JPH0826052B2 - Method for producing quaternary phosphonium organic acid salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a corresponding quaternary phosphonium carbonate by reacting a phosphine with a carbonic acid diester, which is further mixed with an organic acid for decarboxylation. By producing a quaternary phosphonium organic acid salt.

The quaternary phosphonium organic acid salt obtained by the method of the present invention is useful in various fields such as various catalysts such as relative transfer catalysts, electrolytes for aqueous and organic electrolytic solutions, various additives, and chemicals. It is an organic compound.

[Conventional technology]

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

R₃P + R'X → R₃R'P X (X = halogen) Anion exchange reaction of quaternary phosphonium halide salt
When performing, the anion exchange is carried out equilibrium by the reaction shown in the following formula.
It is known how to do it.

 Where A Is the anion species to be exchanged. Exchanged
I H A Is equilibrium on the right side of the equation in the case of a strong acid
Is biased and the target anion exchange reaction proceeds sufficiently
In some cases, it can be made relatively
With weak acid, anion exchange reaction is carried out by such a reaction.
It is extremely difficult to make them.

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

From the above viewpoint, as a method for producing a high-purity quaternary phosphonium organic acid salt, as shown in the following formula, the quaternary phosphonium halide salt is once converted into a quaternary phosphonium hydroxide (reaction a), and then an organic acid is added. The most general method is the method of neutralizing with (reaction b).

R₃R'P X → R₃R'P OH  (Reaction a) R₃R'P OH + H A → R₃R'P A + H₂O (reaction
b) [Problems to be solved by the invention] Production of quaternary phosphonium hydroxide by the above (reaction a)
Various methods are known as methods, but any method
Is expensive as an industrial production method, and especially quaternary hydroxide
Control the content of halogen ions in phonium on the order of ppm
The manufacturing cost is considerably high when manufacturing high-purity products
It will be expensive.

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

[Means for solving problems]

That is, in the present invention, in the method for producing an organic acid salt of quaternary phosphonium, the first step (b) of producing a corresponding quaternary phosphonium carbonate by reacting (a) a phosphine with a carbonic acid diester is carried out. A quaternary phosphonium carbonate, which is characterized in that a secondary phosphonium carbonate is mixed with an organic acid to remove generated carbon dioxide gas out of the system and anion-exchange with a corresponding organic acid. It proposes a method for producing an organic acid salt.

[Specific Description of the Invention]

Examples of the phosphine as a raw material of the present invention include trimethylphosphine, diethylmethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-
Saturated aliphatic phosphines such as butylphosphine, tri-n-pentylphosphine, tri-i-butylphosphine, di-n-butylmethylphosphine, tricyclohexylphosphine, 1,2-bis (dimethylphosphine) ethane, triallylphosphine Such as unsaturated aliphatic phosphines, triphenylphosphine, tribenzylphosphine, di-n-propylphenylphosphine, diethylphenylphosphine, aromatic phosphines such as n-butyl-diphenylphosphine, 1-ethylphosphorane, 1- Examples thereof include alicyclic phosphines such as phenylphosphorane, 1-phenylphosphane, and 1-phenylphosphane.

Examples of the carbonic acid diester include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, and the like, and the one having a smaller number of carbon atoms in the alkyl group such as dimethyl carbonate is preferable because the quaternization reaction proceeds rapidly.

The organic acid is not particularly limited, but anion exchange is completed more quickly in the case of a stronger acid as compared with carbonic acid.
Further, even with a weak acid equal to or less than carbonic acid, anion exchange is possible by shifting the equilibrium by removing the carbonate radical 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, valmitic acid, heptadecanoic acid,
Stearic acid, nonadecanoic acid, arachidic acid, isobutyric acid, isovaleric acid, isocaproic acid, ethyl butyric acid, methyl valeric acid, isocaprilic acid, propyl valeric acid, ethyl caproic 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, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tsuzuic acid, physterin Acids, goshuyuic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, methacrylic acid, 3-methylcrotonic acid, tiglic acid, methylpentenoic acid, cyclopentanecarboxylic acid,
Aliphatic monocarboxylic acids such as cyclohexanecarboxylic acid, trifluoroacetic acid, phenylacetic acid, chloroacetic acid, glycolic acid, lactic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Acid, undecanedioic acid, dodecanedioic acid,
Tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, pentylmalonic acid Acid, hexylmalonic acid, dimethylmalonic acid, methylethylmalonic acid, diethylmalonic acid,
Methylpropylmalonic acid, methylbutylmalonic acid, ethylpropylmalonic acid, dipropylmalonic acid, ethylbutylmalonic acid, propylbutylmalonic acid, dibutylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 2,2-dimethylsuccinic 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-octane dicarboxylic 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, 6-methyl-1,12-dodecanedicarboxylic acid, 6-ethylene-1,12
-Dodecanedicarboxylic acid, 6-ethyl-1,12-dodecanecarboxylic acid, 7-methyl-7-tetradecene-1,14-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-octadecanediene-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 acids, 5-norbornene-2,3-dicarboxylic acids, aliphatic dicarboxylic acids such as malic acid, glutamic acid and tartaric acid, aliphatic polycarboxylic acids such as citric acid,
Furthermore, benzoic acid, toluic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid, butylbenzoic acid,
Isobutylbenzoic acid, secondary butylbenzoic acid, tertiary butylbenzoic acid, hydroxybenzoic acid, anisic acid, ethoxybenzoic acid, propoxybenzoic acid, isopropoxybenzoic acid, butoxybenzoic acid, isobutoxybenzoic acid, secondary butoxybenzoic acid, Tertiary butoxybenzoic acid, aminobenzoic acid, N-methylaminobenzoic acid, N-ethylaminobenzoic acid, N-propylaminobenzoic acid, N-isopropylaminobenzoic acid, N-butylaminobenzoic acid, N-isobutylaminobenzoic acid Aroma such as acid, N-tert-butylaminobenzoic acid, N-tert-butylaminobenzoic acid, N, N-dimethylaminobenzoic acid, N, N-diethylaminobenzoic acid, nitrobenzoic acid, fluorobenzoic acid, resorcinic acid Group monocarboxylic acids (including o, m, p-isomers), phthalic acid, isophthalic acid, terephthalic acid , Nitrophthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, aromatic polycarboxylic acids such as pyromellitic acid, phenol, p
-Fluorophenol, β-naphthol, o-nitrophenol, p-nitrophenol, p-aminophenol, catechol, resorcin, 2-chlorophenol,
Examples thereof include phenols such as 2,4-dichlorophenol and 4,4'-dihydroxydiphenyl-2,2-propane.

The quaternization reaction which is the first step is carried out at a molar ratio of phosphines to carbonic acid diester of 0.2 to 5, more preferably 0.3 to 3, in the presence or absence of a solvent, a reaction temperature of 20 to 200 ° C.,
More preferably, it is carried out at 30 to 160 ° C. Usually, when the phosphine is sufficiently converted to a quaternary compound, the unreacted phosphine or the carbonic acid diester is distilled off together with the solvent when a solvent is used, or if necessary, recrystallized with a suitable organic solvent. , Sent to the second step.

In the second step, usually, a stoichiometric value or a small excess of an organic acid is added dropwise to a quaternary phosphonium carbonate in the presence or absence of a solvent, and the generated carbon dioxide is depressurized or an inert gas is blown into the reaction system. To remove it. The reaction that occurs at this time is represented by the following equation when dimethyl carbonate is used as a raw material.

(In the formula, R ₁ R ₂ R ₃ is a hydrocarbon residue of phosphine, and Y is a conjugate base of an organic acid.) After the reaction, the by-product alcohol and the solvent are distilled off, and the obtained solid is a quaternary compound. Phosphonium organic acid salt. If necessary, a highly pure product can be obtained by recrystallization or the like with an appropriate solvent.

When an organic acid slightly in excess of the stoichiometric value is used to completely remove carbonate ions, the excess organic acid can be removed by a treatment such as recrystallization.

〔The invention's effect〕

According to the method of the present invention, it is possible to efficiently produce various quaternary phosphonium organic acid salts, but at the same time it is also a great feature of the present invention that the desired salt can be obtained in high purity. is there.

〔Example〕

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

Example-1 (1st process) 9.0 g of dimethyl carbonates and tri-n were put into a stirring type autoclave.
-Butylphosphine (18.5 g) was charged and the reaction was carried out at a reaction temperature of 115 ° C and a reaction pressure of 5.0 kg / cm ² G for 15 hours. After the reaction, the autoclave was cooled, the reaction solution was taken out and analyzed by gas chromatography. The conversion rate of tri-n-butylphosphine was 72.8%, and the solid yield after distilling off unreacted materials and solvent was 17.5 g. Was (theoretical yield 63.6%). It was confirmed from elemental analysis and ¹ H-NMR that this solid was tri-n-butylmethylphosphonium carbonate.

(Second step) 10.0 g of tri-n-butylmethylphosphonium carbonate was dissolved in 10.0 g of water, and 4.2 g of maleic acid was dissolved in 5.0 g of water. did. 40 ℃ / 20m to remove carbon dioxide more completely
After degassing at mHg for 2 hours and confirming that carbonate ion was 20 ppm or less by ion chromatography, water was distilled off. The residue was recrystallized from methyl ethyl ketone to give tri-
11.2 g of n-butylmethylphosphonium monomerate (94.1% of theoretical yield, 5 with respect to tri-n-butylphosphine)
9.8% yield).

Example-2 (First step) 9.0 g of dimethyl carbonate and triethylphosphine as raw materials
When the same reaction as in Example 1 1st step was carried out except that 11.8 g and 10.0 g of methanol were used, 17.2 g of a solid was obtained (78.9% of theoretical yield). From elemental analysis, ¹ H-NMR, etc., it was confirmed that this solid was triethylmethylphosphonium carbonate.

(Second Step) Example-1 Second Example except that 10.0 g of triethylmethylphosphonium carbonate, 7.5 g of adipic acid and 10.0 g of water were used.
When the same operation as the step was performed, 13.5 g of triethylmethylphosphonium monoadipate (94.4% of theoretical yield, 74.5% yield based on triethylphosphine) was obtained.

Example-3 (First Step) A reaction similar to that in the first step of Example-1 was carried out except that 9.0 g of dimethyl carbonate, 17.8 g of 1-phenylphosphane were used as raw materials, and 10.0 g of methanol was used as solvent. g
The solid was obtained (71.3% of theoretical yield). Elemental analysis, ¹ H-NM
From R and the like, this solid was confirmed to be 1-methylphenylphosphanium carbonate.

(Second Step) 1-Methylphenylphosphanium 1-methylphenylphosphanium was prepared by the same procedure as in the second step of Example-1 except that 10.0 g of 1-methylphenylphosphanium carbonate, 3.7 g of phenol and 10.0 of water were used. 10.2 g of phenolate (90.3 of theoretical yield)
%, 64.4% yield based on 1-phenylphosphane).

Example-4 (1st step) Dimethyl carbonate 9.0g as a raw material, triphenylphosphine 26.2g Methanol 10.0g was used as a solvent except having used 10.0g, and when the same reaction was performed, it was a solid of 21.3g. Was obtained (theoretical yield 60.5%). From the elemental analysis and ¹ H-NMR, it was confirmed that this solid was triphenylmethylphosphonium carbonate.

(Second step) 10.0 g of triphenylmethylphosphonium carbonate and acetic acid
The same operation as in the second step of Example 1 was carried out except that 1.8 g and 10.0 g of water were used, and 9.6 g of triphenylmethylphosphonium acetate (96.6% of theoretical yield, 58.4% yield based on triphenylphosphine) was obtained. ) Got.

Claims (1)

[Claims] 1. A method for producing a quaternary phosphonium organic acid salt, which comprises: (a) a first step for producing a corresponding quaternary phosphonium carbonate by reacting a phosphine with a carbonic acid diester; and (b) a produced quaternary phosphonium carbonate. A method for producing a quaternary phosphonium organic acid salt, which comprises performing a second step of producing a corresponding organic acid salt by removing carbon dioxide gas generated by mixing the salt with an organic acid to the outside of the system.