JP2553859B2 - Process for producing pyrazol derivative - Google Patents
Process for producing pyrazol derivativeInfo
- Publication number
- JP2553859B2 JP2553859B2 JP62101279A JP10127987A JP2553859B2 JP 2553859 B2 JP2553859 B2 JP 2553859B2 JP 62101279 A JP62101279 A JP 62101279A JP 10127987 A JP10127987 A JP 10127987A JP 2553859 B2 JP2553859 B2 JP 2553859B2
- Authority
- JP
- Japan
- Prior art keywords
- producing
- general formula
- formula
- phosphorus oxychloride
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
【発明の詳細な説明】 本発明は一般式（II）： （式中、R1及びR2は、同一でも異っても良く、低級アル
キル基を示す。）で表わされるピラゾロン類をオキシ塩
化リンの存在下にてジメチルホルムアミド（DMF）と反
応させる際に、一般式（II）で表わされるピラゾロン類
に対してオキシ塩化リンを1.3乃至1.6倍モル使用するこ
とを特徴とする 一般式（Ｉ）： （式中、R1及びR2は前記式Ｉで定義した意味に同じ。）
で表わされるピラゾール誘導体の製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (II): (Wherein R 1 and R 2, which may be the same or different and each represents a lower alkyl group), is reacted with dimethylformamide (DMF) in the presence of phosphorus oxychloride. In the general formula (I), 1.3 to 1.6 times mol of phosphorus oxychloride is used with respect to the pyrazolone represented by the general formula (II). (In the formula, R 1 and R 2 have the same meaning as defined in the above formula I.)
The present invention relates to a method for producing a pyrazole derivative represented by
本発明の製造方法により製造されるピラゾール誘導体
は医薬、農薬及びその他化学品等の原料化合物として有
用な化合物である。The pyrazole derivative produced by the production method of the present invention is a useful compound as a raw material compound for medicines, agricultural chemicals and other chemicals.
ピラゾール誘導体の製造方法としては、ピラゾロン類
をオキシ塩化リン及びDMFと反応させてピラゾール誘導
体を製造する方法が一般的に行なわれている（C.A.197
0.73.3844w参照）。しかしながら、この方法は、オキシ
塩化リンを多量に使用するため、強酸性の廃液の処理に
課題があり、しかも収率も70％程度と低収率である。As a method for producing a pyrazole derivative, a method for producing a pyrazole derivative by reacting a pyrazolone with phosphorus oxychloride and DMF is generally performed (CA197).
See 0.73.3844w). However, since this method uses a large amount of phosphorus oxychloride, there is a problem in treating the strongly acidic waste liquid, and the yield is as low as about 70%.
本発明者等は、より経済的にしかも高収率でピラゾー
ル誘導体を製造する方法を鋭意研究した結果、本発明を
完成させたものである。The present inventors have completed the present invention as a result of earnestly researching a method for producing a pyrazole derivative more economically and in a high yield.
本発明の製造方法は、前記文献に記載の製造方法に比
してオキシ塩化リンの使用量を大巾に低減でき、しかも
90％前後の高収率で一般式（Ｉ）で表わされるピラゾー
ル誘導体を製造することができ、より経済的な製造方法
である。The production method of the present invention can greatly reduce the amount of phosphorus oxychloride used as compared with the production methods described in the above documents, and
The pyrazole derivative represented by the general formula (I) can be produced in a high yield of about 90%, which is a more economical production method.
本発明の製造方法を例えば図式的に示すと下記の如く
例示することができる。The production method of the present invention can be illustrated schematically as follows, for example.
（式中、R1及びR2は前記で定義した意味に同じ。） 即ち、一般式（II）で表わされるピラゾロン類とDMF
とを、不活性溶媒の存在下又は不存在下にて、オキシ塩
化リンを一般式（II）で表わされるピラゾロン類に対し
て1.3乃至1.6倍モル存在させて反応させることにより、
一般式（Ｉ）で表わされるピラゾール誘導体を製造する
ことができる。 (In the formula, R 1 and R 2 have the same meanings as defined above.) That is, pyrazolones represented by the general formula (II) and DMF.
And in the presence or absence of an inert solvent, by reacting phosphorus oxychloride in the presence of 1.3 to 1.6 times the molar amount of pyrazolone represented by the general formula (II),
The pyrazole derivative represented by the general formula (I) can be produced.
本反応で使用するDMFの量は、一般式（II）で表わさ
れるピラゾロン類に対し等モル乃至過剰に使用すれば良
く、好ましくは1.05乃至1.1倍モルの範囲から選択され
る。The amount of DMF used in this reaction may be an equimolar amount to an excess amount to the pyrazolone represented by the general formula (II), and is preferably selected from the range of 1.05 to 1.1 times mol.
オキシ塩化リンの使用量は、一般式（II）で表わされ
るピラゾロン類に対し1.3乃至1.6倍モルの範囲から選択
され、好ましくは1.4乃至1.5倍モル使用すれば良い。The amount of phosphorus oxychloride used is selected from the range of 1.3 to 1.6 times by mole, and preferably 1.4 to 1.5 times by mole with respect to the pyrazolone represented by the general formula (II).
本反応は、一般的には、不活性溶媒の不存在下で行な
われるが、本反応を著しく阻害しない不活性溶媒であれ
ば使用することもできる。This reaction is generally carried out in the absence of an inert solvent, but any inert solvent which does not significantly inhibit this reaction can be used.
反応温度は10℃乃至150℃の範囲から適宜選択すれば
良い。The reaction temperature may be appropriately selected from the range of 10 ° C to 150 ° C.
反応時間は、反応剤の量、反応温度等により一定とな
らないが、１乃至48時間の範囲から選択すれば良い。The reaction time is not constant depending on the amount of the reactants, the reaction temperature, etc., but may be selected from the range of 1 to 48 hours.
反応終了後、反応液に氷水を加え、アルカリで中和す
る等の常法操作を行うことにより、目的化合物である一
般式（Ｉ）で表わされるピラゾール誘導体を製造するこ
とができる。該ピラゾール誘導体は、このまま又は必要
により精製し、原料化合物として供することができる。After completion of the reaction, ice water is added to the reaction solution, and the mixture is subjected to a conventional operation such as neutralization with an alkali, whereby the desired compound of the pyrazole derivative represented by the general formula (I) can be produced. The pyrazole derivative can be used as a raw material compound as it is or after purification if necessary.
以下に本発明の代表的な実施例を示すが、本発明はこ
れらに限定されるものではない。Typical examples of the present invention are shown below, but the present invention is not limited thereto.
実施例1. ５−クロロ−1,3−ジメチルピラゾール−４−ホルミ
ルピラゾールの製造（R1＝R2＝CH3） 乾燥DMF12.1g（0.165モル）にオキシ塩化リン34.5g
（0.225モル）を20〜25℃で、撹拌しながら徐々に滴下
し、滴下終了後同じ温度で30分間撹拌を行った。次いで
1,3−ジメチルピラゾロン16.8g（0.15モル）を加えて溶
解させ、75〜80℃に加熱した。Example 1. 5-chloro -1,3-dimethyl-4-formyl pyrazole (R 1 = R 2 = CH 3) Drying DMF12.1g (0.165 mol) in phosphorus oxychloride 34.5g
(0.225 mol) was gradually added dropwise at 20 to 25 ° C. with stirring, and after completion of the addition, stirring was performed at the same temperature for 30 minutes. Then
16.8 g (0.15 mol) of 1,3-dimethylpyrazolone was added and dissolved and heated to 75-80 ° C.
反応液の温度が100℃になり、塩化水素ガスを放出し
た後、温度が110〜115℃になるように加熱し、その温度
で８時間反応を行った。反応終了後、室温まで冷却し、
更に氷冷した。そして反応液に氷水30mlを加え、濃水酸
化ナトリウム水溶液で中和して、一晩放置すると結晶が
析出した。この析出した結晶を集し、水洗し、そして
乾燥して目的化合物21.6gを得た。After the temperature of the reaction liquid reached 100 ° C. and hydrogen chloride gas was released, the reaction liquid was heated to 110-115 ° C. and reacted at that temperature for 8 hours. After the reaction is complete, cool to room temperature,
It was further ice-cooled. Then, 30 ml of ice water was added to the reaction solution, which was neutralized with a concentrated aqueous solution of sodium hydroxide, and allowed to stand overnight to precipitate crystals. The precipitated crystals were collected, washed with water, and dried to obtain 21.6 g of the target compound.
収率90.9％ 融点78.0℃。Yield 90.9%, melting point 78.0 ° C.
Claims (1)
キル基を示す。）で表わされるピラゾロン類をオキシ塩
化リンの存在下にてジメチルホルムアミドと反応させる
際に、一般式（II）で表わされるピラゾロン類に対して
オキシ塩化リンを1.3乃至1.6倍モル使用することを特徴
とする 一般式（Ｉ）： （式中、R1及びR2は前記式Ｉで定義した意味に同じ。）
で表わされるピラゾール誘導体の製造方法。1. General formula (II): (In the formula, R 1 and R 2 may be the same or different and each represents a lower alkyl group.) When a pyrazolone represented by the general formula is reacted with dimethylformamide in the presence of phosphorus oxychloride, Phosphorus oxychloride is used in an amount of 1.3 to 1.6 times the molar amount of the pyrazolone represented by formula (II). (In the formula, R 1 and R 2 have the same meaning as defined in the above formula I.)
A method for producing a pyrazole derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62101279A JP2553859B2 (en) | 1987-04-24 | 1987-04-24 | Process for producing pyrazol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62101279A JP2553859B2 (en) | 1987-04-24 | 1987-04-24 | Process for producing pyrazol derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63267762A JPS63267762A (en) | 1988-11-04 |
| JP2553859B2 true JP2553859B2 (en) | 1996-11-13 |
Family
ID=14296430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62101279A Expired - Fee Related JP2553859B2 (en) | 1987-04-24 | 1987-04-24 | Process for producing pyrazol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2553859B2 (en) |
-
1987
- 1987-04-24 JP JP62101279A patent/JP2553859B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63267762A (en) | 1988-11-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |