JPH0710864A - Purification of 2-(furfurylthio)acetic acid phenyl derivative - Google Patents
Purification of 2-(furfurylthio)acetic acid phenyl derivativeInfo
- Publication number
- JPH0710864A JPH0710864A JP15563293A JP15563293A JPH0710864A JP H0710864 A JPH0710864 A JP H0710864A JP 15563293 A JP15563293 A JP 15563293A JP 15563293 A JP15563293 A JP 15563293A JP H0710864 A JPH0710864 A JP H0710864A
- Authority
- JP
- Japan
- Prior art keywords
- furfurylthio
- acetic acid
- phenyl derivative
- derivative
- acid phenyl
- 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
Landscapes
- Furan Compounds (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、一般式（Ｉ）The present invention is of the general formula (I)
【０００２】[0002]
【化２】 [Chemical 2]
【０００３】（式中、Ｐｈはｏ−ニトロフェニル基、ｐ
−ニトロフェニル基または２，４−ジニトロフェニル基
を示す。）で表わされる２−（フルフリルチオ）酢酸フ
ェニル誘導体の精製方法に関するものである。(Wherein Ph is an o-nitrophenyl group, p is
Represents a -nitrophenyl group or a 2,4-dinitrophenyl group. The present invention relates to a method for purifying a 2- (furfurylthio) acetic acid phenyl derivative represented by
【０００４】上記の式（Ｉ）で表わされる２−（フルフ
リルチオ）酢酸フェニル誘導体は、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。The 2- (furfurylthio) acetic acid phenyl derivative represented by the above formula (I) 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】前記の式（Ｉ）で表わさ
れる２−（フルフリルチオ）酢酸フェニル誘導体は、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［特開平１−２３０５７６号公報］。2. Description of the Related Art The phenyl 2- (furfurylthio) acetate derivative represented by the above formula (I) is known as an intermediate for producing a drug, particularly an anti-peptic ulcer agent. 1-253076].
【０００６】本発明者らが前記の式（Ｉ）で表わされる
２−（フルフリルチオ）酢酸フェニル誘導体の製造方法
について、鋭意検討を行なった結果、２−（フルフリル
チオ）酢酸とニトロフェノール類とを塩基の存在下、塩
化チオニルを用いて反応させることにより容易に製造す
ることが可能であることを既に見出している。The present inventors have conducted extensive studies on the method for producing the phenyl derivative of 2- (furfurylthio) acetic acid represented by the above formula (I), and as a result, 2- (furfurylthio) acetic acid and nitrophenols are used as bases. It has already been found that it can be easily produced by reacting with thionyl chloride in the presence of.
【０００７】しかしながら、以上のようにして得られる
前記の式（Ｉ）で表わされる２−（フルフリルチオ）酢
酸フェニル誘導体は、若干のタール状副生物を伴ない、
黒褐色油状物もしくは粘土状となる。この回収物は、再
結晶精製に供しても結晶が析出し難いばかりでなく、同
時にタール状副生物も析出してしまうことから、再結晶
による精製は困難である。However, the 2- (furfurylthio) acetic acid phenyl derivative represented by the above formula (I) obtained as described above is accompanied by some tar-like by-products,
It becomes a blackish brown oil or clay. This recovered material is not only difficult to crystallize when subjected to recrystallization purification, but also tar-like by-products are precipitated at the same time, and therefore purification by recrystallization is difficult.
【０００８】[0008]
【問題点を解決するための手段】本発明者らは、かかる
問題点に鑑み、鋭意検討を行なった結果、２−（フルフ
リルチオ）酢酸フェニル誘導体を活性炭と接触させるこ
とにより、タール状副生物は活性炭に容易に吸着されて
除去され、２−（フルフリルチオ）酢酸フェニル誘導体
が高純度で得られることを見出し、本発明に到達した。[Means for Solving the Problems] The inventors of the present invention have made earnest studies in view of such problems, and as a result, by bringing a phenyl derivative of 2- (furfurylthio) acetate into contact with activated carbon, a tar-like by-product was produced. The present invention has been accomplished by finding that a phenyl 2- (furfurylthio) acetate derivative is easily adsorbed and removed by activated carbon to obtain a high purity.
【０００９】すなわち、本発明は、一般式（Ｉ）That is, the present invention has the general formula (I)
【００１０】[0010]
【化３】 [Chemical 3]
【００１１】（式中、Ｐｈはｏ−ニトロフェニル基、ｐ
−ニトロフェニル基または２，４−ジニトロフェニル基
を示す。）で表わされる２−（フルフリルチオ）酢酸フ
ェニル誘導体を活性炭と接触させることを特徴とする２
−（フルフリルチオ）酢酸フェニル誘導体の精製方法で
ある。(Wherein Ph is an o-nitrophenyl group, p
Represents a -nitrophenyl group or a 2,4-dinitrophenyl group. ) The phenyl derivative of 2- (furfurylthio) acetic acid represented by the formula (2) is brought into contact with activated carbon.
A method for purifying a phenyl derivative of (furfurylthio) acetic acid.
【００１２】本発明の前記の一般式（Ｉ）で表わされる
２−（フルフリルチオ）酢酸フェニル誘導体は、例え
ば、前述の本発明者らが見出した方法により製造するこ
とができる。すなわち、２−（フルフリルチオ）酢酸と
ｏ−ニトロフェノール、ｐ−ニトロフェノールまたは
２，４−ジニトロフェノールとをトリエチルアミン、ピ
リジンなどの塩基の存在下、塩化チオニルを用いて反応
させることにより容易に製造することが可能である。こ
の本発明の前記の一般式（Ｉ）で表わされる２−（フル
フリルチオ）酢酸フェニル誘導体を具体的に示すと、２
−（フルフリルチオ）酢酸−ｐ−ニトロフェニル、２−
（フルフリルチオ）酢酸−ｏ−ニトロフェニルおよび２
−（フルフリルチオ）酢酸−２’，４’−ジニトロフェ
ニルである。The 2- (furfurylthio) acetic acid phenyl derivative represented by the general formula (I) of the present invention can be produced, for example, by the method found by the present inventors. That is, it is easily produced by reacting 2- (furfurylthio) acetic acid with o-nitrophenol, p-nitrophenol or 2,4-dinitrophenol in the presence of a base such as triethylamine or pyridine using thionyl chloride. It is possible. Specific examples of the 2- (furfurylthio) acetic acid phenyl derivative represented by the above general formula (I) of the present invention are 2
-(Furfurylthio) acetic acid-p-nitrophenyl, 2-
(Furfurylthio) acetic acid-o-nitrophenyl and 2
-(Furfurylthio) acetic acid-2 ', 4'-dinitrophenyl.
【００１３】以上のようにして得られる前記の一般式
（Ｉ）で表わされる２−（フルフリルチオ）酢酸フェニ
ル誘導体は、常法の後処理により回収される。この回収
物は、若干のタール状副生物を伴ない、黒褐色油状物も
しくは粘土状であるが、これを活性炭と接触させること
により、タール状副生物は容易に活性炭に吸着、除去さ
れ、２−（フルフリルチオ）酢酸フェニル誘導体を高純
度の淡黄色結晶として得ることができる。The phenyl 2- (furfurylthio) acetate derivative represented by the above general formula (I) obtained as described above is recovered by a usual post-treatment. This recovered product is a blackish brown oily substance or clay-like substance with some tar-like by-products, but by contacting it with activated carbon, the tar-like by-products are easily adsorbed on and removed from the activated carbon. A (furfurylthio) acetic acid phenyl derivative can be obtained as highly pure pale yellow crystals.
【００１４】本発明で使用される活性炭の種類として
は、特に限定はなく、石炭系、植物系、石油系など一般
に用いられているものを広く使用することができる。ま
た、活性炭の形状としては、粉状、ペレット状、球状、
破砕状などがあるが、特に限定はなく、どのような形状
のものを用いてもよいが、処理速度の点から考えると表
面積の大きなほうがよく、最も好ましいのは粉状であ
る。また、活性炭の使用量は、特に限定はないが、処理
される前記の一般式（Ｉ）で表わされる２−（フルフリ
ルチオ）酢酸フェニル誘導体に対して５ｗｔ％〜３０ｗ
ｔ％とするのが好ましい。５ｗｔ％より少ないと充分に
精製されないため、好ましくない。また、３０ｗｔ％よ
り多く使用しても効果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。The type of activated carbon used in the present invention is not particularly limited, and widely used ones such as coal type, plant type and petroleum type can be widely used. The shape of the activated carbon is powder, pellet, spherical,
There is no particular limitation, but there is no particular limitation, and any shape may be used, but from the viewpoint of processing speed, the larger the surface area is, the more preferable is the powder. The amount of activated carbon used is not particularly limited, but is 5 wt% to 30 w with respect to the treated 2- (furfurylthio) acetic acid phenyl derivative represented by the general formula (I).
It is preferably t%. If it is less than 5% by weight, it will not be sufficiently purified, which is not preferable. In addition, the use of more than 30 wt% does not change the effect so much and is economically disadvantageous, which is not preferable.
【００１５】また、前記の一般式（Ｉ）で表わされる２
−（フルフリルチオ）酢酸フェニル誘導体と活性炭の接
触は、溶媒中で行なう必要があるが、使用される溶媒と
しては、特に限定はなく、例えば、塩化メチレン、四塩
化炭素、１，２−ジクロロエタン（ＥＤＣ）などのハロ
ゲン化炭化水素類、ジエチルエーテルなどのエーテル
類、ベンゼン、トルエンなどの芳香族炭化水素類などを
使用することができる。Further, 2 represented by the above general formula (I)
The contact between the phenyl (-furfurylthio) acetate derivative and activated carbon needs to be carried out in a solvent, but the solvent used is not particularly limited, and examples thereof include methylene chloride, carbon tetrachloride, and 1,2-dichloroethane (EDC). ) And other halogenated hydrocarbons, diethyl ether and other ethers, benzene, toluene and other aromatic hydrocarbons, and the like.
【００１６】本発明における処理方法としては、バッチ
式処理、連続処理などいかなる方法を用いてもよい。バ
ッチ式処理は、粗生成物を含む溶媒中に活性炭を加え、
攪拌して副生物を吸着させた後、活性炭を除去し、溶媒
を留去することにより前記の一般式（Ｉ）で表わされる
２−（フルフリルチオ）酢酸フェニル誘導体を得る方法
である。また、連続処理は、粗生成物を含む溶媒を活性
炭を充填した充填塔中を通過させて副生物を吸着させた
後、溶媒を留去することにより前記の一般式（Ｉ）で表
わされる２−（フルフリルチオ）酢酸フェニル誘導体を
得る方法である。As the treatment method in the present invention, any method such as batch treatment or continuous treatment may be used. Batchwise processing involves adding activated carbon to a solvent containing the crude product,
This is a method of obtaining a 2- (furfurylthio) acetic acid phenyl derivative represented by the above general formula (I) by stirring, adsorbing a by-product, removing activated carbon, and distilling off the solvent. In the continuous treatment, the solvent containing the crude product is passed through a packed column filled with activated carbon to adsorb a by-product, and then the solvent is distilled off to obtain the compound represented by the above general formula (I) 2 A method for obtaining a phenyl derivative of-(furfurylthio) acetic acid.
【００１７】また、本発明方法における処理温度は、特
に限定はないが、室温程度で充分に精製されるため、操
作性などを考慮すると室温で処理するのが好ましい。The treatment temperature in the method of the present invention is not particularly limited, but since it is sufficiently purified at about room temperature, it is preferable to perform the treatment at room temperature in consideration of operability and the like.
【００１８】[0018]
【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。参考例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. Reference Example 1 Production of methyl 2- (furfurylthio) acetate
【００１９】[0019]
【化４】 [Chemical 4]
【００２０】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）およびポリエチレングリコール−１０
００（ＰＥＧ−１０００）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。Furfuryl mercaptan 11.40 g
(0.1 mol), methyl chloroacetate 10.85 g
(0.1 mol) and polyethylene glycol-10
00 (PEG-1000) 0.11 g toluene 34.
It melt | dissolved in 2 g, 13.82 g of anhydrous potassium carbonate was added, and it stirred at 95 degreeC for 5 hours.
【００２１】冷却後、吸引濾過をすることにより塩を除
去し、溶媒を留去することにより褐色油状物１９．４７
ｇ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, the salt was removed by suction filtration, and the solvent was distilled off to obtain a brown oily substance (19.47).
g was recovered. This was distilled under reduced pressure to obtain methyl 2- (furfurylthio) acetate as a colorless oily substance.
【００２２】収量１６．２１ｇ 収率８７．２％ ｂ．ｐ．１３８℃／１７ｍｍＨｇ ＧＬＣ Ｐｕ．９９．３２％参考例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８．５５ｇ（０．０７５ｍｏ
ｌ）、クロロ酢酸メチル８．１４ｇ（０．０７５ｍｏ
ｌ）および１８−クラウン−６−エーテル０．０３ｇを
トルエン１００ｍｌに溶解し、無水炭酸カリウム１０．
３７ｇを添加し、９５℃で７時間攪拌後、冷却した。こ
のときの有機物組成をガスクロマトグラフィーで分析し
たところ、２−（フルフリルチオ）酢酸メチルは９６．
６９％であった。Yield 16.21 g Yield 87.2% b. p. 138 ° C./17 mmHg GLC Pu. 99.32% Reference Example 2 Preparation of methyl 2- (furfurylthio) acetate Furfuryl mercaptan 8.55 g (0.075 mo
l), 8.14 g of methyl chloroacetate (0.075 mo
1) and 0.03 g of 18-crown-6-ether are dissolved in 100 ml of toluene, and anhydrous potassium carbonate 10.
After adding 37 g and stirring at 95 degreeC for 7 hours, it cooled. When the organic composition at this time was analyzed by gas chromatography, methyl 2- (furfurylthio) acetate was found to be 96.
It was 69%.
【００２３】次に、水５０ｍｌを加えて塩を溶解した
後、分液してトルエン層を回収し、この回収トルエン層
をそのまま参考例４に供した。参考例３ ２−（フルフリルチオ）酢酸の製造 Next, 50 ml of water was added to dissolve the salt, followed by liquid separation to collect a toluene layer, and this recovered toluene layer was directly used in Reference Example 4. Reference Example 3 Production of 2- (furfurylthio) acetic acid
【００２４】[0024]
【化５】 [Chemical 5]
【００２５】２−（フルフリルチオ）酢酸メチル３４．
０ｇ（０．１８３ｍｏｌ）をトルエン１７．０ｇに溶解
し、氷冷下、１５％−ＮａＯＨ水溶液５８．７ｇ（０．
２２０ｍｏｌ）を徐々に滴下し、室温で２時間攪拌し
た。このときのトルエン層をガスクロマトグラフィーで
分析し、２−（フルフリルチオ）酢酸メチルのピークが
消失したことを確認した。Methyl 2- (furfurylthio) acetate 34.
0 g (0.183 mol) was dissolved in 17.0 g of toluene, and 58.7 g (0.
(220 mol) was gradually added dropwise, and the mixture was stirred at room temperature for 2 hours. The toluene layer at this time was analyzed by gas chromatography, and it was confirmed that the peak of methyl 2- (furfurylthio) acetate disappeared.
【００２６】次に、分液して水層を回収し、氷冷下、こ
の水層に１０％−ＨＣｌ水溶液１３３．４ｇを滴下し、
中和酸性とした。このとき、下層に油状物が析出し、こ
れを分液、回収後、さらに水層に塩化メチレン１０２ｇ
を加えて抽出し、塩化メチレン層を回収した。回収油状
物と回収塩化メチレン層を合わせ、飽和食塩水で洗浄
後、乾燥し、溶媒を留去することにより淡黄色油状物の
２−（フルフリルチオ）酢酸を得た。Next, liquid separation was carried out to collect the aqueous layer, and 133.4 g of a 10% HCl aqueous solution was added dropwise to this aqueous layer under ice cooling.
Neutralized acidic. At this time, an oily substance was precipitated in the lower layer, and after separating and collecting this, 102 g of methylene chloride was further added to the aqueous layer.
Was added for extraction, and the methylene chloride layer was collected. The recovered oily matter and the recovered methylene chloride layer were combined, washed with saturated saline and then dried, and the solvent was distilled off to obtain 2- (furfurylthio) acetic acid as a pale yellow oily matter.
【００２７】収量３１．０ｇ 収率９５．８％ ＧＬＣ Ｐｕ．９７．１７％参考例４ ２−（フルフリルチオ）酢酸の製造 参考例２で回収した２−（フルフリルチオ）酢酸メチル
を含むトルエン溶液に２０％−ＫＯＨ水溶液３０ｇを加
え、室温で５時間攪拌した。このときのトルエン層をガ
スクロマトグラフィーで分析し、２−（フルフリルチ
オ）酢酸メチルのピークが消失したことを確認した。Yield 31.0 g Yield 95.8% GLC Pu. 97.17% Reference Example 4 Production of 2- (furfurylthio) acetic acid To a toluene solution containing methyl 2- (furfurylthio) acetate recovered in Reference Example 2, 30 g of 20% -KOH aqueous solution was added, and the mixture was stirred at room temperature for 5 hours. The toluene layer at this time was analyzed by gas chromatography, and it was confirmed that the peak of methyl 2- (furfurylthio) acetate disappeared.
【００２８】次に、分液して水層を回収し、氷冷下、こ
の水層に１０％−ＨＣｌ水溶液１２５ｇを滴下し、中和
酸性とした後、析出した油状物を塩化メチレンで２回抽
出し、飽和食塩水で洗浄後、乾燥し、溶媒を留去するこ
とにより淡黄色油状物を回収した。さらに、減圧蒸留す
ることにより２−（フルフリルチオ）酢酸を得た。Next, the liquid layer was separated and the aqueous layer was recovered. 125 g of a 10% -HCl aqueous solution was added dropwise to the aqueous layer under ice cooling to neutralize and acidify. It was extracted twice, washed with saturated brine, dried, and the solvent was distilled off to recover a pale yellow oily substance. Further, 2- (furfurylthio) acetic acid was obtained by distillation under reduced pressure.
【００２９】収量９．７５ｇ 収率７５．６％ ｂ．ｐ．１４６〜１４７℃／３ｍｍＨｇ ＧＬＣ Ｐｕ．９９．３６％実施例１ ２−（フルフリルチオ）酢酸−ｐ−ニトロフェニルの製
造 Yield 9.75 g Yield 75.6% b. p. 146-147 ° C./3 mmHg GLC Pu. 99.36% Example 1 Preparation of 2- (furfurylthio) acetic acid-p-nitrophenyl
Construction
【００３０】[0030]
【化６】 [Chemical 6]
【００３１】参考例３で得た２−（フルフリルチオ）酢
酸３１．０ｇ（Ｐｕ．９７．１７％、０．１７５ｍｏ
ｌ）およびｐ−ニトロフェノール２５．４ｇ（０．１８
３ｍｏｌ）を塩化メチレン１５７ｇに溶解し、氷冷下、
ピリジン３１．８ｇ（０．４２０ｍｏｌ）を徐々に滴下
した。次に、氷冷下、塩化チオニル２２．９ｇ（０．１
９２ｍｏｌ）−塩化メチレン７８ｇの溶液を徐々に滴下
した。塩化チオニル溶液の滴下終了後、さらに１時間攪
拌を続けた。2- (Furfurylthio) acetic acid obtained in Reference Example 3 (31.0 g, Pu. 97.17%, 0.175 mo)
1) and 25.4 g of p-nitrophenol (0.18
3 mol) was dissolved in 157 g of methylene chloride, and under ice cooling,
31.8 g (0.420 mol) of pyridine was gradually added dropwise. Next, under ice cooling, 22.9 g (0.1% of thionyl chloride)
A solution of (92 mol) -methylene chloride (78 g) was gradually added dropwise. After the addition of the thionyl chloride solution was completed, stirring was continued for another hour.
【００３２】次に、冷水１００ｍｌを徐々に滴下し、過
剰の塩化チオニルを分解すると同時に洗浄した。次に１
０％−ＨＣｌ水溶液１０７ｇで洗浄後、１０％−Ｋ2Ｃ
Ｏ3水溶液５０ｇで２回洗浄し、さらに水１００ｍｌで
洗浄後、乾燥し、溶媒を留去することにより黒褐色粘土
状化合物を得た。Next, 100 ml of cold water was gradually added dropwise to decompose excess thionyl chloride and simultaneously wash. Then 1
After washing with 107 g of 0% -HCl aqueous solution, 10% -K 2 C
It was washed twice with 50 g of an O 3 aqueous solution, further washed with 100 ml of water, dried, and the solvent was distilled off to obtain a blackish brown clay-like compound.
【００３３】この回収物を再度、塩化メチレン２００ｇ
に溶解し、粉末活性炭１０ｇを加え、２時間攪拌後、濾
過して濾液を回収し、溶媒を留去することにより淡黄色
結晶の２−（フルフリルチオ）酢酸−ｐ−ニトロフェニ
ルを得た。This recovered product was again treated with 200 g of methylene chloride.
10 g of powdered activated carbon was added, and the mixture was stirred for 2 hours, filtered, and the filtrate was collected. The solvent was distilled off to give 2- (furfurylthio) acetic acid-p-nitrophenyl as pale yellow crystals.
【００３４】収量４０．９ｇ 収率７８．１％ ＨＰＬＣ Ｐｕ．９８．０％ 上記回収物を酢酸エチル−ｎ−ヘキサン（１：１）で再
結晶した。Yield 40.9 g Yield 78.1% HPLC Pu. 98.0% The recovered product was recrystallized from ethyl acetate-n-hexane (1: 1).
【００３５】ＨＰＬＣ Ｐｕ．９９．８％ ｍ．ｐ．６７．０〜６８．０℃HPLC Pu. 99.8% m. p. 67.0-68.0 ° C
【００３６】[0036]
【発明の効果】本発明の方法により、再結晶などの方法
では精製の困難であった２−（フルフリルチオ）酢酸フ
ェニル誘導体を容易に精製することができ、２−（フル
フリルチオ）酢酸フェニル誘導体を高純度の淡黄色結晶
として得ることができる。According to the method of the present invention, a 2- (furfurylthio) acetic acid phenyl derivative, which has been difficult to purify by a method such as recrystallization, can be easily purified, and the 2- (furfurylthio) acetic acid phenyl derivative can be highly purified. It can be obtained as pale yellow crystals of 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 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 Research Institute of Tokyo (72) Inventor Yoshiyuki Kikuchi 2805, Imafuku Nakadai, Kawagoe City, Saitama Prefecture Central Glass Tokyo Research Institute, Inc.
Claims (1)
ニル基または２，４−ジニトロフェニル基を示す。）で
表わされる２−（フルフリルチオ）酢酸フェニル誘導体
を活性炭と接触させることを特徴とする２−（フルフリ
ルチオ）酢酸フェニル誘導体の精製方法。1. A compound represented by the general formula (I): (In the formula, Ph represents an o-nitrophenyl group, a p-nitrophenyl group or a 2,4-dinitrophenyl group.) A phenyl derivative of 2- (furfurylthio) acetic acid is brought into contact with activated carbon. A method for purifying a 2- (furfurylthio) acetic acid phenyl derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5155632A JP3053715B2 (en) | 1993-06-25 | 1993-06-25 | Purification method of phenyl 2- (furfurylthio) acetate derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5155632A JP3053715B2 (en) | 1993-06-25 | 1993-06-25 | Purification method of phenyl 2- (furfurylthio) acetate derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710864A true JPH0710864A (en) | 1995-01-13 |
| JP3053715B2 JP3053715B2 (en) | 2000-06-19 |
Family
ID=15610233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5155632A Expired - Fee Related JP3053715B2 (en) | 1993-06-25 | 1993-06-25 | Purification method of phenyl 2- (furfurylthio) acetate derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3053715B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009098206A (en) * | 2007-10-12 | 2009-05-07 | Ulvac Seimaku Kk | Method of manufacturing gray tone mask, and gray tone mask |
-
1993
- 1993-06-25 JP JP5155632A patent/JP3053715B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009098206A (en) * | 2007-10-12 | 2009-05-07 | Ulvac Seimaku Kk | Method of manufacturing gray tone mask, and gray tone mask |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3053715B2 (en) | 2000-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3053715B2 (en) | Purification method of phenyl 2- (furfurylthio) acetate derivative | |
| JP3777408B2 (en) | Method for producing carboxylic acid derivative | |
| JP3053713B2 (en) | Method for producing 2- (furfurylthio) acetic acid | |
| JP3053714B2 (en) | Method for producing phenyl 2- (furfurylthio) acetate derivative | |
| JP3086738B2 (en) | Method for producing high-purity tocopheryl retinoate | |
| JPH0710862A (en) | Production of phenyl 2-(furfurylsulfinyl) acetate derivative and phenyl 2-(furfurylsulfonyl) acetate derivative | |
| JPH0720917B2 (en) | Nitrogen-containing perfluorocarboxylic acid optically active substance and method for producing the same | |
| JPS5822139B2 (en) | Optical resolution method of dl-2-(6-methoxy-2-naphthyl)-propionic acid | |
| JPH08319283A (en) | Purification of 2-(furfurylthio)acetic acid derivative | |
| JPH02215790A (en) | Recovery of hexamethyl disiloxane | |
| JPH0139420B2 (en) | ||
| JP3065199B2 (en) | Method for producing 2- (furfurylthio) acetic acid derivative | |
| US4288635A (en) | Method for the preparation of (E)-4-bromo-2-methylbut-2-en-1-al | |
| JPH0586000A (en) | Production of 2-amino-4-fluorobenzoic acid | |
| JP2614108B2 (en) | Method for producing sulfenyl oxime carbamate derivative | |
| JP3230723B2 (en) | Method for producing 2- (furfurylthio) acetic acid derivative | |
| JPH0315624B2 (en) | ||
| JPH0812658A (en) | Production of sydnones | |
| JP3171286B2 (en) | Method for producing high-purity amino olefins | |
| JPH11189566A (en) | Production of fluoroalkylcarboxylic acid | |
| JPS6338976B2 (en) | ||
| JPH05320102A (en) | Production of optically active alpha-(p-chlorophenyl) ethylamine and optically active alpha-(p-chlorophenyl) ethylamine-p-chloromandelic acid salt | |
| JPH08198843A (en) | Production of sulfenylacetic acid derivative | |
| JPH0235740B2 (en) | ||
| JPH023630A (en) | 2,6-diethyl-4-iodoaniline and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |