JPH08143528A - Production of lower alkyl 2-cyano-3-methyl-2-butenoate - Google Patents
Production of lower alkyl 2-cyano-3-methyl-2-butenoateInfo
- Publication number
- JPH08143528A JPH08143528A JP6279534A JP27953494A JPH08143528A JP H08143528 A JPH08143528 A JP H08143528A JP 6279534 A JP6279534 A JP 6279534A JP 27953494 A JP27953494 A JP 27953494A JP H08143528 A JPH08143528 A JP H08143528A
- Authority
- JP
- Japan
- Prior art keywords
- lower alkyl
- methyl
- cyano
- acid
- alkyl ester
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は植物病害防除剤の製造中
間体等として有用な２−シアノ−３−メチル−２−ブテ
ン酸の低級アルキルエステルの製造法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid, which is useful as an intermediate for producing plant disease controlling agents.
【従来の技術および発明が解決しようとする課題】Ｎ−
〔１−（2,４−ジクロロフェニル）エチル〕−２−シア
ノ−3,３−ジメチルブタンアミド等が優れた植物病害防
除効力を有することは、特開平２−７６８４６号公報に
記載されており、該化合物の工業的にも有利な製造法が
望まれていた。PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION N-
The fact that [1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide and the like have excellent plant disease control effect is described in JP-A-2-76846. An industrially advantageous method for producing the compound has been desired.
【０００２】[0002]
【課題を解決するための手段】本発明者らは上記状況に
鑑み、Ｎ−〔１−（2,４−ジクロロフェニル）エチル〕
−２−シアノ−3,３−ジメチルブタンアミド等に導くこ
とのできる２−シアノ−３−メチル−２−ブテン酸の低
級アルキルエステルを工業的にも有利に製造する方法に
ついて鋭意検討した結果、、アセトンとシアノ酢酸の低
級アルキルエステルとを触媒の存在下、ｎ−ヘキサン
（ノルマルヘキサン）を主溶媒として反応させることに
より、２−シアノ−３−メチル−２−ブテン酸の低級ア
ルキルエステルが高収率で得られることを見い出し、本
発明を完成した。すなわち、本発明は、アセトンとシア
ノ酢酸の低級アルキルエステルとを、触媒の存在下、ｎ
−ヘキサンを主溶媒として反応させることを特徴とす
る、２−シアノ−３−メチル−２−ブテン酸の低級アル
キルエステルの製造法を提供する。SUMMARY OF THE INVENTION In view of the above situation, the present inventors have developed N- [1- (2,4-dichlorophenyl) ethyl]
As a result of diligent study on a method for industrially advantageously producing a lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid, which can lead to 2-cyano-3,3-dimethylbutanamide and the like, , Acetone and a lower alkyl ester of cyanoacetic acid are reacted with n-hexane (normal hexane) as a main solvent in the presence of a catalyst, whereby a lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid is increased. The present invention has been completed by finding that the yield can be obtained. That is, in the present invention, acetone and a lower alkyl ester of cyanoacetic acid are added in the presence of a catalyst,
A method for producing a lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid, which comprises reacting -hexane as a main solvent.
【０００３】以下、本発明を詳細に説明する。本発明で
用いられるシアノ酢酸の低級（例えばＣ1 〜Ｃ4 ）アル
キルエステルとしては、例えばシアノ酢酸メチル、シア
ノ酢酸エチル、シアノ酢酸ｎ−プロピル、シアノ酢酸イ
ソプロピル、シアノ酢酸ｎ−ブチル、シアノ酢酸イソブ
チル等があげられ、これらは市販されているものを用い
るか、または、常法により製造することができる。本発
明において、触媒としては、通常、置換されていてもよ
いアニリンおよびカルボン酸が用いられる。置換されて
いてもよいアニリンにおける置換基としては、例えば、
水酸基、メチル基、メトキシ基等があげられ、置換され
ていてもよいアニリンの例としては、アミノフェノール
（ｐ−アミノフェノール、ｏ−アミノフェノール、ｍ−
アミノフェノール等）、トルイジン（ｐ−トルイジン、
ｏ−トルイジン、ｍ−トルイジン）があげられる。カル
ボン酸の例としては、例えば、低級（例えばＣ1 〜
Ｃ4 ）脂肪酸（例えば、酢酸、蟻酸、プロピオン酸等）
や安息香酸があげられる。反応溶媒としてはｎ−ヘキサ
ンを主溶媒として用い、より具体的にはｎ−ヘキサンの
全溶媒に対する使用割合は通常５０〜１００重量％であ
り、ｎ−ヘキサンと混合して用いることのできる反応溶
媒としては、例えば、トルエン、キシレンなどの芳香族
炭化水素溶媒等があげられる。反応温度は通常５０〜１
００℃、反応時間は通常５〜２０時間であり、反応は通
常反応中に生成する水を除きながら行う。反応に用いら
れる反応剤の量は、シアノ酢酸の低級アルキルエステル
１モルに対し、アセトンは通常１から４モルの割合、触
媒は通常0.001 〜0.２モルの割合（置換されていてもよ
いアニリンは通常0.001 から0.１モルの割合；カルボン
酸は通常0.01から0.２モルの割合）である。反応後の反
応液は通常、減圧または常圧下で濃縮し、そのまま蒸留
するか、酢酸エチル、トルエン、キシレン等の溶媒に溶
かして水洗し、その溶液を減圧濃縮して溶媒を除き、必
要ならばさらに蒸留等の精製操作を行うことにより、目
的とする２−シアノ−３−メチル−２−ブテン酸の低級
アルキルエステルを単離することが出来る。The present invention will be described in detail below. Examples of the lower (eg, C 1 -C 4 ) alkyl ester of cyanoacetic acid used in the present invention include methyl cyanoacetate, ethyl cyanoacetate, n-propyl cyanoacetate, isopropyl cyanoacetate, n-butyl cyanoacetate, isobutyl cyanoacetate. Etc., which are commercially available or can be produced by a conventional method. In the present invention, as the catalyst, aniline and carboxylic acid which may be substituted are usually used. Examples of the substituent in the optionally substituted aniline include, for example,
Examples of the aniline which may be substituted include a hydroxyl group, a methyl group, a methoxy group, and the like, and aminophenol (p-aminophenol, o-aminophenol, m-
Aminophenol, etc.), toluidine (p-toluidine,
and o-toluidine and m-toluidine). Examples of the carboxylic acid include, for example, lower (for example, C 1 to
C 4 ) fatty acid (eg, acetic acid, formic acid, propionic acid, etc.)
And benzoic acid. As the reaction solvent, n-hexane is used as a main solvent, and more specifically, the ratio of n-hexane to the total solvent is usually 50 to 100% by weight, and the reaction solvent can be used by mixing with n-hexane. Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene. Reaction temperature is usually 50 to 1
The reaction time is usually 5 to 20 hours at 00 ° C., and the reaction is usually carried out while removing water produced during the reaction. The amount of the reactant used in the reaction is usually 1 to 4 mol of acetone, and 0.001 to 0.2 mol of the catalyst for 1 mol of the lower alkyl ester of cyanoacetic acid (aniline which may be substituted). Is usually 0.001 to 0.1 mol; carboxylic acid is usually 0.01 to 0.2 mol). The reaction solution after the reaction is usually concentrated under reduced pressure or atmospheric pressure and distilled as it is, or dissolved in a solvent such as ethyl acetate, toluene, xylene and washed with water, and the solution is concentrated under reduced pressure to remove the solvent, and if necessary. Further, the desired lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid can be isolated by performing a purification operation such as distillation.
【０００４】本発明の製造法により得られる２−シアノ
−３−メチル−２−ブテン酸の低級（例えばＣ1 〜
Ｃ4 ）アルキルエステルとしては、例えば２−シアノ−
３−メチル−２−ブテン酸メチル、２−シアノ−３−メ
チル−２−ブテン酸エチル、２−シアノ−３−メチル−
２−ブテン酸ｎ−プロピル、２−シアノ−３−メチル−
２−ブテン酸イソプロピル、２−シアノ−３−メチル−
２−ブテン酸ｎ−ブチル、２−シアノ−３−メチル−２
−ブテン酸イソブチル等があげられる。本発明の製造法
により得られる２−シアノ−３−メチル−２−ブテン酸
の低級アルキルエステルは、例えば、Ｊ．Ａｍ．Ｃｈｅ
ｍ．Ｓｏｃ．７２，４７９１（１９５０）および特開平
２−７６８４６号公報に記載の方法等により、該公報等
に記載される、優れた植物病害防除効力を有するＮ−
〔１−（２，４−ジクロロフェニル）エチル〕−２−シ
アノ−３，３−ジメチルブタンアミド等に導くことがで
きる。The lower 2-cyano-3-methyl-2-butenoic acid (eg, C 1
Examples of the C 4 ) alkyl ester include 2-cyano-
Methyl 3-methyl-2-butenoate, ethyl 2-cyano-3-methyl-2-butenoate, 2-cyano-3-methyl-
N-Propyl 2-butenoate, 2-cyano-3-methyl-
Isopropyl 2-butenoate, 2-cyano-3-methyl-
N-Butyl 2-butenoate, 2-cyano-3-methyl-2
-Examples include isobutyl butenoate. The lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid obtained by the production method of the present invention is described in, for example, J. Am. Che
m. Soc. 72 , 4791 (1950) and the method described in Japanese Patent Application Laid-Open No. 2-76846, which has an excellent plant disease control effect described in the publication and the like.
It can be led to [1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide and the like.
【０００５】[0005]
【実施例】以下、本発明を実施例にてさらに詳細に説明
するが、本発明はこれらの例のみに限定されるものでは
ない。尚、反応率は次式により求めた値である。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The reaction rate is a value calculated by the following equation.
【数１】 反応率 ＝ １００ − 残存する原料のシアノ酢酸の低級アルキルエステルの （％） ＧＣ面積比率（％） ガスクロマトグラフイ ー（ＧＣ）の分析条件； 島津ＧＣ−７Ａ、 カラム：１０％ＤＥＸＳＩＬ ３００ＧＣ 直径３ｍｍ
× 長さ１ｍ ＵＮＩＰＯＲＴ ＨＰ １００〜２００ｍｅｓｈ カラム温度：７０〜１５０℃へ５℃／分の割合で昇温 実施例１ シアノ酢酸エチル５0.０ｇ、アセトン５1.３４ｇ、酢酸
1.９９ｇ、ｐ−アミノフェノール0.２４ｇおよびｎ−ヘ
キサン４１mlを仕込み、反応中生成する水を共沸で除き
ながら９時間加熱還流した。ガスクロマトグラフィーで
分析したところ、シアノ酢酸エチルの反応率は９９％で
あった。反応終了後の反応液を減圧濃縮してヘキサン、
酢酸および未反応のアセトンを除いた後、残渣をそのま
ま２０mmHgの減圧下にヘリコイルを充填した３０cmの精
留塔を用いて精留し、１１０〜１１３℃のフラクション
を分取した。蒸留後の２−シアノ−３−メチル−２−ブ
テン酸エチルの収量は６3.６ｇ、収率は９４％であっ
た。## EQU1 ## Reaction rate = 100-(%) residual lower alkyl ester of cyanoacetic acid as raw material GC area ratio (%) Gas chromatographic (GC) analysis conditions; Shimadzu GC-7A, column: 10% DEXSIL 300GC diameter 3mm
× Length 1 m UNIPORT HP 100-200 mesh Column temperature: Temperature rising to 70-150 ° C. at a rate of 5 ° C./min Example 1 Ethyl cyanoacetate 50.0 g, acetone 51.34 g, acetic acid
1.99 g, p-aminophenol 0.24 g and n-hexane 41 ml were charged, and the mixture was heated under reflux for 9 hours while azeotropically removing water produced during the reaction. When analyzed by gas chromatography, the reaction rate of ethyl cyanoacetate was 99%. After completion of the reaction, the reaction solution is concentrated under reduced pressure to give hexane,
After removing acetic acid and unreacted acetone, the residue was rectified as it was under reduced pressure of 20 mmHg using a 30 cm rectification column packed with a helicoil, and fractions at 110 to 113 ° C. were collected. The yield of ethyl 2-cyano-3-methyl-2-butenoate after distillation was 63.6 g, and the yield was 94%.
【０００６】実施例１において、反応溶媒の種類、触媒
の種類、原料の種類（シアノ酢酸の低級アルキルエステ
ルのアルキル）、または反応時間を替える以外は実施例
１と同様にして反応を行った結果をまとめて表１に示
す。尚、表中の収率は原料のシアノ酢酸の低級アルキル
エステルに対する比率を表す。The result of the reaction in Example 1 except that the kind of reaction solvent, kind of catalyst, kind of raw material (alkyl of lower alkyl ester of cyanoacetic acid), or reaction time was changed. Are collectively shown in Table 1. The yield in the table represents the ratio of the raw material cyanoacetic acid to the lower alkyl ester.
【表１】 ＊１．原料のシアノ酢酸の低級アルキルエステルのアルキル。（Ｅｔはエチルを 、Ｍｅはメチルを、Ｂｕはｎ−ブチルを各々表す。） ＊２．蒸留後の収率。 ＊３．重量比。 ＊４．Ａ：ｐ−アミノフェノールおよび酢酸 ＊５．Ｂ：ｐ−トルイジンおよび酢酸 ＊６．Ｃ：ｐ−アミノフェノールおよび安息香酸 ＊７．Ｄ：ｐ−アミノフェノールおよびプロピオン酸[Table 1] * 1. Alkyl of the lower alkyl ester of cyanoacetic acid as the raw material. (Et represents ethyl, Me represents methyl, and Bu represents n-butyl.) * 2. Yield after distillation. * 3. Weight ratio. * 4. A: p-aminophenol and acetic acid * 5. B: p-toluidine and acetic acid * 6. C: p-aminophenol and benzoic acid * 7. D: p-aminophenol and propionic acid
【０００７】[0007]
【発明の効果】本発明により、２−シアノ−３−メチル
−２−ブテン酸の低級アルキルエステルを収率よく製造
することができる。Industrial Applicability According to the present invention, a lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid can be produced in good yield.
Claims (4)
テルとを、触媒の存在下、ｎ−ヘキサンを主溶媒として
反応させることを特徴とする、２−シアノ−３−メチル
−２−ブテン酸の低級アルキルエステルの製造法。1. A lower alkyl 2-cyano-3-methyl-2-butenoic acid, which comprises reacting acetone and a lower alkyl ester of cyanoacetic acid in the presence of a catalyst with n-hexane as a main solvent. Method for producing alkyl ester.
びカルボン酸である請求項１記載の製造法。2. The process according to claim 1, wherein the catalyst is an optionally substituted aniline and a carboxylic acid.
ェノールまたはトルイジンであり、カルボン酸が低級脂
肪酸または安息香酸である請求項２記載の製造法。3. The process according to claim 2, wherein the optionally substituted aniline is aminophenol or toluidine, and the carboxylic acid is a lower fatty acid or benzoic acid.
で反応させる請求項１記載の製造法。4. The production method according to claim 1, wherein the reaction is carried out in a solvent containing 50% by weight or more of n-hexane.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27953494A JP3500735B2 (en) | 1994-11-14 | 1994-11-14 | Method for producing lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid |
| AU34473/95A AU692601B2 (en) | 1994-10-27 | 1995-08-30 | Process for producing N-(1-(2,4-dichlorophenyl)ethyl)-2- cyano-3,3-dimethylbutanamide |
| TW084110752A TW330195B (en) | 1994-10-27 | 1995-10-13 | Method for production of n-[1-(2,4-dichlorophenyl)ethyl]-2-cyano-3,3-dimethylbutane amide |
| KR1019950037251A KR100400799B1 (en) | 1994-10-27 | 1995-10-26 | Process for the preparation of N-[1-2,4-dichlorophenyl)ethyl]-2-cyano-3,3-dimethylbutaneamide |
| BR9504565A BR9504565A (en) | 1994-10-27 | 1995-10-26 | Process for the production of N- [1- (2,4-dichlorophenyl) ethyl] -2- cyano-3,3-dimethylbutanamide compound intermediate products agents and process for controlling rice cresta |
| CO95050571A CO4650095A1 (en) | 1994-10-27 | 1995-10-26 | PROCEDURE FOR PRODUCING N- (1- (2,4-DICHLOROFENIL) ETIL) -2- CIANO-3,3-DIMETILBUTANAMIDA |
| CNB2003101207896A CN1243719C (en) | 1994-10-27 | 1995-10-27 | Process for producing N-[1-(2,4. dichlorophenyl) ethyl]-2-cyan-3.3-dimethyl butane amide |
| CNB2003101207881A CN1243720C (en) | 1994-10-27 | 1995-10-27 | Process for producing n-(1-(2,4-dichlorophenyl)ethyl)-2- cyano-3,3-dimethylbutanamide |
| CNB2005100700669A CN1315780C (en) | 1994-10-27 | 1995-10-27 | Process for producing n-(1-(2,4-dichlorophenyl)ethyl)-2- cyano-3,3-dimethylbutanamide |
| CNB951203592A CN1153762C (en) | 1994-10-27 | 1995-10-27 | Method for preparation of N[1-(2,4-dichlorophenyl)ethyl]-2-cyano-3, 3-dimethyl butane amide |
| KR10200300215881020030021588A KR100433748B1 (en) | 1994-10-27 | 2003-04-07 | N-(α-methyl-2,4-dichlorobenzylidene)-α-(2,4-dichlorophenyl)ethylamine and the process for the preparation therof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27953494A JP3500735B2 (en) | 1994-11-14 | 1994-11-14 | Method for producing lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08143528A true JPH08143528A (en) | 1996-06-04 |
| JP3500735B2 JP3500735B2 (en) | 2004-02-23 |
Family
ID=17612350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27953494A Expired - Lifetime JP3500735B2 (en) | 1994-10-27 | 1994-11-14 | Method for producing lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3500735B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012128265A1 (en) * | 2011-03-23 | 2012-09-27 | 東亞合成株式会社 | Process for producing cyanoacetic acid esters |
-
1994
- 1994-11-14 JP JP27953494A patent/JP3500735B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012128265A1 (en) * | 2011-03-23 | 2012-09-27 | 東亞合成株式会社 | Process for producing cyanoacetic acid esters |
| JP5794296B2 (en) * | 2011-03-23 | 2015-10-14 | 東亞合成株式会社 | Method for producing cyanoacetate ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3500735B2 (en) | 2004-02-23 |
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