JPH0816093B2 - Method for producing 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate - Google Patents
Method for producing 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformateInfo
- Publication number
- JPH0816093B2 JPH0816093B2 JP25832887A JP25832887A JPH0816093B2 JP H0816093 B2 JPH0816093 B2 JP H0816093B2 JP 25832887 A JP25832887 A JP 25832887A JP 25832887 A JP25832887 A JP 25832887A JP H0816093 B2 JPH0816093 B2 JP H0816093B2
- Authority
- JP
- Japan
- Prior art keywords
- tetrahydronaphthoxy
- chlorothioformate
- present
- producing
- alkali metal
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、２−（5,6,7,8−テトラヒドロナフトキ
シ）−クロロチオホルメイトの製造方法に関する。本発
明の製造方法により、製造することができる２−（5,6,
7,8−テトラヒドロナフトキシ）−クロロチオホルメイ
トは、医薬あるいは農薬などの中間体として有名であ
る。TECHNICAL FIELD The present invention relates to a method for producing 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate. It can be produced by the production method of the present invention 2- (5,6,
7,8-Tetrahydronaphthoxy) -chlorothioformate is famous as an intermediate for medicines and agricultural chemicals.
（従来の技術） フェニルクロロチオホルメイト類は、脱ハロゲン化水
素試剤存在下にフェノール類とチオホスゲンの反応によ
り製造できることは公知である。しかし、この方法で
は、5,6,7,8−テトラヒドロ−２−ナフトールのクロロ
チオホルミル化においては通常３％以上の不純物の生成
が見られ、純度97％未満の目的物しか得られない。した
がって工業的原料として使用し得るより純度の高い２−
（5,6,7,8−テトラヒドロナフトキシ）−クロロチオホ
ルメイトの合成方法が望まれていた。(Prior Art) It is known that phenylchlorothioformates can be produced by the reaction of phenols and thiophosgene in the presence of a dehydrohalogenating reagent. However, according to this method, in the chlorothioformylation of 5,6,7,8-tetrahydro-2-naphthol, usually 3% or more of impurities are produced, and only the target substance having a purity of less than 97% can be obtained. Therefore, it is possible to use 2-
A method for synthesizing (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate has been desired.
（本発明が解決しようとする問題点） 本発明の目的は、高純度の２−（5,6,7,8−テトラヒ
ドロナフトキシ）−クロロチオホルメイトを収率良く得
ることである。(Problems to be Solved by the Present Invention) An object of the present invention is to obtain highly pure 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate in good yield.
（問題点を解決するための手段および作用） 本発明者等は、5,6,7,8−テトラヒドロ−２−ナフト
ールをクロロチオホルミル化することにより高純度の２
−（5,6,7,8−テトラヒドロナフトキシ）−クロロチオ
ホルメイトを得る方法について鋭意検討した結果、亜硫
酸ガス，硫化水素ガス及びアルカリ金属硫化物等のイオ
ウ含有の無機還元剤を添加剤として使用することによ
り、高い収率で高純度の該クロロホルメイトを製造でき
ることを見い出し本発明を完成した。すなわち、本発明
は5,6,7,8−テトラヒドロ−２−ナフトールとチオホス
ゲンを脱ハロゲン化水素試剤と亜硫酸ガス，硫化水素ガ
ス及びアルカリ金属硫化物の少なくとも一種の溶存下に
反応させることを特徴とする２−（5,6,7,8−テトラヒ
ドロナフトキシ）−クロロチオホルメイトの製造方法を
提供するものである。(Means and Actions for Solving Problems) The present inventors have made chlorothioformylation of 5,6,7,8-tetrahydro-2-naphthol into a highly pure 2
As a result of extensive studies on a method for obtaining-(5,6,7,8-tetrahydronaphthoxy) -chlorothioformate, sulfur-containing inorganic reducing agents such as sulfurous acid gas, hydrogen sulfide gas and alkali metal sulfide were added as additives. It was found that the chloroformate can be produced in a high yield and a high purity by using the compound as a compound. That is, the present invention is characterized in that 5,6,7,8-tetrahydro-2-naphthol and thiophosgene are reacted in the presence of a dehydrohalogenating reagent and at least one of sulfurous acid gas, hydrogen sulfide gas and alkali metal sulfide dissolved therein. The present invention provides a method for producing 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate.
本発明方法で用いられる添加剤は、亜硫酸ガス，硫化
水素ガス及びアルカリ金属硫化物の中から選ばれる。ア
ルカリ金属硫化物としては、ナトリウム，カリウムなど
のアルカリ金属との塩が用いられ、例えば、硫化ナトリ
ウム，硫化カリウム，水硫化ナトリウム，水硫化カリウ
ムなどを挙げることができる。The additive used in the method of the present invention is selected from sulfurous acid gas, hydrogen sulfide gas and alkali metal sulfides. As the alkali metal sulfide, salts with alkali metals such as sodium and potassium are used, and examples thereof include sodium sulfide, potassium sulfide, sodium hydrosulfide, potassium hydrosulfide and the like.
本発明製造方法に用いる前記添加剤の添加量は、好ま
しくは5,6,7,8−テトラヒドロ−２−ナフトール１モル
に対して0.005〜１モルであり、さらに好ましくは0.02
〜0.1モルの範囲である。これらの添加量が0.005モルよ
り少ない状態で反応を行ったならば、目的物の純度は9
7.9％程度しかなく、充分満足し得る純度の化合物は得
られない。又、１モルを越える量のこれらの塩の存在下
での反応では２−（5,6,7,8−テトラヒドロナフトキ
シ）−２−クロロチオホルメイトの収量は最適条件下で
の反応に比べ大きく減少する。The amount of the additive used in the production method of the present invention is preferably 0.005 to 1 mol, and more preferably 0.02, relative to 1 mol of 5,6,7,8-tetrahydro-2-naphthol.
The range is from 0.1 to 0.1 mol. If the reaction is carried out in a state where the addition amount of these is less than 0.005 mol, the purity of the target product is 9
Since the amount is only 7.9%, a compound having a sufficiently satisfactory purity cannot be obtained. In addition, the yield of 2- (5,6,7,8-tetrahydronaphthoxy) -2-chlorothioformate was higher than that in the presence of more than 1 mol of these salts. It is greatly reduced in comparison.
本発明方法における脱ハロゲン化水素試剤としては、
アルカリ金属水酸化物，アルカリ土類金属水酸化物、そ
して、アルカリ金属炭酸塩等の無機塩、トリエチルアミ
ン，ピリジン，キノリン，イソキノリン等の有機塩基が
挙げられるが、通常は、水酸化ナトリウム，水酸化カリ
ウム等のアルカリ金属水酸化物を水に溶解して用いるこ
とができる。又、反応を円滑に進めるために、ジクロロ
メタン，クロロホルム，四塩化炭素，ジクロロエタン等
のハロゲン化炭化水素溶媒を使用することができる。As the dehydrohalogenating agent in the method of the present invention,
Examples thereof include alkali metal hydroxides, alkaline earth metal hydroxides, inorganic salts such as alkali metal carbonates, and organic bases such as triethylamine, pyridine, quinoline, and isoquinoline. An alkali metal hydroxide such as potassium can be used by dissolving it in water. Further, in order to proceed the reaction smoothly, a halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane or the like can be used.
反応温度は−10℃〜20℃程度であり、好ましくは０℃
〜10℃程度が適当である。The reaction temperature is about -10 ° C to 20 ° C, preferably 0 ° C.
A temperature of ~ 10 ° C is suitable.
（実施例） 以下本発明を実施例によりさらに説明するが、本発明
はこれらにのみ限定されるものではない。(Examples) Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.
実施例１ 5,6,7,8−テトラヒドロ−２−ナフトール14.8g（0.1m
ol）と95％チオホスゲン12.7g（0.105mol）を含む四塩
化炭素75mlの溶液に氷冷攪拌下、添加剤として亜硫酸ガ
ス5mmolを溶解した2N水酸化ナトリウム水溶液50ml（0.1
mol）を15分間で滴下した。反応中温度は10℃以下に保
った。滴下終了後、15時間攪拌を継続した。その反応混
合物をアルカリ洗浄，水洗後減圧蒸留により精製し、1
8.8g（収率82.8％）の２−（5,6,7,8−テトラヒドロナ
フトキシ）−クロロチオホルメイトを得た。Example 1 5,6,7,8-tetrahydro-2-naphthol 14.8 g (0.1 m
ol) and 95% thiophosgene 12.7 g (0.105 mol) in a solution of carbon tetrachloride (75 ml) under ice-cooling with stirring, and 2 ml of 2N aqueous sodium hydroxide solution (0.1 ml) containing 5 mmol of sulfurous acid gas as an additive.
mol) was added dropwise over 15 minutes. During the reaction, the temperature was kept below 10 ° C. After completion of dropping, stirring was continued for 15 hours. The reaction mixture was washed with alkali, washed with water and then purified by vacuum distillation.
8.8 g (82.8% yield) of 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate was obtained.
又、生成物について液体クロマトグラフィー（検出
器:UV-8000,カラム逆相TSKgel ODS-120T（4.6mmφ×25c
m），溶離液：アセトニトリル／水＝80/20）により分析
を行った結果、純度は99.6％であった。Liquid chromatography (detector: UV-8000, column reverse phase TSKgel ODS-120T (4.6mmφ × 25c)
m), eluent: acetonitrile / water = 80/20), and as a result, the purity was 99.6%.
実施例２〜5,比較例 実施例１と同じ反応装置を用い、同じ反応条件で添加
剤の種類及び添加量を変えて実施した場合の結果を以下
に示す。Examples 2 to 5 and Comparative Example The results obtained when the same reactor as in Example 1 was used and the type and amount of the additive were changed under the same reaction conditions are shown below.
（発明の効果） 以上の説明で明らかな様に、本発明の製造方法に従え
ば、高純度の２−（5,6,7,8−テトラヒドロナフトキ
シ）−クロロチオホルメイトを収率良く得ることが出来
る。 (Effect of the invention) As is clear from the above description, according to the production method of the present invention, highly pure 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate can be obtained in good yield. You can get it.
Claims (1)
とチオホスゲンを脱ハロゲン化水素試剤と亜硫酸ガス，
硫化水素ガス及びアルカリ金属硫化物の少なくとも一種
の溶存下反応させることを特徴とする２−（5,6,7,8−
テトラヒドロナフトキシ）−クロロチオホルメイトの製
造方法。1. A dehydrohalogenating reagent containing 5,6,7,8-tetrahydro-2-naphthol and thiophosgene and sulfurous acid gas,
2- (5,6,7,8−) characterized by reacting in the presence of at least one of hydrogen sulfide gas and alkali metal sulfide
Method for producing tetrahydronaphthoxy) -chlorothioformate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25832887A JPH0816093B2 (en) | 1987-10-15 | 1987-10-15 | Method for producing 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25832887A JPH0816093B2 (en) | 1987-10-15 | 1987-10-15 | Method for producing 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01102058A JPH01102058A (en) | 1989-04-19 |
| JPH0816093B2 true JPH0816093B2 (en) | 1996-02-21 |
Family
ID=17318722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25832887A Expired - Lifetime JPH0816093B2 (en) | 1987-10-15 | 1987-10-15 | Method for producing 2- (5,6,7,8-tetrahydronaphthoxy) -chlorothioformate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0816093B2 (en) |
-
1987
- 1987-10-15 JP JP25832887A patent/JPH0816093B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01102058A (en) | 1989-04-19 |
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