JP2905900B2 - Method for producing 2-mercapto-6-halogenobenzoic acid - Google Patents
Method for producing 2-mercapto-6-halogenobenzoic acidInfo
- Publication number
- JP2905900B2 JP2905900B2 JP16944490A JP16944490A JP2905900B2 JP 2905900 B2 JP2905900 B2 JP 2905900B2 JP 16944490 A JP16944490 A JP 16944490A JP 16944490 A JP16944490 A JP 16944490A JP 2905900 B2 JP2905900 B2 JP 2905900B2
- Authority
- JP
- Japan
- Prior art keywords
- mercapto
- acid
- producing
- reducing agent
- halogenobenzoic
- 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
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、農薬の中間体として重要な２−メルカプト
−６−ハロゲノ安息香酸の製法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing 2-mercapto-6-halogenobenzoic acid, which is important as an intermediate for pesticides.
（従来の技術及び発明が解決しようとする問題点） 式 式中、Ｘはハロゲン原子を示す。(Problems to be solved by the prior art and the invention) In the formula, X represents a halogen atom.
で表わされる２−メルカプト−６−ハロゲノ安息香酸
は、上述のように特に農薬の中間体として重要であり、
従来、この一般式で表わされる化合物は、例えばFarmac
o.,Ed.,Sci.,1967,22（12）,989−998に開示されている
以下に示すような方法で製造されていた。2-mercapto-6-halogenobenzoic acid represented by is particularly important as an intermediate for pesticides as described above,
Conventionally, compounds represented by this general formula are, for example, Farmac
o., Ed., Sci., 1967 , 22 (12), 989-998.
然しながら、上記の従来方法は、工程数が多く、しか
もジアゾ化工程などが必要であって製造コストの面で問
題がある等、工業的な製法としていまだ十分なものでは
なかった。 However, the above-mentioned conventional method has not been sufficient as an industrial production method because it involves a large number of steps, requires a diazotization step, and has a problem in production cost.
一方、上記構造式より、対応するベンゾニトリル類を
加水分解すれば、目的とする２−メルカプト−６−ハロ
ゲノ安息香酸が得られるとも考えられ、実際にも、ベン
ゾニトリル類の加水分解により安息香酸を製造する方法
として、例えば特開昭57−118541号公報には、ベンゾニ
トリル類をアルカリ条件で加水分解する方法が開示さ
れ、又、特開昭61−30556号公報には、ベンゾニトリル
類を酸性条件で加水分解する方法が提案されている。On the other hand, from the above structural formula, it is considered that the desired 2-mercapto-6-halogenobenzoic acid can be obtained by hydrolyzing the corresponding benzonitrile, and in fact, benzoic acid is obtained by hydrolysis of the benzonitrile. For example, JP-A-57-118541 discloses a method of hydrolyzing benzonitrile under alkaline conditions, and JP-A-61-30556 discloses benzonitrile. A method for hydrolysis under acidic conditions has been proposed.
然しながら、上記の公知方法をそのまま、本発明の目
的化合物のようなメルカプト基を有する安息香酸の製造
に応用した場合は、スルフィン酸やオキシド類或は他の
副生物が生成し、目的とする２−メルカプト−６−ハロ
ゲノ安息香酸を収率良く得ることはできないことがわか
っている。However, when the above-mentioned known method is directly applied to the production of a benzoic acid having a mercapto group such as the target compound of the present invention, sulfinic acid, oxides or other by-products are formed, and the desired compound 2 is obtained. It has been found that -mercapto-6-halogenobenzoic acid cannot be obtained in good yield.
従って、２−メルカプト−６−ハロゲノ安息香酸を収
率良く、しかも工業的に製造する方法の開発が強く望ま
れていたのである。Therefore, development of a method for industrially producing 2-mercapto-6-halogenobenzoic acid with good yield has been strongly desired.
（課題を解決するための手段） 本発明は、上述した従来技術を背景として完成された
もので、その構成は、一般式 式中、Ｒは水素原子または３−ハロゲノ−２−シアノ−
フェニルチオ基を、Ｘはハロゲン原子をそれぞれ示す。(Means for Solving the Problems) The present invention has been completed on the background of the above-described conventional technology, and the configuration thereof is represented by a general formula In the formula, R represents a hydrogen atom or 3-halogeno-2-cyano-
X represents a phenylthio group, and X represents a halogen atom.
で表されるベンゾニトリル類を、還元剤の存在下に、ア
ルカリ水溶液で扱うことを特徴とするものであり、更に
この構成において、一般式（１）で表されるベンゾニト
リル類を還元剤の存在下にアルカリ水溶液で扱い、次い
で酸析したり、或は、還元剤として、アルカリ条件下で
使用できるものを用いるような態様をも採用できるもの
である。Wherein the benzonitrile represented by the formula (1) is treated with an aqueous alkali solution in the presence of a reducing agent. It is also possible to employ an embodiment in which an alkali aqueous solution is used in the presence and then acid precipitation is performed, or a reducing agent that can be used under alkaline conditions is used.
即ち、本発明の発明者らは、２−メルカプト−６−ハ
ロゲノ安息香酸を収率良く、しかも工業的に得る方法を
開発するため鋭意研究を重ねた結果、意外にも、還元剤
の存在下に、アルカリ水溶液と反応させることにより、
短い工程で、収率よく２−メルカプト−６−ハロゲノ安
息香酸が得られることを認め本発明を完成したのであ
る。That is, the inventors of the present invention have conducted intensive studies to develop a method for industrially obtaining 2-mercapto-6-halogenobenzoic acid with good yield, and as a result, surprisingly, in the presence of a reducing agent. By reacting with an aqueous alkali solution,
The inventors have found that 2-mercapto-6-halogenobenzoic acid can be obtained in a short step and in good yield, and thus completed the present invention.
以下に本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明の原料として使用するベンゾニトリル類は、前
記一般式（１）で表わされるものであり、具体的な化合
物としては、２−メルカプト−６−クロロベンゾニトリ
ル（化合物Ａと略称する） や2,2′−ジチオビス−（６−クロロベンゾニトリル）
（化合物Ｂと略称する） を例示することができる。The benzonitrile used as a raw material of the present invention is represented by the general formula (1), and a specific compound is 2-mercapto-6-chlorobenzonitrile (abbreviated as compound A). And 2,2'-dithiobis- (6-chlorobenzonitrile)
(Abbreviated as Compound B) Can be exemplified.
尚、上記原料中、化合物Ａは、例えば非プロトン性極
性溶媒の存在下に2,6−ジクロロベンゾニトリルと硫化
アルカリ金属とを反応させることにより、又、化合物Ｂ
は、得られた化合物Ａを更に酸化することにより、それ
ぞれ容易に得ることができる。In the above-mentioned raw materials, compound A can be prepared by reacting 2,6-dichlorobenzonitrile with an alkali metal sulfide in the presence of, for example, an aprotic polar solvent.
Can be easily obtained by further oxidizing the obtained compound A.
又、アルカリは、アルカリ金属の水酸化物、炭酸化合
物、炭酸水素化合物或はフッ素化物等を含むものであ
り、反応には、例えば水酸化ナトリウム、水酸化カリウ
ム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウ
ム、炭酸水素カリウム、フッ化カリウム等を水溶液にし
て使用する。The alkali includes an alkali metal hydroxide, a carbonate compound, a hydrogen carbonate compound or a fluoride, and the reaction includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, hydrogen carbonate. An aqueous solution of sodium, potassium bicarbonate, potassium fluoride or the like is used.
還元剤としては、アルカリ条件下で使用できるもので
あれば、差し支えなく用いることができ、具体的には、
硫化ナトリウム、硫化カリウム、ハイドロサルファイト
ナトリウム、水硫化ナトリウム、水硫化カリウム等を例
示することができる。Any reducing agent that can be used under alkaline conditions can be used without any problem.Specifically,
Examples thereof include sodium sulfide, potassium sulfide, sodium hydrosulfite, sodium hydrosulfide, and potassium hydrosulfide.
本発明においては、一般式（１）で示されるベンゾニ
トリル類に対し、アルカリ水溶液を当モル以上、好まし
くは１〜20倍モル加え、又、還元剤は0.1〜５倍モル、
好ましくは0.5〜３倍モル用いて反応させる（いずれも
前記ベンゾニトリル類を基準とする）。In the present invention, an aqueous alkali solution is added in an amount of at least equimolar, preferably 1 to 20 moles, to the benzonitrile represented by the general formula (1), and the reducing agent is 0.1 to 5 moles.
Preferably, the reaction is carried out using 0.5 to 3 moles (all based on the benzonitrile).
反応温度は100〜250℃、好ましくは140〜200℃、反応
時間は１〜30時間程度行なえば良い。The reaction temperature may be 100 to 250 ° C, preferably 140 to 200 ° C, and the reaction time may be about 1 to 30 hours.
本発明における反応は、常圧または加圧どちらで行な
ってもよく、通常は加圧下で行なうが、その圧力は例え
ば0.01〜50Kg/cm2である。The reaction in the present invention may be carried out at normal pressure or under pressure, and is usually carried out under pressure, and the pressure is, for example, 0.01 to 50 kg / cm 2 .
一方、上記反応液からは、例えば後処理時に酸析をす
ることにより、目的物を容易に得ることができ、この酸
析に使用する酸としては、通常当該目的使用されるもの
であれば問題なく用いることができ、例えば、塩酸、硫
酸、酢酸などである。On the other hand, the desired product can be easily obtained from the reaction solution by, for example, performing acid precipitation during post-treatment. For example, hydrochloric acid, sulfuric acid, acetic acid and the like can be used.
［発明の効果］ 本発明は、一般式（１）で示されるベンゾニトリル類
とアルカリ水溶液とを、還元剤の存在下に反応させるこ
とにより、副生物の生成を抑え、目的とする２−メルカ
プト−６−ハロゲノ安息香酸を短い工程で、高収率且つ
安価に製造することができるものであり、工業的な製造
方法として極めて価値の高いものである。[Effects of the Invention] The present invention suppresses the formation of by-products by reacting a benzonitrile represented by the general formula (1) with an aqueous alkali solution in the presence of a reducing agent, thereby reducing the desired 2-mercapto compound. -6-halogenobenzoic acid can be produced in a short process with high yield and at low cost, and is extremely valuable as an industrial production method.
［実施例］ 以下実施例により本発明を具体的に説明する。[Examples] Hereinafter, the present invention will be described specifically with reference to Examples.
実施例１ 冷却器、温度計、攪拌機、圧力計、安全弁を備えた20
0mlのオートクレーブに、２−メルカプト−６−クロロ
ベンゾニトリル17.0g（0.1モル）、硫化ナトリウム・９
水塩21.0g、15％水酸化ナトリウム水溶液133gをいれ、1
70℃まで加熱し、15時間反応させた。Example 1 20 equipped with a cooler, thermometer, stirrer, pressure gauge and safety valve
In a 0 ml autoclave, 17.0 g (0.1 mol) of 2-mercapto-6-chlorobenzonitrile, sodium sulfide-9
Add 21.0 g of water salt and 133 g of 15% aqueous sodium hydroxide solution.
The mixture was heated to 70 ° C. and reacted for 15 hours.
反応終了後、室温まで冷却し、更に氷冷しながら濃塩
酸を加え、pHを１以下にした。エーテルで抽出し、水
洗、濃縮、乾燥して、融点110〜115℃の２−メルカプト
−６−ハロゲノ安息香酸を17.5g得た。収率は92.8％
（２−メルカプト−６−クロロベンゾニトリル基準）で
あった。After completion of the reaction, the mixture was cooled to room temperature, and concentrated hydrochloric acid was added thereto while cooling with ice to adjust the pH to 1 or less. The mixture was extracted with ether, washed with water, concentrated and dried to obtain 17.5 g of 2-mercapto-6-halogenobenzoic acid having a melting point of 110 to 115 ° C. 92.8% yield
(Based on 2-mercapto-6-chlorobenzonitrile).
実施例２ ２−メルカプト−６−クロロベンゾニトリルのかわり
に、2,2′−ジチオビス−（６−クロロベンゾニトリ
ル）16.9g（0.05モル）を加え、14時間反応させた以外
は、実施例１と同様に反応を行なった。Example 2 Example 1 was repeated except that 16.9 g (0.05 mol) of 2,2'-dithiobis- (6-chlorobenzonitrile) was added in place of 2-mercapto-6-chlorobenzonitrile and reacted for 14 hours. The reaction was carried out in the same manner as described above.
その結果、２−メルカプト−６−クロロ安息香酸を1
7.5g得た。収率は92.8％［2,2′−ジチオビス−（６−
クロロベンゾニトリル）基準］であった。As a result, 2-mercapto-6-chlorobenzoic acid was converted to 1
7.5 g were obtained. The yield was 92.8% [2,2'-dithiobis- (6-
Chlorobenzonitrile) standard].
実施例３ 冷却器、温度計、攪拌機、圧力計、安全弁を備えた20
0mlのオートクレーブに、２−メルカプト−６−フルオ
ロベンゾニトリル15.32g（0.1モル）、硫化ナトリウム
・９水塩21.0g、15％水酸化ナトリウム水溶液133gをい
れ、170℃まで加熱し、15時間反応させた。Example 3 20 equipped with a cooler, thermometer, stirrer, pressure gauge and safety valve
In a 0 ml autoclave, 15.32 g (0.1 mol) of 2-mercapto-6-fluorobenzonitrile, 21.0 g of sodium sulfide / 9-hydrate, and 133 g of a 15% aqueous sodium hydroxide solution were added, and the mixture was heated to 170 ° C. and reacted for 15 hours. Was.
反応終了後、室温まで冷却し、更に氷冷しながら濃塩
酸を加え、pHを１以下にした。エーテルで抽出し、水
洗、濃縮、乾燥して、融点120〜125℃の２−メルカプト
−６−フルオロ安息香酸を15.4g得た。収率は89.7％
（２−メルカプト−６−フルオロベンゾニトリル基準）
であった。After completion of the reaction, the mixture was cooled to room temperature, and concentrated hydrochloric acid was added thereto while cooling with ice to adjust the pH to 1 or less. The mixture was extracted with ether, washed with water, concentrated and dried to obtain 15.4 g of 2-mercapto-6-fluorobenzoic acid having a melting point of 120 to 125 ° C. 89.7% yield
(Based on 2-mercapto-6-fluorobenzonitrile)
Met.
実施例４ ２−メルカプト−６−フルオロベンゾニトリルのかわ
りに、2,2′−ジチオビス−（６−フルオロベンゾニト
リル）15.2g（0.05モル）を加え、14時間反応させた以
外は、実施例１と同様に反応を行なった。Example 4 Example 1 was repeated except that instead of 2-mercapto-6-fluorobenzonitrile, 15.2 g (0.05 mol) of 2,2'-dithiobis- (6-fluorobenzonitrile) was added and reacted for 14 hours. The reaction was carried out in the same manner as described above.
その結果、２−メルカプト−６−フルオロ安息香酸を
15.5g得た。収率は90.0％［2,2′−ジチオビス−（６−
フルオロベンゾニトリル）基準］であった。As a result, 2-mercapto-6-fluorobenzoic acid is
15.5 g was obtained. The yield was 90.0% [2,2'-dithiobis- (6-
Fluorobenzonitrile) standard].
比較例１（実施例１の条件で還元剤を使用しない場合） 硫化ナトリウムを使用しない以外は、実施例１と同様
に反応を行なった。Comparative Example 1 (when no reducing agent is used under the conditions of Example 1) The reaction was carried out in the same manner as in Example 1 except that sodium sulfide was not used.
その結果、２−メルカプト−６−クロロ安息香酸を8.
5g得た。収率は45.1％（２−メルカプト−６−クロロベ
ンゾニトリル基準）であった。As a result, 2-mercapto-6-chlorobenzoic acid was added to 8.
5 g was obtained. The yield was 45.1% (based on 2-mercapto-6-chlorobenzonitrile).
比較例２（実施例２の条件で還元剤を使用しない場合） 硫化ナトリウムを使用しない以外は、実施例２と同様
に反応を行なった。Comparative Example 2 (when no reducing agent is used under the conditions of Example 2) The reaction was carried out in the same manner as in Example 2 except that sodium sulfide was not used.
その結果２−メルカプト−６−クロロ安息香酸を9.2g
得た。収率は48.9％［2,2′−ジチオビス−（６−クロ
ロベンゾニトリル）基準］であった。As a result, 9.2 g of 2-mercapto-6-chlorobenzoic acid was obtained.
Obtained. The yield was 48.9% [based on 2,2'-dithiobis- (6-chlorobenzonitrile)].
Claims (3)
フェニルチオ基を、Ｘはハロゲン原子をそれぞれ示す。 で表されるベンゾニトリル類を、還元剤の存在下に、ア
ルカリ水溶液で扱うことを特徴とする２−メルカプト−
６−ハロゲノ安息香酸の製造方法。(1) one general formula In the formula, R represents a hydrogen atom or 3-halogeno-2-cyano-
X represents a phenylthio group, and X represents a halogen atom. Wherein the benzonitrile represented by is treated with an aqueous alkali solution in the presence of a reducing agent.
A method for producing 6-halogenobenzoic acid.
を、還元剤の存在下にアルカリ水溶液で扱い、次いで酸
析することを特徴とする請求項１記載の２−メルカプト
−６−ハロゲノ安息香酸の製造方法。2. The 2-mercapto-6 according to claim 1, wherein the benzonitrile represented by the general formula (1) is treated with an aqueous alkali solution in the presence of a reducing agent, and then subjected to acid precipitation. A method for producing halogenobenzoic acid.
のである請求項１又は２記載の２−メルカプト−６−ハ
ロゲノ安息香酸の製造方法。3. The method for producing 2-mercapto-6-halogenobenzoic acid according to claim 1, wherein the reducing agent can be used under alkaline conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16944490A JP2905900B2 (en) | 1989-09-16 | 1990-06-26 | Method for producing 2-mercapto-6-halogenobenzoic acid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-240406 | 1989-09-16 | ||
| JP24040689 | 1989-09-16 | ||
| JP16944490A JP2905900B2 (en) | 1989-09-16 | 1990-06-26 | Method for producing 2-mercapto-6-halogenobenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03173863A JPH03173863A (en) | 1991-07-29 |
| JP2905900B2 true JP2905900B2 (en) | 1999-06-14 |
Family
ID=26492775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16944490A Expired - Fee Related JP2905900B2 (en) | 1989-09-16 | 1990-06-26 | Method for producing 2-mercapto-6-halogenobenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2905900B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360288B (en) * | 2013-07-29 | 2015-04-01 | 江苏恒安化工有限公司 | Preparation method of 6-chloro-2-mercaptobenzoic acid |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH03173863A (en) | 1991-07-29 |
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