JP2571939B2 - Cyclopentenone derivatives and their production - Google Patents
Cyclopentenone derivatives and their productionInfo
- Publication number
- JP2571939B2 JP2571939B2 JP23786987A JP23786987A JP2571939B2 JP 2571939 B2 JP2571939 B2 JP 2571939B2 JP 23786987 A JP23786987 A JP 23786987A JP 23786987 A JP23786987 A JP 23786987A JP 2571939 B2 JP2571939 B2 JP 2571939B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methyl alcohol
- acetoxy
- structural formula
- cyclopentenone
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明は，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法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound of the formula (I) And a method for producing the cyclopentenone derivative.
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） で示される３−アセトキシ−６−ジアセトキシメチルピ
ラン−２−オンのメチルアルコール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) When the reaction of 3-acetoxy-6-diacetoxymethylpyran-2-one represented by the following formula in methyl alcohol was examined, formation of the cyclopentenone derivative represented by the structural formula (I) was found, and the present invention was completed. I came to.
すなわち，本発明の要旨は，上記構造式（II）で示さ
れる３−アセトキシ−６−ジアセトキシメチルピラン−
２−オンを，メチルアルコールと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 3-acetoxy-6-diacetoxymethylpyran- represented by the above structural formula (II).
A cyclopentenone derivative represented by the structural formula (I) characterized by reacting 2-one with methyl alcohol and a method for producing the same.
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３−アセトキシ−６−ジアセトキシメチ
ルピラン−２−オンは，例えばＤ−グルコフラヌロノ−
6,3−ラクトンを無水酢酸−酢酸ナトリウム系で処理す
ることによって容易に合成することができる。In this reaction, the structural formula (I
3-acetoxy-6-diacetoxymethylpyran-2-one represented by I) is, for example, D-glucofuranurono-
It can be easily synthesized by treating 6,3-lactone with an acetic anhydride-sodium acetate system.
構造式（II）で示される３−アセトキシ−６−ジアセ
トキシメチルピラン−２−オンとメチルアルコールとの
反応は，塩基化合物の共存下に実施される。The reaction between 3-acetoxy-6-diacetoxymethylpyran-2-one represented by the structural formula (II) and methyl alcohol is carried out in the presence of a basic compound.
塩基化合物としては，例えば，水酸化ナトリウム、水
酸化カリウムなどの無機塩基類のほか,4−ジメチルアミ
ノピリジンなどの通常の有機塩基化合物を用いることが
可能であるが，水酸化ナトリウムを用いることが望まし
い。As the basic compound, for example, in addition to inorganic bases such as sodium hydroxide and potassium hydroxide, ordinary organic base compounds such as 4-dimethylaminopyridine can be used. desirable.
塩基化合物の使用量は特に制限されないが，通常原料
である構造式（II）の化合物に対して,1〜1.2倍モル程
度が望ましい。The amount of the basic compound used is not particularly limited, but is preferably about 1 to 1.2 times the molar amount of the compound of the structural formula (II) which is usually the raw material.
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塩基
化合物により,1時間〜40時間の間で任意である。The reaction temperature is optional between -10 ° C and 100 ° C, but is desirably in the range of 0 ° C to 40 ° C, and the reaction time is optional between 1 hour and 40 hours depending on the basic compound 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 the usual separation means such as extraction, liquid 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 described specifically with reference to examples, but the present invention is not limited thereto.
実施例1. ３−アセトキシ−６−ジアセトキシメチルピラン−２
−オン0.477gを30mlの乾燥メチルアルコールに溶解さ
せ，氷冷下で10〜15分間撹拌する。そこに４−ジメチル
アミノピリジン0.204gを10mlの乾燥メチルアルコールに
溶解させた溶液を１時間掛けて滴下したのち０℃〜室温
で22時間撹拌し反応させる。反応終了後，酸性イオン交
換樹脂（DOWEX 50W−X2）を加え、しばらく撹拌した後
イオン交換樹脂を濾取する。瀘液を減圧下に濃縮し，エ
ーテル可溶物を抽出して薄層クロマトグラフィーによっ
て,4−ヒドロキシ−４−メトキシカルボニル−５−アセ
トキシ−２−シクロペンテノンを単離した。（収率11.4
％） 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. 3-acetoxy-6-diacetoxymethylpyran-2
Dissolve 0.477 g of -one in 30 ml of dry methyl alcohol and stir under ice-cooling for 10 to 15 minutes. A solution prepared by dissolving 0.204 g of 4-dimethylaminopyridine in 10 ml of dry methyl alcohol was added dropwise over 1 hour, and the mixture was stirred and reacted at 0 ° C. to room temperature for 22 hours. After completion of the reaction, an acidic ion exchange resin (DOWEX 50W-X2) is added, and the mixture is stirred for a while, and then the ion exchange resin is filtered. The filtrate was concentrated under reduced pressure, the ether-soluble matter was extracted, and 4-hydroxy-4-methoxycarbonyl-5-acetoxy-2-cyclopentenone was isolated by thin-layer chromatography. (Yield 11.4
%) The infrared absorption spectrum data of the compound are shown below.
IR（NaCl）;3450,3080,2950,2845,1730,1585,1432,13
69,1218,1098,1060,1035,958,880,812,764,740cm-1 実施例2. ３−アセトキシ−６−ジアセトキシメチルピラン−２
−オン0.200gを8mlの乾燥メチルアルコールに溶解さ
せ，氷冷下で10〜15分間撹拌する。そこに水酸化ナトリ
ウム0.028gを10mlの乾燥メチルアルコールに溶解させた
溶液を40分掛けて滴下，さらに０℃で1.5時間撹拌しな
がら反応させる。反応終了後，氷冷下にメチルアルコー
ルに懸濁させた酸性イオン交換樹脂（DOWEX 50W−X2）
を加え、しばらく撹拌した後イオン交換樹脂を濾取す
る。瀘液を減圧下に濃縮し，エーテル可溶物を抽出して
薄層クロマトグラフィーによって,4−ヒドロキシ−４−
メトキシカルボニル−５−アセトキシ−２−シクロペン
テノンを単離した。（収率46.4％） 実施例３ ３−アセトキシ−６−ジアセトキシメチルピラン−２
−オン0.156gを6mlのメチルアルコールに溶解させ，氷
冷下で10〜15分間撹はんする。そこに水酸化カリウム0.
031gを3mlの乾燥メチルアルコールに溶解させた溶液を4
0分掛けて滴下，さらに０℃で1.5時間撹拌しながら反応
させる。反応終了後，氷冷下にメチルアルコールに懸濁
させた酸性イオン交換樹脂（DOWEX 50W−X2）を加え、
しばらく撹拌した後イオン交換樹脂を濾取する。瀘液を
減圧下に濃縮し，エーテル可溶物を抽出して薄層クロマ
トグラフィーによって,4−ヒドロキシ−４−メトキシカ
ルボニル−５−アセトキシ−２−シクロペンテノンを単
離した。（収率33.8％）IR (NaCl); 3450,3080,2950,2845,1730,1585,1432,13
69,1218,1098,1060,1035,958,880,812,764,740cm- 1 Example 2. 3-acetoxy-6-diacetoxymethylpyran-2
Dissolve 0.200 g of -one in 8 ml of dry methyl alcohol and stir under ice-cooling for 10 to 15 minutes. A solution prepared by dissolving 0.028 g of sodium hydroxide in 10 ml of dry methyl alcohol was added dropwise over 40 minutes, and the mixture was further reacted at 0 ° C. with stirring for 1.5 hours. After the reaction, acid ion exchange resin (DOWEX 50W-X2) suspended in methyl alcohol under ice cooling
After stirring for a while, the ion-exchange resin is collected by filtration. The filtrate was concentrated under reduced pressure, the ether-soluble matter was extracted, and 4-hydroxy-4-
Methoxycarbonyl-5-acetoxy-2-cyclopentenone was isolated. (Yield 46.4%) Example 3 3-acetoxy-6-diacetoxymethylpyran-2
Dissolve 0.156 g of -one in 6 ml of methyl alcohol and stir under ice-cooling for 10 to 15 minutes. There potassium hydroxide 0.
A solution of 031 g in 3 ml of dry methyl alcohol was added to 4
The mixture is added dropwise over 0 minutes, and the reaction is further performed with stirring at 0 ° C. for 1.5 hours. After completion of the reaction, an acidic ion exchange resin (DOWEX 50W-X2) suspended in methyl alcohol was added under ice cooling,
After stirring for a while, the ion exchange resin is filtered. The filtrate was concentrated under reduced pressure, the ether-soluble matter was extracted, and 4-hydroxy-4-methoxycarbonyl-5-acetoxy-2-cyclopentenone was isolated by thin-layer chromatography. (33.8% yield)
Claims (2)
ラン−２−オンを，メチルアルコールと塩基化合物の共
存下に反応させることを特徴とする構造式 で示されるシクロペンテノン誘導体の製造法。2. The structural formula Reacting 3-acetoxy-6-diacetoxymethylpyran-2-one represented by the formula in the presence of methyl alcohol and a base compound. A method for producing a cyclopentenone derivative represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23786987A JP2571939B2 (en) | 1987-09-22 | 1987-09-22 | Cyclopentenone derivatives and their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23786987A JP2571939B2 (en) | 1987-09-22 | 1987-09-22 | Cyclopentenone derivatives and their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6479141A JPS6479141A (en) | 1989-03-24 |
| JP2571939B2 true JP2571939B2 (en) | 1997-01-16 |
Family
ID=17021621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23786987A Expired - Fee Related JP2571939B2 (en) | 1987-09-22 | 1987-09-22 | Cyclopentenone derivatives and their production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2571939B2 (en) |
-
1987
- 1987-09-22 JP JP23786987A patent/JP2571939B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6479141A (en) | 1989-03-24 |
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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 |