JPH0820569A - Method for purifying t-butyl cyanoacetate - Google Patents
Method for purifying t-butyl cyanoacetateInfo
- Publication number
- JPH0820569A JPH0820569A JP17490194A JP17490194A JPH0820569A JP H0820569 A JPH0820569 A JP H0820569A JP 17490194 A JP17490194 A JP 17490194A JP 17490194 A JP17490194 A JP 17490194A JP H0820569 A JPH0820569 A JP H0820569A
- Authority
- JP
- Japan
- Prior art keywords
- cyanoacetate
- butyl
- butyl cyanoacetate
- alkali
- purifying
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医農薬中間体および工
業製品中間体として用いられるシアノ酢酸ｔ−ブチルの
精製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying t-butyl cyanoacetate used as an intermediate for medicines and agricultural chemicals and an intermediate for industrial products.
【０００２】[0002]
【従来技術とその問題点】従来、シアノ酢酸ｔ−ブチル
の製造法としては、クロロ酢酸ｔ−ブチルとＮａＣＮ
あるいはＫＣＮを反応させる方法［ＤＥ１９５１０３
２；Ｈｅｌｖ．Ｃｈｉｍ．Ａｃｔａ．、４２、１２１
４、１２２２ （１９５９）；Ｊ．Ａｍ．Ｃｈｅｍ．Ｓ
ｏｃ．、６４、２２７４（１９４２）］、シアノアセ
チルハライドとｔ−ブタノールとＮ、Ｎ−ジメチルアニ
リンを反応させる方法［Ｊ．Ｃｈｅｍ．Ｓｏｃ．、（１
９５５） ４２３、４２６；Ｏｒｇ．Ｓｙｎｔｈ．、Ｃ
ｏｌｌ．Ｖｏｌ．５、１７１］およびクロロアセトニ
トリルとＣＯとｔ−ブタノールを反応させるアルコキシ
カルボニレーション法［ＤＥ２４０３４８３］などが知
られている。2. Description of the Related Art Conventionally, t-butyl chloroacetate and NaCN have been used as conventional methods for producing t-butyl cyanoacetate.
Alternatively, a method of reacting KCN [DE195103
2; Helv. Chim. Acta. , 42 , 121
4, 1222 (1959); Am. Chem. S
oc. , 64, 2274 (1942)], a method of reacting cyanoacetyl halide with t-butanol and N, N-dimethylaniline [J. Chem. Soc. , (1
955) 423, 426; Org. Synth. , C
ol. Vol. 5, 171] and an alkoxycarbonation method [DE2403483] in which chloroacetonitrile, CO and t-butanol are reacted with each other.
【０００３】しかしながらの方法では、原料のクロロ
酢酸ｔ−ブチルを入手するのが容易でなく、別途煩雑な
原料合成をしなくてはならない。さらには、反応に伴っ
て副生するＮａＣｌなどの廃棄物が多量に生じてしま
う。However, in the method, t-butyl chloroacetate as a raw material is not easily available, and a complicated and complicated raw material synthesis must be performed. Furthermore, a large amount of waste such as NaCl, which is a byproduct of the reaction, is generated.
【０００４】またでは、原料のシアノアセチルハライ
ドを得るための工程が必要であり、そのために腐蝕性の
高いＰＣｌ5 などを用いる必要があり、装置材質上の制
約が大きくなる。さらに、Ｎ、Ｎ−ジメチルアニリンを
シアノアセチルハライドと等量以上必要とし、反応の進
行に伴いその塩酸塩を副生し、多量の廃棄物を生じてし
まう。In addition, a step for obtaining the cyanoacetyl halide as a raw material is required, and therefore, it is necessary to use PCl 5 or the like, which has a high corrosiveness. Furthermore, N, N-dimethylaniline is required in an amount equal to or more than that of cyanoacetyl halide, and as the reaction progresses, its hydrochloride salt is by-produced to generate a large amount of waste.
【０００５】はＣＯを高圧で反応させなくてはなら
ず、設備的制約が生じる。以上のように、従来のシアノ
酢酸ｔ−ブチルを製造する方法は種々の欠点を有してい
る。[0005] CO has to react with CO at a high pressure, which causes equipment restrictions. As described above, the conventional method for producing t-butyl cyanoacetate has various drawbacks.
【０００６】本発明者らは、上述のような問題点を生じ
ることなく、容易に入手可能な原料から簡便な方法で合
理的にシアノ酢酸ｔ−ブチルを製造する方法として、一
般式ＮＣＣＨ2 ＣＯＯＲ1 （式中Ｒ1 は炭素数１〜３の
アルキル基を示す）で表わされる低級シアノ酢酸エステ
ルとｔ−ブチルアルコールを有機錫系触媒を用いて反応
させ、シアノ酢酸ｔ−ブチルとする方法を提供している
（特願平５−３４４４６６）。この方法を用いた場合、
不純物として未反応原料である一般式ＮＣＣＨ2 ＣＯＯ
Ｒ1 （式中Ｒ1 は炭素数１〜３のアルキル基を示す）で
表わされる低級シアノ酢酸エステルが反応液中に含まれ
るため、分離精製の必要が生じる。しかし、前記不純物
とシアノ酢酸ｔ−ブチルは沸点差が少ないため、蒸留操
作による精製は困難である。The present inventors have proposed a general formula NCCH 2 COOR as a method for rationally producing t-butyl cyanoacetate from a readily available raw material by a simple method without causing the above problems. 1 (wherein R 1 represents an alkyl group having 1 to 3 carbon atoms) and t-butyl alcohol are reacted with an organotin catalyst to obtain t-butyl cyanoacetate. It is provided (Japanese Patent Application No. 5-344466). Using this method,
General formula NCCH 2 COO which is an unreacted raw material as an impurity
Since R 1 to a lower cyanoacetate (wherein R 1 represents an alkyl group having 1 to 3 carbon atoms) represented by is contained in the reaction solution, it is necessary for separation and purification. However, since the impurities and t-butyl cyanoacetate have a small difference in boiling points, purification by distillation is difficult.
【０００７】また、カラムクロマトグラフィーにかけて
精製する方法も考えられるが、溶剤、充填剤を多量に使
用するためコストがかかり工業的利用価値に乏しい。Further, a method of purifying by column chromatography can be considered, but since it uses a large amount of a solvent and a filler, it is costly and has little industrial utility value.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、上述
のような問題点を生じることなく、高純度のシアノ酢酸
ｔ−ブチルを効率よく得るための方法を提供することに
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently obtaining highly pure t-butyl cyanoacetate without causing the above problems.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意検討したところ、一般式ＮＣＣＨ
2 ＣＯＯＲ1 （式中Ｒ1 は炭素数１〜３のアルキル基を
示す）で表わされる低級シアノ酢酸エステルを不純物と
して含有する粗シアノ酢酸ｔ−ブチルをアルカリ水溶液
で処理することにより、低級シアノ酢酸エステルが選択
的に加水分解されてシアノ酢酸塩となり、分液、抽出、
蒸留等の簡便な分離操作により、高純度のシアノ酢酸ｔ
−ブチルが得られることを見出して本発明に到達した。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object and found that the general formula NCCH
2 COOR 1 (wherein R 1 represents an alkyl group having 1 to 3 carbon atoms) is used to treat a crude t-butyl cyanoacetate containing a lower cyanoacetate ester as an impurity with an aqueous alkaline solution to obtain a lower cyanoacetate. The ester is selectively hydrolyzed to the cyanoacetate salt for liquid separation, extraction,
Highly pure cyanoacetic acid t can be obtained by a simple separation operation such as distillation.
The present invention has been reached by finding that -butyl can be obtained.
【００１０】すなわち、本発明は、一般式ＮＣＣＨ2 Ｃ
ＯＯＲ1 （式中Ｒ1 は炭素数１〜３のアルキル基を示
す）で表わされる低級シアノ酢酸エステルを不純物とし
て含有する粗シアノ酢酸ｔ−ブチルをアルカリ水溶液で
処理することを特徴とするシアノ酢酸ｔ−ブチルの精製
法に関する。That is, the present invention has the general formula NCCH 2 C
Crude t-butyl cyanoacetate containing a lower cyanoacetate represented by OOR 1 (wherein R 1 represents an alkyl group having 1 to 3 carbon atoms) as an impurity is treated with an aqueous alkaline solution. It relates to a method for purifying t-butyl.
【００１１】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【００１２】本発明に用いるアルカリは、水溶液中でア
ルカリ性を示すものであれば、有機化合物、無機化合物
を問わず、如何なるものでも用いられるが、好ましくは
Ｌｉ，Ｎａ，Ｋ，Ｒｂ等のアルカリ金属の水酸化物や炭
酸塩、Ｂｅ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ等のアルカリ土類
金属の水酸化物や炭酸塩、アンモニア、炭酸アンモニウ
ム塩、特に好ましくは、Ｌｉ，Ｎａ，Ｋ，Ｒｂ等のアル
カリ金属の水酸化物や炭酸塩、アンモニアを挙げること
ができる。The alkali used in the present invention may be any one, whether it is an organic compound or an inorganic compound, as long as it exhibits alkalinity in an aqueous solution, but alkali metals such as Li, Na, K and Rb are preferred. Hydroxides and carbonates, hydroxides and carbonates of alkaline earth metals such as Be, Mg, Ca, Sr and Ba, ammonia and ammonium carbonate, and particularly preferably Li, Na, K and Rb. Examples thereof include alkali metal hydroxides, carbonates, and ammonia.
【００１３】本発明の実施にあたり、上記アルカリの使
用量は、不純物である一般式ＮＣＣＨ2 ＣＯＯＲ1 （式
中Ｒ1 は炭素数１〜３のアルキル基を示す）で表わされ
る低級シアノ酢酸エステルに対して０．４〜１０モル
％、好ましくは０．６〜２．０モル％、特に好ましくは
０．８〜１．２モル％である。In the practice of the present invention, the amount of the alkali used is the lower cyanoacetic acid ester represented by the general formula NCCH 2 COOR 1 (wherein R 1 represents an alkyl group having 1 to 3 carbon atoms) as an impurity. On the other hand, it is 0.4 to 10 mol%, preferably 0.6 to 2.0 mol%, and particularly preferably 0.8 to 1.2 mol%.
【００１４】アルカリ水溶液の濃度は０．１〜４０ｗｔ
％、好ましくは０．３〜２５ｗｔ％、特に好ましくは、
０．５〜１０ｗｔ％の範囲である。The concentration of the alkaline aqueous solution is 0.1 to 40 wt.
%, Preferably 0.3 to 25 wt%, particularly preferably,
It is in the range of 0.5 to 10 wt%.
【００１５】処理温度は０〜１００℃、好ましくは２０
〜８０℃である。The processing temperature is 0 to 100 ° C., preferably 20.
~ 80 ° C.
【００１６】処理時間は、不純物量、アルカリ濃度、処
理温度等により変動するが、通常１時間以内である。The treatment time varies depending on the amount of impurities, alkali concentration, treatment temperature, etc., but is usually within 1 hour.
【００１７】アルカリ水溶液処理時には溶媒を使用して
も差し支えない。用いられる溶媒の種類としては、エ−
テル類、ケトン類、酢酸エチル、クロロホルム、四塩化
炭素、塩化メチレン、ベンゼン、トルエン、キシレン、
ヘキサン等が挙げられる。A solvent may be used during the treatment with the alkaline aqueous solution. The type of solvent used is
Tells, ketones, ethyl acetate, chloroform, carbon tetrachloride, methylene chloride, benzene, toluene, xylene,
Hexane and the like can be mentioned.
【００１８】本発明の一般的実施様態について説明する
と、温度計、滴下漏斗を備えた反応器に不純物を含む粗
シアノ酢酸ｔ−ブチルを仕込み撹拌しながらアルカリ水
溶液を滴下し、反応させる。To explain the general embodiment of the present invention, crude t-butyl cyanoacetate containing impurities is charged into a reactor equipped with a thermometer and a dropping funnel, and an aqueous alkali solution is added dropwise with stirring to react.
【００１９】反応後、反応液を分液し、有機層を分離、
減圧蒸留することにより、目的物であるシアノ酢酸ｔ−
ブチルを留出させ取得することができる。After the reaction, the reaction solution is separated to separate the organic layer,
By distilling under reduced pressure, t-
Butyl can be distilled and obtained.
【００２０】分液時、シアノ酢酸ｔ−ブチルは上層に分
離するが、水層へのロスを少なくするためには抽剤を使
用しても差し支えない。用いられる溶媒の種類として
は、エ−テル類、ケトン類、酢酸エチル、クロロホル
ム、四塩化炭素、塩化メチレン、ベンゼン、トルエン、
キシレン、ヘキサン等が挙げられる。At the time of liquid separation, t-butyl cyanoacetate is separated into the upper layer, but an extractant may be used to reduce loss to the aqueous layer. Examples of the solvent used include ethers, ketones, ethyl acetate, chloroform, carbon tetrachloride, methylene chloride, benzene, toluene,
Examples include xylene and hexane.
【００２１】また、アルカリ水溶液処理後、分液操作を
行なわずに水を留出させた後、シアノ酢酸ｔ−ブチルを
留出させ取得することもできる。また、水を留出した後
に、シアノ酢酸塩の結晶が析出するため、濾過によりこ
れを除去してから蒸留しても良い。Further, after the treatment with the alkaline aqueous solution, water can be distilled off without performing a liquid separation operation, and then t-butyl cyanoacetate can be distilled off to obtain. Further, crystals of a cyanoacetate salt are precipitated after distilling out water, and thus the crystals may be removed by filtration and then distilled.
【００２２】[0022]
【実施例】次に、実施例により本発明をさらに具体的に
説明するが、本発明はこれら実施例に何ら限定されるも
のでない。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２３】実施例１ 撹拌器、温度計および滴下漏斗を備えたフラスコに、不
純物としてシアノ酢酸メチルを２６ｗｔ％含む粗シアノ
酢酸ｔ−ブチル３０ｇを加えた。温度４０℃にて２．５
ｗｔ％ＮａＯＨ水溶液１２７ｇ（対シアノ酢酸メチル１
モル％）を５分間かけて滴下した後、５分間撹拌した。
抽剤として塩化メチレンを加えて有機相を抜き出し、減
圧蒸留を行なって、精シアノ酢酸ｔ−ブチル２１．８ｇ
を回収した。ガスクロマトグラフィーで分析した結果、
純度９９．８％、回収率９８％であった。Example 1 To a flask equipped with a stirrer, a thermometer and a dropping funnel was added 30 g of crude t-butyl cyanoacetate containing 26 wt% of methyl cyanoacetate as an impurity. 2.5 at a temperature of 40 ° C
127 wt% NaOH aqueous solution (vs. methyl cyanoacetate 1
(Mol%) was added dropwise over 5 minutes and then stirred for 5 minutes.
Methylene chloride was added as an extractant, the organic phase was extracted, and distilled under reduced pressure to obtain 21.8 g of purified t-butyl cyanoacetate.
Was recovered. As a result of analysis by gas chromatography,
The purity was 99.8% and the recovery rate was 98%.
【００２４】実施例２ 不純物としてシアノ酢酸エチルを２６ｗｔ％含む粗シア
ノ酢酸ｔ−ブチル３０ｇを用いた以外は実施例１と同様
の操作で精製した。ガスクロマトグラフィーで分析した
結果、純度９９．８％、回収率９５％であった。Example 2 Purification was carried out in the same manner as in Example 1 except that 30 g of crude t-butyl cyanoacetate containing 26 wt% of ethyl cyanoacetate was used as an impurity. As a result of analysis by gas chromatography, the purity was 99.8% and the recovery rate was 95%.
【００２５】実施例３〜６ アルカリ、温度を下記のように変えた以外は実施例１と
同様の操作で精製した。アルカリ水溶液はすべて２．５
ｗｔ％の濃度で用いた。結果を表１に示す。Examples 3 to 6 Purification was carried out in the same manner as in Example 1 except that the alkali and temperature were changed as follows. 2.5 for all alkaline solutions
Used at a concentration of wt%. The results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例７ 不純物としてシアノ酢酸イソプロピル１８ｗｔ％を含む
粗シアノ酢酸ｔ−ブチル３０ｇを用い、抽剤としての塩
化メチレンを用いずに分液した以外は実施例１と同様に
操作した結果、純度９９．８％、回収率９０％で精シア
ノ酢酸ｔ−ブチルを得た。Example 7 The same operation as in Example 1 was carried out except that 30 g of crude t-butyl cyanoacetate containing 18 wt% of isopropyl cyanoacetate was used as an impurity and liquid separation was performed without using methylene chloride as an extractant. Pure t-butyl cyanoacetate was obtained with a purity of 99.8% and a recovery rate of 90%.
【００２８】実施例８〜１１ 不純物としてシアノ酢酸メチルを下記の量含む粗シアノ
酢酸ｔ−ブチル３０ｇを用いた以外は実施例１と同様の
操作で精製した。結果を表２に示す。Examples 8 to 11 Purification was carried out in the same manner as in Example 1 except that 30 g of crude t-butyl cyanoacetate containing the following amount of methyl cyanoacetate was used as an impurity. Table 2 shows the results.
【００２９】[0029]
【表２】 [Table 2]
【００３０】実施例１２〜１５ アルカリ濃度を下記のように変化させた以外は実施例１
と同様の操作で精製した。結果を表３に示す。Examples 12 to 15 Example 1 except that the alkali concentration was changed as follows.
It refine | purified by the operation similar to. The results are shown in Table 3.
【００３１】[0031]
【表３】 [Table 3]
【００３２】実施例１６〜１７ 処理温度を下記のように変化させた以外は、実施例１と
同様の操作で精製した。結果を表４に示す。Examples 16 to 17 Purification was carried out in the same manner as in Example 1 except that the treatment temperature was changed as follows. The results are shown in Table 4.
【００３３】[0033]
【表４】 [Table 4]
【００３４】[0034]
【発明の効果】本発明により、安価で入手容易な原料で
ある低級シアノ酢酸エステルとｔ−ブチルアルコールの
エステル交換反応により得られた未反応の低級シアノ酢
酸エステルを含むシアノ酢酸ｔ−ブチルの反応液から、
高純度のシアノ酢酸ｔ−ブチルを高収率で、また簡便な
操作および装置で取得することができる。INDUSTRIAL APPLICABILITY According to the present invention, the reaction of t-butyl cyanoacetate containing unreacted lower cyanoacetate obtained by transesterification of lower cyanoacetate which is an inexpensive and easily available raw material with t-butyl alcohol From the liquid
High-purity t-butyl cyanoacetate can be obtained in high yield and with simple operation and equipment.
Claims (2)
炭素数１〜３のアルキル基を示す）で表わされる低級シ
アノ酢酸エステルを不純物として含有する粗シアノ酢酸
ｔ−ブチルをアルカリ水溶液で処理することを特徴とす
るシアノ酢酸ｔ−ブチルの精製法。1. A crude t-butyl cyanoacetate containing a lower cyanoacetate represented by the general formula NCCH 2 COOR 1 (wherein R 1 represents an alkyl group having 1 to 3 carbon atoms) as an impurity in an aqueous alkaline solution. A method for purifying t-butyl cyanoacetate, which comprises treating.
カリ金属炭酸塩およびアンモニアから選ばれた少なくと
も１種である請求項１記載の精製法。2. The purification method according to claim 1, wherein the alkali is at least one selected from alkali metal hydroxides, alkali metal carbonates and ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17490194A JP3556275B2 (en) | 1994-07-05 | 1994-07-05 | Purification method of t-butyl cyanoacetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17490194A JP3556275B2 (en) | 1994-07-05 | 1994-07-05 | Purification method of t-butyl cyanoacetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0820569A true JPH0820569A (en) | 1996-01-23 |
| JP3556275B2 JP3556275B2 (en) | 2004-08-18 |
Family
ID=15986677
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17490194A Expired - Fee Related JP3556275B2 (en) | 1994-07-05 | 1994-07-05 | Purification method of t-butyl cyanoacetate |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645843A (en) * | 2020-12-25 | 2021-04-13 | 复旦大学 | Synthesis method of tert-butyl cyanoacetate |
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1994
- 1994-07-05 JP JP17490194A patent/JP3556275B2/en not_active Expired - Fee Related
Cited By (1)
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| CN112645843A (en) * | 2020-12-25 | 2021-04-13 | 复旦大学 | Synthesis method of tert-butyl cyanoacetate |
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