JPH082850B2 - Method for producing unsaturated carboxylic acid amide - Google Patents
Method for producing unsaturated carboxylic acid amideInfo
- Publication number
- JPH082850B2 JPH082850B2 JP63233633A JP23363388A JPH082850B2 JP H082850 B2 JPH082850 B2 JP H082850B2 JP 63233633 A JP63233633 A JP 63233633A JP 23363388 A JP23363388 A JP 23363388A JP H082850 B2 JPH082850 B2 JP H082850B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- carboxylic acid
- general formula
- acid ester
- formula
- 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 - Lifetime
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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)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、一般式（Ｖ） （式中、R1は一般式（Ｉ）におけるR1に同じ。R4,R5は
式（IV）におけるR4,R5に同じ。）で表されるＮ−置換
不飽和カルボン酸アミド（以下、Ｎ−置換アミドと略す
る。）の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a compound represented by the general formula (V): (Wherein, R 1 is the general formula (same .R 4 to R 1 in I), R 5 is the same. To R 4, R 5 in formula (IV)) N-substituted unsaturated carboxylic acid amides represented by (Hereinafter, abbreviated as N-substituted amide).
本発明によって提供されるＮ−置換アミドは、吸湿
剤、防曇剤、分離膜、樹脂改質剤等の広い用途を有する
有用な化合物である。The N-substituted amide provided by the present invention is a useful compound having a wide range of uses such as a moisture absorbent, an antifogging agent, a separation membrane, and a resin modifier.
本発明のＮ−置換アミドは、一般に不飽和カルボン酸
エステルとアミノ化合物とのアミノリシスにより製造す
ることができる。The N-substituted amide of the present invention can be generally produced by aminolysis of an unsaturated carboxylic acid ester and an amino compound.
ところが、不飽和カルボン酸エステルとアミノ化合物
とのアミノリシスに際しては、アミノ化合物の二重結合
へのマイケル付加がおこり反応における目的物の選択率
が低い。また、マイケル付加物から二重結合を再生する
には、180〜300℃という高温で熱分解をおこない付加し
たアミノ化合物を脱離させる工程が必要となるが、この
際、重合物の生成等の副反応が起こり、目的物の収率が
著しく低下する（特開昭50−111016号）。However, in the aminolysis of an unsaturated carboxylic acid ester and an amino compound, Michael addition to the double bond of the amino compound occurs, and the selectivity of the target compound in the reaction is low. In addition, in order to regenerate the double bond from the Michael adduct, a step of decomposing the added amino compound by performing thermal decomposition at a high temperature of 180 to 300 ° C is required. A side reaction occurs and the yield of the desired product is remarkably reduced (Japanese Patent Laid-Open No. 111016/1975).
この副反応を抑制するために、低級アルコールをまず
二重結合に付加させた後、アミノリシスをおこない、次
いで、高温で脱アルコールをおこない二重結合を再生し
て目的物を得る方法（特開昭49−66623号,USP−253458
5,USP−2702822）が開示されている。In order to suppress this side reaction, a lower alcohol is first added to the double bond, aminolysis is carried out, and then dealcoholation is carried out at a high temperature to regenerate the double bond to obtain the desired product (Japanese Patent Laid-Open Publication No. Sho. 49-66623, USP-253458
5, USP-2702822).
この方法は、低級アルコールより高価なアミノ化合物
が二重結合へ付加して消費されるのを防ぐのには有効な
手段であるが、脱アルコール反応を高温でおこなうため
重合等の副反応をおこし、著しく目的物の収率が低下す
る。このため、このＮ−置換アミド合成法を工業化する
には多大な困難を有する。また、二重結合の保護法とし
てシクロペンタジエンを二重結合へのディールス・アル
ダー反応で付加させ、アミノリシス終了後、熱分解によ
りシクロペンタジエンを脱離させる方法（特開昭49−66
625号他）も開示されている。This method is an effective means for preventing the amino compound, which is more expensive than the lower alcohol, from being added to the double bond and being consumed. However, since the dealcoholization reaction is performed at a high temperature, a side reaction such as polymerization may occur. However, the yield of the desired product is significantly reduced. Therefore, there is a great difficulty in industrializing this N-substituted amide synthesis method. Also, as a method for protecting the double bond, a method in which cyclopentadiene is added to the double bond by a Diels-Alder reaction, and after completion of aminolysis, the cyclopentadiene is eliminated by thermal decomposition (JP-A-49-66).
No. 625) is also disclosed.
しかし、この方法においても、副生成物の生成は免れ
ず、また、脱離したシクロペンタジエンの目的物からの
分離・回収工程を要し、製品中へのシクロペンタジエン
の微量の混入が避けられず、製品品質を低下させる等の
欠点を有する。However, even with this method, the formation of by-products is unavoidable, and a step of separating / recovering the released cyclopentadiene from the target product is required, and a trace amount of cyclopentadiene is unavoidable in the product. However, it has drawbacks such as deterioration of product quality.
本発明者らは、副生成物を伴わずにＮ−置換アミドを
収率よく製造する方法について鋭意検討した結果、一般
式（Ｉ） （式中、R1は水素またはメチル基を示し、R2は炭素数１
〜３のアルキル基を示す。）で表されるアクリル酸エス
テル類またはメタクリル酸エステル類（以下、（メタ）
アクリル酸エステル類とする。）に一般式（II） R3−OH （II） （式中、R3は炭素数１〜３のアルキル基を示す。）で表
される低級アルコール（以下、低級アルコールとす
る。）を触媒を用いて付加させて一般式（III） （式中、R1,R2は一般式（Ｉ）におけるR1,R2に同じ。R3
は一般式（II）におけるR3に同じ。）で表されるβ−ア
ルコキシ置換カルボン酸エステル（以下、β−アルコキ
シ置換カルボン酸エステルとする。）を合成し、次に、
これと一般式（IV） （式中、R4,R5は炭素数１〜５のアルキル基を示す。）
で表される第二級アミン（以下、二級アミンとする。）
とをアミノリシス反応させてβ−アルコキシ置換カルボ
ン酸アミドを合成し、次いで、触媒を用いて温和な条件
でアルコールを脱離させて二重結合を再生することによ
り、高収率で目的物を製造する方法、すなわち、β−ア
ルコキシ置換カルボン酸アミドからのアルコール脱離反
応において触媒を用いて温和な条件で実行することによ
り、特開昭49−66623号記載の方法の欠点を解消し、工
業的に有利にβ−アルコキシ置換カルボン酸エステルを
原料にしてＮ−置換アミドを製造する方法を確立したも
のである。The present inventors diligently studied a method for producing an N-substituted amide in a high yield without accompanying by-products, and as a result, the compound represented by the general formula (I) was obtained. (In the formula, R 1 represents hydrogen or a methyl group, and R 2 has 1 carbon atom.
~ 3 alkyl groups are shown. ) Acrylic acid ester or methacrylic acid ester represented by (hereinafter, (meth)
Acrylic esters. ), A lower alcohol represented by the general formula (II) R 3 —OH (II) (wherein R 3 represents an alkyl group having 1 to 3 carbon atoms) (hereinafter referred to as lower alcohol) is used as a catalyst. With the general formula (III) (Wherein, R 1, R 2 is R 1 in the general formula (I), R 2 the same .R 3
Is the same as R 3 in the general formula (II). ) Represents a β-alkoxy-substituted carboxylic acid ester (hereinafter referred to as a β-alkoxy-substituted carboxylic acid ester), and then
This and general formula (IV) (In the formula, R 4 and R 5 represent an alkyl group having 1 to 5 carbon atoms.)
A secondary amine represented by (hereinafter referred to as a secondary amine)
And β-alkoxy-substituted carboxylic acid amide are synthesized by aminolysis reaction with and then the double bond is regenerated by eliminating alcohol under mild conditions using a catalyst to produce the desired product in high yield. Method, that is, by carrying out under mild conditions using a catalyst in the alcohol elimination reaction from β-alkoxy-substituted carboxylic acid amide, the drawbacks of the method described in JP-A-49-66623 are eliminated, and the method is industrially used. Particularly, a method for producing an N-substituted amide from a β-alkoxy-substituted carboxylic acid ester as a raw material has been established.
すなわち、本発明は、（メタ）アクリル酸エステル類
と低級アルコールとを塩基性触媒存在下に反応させてβ
−アルコキシ置換カルボン酸エステルを合成し、次い
で、これに二級アミンを反応させてβ−アルコキシ置換
カルボン酸アミドを生成させ、次いで、塩基性触媒存在
下に低級アルコールを脱離させることにより不飽和基を
形成せしめることを特徴とするＮ−置換アミドの製造方
法である。That is, in the present invention, (meth) acrylic acid esters and a lower alcohol are reacted in the presence of a basic catalyst to give β
Unsaturated by synthesizing an alkoxy-substituted carboxylic acid ester, then reacting this with a secondary amine to form a β-alkoxy-substituted carboxylic acid amide, and then eliminating the lower alcohol in the presence of a basic catalyst. A method for producing an N-substituted amide, which comprises forming a group.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で使用する（メタ）アクリル酸エステル類とし
ては、アクリル酸メチル、アクリル酸エチル、アクリル
酸ｎ−プロピル、アクリル酸イソプロピル、メタクリル
酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロ
ピル、メタクリル酸イソプロピル等が挙げられる。Examples of the (meth) acrylic acid esters used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate. Etc.
（メタ）アクリル酸エステル類と反応させる低級アル
コールとしては、メタノール、エタノール、ｎ−プロパ
ノール、イソプロパノール等が挙げられる。Examples of the lower alcohol to be reacted with the (meth) acrylic acid ester include methanol, ethanol, n-propanol and isopropanol.
二級アミンとしては、ジメチルアミン、ジエチルアミ
ン、N,N−エチルプロピルアミン、N,N−メチルブチルア
ミン、ジ−ｎ−プロピルアミン、ジイソプロピルアミ
ン、N,N−エチルブチルアミン、ジ−ｎ−ブチルアミ
ン、ジイソブチルアミン、ジペンチルアミン等を挙げる
ことができる。Examples of the secondary amine include dimethylamine, diethylamine, N, N-ethylpropylamine, N, N-methylbutylamine, di-n-propylamine, diisopropylamine, N, N-ethylbutylamine, di-n-butylamine, diisobutyl. Examples thereof include amine and dipentylamine.
本発明においては、先ず前記（メタ）アクリル酸エス
テル類への低級アルコールの付加によりβ−アルコキシ
置換カルボン酸エステルを得る。（メタ）アクリル酸エ
ステル類に対する低級アルコールの仕込みモル比は、0.
3〜３の範囲が好ましく、反応温度は60℃〜125℃が好ま
しい。In the present invention, first, a β-alkoxy-substituted carboxylic acid ester is obtained by adding a lower alcohol to the (meth) acrylic acid ester. The molar ratio of the lower alcohol charged to the (meth) acrylic acid ester was 0.
The range of 3 to 3 is preferable, and the reaction temperature is preferably 60 ° C to 125 ° C.
低級アルコールを付加させる触媒としては塩基性触媒
がよく、例えば、ナトリウムメチラート、水酸化カリウ
ム、水酸化ナトリウム等が挙げられる。As the catalyst for adding the lower alcohol, a basic catalyst is preferable, and examples thereof include sodium methylate, potassium hydroxide, and sodium hydroxide.
次に得られたβ−アルコキシ置換カルボン酸エステル
と二級アミンとのアミノリシスによりβ−アルコキシ置
換カルボン酸アミドを合成することができる。Next, a β-alkoxy-substituted carboxylic acid amide can be synthesized by aminolysis of the resulting β-alkoxy-substituted carboxylic acid ester and a secondary amine.
β−アルコキシ置換カルボン酸エステルに対する二級
アミンの仕込みモル比は、0.3〜３の範囲が好ましい。The molar ratio of the secondary amine charged to the β-alkoxy-substituted carboxylic acid ester is preferably in the range of 0.3 to 3.
反応温度は、40〜180℃が望ましい。アミノリシスに
際しては、副生アルコールの沸点が二級アミンより低い
場合は、副生するアルコールを反応系から留去しながら
反応を進めるのが反応速度を高め転化率を上げるうえで
有利である。また、反応は二級アミンの塩基性のため、
無触媒でも進行するが公知の塩基性のアミノリシス触媒
を添加することも可能である。The reaction temperature is preferably from 40 to 180 ° C. In the aminolysis, when the boiling point of the by-product alcohol is lower than that of the secondary amine, it is advantageous to proceed the reaction while distilling off the alcohol as a by-product from the reaction system in order to increase the reaction rate and increase the conversion rate. Also, because the reaction is basic with secondary amines,
It is possible to add a known basic aminolysis catalyst although it proceeds without a catalyst.
得られたβ−アルコキシ置換カルボン酸アミドは、減
圧蒸留により精製して次の工程に使用してもよいが、反
応終了後、未反応の原料及び低沸副生成物を留去するの
みで次の反応に使用することも可能である。The obtained β-alkoxy-substituted carboxylic acid amide may be purified by vacuum distillation and used in the next step, but after the reaction is completed, only unreacted raw materials and low-boiling by-products are distilled off. It is also possible to use for the reaction of.
次にβ−アルコキシ置換カルボン酸アミドより低級ア
ルコールを脱離させてＮ−置換アミドを合成するが、こ
の際、従来おこなわれている高温でのクラッキングによ
り目的物を製造した場合には重合物等の好ましくない副
生成物を多量に生じ、目的物の精製を煩雑にし収率を著
しく低下させるから、本発明においては、触媒を使用し
て温和な条件でアルコールを脱離させることが肝要であ
る。Next, the lower alcohol is eliminated from the β-alkoxy-substituted carboxylic acid amide to synthesize an N-substituted amide. At this time, when the target product is produced by conventional cracking at high temperature, a polymer or the like is produced. In the present invention, it is important to desorb alcohol under a mild condition using a catalyst, since a large amount of undesired by-products are produced, and the purification of the target compound becomes complicated and the yield is significantly reduced. .
低級アルコールを脱離させる触媒としては、酸塩基触
媒でもよく、特に塩基性触媒が良い。The catalyst for desorbing the lower alcohol may be an acid-base catalyst, particularly a basic catalyst.
塩基性触媒としては、例えば、ナトリウムメチラー
ト、水酸化リチウム、水酸化ナトリウム、水酸化カルシ
ウム等が挙げられる。Examples of the basic catalyst include sodium methylate, lithium hydroxide, sodium hydroxide, calcium hydroxide and the like.
触媒の添加に際しては、不活性な溶剤に溶かして反応
系へ添加することも固体のまま添加することも可能であ
る。When adding the catalyst, it is possible to dissolve it in an inert solvent and add it to the reaction system or add it as a solid.
反応は副反応を抑えるため低温でおこなうことが好ま
しく、反応温度は50〜170℃の範囲が好ましい。The reaction is preferably performed at a low temperature to suppress side reactions, and the reaction temperature is preferably in the range of 50 to 170 ° C.
反応圧力は50〜760mmHgで、生成する低級アルコール
を留去しつつ反応を進めることが反応速度を高める点か
ら望ましい。The reaction pressure is 50 to 760 mmHg, and it is desirable to carry out the reaction while distilling off the generated lower alcohol from the viewpoint of increasing the reaction rate.
副反応を防ぐもう一つの手段として、溶剤を使用する
ことも可能である。本発明においては溶剤を使用しなく
てもよいが、溶剤を使用した場合でも生成物の収率の低
下をまねくことはなく、良好な方法である。溶剤として
は、N,N−ジメチルホルムアミド、N,N−ジメチルアセト
アミド、N,N−ジメチルスルホキシド、トルエン、キシ
レン等が挙げられる。It is also possible to use a solvent as another means for preventing side reactions. In the present invention, a solvent may not be used. However, even if a solvent is used, the yield of a product is not reduced, which is a good method. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, toluene, xylene and the like.
反応終了後、反応液の塩基性触媒を中和するか、抽出
操作により塩基性触媒を除去するか、不溶の塩基性触媒
を濾過または遠心分離により除去した後、目的物を蒸留
等により精製する。After completion of the reaction, the basic catalyst in the reaction solution is neutralized, the basic catalyst is removed by an extraction operation, or the insoluble basic catalyst is removed by filtration or centrifugation, and then the target product is purified by distillation or the like. .
なお、反応中及び目的物の精製中には、公知の重合禁
止剤を添加することが好ましく、重合禁止剤としては、
例えば、ハイドロキノン、ハイドロキノンモノメチルエ
ーテル、フェノチアジン、クペロン等が適当である。During the reaction and during the purification of the target substance, it is preferable to add a known polymerization inhibitor, and as the polymerization inhibitor,
For example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, cuperon and the like are suitable.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
実施例１ 〔アルコール付加〕 還流器をつけたナス型フラスコにメタクリル酸メチル
200.2g（2.0モル）、メタノール160.2g（５モル）、触
媒としてナトリウムメチラート6.0gを入れ、温度を80℃
にして５時間反応させた。Example 1 [Alcohol addition] Methyl methacrylate was placed in an eggplant-shaped flask equipped with a reflux condenser.
200.2g (2.0mol), methanol 160.2g (5mol), sodium methylate 6.0g as a catalyst are added, and the temperature is 80 ° C.
And reacted for 5 hours.
反応終了後、当量の酢酸を加えて触媒を中和した。低
沸分を除去して、β−メトキシイソ酪酸メチル213.6gを
得た。純度は99.0％であった。After completion of the reaction, an equivalent amount of acetic acid was added to neutralize the catalyst. The low boiling point was removed to obtain 213.6 g of methyl β-methoxyisobutyrate. The purity was 99.0%.
撹拌器及び塔頂に分留装置をつけてガラス製ラッシヒ
リングを充填した塔を有する四ツ口フラスコに前記アル
コール付加で得られた反応液を入れ、ジ−ｎ−プロピル
アミン283.3g（2.8モル）を入れ、128℃で生成するメタ
ノールを留去しながら反応を進めた。反応は24時間で終
了し、反応終了後、未反応のジ−ｎ−プロピルアミンを
減圧下で留去した。さらに低沸分留去後321.6gの反応液
を得た。反応液のN,N−ジ−ｎ−プロピル−β−メトキ
シイソブチルアミドの含有率は90％であった。The reaction solution obtained by the alcohol addition was placed in a four-necked flask having a tower equipped with a stirrer and a fractionating device at the top of the tower and filled with glass Raschig rings, and 283.3 g (2.8 mol) of di-n-propylamine was added. Was charged and the reaction was allowed to proceed while distilling off the methanol produced at 128 ° C. The reaction was completed in 24 hours, and after completion of the reaction, unreacted di-n-propylamine was distilled off under reduced pressure. After the low boiling fraction was distilled off, 321.6 g of a reaction solution was obtained. The content of N, N-di-n-propyl-β-methoxyisobutyramide in the reaction solution was 90%.
前記アミノリシスで得られた反応液を前記アミノリシ
スと同様に反応器に入れ、触媒として水酸化リチウム5.
6g、重合禁止剤としてクペロン0.8gを添加して135℃、2
00mmHgで反応をおこなった。反応の際に副生する低級ア
ルコールを反応系から留去しながら反応を進めた。反応
は８時間で終了し、得られた反応液を減圧蒸留で精製し
てN,N−ジ−ｎ−プロピルメタクリルアミド214.6gを得
た。純度は99.8％で、収率は63％（仕込メタクリル酸メ
チル基準）であった。The reaction solution obtained by the above-mentioned aminolysis was put into a reactor in the same manner as the above-mentioned aminolysis, and lithium hydroxide was used as a catalyst.
6g, add 0.8g cuperon as a polymerization inhibitor,
The reaction was performed at 00 mmHg. The reaction proceeded while distilling off the lower alcohol by-produced during the reaction from the reaction system. The reaction was completed in 8 hours, and the obtained reaction liquid was purified by distillation under reduced pressure to obtain 214.6 g of N, N-di-n-propylmethacrylamide. The purity was 99.8% and the yield was 63% (based on the charged methyl methacrylate).
実施例２ 〔アルコール付加〕 還流器をつけたナス型フラスコにアクリル酸メチル17
2.2g（２モル）、メタノール160.2g（５モル）、触媒と
して水酸化カリウム5.0gを入れ、温度を69℃にして４時
間反応させた。反応終了後、当量の酢酸を加えて触媒を
中和した。低沸分を除去して、β−メトキシプロピオン
酸メチル203.5gを得た。純度は98.7％であった。Example 2 [Alcohol addition] Methyl acrylate 17 was added to an eggplant-shaped flask equipped with a reflux condenser.
2.2 g (2 mol), 160.2 g (5 mol) of methanol and 5.0 g of potassium hydroxide as a catalyst were added, and the temperature was raised to 69 ° C. and the reaction was carried out for 4 hours. After completion of the reaction, an equivalent amount of acetic acid was added to neutralize the catalyst. The low boiling point was removed to obtain 203.5 g of methyl β-methoxypropionate. The purity was 98.7%.
撹拌器及び塔頂に分留装置をつけ、ガラス製ラッシヒ
リングを充填した塔を有する四ツ口フラスコに前記アル
コール付加で得られた反応液を入れ、ジ−ｎ−プロピル
アミン364.2g（3.6モル）を入れ、143℃で生成するメタ
ノールを留去しながら反応を進めた。反応は18時間で終
了し、反応終了後、未反応のジ−ｎ−プロピルアミンを
減圧下で留去した。さらに低沸分留去後、310.9gの反応
液を得た。反応液のN,N−ジ−ｎ−プロピル−β−メト
キシプロピオアミドの含有率は92％であった。The reaction solution obtained by the alcohol addition was placed in a four-necked flask equipped with a stirrer and a fractionating device at the top of the tower and filled with a glass Raschig ring, and 364.2 g (3.6 mol) of di-n-propylamine was added. Was charged and the reaction was allowed to proceed while distilling off the methanol produced at 143 ° C. The reaction was completed in 18 hours, and after the reaction was completed, unreacted di-n-propylamine was distilled off under reduced pressure. After further distilling off a low boiling fraction, 310.9 g of a reaction liquid was obtained. The content of N, N-di-n-propyl-β-methoxypropioamide in the reaction solution was 92%.
前記アミノリシスで得られた反応液を前記アミノリシ
スと同様に反応器にいれ、触媒として水酸化カルシウム
9.2g、重合禁止剤としてクペロン0.9gを添加して132
℃、200mmHgで反応をおこなった。反応の際に副生する
低級アルコールを反応系から留去しながら反応を進め
た。反応は６時間で終了し、得られた反応液を減圧蒸留
で精製してN,N−ジ−ｎ−プロピルアクリルアミド258.5
gを得た。純度は99.6％で、収率は68.9％（仕込アクリ
ル酸メチル基準）であった。The reaction solution obtained by the above-mentioned aminolysis is put into a reactor in the same manner as the above-mentioned aminolysis, and calcium hydroxide is used as a catalyst.
132g by adding 9.2g, cuperon 0.9g as a polymerization inhibitor
The reaction was carried out at 200 ° C and 200 mmHg. The reaction proceeded while distilling off the lower alcohol by-produced during the reaction from the reaction system. The reaction was completed in 6 hours, and the obtained reaction solution was purified by vacuum distillation to obtain N, N-di-n-propylacrylamide 258.5.
got g. The purity was 99.6% and the yield was 68.9% (based on charged methyl acrylate).
これまで知られていた高温によるβ−アルコキシ置換
カルボン酸アミドの脱メタノール化の方法は、重合物等
の生成等により著しく収率が低下するという欠点を有
し、このため工業化が困難であったが、本発明のβ−ア
ルコキシ置換カルボン酸アミドからのアルコール脱離を
触媒を用いて温和な条件で実行する方法は、不飽和カル
ボン酸エステルを原料として工業的に有利にＮ−置換ア
ミドを製品品質に問題を生ずることなく製造することを
可能にした。The conventionally known methods for demethanolating β-alkoxy-substituted carboxylic acid amides at high temperatures have a drawback that the yield is remarkably reduced due to the formation of a polymer or the like, and thus industrialization is difficult. However, the method of carrying out the alcohol elimination from the β-alkoxy-substituted carboxylic acid amide of the present invention under mild conditions using a catalyst is an industrially advantageous production of an N-substituted amide using an unsaturated carboxylic acid ester as a raw material. It is possible to manufacture without causing a problem in quality.
Claims (1)
〜３のアルキル基を示す。）で表されるアクリル酸エス
テル類またはメタクリル酸エステル類と一般式（II） R3−OH （II） （式中、R3は炭素数１〜３のアルキル基を示す。）で表
される低級アルコールとを塩基性触媒存在下に反応させ
て一般式（III） （式中、R1,R2は一般式（Ｉ）におけるR1,R2に同じ。R3
は一般式（II）におけるR3に同じ。）で表されるβ−ア
ルコキシ置換カルボン酸エステルを合成し、次いで、こ
れに一般式（IV） （式中、R4,R5は炭素数１〜５のアルキル基を示す。）
で表される第二級アミンを反応させてβ−アルコキシ置
換カルボン酸アミドを生成させ、次いで、塩基性触媒存
在下に低級アルコールを脱離させることにより不飽和基
を形成せしめることを特徴とする一般式（Ｖ） （式中、R1は一般式（Ｉ）におけるR1に同じ。R4,R5は
式（IV）におけるR4,R5に同じ。）で表されるＮ−置換
不飽和カルボン酸アミドの製造方法。1. A general formula (I) (In the formula, R 1 represents hydrogen or a methyl group, and R 2 has 1 carbon atom.
~ 3 alkyl groups are shown. ) Acrylic acid ester or methacrylic acid ester represented by the general formula (II) R 3 —OH (II) (in the formula, R 3 represents an alkyl group having 1 to 3 carbon atoms). Reaction with a lower alcohol in the presence of a basic catalyst gives the compound of general formula (III) (Wherein, R 1, R 2 is R 1 in the general formula (I), R 2 the same .R 3
Is the same as R 3 in the general formula (II). ), A β-alkoxy-substituted carboxylic acid ester represented by the general formula (IV) (In the formula, R 4 and R 5 represent an alkyl group having 1 to 5 carbon atoms.)
Is characterized in that a secondary amine represented by is reacted to form a β-alkoxy-substituted carboxylic acid amide, and then a lower alcohol is eliminated in the presence of a basic catalyst to form an unsaturated group. General formula (V) (Wherein, R 1 is the general formula (same .R 4 to R 1 in I), R 5 is the same. To R 4, R 5 in formula (IV)) N-substituted unsaturated carboxylic acid amides represented by Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233633A JPH082850B2 (en) | 1988-09-20 | 1988-09-20 | Method for producing unsaturated carboxylic acid amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233633A JPH082850B2 (en) | 1988-09-20 | 1988-09-20 | Method for producing unsaturated carboxylic acid amide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0283358A JPH0283358A (en) | 1990-03-23 |
| JPH082850B2 true JPH082850B2 (en) | 1996-01-17 |
Family
ID=16958101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63233633A Expired - Lifetime JPH082850B2 (en) | 1988-09-20 | 1988-09-20 | Method for producing unsaturated carboxylic acid amide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082850B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110263898A1 (en) * | 2008-04-30 | 2011-10-27 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2123631B1 (en) * | 2007-02-20 | 2012-07-18 | Idemitsu Kosan Co., Ltd. | PROCESS FOR PRODUCING ß-ALKOXYPROPIONAMIDE |
| JP5331469B2 (en) * | 2008-12-10 | 2013-10-30 | 出光興産株式会社 | Process for producing β-alkoxypropionamides |
-
1988
- 1988-09-20 JP JP63233633A patent/JPH082850B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110263898A1 (en) * | 2008-04-30 | 2011-10-27 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
| US8969621B2 (en) * | 2008-04-30 | 2015-03-03 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
| US9371273B2 (en) | 2008-04-30 | 2016-06-21 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0283358A (en) | 1990-03-23 |
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