JP3596120B2 - Method for producing lower alkyl ester of α-cyano-tert-butylacetic acid - Google Patents
Method for producing lower alkyl ester of α-cyano-tert-butylacetic acid Download PDFInfo
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- JP3596120B2 JP3596120B2 JP27755295A JP27755295A JP3596120B2 JP 3596120 B2 JP3596120 B2 JP 3596120B2 JP 27755295 A JP27755295 A JP 27755295A JP 27755295 A JP27755295 A JP 27755295A JP 3596120 B2 JP3596120 B2 JP 3596120B2
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Description
【０００１】
【発明の属する技術分野】
本発明は植物病害防除剤の製造中間体等として有用なαーシアノ−ｔｅｒｔ−ブチル酢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。
【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。
【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αーシアノ−ｔｅｒｔ−ブチル酢酸（２−シアノ−３，３−ジメチルブタン酸）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、２−シアノ−３−メチル−２−ブテン酸の低級アルキルエステルとメチルマグネシウムハライドとを銅触媒の存在下に反応させることにより、αーシアノ−ｔｅｒｔ−ブチル酢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、２−シアノ−３−メチル−２−ブテン酸の低級アルキルエステルとメチルマグネシウムハライドとを銅触媒の存在下に反応させることを特徴とする、αーシアノ−ｔｅｒｔ−ブチル酢酸の低級アルキルエステルの製造法（以下、本発明の製造法と記す。）を提供する。
【０００３】
【発明の実施の形態】
以下、本発明の製造法を詳細に説明する。
本発明の製造法で用いられる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。
本発明の製造法で用いられるメチルマグネシウムハライドとしては、メチルマグネシウムクロライド（ＣＨ３ ＭｇＣｌ）、メチルマグネシウムブロマイド（
ＣＨ３ ＭｇＢｒ）、メチルマグネシウムアイオダイド（ＣＨ３ ＭｇＩ）があげられ、これらは市販のものを用いるか、または、マグネシウムと対応するメチルハライドとを常法により反応させて調製することができる。
本発明の製造法において、銅触媒としては、通常、一価の銅塩または二価の銅塩が用いられ、それらの例として例えば塩化銅（Ｉ）（ＣｕＣｌ）、臭化銅（Ｉ）（ＣｕＢｒ）、沃化銅（Ｉ）（ＣｕＩ）、塩化銅（ＩＩ）（ＣｕＣｌ２ ）、臭化銅（ＩＩ）（ＣｕＢｒ２ ）、沃化銅（ＩＩ）（ＣｕＩ２ ）があげられる。
反応は通常有機溶媒中で行い、用いられる有機溶媒としては、例えば、テトラヒドロフラン（以下、ＴＨＦと記す。）、ジエチルエーテル、ジブチルエーテル等のエーテル溶媒、トルエン、キシレン、ベンゼン等の芳香族炭化水素溶媒、エーテル溶媒と芳香族炭化水素溶媒の混合溶媒等があげられる。
反応温度は通常１０〜６０℃、反応時間は通常０．５〜１０時間であり、反応に用いられる反応剤の量は、２−シアノ−３−メチル−２−ブテン酸の低級アルキルエステル１モルに対しメチルマグネシウムハライドは通常１〜２モルの割合、２−シアノ−３−メチル−２−ブテン酸の低級アルキルエステル１重量部に対し銅触媒は通常０．０００５〜０．１重量部の割合である。
反応後の反応液は通常、例えば、水、塩化アンモニウム水、希硫酸水等で処理したのち有機層を濃縮し、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αーシアノ−ｔｅｒｔ−ブチル酢酸の低級アルキルエステルを単離することが出来る。
【０００４】
本発明の製造法において原料化合物として用いられる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、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（以下、原料の製造法と記す。）させることにより効率的に製造することができる。
以下、原料の製造法について詳しく説明する。
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。
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５０〜１００℃、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。
【０００５】
本発明の製造法により得られるαーシアノ−ｔｅｒｔ−ブチル酢酸の低級アルキルエステルは、例えば、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。
【０００６】
【実施例】
以下、本発明の製造法を実施例等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。
実施例１
メチルクロライド１１９ｇ、マグネシウム４９．６ｇおよびＴＨＦ５０９ｇから調製したメチルマグネシウムクロライドの溶液中へ、３５〜４０℃で沃化銅（Ｉ）６．０ｇを添加した後、２−シアノ−３−メチル−２−ブテン酸エチル
２４０ｇをトルエン４８０ｇに溶かした溶液を同温度で約１時間かけて滴下した。滴下完了後、さらに同温度で１時間反応させた。反応混合液を２０〜３０℃まで冷却したのち、２０％塩化アンモニウム水１７４２ｇの中へ１０〜２０℃で注加した。室温で静置、分液の後、水層を酢酸エチル４８０ｍｌで２回抽出し、有機層を合わせて飽和食塩水４８０ｇで２回洗浄した。有機層を無水硫酸マグネシウムで乾燥したのち、減圧濃縮し、残渣をそのまま蒸留（主留分の沸点：８０〜８６℃／１２〜１５ｍｍＨｇ）して目的物を得た。蒸留後のαーシアノ−ｔｅｒｔ−ブチル酢酸エチルの収量は２４９ｇ、収率は９４％であった。
実施例１において、反応溶媒の種類、触媒の種類もしくは量、または原料の種類（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アルキル）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（実施例２〜８）を実施例１と共にまとめて表１に示す。尚、表中の収率は原料の２−シアノ−３−メチル−２−ブテン酸の低級アルキルエステルに対する比率を表す。
【表１】
実施例９
メチルクロライド２４．２ｇ、マグネシウム１１．７ｇおよびＴＨＦ１２１ｇから調製したメチルマグネシウムクロライドの溶液中へ、１５〜２５℃で塩化銅（ＩＩ）０．６ｇを添加した後、２−シアノ−３−メチル−２−ブテン酸エチル６１．３ｇをトルエン６１ｇに溶かした溶液を同温度で約３時間かけて滴下した。滴下完了後、さらに同温度で２時間反応させた。反応混合液を冷却したのち、１５％硫酸水溶液１７３ｇの中へ５〜１５℃で注加した。該混合物を５０〜６０℃に加温した後、同温度で静置し、分液した。水層をトルエン３１ｇで１回抽出し、有機層を合わせて５％炭酸水素ナトリウム水溶液６７ｇおよび水３１ｇで順次洗浄した。有機層を合わせてフタル酸ジ−ｎ−プロピルを内部標準としてガスクロマトグラフィー分析に付した。その結果、αーシアノ−ｔｅｒｔ−ブチル酢酸エチルの収量は６５ｇ、収率は９６％であった。
実施例１０
塩化銅（ＩＩ）０．６ｇにかえて塩化銅（ＩＩ）３．０ｇを用いる以外は実施例９と同様の操作を繰り返した。その結果、αーシアノ−ｔｅｒｔ−ブチル酢酸エチルの収量は６４ｇ、収率は９５％であった。
【０００８】
次に原料の製造法の製造例を示す。
尚、反応率は次式により求めた値である。
【数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。
【０００９】
原料の製造例１において、反応溶媒の種類、触媒の種類、シアノ酢酸の低級アルキルエステルのアルキルの種類、または反応時間を替える以外は原料の製造例１と同様にして反応を行った結果をまとめて表２に示す。尚、表中の収率は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。
【表２】
【発明の効果】
本発明により、αーシアノ−ｔｅｒｔ−ブチル酢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。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a lower alkyl ester of α-cyano-tert-butylacetic acid, which is useful as an intermediate for producing a plant disease controlling agent and the like.
2. Description of the Related Art
The fact that N- [1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide and the like have excellent plant disease control effects is described in JP-A-2-76846. Therefore, an industrially advantageous production method of the compound has been desired.
[0002]
[Means for Solving the Problems]
In view of the above situation, the present inventors have found that α-cyano-tert-butyl acetic acid (which can lead to N- [1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide and the like) As a result of intensive studies on a method of industrially and advantageously producing a lower alkyl ester of 2-cyano-3,3-dimethylbutanoic acid), the lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid and methyl The present inventors have found that a lower alkyl ester of α-cyano-tert-butylacetic acid can be obtained in a high yield by reacting magnesium halide with a copper catalyst, thereby completing the present invention.
That is, the present invention comprises reacting a lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid with methyl magnesium halide in the presence of a copper catalyst, wherein α-cyano-tert-butyl acetic acid is used. Provided is a method for producing a lower alkyl ester (hereinafter, referred to as the production method of the present invention).
[0003]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the production method of the present invention will be described in detail.
Examples of the lower (e.g. C 1 -C 4) alkyl esters of 2-cyano-3-methyl-2-butenoic acid to be used in the production method of the present invention, for example 2-cyano-3-methyl-2-butenoate, Ethyl 2-cyano-3-methyl-2-butenoate, n-propyl 2-cyano-3-methyl-2-butenoate, isopropyl 2-cyano-3-methyl-2-butenoate, 2-cyano-3- N-butyl methyl-2-butenoate, isobutyl 2-cyano-3-methyl-2-butenoate and the like.
As the methyl magnesium halide used in the production method of the present invention, methyl magnesium chloride (CH 3 MgCl), methyl magnesium bromide (
CH 3 MgBr) and methylmagnesium iodide (CH 3 MgI) can be used, and these can be prepared using commercially available products or by reacting magnesium and the corresponding methyl halide by a conventional method.
In the production method of the present invention, a monovalent copper salt or a divalent copper salt is usually used as a copper catalyst, and examples thereof include copper chloride (I) (CuCl), copper bromide (I) ( CuBr), copper (I) (CuI), copper (II) chloride (CuCl 2 ), copper (II) bromide (CuBr 2 ), and copper (II) iodide (CuI 2 ).
The reaction is usually performed in an organic solvent. Examples of the organic solvent used include ether solvents such as tetrahydrofuran (hereinafter referred to as THF), diethyl ether and dibutyl ether, and aromatic hydrocarbon solvents such as toluene, xylene and benzene. And a mixed solvent of an ether solvent and an aromatic hydrocarbon solvent.
The reaction temperature is usually 10 to 60 ° C., the reaction time is usually 0.5 to 10 hours, and the amount of the reactant used for the reaction is 1 mol of lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid. The methyl catalyst is usually in a proportion of 1 to 2 mol, and the copper catalyst is usually in a proportion of 0.0005 to 0.1 part by weight based on 1 part by weight of the lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid. It is.
The reaction solution after the reaction is usually treated with, for example, water, aqueous ammonium chloride, dilute sulfuric acid, and the like, and then the organic layer is concentrated. If necessary, a purification operation such as distillation is performed to obtain the desired α-cyano- The lower alkyl ester of tert-butyl acetic acid can be isolated.
[0004]
The lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid used as a starting compound in the production method of the present invention may be, for example, a mixture of acetone and a lower alkyl ester of cyanoacetic acid in the presence of a catalyst in n-hexane. Is used as a main solvent for the reaction (hereinafter, referred to as a raw material production method) to efficiently produce the compound.
Hereinafter, a method for producing a raw material will be described in detail.
Examples of the lower (e.g. C 1 -C 4) alkyl esters of cyanoacetic acid used, for example like methyl cyanoacetate, ethyl cyanoacetate, cyanoacetic acid n- propyl, isopropyl cyanoacetate, cyanoacetate n- butyl, isobutyl cyanoacetate etc. These are commercially available or can be produced by a conventional method.
As the catalyst, an optionally substituted aniline and a carboxylic acid are usually used.
Examples of the substituent in the optionally substituted aniline include a hydroxyl group, a methyl group, and a methoxy group. Examples of the optionally substituted aniline include aminophenol (p-aminophenol, o-amino Phenol, m-aminophenol, etc.) and toluidine (p-toluidine, o-toluidine, m-toluidine).
Examples of carboxylic acids include, for example, lower (eg, C 1 -C 4 ) fatty acids (eg, acetic acid, formic acid, propionic acid, etc.) and benzoic acid.
As a reaction solvent, n-hexane is used as a main solvent. More specifically, the use ratio of n-hexane to the total solvent is usually 50 to 100% by weight, and a reaction solvent which can be used by mixing with n-hexane. Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene.
The reaction temperature is usually 50 to 100 ° C., the reaction time is usually 5 to 20 hours, and the reaction is usually performed while removing water generated during the reaction.
The amount of the reactant used in the reaction is usually 1 to 4 mol of acetone and 1 mol of catalyst is usually 0.001 to 0.2 mol (1 mol of lower alkyl ester of cyanoacetic acid). Good anilines are usually in a proportion of 0.001 to 0.1 mol; carboxylic acids are usually in a proportion of 0.01 to 0.2 mol).
The reaction solution after the reaction is usually concentrated under reduced pressure or normal pressure and distilled as it is, or dissolved in a solvent such as ethyl acetate, toluene or xylene and washed with water, and the solution is concentrated under reduced pressure to remove the solvent, if necessary. Further, by performing a purification operation such as distillation, the intended lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid can be isolated.
[0005]
The lower alkyl ester of α-cyano-tert-butylacetic acid obtained by the production method of the present invention can be used, for example, by the method described in JP-A-2-76846, etc., for the excellent control of plant diseases described in the same. It can be led to N- [1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide and the like having an effect.
[0006]
【Example】
Hereinafter, the production method of the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to only these examples.
Example 1
To a solution of methyl magnesium chloride prepared from 119 g of methyl chloride, 49.6 g of magnesium and 509 g of THF was added 6.0 g of copper (I) iodide at 35 to 40 ° C., and then 2-cyano-3-methyl-2-methyl-2-chloride was added. A solution of 240 g of ethyl butenoate dissolved in 480 g of toluene was added dropwise at the same temperature over about 1 hour. After the completion of the dropwise addition, the reaction was further performed at the same temperature for 1 hour. After the reaction mixture was cooled to 20 to 30 ° C, it was poured into 1742 g of 20% aqueous ammonium chloride at 10 to 20 ° C. After standing at room temperature and liquid separation, the aqueous layer was extracted twice with 480 ml of ethyl acetate, and the organic layers were combined and washed twice with 480 g of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was distilled as it was (the boiling point of the main fraction: 80 to 86 ° C / 12 to 15 mmHg) to obtain the desired product. The yield of ethyl α-cyano-tert-butyl acetate after distillation was 249 g, and the yield was 94%.
In the same manner as in Example 1, except that the type of the reaction solvent, the type or amount of the catalyst, or the type of the raw material (the alkyl of the lower alkyl ester of 2-cyano-3-methyl-2-butenoic acid) was changed. Table 1 shows the results of the reaction (Examples 2 to 8) together with Example 1. In addition, the yield in a table | surface shows the ratio with respect to the lower alkyl ester of the raw material 2-cyano-3-methyl-2-butenoic acid.
[Table 1]
Example 9
To a solution of methyl magnesium chloride prepared from 24.2 g of methyl chloride, 11.7 g of magnesium and 121 g of THF was added 0.6 g of copper (II) chloride at 15 to 25 ° C., and then 2-cyano-3-methyl-2 was added. A solution of 61.3 g of ethyl butenoate in 61 g of toluene was added dropwise at the same temperature over about 3 hours. After completion of the dropwise addition, the reaction was further performed at the same temperature for 2 hours. After cooling the reaction mixture, the mixture was poured into 173 g of a 15% aqueous sulfuric acid solution at 5 to 15 ° C. After heating the mixture to 50 to 60 ° C., the mixture was allowed to stand at the same temperature and separated. The aqueous layer was extracted once with 31 g of toluene, and the combined organic layers were sequentially washed with 67 g of a 5% aqueous sodium hydrogen carbonate solution and 31 g of water. The organic layers were combined and subjected to gas chromatography analysis using di-n-propyl phthalate as an internal standard. As a result, the yield of ethyl α-cyano-tert-butyl acetate was 65 g, and the yield was 96%.
Example 10
The same operation as in Example 9 was repeated except that 3.0 g of copper (II) chloride was used instead of 0.6 g of copper (II) chloride. As a result, the yield of ethyl α-cyano-tert-butyl acetate was 64 g, and the yield was 95%.
[0008]
Next, a production example of a method for producing a raw material will be described.
The reaction rate is a value determined by the following equation.
(Equation 1)
50.0 g of ethyl cyanoacetate, 51.34 g of acetone, 1.99 g of acetic acid, 0.24 g of p-aminophenol and 41 ml of n-hexane were charged, and the mixture was heated and refluxed for 9 hours while azeotropically removing water produced during the reaction. When analyzed by gas chromatography, the conversion of ethyl cyanoacetate was 99%. After completion of the reaction, the reaction solution was concentrated under reduced pressure to remove hexane, acetic acid and unreacted acetone, and the residue was rectified as it was under a reduced pressure of 20 mmHg using a 30 cm rectification column filled with a helicoil to obtain 110 to 110. A fraction at 113 ° C. was collected. The yield of ethyl 2-cyano-3-methyl-2-butenoate after distillation was 63.6 g, and the yield was 94%.
[0009]
The results obtained by conducting the reaction in the same manner as in Production Example 1 of the raw material except that the type of the reaction solvent, the type of the catalyst, the type of the alkyl of the lower alkyl ester of cyanoacetic acid, or the reaction time were changed in Production Example 1 of the raw material are summarized. The results are shown in Table 2. The yields in the table represent the ratio of cyanoacetic acid to lower alkyl ester.
[Table 2]
【The invention's effect】
According to the present invention, a lower alkyl ester of α-cyano-tert-butylacetic acid can be produced with a high yield.
Claims (4)
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| JP27755295A JP3596120B2 (en) | 1994-11-14 | 1995-10-25 | Method for producing lower alkyl ester of α-cyano-tert-butylacetic acid |
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| JP27953594 | 1994-11-14 | ||
| JP6-279535 | 1994-11-14 | ||
| JP27755295A JP3596120B2 (en) | 1994-11-14 | 1995-10-25 | Method for producing lower alkyl ester of α-cyano-tert-butylacetic acid |
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| JP3596120B2 true JP3596120B2 (en) | 2004-12-02 |
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