JPH0830047B2 - Method for producing quaternary ammonium organic acid salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a method for producing a quaternary ammonium organic acid salt by mixing quaternary ammonium methyl carbonate, water and an organic acid anhydride to decarboxylate the mixture. Regarding

The quaternary ammonium organic acid salt obtained by the method of the present invention is a useful organic compound used in a wide variety of fields as a phase transfer catalyst, an electrolyte for aqueous and organic electrolytes, various additives, and a chemical. .

[Conventional technology]

As a method for synthesizing an organic acid salt of quaternary ammonium, generally known is a method in which a tertiary amine is quaternized with an alkyl halide or dialkyl sulfuric acid under heating, and then a halide anion or a sulfate anion is exchanged with an organic acid. ing. For example, when an alkyl halide is used as a quaternization reagent, the quaternization reaction is represented by the following formula.

R ₃ N + R′X → R ₃ R′N ⁺ X ⁻ (X = halogen) When anion exchange reaction of a quaternary ammonium halide salt is carried out, a method of equilibrium anion exchange by the reaction shown in the following formula is known. Has been.

_{^{R 3 R'N + X - + H}} + A - → R 3 R'N + A - + H + X - where A ^- is the anion species you want to exchange. Want to exchange
When H ⁺ A ^- is a fairly strong acid, the equilibrium is biased to the right side of the equation, and the target anion exchange reaction may be able to proceed sufficiently, but in relatively weak acids such as organic acids, It is extremely difficult to carry out the anion exchange reaction by such a reaction.

Other methods include a method of reacting a quaternary ammonium halide salt with an organic acid salt of an alkali metal or an alkaline earth metal, a method of reacting a quaternary ammonium halide salt with an organic acid silver, and the like. In the method, it is quite difficult to completely remove the starting material anion in the target quaternary ammonium organic acid salt, and it is unsuitable as a method for obtaining a high-purity quaternary ammonium organic acid salt. The method using organic acid silver is expensive and unsuitable as an industrial production method.

From the above viewpoint, as a method for producing a high-purity quaternary ammonium organic acid salt, as shown in the following formula, the quaternary ammonium halide salt is once converted to quaternary ammonium hydroxide (reaction a), and then the organic acid is added. The most general method is to neutralize (reaction b) with or by reacting with an organic acid anhydride.

_{^{R 3 R'N + X - → R}} 3 R'N + OH - ( reaction _{^{a) R 3 R'N + OH -}} + H + A - → R 3 R'N + A - + H 2 O ( Reaction b) However However, this method is also expensive as an industrial manufacturing method, and the manufacturing cost is considerably high particularly when a high-purity product in which the content of halogen ions in the quaternary ammonium hydroxide is controlled in the ppm order is manufactured.

[Problems to be Solved by the Invention]

As a method for producing a high-purity quaternary ammonium organic acid salt with a low production cost, carbon dioxide gas generated by mixing a quaternary ammonium methyl carbonate and an organic acid is removed out of the system (reaction c). There is a way.

R ₄ N ⁺ MeCO ₃ ⁻ + H ⁺ A ⁻ → R ₄ N ⁺ A ⁻ + MeOH + CO ₂ (Reaction c) In the method for producing the quaternary ammonium organic acid salt according to the above (reaction c), when an organic acid anhydride is used Has
Since the organic acid methyl ester is generated, the purity of the quaternary ammonium organic acid salt cannot be sufficiently obtained.

The present invention is intended to provide a new technique for producing a quaternary ammonium organic acid salt having a high purity, which enables efficient production as compared with the conventional method and has a high purity.

[Means for solving the problem]

The present invention relates to a method for producing a corresponding quaternary ammonium organic acid salt by mixing quaternary ammonium methyl carbonate, water and an organic acid anhydride, wherein the quaternary ammonium methyl carbonate is dissolved in water to produce methanol. Is removed from the system and then mixed with an organic acid anhydride to produce organic acid methyl ester, the generated carbon dioxide is removed to the outside of the system to produce the corresponding organic acid salt with high purity. The present invention provides a method for producing a quaternary ammonium organic acid salt.

[Specific Description of the Invention]

Examples of the quaternary ammonium methyl carbonate as a raw material of the present invention include tetramethylammonium, trimethylethylammonium, trimethyl-n-propylammonium, trimethyl-n-butylammonium, trimethyl-n-hexylammonium and trimethyl-i-propylammonium. Aliphatic ammonium methyl carbonates such as triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trihexylmethylammonium, diethyldimethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium,
N, N-dimethylpyrrolidinium, N, N-ethylmethylpyrrolidinium, N, N-propylmethylpyrrolidinium, N, N
-Butylmethylpyrrolidinium, N, N-hexylmethylpyrrolidinium, N, N-diethylpyrrolidinium, N, N-
Dimethylpiperidinium, N, N-ethylmethylpiperidinium, N, N-propylmethylpiperidinium, N, N-butylmethylpiperidinium, N, N-hexylmethylpiperidinium, N, N-diethyl Piperidinium, N, N-dimethylhexahydroazepinium, N, N-ethylmethylhexahydroazepinium, N, N-propylmethylhexahydroazepinium, N, N-butylmethylhexahydroazepinium , N, N-hexylmethylhexahydroazepinium, N, N-diethylhexahydroazepinium,
N, N-dimethylmorpholinium, N, N-ethylmethylmorpholinium, N, N-butylmethylmorpholinium, N, N-
Diethylmorpholinium, N, N, N ', N'-tetramethylpiperazinium, N, N'-diethyl-N, N'-dimethylpiperazinium, 1-methyl-1-azonia-5-azabicyclo [ 4,3,0] -5-nonene, 1-ethyl-1-azonia-5-azabicyclo [4,3,0] -5-nonene, 1-
Methyl-1-azonia-8-azabicyclo [5,4,0]-
Alicyclic ammonium methyl carbonates such as undecene, 1-ethyl-1-azonia-8-azabicyclo [5,4,0] -undecene, N-methylpyridinium, N, N'-dimethylimidazolium, N, N ' Examples thereof include nitrogen-containing heterocyclic aromatic ammonium methyl carbonates such as dimethylbenzimidazolium and N-methylquinolinium.

The organic acid anhydride is not particularly limited, but specific examples include acetic anhydride, aliphatic monocarboxylic acid anhydrides such as propionic anhydride, maleic anhydride, citraconic acid anhydride, and 1,2-cyclohexanedicarboxylic anhydride. Aromatic polycarboxylic acid anhydrides such as aliphatic dicarboxylic acid anhydrides such as acids, phthalic anhydride, nitrophthalic anhydride (including 3-nitro and 4-nitro compounds), trimetritic anhydride, pyrometritic anhydride Can be illustrated.

The reaction that occurs in the method of the present invention is represented by the following formula.

_{^{R 4 N + MeCO 3 - +}} H 2 OR 4 N + HCO 3 - + MeOH (1) R 4 N + HCO 3 - + HAn → R 4 N + A - + CO 2 (2) ( where HAn the organic acid anhydride In the method of the present invention, the equilibrium of formula (1) is biased to the right side by first dissolving the quaternary ammonium methyl carbonate in water and removing the generated MeOH out of the system. After that, the organic acid anhydride is mixed and reacted with the organic acid anhydride as shown in formula (2).

At this time, the step of removing MeOH out of the system is performed in the presence of water.
The reaction temperature is 0 to 200 ° C, more preferably 20 to 80 ° C, and the reaction is carried out under reduced pressure or normal pressure.

The amount of water is usually 0.1 to 100, more preferably 0.5 to 10 by weight ratio with respect to the quaternary ammonium methyl carbonate.

The degree of MeOH removal is 11% or less, preferably 6.0% or less of the quaternary ammonium bicarbonate produced.
% Or less is desirable.

In the reaction step with the organic acid anhydride, a stoichiometric value or a small excess amount of the organic acid anhydride is mixed with the quaternary ammonium bicarbonate in the presence of water, and the reaction temperature is 0 to 200 ° C., more preferably 20 to 200 ° C. 8
Carbon dioxide gas generated at 0 ° C. is removed from the reaction system under reduced pressure or normal pressure.

Mixing of the organic acid anhydride is in a weight ratio to the organic acid anhydride.
0.5 to 100, more preferably 1 to 10 water was added to the suspension, and a quaternary ammonium bicarbonate solution (95 wt% to 0.1 wt.
%, More preferably 70 to 10 wt%) and vice versa.
1% by weight, more preferably 70 to 10% by weight), or an organic acid anhydride as it is, or a mixture with a water in a weight ratio of 0.01 to 100 is added.

After the reaction, the solvent is distilled off and the resulting solid is the desired quaternary ammonium organic acid salt. If necessary, a highly pure product can be obtained by recrystallization or the like with an appropriate solvent.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example-1 A thermometer and a cooling tube were attached to a 500 ml three-necked flask, 53.2 g of tetramethylammonium methyl carbonate was dissolved in 53.2 g of water, and Me was added while refluxing water at 40 ° C. and 20 mmHg for 1 hour.
OH was distilled off. When the reaction solution was taken out and analyzed by gas chromatography, the content of MeOH was 0.01% or less.
When 52.8 g of phthalic anhydride was added to this solution and heated and stirred at 50 ° C., carbon dioxide gas vigorously foamed. After 1 hour, any unreacted phthalic anhydride that had been suspended was also dissolved, foaming was suppressed, and a colorless transparent solution was formed. In order to remove carbon dioxide more completely, the mixture was degassed at 40 ° C. and 20 mmHg for 1 hour, and then water was distilled off to obtain 85.2 g of a white solid (99.9% yield based on tetramethylammonium methyl carbonate). From elemental analysis, ¹ H-NMR and liquid chromatograph, it was confirmed that this was mono-tetramethylammonium phthalate and the content of monomethylphthalate was 0.1% or less. The resulting mono - where having conducted the ion analysis of tetramethylammonium phthalate, Cl ^-, Br ^-,
Impurities such as SO ₄ ²⁻ and NO ₃ ⁻ are below 1ppm,
It was confirmed to be an extremely high purity salt.

Comparative Example A thermometer and a cooling tube were attached to a 500 ml three-necked flask, 50.5 g of tetramethylammonium methyl carbonate was dissolved in 50.5 g of water, and 50.1 g of phthalic anhydride was added and heated and stirred at 50 ° C., and carbon dioxide gas became violent. It has been foaming. After 1 hour, any unreacted phthalic anhydride that had been suspended was also dissolved, foaming was suppressed, and a colorless transparent solution was formed. In order to more completely remove carbon dioxide, the mixture was degassed at 40 ° C. and 20 mmHg for 1 hour and then water was distilled off to obtain 83.5 g of a white solid. ^{By 1} H-NMR and liquid chromatography, it was confirmed that the obtained white solid contained 8.9% of mono-methyl phthalate in addition to mono-tetramethyl ammonium phthalate.

Example-2N, N-dimethylpyrrolidinium methyl carbonate as a raw material 17.5 g, water 17.5 g, N, N- dimethyl by performing the same operation as in Example 1 except using maleic anhydride 9.8 g 21.4 g (99.6% yield) of pyrrolidinium malate was obtained. The content of monomethylmalate was 0.1% or less, and the impurity ions were all 1 ppm or less.

Example-3 Methyltriethylammonium malate 10.6 g (100%) was prepared in the same manner as in Example 1 except that methyltriethylammonium methyl carbonate 8.8 g, water 8.8 g, and maleic anhydride 4.5 g were used as raw materials. Yield) was obtained. The content of monomethylmalate was 0.1% or less, and the impurity ions were all 1 ppm or less.

Example-4 Trimethylethylammonium malate 9.7 g (99.9%) was prepared in the same manner as in Example 1 except that 7.8 g of trimethylethylammonium methyl carbonate as a raw material, 7.8 g of water and 4.7 g of maleic anhydride were used. Yield) was obtained. The content of monomethylmalate was 0.1% or less, and the impurity ions were all 1 ppm or less.

Example-5 N, N-dimethyl was prepared in the same manner as in Example-1 except that 19.1 g of N, N-dimethylmorpholinium methyl carbonate, 19.1 g of water and 9.8 g of maleic anhydride were used as raw materials. 23.0 g (99.9% yield) of morpholinium malate was obtained. The content of monomethylmalate was 0.1% or less, and the impurity ions were all 1 ppm or less.

Example-6 N, N-dimethyl was prepared in the same manner as in Example-1 except that 18.9 g of N, N-dimethylpiperidinium methyl carbonate, 18.9 g of water and 9.8 g of maleic anhydride were used as raw materials. 22.9 g (100% yield) of piperidinium malate was obtained. The content of monomethylmalate was 0.1% or less, and the impurity ions were all 1 ppm or less.

Example-7 N, N-Dimethylpyrrolidinium methylcarbonate 17.5 g, water 17.5 g, and anhydrous citracon 11.2 g were used as raw materials, and the same operation as in Example-1 was carried out. 22.8 g (99.6% yield) of dinium citracone was obtained. The content of monomethyl citraconic acid was less than 0.1%, and the impurity ions were all less than 1 ppm.

Claims (1)

[Claims] 1. A method for producing a corresponding quaternary ammonium organic acid salt by mixing quaternary ammonium methyl carbonate, water and an organic acid anhydride, which is produced by dissolving quaternary ammonium methyl carbonate in water. A method for producing a quaternary ammonium organic acid salt, which comprises removing carbon dioxide generated by mixing methanol with an organic acid anhydride after removing methanol out of the system.