JPH10147590A - Quaternary phosphonium inorganic acid salt and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject new high-purity compound, containing no halogen and useful as a catalyst, an electrolyte, an additive, etc., in the field of electronic materials such as a semiconductor element by reacting a triorganophosphine with an unsarurated carboxylic acid compound and then reacting the resultant compound with an inorganic acid. SOLUTION: This new quaternary phosphonium inorganic acid salt is represented by formula I (R1 to R3 are each a 1-8C alkyl; X is H, a 1-4C alkyl, phenyl, carboxyl or a carboxyl ester; Y is H, methyl or carboxymethyl; A<-> is an anion of an inorganic acid), has >=95% purity without containing a free halogen and is useful as a catalyst, an electrolyte, an additive, etc., in the field of electronic materials such as a semiconductor element, a battery or a cell or a capacitor. The compound is produced by reacting a triorganophosphine represented by the formula PR1 R2 R3 with an unsaturated carboxylic acid compound represented by formula II, providing a phosphonium salt, represented by formula III and having a betaine structure and then reacting the resultant compound with an inorganic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a quaternary phosphonium salt of high purity and a method for producing the same. In particular, the quaternary phosphonium inorganic acid salt of the present invention is produced by a method using no free halogen as a raw material, so that it is difficult to mix even a minute amount of halogen ions in the field of electronic materials such as semiconductor elements, batteries, and capacitors. It is particularly suitable for catalysts, electrolytes, additives, etc.

[0002]

2. Description of the Related Art Conventionally, quaternary phosphonium inorganic acid salts are:
Due to the high cost of the compounds and the difficulty in obtaining them with high purity, their uses have been considerably limited. At present, a known method for producing a quaternary phosphonium inorganic acid salt includes a trialkylphosphine represented by the general formula (R) ₃ P,
The following general formula (5):

[0003]

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(Wherein R ₅ is hydrogen or a hydrocarbyl group, R ₄ is hydrogen, an alkyl group having 1 to 20 carbon atoms, a carboxy group, or an alkoxycarbonyl group having 1 to 20 carbon atoms, and n is 0 to 20) ) By the reaction with α-chloroacid represented by the following general formula (6):

[0005]

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Or a method of obtaining a quaternary phosphonium inorganic acid salt by anion exchange of an anion of the general formula (6) by an ion exchange resin method (JP-A-52-108499). Gazettes) are known. However, since a quaternary phosphonium halogen is used as a raw material, halogen remains in the obtained quaternary phosphonium inorganic acid salt, and the ion exchange method is performed by ion exchange with an ion exchange resin, so that the ion is released from the resin. Amines are mixed in products, and the products obtained in any case are not suitable for electronic materials that require high purity.

[0007]

In view of the above problems, the present inventors have conducted intensive studies on a method for producing a novel quaternary phosphonium inorganic acid salt. As a result, triorganophosphine and unsaturated carboxylic acid compound To produce a phosphonium salt having a betaine structure, and further reacting the compound with an inorganic acid to obtain a high-purity quaternary phosphonium inorganic acid salt containing no halogen as an impurity. The present invention has been completed.
That is, an object of the present invention is to provide a high-purity quaternary phosphonium inorganic acid salt containing substantially no halogen as an impurity and a method for producing the same.

[0008]

The quaternary phosphonium inorganic acid salt to be provided by the present invention is represented by the following general formula (1):

[0009]

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(Wherein R ₁ , R ₂ and R ₃ are a linear or branched alkyl group having 1 to 8 carbon atoms, X is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms) A phenyl group, a carboxyl group or a carboxyl ester group of an alkyl group having 1 to 4 carbon atoms, Y represents hydrogen, a methyl group, a carboxymethyl group, and A ⁻ represents an anion of an inorganic acid.) An acid salt having a purity of 95
% Or higher and a halogen-free high purity phosphonium salt. Also, the manufacturing method is
The following general formula (2):

[0011]

Embedded image PR ₁ R ₂ R ₃ (2)

Wherein R ₁ , R ₂ and R _{3 each} represent a linear or branched alkyl group having 1 to 8 carbon atoms, and a triorganophosphine represented by the following general formula (3):

[0013]

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(Where X is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group or a carboxyl ester group of an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, A methyl group or a carboxymethyl group), and reacting with an unsaturated carboxylic acid compound represented by the following general formula (4):

[0015]

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(Wherein R ₁ , R ₂ , R ₃ , X and Y have the same meanings as described above), a first step of obtaining a phosphonium salt having a betaine structure represented by the following formula: And a second step of reacting the phosphonium salt with the organic acid.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Starting Materials) (Triorganophosphine) The triorganophosphine used in the production of the quaternary phosphonium inorganic acid salt of the present invention is a compound having a linear or branched alkyl group having 1 to 8 carbon atoms, each of R ₁ and R ₁ . ₂ and R ₃ . R ₁ , R ₂ and R ₃
May or may not be the same group, for example, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, 1-methylpentyl, 2-methylpentyl Group, 5-methylhexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-
Examples thereof include a butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, and an isohexyl group. Examples of these triorganophosphines include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine and the like.

(Unsaturated carboxylic acid) In the first step of the production method of the present invention, the unsaturated carboxylic acid to be reacted with the triorganophosphine has the structure of the above general formula (3), and X represents a hydrogen atom , Methyl group, ethyl group, propyl group,
Examples include an alkyl group such as a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group, a phenyl group, a carboxyl group, a carboxymethoxy group, a carboxyethoxy group, and a carboxypropoxy group. Examples of Y include a hydrogen atom, a methyl group, a carboxymethyl group, and the like. Examples of these unsaturated carboxylic acids include:
Examples include acrylic acid, maleic acid, crotonic acid, trans-cinnamic acid, and itaconic acid.

(Inorganic Acid) As the inorganic acid used in the second step of the production method of the present invention, a wide range of inorganic acids can be used, and there is no particular limitation. The inorganic acid can be represented by the general formula (AH), from which an anion that has released a proton is
A in the formula (1) ^- constituting. Specific examples of inorganic acid anions include sulfuric acid, sulfurous acid, amidosulfuric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, perchloric acid, and periodic acid. Acid, orthoperiodic acid, permanganic acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, arsenic acid, arsenous acid, boric acid, borofluorohydrofluoric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, hexafluoric acid Arsenic acid, chromic acid,
Hydrochloric acid, chlorous acid, hypochlorous acid, selenic acid, selenous acid,
Examples thereof include anions such as cyanic acid, thiocyanic acid, telluric acid, telluric acid, silicic acid, hydrofluoric acid, hexafluorosilicic acid, polyphosphoric acid, metaphosphoric acid, and molybdic acid.

(Target Product: Quaternary Phosphonium Inorganic Acid Salt) The quaternary phosphonium inorganic acid salt of the above general formula (1) which is the target compound of the present invention is, for example, triethyl (2-
(Carboxyethyl) phosphonium / p-toluenesulfonate, triethyl (2-carboxyethyl) phosphonium / methanesulfonate, triethyl (2-carboxyethyl) phosphonium chloride, triethyl (2
-Carboxyethyl) phosphonium tetrafluoroborate, triethyl (2-carboxyethyl) phosphonium fluoride, triethyl (2-carboxyethyl) phosphonium sulfate, tri-n-butyl (2-carboxyethyl) phosphonium p-toluenesulfonate, Tri-n-butyl (2-carboxyethyl) phosphonium methanesulfonate, tri-n-butyl (2-carboxyethyl) phosphonium tetrafluoroborate, tri-n-butyl (2-carboxyethyl) phosphonium fluoride, tri- n-butyl (2-carboxyethyl) phosphonium sulfate, tri-n-octyl (2-carboxyethyl) phosphonium p-toluenesulfonate, tri-n-octyl (2-carboxy) Chill) phosphonium methanesulfonate, tri -n- octyl (2-carboxyethyl) phosphonium fluoride, tri -n- octyl (2-carboxyethyl) phosphonium sulfate, triethyl (2-carboxy-1-methylethyl)
Phosphonium ・ p-toluenesulfonate, triethyl (2-carboxy-1-methylethyl) phosphonium
Methanesulfonate, triethyl (2-carboxy-1
-Methylethyl) phosphonium tetrafluoroborate, triethyl (2-carboxy-1-methylethyl)
Phosphonium fluoride, triethyl (2-carboxy-1-methylethyl) phosphonium sulfate, tri-n-butyl (2-carboxy-1-methylethyl) phosphonium p-toluenesulfonate, tri-n-butyl (2-carboxy -1-methylethyl) phosphonium methanesulfonate, tri-n-butyl (2-carboxy-1-methylethyl) phosphonium.
Tetrafluoroborate, tri-n-butyl (2-carboxy-1-methylethyl) phosphonium fluoride, tri-n-butyl (2-carboxy-1-methylethyl) phosphonium sulfate, tri-n-butyl (2- Carboxy-1-phenylethyl) phosphonium / p-toluenesulfonate, tri-n-butyl (2-
Carboxy-1-phenylethyl) phosphonium methanesulfonate, tri-n-butyl (2-carboxy-
1-phenylethyl) phosphonium tetrafluoroborate, tri-n-butyl (2-carboxy-1-phenylethyl) phosphonium fluoride, tri-n-
Butyl (2-carboxy-1-phenylethyl) phosphonium sulfate, tri-n-octyl (2-carboxy-1-phenylethyl) phosphonium / p-toluenesulfonate, tri-n-octyl (2-carboxy-1-phenyl) Ethyl) phosphonium methanesulfonate, tri-n-octyl (2-carboxy-1-phenylethyl) phosphonium tetrafluoroborate, tri-n-octyl (2-carboxy-1-phenylethyl) phosphonium fluoride, tri-n -Octyl (2-carboxy-1-phenylethyl) phosphonium sulfate, tri-n-butyl (2,3-dicarboxypropyl) phosphonium p-toluenesulfonate, tri-n-butyl (2,3-dicarboxypropyl) ) Phosphonium Methanesulfonate, tri -n
-Butyl (2,3-dicarboxypropyl) phosphonium tetrafluoroborate, tri-n-butyl (2,
3-dicarboxypropyl) phosphonium fluoride, tri-n-butyl (2,3-dicarboxypropyl) phosphonium sulfate and the like.

(Manufacturing method) (First step) The first step of the present invention comprises, for example, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n
Trioctanophosphine represented by the general formula (2) such as octylphosphine; and unsaturated compound represented by the general formula (3) such as acrylic acid, maleic acid, crotonic acid, and trans-cinnamic acid. By reacting a carboxylic acid compound, for example, 3-carboxy-3-triethylphosphoniopropanate, 3-carboxy-3-tri-n-butylphosphoniopropanoate, 3-carboxy-3-tri-n-octylphosphonate Niopropanate, 3-carboxy-3-triethylphosphoniobtanate, 3-carboxy-3-tri-n-butylphosphoniobtanate, 3
-Phenyl-3-tri-n-butylphosphoniopropanate, 3-phenyl-3-tri-n-octylphosphoniopropanate, 2-carboxymethyl-3-triethylphosphoniopropanate, 2-carboxymethyl-3
A step of obtaining a phosphonium salt having a betaine structure represented by the general formula (4), such as -tri-n-butylphosphoniopropanoate, 2-carboxymethyl-3-tri-n-octylphosphoniopropanoate, or the like. .

The reaction conditions in the first step are as follows.
The reaction temperature is 0 to 100 ° C, preferably 30 to 80 ° C, and the reaction time is usually 1 to 24 hours, preferably 2 to 15 hours. The reaction may be performed at normal pressure or under pressure.
The molar ratio of the reaction between the triorganophosphine and the carboxylic acid compound is 1: 1 to 1: 5, preferably 1: 1 to 1:
2 mol is suitable. After completion of the reaction, the precipitated crystals are filtered or the reaction solution is concentrated to obtain a phosphonium salt having a betaine structure.

(Second Step) Next, the second step to be performed is to prepare the phosphonium salt having a betaine structure obtained above,
In this step, the desired inorganic acid shown above is reacted in a reaction solvent to obtain a quaternary phosphonium inorganic acid salt represented by the general formula (4). The reaction temperature is usually 10 to 100 ° C,
Preferably it is 20-50 degreeC. The reaction time is usually 0.1
３3 hours, preferably 0.3-1 hour. The molar ratio of the reaction between the phosphonium salt having a betaine structure and the inorganic acid is from 1: 1 to 1: 5, preferably 1: 1. After completion of the reaction, the target compound can be obtained by concentrating the reaction solution by a conventional method. Further, if necessary, a higher purity product can be obtained by performing a recrystallization method or other purification operations.

The reaction solvent in the first step and the second step is not particularly limited as long as it is an inert solvent which does not react with the raw material and the product. For example, alcohols such as water, acetonitrile, methanol, ethanol and propanol are used. , Hexane, linear hydrocarbons such as octane, benzene, xylene, aromatic hydrocarbons such as toluene, dichloromethane,
Halogenated hydrocarbons such as dichloroethane;
Since the quaternary phosphonium inorganic acid salt obtained by the production method of the present invention does not substantially contain halogens as impurities and has a high purity, it can be used in various industrial fields, for example, semiconductors which are reluctant to mix even small amounts of halogen ions. It is particularly suitable for catalysts, electrolytes, additives and the like in the field of electronic materials such as elements, batteries and capacitors. Further, a polymer compound having a phosphonium base can be obtained by reacting with a carboxyl group at the terminal of a quaternary phosphonium inorganic acid salt. Such a functional polymer compound is useful as a polymer compound having antibacterial properties, antistatic properties, conductivity, and flame retardancy.

In the compound according to the present invention as described above, "substantially free of halogen" means that the compound does not contain free halogen ions, and 1 ppm or less as a halogen element. In addition, all of these compounds are characterized by high purity of 95% or more.

[0026]

The present invention will be further described below with reference to examples. Example 1 (Synthesis of tri-n-butyl (2-carboxyethyl) phosphonium.p-toluenesulfonate) A 1-L four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel was sufficiently purged with nitrogen. 202.3 g (1.0 mol) of tri-n-butylphosphine and 300 ml of water were charged. The temperature was raised to 50 ° C., and 75.7 g (1.05 mol) of acrylic acid was gradually added dropwise. After the completion of the dropping, the liquid temperature was raised to 80 ° C., and the mixture was aged for 3 hours. After cooling, unreacted alkylphosphine was checked with carbon disulfide, but was not detected. The reaction solution was concentrated by an evaporator and further dried by a vacuum pump to obtain 278.5 g of a white solid.
I got This solid was dissolved in acetone-ethyl acetate (1: 1).
Recrystallized and dried with a vacuum pump to obtain white crystals 254.
8 g were obtained. The purity determined by perchloric acid titration is 98.
At 8%, the yield was 91.7%. The analysis results were as follows.

[0027] mp; 161.5~162.8 ℃ FAB-MS: 275 [M + H] + 1 H-NMR (TMS, δ): 0.96 (9H, t, J =
7.1 Hz), 1.41 to 1.63 (12H, m), 2.1
9 to 2.35 (6H, m), 2.35 to 2.43 (2H,
m), 2.43-2.61 (2H, m) FT-IR (KBr, cm ^-1 ): 2961, 2934;
2874, 1584, 1466, 1391, 1099,
918

138.7 g (0.5 mol) of 3-tri-n-butylphosphoniopropanoate obtained above was added in 1 L.
And dissolved in 200 ml of pure water. While stirring the solution, a solution prepared by dissolving 95.1 g (0.5 mol) of p-toluenesulfonic acid monohydrate in 200 ml of pure water was added. After stirring at room temperature for 30 minutes, the mixture was concentrated with an evaporator and further dried with a vacuum pump to obtain 222.6 g of a white solid having a melting point of 78 to 81 ° C. The purity of the non-aqueous neutralization titration with perchloric acid is 98.3%
The silver ion concentration by silver nitrate titration is 1 ppm
It was below. The analysis results were as follows.

FAB-MS (Pos.): 275 ¹ H-NMR (TMS, δ): 0.92 (9H, t, J =
6.8 Hz), 1.31 to 1.72 (12H, m), 2.1
9 to 2.41 (6H, m), 2.40 (3H, s), 2.
50 to 2.68 (2H, m), 2.95 to 3.12 (2
H, m), 7.11 to 7.29 (2H, m), 7.71 to
7.89 (2H, m), 9.8 (1H, s) FT-IR (KBr, cm ^-1 ): 3450, 2961,
2933, 2874, 1736, 1240, 1119,
1011 and 682

Example 2 (Synthesis of tri-n-butyl (2-carboxyethyl) phosphonium tetrafluoroborate) By the same procedure as in Example 1, 3-tri-n-butylphosphoniopropanoate was obtained. 138.7 g (0.5 mol) of the compound
The mixture was placed in an L-shaped flask and dissolved in 400 ml of pure water. While stirring, 104.5 g (0.5 mol) of 42% hydrofluoric acid was added to the solution. After stirring at room temperature for 30 minutes, the mixture was concentrated by an evaporator and dried by a vacuum pump to obtain 180.2 g of a colorless transparent viscous liquid. The purity of the neutralization titration with perchloric acid is 98.5%
The silver ion concentration by silver nitrate titration is 1 ppm
It was below.

FAB-MS (Pos.): 275 ¹ H-NMR (TMS, δ): 0.92 (9H, t, J)
= 6.9 Hz), 1.39 to 1.72 (12H, m), 2.
06 to 2.31 (6H, m), 2.48 to 2.56 (2H
, M), 2.66 to 2.82 (2H, m), 8.08 (1
H, s) FT-IR (liquid film, cm ^-1 ): 3450, 2963, 2
937, 2876, 1740, 1467, 1418, 1
240, 1188, 1061, 821

Example 3 (Synthesis of tri-n-butyl (2-carboxyethyl) phosphonium fluoride)
-Tri-n-butylphosphoniopropanoate was obtained, and then 138.7 g (0.5 mol) of the compound was placed in a 1 L eggplant type flask and dissolved in 400 ml of pure water. While stirring this solution, 21.7 g (0.4%) of 47% hydrofluoric acid was added.
5 mol) was added. After stirring at room temperature for 30 minutes, the mixture was concentrated by an evaporator and dried by a vacuum pump to obtain 149.4 g of a colorless transparent viscous liquid. The purity of the neutralization titration with perchloric acid was 99.5%, and the halogen ion concentration by silver nitrate titration was 1 ppm or less. The analysis results were as follows.

FAB-MS (Pos.): 275 ¹ H-NMR (TMS, δ): 0.96 (9H, t, J)
= 7.1 Hz), 1.49 to 1.68 (12H, m), 2.
18 to 2.40 (6H, m), 2.40 to 2.52 (2
H, m), 2.52-2.70 (2H, m), 11.53
(1H, s) FT-IR (liquid film, cm ^-1 ): 2961, 2935, 2
874, 1723, 1466, 1412, 1239, 1
099,817

Example 4 (Synthesis of tri-n-octyl (2-carboxyethyl) phosphonium tetrafluoroborate) The same apparatus as in Example 1 was sufficiently substituted with nitrogen, and 370.6 g of trioctylphosphine (1. (0 mol). Acrylic acid 7
5.7 g (1.05 mol) was dissolved in 300 ml of water and added dropwise in about 30 minutes. Further, it was aged at 80 ° C. for 6 hours.
Unreacted alkylphosphine was checked with carbon disulfide, but was not detected. The reaction solution was concentrated by an evaporator and further dried by a vacuum pump to obtain white crystals.
0.4 g was obtained. The purity determined by perchloric acid titration is 9
At 7.9%, the yield was 95.2%. As a result of measurement by FAB-MS, the product was 3-tri-n-octylphosphoniopropanate. 226.1 g (0.5 mol) of 3-tri-n-octylphosphoniopropanoate was added to 1
The mixture was placed in an L-shaped flask and dissolved in 400 ml of pure water. While stirring, 104.5 g (0.5 mol) of 42% hydrofluoric acid was added to the solution. After stirring at room temperature for 30 minutes, the mixture was concentrated with an evaporator and dried with a vacuum pump to obtain 264.5 g of a colorless transparent viscous liquid. The purity of the neutralization titration with perchloric acid is 98.3%
The silver ion concentration by silver nitrate titration is 1 ppm
It was below.

FAB-MS (Pos.): 443 ¹ H-NMR (TMS, δ): 0.88 (9H, t, J)
= 6.6 Hz), 1.18 to 1.63 (36H, m), 2.
08 to 2.31 (6H, m), 2.38 to 2.51 (2
H, m), 2.70 to 2.86 (2H, m), 8.81
(1H, s) FT-IR (KBr, cm ^-1 ): 3450, 2957,
2927, 2857, 1741, 1466, 1418,
1243, 1065, 819

Example 5 (Synthesis of tri-n-butyl (1,2-dicarboxyethyl) phosphonium sulfate) A 1 L four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel was sufficiently filled with nitrogen. Substituted, tri-n-butylphosphine 20
2.3 g (1.0 mol) were charged. Maleic acid 118.
A solution of 4 g (1.02 mol) dissolved in 300 ml of pure water was gradually added dropwise with stirring over about 30 minutes.
The liquid temperature rose from 16 ° C to 51 ° C. Further, at 60 ° C
For 3 hours. Unreacted alkylphosphine was checked with carbon disulfide, but was not detected. When the reaction solution was cooled, white crystals precipitated at around 40 ° C.
The obtained crystals were separated by filtration and dried with a vacuum pump to obtain 309.5 g of white crystals. As a result of differential thermal analysis of the crystals, the crystals contained 1 mol of water of crystallization, the purity determined by perchloric acid titration was 98.9%, and the yield was 91.0%. The results of various analyzes of this product were as follows.

[0037] mp; 99~100 ℃ FAB-MS: 319 [M + H] + 1 H-NMR (TMS, δ): 0.96 (9H, t, J =
6.0 Hz), 1.1-1.9 (12H, m), 1.9-
2.6 (6H, m), 2.65 to 3.25 (2H, m),
3.38 to 4.02 (1H, m), 7.8 (1H, s) IR (KBr, cm ^-1 ): 3440, 2970, 171
0, 1605, 1465, 1345, 1280, 109
8,902

The obtained 3-carboxy-3-tri-n-
Butylphosphoniopropanate monohydrate 171.6g
(0.5 mol) in a 1 L flask, and add 4 mL of pure water.
Dissolved in 00 ml. While stirring, 25.3 g (0.25 mol) of concentrated sulfuric acid was added to the solution. After stirring at room temperature for 30 minutes, the mixture was concentrated with an evaporator and further dried with a vacuum pump to obtain 179.7 g of a white solid having a melting point of 114 to 115 ° C. The purity of the neutralization titration with perchloric acid was 98.0%, and the halogen ion concentration by silver nitrate titration was 1 ppm or less. The analysis results were as follows.

FAB-MS (Pos.): 319 ¹ H-NMR (TMS, δ): 0.99 (9H, t, J)
= 6.9 Hz), 1.45 to 1.62 (12H, m), 2.
29-2.50 (6H, m), 2.75-2.88 (2
H, m), 3.61-3.72 (1H, m), 9.81
(2H, s) FT-IR (KBr, cm ^-1 ): 3450, 2964,
2936, 2876, 1735, 1466, 1402,
1229, 1119, 837, 620

Example 6 (Synthesis of tri-n-butyl (1,2-dicarboxyethyl) phosphonium chloride) In the same manner as in Example 6, 3-carboxy-3-tri-n-butylphosphoniopropanoate was used. Obtaining the monohydrate and then the compound 171.6
g (0.5 mol) was placed in a 1 L eggplant type flask and dissolved in 400 ml of pure water. While stirring this solution, 3
52.1 g (0.5 mol) of 5% hydrochloric acid were added. After stirring at room temperature for 30 minutes, the mixture was concentrated by an evaporator and dried by a vacuum pump to obtain 178.3 g of a white solid having a melting point of 138 to 139 ° C. The purity of the neutralization titration with perchloric acid was 97.1%, and the halogen ion concentration by silver nitrate titration was 1 ppm or less. The analysis results were as follows.

FAB-MS (Pos.): 319 ¹ H-NMR (TMS, δ): 0.99 (9H, t, J)
= 6.9 Hz), 1.45 to 1.62 (12H, m), 2.
29 to 2.50 (6H, m), 2.91 to 3.08 (2
H, m), 3.82 to 4.00 (1H, m), 9.18
(2H, s) FT-IR (KBr, cm ^-1 ): 3450, 2962,
2934, 2876, 1737, 1401, 1354,
1199, 820

Example 7 (Synthesis of tri-n-butyl (1,2-dicarboxyethyl) phosphonium fluoride) In the same manner as in Example 6, 3-carboxy-3-tri-n-butylphosphoniopropanoate was used. Obtaining the monohydrate, followed by the compound 171.
6 g (0.5 mol) was placed in a 1 L Erlenmeyer flask made of Teflon and dissolved in 400 ml of pure water. While stirring, 21.7 g (0.5 mol) of 47% hydrofluoric acid was added to the solution. After stirring at room temperature for 30 minutes, the mixture was concentrated with an evaporator and further dried with a vacuum pump to obtain a melting point of 6%.
173.9 g of a white solid at 1-74 ° C. were obtained. The purity of the neutralization titration with perchloric acid was 95.2%, and the halogen ion concentration by silver nitrate titration was 1 ppm or less. The analysis results were as follows.

FAB-MS (Pos.): 319 ¹ H-NMR (TMS, δ): 0.96 (9H, t, J)
= 6.8 Hz), 1.45 to 1.62 (12H, m), 2.
28 to 2.49 (6H, m), 2.80 to 3.18 (2
H, m), 3.62 to 3.81 (1H, m), 9.55
(2H, s) FT-IR (KBr, cm ^-1 ): 3450, 2958,
2932, 2873, 1730, 1466, 1212,
903, 725

Example 8 (Synthesis of tri-n-butyl (1,2-dicarboxyethyl) phosphonium methanesulfonate) In the same manner as in Example 6, 3-carboxy-3-tri-n-butylphosphonate was synthesized. Niopropanate monohydrate was obtained, and then 171.6 g (0.5 mol) of the compound was placed in a 1 L eggplant type flask and dissolved in 400 ml of pure water. While stirring, 48.1 g (0.5 mol) of methanesulfonic acid was added to the solution. After stirring at room temperature for 30 minutes, the mixture was concentrated with an evaporator and dried with a vacuum pump to obtain a compound having a melting point of 91%.
205.3 g of a white solid at ９３93 ° C. were obtained. The purity of the neutralization titration with perchloric acid was 98.8%, and the concentration of halogen ions by silver nitrate titration was 1 ppm or less. The analysis results were as follows.

FAB-MS (Pos.): 319 ¹ H-NMR (TMS, δ): 0.97 (9H, t, J)
= 6.8 Hz), 1.45 to 1.71 (12H, m), 2.
22-2.50 (6H, m), 2.79 (3H, s),
3.00 to 3.21 (2H, m), 3.85 to 4.00 (1
H, m), 8.96 (2H, s) FT-IR (KBr, cm ^-1 ): 3540, 2965,
2936, 2875, 1736, 1466, 1407,
1201, 1060, 785

Example 9 (Synthesis of triethyl (1,2-dicarboxyethyl) phosphonium tetrafluoroborate) By the same procedure as in Example 10, 3-carboxy-3-triethylphosphoniopropanoate monohydrate was obtained. And then the compound 127.
9 g (0.5 mol) was placed in a 1 L eggplant type flask, and dissolved in 400 ml of methanol. While stirring, 104.5 g (0.5 mol) of 42% hydrofluoric acid was added to the solution. After stirring at room temperature for 30 minutes, the mixture was concentrated by an evaporator and further dried by a vacuum pump,
160.2 g of a colorless transparent viscous liquid were obtained. The purity of the neutralization titration with perchloric acid was 98.4%, and the halogen ion concentration by silver nitrate titration was 1 ppm or less.

FAB-MS (Pos.): 235 ¹ H-NMR (TMS, δ): 0.98 to 1.42 (9
H, m), 2.18-2.50 (6H, m), 2.80-
3.00 (2H, m), 3.71 to 3.89 (1H,
m), 9.18 (2H, s) FT-IR (KBr, cm ^-1 ): 3450, 2953,
2930, 2894, 1733, 1412, 1234,
1172, 1068, 782

Example 10 (tri-n-butyl (2,3-dicarboxypropyl)
Synthesis of phosphonium methanesulfonate) A 1-L four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel was sufficiently purged with nitrogen, and 202.3 g (1.0 mol) of tri-n-butylphosphine, itacon 132.7 acid
g (1.02 mol) and 300 ml of pure water were charged. The temperature was gradually raised, and the reaction was carried out at 80 ° C. for 4 hours. Unreacted alkylphosphine was checked with carbon disulfide, but was not detected. The reaction solution was concentrated by an evaporator and dried by a vacuum pump to obtain 337.2 g of a white solid.
I got Further, purification by recrystallization from ethyl acetate gave 306.9 g of white crystals having a melting point of 163 to 164 ° C. The analysis results were as follows, and it was 2-carboxymethyl-3-tri-n-butylphosphoniopropanoate. The purity by perchloric acid titration was 99.2%, and the yield after purification was 91.6%.

[0049] FAB-MS: 333 [M + H] + 1 H-NMR (TMS, δ): 0.97 (9H, t, J
= 6.9 Hz), 1.42 to 1.61 (12H, m), 2.
20 to 2.31 (6H, m), 2.31 to 2.68 (2
H, m), 2.68 to 2.78 (2H, m), 2.98 to
3.10 (1H, m) FT-IR (KBr, cm ^-1 ): 3424, 2961,
2935, 2874, 1580, 1467, 1382,
1099, 719, 592

167.6 g (0.5 mol) of 2-carboxymethyl-3-tri-n-butylphosphoniopropanoate
Was placed in a 1 L eggplant type flask and dissolved in 300 ml of pure water. While stirring this solution, methanesulfonic acid 4
8.1 g (0.5 mol) were added. After stirring at room temperature for 30 minutes, the mixture was concentrated by an evaporator, and further dried by a vacuum pump to obtain a white solid 214.
8 g were obtained. The purity of the neutralization titration with perchloric acid is 98.
0%, the silver ion concentration by silver nitrate titration is 1p
pm or less. The analysis results were as follows.

FAB-MS (Pos.): 333 ¹ H-NMR (TMS, δ): 0.96 (9H, t, J)
= 6.6 Hz), 1.42 to 1.61 (12H, m), 2.
20 to 2.32 (6H, m), 2.32 to 2.75 (2
H, m), 2.77 (3H, s), 2.78-3.00
(2H, m), 3.18-3.25 (1H, m), 8.6
9 (2H, s) FT-IR (KBr, cm ^-1 ): 2963, 2931,
2875, 1725, 1466, 1413, 1201,
1060, 786, 563

[0052]

As described above, the quaternary phosphonium inorganic acid salt of the present invention is a compound having a purity of 95% or more and being substantially free of halogens.
For example, it is particularly suitable for catalysts, electrolytes, additives, and the like in the field of electronic materials such as semiconductor elements, batteries, and capacitors that do not like to be mixed even in a trace amount of halogen ions. Also,
According to the production method of the present invention, it can be obtained by an industrially advantageous method, so that its industrial value is extremely large.

Claims (2)

[Claims] 1. The following general formula: (Wherein, R ₁ , R ₂ , and R ₃ are a linear or branched alkyl group having 1 to 8 carbon atoms, X is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group. A carboxyl group or a carboxyl ester group of an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, a methyl group, a carboxymethyl group,
A ^- is a quaternary phosphonium salt of an inorganic acid represented by an anion of a mineral acid), wherein the purity of 95% or more, and is substantially free pure phosphonium salt containing no halogen Quaternary phosphonium mineral salts. 2. A compound represented by the following general formula (2): PR ₁ R ₂ R ₃ (2) (wherein R ₁ , R ₂ and R ₃ are linear or branched having 1 to 8 carbon atoms) A triorganophosphine represented by the following general formula (3): (Wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group or a carboxyl ester group of an alkyl group having 1 to 4 carbon atoms,
Y represents hydrogen, a methyl group, or a carboxymethyl group), and is reacted with an unsaturated carboxylic acid compound represented by the following general formula (4): (Wherein R ₁ , R ₂ , R ₃ , X and Y have the same meanings as described above), a first step of obtaining a phosphonium salt having a betaine structure, and the resulting phosphonium salt having the betaine structure The method for producing a quaternary phosphonium inorganic acid salt according to claim 1, comprising a second step of reacting the inorganic acid with an inorganic acid.