JPS62174036A - Production of quaternary ammonium organic carboxylate - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as a surfactant or raw material for medicines, cosmetics, etc., in high purity and yield and in a short time, by reacting an organic carboxylic acid ester with a tertiary amine in the presence of a polar solvent. CONSTITUTION:An organic carboxylic acid ester expressed by formula I (R1 is H or 1-20C alkyl, alkenyl, aromatic group, etc.; R2 is alkyl, phenyl or benzyl) is reacted with a tertiary amine expressed by formula II (R3R4R5 is 1-20C alkyl, alkenyl, phenyl or benzyl) at 1:0.1-10 mol ratio at 100-200 deg.C in the presence of a polar solvent to afford the titled substance. A 1-3C aliphatic alcohol, glycol, aromatic alcohol, acid amide, nitrile, lactone, etc., is used as the polar solvent in an amount of 0.5-30 times, preferably 2-10 times based on either one of the raw materials.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a quaternary ammonium organic carboxylate.

Quaternary ammonium organic carboxylates are widely used as surfactants and are also useful as raw materials for pharmaceuticals and cosmetics. In recent years, quaternary ammonium hydroxide derived from quaternary ammonium organic carboxylic acid salts has been used as a cleaning agent for semiconductor substrates, or as a developer for etching and resist in the manufacturing process of ICs and LSIs.

[Prior art and its problems]

Conventionally, methods for producing quaternary ammonium organic carboxylates include J, Am, Chem, Sac,
86.2965 (1964) describes a method for reacting quaternary ammonium hydroxides with carboxylic acids. Further, JP-A-59-116251 reports a method of treating quaternary ammonium acid sulfate with barium hydroxide and carboxylic acid. However, these methods involve complicated steps and are industrially expensive and impractical.

On the other hand, as a method for producing a quaternary ammonium organic carboxylate by reacting an organic carboxylic acid ester and a tertiary amine, for example, Chemishe Bericht
eVol, pp. 35, 2795-2761, it is described that a carboxylic acid ester such as methyl benzoate, methyl acetate, dimethyl oxalate, dimethyl phthalate, etc. is reacted with a tertiary amine such as trimethylamine.

Also, Tetrahedron Letters No.
, pp. 231817-1822 (1965) describes an example of the reaction between methyl salicylate and 2-dimethylaminoethanol. Furthermore, Chem, Pharm, B
ll, Vol., pp. 3129-136, the reaction of aliphatic carboxylic acid esters with tertiary amines such as triethylamine, 2-dimethylaminoethanol, pyridine, isoquinoline, etc., the reaction of aromatic carboxylic acid esters with triethylamine, 2-dimethylaminoecule, etc. Examples of reactions with tertiary amines such as , pyridine, and inquinoline are described.

However, these examples generally have slow reaction rates, require a long time, and have low yields, so they are not industrially practical methods.

In view of the above-mentioned current situation, it is an object of the present invention to obtain a quaternary ammonium organic acid salt having a fast reaction rate, a high yield, and a high purity in a short time.

[Means to try to solve problems]

The present inventors have made various studies to solve the above problems, and have discovered that by reacting an organic carboxylic acid ester and a tertiary amine in the presence of a polar solvent, the reaction progresses in a short time and achieves high yield. It has been found that the target product can be obtained with high purity.

That is, the present invention relates to a method for producing a quaternary ammonium organic carboxylate salt, which is characterized by reacting an organic carboxylic acid ester and a tertiary amine in the presence of a polar solvent.

The polar solvent used in the present invention has good solubility in organic carboxylic acid esters of raw materials such as aliphatic alcohols having 1 to 3 carbon atoms, glycols, aromatic alcohols, acid amides, nitriles, and γ-lactones. and those with relatively low boiling points are used.

Examples of such polar solvents include methanol,
Aliphatic alcohols with 1 to 3 carbon atoms such as ethanol and propatool, aromatic alcohols such as benzyl alcohol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and low molecular weight polyethylene glycol, formamide, N-methylformamide , N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N-ethylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone , N-ethylpyrrolidone, amides such as acetonitrile, propionitrile, butyronitrile, valeronitrile, acrylonitrile, methacrylonitrile, benzonitrile,
Nitriles such as, rough 1 such as γ-butyrolactone
Examples include -ones, which may be used alone or in combination of two or more. Among these, methanol, ethanol, propatool, benzyl alcohol, ethylene glycol, N,N-dimethylformamide, N-methylformamide, N-methylpyrrolidone, acetonitrile, benzonitrile, γ-butyrolactone and the like are preferred.

In the method of the present invention, it is preferable to use a large amount of these polar solvents, but if the amount is too large, it will take a long time to separate and remove the solvent after the reaction, which is not economically advantageous. Therefore,
In the present invention, the amount used is 0.5 to 30 times (by weight), usually 1 to 20 times, preferably 2 to 10 times the amount of organic carboxylic acid ester or tertiary amine used as the raw material. Ru.

The organic carboxylic acid ester used in the present invention is
General formula R, C00R2 (R, is H or C1-C2o
represents an alkyl group, alkenyl group, aromatic group, substituted aromatic group, R2 is a C4-C alkyl group, phenyl group,
(representing a benzyl group).

Specifically, the organic acid carboxylic acid ester represented by the above general formula includes methyl formate, ethyl formate, propyl formate, butyl formate, benzyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate. , allyl acetate, phenyl acetate, benzyl acetate 1, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl butyrate, propyl butyrate, methyl laurate, ethyl laurate, propyl laurate, methyl stearate, stearic acid Ethyl, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, glycolic acid Methyl, ethyl glycolate, methyl lactate, ethyl lactate, methyl benzoate, methyl toluate, methyl salicylate, ethyl salicylate, methyl hydroxybenzoate,
Ethyl droxybenzoate, methyl nitrobenzoate, methyl methoxybenzoate, dimethyl phthalate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl maleate, diethyl maleate , dimethyl fumarate, diethyl fumarate, dimethyl adipate, dimethyl itaconate, dimethyl citrate, diethyl citrate, and the like. Among these, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, methyl acrylate, methyl methacrylate, methyl lactate, oxalic acid Methyl, methyl benzoate, etc. are preferred.

However, it is not limited to these, and can be appropriately selected depending on the type of the target quaternary ammonium organic carboxylate.

In addition, the tertiary amine has the general formula (RJ4R5) 3N
(In the formula, R-R4Rs is a C1-C2 (l alkyl group,
alkenyl group, phenyl group, benzyl group), specifically trimethylamine, triethylamine,
tripropylamine, tributylamine, trihexylamine, trioctylamine, dimethylethylamine,
Diethylmethylamine, dimethylpropylamine, dipropylmethylamine, dimethyldecylamine, dimethyllaurylamine, dimethyloctylamine, dimethylstearylamine, methyldilaurylamine, dimethyldodecylamine, dimethylhexadecylamine, dimethyloctadecylamine, N, trimethyl Ethanolamine, N,N-diethylethanolamine, N,N-diisopropylethanolamine, N.

N-dibutylethanolamine, N-methyljetanolamine, triethanolamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, N,
Examples include N-dimethylaniline, N,N-dimethylcyclohexylamine, N,N'-tetramethylethyldiamine, and N,N'-tetramethyl-1,3propanediamine. Among these, amines with relatively low boiling points such as trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, and diethylmethylamine are preferred. However, these amines are also selected depending on the type of the target quaternary ammonium organic erphonate.

In the method of the present invention, the amounts of the organic carboxylic acid ester and tertiary amine to be used are appropriately selected in consideration of the types of organic carboxylic acid ester and tertiary amine, reaction conditions, etc. The molar ratio of organic carboxylic acid ester to tertiary amine is in the range of 0.05 to 20, preferably in the range of 0.1 to 10.

The reaction temperature when carrying out the method of the present invention is generally 5
The temperature is in the range of 0 to 300°C, but it is necessary to take into account the reaction rate, the type of solvent used, and the decomposition of the organic carboxylic acid ester as the raw material and the quaternary ammonium organic carboxylate as the target product. is 80-250°C, preferably 100-200°C.

In addition, in the present invention, the reaction can be carried out in an atmosphere that does not affect the reaction, such as nitrogen, argon, helium, -carbon oxide, or hydrogen gas, if necessary.

Furthermore, the method of the present invention can be carried out in any of the batch, semi-batch and continuous methods.

[Effects of the present invention]

According to the method of the present invention, the reaction between an organic carboxylic acid ester and a tertiary amine can be carried out in a short time and in high yield, and a highly pure quaternary ammonium organic carboxylate can be obtained, This is an extremely meaningful method industrially.

〔Example〕

Example 1 100+nj! Into an autoclave with an internal volume of 12.6 g of methyl formate, 11.8 g of alimethylamine, and 24 g of methanol. 'Introduce Og, heat, and shake.

After the temperature inside the autoclave reached 150°C, the reaction was continued at that temperature for 5 hours. After the reaction was completed, the autoclave was cooled and returned to normal pressure, and the contents were analyzed. As a result, tetramethylammonium formate was 95.8% (
mol) (based on trimethylamine). After separating the above liquid reactant from the reaction solvent, it was concentrated and dried as a white solid substance of tetramethylammonium formate 22.7
I got g. The purity of this white solid material was greater than 99%.

Comparative Example 1 The same procedure as in Example 1 was carried out except that no solvent was used in Example 1. As a result, the yield of tetramethylammonium formate was 27.6% (mol) (based on trimethylamine).

Examples 2 to 11 The experiments were carried out under the same conditions as in Example 1 except that the type of solvent was changed. The yield of tetramethylammonium formate is shown in Table 1.

Table 1 Note) Ratios indicate comparative examples.

Examples 12 to 16 The trimethylamine in Example 1 was changed to the tertiary amine shown in the table, and the reaction was carried out under the conditions shown in the table. Table 2 shows the yield of quaternary tetramethylammonium produced (based on tertiary amine).

Examples 17 to 23 The types of organic carboxylic acid esters were varied and reactions were carried out under the conditions shown in the table. Table 3 shows the yield of quaternary tetramethylammonium produced (based on tertiary amine).

Table-5 (1 continuation)

Claims (4)

[Claims] (1) A method for producing a quaternary ammonium organic carboxylate salt, which comprises reacting an organic carboxylic acid ester and a tertiary amine in the presence of a polar solvent. (2) the polar solvent is an aliphatic alcohol having 1 to 3 carbon atoms;
Glycols, aromatic alcohols, acid amides, nitriles,
The method according to claim 1, which is at least one selected from lactones. (3) The polar solvent is methanol, ethanol, propanol, benzyl alcohol, ethylene glycol, N,
N-dimethylformamide, N-methylformamide,
The method according to claim 1, which is one selected from N-methylpyrrolidone, acetamide, benzonitrile, and γ-butyrolactone. (4) The method according to claim 1, wherein the polar solvent is used 0.5 to 30 times (by weight) relative to the raw material organic carbonic acid ester or tertiary amine.