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
- 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.)
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- Plural Heterocyclic Compounds (AREA)
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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20796893A JP3562653B2 (en) | 1993-08-23 | 1993-08-23 | Method for producing mercaptopyrazoles |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0761972A true JPH0761972A (en) | 1995-03-07 |
JP3562653B2 JP3562653B2 (en) | 2004-09-08 |
Family
ID=16548503
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20796893A Expired - Fee Related JP3562653B2 (en) | 1993-08-23 | 1993-08-23 | Method for producing mercaptopyrazoles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3562653B2 (en) |
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 |
-
1993
- 1993-08-23 JP JP20796893A patent/JP3562653B2/en not_active Expired - Fee Related
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 |
Also Published As
Publication number | Publication date |
---|---|
JP3562653B2 (en) | 2004-09-08 |
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