JP3617556B2 - Production of methyl cyanoisobutyrate - Google Patents
Production of methyl cyanoisobutyrate Download PDFInfo
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- JP3617556B2 JP3617556B2 JP22519295A JP22519295A JP3617556B2 JP 3617556 B2 JP3617556 B2 JP 3617556B2 JP 22519295 A JP22519295 A JP 22519295A JP 22519295 A JP22519295 A JP 22519295A JP 3617556 B2 JP3617556 B2 JP 3617556B2
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- Prior art keywords
- hydrogen cyanide
- methyl
- cyanoisobutyrate
- solvent
- hours
- 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.)
- Expired - Fee Related
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、シアン化水素のメタクリル酸メチルへの付加反応により合成されるシアノイソ酪酸メチルの製造法に関する。シアノイソ酪酸メチルは反応性に富み、カルボン酸等への工業的に有用な中間原料であり、また、ポリマ−の溶剤としても大量に使用されており、工業的に極めて重要な化学品である。
【0002】
【従来の技術】
炭素二重結合へのシアン化水素の付加は、二重結合に対して共役するシアノ基、ケト基、ニトロ基、カルバルコキシ基、その他のカルボキシル誘導体基を有する置換オレフィン系化合物に、触媒としてアルカリ金属、アルカリ土類金属のシアン化物や、アミン類等を使用して高温・高圧で行うことが知られている(German published aplication1,068,688,G.P808,835,U.S.P2,810,742)。しかし、これらは、工業的に経費のかかる高圧設備を必要とする。
また常圧での、メタクリル酸メチル二重結合へのシアン化水素の付加は、アルカリ金属のシアン化物の存在下、ピロリドン−2、あるいはアルキル置換ピロリドン類(U.S.P3,644,468)を溶媒として使用する方法が知られているが,シアン化水素に対する溶媒の重量比を減少させると、それに伴い収率の低下が生じる。
さらにアルカリ金属のシアン化物の存在下ジメチルスルホキシド(U.S.P3,644,467)を溶媒に使用する方法も知られている。しかしこの場合には、反応系に過剰のシアン化水素を存在させる必要があるため,反応後未反応のシアン化水素の回収工程を要すると共に使用溶媒自身が高価である。
以上のようにMMAの炭素二重結合へのシアン化水素の付加反応は、高温・高圧で行われたり、常圧で行う場合には溶媒使用量の減少に伴う収率の低下や反応後のシアン化水素の回収工程を要する等の欠点がある。
【0003】
【発明が解決しようとする課題点】
常圧でメタクリル酸メチルへのシアン化水素の付加反応を行うに際し、未反応シアン化水素の回収工程を要せず,安価な溶媒を使用し,さらにその溶媒使用量を減少しても収率低下をきたさず、高収率でシアノイソ酪酸メチルを製造する方法を提供することにある。
【0004】
【課題を解決するための手段】
有機酸のアルカリ金属塩を触媒とし、常圧で、アミド溶媒中でシアン化水素をメタクリル酸メチルに付加させると、高収率でシアノイソ酪酸メチルが得られることを見いだし本発明に至った。
【0005】
【発明の実施の形態】
本発明では、アルカリ金属であるナトリウム、カリウム、リチウムと炭素数1〜4の有機酸からなる有機酸のアルカリ金属塩を触媒として使用することを特徴とし、特に、酢酸カリウムが好ましい。有機酸金属塩の使用量は、シアン化水素に対して0.4〜10mol%であり、好ましくは、1.4〜8.4mol%である。
【0006】
本発明の反応溶媒にはアミド溶媒、好ましくはN,N−ジアルキル脂肪族アミド、更に好ましくはジメチルアセトアミド、ジメチルホルムアミドまたはこれらの混合物が用いられる。反応溶媒としてジメチルアセトアミドあるいはジメチルホルムアミドを用い、触媒として水酸化カリウム、シアン化カリウム、トリエチルアミン等を使用した場合、溶媒であるジメチルアセトアミドあるいはジメチルホルムアミドのシアン化水素に対する重量比を減少させると、付加物の収率は低下する傾向にあるが、有機酸のカリウム塩、特に酢酸カリウムを触媒として用いた場合には、溶媒のシアン化水素に対する重量比を下げても高収率で付加物が得られる。アミド溶媒のシアン化水素に対する重量比は、1.5以上であり、好ましくは、2.0以上である。
【0007】
本発明を実施する際の反応方法としては、溶媒中にシアン化水素とメタクリル酸メチルを同時にフィ−ドする方法や、溶媒、メタクリル酸メチル中にシアン化水素をフィ−ドする方法等があるが、前者の方が好ましい。反応条件は、常圧で、シアン化水素のフィ−ド時間が1〜10時間、好ましくは2〜5時間であり、熟成時間は1〜6時間、好ましくは、0.5〜3時間である。反応温度は、40℃〜170℃であり、好ましくは、70℃〜140℃である。これ以下の温度では反応の進行が遅く、これ以上の温度では、原料であるシアン化水素またはメタクリル酸メチルの重合が生じやすい。
【0008】
【発明の効果】
有機酸のアルカリ金属塩を触媒とし、常圧で、アミド溶媒中でシアン化水素をメタクリル酸メチルに付加させると、高収率でシアノイソ酪酸メチルが得られ、生産性が向上する。
【0009】
【実施例】
実施例1
撹拌器、還流冷却器、内部温度計、シアン化水素およびメタクリル酸メチルのフィ−ドラインを設けた4ツ口のフラスコ中にジメチルアセトアミド101.6gおよび酢酸カリウム2.06gを装入し、120℃に加熱した。シアン化水素40.0g(1.48モル)とメタクリル酸メチル163.3g(1.63モル)を4時間でフィ−ドし、溶液をさらに2時間、120℃で加熱した。96.4%シアン化水素変換率で、β−シアノイソ酪酸メチルが得られ、これは反応したシアン化水素に対して98.6%の収率に相当する。
【0010】
実施例2
実施例1と同様に、ジメチルホルムアミド101.6gおよび酢酸カリウム2.04gを装入し、120℃に加熱した。シアン化水素39.2g(1.45モル)とメタクリル酸メチル165.9g(1.66モル)を約4時間でフィ−ドし、溶液をさらに2時間、120℃で加熱した。95.8%シアン化水素変換率で、β−シアノイソ酪酸メチルが得られ、これは反応したシアン化水素に対して98.8%の収率に相当する。
【0011】
実施例3
実施例1と同様に、ジメチルアセトアミド101.6gおよびプロピオン酸ナトリム1.93gを装入し、120℃に加熱した。シアン化水素38.8g(1.43モル)とメタクリル酸メチル159.4g(1.59モル)を4時間でフィ−ドし、溶液をさらに2時間、120℃で加熱した。93.2%シアン化水素変換率で、β−シアノイソ酪酸メチルが得られ、これは反応したシアン化水素に対して94.3%の収率に相当する。
【0012】
実施例4
実施例1と同様に、ジメチルアセトアミド101.6gおよびメタクリル酸カリウム2.58gを装入し、120℃に加熱した。シアン化水素38.2g(1.41モル)とメタクリル酸メチル158.3g(1.58モル)を約4時間でフィ−ドし、溶液をさらに2時間、120℃で加熱した。91.6%シアン化水素変換率で、β−シアノイソ酪酸メチルが得られ、これは反応したシアン化水素に対して95.4%の収率に相当する。
【0013】
比較例1
実施例1の酢酸カリウムの替わりに、水酸化カリウム1.43gを装入し、5時間でシアン化水素をフィ−ドし、同様に反応を行った。81.7%シアン化水素変換率で、β−シアノイソ酪酸メチルが得られ、これは反応したシアン化水素に対して89.7%の収率に相当する。
【0014】
比較例2
実施例2の酢酸カリウムの替わりに水酸化カリウムを1.42g、ジメチルホルムアミド123.5gを装入し、120℃に加熱した。シアン化水素43.0g(1.59モル)とメタクリル酸メチル189.7g(1.89モル)を4.5時間でフィ−ドし、溶液をさらに2時間、120℃で加熱した。86.5%シアン化水素変換率で、β−シアノイソ酪酸メチルが得られ、これは反応したシアン化水素に対して88.0%の収率に相当する。
【0015】
比較例 3
比較例1の、ジメチルアセトアミドを203.3gとし、同様に反応を行った。99.7%シアン化水素変換率で、β−シアノイソ酪酸メチルが得られ、これは反応したシアン化水素に対して94.9%の収率に相当する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing methyl cyanoisobutyrate synthesized by an addition reaction of hydrogen cyanide to methyl methacrylate. Methyl cyanoisobutyrate is rich in reactivity, is an industrially useful intermediate material for carboxylic acids, etc., and is also used in large quantities as a solvent for polymers, and is an industrially extremely important chemical product.
[0002]
[Prior art]
Addition of hydrogen cyanide to a carbon double bond can be carried out by using a substituted olefin compound having a cyano group, a keto group, a nitro group, a carbalkoxy group or other carboxyl derivative group conjugated to the double bond as an alkali metal, It is known to carry out at high temperature and high pressure using cyanides of earth metals, amines, etc. (German published application 1,068,688, G.P808,835, USP2,810,742) ). However, these require industrially expensive high pressure equipment.
Addition of hydrogen cyanide to a methyl methacrylate double bond at normal pressure is performed by using pyrrolidone-2 or alkyl-substituted pyrrolidones (USP 3,644,468) as a solvent in the presence of an alkali metal cyanide. However, when the weight ratio of the solvent to hydrogen cyanide is decreased, the yield decreases accordingly.
Furthermore, a method of using dimethyl sulfoxide (USP 3,644,467) as a solvent in the presence of an alkali metal cyanide is also known. However, in this case, since it is necessary to make excess hydrogen cyanide exist in the reaction system, a step for recovering unreacted hydrogen cyanide after the reaction is required, and the solvent itself is expensive.
As described above, the addition reaction of hydrogen cyanide to the carbon double bond of MMA is carried out at high temperature and high pressure, and when it is carried out at normal pressure, the yield decreases with the decrease in the amount of solvent used and the hydrogen cyanide after the reaction There are drawbacks such as requiring a recovery step.
[0003]
[Problems to be solved by the invention]
When adding hydrogen cyanide to methyl methacrylate at normal pressure, the recovery process of unreacted hydrogen cyanide is not required, an inexpensive solvent is used, and even if the amount of solvent used is reduced, the yield does not decrease. Another object of the present invention is to provide a method for producing methyl cyanoisobutyrate in a high yield.
[0004]
[Means for Solving the Problems]
The inventors have found that methyl cyanoisobutyrate can be obtained in high yield when hydrogen cyanide is added to methyl methacrylate in an amide solvent at normal pressure using an alkali metal salt of an organic acid as a catalyst.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In this invention, it is characterized by using the alkali metal salt of the organic acid which consists of sodium, potassium, lithium which is alkali metal, and a C1-C4 organic acid as a catalyst, and potassium acetate is especially preferable. The usage-amount of organic acid metal salt is 0.4-10 mol% with respect to hydrogen cyanide, Preferably, it is 1.4-8.4 mol%.
[0006]
As the reaction solvent of the present invention, an amide solvent, preferably an N, N-dialkyl aliphatic amide, more preferably dimethylacetamide, dimethylformamide or a mixture thereof is used. When dimethylacetamide or dimethylformamide is used as a reaction solvent and potassium hydroxide, potassium cyanide, triethylamine or the like is used as a catalyst, the yield of the adduct is reduced by reducing the weight ratio of dimethylacetamide or dimethylformamide as a solvent to hydrogen cyanide. Although it tends to decrease, when a potassium salt of an organic acid, particularly potassium acetate, is used as a catalyst, an adduct can be obtained in a high yield even if the weight ratio of the solvent to hydrogen cyanide is lowered. The weight ratio of the amide solvent to hydrogen cyanide is 1.5 or more, and preferably 2.0 or more.
[0007]
Examples of the reaction method for carrying out the present invention include a method in which hydrogen cyanide and methyl methacrylate are fed simultaneously in a solvent, a method in which hydrogen cyanide is fed into a solvent and methyl methacrylate, and the like. Is preferred. The reaction conditions are normal pressure, hydrogen cyanide feed time of 1 to 10 hours, preferably 2 to 5 hours, and aging time of 1 to 6 hours, preferably 0.5 to 3 hours. The reaction temperature is 40 ° C to 170 ° C, preferably 70 ° C to 140 ° C. At a temperature lower than this, the progress of the reaction is slow, and at temperatures higher than this, polymerization of the raw material hydrogen cyanide or methyl methacrylate tends to occur.
[0008]
【The invention's effect】
When hydrogen cyanide is added to methyl methacrylate in an amide solvent at normal pressure using an alkali metal salt of an organic acid as a catalyst, methyl cyanoisobutyrate is obtained in high yield and productivity is improved.
[0009]
【Example】
Example 1
A four-necked flask equipped with a stirrer, reflux condenser, internal thermometer, hydrogen cyanide and methyl methacrylate feed line was charged with 101.6 g of dimethylacetamide and 2.06 g of potassium acetate and heated to 120 ° C. did. 40.0 g (1.48 mol) of hydrogen cyanide and 163.3 g (1.63 mol) of methyl methacrylate were fed over 4 hours, and the solution was heated at 120 ° C. for an additional 2 hours. At 96.4% hydrogen cyanide conversion, methyl β-cyanoisobutyrate is obtained, which corresponds to a yield of 98.6% based on the reacted hydrogen cyanide.
[0010]
Example 2
In the same manner as in Example 1, 101.6 g of dimethylformamide and 2.04 g of potassium acetate were charged and heated to 120 ° C. 39.2 g (1.45 mol) of hydrogen cyanide and 165.9 g (1.66 mol) of methyl methacrylate were fed in about 4 hours, and the solution was heated at 120 ° C. for a further 2 hours. At 95.8% hydrogen cyanide conversion, methyl β-cyanoisobutyrate is obtained, which corresponds to a yield of 98.8% based on the reacted hydrogen cyanide.
[0011]
Example 3
As in Example 1, 101.6 g of dimethylacetamide and 1.93 g of sodium propionate were charged and heated to 120 ° C. 38.8 g (1.43 mol) of hydrogen cyanide and 159.4 g (1.59 mol) of methyl methacrylate were fed over 4 hours and the solution was heated at 120 ° C. for a further 2 hours. At 93.2% hydrogen cyanide conversion, methyl β-cyanoisobutyrate is obtained, which corresponds to a yield of 94.3% based on the reacted hydrogen cyanide.
[0012]
Example 4
In the same manner as in Example 1, 101.6 g of dimethylacetamide and 2.58 g of potassium methacrylate were charged and heated to 120 ° C. 38.2 g (1.41 mol) of hydrogen cyanide and 158.3 g (1.58 mol) of methyl methacrylate were fed in about 4 hours, and the solution was heated at 120 ° C. for another 2 hours. At 91.6% hydrogen cyanide conversion, methyl β-cyanoisobutyrate is obtained, corresponding to a yield of 95.4% based on the reacted hydrogen cyanide.
[0013]
Comparative Example 1
Instead of potassium acetate in Example 1, 1.43 g of potassium hydroxide was charged, hydrogen cyanide was fed in 5 hours, and the reaction was carried out in the same manner. With 81.7% hydrogen cyanide conversion, methyl β-cyanoisobutyrate is obtained, which corresponds to a yield of 89.7% with respect to the reacted hydrogen cyanide.
[0014]
Comparative Example 2
Instead of the potassium acetate of Example 2, 1.42 g of potassium hydroxide and 123.5 g of dimethylformamide were charged and heated to 120 ° C. 43.0 g (1.59 mol) of hydrogen cyanide and 189.7 g (1.89 mol) of methyl methacrylate were fed over 4.5 hours, and the solution was heated at 120 ° C. for an additional 2 hours. With 86.5% hydrogen cyanide conversion, methyl β-cyanoisobutyrate is obtained, which corresponds to a yield of 88.0% based on the reacted hydrogen cyanide.
[0015]
Comparative Example 3
In Comparative Example 1, 203.3 g of dimethylacetamide was used, and the reaction was performed in the same manner. With 99.7% hydrogen cyanide conversion, methyl β-cyanoisobutyrate is obtained, which corresponds to a yield of 94.9% based on the reacted hydrogen cyanide.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP22519295A JP3617556B2 (en) | 1995-09-01 | 1995-09-01 | Production of methyl cyanoisobutyrate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22519295A JP3617556B2 (en) | 1995-09-01 | 1995-09-01 | Production of methyl cyanoisobutyrate |
Publications (2)
Publication Number | Publication Date |
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JPH0967330A JPH0967330A (en) | 1997-03-11 |
JP3617556B2 true JP3617556B2 (en) | 2005-02-09 |
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JP22519295A Expired - Fee Related JP3617556B2 (en) | 1995-09-01 | 1995-09-01 | Production of methyl cyanoisobutyrate |
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JP4746019B2 (en) * | 2007-08-30 | 2011-08-10 | 三菱レイヨン株式会社 | Optically active β-cyanoisobutyric acid and process for producing the same |
JP2013129636A (en) * | 2011-12-22 | 2013-07-04 | Mitsubishi Gas Chemical Co Inc | Method of manufacturing carvone nitrile |
JP6889322B1 (en) | 2020-09-30 | 2021-06-18 | 住友化学株式会社 | Composition |
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