JPH0761972A - Production of mercaptopyrazoles - Google Patents
Production of mercaptopyrazolesInfo
- Publication number
- JPH0761972A JPH0761972A JP20796893A JP20796893A JPH0761972A JP H0761972 A JPH0761972 A JP H0761972A JP 20796893 A JP20796893 A JP 20796893A JP 20796893 A JP20796893 A JP 20796893A JP H0761972 A JPH0761972 A JP H0761972A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- sodium
- substituent
- sodium hydrosulfide
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医薬および農薬等の中
間体して有用なメルカプトピラゾール類の製造方法に関
するものである。特に本発明は、水稲用除草剤（特開昭
５９−１２２４８８号公報記載）およびトウモロコシ用
除草剤（特開昭６０−２０８９７７号公報記載）の中間
体として有用な５−メルカプトピラゾール−４−カルボ
ン酸エチルエステルおよび３−クロロ−５−メルカプト
ピラゾール−４−カルボン酸メチルエステルの製造方法
として有効である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing mercaptopyrazoles which are useful as intermediates for medicines and agricultural chemicals. Particularly, the present invention relates to 5-mercaptopyrazole-4-carboxylic acid which is useful as an intermediate for paddy rice herbicides (described in JP-A-59-122488) and corn herbicides (described in JP-A-60-208977). It is effective as a method for producing acid ethyl ester and 3-chloro-5-mercaptopyrazole-4-carboxylic acid methyl ester.
【０００２】[0002]
【従来の技術】５−ハロゲノピラゾール類から、５−メ
ルカプトピラゾール類を製造する方法としては、リービ
ッヒス・アナーレン・デル・セミー (Liebigs Annalen
der Chemie) ，３３８巻，１８３頁（１９０５年）に、
エタノール中過剰量の硫化ナトリウムを用いて製造する
例がある。また、特開昭６２−４２７２号公報に、Ｎ，
Ｎ−ジメチルホルムアミド中水硫化ナトリウムを用いる
例がある。2. Description of the Related Art As a method for producing 5-mercaptopyrazoles from 5-halogenopyrazoles, Liebigs Annalen del Semi (Liebigs Annalen
der Chemie), 338, 183 (1905),
There is an example of production using an excess amount of sodium sulfide in ethanol. Further, in Japanese Patent Application Laid-Open No. 62-4272, N,
There is an example of using sodium hydrosulfide in N-dimethylformamide.
【０００３】[0003]
【発明が解決しようとする課題】硫化剤として硫化ナト
リウムを使用する方法では、原料に対して当量から若干
過剰量で反応は進行するが、硫化ナトリウムが強アルカ
リ性のため、原料にエステル等の加水分解を受けやすい
置換基を有している場合、収率低下を引き起こす。一
方、硫化剤として水硫化ナトリウムを使用する方法で
は、上記のような加水分解の心配はないが、水硫化ナト
リウムが原料に対して２当量以上必要であり、経済的に
不利であるうえ、副生する硫化水素の処理などの問題が
ある。In the method of using sodium sulfide as a sulfiding agent, the reaction proceeds in an equivalent amount to a slight excess amount relative to the raw material, but since sodium sulfide is strongly alkaline, the starting material is hydrolyzed with an ester or the like. When it has a substituent that is susceptible to decomposition, it causes a decrease in yield. On the other hand, in the method of using sodium hydrosulfide as the sulfiding agent, there is no fear of hydrolysis as described above, but since sodium hydrosulfide is required in an amount of 2 equivalents or more relative to the raw material, it is economically disadvantageous. There are problems such as the treatment of the generated hydrogen sulfide.
【０００４】[0004]
【問題を解決するための手段】本発明者らは、メルカプ
トピラゾール類を収率良く経済的に得る方法について鋭
意検討した結果、硫化剤として硫化ナトリウム、水硫化
ナトリウムの反応性、溶媒に対する溶解性の違い、およ
び反応中生成する硫化水素の反応性に着目した。[Means for Solving the Problem] The inventors of the present invention have made earnest studies on a method for obtaining mercaptopyrazoles in good yield and economically. , And the reactivity of hydrogen sulfide generated during the reaction.
【０００５】硫化反応の反応性は、硫化ナトリウムより
水硫化ナトリウムの方が高く、溶媒に対する溶解度も水
硫化ナトリウムの方が大きい。また、水硫化ナトリウム
との反応により副生する硫化水素は、硫化ナトリウムと
反応して再び水硫化ナトリウムを生成する。そこで、硫
化ナトリウムに水硫化ナトリウムを共存させることによ
り、水硫化ナトリウムを実際の反応剤として、硫化ナト
リウムを硫化水素との反応による水硫化ナトリウム発生
剤として利用することができることを見出し、本発明を
完成するに至った。The reactivity of the sulfurization reaction is higher with sodium hydrosulfide than with sodium sulfide, and the solubility in the solvent is also higher with sodium hydrosulfide. Further, hydrogen sulfide, which is a byproduct of the reaction with sodium hydrosulfide, reacts with sodium sulfide to generate sodium hydrosulfide again. Therefore, it was found that by coexisting sodium hydrosulfide with sodium sulfide, it is possible to utilize sodium hydrosulfide as an actual reactant and sodium sulfide as a sodium hydrosulfide generator by the reaction with hydrogen sulfide, and the present invention It came to completion.
【０００６】即ち、本発明は、５−ハロゲノピラゾール
類から硫化ナトリウムで５−メルカプトピラゾール類を
製造する方法において、水硫化ナトリウムを共存させる
ことを特徴とする方法に関するものである。５−ハロゲ
ノピラゾール類としては、例えば、式（１）That is, the present invention relates to a method for producing 5-mercaptopyrazoles from 5-halogenopyrazoles with sodium sulfide, which is characterized by the coexistence of sodium hydrosulfide. Examples of 5-halogenopyrazoles include compounds represented by the formula (1)
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】〔式中、Ｒ1 は水素原子、炭素原子数１〜
６のアルキル基、炭素原子数１〜７のシクロアルキル
基、置換基を有していてもよいフェニル基または置換基
を有していてもよい芳香族複素環を表し、Ｒ2 は水素原
子、炭素原子数１〜６のアルキル基、炭素原子数１〜６
のアルコキシ基、炭素原子数１〜６のアルコキシカルボ
ニル基、ハロゲン原子、シアノ基、置換基を有していて
もよいフェニル基または置換基を有していてもよい芳香
族複素環を表し、Ｒ3 は炭素原子数１〜６のアルコキシ
カルボニル基、炭素原子数１〜６のアルキルスルホニル
基、ニトロ基、ハロゲン原子またはシアノ基を表し、Ｘ
は、ハロゲン原子を表す。〕があげられる。[In the formula, R 1 is a hydrogen atom or a carbon atom number 1 to
An alkyl group having 6 carbon atoms, a cycloalkyl group having 1 to 7 carbon atoms, a phenyl group which may have a substituent or an aromatic heterocycle which may have a substituent, R 2 represents a hydrogen atom, Alkyl groups having 1 to 6 carbon atoms, 1 to 6 carbon atoms
Represents an alkoxy group, an alkoxycarbonyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a phenyl group which may have a substituent or an aromatic heterocycle which may have a substituent, R 3 represents an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a nitro group, a halogen atom or a cyano group, X
Represents a halogen atom. ] Is given.
【０００９】より具体的には、式（１）中、Ｒ1 がメチ
ル基を表し、Ｒ2 が水素原子または塩素原子を表し、Ｒ
3 がメトキシカルボニル基またはエトキシカルボニル基
を表し、Ｘが塩素原子を表す５−ハロゲノピラゾール類
があげられる。硫化剤の使用量は、５−ハロゲノピラゾ
ール類に対して硫化ナトリウムが通常０．５〜１．４モ
ル倍、好ましくは０．６〜１．１モル倍、共存させる水
硫化ナトリウムが通常１．０〜０．０１モル倍、好まし
くは０．８〜０．０１モル倍である。More specifically, in the formula (1), R 1 represents a methyl group, R 2 represents a hydrogen atom or a chlorine atom, and R 1
3 represents a methoxycarbonyl group or ethoxycarbonyl group, X is 5-halogeno-pyrazoles which represents a chlorine atom. The amount of the sulfurizing agent used is usually 0.5 to 1.4 mole times, preferably 0.6 to 1.1 mole times, of sodium 5-sulfide with respect to the 5-halogenopyrazoles, and sodium hydrosulfide to coexist is usually 1. It is 0 to 0.01 molar times, preferably 0.8 to 0.01 molar times.
【００１０】硫化剤の使用量は、５−ハロゲノピラゾー
ル類に対して硫化ナトリウムと共存させる水硫化ナトリ
ウムの合計で通常１．０〜１．５当量好ましくは１．０
〜１．２当量である。硫化剤は、反応初期から全量仕込
んでもよいが、分割投入により徐々に加えても同様に好
ましい結果を与える。The amount of the sulfurizing agent used is usually 1.0 to 1.5 equivalents, preferably 1.0, by the total amount of sodium hydrosulfide coexisting with sodium sulfide with respect to the 5-halogenopyrazoles.
~ 1.2 equivalents. The sulfurizing agent may be charged in the whole amount from the initial stage of the reaction, but may be gradually added by divided addition to give the same preferable result.
【００１１】使用される溶媒は、反応に不活性なもので
あれば特に制限はないが、例えば、Ｎ，Ｎ−ジメチルホ
ルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチル
スルホキシド、Ｎ−メチルピロリドン、ピリジン等の極
性溶媒類およびメタノール、エタノール等のアルコール
類、水等があげられる。反応温度は、通常０〜２００
℃、好ましくは１０〜１００℃である。特に、最初は低
温で反応後、さらに高温で反応させると好結果を与え
る。また、溶媒の沸点により反応温度が上げられない場
合は、加圧下に反応を行なうことができる。The solvent used is not particularly limited as long as it is inert to the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine, etc. And polar solvents, alcohols such as methanol and ethanol, and water. The reaction temperature is usually 0 to 200.
C, preferably 10 to 100C. In particular, good results are obtained when the reaction is carried out initially at a low temperature and then at a higher temperature. If the reaction temperature cannot be raised due to the boiling point of the solvent, the reaction can be carried out under pressure.
【００１２】反応時間は、通常０．１〜１００時間、好
ましくは１〜１０時間である。The reaction time is usually 0.1 to 100 hours, preferably 1 to 10 hours.
【００１３】[0013]
【発明の効果】本発明の方法に従えば、副反応を抑制す
ることができ、５−ハロゲノピラゾール類から容易に高
収率で５−メルカプトピラゾール類を得ることができ
る。According to the method of the present invention, side reactions can be suppressed, and 5-mercaptopyrazoles can be easily obtained from 5-halogenopyrazoles in high yield.
【００１４】[0014]
【実施例】以下、実施例をあげ、本発明をさらに詳細に
説明するが、本発明はこれらに限定されるものではな
い。 〔実施例１〕５−クロロ−１−メチルピラゾール−４−
カルボン酸エチルエステル３５．２ｇ（０．１８７モ
ル）をＮ，Ｎ−ジメチルホルムアミド９０ｇに溶解し、
室温撹拌下６０％硫化ナトリウム１７．０ｇ（０１３１
モル）および７０％水硫化ナトリウム１０．５ｇ（０．
１３１モル）を加え、６５℃で３時間反応させた後、さ
らに９０℃で３時間反応させた。反応終了後、Ｎ，Ｎ−
ジメチルホルムアミドを留去し、水を加えて溶解した。
３５％塩酸を加えると、白色結晶が析出したが、これを
１，２−ジクロロエタンで溶解抽出した。この１，２−
ジクロロエタン層のＨＰＬＣによる内標分析により３
３．７ｇ（収率９７．０％）の５−メルカプト−１−メ
チルピラゾール−４−カルボン酸エチルエステルを確認
した。The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. [Example 1] 5-chloro-1-methylpyrazole-4-
35.2 g (0.187 mol) of carboxylic acid ethyl ester was dissolved in 90 g of N, N-dimethylformamide,
With stirring at room temperature, 17.0 g of 60% sodium sulfide (0131
1) and 70% sodium hydrosulfide 10.5 g (0.
131 mol) was added, and the mixture was reacted at 65 ° C. for 3 hours and then at 90 ° C. for 3 hours. After completion of the reaction, N, N-
Dimethylformamide was distilled off, and water was added to dissolve it.
When 35% hydrochloric acid was added, white crystals were precipitated, which were dissolved and extracted with 1,2-dichloroethane. This 1,2-
3 by internal standard analysis of the dichloroethane layer by HPLC
3.7 g (yield 97.0%) of 5-mercapto-1-methylpyrazole-4-carboxylic acid ethyl ester was confirmed.
【００１５】〔実施例２〕３，５−ジクロロ−１−メチ
ルピラゾール−４−カルボン酸メチルエステル５８．９
ｇ（０．２８２モル）をＮ，Ｎ−ジメチルホルムアミド
１６５ｇに溶解し、室温撹拌下６０％硫化ナトリウム３
３．０ｇ（０．２５３モル）および７０％水硫化ナトリ
ウム ６．８ｇ（０．０８５モル）を加え、４０℃で３
時間反応させた後、さらに６０℃で３時間反応させた。
反応終了後、水 ５００mlを加えて溶解した。次いで、
３５％塩酸５０ｇを加えると、白色結晶が析出したが、
これを１，２−ジクロロエタンで溶解抽出した。この
１，２−ジクロロエタン層のＨＰＬＣによる内標分析に
より５７．１ｇ（収率９８．０％）の３−クロロ−５−
メルカプト−１−メチルピラゾール−４−カルボン酸メ
チルエステルを確認した。Example 2 3,5-Dichloro-1-methylpyrazole-4-carboxylic acid methyl ester 58.9
g (0.282 mol) was dissolved in 165 g of N, N-dimethylformamide, and 60% sodium sulfide was added under stirring at room temperature.
Add 3.0 g (0.253 mol) and 70% sodium hydrosulfide 6.8 g (0.085 mol), and add 3 at 40 ° C.
After reacting for a time, it was further reacted at 60 ° C. for 3 hours.
After completion of the reaction, 500 ml of water was added and dissolved. Then
When 50 g of 35% hydrochloric acid was added, white crystals were precipitated,
This was dissolved and extracted with 1,2-dichloroethane. According to internal standard analysis of the 1,2-dichloroethane layer by HPLC, 57.1 g (yield 98.0%) of 3-chloro-5-
Mercapto-1-methylpyrazole-4-carboxylic acid methyl ester was confirmed.
【００１６】〔実施例３〕 ３，５−ジクロロ−１−メ
チルピラゾール−４−カルボン酸メチルエステル２０．
９ｇ（０．１０モル）をＮ，Ｎ−ジメチルホルムアミド
１０５ｇに溶解し、室温撹拌下６０％硫化ナトリウム１
３．０ｇ（０．１０モル）および７０％水硫化ナトリウ
ム０．８ｇ（０．０１０モル）を加え、４０℃で３時間
反応させた後、さらに６０℃で３時間反応させた。実施
例３と同様な後処理を経て、ＨＰＬＣによる内標分析に
より２０．１ｇ（収率９７．５％）の３−クロロ−５−
メルカプト−１−メチルピラゾール−４−カルボン酸メ
チルエステルを確認した。Example 3 3,5-Dichloro-1-methylpyrazole-4-carboxylic acid methyl ester 20.
9 g (0.10 mol) was dissolved in 105 g of N, N-dimethylformamide, and 60% sodium sulfide was added under stirring at room temperature.
3.0 g (0.10 mol) and 0.8 g (0.010 mol) of 70% sodium hydrosulfide were added, and the mixture was reacted at 40 ° C. for 3 hours and then at 60 ° C. for 3 hours. After the same post-treatment as in Example 3, 20.1 g (yield 97.5%) of 3-chloro-5--5 was obtained by internal standard analysis by HPLC.
Mercapto-1-methylpyrazole-4-carboxylic acid methyl ester was confirmed.
【００１７】〔参考例〕 ５−クロロ−１−メチルピラ
ゾール−４−カルボン酸エチルエステル１８．９ｇ
（０．１０モル）をＮ，Ｎ−ジメチルホルムアミド９５
ｇに溶解し、室温撹拌下６０％硫化ナトリウム１４．３
ｇ（０．１１モル）を加えて、６５℃で３時間反応させ
た後、さらに９０℃で３時間反応させた。反応終了後、
Ｎ，Ｎ−ジメチルホルムアミドを留去し、水を加えて溶
解した。３５％塩酸を加えると、白色結晶が析出した
が、これを１，２−ジクロロエタンで溶解抽出した。こ
の１，２−ジクロロエタン層のＨＰＬＣによる内標分析
により１５．９ｇ（収率８５．７％）の５−メルカプト
−１−メチルピラゾール−４−カルボン酸メチルエステ
ルを確認した。このとき、加水分解物の５−メルカプト
−１−メチルピラゾール−４−カルボン酸が１３％副生
していた。Reference Example 5-Chloro-1-methylpyrazole-4-carboxylic acid ethyl ester 18.9 g
(0.10 mol) of N, N-dimethylformamide 95
g, and stirred at room temperature with 60% sodium sulfide 14.3
g (0.11 mol) was added and the mixture was reacted at 65 ° C. for 3 hours and then at 90 ° C. for 3 hours. After the reaction,
N, N-dimethylformamide was distilled off, and water was added to dissolve it. When 35% hydrochloric acid was added, white crystals were precipitated, which were dissolved and extracted with 1,2-dichloroethane. By HPLC internal standard analysis of this 1,2-dichloroethane layer, 15.9 g (yield 85.7%) of 5-mercapto-1-methylpyrazole-4-carboxylic acid methyl ester was confirmed. At this time, 13% of 5-mercapto-1-methylpyrazole-4-carboxylic acid as a hydrolyzate was by-produced.
フロントページの続き (72)発明者 橋場 功 千葉県船橋市坪井町722番地１日産化学工 業株式会社中央研究所内Front page continuation (72) Inventor Isao Hashiba 722 Tsuboi-cho, Funabashi City, Chiba 1 Nissan Chemical Industry Co., Ltd. Central Research Laboratory
Claims (5)
リウムで５−メルカプトピラゾール類を製造する方法に
おいて、水硫化ナトリウムを共存させることを特徴とす
る方法。1. A method for producing 5-mercaptopyrazoles from 5-halogenopyrazoles with sodium sulfide, which comprises coexisting sodium hydrosulfide.
基、炭素原子数１〜７のシクロアルキル基、置換基を有
していてもよいフェニル基または置換基を有していても
よい芳香族複素環を表し、 Ｒ2 は水素原子、炭素原子数１〜６のアルキル基、炭素
原子数１〜６のアルコキシ基、炭素原子数１〜６のアル
コキシカルボニル基、ハロゲン原子、シアノ基、置換基
を有していてもよいフェニル基または置換基を有してい
てもよい芳香族複素環を表し、 Ｒ3 は炭素原子数１〜６のアルコキシカルボニル基、炭
素原子数１〜６のアルキルスルホニル基、ニトロ基、ハ
ロゲン原子またはシアノ基を表し、 Ｘはハロゲン原子を表す。〕で表される請求項１記載の
方法。2. A 5-halogenopyrazole is represented by the formula (1): [In the formula, R 1 has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 1 to 7 carbon atoms, a phenyl group which may have a substituent or a substituent Represents an aromatic heterocycle, R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a halogen atom, cyano. Group, a phenyl group which may have a substituent or an aromatic heterocycle which may have a substituent, R 3 is an alkoxycarbonyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Represents an alkylsulfonyl group, a nitro group, a halogen atom or a cyano group, and X represents a halogen atom. ] The method of Claim 1 represented by these.
または塩素原子を表し、Ｒ3 がメトキシカルボニル基ま
たはエトキシカルボニル基を表し、Ｘが塩素原子を表す
請求項２記載の方法。3. The method according to claim 2 , wherein R 1 represents a methyl group, R 2 represents a hydrogen atom or a chlorine atom, R 3 represents a methoxycarbonyl group or an ethoxycarbonyl group, and X represents a chlorine atom.
ナトリウムが０．５〜１．４モル倍、水硫化ナトリウム
が１．０〜０．０１モル倍である請求項１記載の方法。4. The method according to claim 1, wherein the amount of sodium sulfide is 0.5 to 1.4 times and the amount of sodium hydrosulfide is 1.0 to 0.01 times the amount of 5-halogenopyrazoles.
ナトリウムが０．６〜１．１モル倍、水硫化ナトリウム
が０．８〜０．０１モル倍である請求項１記載の方法。5. The method according to claim 1, wherein the sodium sulfide is 0.6 to 1.1 mole times and the sodium hydrosulfide is 0.8 to 0.01 mole times with respect to the 5-halogenopyrazoles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20796893A JP3562653B2 (en) | 1993-08-23 | 1993-08-23 | Method for producing mercaptopyrazoles |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20796893A JP3562653B2 (en) | 1993-08-23 | 1993-08-23 | Method for producing mercaptopyrazoles |
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| Publication Number | Publication Date |
|---|---|
| JPH0761972A true JPH0761972A (en) | 1995-03-07 |
| JP3562653B2 JP3562653B2 (en) | 2004-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP20796893A Expired - Fee Related JP3562653B2 (en) | 1993-08-23 | 1993-08-23 | Method for producing mercaptopyrazoles |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6703528B2 (en) | 2000-08-11 | 2004-03-09 | Sumitomo Chemical Company, Limited | Process for producing carbonyl or hydroxy compound |
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1993
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6703528B2 (en) | 2000-08-11 | 2004-03-09 | Sumitomo Chemical Company, Limited | Process for producing carbonyl or hydroxy compound |
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