JP2972709B2 - Method for producing nitrogen-containing heterocyclic quaternary ammonium organic acid salt - Google Patents

Description

Description: TECHNICAL FIELD [0001] The present invention relates to a reaction between a nitrogen-containing heterocyclic tertiary amine and a carbonic acid diester.
Corresponding mono - nitrogen-containing and heterocyclic quaternary ammonium carbonate, further thereto an organic acid were mixed for <br/> by Ri electrolyte to decarboxylation mono - nitrogen-containing heterocyclic quaternary ammonium organic acid It relates to a method for producing a salt. Nitrogen-containing heterocyclic quaternary ammonium organic acid salt obtained by the process of the present invention are useful organic compounds to be used as the electrolyte for the electrolytic solution of water-based and organic-based. [0002] As a method for synthesizing an organic acid salt of quaternary ammonium, generally, a tertiary amine is quaternized with an alkyl halide, dialkyl sulfate or the like under heating, and then a halide anion and a sulfate anion are converted to an organic acid salt. A method of exchanging for an acid is known. For example, when an alkyl halide is used as a quaternizing reagent, the quaternizing reaction is represented by the following formula. [0003] [0004] Further, when an anion exchange reaction of a quaternary ammonium halide salt is carried out, there is known a method in which anion exchange is carried out in an equilibrium manner by a reaction represented by the following formula. [0005] Here, A is an anion species to be exchanged.
When the HA to be exchanged is a very strong acid, the equilibrium is biased on the right side of the equation, and the desired anion exchange reaction may be able to proceed sufficiently. It is extremely difficult to perform an 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, and a method of reacting a quaternary ammonium halide salt with a silver organic acid. In these methods, it is quite difficult to completely remove the starting material anion in the desired quaternary ammonium organic acid salt, which is unsuitable as a production method for obtaining a high-purity quaternary ammonium organic acid salt. . The method using silver organic acid is expensive and unsuitable for industrial production. In view of the above, as a method for producing a high-purity quaternary ammonium organic acid salt, as shown in the following formula,
The most common method is to convert the quaternary ammonium inorganic acid salt into quaternary ammonium hydroxide once (reaction a) and then neutralize with an organic acid (reaction b). [0009] [0010] Various methods are known for producing quaternary ammonium hydroxide by the above (reaction a), but all methods are expensive as industrial methods. In particular, in the case of producing a high-purity product in which the content of the inorganic acid in the quaternary ammonium hydroxide is controlled on the order of ppm, the production cost is considerably high. The present invention enables efficient production in comparison with the method via a conventional hydroxide quaternary ammonium, and high purity of the target product mono
-To provide a new technique for producing a nitrogen-containing heterocyclic quaternary ammonium organic acid salt. According to the present invention, there is provided a method for producing an organic acid salt of a nitrogen-containing heterocyclic quaternary ammonium, comprising the steps of (a) reacting a nitrogen-containing heterocyclic tertiary amine with a carbonic acid diester. the corresponding mono - first step of producing a nitrogen-containing heterocyclic quaternary ammonium carbonate, (b) the resulting mono - mixed with nitrogen-containing heterocyclic quaternary ammonium carbonate and organic acids, carbon dioxide gas generated electrolysis, characterized in that through the second step of anion-exchange organic acid corresponding to allowed removal out of the system, a two-step process consisting of
The present invention proposes a method for producing a mono- nitrogen-containing heterocyclic quaternary ammonium organic acid salt for a liquid . DETAILED DESCRIPTION OF THE INVENTION The nitrogen-containing heterocyclic tertiary amine used as a raw material in the present invention includes N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, Nn- Butylpiperidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine,
N-methylmorpholine, N-butylmorpholine, N,
Including N'-dimethylpiperazine, N, N'-diethylpiperazine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0] -7-undecene and the like. Examples include nitrogen-containing heterocyclic aliphatic amines, pyridine, 4-dimethylaminopyridine, picolines, nitrogen-containing heterocyclic aromatic amines such as N-methylimidazole, N-methylbenzimidazole, quinoline, and 4,4-dipyridyl. be able to. Examples of the carbonate ester include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate and the like. The lower the carbon number of the alkyl group such as dimethyl carbonate, the faster the quaternary reaction proceeds. It can be said to be a preferable raw material. The organic acid is not particularly limited, but the exchange is completed more quickly as the acid is stronger than carbonic acid.
Anion exchange is possible even for a weak acid equal to or less than carbonic acid by shifting the equilibrium by removing carbonate groups in the system as carbon dioxide gas. Specific examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,
Enanthic acid, caprylic acid, pelargonic acid, capric acid,
Undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid,
Stearic acid, nonadecanoic acid, arachidic acid, isobutyric acid, isovaleric acid, isocaproic acid, ethylbutyric acid, methylvaleric acid, isocaprylic acid, propylvaleric acid, ethylcaproic acid, isocapric acid, tuberculostearic acid,
Pivalic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2,2-dimethylhexanoic acid, 2,2
-Dimethylheptanoic acid, 2,2-dimethyloctanoic acid,
2-methyl-2-ethylbutanoic acid, 2-methyl-2-ethylpentanoic acid, 2-methyl-2-ethylhexanoic acid,
2-methyl-2-ethyl-heptanoic acid, 2-methyl-2
-Propylpentanoic acid, 2-methyl-2-propylhexanoic acid, 2-methyl-2-propylheptanoic acid, acrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid , Nonenic acid, decenoic acid, undecenoic acid, dodecenoic acid, tsudunic acid, fisteric acid, goshuyuic acid, palmitoleic acid,
Petroserinic acid, oleic acid, elaidic acid, vaccenic acid, gadolinic acid, methacrylic acid, 3-methylcrotonic acid, tiglic acid, methylpentenoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, trifluoroacetic acid, phenylacetic acid, chloroacetic acid, glycol Aliphatic monocarboxylic acids such as acid and lactic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecane Diacid, tetradecandioic acid, pentadecandioic acid, hexadecandioic acid, heptadecandioic acid, octadecandioic acid, nonadecandioic acid, eicosandioic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, pentylmalonic acid , Hexylmalonic acid, di Methylmalonic acid, methylethylmalonic acid, diethylmalonic acid, methylpropylmalonic acid, methylbutylmalonic acid, ethylpropylmalonic acid, dipropylmalonic acid, ethylbutylmalonic acid, propylbutylmalonic acid, dibutylmalonic acid, methylsuccinic acid, Ethyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, 2-methyl glutaric acid, 3-methyl glutaric acid, 3-methyl-3-ethyl glutaric acid, 3,3-diethyl glutaric acid, maleic Acid, citraconic acid, itaconic acid, methylene glutaric acid, monomethyl maleate, 1,5-octanedicarboxylic acid, 5,6-decanedicarboxylic acid, 1,7-decanedicarboxylic acid, 4,6-dimethyl-4-nonene- 1,2-
Dicarboxylic acid, 4,6-dimethyl-1,2-nonanedicarboxylic acid, 1,7-dodecanedicarboxylic acid, 5-ethyl-1,10-decanedicarboxylic acid, 6-methyl-6-dodecene-1,12-dicarboxylic acid Acid, 6-methyl-1,1
2-dodecanedicarboxylic acid, 6-ethylene-1,12-
Dodecanedicarboxylic acid, 6-ethyl-1,12-dodecanecarboxylic acid, 7-methyl-7-tetradecene-1,1
4-dicarboxylic acid, 7-methyl-1,14-tetradecanedicarboxylic acid, 3-hexyl-4-decene-1,2-
Dicarboxylic acid, 3-hexyl-1,2-decanedicarboxylic acid, 6-ethylene-9-hexadecene-1,16-dicarboxylic acid, 6-ethyl-1,16-hexadecanedicarboxylic acid, 6-phenyl-1,12- Dodecanedicarboxylic acid, 7,12-dimethyl-7,11-octadecadien-1,18-dicarboxylic acid, 7,12-dimethyl-
1,18-octadecanedicarboxylic acid, 6,8-diphenyl-1,14-tetradecanedicarboxylic acid, 1,1-
Cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 5-norbornene-2,
Aliphatic dicarboxylic acids such as 3-dicarboxylic acid, malic acid, glutamic acid, and tartaric acid; aliphatic polycarboxylic acids such as citric acid; and benzoic acid, toluic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid, Butylbenzoic acid, isobutylbenzoic acid, sec-butylbenzoic acid, tert-butylbenzoic acid, hydroxybenzoic acid, anisic acid, ethoxybenzoic acid, propoxybenzoic acid, isopropoxybenzoic acid, butoxybenzoic acid, isobutoxybenzoic acid, second Butoxybenzoic acid, tert-butoxybenzoic acid,
Aminobenzoic acid, N-methylaminobenzoic acid, N-ethylaminobenzoic acid, N-propylaminobenzoic acid, N-
Isopropylaminobenzoic acid, N-butylaminobenzoic acid, N-isobutylaminobenzoic acid, N-sec-butylaminobenzoic acid, N-tert-butylaminobenzoic acid, N, N
Aromatic monocarboxylic acids (including o, m, p-isomers) such as -dimethylaminobenzoic acid, N, N-diethylaminobenzoic acid, nitrobenzoic acid, fluorobenzoic acid, resorcinic acid, phthalic acid, isophthalic acid Aromatic polycarboxylic acids such as terephthalic acid, nitrophthalic acid, trimellitic acid, hemmellitic acid, trimesic acid and pyromellitic acid; phenol, p-fluorophenol, β-
Phenols such as naphthol, o-nitrophenol, p-nitrophenol, p-aminophenol, catechol, resorcinol, 2-chlorophenol, 2,4-dichlorophenol, 4,4'-dihydroxydiphenyl-2,2-propane Can be exemplified. In the first step, the quaternization reaction, the molar ratio of the nitrogen-containing heterocyclic tertiary amine to the carbonic acid diester is 0.2 to 0.2.
5, more preferably from 0.3 to 3, in the presence or absence of a solvent, at a reaction temperature of from 20 to 200 ° C, more preferably from 3 to 3.
Performed at 0-160 ° C. Normally, when the tertiary amine is sufficiently converted to a quaternary compound, the unreacted amine or carbonic acid diester is distilled off together with the solvent, if used, or recrystallized with an appropriate organic solvent if necessary. And sent to the second step. In the second step, a stoichiometric or small excess amount of an organic acid is usually added dropwise to a quaternary ammonium carbonate in the presence or absence of a solvent, and the generated carbon dioxide is reduced in pressure or reacted with an inert gas. Remove by blowing into the system. At this time, the reaction that takes place is represented by the following formula when the nitrogen-containing heterocyclic aliphatic tertiary amine and dimethyl carbonate are used as raw materials. Embedded image Embedded image (Wherein, R ₁ R ₂ R ₃ is a residue constituting a nitrogen-containing heterocyclic aliphatic tertiary amine, and Y is a conjugate base of an organic acid). When a solvent is used, the solid obtained after distilling off the solvent is the desired nitrogen-containing heterocyclic quaternary ammonium organic acid salt. If necessary, a high-purity product can be obtained by recrystallization or the like using an appropriate solvent. When an organic acid slightly exceeding the stoichiometric value is used to completely remove carbonate ions, the excess organic acid can be removed by a treatment such as recrystallization. The present invention will be described in more detail with reference to the following examples. Example 1 (First step) Dimethyl carbonate 6 was added to a stirring type autoclave.
8.8 g, 65.0 g of N-methylpyrrolidine and 60.0 g of methanol as a solvent were charged.
The reaction was conducted at a temperature of 3 ° C. and a reaction pressure of 3 kg / cm ² G for 6 hours. After the reaction, the autoclave was cooled, and the reaction solution was taken out and analyzed by gas chromatography. As a result, the conversion of N-methylpyrrolidine was 98.1%. When unreacted materials and the solvent were distilled off, 130.6 g of a solid was recovered (97.6% of theory). From the results of elemental analysis and H-MNR, this solid was found to be N, N-dimethylpyrrolidinium methyl. It was confirmed to be carbonate. (Second step) 10.0 g of N, N-dimethylpyrrolidinium methyl carbonate was dissolved in 30.0 g of water, and 8.3 g of adipic acid was gradually added to the solution. . Degassing was performed at 40 ° C./20 mmHg for 2 hours to remove carbon dioxide more completely. 20 carbonate ions by ion chromatography
After confirming that the concentration was not more than ppm, water was distilled off. When the residue was recrystallized from methyl ethyl ketone,
12.7 g of N, N-dimethylpyrrolidinium adipate
(88.5% yield based on N-methylpyrrolidine). The resulting mono -N, was subjected to ion analysis of N- dimethyl pyrrolidinium azide Pate, Cl ^-, B
^{_{r -, SO 4 2-, NO}} 3 - Any impurities such as 1p
pm or less, and it was confirmed that the salt was extremely high purity. Example 2 The procedure of Example 1 was repeated except that 10.0 g of N, N-dimethylpyrrolidinium methyl carbonate and 5.4 g of phenol were used in the second step of Example 1. 10.7 g of dinium phenolate (N
94.7% yield based on -methylpyrrolidine). Example 3 (First step) Dimethyl carbonate was added to a stirred autoclave.
8 g, pyridine 10.0 g and methanol 1 as a solvent.
0.0 g, a reaction temperature of 115 ° C. and a reaction pressure of 5.0
The reaction was performed at kg / cm ² G for 12 hours. The reaction product was worked up as in Example 1 to give 16.8 g of a solid (78.5% of theory). Elemental analysis, H-NMR, and the like confirmed that this solid was N-methylpyridinium methyl carbonate. (Second step) Example 1 except that 10.0 g of N-methylpyridinium methyl carbonate and 3.1 g of acetic acid were used.
8.7 g of N-methylpyridinium acetate (75.4% yield based on pyridine) in the same manner as in the (second step).
I got Example 4 The N-methylpyridinium methyl carbonate synthesized in Example 3 (first step) was mixed with an equimolar amount of maleic acid, and the mixture was subjected to the method of Example 3 (second step). -N-methylpyridinium malate was synthesized. Recrystallization gives 96.0% of theory (75.7 relative to pyridine).
(4% yield). Example 5 (First step) Dimethyl carbonate 1 was added to a stirring type autoclave.
7.0 g, 1,5-diazabicyclo [4,3,0] -5
10.0% nonene and 20.0% methanol as solvent
g at a reaction temperature of 115 ° C. and a reaction pressure of 5 kg / cm.
^The reaction was performed at ² G for 12 hours. The reaction product was worked up as in Example 1 to give 12.6 g of a viscous liquid (theoretical 7
2.8%). Elemental analysis, H-NMR, MS, and the like confirmed that the viscous liquid was 1-methyl-1-azonia-5-azabicyclo [4,3,0] -5-nonenemethyl carbonate. (Second step) 1-methyl-1-azonia
The same operation as in Example 1 was carried out except that 8.0 g of 5-azabicyclo [4,3,0] -5-nonenemethyl carbonate and 4.3 g of maleic acid were used.
1-azonia-5-azabicyclo [4,3,0] -5
8.7 g of nonene monomalate (66.7% yield based on 1,5-diazabicyclo [4,3,0] -5-nonene) was obtained. As described above, according to the method of the present invention, it is possible to efficiently produce mono- nitrogen-containing heterocyclic quaternary ammonium organic acid salts for various electrolytic solutions. However, a feature of the present invention is that the target salt can be obtained with high purity at the same time.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-211254 (JP, A) West German Patent Application Publication 24673 (DE, A1) (58) Searched fields (Int. Cl. ⁶ , DB name) ) C07D 213/00-213/20 C07D 295/00-295/02 C07D 487/00-487/04 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] A process for producing a nitrogen-containing heterocyclic quaternary ammonium organic acid salt, comprising: (a) reacting a nitrogen-containing heterocyclic tertiary amine with a carbonic acid diester to produce a corresponding mono-nitrogen-containing heterocyclic quaternary ammonium carbonate. (B) a second step of mixing the generated mono-nitrogen-containing heterocyclic quaternary ammonium carbonate with an organic acid to remove generated carbon dioxide gas out of the system and exchanging anions with the corresponding organic acid; A method for producing a mono- nitrogen-containing heterocyclic quaternary ammonium organic acid salt for an electrolytic solution, comprising the steps of: 2. 2. The electrolyte for an electrolytic solution according to claim 1, wherein the nitrogen-containing heterocyclic tertiary amine is a nitrogen-containing heterocyclic aliphatic amine .
A method for producing a mono- nitrogen-containing heterocyclic quaternary ammonium organic acid salt of the above. 3. 2. The electrolyte for an electrolytic solution according to claim 1, wherein the nitrogen-containing heterocyclic tertiary amine is a nitrogen-containing heterocyclic aromatic amine .
A method for producing a mono- nitrogen-containing heterocyclic quaternary ammonium organic acid salt of the above. 4. The mono for an electrolytic solution according to any one of claims 1 to 3, wherein the organic acid is a monocarboxylic acid.
- method for producing nitrogen-containing heterocyclic quaternary ammonium organic acid salt. 5. 4. The mono-acid for an electrolytic solution according to claim 1, wherein the organic acid is a dicarboxylic acid.
A method for producing a nitrogen-containing heterocyclic quaternary ammonium organic acid salt.