JPH0768163B2 - Process for producing cyclopentenone derivative - Google Patents
Process for producing cyclopentenone derivativeInfo
- Publication number
- JPH0768163B2 JPH0768163B2 JP1065286A JP6528689A JPH0768163B2 JP H0768163 B2 JPH0768163 B2 JP H0768163B2 JP 1065286 A JP1065286 A JP 1065286A JP 6528689 A JP6528689 A JP 6528689A JP H0768163 B2 JPH0768163 B2 JP H0768163B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- structural formula
- acetic anhydride
- cyclopentenone derivative
- glucofuranurono
- 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
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (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 structural formula (I) 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 structural formula (I) is a novel compound synthesized by the present inventors for the first time, and is a valuable compound as an intermediate for perfumes and pharmaceuticals.
構造式（II） で示されるＤ−グルコフラヌロノ−6,3−ラクトントリ
アセテート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
見出し、本発明を完成するに至った。Structural formula (II) When the reaction of D-glucofuranurono-6,3-lactone triacetate represented by the following formula in acetic anhydride was examined, the formation of the cyclopentenone derivative represented by the structural formula (I) 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Ｄ−グルコフラヌロノ−6,3−ラクトントリアセテー
トを、無水酢酸中ピリジンの共存下に反応させた後、更
に無水酢酸中酸触媒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 react D-glucofuranurono-6,3-lactone triacetate represented by the structural formula (II) in the presence of pyridine in acetic anhydride, and then in the presence of an acid catalyst in acetic anhydride. The cyclopentenone derivative represented by the structural formula (I) 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（II）
で示されるＤ−グルコフラヌロノ−6,3−ラクトントリ
アセテートは、市販されているＤ−グルコフラヌロノ−
6,3−ラクトンを無水酢酸−ピリイン系等の通常のアセ
チル化条件下で反応させることによって容易に合成する
ことが出来る。Structural formula (II) used as a raw material in this reaction
D-glucofuranurono-6,3-lactone triacetate represented by is commercially available D-glucofuranurono-
It can be easily synthesized by reacting 6,3-lactone under normal acetylation conditions such as acetic anhydride-pyriyne system.
構造式（II）で示されるＤ−グルコフラヌロノ−6,3−
ラクトントリアセテートの無水酢酸中での反応は先ずピ
リジンの共存下で実施される。D-glucofuranurono-6,3-represented by structural formula (II)
The reaction of lactone triacetate in acetic anhydride is first carried out in the presence of pyridine.
ピリジンの使用量は、通常、原料の構造式（II）の化合
物に対して、１〜10倍モルであるが、特に等モルが適当
である。The amount of pyridine used is usually 1 to 10 times the molar amount of the compound represented by the structural formula (II), but an equimolar amount is particularly suitable.
反応温度は、80〜150℃の間で任意であるが、100℃付近
が望ましい。反応時間は反応温度により、５〜30時間の
間で任意である。The reaction temperature is optional between 80 and 150 ° C, but is preferably around 100 ° C. The reaction time is optional between 5 and 30 hours depending on the reaction temperature.
このような反応の後、減圧下に濃縮することによって得
られる油状混合物から、ジイソプロピルエーテル可溶部
分を抽出分離する。得られた油状物を、無水酢酸中、酸
触媒の共存下で処理することによって、構造式（Ｉ）で
示されるシクロペンテノン誘導体が容易に得られる。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を用いるこ
とが可能である。After such a reaction, the diisopropyl ether-soluble portion is extracted and separated from the oily mixture obtained by concentrating under reduced pressure. By treating the obtained oily substance in acetic anhydride in the presence of an acid catalyst, the cyclopentenone derivative represented by the structural formula (I) can be easily obtained. As the acid catalyst, for example, sulfonic acid type ion exchange resin,
It is possible to use sulfonic acid derivatives and trifluoroacetic acid.
酸触媒の使用量は特に制限されないが、反応を短時間で
完結させるためには、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, it is necessary to add 5 to the compound of the structural formula (II).
Approximately 20 times the molar amount 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 arbitrary between −10 ° C. and 100 ° C., preferably 0 ° C. to 40 ° C., and the reaction time is arbitrary between 0.2 and 40 hours depending on the amount of the acid catalyst used.
このような２段階の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等により反
応混合物から単離精製することができる。The cyclopentenone derivative represented by the structural formula (I), which is a compound of the present invention, can be obtained by such a two-step reaction and can be carried out by a conventional separation means such as extraction, liquid separation, concentration, thin layer chromatography, column chromatography. Isolation and purification from the reaction mixture can be carried out by the method described above.
以下に実施例を挙げ、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。The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
実施例1. Ｄ−グルコフラヌロノ−6,3−ラクトントリアセテート
0.3gに無水酢酸5ml、およびピリジン0.081mlを加え、10
0℃において７時間撹拌し反応させる。反応混合物を減
圧下に濃縮し、ジイソプロピルエーテルによって可溶成
分を抽出する。得られたジイソプロピルエーテル溶液を
濃縮し、油状残渣を3mlの無水酢酸と1mlのトリフルオロ
酢酸を加え、室温で３時間反応させる。反応終了後、反
応に混合物を減圧下に濃縮し、薄層クロマトグラフィー
により、4,5−ジアセトキシ−２−シクロペンテノンを
得た。（収率24.7％） 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. D-Glucofuranurono-6,3-lactone triacetate
Add acetic anhydride 5 ml and pyridine 0.081 ml to 0.3 g,
Stir for 7 hours at 0 ° C. to react. The reaction mixture is concentrated under reduced pressure and the soluble component is extracted with diisopropyl ether. The obtained diisopropyl ether solution is concentrated, and the oily residue is added with 3 ml of acetic anhydride and 1 ml of trifluoroacetic acid and reacted at room temperature for 3 hours. After the reaction was completed, the mixture was concentrated under reduced pressure in the reaction, and 4,5-diacetoxy-2-cyclopentenone was obtained by thin layer chromatography. (Yield 24.7%) The infrared absorption spectrum data of the compound is shown below.
IR（KBr）;3070,2930,1585,1420,1370,1220,1025,890,7
90cm-1 実施例2. Ｄ−グルコフラヌロノ−6,3−ラクトントリアセテート
0.3gに無水酢酸6ml、およびピリジン0.081mlを加え、10
0℃において10時間撹拌し反応させる。反応混合物を減
圧下に濃縮し、ジイソプロピルエーテルによって可溶成
分を抽出する。得られたジイソプロピルエーテル溶液を
濃縮し、油状残渣に3mlの無水酢酸と2mlのトリフルオロ
酢酸を加え、室温で４時間反応させる。反応終了後、反
応に混合物を減圧下に濃縮し、薄層クロマトグラフィー
により、4,5−ジアセトキシ−２−シクロペンテノンを
得た。（収率33.0％） 実施例3. Ｄ−グルコフラヌロノ−6,3−ラクトントリアセテート
0.3gに無水酢酸5ml、およびピリジン0.081mlを加え、10
0℃において24時間撹拌し反応させる。反応混合物を減
圧下に濃縮し、ジイソプロピルエーテルによって可溶成
分を抽出する。得られたジイソプロピルエーテル溶液を
濃縮し、油状残渣に3mlの無水酢酸と1mlのトリフルオロ
酢酸を加え、室温で３時間反応させる。反応終了後、反
応に混合物を減圧下に濃縮し、薄層クロマトグラフィー
により、4,5−ジアセトキシ−２−シクロペンテノンを
得た。（収率17.7％）IR (KBr); 3070,2930,1585,1420,1370,1220,1025,890,7
90 cm -1 Example 2. D-glucofuranurono-6,3-lactone triacetate
To 0.3 g, add 6 ml of acetic anhydride and 0.081 ml of pyridine,
Stir for 10 hours at 0 ° C to react. The reaction mixture is concentrated under reduced pressure and the soluble component is extracted with diisopropyl ether. The obtained diisopropyl ether solution is concentrated, 3 ml of acetic anhydride and 2 ml of trifluoroacetic acid are added to the oily residue, and the mixture is reacted at room temperature for 4 hours. After the reaction was completed, the mixture was concentrated under reduced pressure in the reaction, and 4,5-diacetoxy-2-cyclopentenone was obtained by thin layer chromatography. (Yield 33.0%) Example 3. D-glucofuranurono-6,3-lactone triacetate
Add acetic anhydride 5 ml and pyridine 0.081 ml to 0.3 g,
Stir for 24 hours at 0 ° C. to react. The reaction mixture is concentrated under reduced pressure and the soluble component is extracted with diisopropyl ether. The obtained diisopropyl ether solution is concentrated, 3 ml of acetic anhydride and 1 ml of trifluoroacetic acid are added to the oily residue, and the mixture is reacted at room temperature for 3 hours. After the reaction was completed, the mixture was concentrated under reduced pressure in the reaction, and 4,5-diacetoxy-2-cyclopentenone was obtained by thin layer chromatography. (Yield 17.7%)
───────────────────────────────────────────────────── 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // C07B 61/00 300
Claims (1)
テートを無水酢酸中ピリジンの共存下に反応させた後、
さらに無水酢酸中酸触媒の共存下に処理することを特徴
とする構造式 で示されるシクロペンテノン誘導体の製法。1. Structural formula After reacting D-glucofuranurono-6,3-lactone acetate represented by the following in acetic anhydride in the presence of pyridine,
Further, the structural formula is characterized in that the treatment is carried out in the presence of an acid catalyst in acetic anhydride. A method for producing a cyclopentenone derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1065286A JPH0768163B2 (en) | 1989-03-17 | 1989-03-17 | Process for producing cyclopentenone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1065286A JPH0768163B2 (en) | 1989-03-17 | 1989-03-17 | Process for producing cyclopentenone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02247151A JPH02247151A (en) | 1990-10-02 |
| JPH0768163B2 true JPH0768163B2 (en) | 1995-07-26 |
Family
ID=13282538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1065286A Expired - Lifetime JPH0768163B2 (en) | 1989-03-17 | 1989-03-17 | Process for producing cyclopentenone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768163B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998013328A1 (en) * | 1996-09-27 | 1998-04-02 | Takara Shuzo Co., Ltd. | Cyclopentenones, process for preparing the same, and the use thereof |
| EA001808B1 (en) * | 1997-03-11 | 2001-08-27 | Такара Сузо Ко., Лтд. | Cyclopentenone derivatives |
| ATE274903T1 (en) * | 1997-03-17 | 2004-09-15 | Takara Bio Inc | ANTIVIRAL AGENTS |
| US6194467B1 (en) * | 1997-03-28 | 2001-02-27 | Takara Shuzo Co., Ltd. | Diabetes remedies |
| US6284801B1 (en) * | 1997-04-01 | 2001-09-04 | Takara Shuzo Co., Ltd. | Antirheumatic agents |
| WO1999000349A1 (en) * | 1997-06-30 | 1999-01-07 | Takara Shuzo Co., Ltd. | Cyclopentenone derivatives |
| WO2000010560A1 (en) * | 1998-08-18 | 2000-03-02 | Takara Shuzo Co., Ltd. | Remedies or preventives containing cyclopentenone compounds as the active ingredient |
-
1989
- 1989-03-17 JP JP1065286A patent/JPH0768163B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| ＴｅｔｒａｈｅｄｒｏｎＬｅｔｔｅｒｓ，２１（１９７８），１８３３−１８３６ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02247151A (en) | 1990-10-02 |
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