JP2001089487A - Method for producing phosphazenium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple and efficient method for producing a high-purity phosphazenium salts. SOLUTION: This method for producing a phosphazenium salt comprises controlling a water content in a reaction solution to <=1 wt.%, reacting a salt of a phosphazenium cation and an inorganic anion with 0.5-2 equivalents of a basic compound and then separating the salt of the basic compound and the inorganic anion from the reaction solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a phosphazenium salt. Specifically, the present invention relates to a method for producing a basic phosphazenium salt in which a neutral phosphazenium salt comprising an inorganic anion is anion-exchanged with a basic compound.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 10-77289 discloses that a basic phosphazenium salt is a compound useful as a polymerization catalyst for alkylene oxide when producing a polyoxyalkylene polyol. Furthermore,
The publication discloses a method for producing a phosphazenium salt comprising an anion such as a hydroxy anion or an alkoxy anion, which comprises treating a phosphazenium salt comprising an inorganic anion such as chloride with a hydroxide or alkoxide of an alkali metal or an alkaline earth metal. And a method using an ion exchange resin (page 21, column 40, lines 8 to 19). However, this publication does not disclose any detailed production conditions or the composition of the obtained phosphazenium salt in the method of treating with a hydroxide or alkoxide of an alkali metal or alkaline earth metal.

As a method for producing phosphazenium hydroxide, a method using an ion exchange resin is exemplified. Phosphazenium chloride which is a precursor of phosphazenium hydroxide, for example, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride (JP-A-10-77289,
Page 28, column 53, described in Comparative Example 1).
Since the compound hardly dissolves in water, it is formed because it is necessary to dilute the concentration of the compound in a solution when dissolved in water and a mixed solvent with an organic solvent compatible with water. The concentration of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide is also reduced, and a concentration step is required. Therefore, when the production scale is increased, the production time of the phosphazenium salt becomes longer. Further, when the ion-exchange resin is packed into a column and used, in the operation of exchanging the ion-exchange groups in the ion-exchange resin for hydroxyl groups, a large amount of wastewater must be treated. Thus, a method for producing a phosphazenium salt has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a simple method for preparing a neutral phosphazenium salt comprising an inorganic anion.
Another object of the present invention is to provide a method for efficiently producing a basic phosphazenium salt comprising a high-purity organic anion or hydroxy anion.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a solution comprising a salt comprising a phosphazenium cation and an inorganic anion, and a solution comprising an organic solvent, In producing a basic phosphazenium salt comprising a phosphazenium cation and an organic anion or a hydroxy anion by contacting a basic compound, a specific amount of basic It was found that the above problem could be solved by controlling the water content of the reaction solution at the time of contact to a specific amount or less using a compound, and then separating the salt between the basic compound and the inorganic anion. Was completed. That is, the present invention provides a compound represented by the chemical formula (1):
[Formula 3]

[0006]

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(A, b, c and d in the chemical formula (1) are:
All are integers from 0 to 3 that do not become 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations, and T ^r− represents an inorganic anion having a valence of r), and a salt of a phosphazenium cation and an inorganic anion. A basic compound is added to a solution comprising an organic solvent and reacted to obtain a compound represented by the following chemical formula (2).

[0008]

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(A, b, c and d in the chemical formula (2) are
All are integers from 0 to 3 that do not become 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine to form a ring structure. Q ⁻ represents a hydroxy anion or an alkoxy anion having 1 to 4 carbon atoms), and is a method for producing a phosphazenium salt represented by the formula (1). The reaction is performed by controlling the water content of the reaction solution to 1% by weight or less using 5 to 2 equivalents, and then separating a salt of a basic compound and an inorganic anion by a chemical formula (2). It is a manufacturing method of the represented phosphazenium salt.

[0010] As a preferred production method according to the present invention,
^Tr- in the chemical formula (1) is such that T is chloride,
The above-mentioned production method wherein r is 1 is exemplified. Further, the above-mentioned production method may be mentioned in which at least an equimolar amount of water is added to a solution obtained by separating a salt of a basic compound and an inorganic anion with respect to a phosphazenium cation. The latter method is particularly preferable as a method for producing a phosphazenium salt in which Q ⁻ in chemical formula (2) is a hydroxy anion.

According to the present invention, it is possible to provide a simple, efficient, and highly pure method for producing a basic phosphazenium salt with high purity without going through a complicated operation such as an ion exchange resin method. Therefore, the phosphazenium salt obtained by the production method of the present invention is a very useful compound that can be used not only for organic reactions but also for polymer reactions. In particular, it is useful as a catalyst for addition polymerization of an alkylene oxide to an active hydrogen compound.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a process for preparing a hydroxy anion from a neutral phosphazenium salt comprising an inorganic anion.
And a novel method for producing a basic phosphazenium salt comprising at least one anion selected from alkoxy anions having 1 to 4 carbon atoms.

First, the phosphazenium salt represented by the chemical formula (2) will be described. The phosphazenium salt represented by the chemical formula (2) is the same as the compound described in JP-A-10-77289 (corresponding to the chemical formula (7) described in the publication). In the present invention, in Chemical Formula (2), a,
b, c, and d are integers from 0 to 3 that are not all 0 at the same time. Preferably, regardless of the order of a, b, c and d, (1,1,1,1), (0,1,1,1), (0,1,1)
(0,1,1), (0,0,0,1), and most preferably (1,1,1,1), (0,1,1).
1, 1, 1).

R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine to form a ring structure. R is methyl,
Ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-
Methyl-1-butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl, 1,
1-dimethyl-3,3-dimethylbutyl (tert-octyl), nonyl, decyl, phenyl, 4-toluyl,
Examples thereof include an aliphatic or aromatic hydrocarbon group such as benzyl, 1-phenylethyl, or 2-phenylethyl. Of these, methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl,
An aliphatic hydrocarbon group having 1 to 10 carbon atoms such as tert-octyl is preferred. Most preferred is a methyl group or an ethyl group.

Q ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, or a mixture thereof. The alkoxy anion having 1 to 4 carbon atoms is derived from aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol. The alkoxy anion is preferably methoxy, ethoxy, n-propoxy, and most preferably methoxy, ethoxy. Q ^- is at least one form selected from a hydroxy anion and an alkoxy anion having 1 to 4 carbon atoms, and the abundance ratio of these anions is not particularly limited. Form is determined ^- Q by reaction system for synthesizing a phosphazenium salt. Depending on the composition of the organic solvent used when producing the phosphazenium salt, the molar ratio between the hydroxy anion and the alkoxy anion is from 99.99 / 0.01 to 0.099.
1 / 99.99.

Compounds represented by the chemical formula (2) include tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide,
Tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium methoxide, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium ethoxide, tetrakis [tris (pyrrolidin-1-yl) phospho Ranylideneamino]
Examples thereof include phosphonium tert-butoxide. Preferably, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium methoxide, tetrakis [tris (dimethylamino) phosphonate] [Ranylideneamino] phosphonium ethoxide.

Next, the phosphazenium salt represented by the chemical formula (1) which is a precursor of the phosphazenium salt of the chemical formula (2) will be described. As with the chemical formula (2), the phosphazenium salt of the chemical formula (1) is also disclosed in
It is the same as the compound described in JP-A-77289 (corresponding to the chemical formula (5) in the publication). Also, the manufacturing method is described in Japanese Patent Application Laid-Open No. H10-77289 (page 13
(From column 4, line 12 to page 14, column 26, line 27). Further, in the chemical formula (1), a, b, c, d,
And R are the same as those described in the description of the chemical formula (2).

[0018] r in the formula (1) is an integer of 1 to 3, represents the number of phosphazenium cations, T ^r- is
It shows an inorganic anion having a valence of r. As the inorganic anion,
For example, bromine, chlorine, fluorine, iodine, boric acid, tetrafluoroboric acid, hydrocyanic acid, thiocyanic acid, hydrofluoric acid, hydrochloric acid, or hydrohalic acid such as oxalic acid, nitric acid, sulfuric acid, phosphoric acid , Phosphorous acid, hexafluorophosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafluorothallic acid and perchloric acid. HSO ₄ ⁻ , HCO
₃ ^- There is also. Among these inorganic anions, bromine, chlorine, sulfuric acid, phosphoric acid, phosphorous acid and carbonate ions are preferred, and chlorine, phosphoric acid, phosphorous acid and carbonate ions are most preferred.

In order to obtain the phosphazenium salt represented by the above formula (2), a phosphazenium salt of an inorganic anion is dissolved in an organic solvent, and a required amount of a basic compound is added to the phosphazenium salt of the inorganic anion. Add.

As the organic solvent for dissolving the phosphazenium salt of the inorganic anion, the phosphazenium salt and the basic compound are not chemically changed even when the basic compound is added.
It is preferable that the salt formed from the inorganic anion of the phosphazenium salt and the cation of the basic compound be insoluble at a water content of 1% by weight or less. Examples of such an organic solvent include saturated aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, nonane, and decane; benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. , N-propylbenzene, cumene, 1,2,3-trimethylbenzene, 1,
2,4-trimethylbenzene, mesitylene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 1,2-diisopropylbenzene, 1,3 -Diisopropylbenzene,
Examples thereof include alkyl-substituted aromatic hydrocarbons such as 1,4-diisopropylbenzene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, and dodecylbenzene.

Further, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, o-dibromobenzene, m
Halogenated aromatic hydrocarbons such as -dibromobenzene, 1-bromo-2-chlorobenzene, 1-bromo-3-chlorobenzene, 1-chloronaphthalene or 1-bromonaphthalene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2-bromotoluene, 3-
Bromotoluene, 2,4-dichlorotoluene, 3,4-
Dichlorotoluene, 1-chloro-2-ethylbenzene,
1-chloro-4-ethylbenzene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 1-
Chloro-4-isopropylbenzene, 1-bromo-4-
Examples include halogenated alkyl-substituted aromatic hydrocarbons such as isopropylbenzene, mesityl chloride, 2-chloro-o-xylene and 4-chloro-o-xylene.

Of these, preferred are the above-mentioned saturated aliphatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, and
Halogenated aromatic hydrocarbons. More preferably,
Organic solvents for alkyl-substituted aromatic hydrocarbons and halogenated aromatic hydrocarbons. These organic solvents capable of dissolving the phosphazenium salt of an inorganic anion may be used alone or in combination. The amount of the organic solvent used for dissolving the phosphazenium salt of the inorganic anion is not particularly limited, but is usually 0.5 to 500 parts by weight based on 1 part by weight of the phosphazenium salt. Preferably 0.7 to
The amount is 100 parts by weight, more preferably 1 to 20 parts by weight.

The solution containing a phosphazenium salt of an inorganic anion is a solution in which the separated phosphazenium salt is once dissolved in the above-mentioned organic solvent, and a partially insoluble phosphazenium salt may coexist. This solution is mixed with phosphorus pentachloride and formula (3)

[0024]

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(R in the chemical formula (3) is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same carbon atom may combine to form a ring structure. ), A reaction solution containing a phosphazenium salt of an inorganic anion obtained by reacting the compound with the imino compound represented by the formula (4).

[0026]

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(R in the chemical formula (4) is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine to form a ring structure. ), Which is a solution obtained by solid-liquid separation of a normally solid imino compound hydrochloride, and if necessary, a method of distilling off the solvent of the solution thus obtained. It is a solution or the like in which the desired organic solvent is replaced after the removal.

Of these solutions, a reaction solution containing a phosphazenium salt of an inorganic anion obtained by reacting phosphorus pentachloride with an imino compound of the formula (3) usually produces a by-product of the formula (4) by-produced in this reaction. It is important to use a solution from which solid imino compound hydrochloride is removed by solid-liquid separation from the viewpoint of producing a phosphazenium salt with high purity. Further, as such a solution, a reaction solution in which phosphorus pentachloride and an imino compound of the formula (3) are reacted at a temperature of 10 to 200 ° C. at a molar ratio of the imino compound to phosphorus pentachloride of 7 to 12 is used. It is preferably a solution obtained from When the molar ratio of the imino compound of the formula (3) to phosphorus pentachloride is less than 7, the yield of the phosphazenium salt of the inorganic anion is remarkably reduced, and when the molar ratio exceeds 12, excess imino compound is wasted. In addition, there is a concern that the step of removing the obtained inorganic anion from the phosphazenium salt may be lengthened.

In the present invention, for the purpose of removing the phosphazenium salt of the inorganic anion and the water-soluble impurities contained in the solution in which the phosphazenium salt is dissolved in the above-mentioned organic solvent, washing with water is carried out before contact with the basic compound. May be performed. The washing with water may be any method as long as the solution containing the phosphazenium salt and water are sufficiently contacted. Usually, a method of removing the aqueous phase after the organic phase and the aqueous phase are separated after washing with water is preferably used. When water is mixed in the organic phase, the water can be distilled off under reduced pressure or atmospheric pressure.

The amount of water used in the washing is not particularly limited, but is usually 5 to 500 parts by weight based on 100 parts by weight of the solution containing a phosphazenium salt of an inorganic anion. Depending on the amount of water, the solution can be washed several times. As a preferred method, washing is performed 2 to 5 times with 5 to 100 parts by weight of water per 100 parts by weight of the solution. The temperature and washing time during this operation are not particularly limited, but are usually 10 to 80.
° C, preferably 15 to 40 ° C, more preferably 17 to 3 ° C.
The temperature is 5 ° C. The washing time is within 3 hours, preferably 0.01 to 1 hour, more preferably 0.05 to 0.5 hour. The water content in the solution after the water washing operation is preferably reduced as much as possible in order to improve the purity of the target phosphazenium salt.

Next, a basic compound which is added to a solution containing a phosphazenium salt of an inorganic anion and reacted with the phosphazenium salt in the method of the present invention will be described. Examples of the basic compound used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, alkali metal hydroxides such as cesium hydroxide, and, for example, magnesium hydroxide, hydroxide Alkaline earth metal hydroxides such as calcium, strontium hydroxide and barium hydroxide, and quaternary ammonium salts such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide and trimethylbenzylammonium hydroxide Oxides and the like. Alkoxides of alkali metals, alkaline earth metals, and quaternary ammoniums can also be used. Examples of the alkoxide include alkoxides of aliphatic alcohols having 1 to 4 carbon atoms. These alkoxy anions are derived, for example, from aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol. The alkoxy anion having 1 to 4 carbon atoms is preferably methoxy, ethoxy, or n-propoxy, and most preferably methoxy or ethoxy.

Among these basic compounds, preferred are alkali metal hydroxides and alkali metal alkoxides. More preferred are alkoxides of these alkali metals derived from sodium hydroxide, potassium hydroxide, cesium hydroxide, and aliphatic alcohols having 1 to 4 carbon atoms. Particularly preferred are sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide. These basic compounds may be used alone or in combination.

The amount of the basic compound to be used is 0.5 to 2 equivalents to the phosphazenium salt of the inorganic anion from the viewpoint of the purity of the phosphazenium salt of the desired organic anion or hydroxy anion. Preferably 0.86
To 1.6 equivalents, more preferably 0.91 to 1.3 equivalents.
Equivalent, more preferably 0.95 to 1.2 equivalent. If the amount of the basic compound used is less than 0.5 equivalent, the residual amount of the phosphazenium salt of the inorganic anion in the reaction product increases. When the amount of the phosphazenium salt of the inorganic anion increases, the activity of the phosphazenium salt per unit weight decreases when the target phosphazenium salt is used as a catalyst for an organic reaction or a polymer reaction. In the present invention, the reaction product refers to a compound present in the reaction system after reacting a phosphazenium salt of an inorganic anion with a basic compound. In order to maintain the activity per unit weight of the phosphazenium salt, the amount of the phosphazenium salt of the inorganic anion in the reaction product is preferably reduced as much as possible.

On the other hand, when the amount of the basic compound used exceeds 2 equivalents to the phosphazenium salt of the inorganic anion, the concentration of the basic compound in the total reaction product increases. Depending on the reaction system, since the basic compound reduces the catalytic effect of the phosphazenium salt, the amount of the basic compound needs to be controlled to 2 equivalents or less.

In order to efficiently contact a solution containing a phosphazenium salt of an inorganic anion with a basic compound,
It is preferable to use an organic solvent that dissolves the basic compound. Such organic solvents include, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert
-Aliphatic alcohols such as butanol, propylene glycol, ethylene glycol, diethylene glycol, and glycerin; nitriles such as acetonitrile; and ethers such as tetrahydrofuran.

Among these organic solvents, preferred are aliphatic alcohols. Particularly preferred are methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert.
-Aliphatic alcohols having 1 to 4 carbon atoms such as butanol, ethylene glycol, propylene glycol, diethylene glycol and glycerin. These organic solvents may be used alone or in combination. The amount of these solvents is not particularly limited as long as the basic compound can be sufficiently dissolved, but is usually 0.01 to 5 parts by weight based on 1 part by weight of a solution containing a phosphazenium salt of an inorganic anion. Preferably it is 0.02 to 3 parts by weight, more preferably 0.03 to 2 parts by weight.

As a method of adding a basic compound to a solution containing a phosphazenium salt of an inorganic anion, a method of adding a basic compound or a solution containing a basic compound to the solution containing a phosphazenium salt at one time, or ,
A method in which a basic compound or a solution containing a basic compound is dropped is exemplified.

The reaction conditions after adding the basic compound or the solution containing the basic compound to the solution containing the phosphazenium salt of the inorganic anion are not particularly limited, but the reaction temperature is usually 5 to 5. 180 ° C. Preferably it is 10-50 degreeC, More preferably, it is 15-45 degreeC. The reaction pressure may be either under atmospheric pressure or under pressure. When performing a pressure reaction, 0.8 MPaG or less, preferably 0.5 MPaG or less, more preferably 0.4 M
PaG or less. The reaction time is 0.2 to 3 hours, preferably 0.3 to 2.5 hours, more preferably 0.3 to 1 hour.

As described above, by bringing the phosphazenium salt of the inorganic anion into contact with the basic compound, the inorganic anion is exchanged with one or more anions of an alkoxy anion having 1 to 4 carbon atoms and a hydroxy anion. A phosphazenium salt and a salt in which at least one kind of anion comprising a hydroxy anion of the basic compound and an alkoxy anion having 1 to 4 carbon atoms are replaced with an inorganic anion are produced. At the same time, an inorganic salt of the inorganic anion and the basic substance in the chemical formula (1) is by-produced. The inorganic salt by-produced is separated from the reaction solution. As a method of separating, a method of filtering is exemplified.

A phosphazenium salt of an inorganic anion as a starting material and a phosphazenium salt of at least one anion selected from a hydroxy anion and an alkoxy anion having 1 to 4 carbon atoms as an objective substance are as follows:
It is soluble in a mixture of an organic solvent in which a starting material is dissolved and an organic solvent in which a basic compound is dissolved (hereinafter abbreviated as a reaction solution). However, when the water content in the reaction solution is 1% by weight or less, inorganic salts such as sodium chloride by-produced are hardly soluble in the reaction solution, and therefore, are usually easily removed by a filtration operation or the like. it can. Excessive basic compound present in the reaction solution can also be filtered off after the organic solvent dissolving the basic compound is distilled off from the reaction solution and precipitated as a solid.

On the other hand, if water exceeds 1% by weight in the reaction solution, this water dissolves a phosphazenium salt of an inorganic anion and an inorganic salt by-produced from a basic compound.
It is difficult to separate the inorganic salt from the reaction solution by filtration, which causes a decrease in the yield of the target phosphazenium salt. Therefore, it is preferable to reduce as much as possible the water in the solvent that dissolves the phosphazenium salt of the inorganic anion and the water that dissolves the basic compound. Further, it is preferable to reduce as much as possible the moisture in the reaction solution containing the phosphazenium salt of the inorganic anion and the basic compound. Specifically, the water content in the reaction solution is preferably 1% by weight or less. It is more preferably at most 7000 ppm, even more preferably at most 5,000 ppm.

Further, at least one selected from the group consisting of a hydroxy anion and an alkoxy anion having 1 to 4 carbon atoms in a reaction solution after filtering off a phosphazenium salt of an inorganic anion and an inorganic salt by-produced from a basic compound. The phosphazenium salt of the anion readily forms the phosphazenium salt of the hydroxy anion and an alcohol derived from the alkoxy anion in the presence of water. Therefore, the phosphazenium salt whose purity has been improved by removing the inorganic salt as an impurity by filtration can be converted into a phosphazenium salt of a hydroxy anion by addition of water and stored. At this time, it is preferable to use at least one equivalent of water with respect to the phosphazenium cation. By adding a larger amount, it can be efficiently converted to a hydroxy anion.

An organic solvent is distilled off from the thus obtained solution containing a phosphazenium salt of at least one anion selected from the hydroxy anion and the alkoxy anion having 1 to 4 carbon atoms, to thereby obtain an optional solvent. A concentration of the phosphazenium salt solution can be obtained. Further, if necessary, a purification operation such as recrystallization can be performed on the dried product. The phosphazenium salt obtained by the production method of the present invention is a very useful compound that can be used not only for organic reactions but also for polymer reactions.

[0044]

EXAMPLES Examples of the present invention will be shown below to further clarify aspects of the present invention. First, the compounds used will be described.

(A) Phosphazenium salt of inorganic anion In the chemical formula (1), (a, b, c, d) = (1,
1,1,1), wherein R is a methyl group, r = 1, T = C
l phosphazenium salt of Cl ⁻ (chloride ion) (tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride} [(Me
₂ N) ₃ P = N] ₄ P ⁺ Cl ⁻ ｝ (manufactured by Fluka), hereinafter abbreviated as P5Cl).

(B) Organic solvent dissolving a phosphazenium salt of an inorganic anion (b-1): Toluene (special grade reagent, Wako Pure Chemical Industries, Ltd.). Before the reaction, molecular sieves (manufactured by Union Showa
Model: 4AXH-5) at 10% by weight based on toluene
After the addition and mixing, the mixture was allowed to stand overnight to remove moisture.
Karl Fischer measurement (Measurement device: Hiranuma Sangyo Co., Ltd.)
The product had a water content of 57 ppm in toluene as determined by AQUACOUNTER AQV-7). (B-2): orthodichlorobenzene [Mitsui Chemicals, Inc., dehydrated product. Karl Fischer measurement, (b-1)
In the ortho-dichlorobenzene was 44 ppm. Hereinafter, abbreviated as ODCB].

(C) Basic compound (c-1): sodium hydroxide (special grade reagent, Wako Pure Chemical Industries, Ltd .; hereinafter abbreviated as NaOH). (C-2): Potassium hydroxide (Wako Pure Chemical Industries, Ltd. reagent special grade; hereinafter abbreviated as KOH). (C-3): barium hydroxide (. By Wako Pure Chemical Industries, Ltd. special grade hereinafter abbreviated as _{Ba (OH) 2 · 8H 2} O). (C-4): Sodium methoxide (Wako Pure Chemical Industries, Ltd. reagent grade, hereinafter abbreviated as NaOMe).

(D) Organic solvent dissolving the basic compound (d-1): Methanol [Katayama Chemical Co., Ltd. reagent special grade, dehydrated product. The water content in methanol determined by Karl Fischer measurement (same apparatus as in (b)) was 138 ppm. Hereinafter, it is abbreviated as MeOH]. (D-2): ethanol [Wako Pure Chemical Industries, Ltd. reagent special grade, dehydrated product. Karl Fischer measurement (same device as in (b))
The water content in ethanol determined by the above was 141 ppm. Hereinafter, it is abbreviated as EtOH]. (D-3: isopropanol [special grade, dehydrated product of Wako Pure Chemical Industries, Ltd .; water in isopropanol determined by Karl Fischer measurement (same apparatus as in (b)) is 10%.
It was 5 ppm. Hereinafter, abbreviated as IPA]. (D-4): n-butanol [Wako Pure Chemical Industries, Ltd., reagent grade, dehydrated. The water content in n-butanol determined by Karl Fischer measurement (the same device as in (b)) was 93 p.
pm. Hereinafter, abbreviated as n-BuOH].

(E) Imino compound for producing P5Cl by reacting with phosphorus pentachloride In the chemical formula (3), iminotris (dimethylamino) phospholane ((Me ₂ N) ₃ P wherein R is a methyl group
= NH (Fluka). Hereinafter, it is abbreviated as P1 imine].

By using the above compound, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me ₂ N) ₃ P, a phosphazenium salt of hydroxy anion
^{_{= N] 4 P + OH -}} , hereinafter abbreviated as P5OH}, and,
A phosphazenium salt of an alkoxy anion, for example, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium methoxide} [(Me ₂
N) ₃ P = N] ₄ P ⁺ OMe ⁻ , which is hereinafter referred to as P5OMe. At the time of analysis, a sample was used in which an organic solvent in which P5Cl was dissolved and an organic solvent in which NaOH was dissolved were distilled off from the reaction solution at 60 ° C. and 665 Pa.

The method for analyzing each component in the reaction product will be described below. (1) Phosphazenium salt of inorganic anion (P5Cl)
Concentration (unit: wt%) The chlorine ion concentration (unit: ppm) in the reaction product is determined, the value is divided by the atomic weight of chlorine (unit: g / mol), and the molecular weight of P5Cl (unit: g) / Mol) to calculate the P5Cl concentration in the reaction product. Hereinafter, a method for measuring the chloride ion concentration in the reaction product will be described.

After weighing about 60 mg of a sample on a quartz board,
In an electric furnace, heated to 900 ° C. in an argon / oxygen mixed gas, the mixed gas was absorbed in an aqueous solution of hydrogen peroxide having a concentration of 1 vol%, and ultrapure water (MILLIPORE, small-sized pure water production apparatus, model: MILL) A solution adjusted to a volume of 10 ml with -Q Labo (water adjusted to a specific resistance of 17 MΩ-cm) is used as a test solution. Then, ion chromatography of the test solution (manufactured by Dionex, model: DX-300)
The analysis is performed to determine the chloride ion concentration in the reaction product.
The separation column uses IonPacAS12A (manufactured by Dionex), and uses a 2.7 mM aqueous sodium carbonate solution and a 0.3 mM aqueous sodium hydrogen carbonate solution as eluents.

(2) Concentration of phosphazenium salt of hydroxy anion and alkoxy anion (unit:% by weight) A sample of P5OH was synthesized and measured using the analytical method shown below to obtain the reaction product. And quantification of phosphazenium salts of hydroxy anions and alkoxy anions. First, a production example of P5OH and an analysis method thereof will be described.

31.02 g of P5Cl (manufactured by Fluka)
(40 mmol) was dissolved in 200 ml of a 50% by weight methanol-water mixed solvent to prepare a 0.2 mol / l solution. This solution was distributed at room temperature through a column (diameter 20 mm, height 450 mm) packed with 140 ml of an anion exchange resin (trade name: Levatit MP500, manufactured by Bayer Corp.) exchanged into a hydroxyl group type at a rate of 140 ml / h. did. Subsequently, 450 ml of a 50% by weight methanol-water mixed solvent was flowed at the same speed. After the effluent was concentrated, it was dried at 80 ° C. and 665 Pa to obtain a solid. This solid was dissolved in a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:15 and then recrystallized to obtain 28.76 g of a colorless compound. The yield was 95%.

³¹ P-NMR of tri-n-butyl phosphate as an internal standard compound in a deuterated dimethyl sulfoxide solution (nuclear magnetic resonance apparatus manufactured by JEOL Ltd.)
Has a chemical shift of −33.3 (quintuple, 1P) ppm,
7.7 (doublet, 4P) ppm, assigned as the central phosphorus atom in the tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium cation and the four surrounding phosphorus atoms . The chemical shift of ¹ H-NMR using tetramethylsilane as an internal standard was 2.6 ppm, which was attributed to the methyl group in the tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium cation, Due to coupling with an atom, it is observed as a double line. Elemental analysis value (% by weight) was C: 38.28, H: 9.82, N: 29.4.
3, P: 19.94 (theoretical, C: 38.09, H:
9.72, N: 29.61, P: 20.46). The above is the analysis method of P5OH.

[0056] alkoxy anions phosphazenium salt, for example with respect to the P5OMe analysis method, described above, ³¹
The tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium cation was measured by P-NMR, and the methyl group of the methoxyanion group was measured by ¹ H-NMR using tetramethylsilane as an internal standard. 3.2 ppm). Then, P5O
The following analysis is performed to measure the P5OMe concentration in the case where H and P5OMe are mixed.

The reaction product was previously dissolved in tetrahydrofuran which had been dehydrated with metallic sodium, and 5% by weight of ultrapure water was added to the reaction product, whereby the released methanol was subjected to gas chromatography (Shimadzu). Quantitative measurement is performed using a model (GC-14A, manufactured by Seisakusho Co., Ltd.).
By dividing the methanol concentration (unit: wt%) by its molecular weight and then multiplying by the molecular weight of P5OMe,
The P5OMe concentration (unit:% by weight) is calculated. Further, the reaction product, a phosphoric acid tri -n- butyl as an internal standard compound, was dissolved in deuterated dimethyl sulfoxide, ³¹ P
-NMR (nuclear magnetic resonance apparatus manufactured by JEOL Ltd.) is measured to determine the concentration (unit: mol) of the tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium structure. Then, from the value,
The number of moles of P5OH was determined by subtracting the number of moles obtained by dividing the P5Cl and P5OMe concentrations by the molecular weight of each component,
By multiplying the value by the molecular weight of P5OH, the concentration (unit: wt%) of P5OH in the reaction product is determined.

Except for Examples 4 and 12, and Comparative Example 6, the phosphazenium salts of hydroxy anions and alkoxy anions were called phosphazenium salts of organic anions, and the sum of the concentrations of both was shown. As described above, by the method described in detail,
The composition of the reaction product was determined. The components other than (1) and (2) were confirmed by ion chromatography measurement of the reaction product to be remaining basic compounds, by-product inorganic salts, and compounds derived from the added basic compounds.

Example 1 P5Cl was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel under a nitrogen atmosphere of phosphazenium salt A.
Was added thereto, and toluene (81.9 g) was added to adjust the P5Cl concentration to 17% by weight. With stirring at 25 ° C., a 4.8% by weight solution of sodium hydroxide in MeOH (NaOH 19.
53 mmol, 0.9 equivalent to P5Cl)
It was added dropwise over a period of minutes. After stirring at 25 to 27 ° C for 30 minutes, the temperature was raised to 80 ° C, and the mixture was further stirred for 3 hours to obtain a white suspension. The water content in the reaction solution determined by Karl Fischer measurement was 0.31% by weight. This suspension was filtered under reduced pressure using a 0.45 μm Teflon membrane filter. The obtained filtrate was concentrated and dried at 60 ° C. and 399 Pa to obtain a white solid. As a result of analyzing the white solid by the method described above, the concentration of the phosphazenium salt of the organic anion was 88.3% by weight.
And the concentration of the phosphazenium salt of the inorganic anion is 1
It was 1.5% by weight.

Example 2 The procedure was the same as in Example 1, except that the amount of NaOH used was increased to 1.0 equivalent relative to the phosphazenium salt BP5Cl. The water content in the reaction solution determined by Karl Fischer measurement was 0.3
It was 4% by weight. Analysis of the white solid obtained from the filtrate showed that the concentration of the phosphazenium salt of the organic anion was 9%.
It was 8.4% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.52% by weight. On the other hand, the filter was dried under reduced pressure to obtain 1.25 g of a white solid. KBr
As a result of IR measurement by the method, a broad absorption was observed at around 500 cm ^-1 , and the analysis result of the chlorine content was 59.2% by weight. 7% by weight).

Example 3 The procedure was the same as in Example 1, except that the amount of NaOH used was increased to 1.2 equivalents relative to the phosphazenium salt CP5Cl. The water in this reaction solution determined by Karl Fischer measurement is
It was 0.40% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 97.0% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.51% by weight.

Example 4 The same method as in Example 2 was used except that a 6.5% by weight solution of NaOMe in methanol was used as the phosphazenium salt DP5Cl. The water content in this reaction solution determined by Karl Fischer measurement was 0.01% by weight. The equivalent ratio of P5OH / P5OMe in the filtrate obtained by filtering the reaction solution was 9
9/1. Analysis of the white solid obtained from the filtrate showed that the concentration of the phosphazenium salt of the organic anion was 9%.
It was 8.8% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.13% by weight.

Example 5 Phosphazenium salt E The procedure was the same as in Example 2 except that a MeOH solution of NaOH was replaced by a 5.0% by weight MeOH solution of KOH. The water content in the reaction solution determined by Karl Fischer measurement was 0.32% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 98.6% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.32% by weight.

Example 6 The solvent in which the phosphazenium salt FP5Cl was dissolved was O instead of toluene.
Using DCB, KO instead of MeOH solution of KOH
Example 5 was repeated except that a 4.2 wt% H solution of H in EtOH was used. The water content in the reaction solution determined by Karl Fischer measurement was 0.31% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 98.2% by weight,
The concentration of the phosphazenium salt of the inorganic anion was 1.71% by weight.

Example 7 Phosphazenium salt G 4.0% by weight of KOH instead of KOH in MeOH
The procedure was the same as in Example 5, except that the IPA solution was used.
The water content in the reaction solution determined by Karl Fischer measurement was 0.31% by weight. As a result of analyzing a white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 97.1% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 2.80% by weight.

Example 8 The phosphazenium salt H KOH was replaced by a MeOH solution of 3.0% n-KOH
Example 5 was repeated except that a BuOH solution was used. The water content in this reaction solution determined by Karl Fischer measurement was 0.29% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 96.7% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 3.19% by weight.

Example 9 Instead of MeOH solution of phosphazenium salt I KOH, Ba (OH) ₂ .8H ₂
Example 5 except that a 2.2% MeOH solution of O was used.
Same as. The water content in this reaction solution determined by Karl Fischer measurement was 0.11% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 97.4% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 2.5% by weight.

Example 10 Phosphazenium salt J 25.44 g of phosphorus pentachloride in a 1 Lt glass reactor
(0.122 mol) and 251.83 g of ODCB
Was charged. The temperature was raised to 40 ° C with stirring,
185.03g (1.038mo
l) P1 imine (model of P1 imine relative to phosphorus pentachloride)
Is 8.51) over 1.0 hour.
After completion of the dropwise addition, the temperature was further maintained at 40 ° C. for 1.0 hour. Then about
The temperature was raised to 170 ° C. over 1 hour and reacted for 9.0 hours.
Was. (At this point, a part of the reaction solution was collected and mass spectrometry was performed.
Corresponding to the molecular weight of the cation portion of P5Cl
A molecular ion spectrum of 740 was observed. Also, heavy
Using hydrogenated dimethyl sulfoxide solvent, triphosphate
n-butyl was used as an internal standard compound³¹By P-NMR
From the quantitative analysis, it was found that 0.120 mol of P5Cl
Is generated). Reaction solution is uniform when hot
Liquid, but when cooled to room temperature, a white solid precipitated.
I was This white solid is filtered through a 1-liter pressure filter.
The solid was filtered using 104.6 g of ODCB.
And washed. This white solid is deuterated dimethyl sulfo
Using an oxide solvent, tri-n-butyl phosphate as an internal standard
Compound ³¹From quantitative analysis by P-NMR, P1
It was found to be 0.476 mol of the min hydrochloride. Chemistry
The shift is 43.4 (single line, 1P) ppm,
Assigned as the phosphorus atom in the P1 imine cation.

The obtained filtrate was transferred to a 1 Lt separating funnel, and 77 g of water was added thereto. By vigorously shaking at room temperature for 0.2 hours, the two phases were brought into good contact with each other and washed. After standing, the organic phase and the aqueous phase were separated and separated. The organic phase was again transferred to a separating funnel, and this water washing operation was performed twice more in the same manner. 10 of the organic phases thus washed with water
2.78 g was charged into a 300 ml eggplant flask equipped with a thermometer and a stirrer. P5 confirmed by quantitative analysis by ³¹ P-NMR using a deuterated dimethyl sulfoxide solvent and tri-n-butyl phosphate as an internal standard compound
The Cl concentration was 25.0% (0.0266 mol). While stirring this solution at room temperature, a 4.5% MeOH solution of sodium hydroxide (NaOH 0.1%) was added from a dropping funnel.
[0279 mol, 1.12 g) was added dropwise over 10 minutes. After stirring at room temperature for 1 hour, a white suspension was obtained. The water in this reaction solution determined by Karl Fischer measurement is
It was 0.47% by weight. This suspension was filtered under reduced pressure using a 0.45 μm Teflon filter. The results of ³¹ P-NMR and ¹ H-NMR of the product in the obtained filtrate were the same as those of the above-mentioned analytical method (2), and the yield determined by potentiometric titration was 98%. The obtained filtrate was concentrated to dryness to obtain 19.72 g of a white solid.
As a result of analyzing the obtained white solid, the concentration of the phosphazenium salt of the organic anion was 98.1% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.75% by weight. On the other hand, the filter cake was dried under reduced pressure.
2 g of a white solid were obtained. As a result of IR measurement by the KBr method, a broad absorption was observed at around 500 cm ^-1 , and the analysis result of the chlorine content was 59.6% by weight. .7
% By weight).

Example 11 Phosphazenium Salt K A solvent in which a phosphazenium salt of an inorganic anion was dissolved was dissolved in O
Water was added to DCB to 0.8% by weight, and 4.8% by weight of NaOH in MeOH was used instead of the MeOH solution of KOH.
Example 6 was repeated except that the H solution was used. The water content in the reaction solution determined by Karl Fischer measurement was 0.90% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 86.2% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 12.9% by weight.

Example 12 Phosphazenium salt L 30.96 g of a white suspension containing a phosphazenium salt of an organic anion obtained in Example 4 (23.9% by weight of phosphazenium cation, 0.0100 mol) were added to a filtrate.
0.189 g of water (0.0105 mol, 1.05 equivalent based on the phosphazenium cation) was added, and 1 hour,
Stir at room temperature. The equivalent ratio of P5OH / P5OMe determined by analyzing the released MeOH is 100/0
Met.

Example 13 Phosphazenium Salt M 37.15 g (23.9% by weight of phosphazenium cation, 0.0120 mol) of a filtrate of a reaction solution containing a phosphazenium salt of an organic anion obtained in Example 4 was added with water 0 .198 g (0.011 mol, 0.92 equivalents) was added and stirred at room temperature for 24 hours. The equivalent ratio of P5OH / P5OMe determined by analyzing the released MeOH was 93/7.

Comparative Example 1 The procedure was the same as in Example 1 except that the amount of NaOH used was reduced to 0.4 equivalent relative to the phosphazenium salt NP5Cl. The water content of the reaction solution determined by Karl Fischer measurement was 0.15% by weight. As a result of analyzing a white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 37.
4% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 62.4% by weight.

Comparative Example 2 The procedure was the same as in Example 1 except that the amount of NaOH used was increased to 2.1 equivalents relative to the phosphazenium salt OP5Cl. The water content of the reaction solution determined by Karl Fischer measurement was 0.61% by weight. As a result of analyzing a white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 91.
It was 8% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.42% by weight.

Comparative Example 3 Phosphazenium Salt P Solvent O in which a phosphazenium salt of an inorganic anion was dissolved
Water was added to DCB to 1% by weight, and EtOH of KOH was added.
Example 6 was repeated except that a 4.8% by weight MeOH solution of NaOH was used instead of the OH solution. The water content of this reaction solution determined by Karl Fischer measurement was 1.
It was 04% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 78.9% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 19.4% by weight.

Comparative Example 4 Phosphazenium Salt Q A solvent in which a phosphazenium salt of an inorganic anion was dissolved was dissolved in O
Water was added to DCB to 2% by weight and EtOH of KOH was added.
Example 6 was repeated except that a 4.8% by weight MeOH solution of NaOH was used instead of the OH solution. The water content of this reaction solution determined by Karl Fischer measurement was 1.
It was 74% by weight. As a result of analyzing the white solid obtained from the filtrate, the concentration of the phosphazenium salt of the organic anion was 67.2% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 32.0% by weight.

Comparative Example 5 ODCB was used as a solvent for dissolving the phosphazenium salt RP5Cl,
Example 2 was carried out in the same manner as in Example 2 except that a 5% aqueous solution of NaOH was used instead of the MeOH solution of OH. An aqueous NaOH solution was added dropwise to the P5Cl solution over 15 minutes. 25-
The mixture was stirred at 27 ° C for 1 hour. Collect the reaction solution while stirring,
The water content determined by Karl Fischer measurement was 14.55.
% By weight. When the stirring was stopped, an organic phase and an aqueous phase were separated. As a result of analyzing the white solid obtained by concentrating and drying the organic phase separated by a 200-ml separating funnel, the concentration of the phosphazenium salt of the organic anion was 0.0% by weight,
The concentration of the phosphazenium salt of the inorganic anion was 99.9% by weight. Above, Examples 1 to 13 and Comparative Examples 1 to
The results of No. 5 are summarized in [Table 1] to [Table 3].

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

<Consideration of Examples> In Examples 1 to 13 in which the use amount of the basic compound with respect to the phosphazenium salt (P5Cl) of the inorganic anion is within the range of the present invention, the P5Cl concentration in the reaction product was 15% by weight. % Or less. However, when the amount of the basic compound used is lower than the range of the present invention (Comparative Example 1), the P5Cl concentration becomes 62.4% by weight, and the concentration of the target phosphazenium salt decreases. On the other hand, when the amount of the basic compound used exceeds the upper limit of the present invention (Comparative Example 2), the P5Cl concentration is 15% by weight or less, and the concentration of the phosphazenium salt of the organic anion is 91.
Although the value is as high as 8% by weight, the concentration of a compound derived from a basic compound other than the phosphazenium compound is as high as 6.78% by weight.

Examples 1 to 13 show that the desired phosphazenium salt can be easily and easily produced by adding a basic compound to a solution containing P5Cl and bringing the solution into contact with the solution. From Example 10, a white solid imino compound hydrochloride represented by the chemical formula (4) was obtained from a solution of a phosphazenium salt of an inorganic anion obtained by reacting phosphorus pentachloride with an imino compound represented by the chemical formula (3). It can be seen that using the solution from which the phosphazenium salt of the inorganic anion can be produced in good yield without having to once isolate and purify the phosphazenium salt of the inorganic anion. According to Examples 1 to 13, when the water content in the reaction solution is 1% by weight or less,
It can be seen that a salt of a basic compound and an inorganic anion is substantially insoluble in the reaction solution and the salt can be easily separated, so that a highly pure basic phosphazenium salt can be obtained.
According to Examples 4 and 12, a phosphazenium salt composed of a hydroxy anion and an alkoxy anion was efficiently obtained by adding water of an equimolar amount or more to a phosphazenium cation to a filtrate of a reaction solution from which a salt of a basic compound and an inorganic anion had been separated. It can be seen that the compound can be converted to a phosphazenium salt of a hydroxy anion. On the other hand, Comparative Examples 3 to 5 show that when the water content in the reaction solution exceeds 1% by weight, the residual amount of the phosphazenium salt of the inorganic anion increases, and the yield and purity of the target phosphazenium salt decrease.

[0083]

According to the method of the present invention, a simple, efficient and highly pure phosphazenium salt can be produced without a complicated operation such as an ion exchange resin method. Therefore, the phosphazenium salt obtained by the production method of the present invention is a very useful compound that can be used not only for organic reactions but also for polymer reactions.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoshi Yamazaki 2-1-1 Tango-dori, Minami-ku, Nagoya City, Aichi Prefecture Inside Mitsui Chemicals Co., Ltd. Inventor Saku Izukawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi, Japan Mitsui Chemicals Co., Ltd. (72) Inventor Tadahito 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Pref. 3190 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 4H050 AA02 BB11 BB12 BC10 BC30 BC31 BE10 BE11 BE14 BE60

Claims (7)

[Claims] [Chemical formula 1] [Chemical formula 1] (A, b, c and d in the chemical formula (1) are each an integer of 0 to 3 which are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, In some cases, two Rs on the same nitrogen atom may combine to form a ring structure, r is an integer of 1 to 3, and represents the number of phosphazenium cations, and ^Tr- is a valence. r), a basic compound is added to and reacted with a solution comprising a salt of a phosphazenium cation represented by the formula (2) and an inorganic anion, and an organic solvent. ] (A, b, c, and d in the chemical formula (2) are each an integer of 0 to 3 that is not simultaneously 0. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, Two Rs on the same nitrogen atom may combine to form a ring structure. Q ^- represents a hydroxy anion or an alkoxy anion having 1 to 4 carbon atoms) to produce a phosphazenium salt represented by the following formula: A method comprising using 0.5 to 2 equivalents of a basic compound with respect to a salt represented by the chemical formula (1), and
A method for producing a phosphazenium salt represented by the chemical formula (2), wherein the reaction is performed by controlling the water content of the reaction solution to 1% by weight or less, and then a salt of a basic compound and an inorganic anion is separated. 2. The method for producing a phosphazenium salt according to claim 1, wherein T of T ^{r− in} the chemical formula (1) is chloride and r is 1. 3. The phospha according to claim 1, wherein, after separating the salt of the basic compound and the inorganic anion, at least equimolar water is added to the reaction solution with respect to the phosphazenium cation. A method for producing xenium hydroxide. 4. A solvent of a solution comprising a salt represented by the chemical formula (1) and an organic solvent, wherein the solvent is a saturated aliphatic hydrocarbon, an alkyl-substituted aromatic hydrocarbon, a halogenated aromatic hydrocarbon,
2. The method for producing a phosphazenium salt according to claim 1, wherein the organic solvent is at least one organic solvent selected from a group consisting of a halogenated alkyl-substituted aromatic hydrocarbon. 5. The basic compound is at least one compound selected from hydroxides of alkali metals, alkaline earth metals, or quaternary ammoniums, and alkoxides having 1 to 4 carbon atoms. 2. The method according to claim 1, wherein
A method for producing the phosphazenium salt described above. 6. The basic compound is at least one compound selected from an alkali metal hydroxide and an alkali metal alkoxide having 1 to 4 carbon atoms, wherein the compound is an aliphatic alcohol having 1 to 4 carbon atoms. The method for producing a phosphazenium salt according to claim 1, wherein the method is used as a solution. 7. The method for producing phosphazenium hydroxide according to claim 1, wherein the reaction temperature is 5 to 180 ° C.