JP4061461B2 - Method for producing quaternary ammonium organic acid salt - Google Patents

Description

【０００４】
【発明が解決しようとする課題】
本発明の目的は、一級または二級アミンを原料とし、工業的に有利な四級アンモニウム有機酸塩の製造方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは、上記の課題について鋭意検討した結果、驚くべきことに一級または二級アミンとカルボン酸エステルを反応させることにより、Ｎ−アルキル化と四級化の両方を行わせることができ、また、反応条件を選択することにより、トランスアルキル化反応により各種混合アルキル四級アンモニウム塩が生成することを見出し本発明に到達した。
【０００６】
すなわち、本発明は、下記一般式（１）で表される一級または二級アミンと下記一般式（２）で表されるカルボン酸エステルを反応させることを特徴とする下記一般式（３）で表される四級アンモニウム有機酸塩の製造方法に関するものである。
【０００７】
【化５】

（式中、Ｒ¹は、置換基を有していてもよい炭素数１〜２０のアルキル基、アルケニル基、アラルキル基、芳香族基を表し、Ｒ²は、水素又は置換基を有していてもよい炭素数１〜２０のアルキル基、アルケニル基、アラルキル基、若しくは芳香族基を表す。）
【０００８】
【化６】

（式中、Ｒ³は、置換基を有していてもよい炭素数１〜２０のアルキル基、アルケニル基、アラルキル基、芳香族基を表し、Ｒ⁴は、水素又は置換基を有していてもよい炭素数１〜２０のアルキル基、アルケニル基、アラルキル基、若しくは芳香族基を表す。）
【０００９】
【化７】

（式中、ｎは１〜２の整数、Ｒ¹〜Ｒ⁴は前記に同じ。）
【００１０】
【発明の実施の形態】
以下、本発明を詳細に説明する。本反応は、下記反応式（５）で表され、一級または二級アミンとカルボン酸エステルから最初にエステル基が一つ入った四級アンモニウムカルボン酸塩が生成する。生成した四級アンモニウムカルボン酸塩はさらに過剰のカルボン酸エステルと反応して、アルキル基がエステル基に置換される。
【００１１】
【化８】

【００１２】
一級または二級アミンの具体例としては、メチルアミン、エチルアミン、ｎ−プロピルアミン、イソプロピルアミン、ｎ−ブチルアミン、イソブチルアミン、アリルアミン、アニリン、ジメチルアミン、ジエチルアミン、ジ−ｎ−プロピルアミン、ジイソプロピルアミン、ジ−ｎ−ブチルアミン、ジイソブチルアミン、ジアリルアミン、またはジフェニルアミン等が挙げられる。
【００１３】
カルボン酸エステルの具体例としては、ギ酸、酢酸、プロピオン酸、酪酸、アクリル酸、メタクリル酸、乳酸、グリコール酸、シュウ酸、安息香酸、サリチル酸、または２−ヒドロキシイソ酪酸のメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、アリル、ベンジル、もしくはフェニルエステル等が挙げられる。中でも２−ヒドロキシイソ酪酸メチルは、ＡＣＨ新法（副生硫酸塩を生成しない方法）と呼ばれるメタクリル酸メチルの製造法の中間体として工業的に製造されており好適に用いることができる。カルボン酸エステルの使用量は、一級または二級アミンに対して１〜１００モル比、好ましくは２〜１０モル比である。
【００１４】
反応は、回分式、流通式どちらの方法でも実施できる。回分式では、一級または二級アミンとカルボン酸エステルを反応槽に仕込み加熱する事により行われる。原料の仕込み方法は特に制限されないが、バッチ操作の場合はすべての原料を一括して仕込むことができる。反応温度は５０〜３００℃の範囲、好ましくは１００〜２００℃の範囲である。これより反応温度が低い場合、四級化速度が遅く、これより高い場合には分解により収率が低下する。反応圧力は、特に制限されないが、常圧下または反応温度に対応する反応混合物の蒸気圧以上が好ましい。反応時間は、原料の種類及び目的とする混合四級アンモニウム有機酸塩の組成、反応温度等により一概に言えないが、通常０．５〜２０時間の範囲である。
【００１５】
本発明では、カルボン酸エステル過剰系で行うため溶媒なしで反応は好適に進むが、必要であればアルコール等の極性溶媒を含む任意の溶媒やカルボン酸等の添加剤を用いて反応を行うこともできる。本発明では、必要に応じて窒素、アルゴン、ヘリウム等の不活性ガス雰囲気下で行うこともできる。反応生成液からの四級アンモニウム有機酸塩は常法、例えば低沸点留分を留去、必要に応じて再結晶することにより容易に得ることができる。
【００１６】
【実施例】
以下に、実施例によって本発明をさらに具体的に説明する。本発明は、これらの実施例によって限定されるものではない。
【００１７】
実施例１
内容積１００ｍｌのＳＵＳ３１６製の振とう式オートクレーブに、ジエチルアミン７．１ｇ（０．１モル）、２−ヒドロキシイソ酪酸メチル５９．０ｇ（０．５モル）を仕込み振とうしながら加熱する。オートクレーブ内の温度が１６０℃に達した後、４時間その温度で反応を継続した。この際の圧力は０．４ＭＰａ（ゲージ圧）であった。反応終了後冷却し、反応生成液から低沸分を留去することによりうす黄色の釜残２６．５ｇを得た。釜残をイオンクロマトグラフィーにて分析したところ四級アンモニウム有機酸塩中ジエチルジメチルアンモニウム２−ヒドロキシイソ酪酸塩９０．８重量％とトリメチルエチルアンモニウム２−ヒドロキシイソ酪酸塩５．４重量％の混合物であり、ジエチルアミン基準の四級アンモニウム有機酸塩の収率は合計８８．２モル％であった。
【００１８】
実施例２
内容積１００ｍｌのＳＵＳ３１６製の振とう式オートクレーブに、ジ−ｎ−ブチルアミン１０．３ｇ（０．０８モル）、２−ヒドロキシイソ酪酸メチル４７．３ｇ（０．４モル）を仕込み振とうしながら加熱する。オートクレーブ内の温度が１６０℃に達した後、４時間その温度で反応を継続した。この際の圧力は、０．３ＭＰａ（ゲージ圧）であった。反応終了後冷却し、反応生成液から低沸分を留去することにより薄黄色の釜残２２．３ｇを得た。釜残をイオンクロマトグラフィーにて分析したところ四級アンモニウム有機酸塩中、ジ−ｎ−ブチルジメチルアンモニウム２−ヒドロキシイソ酪酸塩９７．２重量％とトリメチル−ｎ−ブチルアンモニウム２−ヒドロキシイソ酪酸塩２．８重量％の混合物であり、ジ−ｎ−ブチルアミン基準の四級アンモニウム有機酸塩の収率は合計７６．２モル％であった。
【００１９】
実施例３
内容積１００ｍｌのＳＵＳ３１６製の振とう式オートクレーブに、モノエチルアミン４．５ｇ（０．１モル）、２−ヒドロキシイソ酪酸メチル５９．１ｇ（０．５モル）を仕込み振とうしながら加熱する。オートクレーブ内の温度が１６０℃に達した後、８時間その温度で反応を継続した。この際の圧力は０．５ＭＰａ（ゲージ圧）であった。反応終了後冷却し、反応生成液から低沸分を留去することによりうす黄色の釜残１９．８ｇを得た。釜残をイオンクロマトグラフィーにて分析したところ四級アンモニウム有機酸塩中トリメチルエチルアンモニウム２−ヒドロキシイソ酪酸塩９１．１重量％とテトラメチルアンモニウム２−ヒドロキシイソ酪酸塩５．６重量％の混合物であり、モノエチルアミン基準の四級アンモニウム有機酸塩の収率は合計５２．９モル％であった。
【００２０】
実施例４
内容積１００ｍｌのＳＵＳ３１６製の振とう式オートクレーブに、ジエチルアミン７．１ｇ（０．１モル）、２−ヒドロキシイソ酪酸メチル５９．０ｇ（０．５モル）を仕込み振とうしながら加熱する。オートクレーブ内の温度が１６０℃に達した後、８時間その温度で反応を継続した。この際の圧力は０．４ＭＰａ（ゲージ圧）であった。反応終了後冷却し、反応生成液から低沸分を留去することにより薄黄色の釜残２７．７ｇを得た。釜残をイオンクロマトグラフィーにて分析したところ四級アンモニウム有機酸塩中ジエチルジメチルアンモニウム２−ヒドロキシイソ酪酸塩８１．２重量％とトリメチルエチルアンモニウム２−ヒドロキシイソ酪酸塩１２．３重量％の混合物であり、ジエチルアミン基準の四級アンモニウム有機酸塩の収率は合計９２．２モル％であった。
【００２１】
比較例１
２−ヒドロキシイソ酪酸メチルのかわりに炭酸ジメチル４５．０ｇ（０．５モル）を用いる以外は、実施例１と同様に反応を行った。反応開始から徐々に圧力が上昇し、４時間後には３．６ＭＰａとなった。反応終了後冷却し、反応生成液から低沸分を留去することにより薄茶色の釜残９．３ｇを得た。釜残をイオンクロマトグラフィーにて分析したところ四級アンモニウム有機酸塩中ジエチルジメチルアンモニウム２−ヒドロキシイソ酪酸塩７４．０重量％とトリメチルエチルアンモニウム２−ヒドロキシイソ酪酸塩２３．９重量％の混合物であり、ジエチルアミン基準の四級アンモニウム有機酸塩の収率は合計５２．７モル％であった。また、留去した低沸分にはＮ，Ｎ−ジエチルカルバミン酸メチルが含まれていた。
【００２２】
【発明の効果】
本発明により、一級または二級アミンとカルボン酸エステルから四級アンモニウム有機酸塩組成物を工業的に有利に製造でき、工業的意義は極めて大きい。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a quaternary ammonium organic acid salt. Quaternary ammonium organic acid salts are useful as raw materials for surfactants, phase transfer catalysts, pharmaceuticals, and cosmetics. In addition, high purity quaternary ammonium organic acid salts are required for electronic materials such as cleaning agents for electronic materials, resist developers, and electrolytes for capacitors.
[0002]
[Prior art]
Conventionally, as a method using a primary or secondary amine as a raw material, there is a method of obtaining a quaternary ammonium alkyl carbonate from a secondary amine represented by the following reaction formula (4) and a dialkyl carbonate (Italian Patent No. 115350). However, this method has a drawback that carbon dioxide is generated and the reaction pressure is increased.
[0003]
[Formula 4]

[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an industrially advantageous method for producing a quaternary ammonium organic acid salt using a primary or secondary amine as a raw material.
[0005]
[Means for Solving the Problems]
As a result of intensive studies on the above problems, the present inventors have surprisingly been able to cause both N-alkylation and quaternization by reacting a primary or secondary amine with a carboxylic acid ester. In addition, the present inventors have found that various mixed alkyl quaternary ammonium salts are produced by transalkylation reaction by selecting reaction conditions.
[0006]
That is, this invention is the following general formula (3) characterized by reacting the primary or secondary amine represented by the following general formula (1) with the carboxylic acid ester represented by the following general formula (2). The present invention relates to a method for producing the quaternary ammonium organic acid salt represented.
[0007]
[Chemical formula 5]

(In the formula, R ¹ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, and an aromatic group, and R ² has hydrogen or a substituent. And represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, or an aromatic group.
[0008]
[Chemical 6]

(In the formula, R ³ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, or an aromatic group, and R ⁴ has hydrogen or a substituent. And represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, or an aromatic group.
[0009]
[Chemical 7]

(In the formula, n is an integer of 1 to 2, and R ^{1 to} R ⁴ are the same as above.)
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. This reaction is represented by the following reaction formula (5), and a quaternary ammonium carboxylate containing one ester group first is formed from a primary or secondary amine and a carboxylic acid ester. The produced quaternary ammonium carboxylate further reacts with an excess of carboxylic acid ester, whereby the alkyl group is replaced with an ester group.
[0011]
[Chemical 8]

[0012]
Specific examples of the primary or secondary amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, allylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, Examples include di-n-butylamine, diisobutylamine, diallylamine, diphenylamine, and the like.
[0013]
Specific examples of the carboxylic acid ester include formic acid, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, lactic acid, glycolic acid, oxalic acid, benzoic acid, salicylic acid, or 2-hydroxyisobutyric acid methyl, ethyl, propyl, Examples include butyl, pentyl, hexyl, allyl, benzyl, or phenyl ester. Among them, methyl 2-hydroxyisobutyrate is industrially produced as an intermediate of a method for producing methyl methacrylate called a new ACH method (a method that does not produce a by-product sulfate) and can be suitably used. The amount of the carboxylic acid ester used is 1 to 100 mole ratio, preferably 2 to 10 mole ratio, relative to the primary or secondary amine.
[0014]
The reaction can be carried out by either a batch method or a flow method. In the batch system, the reaction is performed by charging a primary or secondary amine and a carboxylic acid ester into a reaction vessel and heating. The raw material charging method is not particularly limited, but in the case of batch operation, all raw materials can be charged at once. The reaction temperature is in the range of 50 to 300 ° C, preferably in the range of 100 to 200 ° C. If the reaction temperature is lower than this, the quaternization rate is slow, and if it is higher than this, the yield decreases due to decomposition. The reaction pressure is not particularly limited, but is preferably normal pressure or higher than the vapor pressure of the reaction mixture corresponding to the reaction temperature. The reaction time cannot be generally specified depending on the type of raw material, the composition of the target mixed quaternary ammonium organic acid salt, the reaction temperature, etc., but is usually in the range of 0.5 to 20 hours.
[0015]
In the present invention, since the reaction is carried out in an excess of carboxylic acid ester, the reaction proceeds suitably without a solvent. However, if necessary, the reaction is carried out using any solvent containing a polar solvent such as alcohol or an additive such as carboxylic acid. You can also. In this invention, it can also carry out in inert gas atmosphere, such as nitrogen, argon, and helium, as needed. The quaternary ammonium organic acid salt from the reaction product liquid can be easily obtained by a conventional method, for example, by distilling off a low boiling fraction and recrystallizing as necessary.
[0016]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples.
[0017]
Example 1
In a shaking autoclave made of SUS316 having an internal volume of 100 ml, 7.1 g (0.1 mol) of diethylamine and 59.0 g (0.5 mol) of methyl 2-hydroxyisobutyrate are charged and heated while shaking. After the temperature in the autoclave reached 160 ° C., the reaction was continued at that temperature for 4 hours. The pressure at this time was 0.4 MPa (gauge pressure). The reaction mixture was cooled after completion of the reaction, and the low boiling content was distilled off from the reaction product solution to obtain 26.5 g of a pale yellow kettle residue. The residue in the kettle was analyzed by ion chromatography. As a result, the mixture was found to be 90.8% by weight of diethyldimethylammonium 2-hydroxyisobutyrate and 5.4% by weight of trimethylethylammonium 2-hydroxyisobutyrate in the quaternary ammonium organic acid salt. The total yield of the quaternary ammonium organic acid salt based on diethylamine was 88.2 mol%.
[0018]
Example 2
A shake type autoclave made of SUS316 having an internal volume of 100 ml was charged with 10.3 g (0.08 mol) of di-n-butylamine and 47.3 g (0.4 mol) of methyl 2-hydroxyisobutyrate and heated while shaking. To do. After the temperature in the autoclave reached 160 ° C., the reaction was continued at that temperature for 4 hours. The pressure at this time was 0.3 MPa (gauge pressure). After completion of the reaction, the reaction mixture was cooled and the low boiling point was distilled off from the reaction product solution to obtain 22.3 g of a light yellow kettle residue. When the residue of the kettle was analyzed by ion chromatography, 97.2% by weight of di-n-butyldimethylammonium 2-hydroxyisobutyrate and trimethyl-n-butylammonium 2-hydroxyisobutyrate in the quaternary ammonium organic acid salt The yield of the quaternary ammonium organic acid salt based on di-n-butylamine was 76.2 mol% in total.
[0019]
Example 3
A shake type autoclave made of SUS316 having an internal volume of 100 ml is charged with 4.5 g (0.1 mol) of monoethylamine and 59.1 g (0.5 mol) of methyl 2-hydroxyisobutyrate and heated while shaking. After the temperature in the autoclave reached 160 ° C., the reaction was continued at that temperature for 8 hours. The pressure at this time was 0.5 MPa (gauge pressure). After completion of the reaction, the reaction mixture was cooled and low boiling content was distilled off from the reaction product solution to obtain 19.8 g of a pale yellow kettle residue. The residue in the kettle was analyzed by ion chromatography. As a result, the mixture was found to be 91.1% by weight of trimethylethylammonium 2-hydroxyisobutyrate and 5.6% by weight of tetramethylammonium 2-hydroxyisobutyrate in quaternary ammonium organic acid salt. The total yield of quaternary ammonium organic acid salt based on monoethylamine was 52.9 mol%.
[0020]
Example 4
In a shaking autoclave made of SUS316 having an internal volume of 100 ml, 7.1 g (0.1 mol) of diethylamine and 59.0 g (0.5 mol) of methyl 2-hydroxyisobutyrate are charged and heated while shaking. After the temperature in the autoclave reached 160 ° C., the reaction was continued at that temperature for 8 hours. The pressure at this time was 0.4 MPa (gauge pressure). After the completion of the reaction, the reaction mixture was cooled and the low boiling point was distilled off from the reaction product solution to obtain 27.7 g of a light yellow kettle residue. The residue in the kettle was analyzed by ion chromatography. As a result, it was found to be a mixture of 81.2% by weight of diethyldimethylammonium 2-hydroxyisobutyrate and 12.3% by weight of trimethylethylammonium 2-hydroxyisobutyrate in the quaternary ammonium organic acid salt. The total yield of quaternary ammonium organic acid salt based on diethylamine was 92.2 mol%.
[0021]
Comparative Example 1
The reaction was performed in the same manner as in Example 1 except that 45.0 g (0.5 mol) of dimethyl carbonate was used instead of methyl 2-hydroxyisobutyrate. The pressure gradually increased from the start of the reaction and reached 3.6 MPa after 4 hours. After completion of the reaction, the reaction mixture was cooled and the low boiling point was distilled off from the reaction product solution to obtain 9.3 g of a light brown kettle residue. The residue of the kettle was analyzed by ion chromatography. As a result, it was found to be a mixture of 74.0% by weight of diethyldimethylammonium 2-hydroxyisobutyrate and 23.9% by weight of trimethylethylammonium 2-hydroxyisobutyrate in the quaternary ammonium organic acid salt. The total yield of quaternary ammonium organic acid salt based on diethylamine was 52.7 mol%. Further, the low boiling point distilled off contained methyl N, N-diethylcarbamate.
[0022]
【The invention's effect】
According to the present invention, a quaternary ammonium organic acid salt composition can be industrially advantageously produced from a primary or secondary amine and a carboxylic acid ester, and the industrial significance is extremely great.

Claims (2)

A quaternary represented by the following general formula (3), characterized by reacting a primary or secondary amine represented by the following general formula (1) with a carboxylic acid ester represented by the following general formula (2): Method for producing ammonium organic acid salt.

(In the formula, R ¹ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, and an aromatic group, and R ² has hydrogen or a substituent. And represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, or an aromatic group.

(In the formula, R ³ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, or an aromatic group, and R ⁴ has hydrogen or a substituent. And represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group, or an aromatic group.

(In the formula, n is an integer of 1 to 2, and R ^{1 to} R ⁴ are the same as above.) The method for producing a quaternary ammonium organic acid salt according to claim 1, wherein the carboxylic acid ester is methyl 2-hydroxyisobutyrate.