JPH11222492A - Production of iminotris(dimethylamino)phosphorane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing iminotris(dimethylamino) phosphorane from aminotris(dimethylamino)phosphonium chloride in a high purity and in a high yield. SOLUTION: This method for producing iminotris(dimethylamino)phosphorane comprises reacting iminotris(dimethylamino)phosphonium chloride with an alkali metal or alkaline earth metal hydroxide in an aqueous solution in the presence of a solvent slightly dissolving the alkali metal or alkaline earth metal chloride or hydroxide, distilling off water from the reaction mixture containing the produced iminotris(dimethylamino)phosphorane at <=70 deg.C, subjecting the water- removed reaction mixture to a solid-liquid separation treatment to remove the solid contents, and subsequently distilling the filtrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aminotris
(Dimethylamino) phosphonium chloride or [(CH _Three)_Two
N]_ThreeP⁺(NH_Two), Cl^-From iminotris (dimethyla
Mino) phosphorane, also known as 2,2,2-tris (dimethi)
Ruamino) -2λ^FivePhosphazene｝, ie [(CH_Three)_TwoN]_Three
It relates to a simple and effective method for producing P = NH. Imino
Tris (dimethylamino) phosphorane is an alkylene
Phosphazenbe very useful as a catalyst for the polymerization of oxides
Important as an intermediate for synthesis of phosphazenium compounds
Compound.

[0002]

2. Description of the Related Art Aminotris (dimethylamino) phosphonium chloride is reacted with an alkali metal methoxide, or aminotris (dimethylamino) phosphonium tetrafluoroborate is reacted with an alkali metal methoxide in methanol in which these are dissolved. And the method for producing iminotris (dimethylamino) phosphorane are described in "Nahiriten Hemy Technique Laboratorium", Vol. 38, No. 10, p.
m. Tec. Lab., 38 (10), 1990, 1216) or "Liebig Annalen," 1996, p. 1067 (Liebig).
s Ann. 1996, 1067). If a solvent that dissolves these reaction materials is used, the unreacted materials are dissolved, and the alkali metal chloride or tetrafluoroborate by-produced in the reaction is also easily dissolved. Cannot be removed. Therefore, it is necessary to purify the filtrate by distillation. Iminotris (dimethylamino) obtained by further distilling the filtrate
Phosphorane yields were not satisfactory. Further, in producing iminotris (dimethylamino) phosphorane from aminotris (dimethylamino) phosphonium chloride, there is no example in which an aqueous solution of a hydroxide of an alkali metal or an alkaline earth metal, which is widely used industrially, is used.

"Journal of Organometallic Chemistry", Vol. 71, p. 164 of 1974 (J. Org
anometallic Chem., 71, 1974, 164) discloses a method for obtaining iminotris (dimethylamino) phosphorane by hydrolyzing trimethylsilyliminotris (dimethylamino) phosphorane in the presence of an acid catalyst. However, as described on page 162 of the document, the starting material, trimethylsilyl imino tris (dimethylamino) phosphorane, is produced from trimethylsilyl azide, which has a very high explosive property, and there remains an industrial problem.

[0004]

An object of the present invention is to provide a safe method for obtaining iminotris (dimethylamino) phosphorane from aminotris (dimethylamino) phosphonium chloride, and moreover, industrially as a base to be reacted with the chloride, An advantageous alkali metal or alkaline earth metal hydroxide can be used as an aqueous solution, and the reaction results are high. In addition, iminotris (dimethylamino) phosphorane can be obtained with high purity and high yield upon distillation. Is to provide a way.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and found that aminotris (dimethylamino) phosphonium chloride and an aqueous solution of alkali metal or It has been found that when reacted with an alkaline earth metal hydroxide, aminotris (dimethylamino) phosphonium chloride is almost completely consumed and iminotris (dimethylamino) phosphorane is formed in a very high reaction yield. Furthermore, if at least water is distilled off from the reaction mixture at a specific temperature or lower, hydroxides of alkali metal or alkaline earth metal remaining unreacted when used in excess and those metals by-produced in the reaction are removed. Chlorides and the like are sufficiently precipitated as solids and can be easily separated by solid-liquid separation, and if the mother liquor is distilled after removing water and their solid components, surprisingly high distillation can be achieved. The inventors have found that iminotris (dimethylamino) phosphorane is obtained in high yield and high purity, and that the total yield from aminotris (dimethylamino) phosphonium chloride is extremely high, thus completing the present invention.

That is, the present invention relates to a method for preparing aminotris (dimethylamino) phosphonium chloride and an aqueous solution of alkali metal or alkaline earth metal in the presence of a solvent in which chlorides and hydroxides of alkali metals or alkaline earth metals are hardly soluble. By reacting with a hydroxide of a similar metal to form iminotris (dimethylamino) phosphorane, water is distilled off from the reaction mixture at 70 ° C. or lower, and solids are removed by solid-liquid separation. A process for producing iminotris (dimethylamino) phosphorane, comprising obtaining iminotris (dimethylamino) phosphorane by distillation.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Solvents in which chlorides and hydroxides of alkali metals or alkaline earth metals are poorly soluble in the method of the present invention include, for example, normal-pentane,
Aliphatic hydrocarbons such as normal-hexane or cyclohexane, for example, dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether,
Tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, anisole, o-dimethoxybenzene,
Ethers such as ethyl phenyl ether, butyl phenyl ether and o-diethoxy benzene; for example, benzene, toluene, xylene, ethyl benzene, cumene, mesitylene, tetralin, butyl benzene, p-
Cymene, diethylbenzene, diisopropylbenzene,
Aromatic hydrocarbons such as triethylbenzene, cyclohexylbenzene, dipentylbenzene and dodecylbenzene, for example, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, o-dibromo Examples thereof include halogenated aromatic hydrocarbons such as benzene, bromochlorobenzene, o-chlorotoluene, p-chlorotoluene, p-chloroethylbenzene, and 1-chloronaphthalene. In addition, any solvent may be used as long as chlorides and hydroxides of alkali metals or alkaline earth metals are hardly soluble and do not interfere with the object of the method of the present invention.

Of these, preferred are those having 4 carbon atoms such as, for example, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, anisole, o-dimethoxybenzene or ethyl phenyl ether. To 8 ethers such as benzene, toluene, xylene, ethylbenzene, cumene, mesitylene,
Aromatic hydrocarbons having 6 to 10 carbon atoms such as tetralin, butylbenzene, p-cymene or diethylbenzene, such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, o-chlorotoluene,
and chlorinated aromatic hydrocarbons having 6 to 8 carbon atoms such as p-chlorotoluene and p-chloroethylbenzene. Further, among these, those having a higher boiling point than water are more preferable. These solvents may be used alone or in combination of two or more.

The use amount of these solvents is not particularly limited, but is usually 200 parts by weight or less, preferably 1.0 to 100 parts by weight, per 1 part by weight of aminotris (dimethylamino) phosphonium chloride as a raw material. Department
More preferably, it is 1.5 to 20 parts by weight. The chloride may be completely dissolved, but may be partially or entirely insoluble.

The aminotris (dimethylamino) phosphonium chloride used in the method of the present invention may be produced by any method as long as the method of the present invention is not inhibited. For example, "Liebig Annalen" 1
It is obtained by reacting phosgene with hexamethylphosphoric triamide and then reacting with ammonia, as described on page 1066 of 996 (Liebigs Ann. 1996, 1066).
It may be aminotris (dimethylamino) phosphonium chloride in a reaction mixture co-existing with by-product ammonium chloride, or may be isolated from the reaction mixture, or may be isolated from Liebig Annalen, 1996.
Reaction of phosphorus pentachloride with three molecules of dimethylamine as described on page 7 (Liebigs Ann. 1996, 1067)
Aminotris (dimethylamino) phosphonium chloride in the reaction mixture or a mixture isolated from the reaction mixture, which coexists with dimethylammonium chloride and / or ammonium chloride as a by-product obtained by reacting molecular ammonia. Good.

Also, aminotris (dimethylamino) phosphonium chloride converts phosphorus pentachloride to dimethylamine,
Then, in a method for producing aminotris (dimethylamino) phosphonium chloride by reacting with ammonia,
The amount of water introduced into the reaction system is set at 0.
9% by weight or less, phosphorus pentachloride and dimethylamine in the presence of aromatic hydrocarbons, using 5.80 to 6.30 mol of dimethylamine with respect to 1 mol of phosphorus pentachloride, at 0 to 80 ° C. Temperature and 0.001 to 1.
The reaction is carried out under a pressure of 00 MPa (absolute pressure, the same applies hereinafter) to form tris (dimethylamino) phosphonium dichloride. Subsequently, the tris (dimethylamino) phosphonium dichloride and ammonia are used to form one of phosphorus pentachloride used. In a reaction mixture obtained by reacting 1.8 to 50 mol of ammonia with respect to mol at a temperature of 0 to 60 ° C. and a pressure of 0.001 to 1.00 MPa, or a reaction mixture thereof May be isolated from the same.

Furthermore, aminotris (dimethylamino) by-produced when tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride is produced by reacting phosphorus pentachloride with four molecules of iminotris (dimethylamino) phosphorane. As in the case of phosphonium chloride, a product obtained by reacting iminotris (dimethylamino) phosphorane with hydrogen chloride in the reaction and isolating the chloride from the reaction mixture may be used.

When aminotris (dimethylamino) phosphonium chloride is used in the above reaction mixture, if the solvent is the same as the solvent in the method of the present invention, the reaction mixture is used as it is. be able to. When the solvent is not the same, the solvent can be used after the solvent is once distilled off by an appropriate method and then replaced with the solvent in the present invention.

The alkali metal or alkaline earth metal hydroxide in the method of the present invention is, for example, an alkali metal hydroxide such as lithium, sodium, potassium, rubidium or cesium, such as magnesium, calcium, strontium, or the like. Examples include hydroxides of alkaline earth metals such as barium. Of these, alkali metal hydroxides are preferred, and sodium hydroxide or potassium hydroxide is more preferred.

The alkali metal or alkaline earth metal hydroxides may be used alone or in combination. These alkali metal or alkaline earth metal hydroxides are used as an aqueous solution. The concentration of these aqueous solutions is not uniform depending on the kind of the alkali metal or alkaline earth metal hydroxide used, but is usually 80% by weight or less, preferably 5 to 60% by weight.

The amount of the alkali metal or alkaline earth metal hydroxide used is not particularly limited, but is usually 0.7 to 3.0 gram equivalent relative to 1 mol of aminotris (dimethylamino) phosphonium chloride. , Preferably 0.9 to 2.0 gram equivalents, more preferably 1.0 to 1.5 gram equivalents. When dimethylammonium chloride and / or ammonium chloride which consumes an alkali metal or alkaline earth metal hydroxide coexist in the system, the amount of the hydroxide is the same as the total gram equivalent of these compounds. Is used.

In the method of the present invention, aminotris (dimethylamino) phosphonium chloride and an aqueous solution of an alkali metal or alkaline earth metal are dissolved in the presence of a solvent in which chlorides and hydroxides of alkali metals or alkaline earth metals are hardly soluble. The reaction with a hydroxide of a similar metal is carried out, but there is no particular limitation on the method of contacting them. Usually, aminotris (dimethylamino) phosphonium chloride is added to the solvent and then added to the alkali metal or alkaline earth metal. An aqueous solution of the hydroxide is added.

The reaction temperature is generally 70 ° C. or lower, preferably 10 to 65 ° C., more preferably 15 ° C.
To 60 ° C. The reaction time is usually within 24 hours, preferably 0.01 to 10 hours, more preferably 0.02 to 5 hours. The reaction can be carried out under reduced pressure, normal pressure or increased pressure, but usually at normal pressure.

This reaction involves dehydrochlorination,
With the formation of iminotris (dimethylamino) phosphorane, the hydrogen chloride is by-produced as an alkali metal or alkaline earth metal chloride and water. Alkali metal or alkaline earth metal chlorides are usually mostly deposited as solids.

The reaction mixture is not necessarily uniform depending on the concentration of the solvent used and the aqueous solution of the alkali metal or alkaline earth metal hydroxide, and other conditions, but usually the aqueous phase, the organic phase and The iminotris (dimethylamino) phosphorane formed is a liquid phase and is usually dissolved in both the aqueous phase and the organic phase. In this manner, iminotris (dimethylamino) phosphorane can be produced in an extremely high yield using an aqueous solution of a hydroxide of an alkali metal or an alkaline earth metal which is more widely used in industry.

In the method of the present invention, at least water is distilled off from the reaction mixture at a temperature of 70 ° C. or lower. If necessary, solids in the reaction mixture may be removed in advance. As a method for distilling off the water, any method may be used as long as the object of the method of the present invention is not hindered. For example, water can be distilled off by vacuum distillation or a method of sending an inert gas and accompanying it. Usually, vacuum distillation is used. This method can be carried out either by simple distillation or rectification depending on the purpose, and can be carried out either batchwise or continuously.

The state of the concentrated liquid after the water is distilled off depends on the boiling point and the amount of the solvent used. If the solvent has a boiling point lower than that of water, the solvent is distilled off before or together with water, and no or almost no solvent remains in the concentrated solution, and the solvent has a boiling point higher than that of water. If so, the solvent may be partially distilled off with the water, but most of the solvent remains in the concentrated liquid. It is preferable to use a solvent having a boiling point higher than that of water and evaporate water first, or evaporate water together with a part of the solvent to leave the solvent. Iminotris (dimethylamino) phosphorane has a much higher boiling point than water and remains in the concentrate after the water has been distilled off.

In the process of the present invention, it is important to remove at least water from the reaction mixture at a temperature of 70 ° C. or lower. If the temperature is exceeded, the yield of iminotris (dimethylamino) phosphorane will be extremely reduced. This is because at a high temperature, iminotris (dimethylamino) phosphorane reacts with water and the formation of aminohydroxytris (dimethylamino) phosphorane and the like becomes remarkable. Preferably it is 10 to 65 ° C, more preferably 15 to 60 ° C. The pressure at which the distillation is carried out under reduced pressure changes in accordance with these temperatures. Although water is distilled off in this manner, it is preferable that the water content in the concentrated liquid after the water is distilled off is as small as possible. However, iminotris (dimethylamino) phosphorane, which is usually present in the concentrated liquid, is preferably used.
It is 3 mol% or less based on the mol. This value is the normal 7
Vacuum distillation at a temperature of 0 ° C. or less can sufficiently achieve this.

In the concentrated solution thus obtained, depending on the boiling point of the solvent, iminotris (dimethylamino) phosphorane exists as an oily substance or is dissolved in the remaining solvent. On the other hand, when an excess amount of an alkali metal or alkaline earth metal hydroxide is used, the unreacted hydroxide is solid, and the alkali metal or alkaline earth metal produced as a by-product of the reaction is converted into a solid. The matter, of course, was not removed before distilling off the water,
Even in the case of carrying out, the water is newly precipitated by the distillation of water and exists as an insoluble solid. These solid components are removed from the concentrated solution by solid-liquid separation. If a solvent remains, if necessary, a part or all of the solvent may be further removed before solid-liquid separation. The method of solid-liquid separation is not particularly limited, but a general-purpose method such as filtration or centrifugation is generally used. Even if the mother liquor from which water has been distilled off to remove solid components is heated to a temperature exceeding 70 ° C., an extreme decrease in the yield of the desired product no longer poses a problem. In the method of the present invention, water is distilled off at 70 ° C. or lower and solids are removed by solid-liquid separation, and then the mother liquor is distilled to obtain iminotris (dimethylamino) phosphorane. The rectification is carried out using a rectification tower such as a packed tower using a usual packing material such as a bubble column tower or a perforated plate tower. The rectification can be carried out either batchwise or continuously. The overhead temperature for distilling iminotris (dimethylamino) phosphorane is usually 17
0 ° C. or lower, preferably 55 to 155 ° C., and more preferably 75 to 135 ° C. The pressure during distillation varies with temperature.

By this distillation, high-purity iminotris (dimethylamino) phosphorane can be obtained with a sufficiently high distillation yield. As described above, both the production yield and the distillation yield of iminotris (dimethylamino) phosphorane are sufficiently high, and iminotris (dimethylamino) phosphorane can be obtained from aminotris (dimethylamino) phosphonium chloride in a high total yield.

[0026]

The following examples further illustrate the present invention, but are not to be construed as limiting, but merely as illustrative. Example 1 1.09 kg of o-dichlorobenzene was weighed into a 2 L reactor equipped with a stirrer, a thermometer and a dropping funnel, and then 250 g (1.16 mol) of aminotris (dimethylamino) phosphonium chloride was added. . 50 ℃
Then, 114 g of a 45% by weight aqueous sodium hydroxide solution (containing 1.28 mol of sodium hydroxide; equivalent to 1.1 gram equivalent to the chloride) was added dropwise with stirring over 20 minutes. did. After completion of the dropwise addition, the mixture was stirred at the same temperature for 3 hours and then returned to room temperature over about 30 minutes. The reaction mixture was in three phases: aqueous, organic and solid. This was stirred vigorously, a part of it was sampled homogeneously, and quantitative analysis was performed by gas chromatography.
Iminotris (dimethylamino) phosphorane was produced at a reaction yield of 99 mol%. Further, while maintaining the temperature of the reaction mixture at 55 ° C., the pressure was increased from 118 mmHg to 1
Water and o-dichlorobenzene were distilled off by simple distillation while gradually changing the pressure to 0 mmHg. The distilled water and o-dichlorobenzene were 83.4 g and 78.5 g, respectively. The total amount of water calculated has been removed. Then 55
And o-dichlorobenzene 870 at 10 mmHg.
g was distilled off. The obtained concentrate was filtered. A pale yellow transparent filtrate was obtained. The filtered solid was washed twice with 70.0 g of o-dichlorobenzene. The solution obtained by combining the filtrate and the washing solution was charged into a 750 ml non-type flask equipped with a rectification tower in which a tower having a diameter of 30 mm and a total length of 400 mm was filled with a saddle-shaped filler (McMahon packing) made of stainless steel, and a pressure of 10 mmHg. Bottom, overhead temperature 52.5 to 5
A forerunner at 4.0 ° C. was taken, and o-dichlorobenzene was almost completely distilled off. Then, at the same pressure, the top temperature was 96.5.
Up to 17.5 g and 96.5 to 9
158 g of main fraction in the range of 8.0 ° C. were obtained. When the distilling amount was reduced, the operation of slightly raising the temperature of the contents of the flask was repeated, and the rear distillate of the column having a top temperature of 96.0 to 98.0 ° C. was reduced by one.
4.2 g were distilled off. Only a small amount of residue remained. All fractions were colorless and transparent liquids. The ¹ H-NMR and ³¹ P-NMR spectra were identical to those of standard iminotris (dimethylamino) phosphorane, and the purity was 99.0, 99.9 and 99.9% by weight, respectively, as determined by gas chromatography. It was extremely high. Distillation yield of iminotris (dimethylamino) phosphorane obtained by combining the first fraction, the main fraction and the second fraction [This represents the yield based on the iminotris (dimethylamino) phosphorane formed in the reaction. Hereinafter the same) is 92 mol%, and the total yield is 91 mol% based on the raw material aminotris (dimethylamino) phosphonium chloride.
Gave iminotris (dimethylamino) phosphorane.

Comparative Example 1 The simple distillation under reduced pressure of 55 ° C. in the reaction mixture when distilling off water and o-dichlorobenzene from the reaction mixture in Example 1 was changed to the simple distillation of normal pressure at 104 to 105 ° C. Except having changed, it carried out exactly like Example 1, and carried out the first fraction to 96.5 degreeC, the main fraction of 96.5 to 98.0 degreeC, and 9 parts.
4.89 to 98.9 ° C. of the subsequent fractions are each 4.89
g, 53.4 g and 5.92 g. The purity of each fraction was 98.9, 99.8 and 99.8% by weight. The combined distillation yield of the first fraction, the main fraction and the second fraction was 32 mol%, and the total yield was only 31 mol%.

A large amount of solid remained in the still. As a result of analysis, it was confirmed that this solid was mainly composed of aminohydroxytris (dimethylamino) phosphorane. This is considered to be caused by the addition reaction of iminotris (dimethylamino) phosphorane with water at a high temperature.

Comparative Example 2 Example 1 was repeated except that the same weight of methanol was used in place of o-dichlorobenzene and the same gram equivalent of sodium methoxide was used instead of a 45% by weight aqueous sodium hydroxide solution. The reaction was performed in exactly the same manner as described above. The reaction mixture was two phases, an organic phase and a solid phase. Example 1
As a result of the same quantitative analysis, iminotris (dimethylamino) phosphorane was produced at a reaction yield of 97 mol%. The reaction mixture was filtered to obtain a colorless and transparent filtrate. The filtered solid was washed twice with 70.0 g of methanol. 50 ° C., 400 m from the combined solution of the filtrate and the washing solution
At mHg, 1.02 kg of methanol was distilled off by simple distillation. The concentrated liquid was yellow, and a solid was precipitated therein. This was charged into a flask equipped with a rectification column similar to that in Example 1, and methanol was distilled out almost completely under a pressure of 400 mmHg at a column top temperature of about 49 ° C. as a forerunner. Then, rectification was performed in the same manner as in Example 1 under a pressure of 10 mmHg. 12.0 g of an initial fraction up to a temperature of 96.5 ° C. and 119 of a main fraction in the range of 96.5 to 98.5 ° C.
g and a 96.0-98.0 ° C. rear cut.
0 g was obtained. The distillation residue was 18.6 g. The purity of each fraction was 99.1, 99.8 and 99.9% by weight. The distillation yield of iminotris (dimethylamino) phosphorane including the first fraction, the main fraction and the second fraction was significantly reduced to 70 mol%. The total yield based on aminotris (dimethylamino) phosphonium chloride was 68 mol%.

Comparative Example 3 The procedure of Example 1 was repeated, except that the filtration was not carried out. The initial fraction up to 95 ° C., the main fraction at 96.5 to 98.0 ° C., and 96. 0 to 98.0 ° C
12.3 g, 111 g and 10.
0 g was obtained. The residue weighed 83.5 g and contained a lot of solids. The purity of each fraction was 99.0, 99.8 and 99.8% by weight. The distillation yield of the first fraction, the main fraction and the later fraction combined was low at 65 mol%, and the total yield was 64 mol%.

Example 2 In Example 1, the same weight of toluene was used instead of o-dichlorobenzene, and the same gram equivalent of a 50% by weight aqueous solution of potassium hydroxide was used instead of the 45% by weight aqueous solution of sodium hydroxide. Except for the above, the reaction was carried out in exactly the same manner as in Example 1. Iminotris (dimethylamino) phosphorane was produced at a reaction yield of 98 mol%. Further, while maintaining the temperature of the reaction mixture at 55 ° C., the pressure was increased to 118 mmH
g and 100 mmHg were gradually changed, and water and toluene were distilled off by simple distillation. The distilled water and toluene were 112 g and 766 g, respectively. Then, at 55 ° C, 10
At 0 mmHg, 140 g of toluene was further distilled. The obtained concentrate was filtered. Filtered solid was toluene 70.0
g twice. The solution obtained by combining the filtrate and the washing solution was charged into a flask equipped with the same rectification column as in Example 1,
Under a pressure of 0 mmHg, toluene was almost completely distilled off as a forerunner at an overhead temperature of about 52 ° C. Then 10mmHg
And rectified in the same manner as in Example 1. Tower temperature is 9
15.5 g initial fraction up to 6.5 ° C. and 155 g main fraction ranging from 96.5 to 98.0 ° C .;
15.4 g of a 0 to 98.0 ° C. rear distillate were obtained. Purities were 99.3, 99.8 and 99.9% by weight, respectively. The distillation yield was 91 mol%, and the total yield was 89
Mole%.

Example 3 Example 1 was repeated, except that the same weight of chlorobenzene was used in place of o-dichlorobenzene in Example 1 and the reaction conditions at 50 ° C. for 3 hours were changed to 55 ° C. for 0.5 hour. The reaction was carried out exactly as in 1. Iminotris (dimethylamino) phosphorane was produced at a reaction yield of 99 mol%. Further, while maintaining the temperature of the reaction mixture at 55 ° C,
The pressure was gradually changed from 118 mmHg to 50 mmHg, and water and chlorobenzene were distilled off by simple distillation. 83.4 g and 789 g of distilled water and chlorobenzene, respectively.
Met. Thereafter, 210 g of chlorobenzene was further distilled off at 55 ° C. and 50 mmHg. The obtained concentrate was filtered. The filtered solid was washed twice with 70.0 g of chlorobenzene. The solution obtained by combining the filtrate and the washing solution was charged into a flask equipped with a rectification column similar to that in Example 1, and chlorobenzene was almost completely distilled off as a forerunner under a pressure of 50 mmHg at a column top temperature of about 53 ° C. I let it. Then, rectification was performed in the same manner as in Example 1 under a pressure of 10 mmHg. The top temperature is 96.5 ° C
Up to 23.0 g and 96.5 to 98.
152 g of main fraction in the range of 0 ° C. and 6.09 g of a post-fraction of 96.0 to 98.0 ° C. were distilled off. Purities were 99.0, 99.9 and 99.8% by weight, respectively. The distillation yield was 88 mol%, and the total yield was 87 mol%.

Example 4 1.60 kg of tetrahydrofuran was weighed into a 5 L reactor equipped with a stirrer, a thermometer and a dropping funnel, and then 250 g (1.16 mol) of aminotris (dimethylamino) phosphonium chloride was added. . This was heated to 55 ° C. and, with stirring, 2.29 kg of a 5.6% by weight aqueous barium hydroxide solution (containing 0.83 mol of barium hydroxide. This corresponds to 1.1 gram equivalent to the chloride). ) Was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 30 minutes, and then returned to room temperature over about 30 minutes. Iminotris (dimethylamino) phosphorane was produced at a reaction yield of 99 mol%. Further, while maintaining the temperature of the reaction mixture at 55 ° C, the pressure was increased from 650 mmHg to 100
The pressure was gradually changed to mmHg, and tetrahydrofuran and water were distilled off by simple distillation. The amounts of distilled off tetrahydrofuran and water were 1.60 kg and 2.18 kg, respectively. The obtained concentrate was filtered. The filtered solid was washed twice with 110 g of tetrahydrofuran. The solution obtained by combining the filtrate and the washing solution was charged into a flask equipped with a rectification column similar to that in Example 1, and tetrahydrofuran was almost completely distilled off as a forerunner under a pressure of 650 mmHg at a top temperature of about 52 ° C. Was.
Then, rectification was performed in the same manner as in Example 1 under a pressure of 10 mmHg. 12.9 g of an initial fraction up to a temperature of 96.5 ° C. and 160 parts of a main fraction in the range of 96.5 to 98.0 ° C.
g and a 96.0-98.0 ° C. rear cut.
4 g were distilled off. Purity is 99.2 and 99.9 respectively
And 99.9% by weight. Distillation yield is 91 mol%
And the total yield was 90 mol%.

Example 5 417 g (2.00 mol) of phosphorus pentachloride was weighed and measured in a nitrogen-substituted 5 L glass-lined pressurized reactor, which was previously dehydrated using molecular sieves 3A. 2.50 kg of dichlorobenzene (the water content was 18 ppm by weight according to the Karl Fischer moisture measurement method) was fed in under nitrogen pressure. The water content in dimethylamine and ammonia used in this example is below the detection limit, and phosphorus pentachloride is anhydrous. Therefore, the amount of water brought into the reactor is approximated by the amount of water brought from the solvent. At this time, the water content in the reaction system was 0.011% by weight based on phosphorus pentachloride. While stirring the contents of the reactor, 84.0 g of gaseous dimethylamine was added thereto.
/ Hr for 6.5 hours. At this time, the reaction temperature was controlled to be maintained at 60 ° C., and the pressure during the reaction was 0.18 MPa at maximum (absolute pressure, the same hereinafter). The exact amount of dimethylamine introduced was determined from the weight loss of the storage tank and was 547 g (12.1 mol), which was 6.05 mol per mol of phosphorus pentachloride. After completion of the introduction, stirring was continued at this temperature for 1 hour. Thereafter, the temperature was returned to normal temperature, the residual gas in the reactor was released, and then gaseous ammonia was introduced into the reactor at a rate of 77.0 g / hr for 4.0 hours. At this time, the reaction temperature was controlled to maintain 40 ° C., the reaction pressure was set at 0.25 MPa at the outlet valve,
An opening control for maintaining this pressure was performed. When the exact amount of introduced ammonia was determined from the weight loss of the storage tank, it was 309.
g (18.1 moles) per mole of phosphorus pentachloride.
05 mol. After completion of the introduction, stirring was continued at this temperature for 2 hours, and then returned to room temperature to obtain a suspension of o-dichlorobenzene. Analysis showed that aminotris (dimethylamino) phosphonium chloride 42
1 g (1.96 mol, yield 98.0 based on phosphorus pentachloride)
%. ), 148 g of dimethylammonium chloride
(1.81 mol) and 331 g of ammonium chloride
(6.19 mol), and no phosphorus pentachloride was detected.

This suspension was charged to a 7 L reactor equipped with a stirrer, a thermometer and a dropping funnel. This is 50
The temperature was raised to 20 ° C. and, with stirring, 2.09 kg of a 20% by weight aqueous sodium hydroxide solution (10.5 mol of sodium hydroxide. This amount includes dimethylammonium chloride and 8.0 mol consumed by ammonium chloride). ) Was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 0.5 hour and returned to room temperature over about 30 minutes. The reaction mixture is an aqueous phase,
There were three phases, an organic phase and a solid phase. Analysis of the liquid phase indicated that iminotris (dimethylamino) phosphorane was formed in a 98 mol% reaction yield with respect to aminotris (dimethylamino) phosphonium chloride in the suspension used. Further, while maintaining the temperature of the reaction mixture at 55 ° C,
The pressure was gradually changed from 118 mmHg to 10 mmHg, and water and o-dichlorobenzene were distilled off by simple distillation.
The distilled water and o-dichlorobenzene were 1.85 each.
kg and 1.23 kg. The total amount of water calculated has been removed. Thereafter, 570 g of o-dichlorobenzene was further distilled off at 58 ° C. and 10 mmHg. The obtained concentrate was filtered. A pale yellow transparent filtrate was obtained. The filtered solid was washed twice with 300 g of o-dichlorobenzene. The solution obtained by combining the filtrate and the washing solution was charged into a 2 L non-type flask equipped with the same rectification column as in Example 1, and 10 mm
Under a pressure of Hg, at the top temperature of about 53 ° C., o-dichlorobenzene was almost completely distilled off as a forerunner. Then, rectification was performed in the same manner as in Example 1 under the same pressure. The top temperature is 96.5 ° C
Up to 25.0 g and 96.5 to 98.
274 g of the main fraction in the range of 0 ° C. and 24.7 g of the fraction after 96.0 to 98.0 ° C. were distilled off. Purities were 98.2, 99.8 and 99.9% by weight, respectively. The total distillation yield of the first fraction, the main fraction and the second fraction was 91 mol%, and the total yield based on aminotris (dimethylamino) phosphonium chloride in the suspension used was 90 mol%. .

[0036]

According to the method of the present invention, a safer method for obtaining iminotris (dimethylamino) phosphorane from aminotris (dimethylamino) phosphonium chloride, and more industrially advantageous alkali metal or alkaline earth metal can be obtained. The use of hydroxides allows the production of iminotris (dimethylamino) phosphorane with high purity and high yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Katsuhiko Funaki 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture (72) Inventor Takaomi Hayashi 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Mitsui Chemicals Corporation ( 72) Inventor Atsushi Shibahara 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture (72) Inventor Kazumi Mizutani 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. Osamu 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Chemicals, Inc.

Claims (7)

[Claims] 1. In the presence of a solvent in which chlorides and hydroxides of alkali metals or alkaline earth metals are hardly soluble,
Aminotris (dimethylamino) phosphonium chloride is reacted with an alkali metal or alkaline earth metal hydroxide in an aqueous solution to form iminotris (dimethylamino) phosphorane.
A process for producing iminotris (dimethylamino) phosphorane, comprising removing solids by solid-liquid separation after distilling the solution at 0 ° C. or lower, and distilling the mother liquor to obtain iminotris (dimethylamino) phosphorane. 2. Solvents in which chlorides and hydroxides of alkali metals or alkaline earth metals are hardly soluble include ethers having 4 to 8 carbon atoms, 6 to 10 carbon atoms.
2. The method according to claim 1, wherein the aromatic hydrocarbons are selected from the group consisting of aromatic hydrocarbons and chlorinated aromatic hydrocarbons having 6 to 8 carbon atoms. 3. A reaction mixture obtained by reacting phosphorus pentachloride with three molecules of dimethylamine and then reacting one molecule of ammonia with aminotris (dimethylamino) phosphonium chloride, or a reaction mixture thereof. 3. The method according to claim 1, wherein the method is isolated from a liquid. 4. In a method for producing aminotris (dimethylamino) phosphonium chloride by reacting phosphorus pentachloride with dimethylamine and then with ammonia, the aminotris (dimethylamino) phosphonium chloride removes water introduced into the reaction system. 0.9 for phosphorus pentachloride
Weight percent or less, using phosphorus pentachloride and dimethylamine in the presence of aromatic hydrocarbons, using 5.80 to 6.30 mol of dimethylamine with respect to 1 mol of phosphorus pentachloride,
0-80 ° C. and 0.001-1.00
The reaction is carried out under a pressure of MPa (absolute pressure, the same applies hereinafter) to form tris (dimethylamino) phosphonium dichloride. Subsequently, the tris (dimethylamino) phosphonium dichloride and ammonia are used to form one of phosphorus pentachloride used. In a reaction mixture obtained by reacting 1.8 to 50 mol of ammonia with respect to mol at a temperature of 0 to 60 ° C. and a pressure of 0.001 to 1.00 MPa, or a reaction mixture thereof The method according to claim 1, wherein the method is isolated from 5. The method according to claim 1, wherein the alkali metal or alkaline earth metal hydroxide is sodium hydroxide or potassium hydroxide. 6. The method according to claim 1, wherein the concentration of the aqueous solution of the alkali metal or alkaline earth metal hydroxide is 5 to 60% by weight. 7. The method according to claim 1, wherein the temperature of the reaction mixture when distilling off water from the reaction mixture is 10 to 65 ° C.