JPH0710863A - Production of 2-(furfurylthio)acetic acid - Google Patents
Production of 2-(furfurylthio)acetic acidInfo
- Publication number
- JPH0710863A JPH0710863A JP5155629A JP15562993A JPH0710863A JP H0710863 A JPH0710863 A JP H0710863A JP 5155629 A JP5155629 A JP 5155629A JP 15562993 A JP15562993 A JP 15562993A JP H0710863 A JPH0710863 A JP H0710863A
- Authority
- JP
- Japan
- Prior art keywords
- acetic acid
- furfurylthio
- acid derivative
- water
- reaction
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、一般式（III）The present invention relates to the general formula (III)
【０００２】[0002]
【化４】 [Chemical 4]
【０００３】（式中、Ｙはアルコキシル基または−ＮＨ
2を示す。）で表わされる２−（フルフリルチオ）酢酸
誘導体の製造方法に関するものである。(In the formula, Y is an alkoxyl group or --NH
2 is shown. The present invention relates to a method for producing a 2- (furfurylthio) acetic acid derivative represented by
【０００４】上記の一般式（III）で表わされる２−
（フルフリルチオ）酢酸誘導体は、医薬品、農薬あるい
は各種機能材料などの製造中間体として有用な化合物で
ある。2- represented by the above general formula (III)
The (furfurylthio) acetic acid derivative is a compound useful as a production intermediate for pharmaceuticals, agricultural chemicals, various functional materials and the like.
【０００５】[0005]
【従来技術およびその問題点】前記の一般式（III）で
表わされる２−（フルフリルチオ）酢酸誘導体は、医薬
品、特に抗消化性潰瘍剤を製造するための中間体として
知られている［特開昭６２−１５３２６８号公報］。2. Description of the Related Art The 2- (furfurylthio) acetic acid derivative represented by the above general formula (III) is known as an intermediate for producing a drug, particularly an anti-peptic ulcer agent. No. 62-153268].
【０００６】従来、前記の一般式（III）で表わされる
２−（フルフリルチオ）酢酸誘導体は、前記の式（Ｉ）
で表わされるフルフリルメルカプタンと前記の一般式
（II）で表わされる酢酸誘導体とを塩基の存在下、反応
溶媒としてアセトニトリルなどの水と混和する非プロト
ン性有機溶媒を用い、縮合する方法により製造されてい
た。Conventionally, the 2- (furfurylthio) acetic acid derivative represented by the above general formula (III) has been prepared by the following formula (I).
Is produced by a method of condensing a furfuryl mercaptan represented by and an acetic acid derivative represented by the general formula (II) in the presence of a base, using an aprotic organic solvent miscible with water such as acetonitrile as a reaction solvent. Was there.
【０００７】しかしながら、従来の製造方法において
は、反応溶媒としてアセトニトリルなどの水と混和する
非プロトン性有機溶媒を使用することから、反応終了
後、塩基の固体を濾過により除去したり、一旦、水と混
和する有機溶媒を留去して水と混和しない有機溶媒と置
換した後、水洗などの処理をする必要があるなど反応終
了後の後処理操作が非常に煩雑であり、また、そのため
に工程数が多くなるなど工業的製造方法としては問題の
多い方法である。However, in the conventional production method, since an aprotic organic solvent miscible with water such as acetonitrile is used as the reaction solvent, the solid base is removed by filtration after the completion of the reaction, or once the water is removed. The post-treatment operation after the reaction is very complicated, such as the need to perform treatment such as washing with water after distilling off the organic solvent miscible with and replacing it with an organic solvent immiscible with water, and for that purpose, This is a method with many problems as an industrial manufacturing method, such as an increase in the number.
【０００８】[0008]
【問題点を解決するための手段】本発明者らは、かかる
従来の製造方法の問題点に鑑み、鋭意検討を行なった結
果、反応溶媒として水と混和しない溶媒を使用しても塩
基および相間移動触媒を添加することにより反応が進行
し、目的の２−（フルフリルチオ）酢酸誘導体を容易に
高純度で得ることができ、また、それにより反応終了後
の後処理操作を非常に簡略化できることを見出し、本発
明に到達した。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in view of the problems of the conventional production method, and as a result, have found that even if a solvent immiscible with water is used as the reaction solvent, the base and the phase By adding a transfer catalyst, the reaction proceeds, the desired 2- (furfurylthio) acetic acid derivative can be easily obtained in high purity, and the post-treatment operation after completion of the reaction can be greatly simplified. Heading, arrived at the present invention.
【０００９】すなわち、本発明は、式（Ｉ）That is, the present invention relates to the formula (I)
【００１０】[0010]
【化５】 [Chemical 5]
【００１１】で表わされるフルフリルメルカプタンと一
般式（II）The furfuryl mercaptan represented by the general formula (II)
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】（式中、Ｘはハロゲン原子を示し、Ｙはア
ルコキシル基または−ＮＨ2を示す。）で表わされる酢
酸誘導体とを塩基および相間移動触媒の存在下、水と混
和しない溶媒中で反応させることを特徴とする一般式
（III）(Wherein, X represents a halogen atom and Y represents an alkoxyl group or --NH 2 ), and the acetic acid derivative is reacted in the presence of a base and a phase transfer catalyst in a solvent immiscible with water. General formula (III) characterized by
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】（式中、Ｙはアルコキシル基または−ＮＨ
2を示す。）で表わされる２−（フルフリルチオ）酢酸
誘導体の製造方法である。本発明の原料である前記の一
般式（II）で表わされる酢酸誘導体としては、例えば、
クロロ酢酸メチル、ブロモ酢酸メチル、クロロ酢酸エチ
ル、ブロモ酢酸エチル、クロロ酢酸プロピル、ブロモ酢
酸プロピル、クロロ酢酸アミド、ブロモ酢酸アミドなど
を使用することができる。(Wherein Y is an alkoxyl group or --NH
2 is shown. ) Is a method for producing a 2- (furfurylthio) acetic acid derivative. Examples of the acetic acid derivative represented by the general formula (II), which is the raw material of the present invention, include:
Methyl chloroacetate, methyl bromoacetate, ethyl chloroacetate, ethyl bromoacetate, propyl chloroacetate, propyl bromoacetate, chloroacetic acid amide, bromoacetic acid amide and the like can be used.
【００１６】本発明の生成物である前記の一般式（II
I）で表わされる２−（フルフリルチオ）酢酸誘導体
は、前記の式（Ｉ）で表わされるフルフリルメルカプタ
ンと上記に例示したような一般式（II）で表わされる酢
酸誘導体とを塩基および相間移動触媒の存在下、水と混
和しない反応溶媒中で反応させることにより製造するこ
とができる。この本発明の生成物である前記の一般式
（III）で表わされる２−（フルフリルチオ）酢酸誘導
体を具体的に示すと、２−（フルフリルチオ）酢酸メチ
ル、２−（フルフリルチオ）酢酸エチル、２−（フルフ
リルチオ）酢酸プロピル、２−（フルフリルチオ）酢酸
アミドなどである。The above-mentioned general formula (II
The 2- (furfurylthio) acetic acid derivative represented by I) is a furfuryl mercaptan represented by the above formula (I) and an acetic acid derivative represented by the above general formula (II) as a base and a phase transfer catalyst. It can be produced by reacting in a reaction solvent immiscible with water in the presence of. Specific examples of the 2- (furfurylthio) acetic acid derivative represented by the general formula (III), which is the product of the present invention, include 2- (furfurylthio) methyl acetate, 2- (furfurylthio) ethyl acetate, and 2- (furfurylthio) ethyl acetate. Examples are (furfurylthio) propyl acetate and 2- (furfurylthio) acetic acid amide.
【００１７】本発明の式（Ｉ）で表わされるフルフリル
メルカプタンと一般式（II）で表わされる酢酸誘導体と
の反応は、当モル反応であるので、これらを反応させる
際の割合はモル比で１：１とするのがよい。Since the reaction between the furfuryl mercaptan represented by the formula (I) and the acetic acid derivative represented by the general formula (II) of the present invention is an equimolar reaction, the ratio in reacting them is a molar ratio. 1: 1 is recommended.
【００１８】本発明で使用される塩基としては、例え
ば、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウ
ム、炭酸水素ナトリウム、水酸化ナトリウム、水酸化カ
リウムなどを挙げることができる。塩基の使用量は、炭
酸カリウム、炭酸ナトリウムなどの場合、原料のフルフ
リルメルカプタンに対して０．５当量以上とすればよ
く、通常は０．５当量〜２当量とするのがよい。２当量
より多く添加しても反応にさほど変化はなく、経済的に
不利になるだけであり、また、過剰の塩基を除去するた
めに後処理に負担がかかるため、好ましくない。より望
ましくは０．６当量〜１．５当量使用するのがよい。ま
た、炭酸水素カリウム、炭酸水素ナトリウム、水酸化ナ
トリウム、水酸化カリウムなどの場合、原料のフルフリ
ルメルカプタンに対して１当量以上とすればよく、通常
は１当量〜４当量とするのがよい。４当量より多く添加
しても反応にさほど変化はなく、経済的に不利になるだ
けであり、また、過剰の塩基を除去するために後処理に
負担がかかるため、好ましくない。より望ましくは１．
２当量〜３当量使用するのがよい。Examples of the base used in the present invention include potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like. In the case of potassium carbonate, sodium carbonate, etc., the amount of the base used may be 0.5 equivalent or more with respect to furfuryl mercaptan as a raw material, and usually 0.5 equivalent to 2 equivalents. If more than 2 equivalents are added, the reaction does not change so much, it is economically disadvantageous, and the post-treatment is burdened to remove the excess base, which is not preferable. It is more preferable to use 0.6 equivalent to 1.5 equivalents. Further, in the case of potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, etc., it may be 1 equivalent or more with respect to the furfuryl mercaptan as a raw material, and usually 1 equivalent to 4 equivalents. If more than 4 equivalents are added, the reaction does not change so much, it is economically disadvantageous, and the post-treatment is burdened to remove the excess base, which is not preferable. More preferably 1.
It is preferable to use 2 to 3 equivalents.
【００１９】本発明の反応においては、塩基を活性化
し、反応を円滑に行なわせるために相間移動触媒を添加
する必要がある。相間移動触媒としては、例えば、１８
−クラウン−６−エーテルなどのクラウンエーテル類、
ポリエチレングリコールなどのポリエーテル類、テトラ
フェニルホスホニウムクロリドなどの４級ホスホニウム
塩類、テトラブチルアンモニウムブロミド、硫酸水素テ
トラブチルアンモニウムなどの４級アンモニウム塩類な
どが使用される。相間移動触媒の使用量は、触媒の種類
により異なるが、求める反応速度に応じて適宜調節すれ
ばよく、通常は原料のフルフリルメルカプタンに対して
０．０００１モル％〜２０モル％が適当である。０．０
００１モル％より少ないと充分な反応速度を得ることが
できず、反応時間が非常に長くなるため、好ましくな
い。また、２０モル％より多く添加しても反応にさほど
変化はなく、経済的に不利になるだけであるので好まし
くない。より望ましくは０．００１モル％〜１０モル％
である。In the reaction of the present invention, it is necessary to add a phase transfer catalyst in order to activate the base and carry out the reaction smoothly. As the phase transfer catalyst, for example, 18
-Crown ethers such as crown-6-ether,
Polyethers such as polyethylene glycol, quaternary phosphonium salts such as tetraphenylphosphonium chloride, tetrabutylammonium bromide, quaternary ammonium salts such as tetrabutylammonium hydrogen sulfate and the like are used. Although the amount of the phase transfer catalyst used varies depending on the type of the catalyst, it may be appropriately adjusted according to the desired reaction rate, and usually 0.0001 mol% to 20 mol% based on the furfuryl mercaptan of the raw material is suitable. . 0.0
If it is less than 001 mol%, a sufficient reaction rate cannot be obtained and the reaction time becomes very long, which is not preferable. In addition, addition of more than 20 mol% does not change the reaction so much and is economically disadvantageous, which is not preferable. More desirably 0.001 mol% to 10 mol%
Is.
【００２０】また、さらに反応を円滑に行なわせるため
にヨウ化カリウムなどの塩類を添加することも可能であ
る。本発明で使用される反応溶媒は、水と混和しない有
機溶媒であり、例えば、ベンゼン、トルエン、キシレン
などの芳香族炭化水素類、ヘキサン、シクロヘキサンな
どの脂肪族炭化水素類、酢酸エチル、酢酸ブチルなどの
エステル類、ジエチルエーテル、ジブチルエーテルなど
のエーテル類、四塩化炭素、１，２−ジクロロエタンな
どのハロゲン化炭化水素類などを使用することができ
る。It is also possible to add salts such as potassium iodide to further facilitate the reaction. The reaction solvent used in the present invention is an organic solvent which is immiscible with water, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and cyclohexane, ethyl acetate and butyl acetate. And the like, ethers such as diethyl ether and dibutyl ether, carbon tetrachloride, halogenated hydrocarbons such as 1,2-dichloroethane, and the like can be used.
【００２１】本発明の反応は、発熱反応であり、室温〜
２００℃で良好に進行する。室温より低い温度では反応
速度が遅く、反応時間が非常に長くなるため、好ましく
ない。また、２００℃より高い温度では分解が激しくな
り、収率低下の原因となり、また、場合によっては蒸留
もしくは再結晶などによる精製が必要となり、後処理に
負担がかかるため、好ましくない。より効率よく反応を
行なうには４０〜１５０℃で行なうことが望ましい。The reaction of the present invention is an exothermic reaction at room temperature to
Good progress at 200 ° C. At a temperature lower than room temperature, the reaction rate is slow and the reaction time becomes very long, which is not preferable. Further, if the temperature is higher than 200 ° C., the decomposition becomes severe, which causes a decrease in the yield, and in some cases, purification by distillation or recrystallization is required, which imposes a burden on the post-treatment, which is not preferable. In order to carry out the reaction more efficiently, it is desirable to carry out at 40 to 150 ° C.
【００２２】反応終了後の後処理は、反応溶媒に水と混
和しない有機溶媒を使用しているため、従来の水と混和
するアセトニトリルなどの非プロトン性有機溶媒を用い
た場合と比較し、非常に容易である。すなわち、反応液
に単に水を加え、塩を溶解した後、生成物を含有する有
機溶媒層を分離、回収すればよい。したがって、従来の
方法の塩の濾過や水と混和する有機溶媒の留去などの操
作が不要であり、工程を大幅に短縮することができるた
め、本発明の方法は工業的に非常に有利な前記の一般式
（III）で表わされる２−（フルフリルチオ）酢酸誘導
体の製造方法である。The post-treatment after completion of the reaction uses an organic solvent which is immiscible with water as a reaction solvent, and therefore is much more difficult than the conventional case where an aprotic organic solvent such as acetonitrile which is miscible with water is used. Easy to. That is, water may be simply added to the reaction solution to dissolve the salt, and then the organic solvent layer containing the product may be separated and collected. Therefore, operations such as filtration of salts and distillation of an organic solvent miscible with water in the conventional method are unnecessary, and the process can be significantly shortened. Therefore, the method of the present invention is industrially very advantageous. It is a method for producing a 2- (furfurylthio) acetic acid derivative represented by the general formula (III).
【００２３】上記の回収した有機溶媒層は、水洗、乾燥
などの通常の処理を行なった後、溶媒を留去することに
より、生成物である前記の一般式（III）で表わされる
２−（フルフリルチオ）酢酸誘導体を純度よく回収する
ことができるが、溶媒を留去することなく、そのまま次
反応工程に供することもできる。また、溶媒留去後、蒸
留もしくは再結晶などにより生成物である前記の一般式
（III）で表わされる２−（フルフリルチオ）酢酸誘導
体をより高純度で回収することもできる。The recovered organic solvent layer is subjected to usual treatments such as washing with water and drying, and then the solvent is distilled off to give a product represented by the general formula (III) 2- (2). Although the furfurylthio) acetic acid derivative can be recovered with high purity, it can be directly used for the next reaction step without distilling the solvent. Further, after distilling off the solvent, the 2- (furfurylthio) acetic acid derivative represented by the general formula (III), which is a product, can be recovered with higher purity by distillation or recrystallization.
【００２４】[0024]
【実施例】以下、実施例により本発明をさらに詳細に説
明する。実施例１ ２−（フルフリルチオ）酢酸メチルの製造 The present invention will be described in more detail with reference to the following examples. Example 1 Preparation of methyl 2- (furfurylthio) acetate
【００２５】[0025]
【化８】 [Chemical 8]
【００２６】フルフリルメルカプタン１１．４０ｇ
（０．１ｍｏｌ）、クロロ酢酸メチル１０．８５ｇ
（０．１ｍｏｌ）および１８−クラウン−６−エーテル
０．０１１ｇをトルエン１５０ｍｌに溶解し、無水炭酸
カリウム１３．８２ｇを添加し、９０℃で１０時間攪拌
した。Furfuryl mercaptan 11.40 g
(0.1 mol), methyl chloroacetate 10.85 g
(0.1 mol) and 0.011 g of 18-crown-6-ether were dissolved in 150 ml of toluene, 13.82 g of anhydrous potassium carbonate was added, and the mixture was stirred at 90 ° C. for 10 hours.
【００２７】冷却後、水７０ｍｌを加え、塩を溶解後、
分液し、さらに水洗後、溶媒を留去し、褐色油状物を得
た。これを減圧下、蒸留することにより無色油状物とし
て２−（フルフリルチオ）酢酸メチルを得た。After cooling, 70 ml of water was added to dissolve the salt,
The layers were separated, washed with water, and the solvent was evaporated to give a brown oil. This was distilled under reduced pressure to obtain methyl 2- (furfurylthio) acetate as a colorless oily substance.
【００２８】収量１５．６３ｇ 収率８４．０％ ｂ．ｐ．１３８℃／１７ｍｍＨｇ ＧＬＣ Ｐｕ．９９．１３％実施例２ ２−（フルフリルチオ）酢酸メチルの製造 フルフリルメルカプタン１１．４０ｇ（０．１ｍｏ
ｌ）、クロロ酢酸メチル１０．８５ｇ（０．１ｍｏｌ）
およびポリエチレングリコール−１０００（ＰＥＧ−１
０００）０．１１ｇをトルエン３４．２ｇに溶解し、無
水炭酸カリウム１３．８２ｇを添加し、９５℃で５時間
攪拌した。Yield 15.63 g Yield 84.0% b. p. 138 ° C./17 mmHg GLC Pu. 99.13% Example 2 Preparation of methyl 2- (furfurylthio) acetate Furfuryl mercaptan 11.40 g (0.1 mo
l), 10.85 g (0.1 mol) of methyl chloroacetate
And polyethylene glycol-1000 (PEG-1
000) 0.11 g was dissolved in toluene 34.2 g, anhydrous potassium carbonate 13.82 g was added, and the mixture was stirred at 95 ° C. for 5 hours.
【００２９】冷却後、吸引濾過をし、残渣をトルエンで
洗浄した後、溶媒を留去し、褐色油状物１９．４７ｇを
回収した。これを減圧下、蒸留することにより無色油状
物として２−（フルフリルチオ）酢酸メチルを得た。After cooling, suction filtration was carried out, the residue was washed with toluene, and then the solvent was distilled off to recover 19.47 g of a brown oily substance. This was distilled under reduced pressure to obtain methyl 2- (furfurylthio) acetate as a colorless oily substance.
【００３０】収量１６．２１ｇ 収率８７．２％ ｂ．ｐ．１３８℃／１７ｍｍＨｇ ＧＬＣ Ｐｕ．９９．３２％実施例３ ２−（フルフリルチオ）酢酸メチルの製造 フルフリルメルカプタン１１．４０ｇ（０．１ｍｏ
ｌ）、クロロ酢酸メチル１０．８５ｇ（０．１ｍｏｌ）
および硫酸水素テトラブチルアンモニウム１．００ｇを
トルエン１００ｍｌに溶解し、無水炭酸カリウム１０．
３７ｇを添加し、１００℃で７時間攪拌した。Yield 16.21 g Yield 87.2% b. p. 138 ° C./17 mmHg GLC Pu. 99.32% Example 3 Preparation of methyl 2- (furfurylthio) acetate Furfuryl mercaptan 11.40 g (0.1 mo
l), 10.85 g (0.1 mol) of methyl chloroacetate
And 1.00 g of tetrabutylammonium hydrogensulfate are dissolved in 100 ml of toluene, and anhydrous potassium carbonate 10.
37 g was added, and the mixture was stirred at 100 ° C. for 7 hours.
【００３１】冷却後、吸引濾過をし、残渣をトルエンで
洗浄した後、溶媒を留去し、褐色油状物を回収した。こ
れを減圧下、蒸留することにより無色油状物として２−
（フルフリルチオ）酢酸メチルを得た。After cooling, suction filtration was performed, the residue was washed with toluene, the solvent was distilled off, and a brown oily substance was recovered. This is distilled under reduced pressure to give a colorless oily substance 2-
Methyl (furfurylthio) acetate was obtained.
【００３２】収量１４．００ｇ 収率７５．３％ ｂ．ｐ．１２９℃／１１ｍｍＨｇ ＧＬＣ Ｐｕ．９８．５６％実施例４ ２−（フルフリルチオ）酢酸アミドの製造 Yield 14.00 g Yield 75.3% b. p. 129 ° C./11 mmHg GLC Pu. 98.56% Example 4 Preparation of 2- (furfurylthio) acetic acid amide
【００３３】[0033]
【化９】 [Chemical 9]
【００３４】フルフリルメルカプタン２２．８０ｇ
（０．２ｍｏｌ）、クロロ酢酸アミド１８．７０ｇ
（０．２ｍｏｌ）およびポリエチレングリコール−１０
００（ＰＥＧ−１０００）０．２２８ｇを酢酸エチル１
５０ｍｌに溶解し、無水炭酸カリウム２０．７ｇを添加
し、還流温度で４時間攪拌した。22.80 g of furfuryl mercaptan
(0.2 mol), chloroacetic acid amide 18.70 g
(0.2 mol) and polyethylene glycol-10
0.228 g of 00 (PEG-1000) was added to ethyl acetate 1
It was dissolved in 50 ml, 20.7 g of anhydrous potassium carbonate was added, and the mixture was stirred at reflux temperature for 4 hours.
【００３５】冷却後、水１００ｍｌを加え、塩を溶解
後、分液し、２０％食塩水１００ｍｌ、飽和食塩水１０
０ｍｌで洗浄後、無水硫酸マグネシウムおよび活性炭で
脱水、脱色後、溶媒を留去し、３０．８０ｇの固体を回
収した。これを酢酸エチル−ｎ−ヘキサンで再結晶し、
２−（フルフリルチオ）酢酸アミドを得た。After cooling, 100 ml of water was added to dissolve the salt, followed by liquid separation, and 100 ml of 20% saline and 10 ml of saturated saline.
After washing with 0 ml, dehydration with anhydrous magnesium sulfate and activated carbon and decolorization, the solvent was distilled off, and 30.80 g of a solid was recovered. This was recrystallized from ethyl acetate-n-hexane,
2- (Furfurylthio) acetic acid amide was obtained.
【００３６】収量２６．５０ｇ 収率７７．５％ ｍ．ｐ．６８．０〜６８．５℃ ＧＬＣ Ｐｕ．９９．８５％Yield 26.50 g Yield 77.5% m.p. p. 68.0-68.5 ° C GLC Pu. 99.85%
【００３７】[0037]
【発明の効果】本発明の方法により、従来の２−（フル
フリルチオ）酢酸誘導体の製造方法においては非常に煩
雑であった後処理操作を非常に簡略化でき、２−（フル
フリルチオ）酢酸誘導体を効率よく高純度で製造するこ
とができる。INDUSTRIAL APPLICABILITY According to the method of the present invention, the post-treatment operation, which was very complicated in the conventional method for producing a 2- (furfurylthio) acetic acid derivative, can be greatly simplified, and the 2- (furfurylthio) acetic acid derivative can be efficiently produced. It can be manufactured with high purity.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石井 章央 埼玉県川越市今福中台2805番地 セントラ ル硝子株式会社東京研究所内 (72)発明者 森野 譲 埼玉県川越市今福中台2805番地 セントラ ル硝子株式会社東京研究所内 (72)発明者 菊池 祥之 埼玉県川越市今福中台2805番地 セントラ ル硝子株式会社東京研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Ishii 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Glass Co., Ltd.Tokyo Research Laboratories (72) Inventor Yu Morino 2805 Imafuku Nakadai, Kawagoe City, Saitama Prefecture Central Glass Tokyo Research Laboratory Co., Ltd. (72) Inventor Yoshiyuki Kikuchi 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Glass Co., Ltd. Tokyo Research Laboratory
Claims (1)
または−ＮＨ2を示す。）で表わされる酢酸誘導体とを
塩基および相間移動触媒の存在下、水と混和しない溶媒
中で反応させることを特徴とする一般式（III） 【化３】 （式中、Ｙはアルコキシル基または−ＮＨ2を示す。）
で表わされる２−（フルフリルチオ）酢酸誘導体の製造
方法。1. The following formula (I): A furfuryl mercaptan represented by the general formula (II) (Wherein, X represents a halogen atom, Y represents an alkoxyl group or —NH 2 ), and is reacted in the presence of a base and a phase transfer catalyst in a solvent immiscible with water. Characterized by the general formula (III): (Wherein, Y represents an alkoxyl group or -NH 2.)
A method for producing a 2- (furfurylthio) acetic acid derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5155629A JP3065199B2 (en) | 1993-06-25 | 1993-06-25 | Method for producing 2- (furfurylthio) acetic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5155629A JP3065199B2 (en) | 1993-06-25 | 1993-06-25 | Method for producing 2- (furfurylthio) acetic acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710863A true JPH0710863A (en) | 1995-01-13 |
| JP3065199B2 JP3065199B2 (en) | 2000-07-12 |
Family
ID=15610176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5155629A Expired - Lifetime JP3065199B2 (en) | 1993-06-25 | 1993-06-25 | Method for producing 2- (furfurylthio) acetic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3065199B2 (en) |
-
1993
- 1993-06-25 JP JP5155629A patent/JP3065199B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3065199B2 (en) | 2000-07-12 |
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