 1 to 2 carbon atoms, and a method for producing the same.
上記構造式（Ｉ）で示されるシクロペンテノン誘導体
は本発明者により初めて合成された新規化合物であり、
香料や医薬品の中間体として価値ある化合物である。The cyclopentenone derivative represented by the above structural formula (I) is a novel compound synthesized for the first time by the present inventors,
It is a valuable compound as an intermediate for fragrances and pharmaceuticals.
構造式（II） （式中、Ｒ′は前記と同じ意味を有する。） で示される４−アセトキシ−５−アルコキシペンタジエ
ナールの無水酢酸中での反応を検討したところ、構造式
（Ｉ）で示されるシクロペンテノン誘導体の生成を見い
だし、本発明を完成するに至った。Structural formula (II) (In the formula, R ′ has the same meaning as described above.) The reaction of 4-acetoxy-5-alkoxypentadienal in acetic anhydride was examined, and the cyclopentene represented by the structural formula (I) was examined. The generation of a tenone derivative was found, and the present invention was completed.
すなわち、本発明の要旨は、上記構造式（II）で示さ
れる４−アセトキシ−５−アルコキシペンタジエナール
を、無水酢酸中で酸触媒の共存下に反応させることを特
徴とする構造式（Ｉ）で示されるシクロペンテノン誘導
体及びその製造方法である。That is, the gist of the present invention is to provide a compound represented by the structural formula (I) in which 4-acetoxy-5-alkoxypentadienal represented by the structural formula (II) is reacted in acetic anhydride in the presence of an acid catalyst. ) And a method for producing the cyclopentenone derivative.
かかる反応は、本発明者によって初めて明らかにされ
た新規な反応である。Such a reaction is a novel reaction first revealed by the present inventors.
この反応において、原料として用いられる構造式（I
I）で示される４−アセトキシ−５−アルコキシペンタ
ジエナールは，例えばＤ−グルコフラヌロノー6,3−ラ
クトントリアセテートをクロロホルム中、当量のアルコ
ールと塩基触媒共存下反応させることによって容易に合
成することが出来る。In this reaction, the structural formula (I
The 4-acetoxy-5-alkoxypentadienal represented by I) can be easily synthesized, for example, by reacting D-glucofuranurono 6,3-lactone triacetate in chloroform with an equivalent amount of alcohol in the presence of a base catalyst. I can do it.
構造式（II）で示される４−アセトキシ−５−アルコ
キシペンタジエナールの無水酢酸中での構造式（Ｉ）で
示されるシクロペンテノン誘導体への変換反応は酸触媒
の共存下に実施される。The conversion of 4-acetoxy-5-alkoxypentadienal represented by the structural formula (II) into the cyclopentenone derivative represented by the structural formula (I) in acetic anhydride is carried out in the presence of an acid catalyst. .
酸触媒としては、例えば、スルホン酸型イオン交換樹
脂、スルホン酸誘導体、およびトリフルオロ酢酸などの
有機酸を用いることが可能であるが、特にスルホン酸型
イオン交換樹脂は、反応後直ちに反応系外に除去できる
こと及び再使用が可能である等の利点がある。As the acid catalyst, for example, an organic acid such as a sulfonic acid type ion exchange resin, a sulfonic acid derivative, and trifluoroacetic acid can be used. It has the advantage that it can be removed and reused.
酸触媒の使用量は特に制限されないが、反応を短時間
で完結させる為には、構造式（II）の化合物に対し、５
〜20倍モル程度が望ましい。The amount of the acid catalyst used is not particularly limited, but in order to complete the reaction in a short time, 5
About 20-fold molar is desirable.
反応温度は，−10℃〜100℃の間で任意であるが、望
ましくは０℃〜40℃の範囲であり、反応時間は用いる酸
触媒の量により0.2〜40時間の間で任意である。The reaction temperature is optional between -10 ° C and 100 ° C, but preferably in the range of 0 ° C to 40 ° C, and the reaction time is optional between 0.2 and 40 hours depending on the amount of the acid catalyst used.
このような反応によって、本発明の化合物である構造
式（Ｉ）で示されるシクロペンテノン誘導体が得られ、
通常の分離手段、例えば抽出、分液、濃縮、薄層クロマ
トグラフィー、カラムクロマトグラフィーなどにより、
反応混合物から単離精製することができる。By such a reaction, a cyclopentenone derivative represented by the structural formula (I) which is a compound of the present invention is obtained,
By ordinary separation means, such as extraction, separation, concentration, thin-layer chromatography, column chromatography, etc.
It can be isolated and purified from the reaction mixture.
以下に実施例を挙げて本発明の方法を具体的に説明す
るが、本発明はこれによって何等制限されるものではな
い。Hereinafter, the method of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
実施例1. ４−アセトキシ−５−エトキシペンタジエナール0.03
7gに無水酢酸1mlとトリフルオロ酢酸0.1mlを加え、氷冷
下で10分間攪拌し反応させる。反応終了後、反応混合物
を減圧下に濃縮し、薄層クロマトグラフィーによって、
４−ヒドロキシ−５−エトキシ−２−シクロペンテノン
を単離した。（収率60.1％） 以下に当該化合物の赤外線吸収スペクトルデーターを
示す。Example 1. 4-acetoxy-5-ethoxypentadienal 0.03
1 ml of acetic anhydride and 0.1 ml of trifluoroacetic acid are added to 7 g, and the mixture is stirred and reacted under ice-cooling for 10 minutes. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and by thin-layer chromatography,
4-Hydroxy-5-ethoxy-2-cyclopentenone was isolated. (Yield 60.1%) The infrared absorption spectrum data of the compound are shown below.
IR（KBr）;2980,2940,2880,1720,1590,1480,1440,137
0,1360,1320,1220,1110,1060,1020,960,900,880,780cm
-1 実施例2. ４−アセトキシ−５−エトキシペンタジエナール0.10
3gに無水酢酸3mlとトリフルオロ酢酸0.1mlを加え、氷冷
下で14.5時間攪拌し反応させる。反応終了後、反応混合
物を減圧下に濃縮し、薄層クロマトグラフィーによっ
て、４−ヒドロキシ−５−エトキシ−２−シクロペンテ
ノンを単離した。（収率43.8％） 実施例３ ４−アセトキシ−５−メトキシペンタジエナール0.19
4gに無水酢酸3mlとトリフルオロ酢酸1mlを加え、20℃に
於て１時間攪拌し反応させる。反応終了後、反応混合物
を減圧下に濃縮し、薄層クロマトグラフィーによって、
４−アセトキシ−５−メトキシ−２−シクロペンテノン
を単離した。（収率61.8％） 実施例４ ４−アセトキシ−５−ベンジルオキシペンタジエナー
ル0.14gに無水酢酸3mlとトリフルオロ酢酸1mlを加え、2
0℃に於て１時間攪拌し反応させる。反応終了後、反応
混合物を減圧下に濃縮し、薄層クロマトグラフィーによ
って、４−アセトキシ−５−ベンジルオキシ−２−シク
ロペンテノンを単離した。（収率69.0％） 実施例５ ４−アセトキシ−５−メトキシペンタジエナール0.05
gに無水酢酸1mlを加え、0.05gの酸性イオン交換樹脂（D
OWEX 50W−X2）の共存下、20℃に於て１時間攪拌し反応
させる。反応終了後、反応溶液を減圧下に濃縮し、薄層
クロマトグラフィーによって、４−アセトキシ−５−メ
トキシ−２−シクロペンテノンを単離した。（収率33.0
％）IR (KBr); 2980,2940,2880,1720,1590,1480,1440,137
0,1360,1320,1220,1110,1060,1020,960,900,880,780cm
-1 Example 2. 4-acetoxy-5-ethoxypentadienal 0.10
3 ml of acetic anhydride and 0.1 ml of trifluoroacetic acid are added to 3 g, and the mixture is stirred and cooled under ice cooling for 14.5 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 4-hydroxy-5-ethoxy-2-cyclopentenone was isolated by thin-layer chromatography. Example 4 4-acetoxy-5-methoxypentadienal 0.19 (yield 43.8%)
3 ml of acetic anhydride and 1 ml of trifluoroacetic acid are added to 4 g, and the mixture is stirred and reacted at 20 ° C. for 1 hour. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and by thin-layer chromatography,
4-acetoxy-5-methoxy-2-cyclopentenone was isolated. (Yield 61.8%) Example 4 To 0.14 g of 4-acetoxy-5-benzyloxypentadienal was added 3 ml of acetic anhydride and 1 ml of trifluoroacetic acid.
Stir at 0 ° C for 1 hour to react. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 4-acetoxy-5-benzyloxy-2-cyclopentenone was isolated by thin-layer chromatography. (Yield: 69.0%) Example 5 4-acetoxy-5-methoxypentadienal 0.05
g of acetic anhydride and 0.05 g of an acidic ion exchange resin (D
In the coexistence of OWEX 50W-X2), the mixture is stirred and reacted at 20 ° C for 1 hour. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 4-acetoxy-5-methoxy-2-cyclopentenone was isolated by thin-layer chromatography. (Yield 33.0
%)
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical display location C07B 61/00 300 C07B 61/00 300
Claims (2)
〜２のアルキル基またはベンジル基を表す。） で示されるシクロペンテノン誘導体。1. Structural formula Wherein R is hydrogen or an acetyl group, and R ′ is
Represents an alkyl group or a benzyl group. ) A cyclopentenone derivative represented by the formula:
ル基を表す。） で示される４−アセトキシ−５−アルコキシペンタジエ
ナールを、無水酢酸中酸触媒の共存下に反応させること
を特徴とする構造式 （式中、Ｒは水素またはアセチル基を、Ｒ′は炭素数１
〜２のアルキル基またはベンジル基を表す。） で示されるシクロペンテノン誘導体の製造法。2. The structural formula (Wherein R ′ represents an alkyl group having 1 to 2 carbon atoms or a benzyl group). The reaction of 4-acetoxy-5-alkoxypentadienal represented by the following formula in the presence of an acid catalyst in acetic anhydride. Characteristic structural formula Wherein R is hydrogen or an acetyl group, and R ′ is
Represents an alkyl group or a benzyl group. A method for producing a cyclopentenone derivative represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057961A JP2571950B2 (en) | 1988-03-11 | 1988-03-11 | Cyclopentenone derivatives and their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057961A JP2571950B2 (en) | 1988-03-11 | 1988-03-11 | Cyclopentenone derivatives and their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01233255A JPH01233255A (en) | 1989-09-19 |
| JP2571950B2 true JP2571950B2 (en) | 1997-01-16 |
Family
ID=13070608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63057961A Expired - Fee Related JP2571950B2 (en) | 1988-03-11 | 1988-03-11 | Cyclopentenone derivatives and their production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2571950B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117057C (en) * | 1996-09-27 | 2003-08-06 | 宝酒造株式会社 | Cyclopentenones, process for preparing same, and use thereof |
| ATE274903T1 (en) * | 1997-03-17 | 2004-09-15 | Takara Bio Inc | ANTIVIRAL AGENTS |
| EA001763B1 (en) * | 1997-03-28 | 2001-08-27 | Такара Сузо Ко., Лтд. | Therapeutic agent for diabetes |
| US6284801B1 (en) * | 1997-04-01 | 2001-09-04 | Takara Shuzo Co., Ltd. | Antirheumatic agents |
| CN1129569C (en) * | 1997-06-30 | 2003-12-03 | 宝酒造株式会社 | Cyclopentenone derivatives |
-
1988
- 1988-03-11 JP JP63057961A patent/JP2571950B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01233255A (en) | 1989-09-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |