JP2001233885A - Method for producing tris[tris(dimethyl-amino) phosphoranylideneamino]phosphine oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for more industrially practically obtaining high- purity tris[tris(dimethylamino)phosphoranyl-ideneamino]phosphine oxide in high yield, capable of practicing by a simple purification method and using iminotris(dimethylamino)phosphorane in an amount not smaller than stoichiometric amount in a method for producing tris[tris(dimethylamino) phosphoranylideneamino]phosphine oxide by reacting iminotris(dimethylamino) phosphorane with phosphorus oxychloride. SOLUTION: Iminotris(dimethylamino)phosphorane is reacted with phosphorus oxychloride in aliphatic hydrocarbons as solvents under specific reaction conditions to provide a reaction solution containing tris[tris(dimethylamino) phosphoranyl-ideneamino]phosphine oxide, aminotris(dimethylamino)-phosphonium chloride simultaneously produced as a by-product and a by-product which is insoluble to the above solvent and the above chloride and the by-product are simultaneously removed by solid-liquid separation from the reaction solution and the solution is distilled.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide by reacting iminotris (dimethylamino) phosphorane with phosphorus oxychloride. Tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide is known to be extremely effective as a polymerization catalyst for alkylene oxide compounds (JP-A-11-302371).

[0002]

2. Description of the Related Art Known literature on tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide is disclosed in GD. N. Koidan (GN Koidan)
Et al., Journal of General Chemistry of the USSR, vol. 55, p. 1453 (1
985) (Journal of general chemistry of the USS)
R, 55 , 1453 (1985)). In this document, iminotris (dimethylamino) phosphorane [HN = P (NMe ₂ ) ₃ ] referred to in the present application is called hexamethyltriamidophosphazohydride, and tris [tris (dimethylamino) phosphoranylideneamino] referred to in the present application. The phosphine oxide [O = P [N = P (NMe ₂ ) ₃ ] ₃ ] is tris [tris (N,
N-dimethylamido) phosphazo] phosphate. The aminotris (dimethylamino) phosphonium chloride [[H ₂ NP ⁺ (NMe ₂ ) ₃ ] Cl ⁻ ] referred to in the present application is called hexamethyltriamide phosphazohydride hydrochloride [[HN = P (NMe _{2 3} ) .HCl], but the same compound. Here, the expressions of the present application are used for the above three compounds.

This document describes the reaction of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide with methyl iodide. It discloses a method for producing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide, which is a raw material for the reaction. There, a petroleum ether solution of phosphorus oxychloride at 20 ° C. was added to a petroleum ether solution of the phosphomine at 20 ° C. so that the molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride was exactly 6: 1.
The mixture was added dropwise with stirring for 0 minutes, and thereafter (time is not specified), a precipitate of aminotris (dimethylamino) phosphonium chloride by-produced was separated, the precipitate was washed with petroleum ether, and the filtrate was concentrated. The residue was crystallized from a small amount of petroleum ether to give a 85% yield of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide.

However, when the present inventors carried out this method under the same conditions, after the addition of phosphorus oxychloride at 20 ° C. for 30 minutes, the target product was hardly formed. Thereafter, even if the reaction temperature is raised to 40 ° C. and the reaction is carried out for 24 hours, the yield of the target substance is about 60%, and
Even after reacting for an hour, the yield was only about 73%.

[0005] In addition, the document only mentions "crystallized from a small amount of petroleum ether" but does not give a detailed explanation of recrystallization. The present inventors firstly filtered out the precipitate from the reaction solution obtained by reacting at 40 ° C. for 48 hours as described above, and then concentrated the filtrate to dryness to obtain a solid, as described in the above literature. Tried crystallization. As a result, a small amount of crystals were precipitated only after cooling to -10 ° C, and crystals were finally obtained at an extremely low temperature of -20 ° C. The yield of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide of this crystal was as low as 20%.

In producing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide by reacting iminotris (dimethylamino) phosphorane with phosphorus oxychloride, one molecule of iminotris (dimethylamino) is added to one molecule of phosphorus oxychloride. When one molecule of phosphorane reacts, one molecule of hydrogen chloride is produced at the same time. This hydrogen chloride immediately reacts with iminotris (dimethylamino) phosphorane to produce aminotris (dimethylamino) phosphonium chloride. Thus, stoichiometrically, 6 moles of iminotris (dimethylamino) phosphorane are required to react all three chlorines of one mole of phosphorus oxychloride. That is, 6 HN = P (NMe ₂ ) ₃ + O = PCl ₃ → O =
_{P [N = P (NMe 2} ) 3] + 3 [H 2 NP + (NMe 2) 3] Cl - represented by.

In the method described in the above-mentioned literature, iminotris (dimethylamino) phosphorane and phosphorus oxychloride are reacted at a molar ratio (stoichiometric amount) of 6: 1. It has been found that the reaction can be carried out using an amount of the phosphorane to increase the yield. However, in the purification method described in the literature, unreacted iminotris (dimethylamino) phosphorane when used in excess cannot be sufficiently removed, and after recrystallization, tris [tris (dimethylamino) phosphoranylideneamino] The result was a reduction in the purity of the phosphine oxide.

The method for producing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide thus disclosed has a low yield, a purification method requires an extremely low temperature, and furthermore an improvement in yield. Therefore, if one of the reactants is used in excess, it cannot be sufficiently removed, so that it is extremely insufficient as an industrial production method.

As a result of studying the improvement of the method described in the above-mentioned literature, it was found that when aromatic hydrocarbons were used instead of petroleum ether as the reaction solvent, the reaction rate was improved and the yield was also improved. Furthermore, by washing the solution obtained by solid-liquid separation with water, excess iminotris (dimethylamino) phosphorane can be removed, and recrystallization at low temperature becomes unnecessary, and the product can be obtained more easily. Was.

However, in the method in which aromatic hydrocarbons are used in place of petroleum ether as the reaction solvent, since the by-products generated during the reaction dissolve in the aromatic hydrocarbons as the solvent, solid-liquid separation is not possible. When performing, there is a problem that the purity of the target substance is reduced by being mixed into the same solution side as the target substance. In order to improve the purity of the target product, the aromatic hydrocarbons used as a solvent are once distilled off, and then the target product is dissolved by adding a new aliphatic hydrocarbon to the aliphatic hydrocarbons. It is necessary to carry out a purification step of removing insoluble by-products by solid-liquid separation and distilling off aliphatic hydrocarbons from the obtained solution to obtain a target product. In addition, it is substantially difficult to recover the excess iminotris (dimethylamino) phosphorane removed from the water by water washing, resulting in loss of iminotris (dimethylamino) phosphorane. As described above, the method of changing the reaction solvent from petroleum ether to aromatic hydrocarbons and washing with water to remove excess iminotris (dimethylamino) phosphorane is still insufficient as an industrial production method, and is simpler. There has been a demand for a method for producing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide in a cost-effective manner.

[0011]

An object of the present invention is to provide a method for producing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide by reacting iminotris (dimethylamino) phosphorane with phosphorus oxychloride. Of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide with high yield and high purity by an industrially more practical method, which can be carried out by a simple purification method and can use the phosphorane in a stoichiometric amount or more. To provide a way to obtain

[0012]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and found that tris [tris (dimethylamino) phosphorane is reacted with iminotris (dimethylamino) phosphorane and phosphorus oxychloride. In producing phosphoranylideneamino] phosphine oxide,
When an aliphatic hydrocarbon is used instead of petroleum ether as the reaction solvent and the reaction temperature is set to 40 to 180 ° C.,
It has been found that the reaction rate is improved and the yield is also improved. Furthermore, they have found that when an aliphatic hydrocarbon is used, solid aminotris (dimethylamino) phosphonium chloride by-produced during the reaction and by-products insoluble in the solvent can be simultaneously removed by solid-liquid separation. Even more surprisingly, very simple and high-purity tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide is obtained by distilling off the solvent and the excess iminotris (dimethylamino) phosphorane in the solution. Was found to be able to be obtained. This eliminates the need for recrystallization at low temperature, and also eliminates the need for water washing, and it is also possible to use a stoichiometric or more iminotris (dimethylamino) phosphorane to further increase the yield. A series of synergistic effects was found. Further, conventionally, excess iminotris (dimethylamino) phosphorane has been removed by washing with water, and it is very difficult to recover the removed excess iminotris (dimethylamino) phosphorane. Was enough,
In the present invention, it has been found that an effect that excess iminotris (dimethylamino) phosphorane can be easily recovered by thin-film evaporation can be obtained at the same time.

That is, the present invention relates to the production of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide by reacting iminotris (dimethylamino) phosphorane with phosphorus oxychloride, using aliphatic hydrocarbons as a solvent. The reaction is carried out at a molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride of more than 6 and 10 or less at a reaction temperature of 40 ° C. to 180 ° C. to give tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. At the same time, a reaction solution containing solid by-produced solid aminotris (dimethylamino) phosphonium chloride is obtained, and aminotris (dimethylamino) phosphonium chloride and by-products insoluble in the solvent are simultaneously subjected to solid-liquid separation from the reaction solution. And the solvent contained in the resulting solution in excess Tris [tris (dimethylamino) phosphoranylideneamino] phosphine, characterized in that tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide is obtained by removing the iminotris (dimethylamino) phosphorane by distillation. This is a method for producing an oxide.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide in the method of the present invention is represented by the formula (1)

[0015]

Embedded image

This is a compound represented by the following formula: Although the center phosphorus atom and the oxygen atom are represented by a double bond, electrons are biased on the oxygen atom to become anions, and a cation is formed on the phosphorus atom (P
⁺ -O - limiting structure ^of) also can take. Also, the cation on the phosphorus atom can be totally delocalized through a conjugated system. Tris [tris (dimethylamino) phosphoranylideneamino] represented by formula (1) in the method of the present invention
Phosphine oxide is to be understood as a resonance hybrid including all of these.

Both raw materials, namely phosphorus oxychloride and iminotris (dimethylamino) phosphorane, are both commercially available and readily available.

In the method of the present invention, examples of the aliphatic hydrocarbon used as a solvent include n-hexane,
2-dimethylbutane, 2,3-dimethylbutane, 2-methylpentane, n-heptane, n-octane, 2,3
3-trimethylpentane, isooctane, n-nonane,
It is a saturated aliphatic hydrocarbon such as 2,2,5-trimethylhexane, n-decane, n-undecane, n-dodecane, and a fat such as cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, bicyclohexyl, decalin, etc. It is a cyclic hydrocarbon. In addition to these,
Any aliphatic hydrocarbons may be used as long as this method is not hindered, but they are usually selected appropriately according to the reaction temperature and reaction pressure to be applied. In consideration of the relationship between the reaction temperature and the reaction pressure and the boiling point and the ease of removing the solvent after the reaction, it is preferable to use, for example, n-hexane, cyclohexane, 2-methylpentane, n-heptane, methyl Cyclohexane, n-
It is an aliphatic hydrocarbon having 6 to 10 carbon atoms such as octane, ethylcyclohexane, n-nonane, n-decane and decalin. These aliphatic hydrocarbons may be used alone or in combination of two or more. The use amount of these solvents is not particularly limited, but is generally 500 parts by weight or less, preferably 1 to 100 parts by weight, more preferably 1.5 to 50 parts by weight, per 1 part by weight of the raw material phosphorus oxychloride. Parts by weight. Some of the liquid phosphorus oxychloride may be insoluble in these solvents.

In the method of the present invention, the molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is more than 6 and 10 or less, preferably 6.1 to 8.0. When the reaction is carried out at a molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride of 6 or less (stoichiometric amount or less), the purity and yield are reduced, which is not preferable as an industrial production method. The reaction can be carried out without any problem even if the molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is more than 10, but the amount of excess iminotris (dimethylamino) phosphorane recovered increases, It is not preferable because the load in the purification step increases.

The method of the reaction between iminotris (dimethylamino) phosphorane and phosphorus oxychloride is not particularly limited as long as it is carried out by mixing the two in the presence of the above-mentioned solvent. Examples of the reaction method include a method in which the reaction is carried out using a tank reactor or a tube reactor, and a method of mixing using a tank reactor is usually used. The method of mixing is not particularly limited, but usually, one of iminotris (dimethylamino) phosphorane and phosphorus oxychloride is charged into a reactor as a solvent solution, and the other is dropped and mixed therein. Do. If necessary, the solution can be mixed by diluting the dropping side with a solvent. As a reaction system, any of a batch system and a continuous system can be used.

The reaction temperature is not uniform depending on the amount of the solvent, the molar ratio of the raw materials and the like, but is usually 40 to 180 ° C.
Preferably it is 50 to 140 ° C, more preferably 60 to 100 ° C. When the reaction is carried out at a low temperature of less than 40 ° C., the reaction is slow and a very long reaction time is required, and the yield is lowered, which is not practically preferable. 1
It is not preferable to carry out the reaction at a high temperature exceeding 80 ° C. because the amount of by-products (impurities) generated during the reaction increases.
In the reaction, for example, the temperature can be set in multiple stages, for example, at a lower temperature in the initial stage and at a higher temperature in the final stage. The reaction pressure may be reduced, normal, or increased, but is usually normal. The reaction time varies depending on the reaction temperature and other factors, but is usually 0.1 to 100 hours, preferably 0.5 to 50 hours, more preferably 1 to 50 hours.
Or 30 hours.

The reaction solution thus obtained contains a small amount of a by-product insoluble in a solvent which is an aliphatic hydrocarbon, for example, n-heptane, and a large amount of aminotris (dimethylamino) phosphonium chloride as a white solid. Has been deposited. This is simultaneously removed by solid-liquid separation, but any method may be used, but usually filtration, centrifugation,
Or a general-purpose method such as decantation is used,
Of these, filtration is preferred. If necessary, the filter cake is washed with an aliphatic hydrocarbon solvent, and the washing solution can be combined with the filtrate.

The aliphatic hydrocarbons used for washing the filter cake are not particularly limited, and may be the same or different from the aliphatic hydrocarbons used in the reaction solvent.
The same aliphatic hydrocarbon as the solvent used in the reaction is used.
In addition, these aliphatic hydrocarbons may be used alone or in combination of two or more.

In the method of the present invention, the solvent and excess iminotris (dimethylamino) phosphorane in the solution obtained by solid-liquid separation are removed by distillation to remove tris [tris (dimethylamino) phosphoranylideneamino]. Obtain phosphine oxide. As a method of distillation, a method such as distillation, evaporation, thin film evaporation and the like can be appropriately selected and used, and a plurality of methods can be used in combination, but preferably obtained by solid-liquid separation. The solvent in the solution is removed by a general method such as distillation and evaporation to obtain a concentrated solution containing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide and an excess amount of iminotris (dimethylamino) phosphorane. Subsequently, a method of evaporating and removing excess iminotris (dimethylamino) phosphorane from the concentrated solution using a thin film evaporator is used. On this occasion,
Excess iminotris (dimethylamino) removed by evaporation
Phosphorane can be recovered and reused.

The conditions for evaporation or recovery by the thin film evaporator used in this method are not particularly limited, but the heating temperature is preferably 80 to 300 ° C., more preferably 1 to 300 ° C.
00-280 ° C, most preferably 120-26 ° C
0 ° C. The degree of vacuum varies depending on the heating temperature, but is preferably 0.1 to 100 kPa, more preferably 0.1 to 100 kPa.
1 to 10 kPa, most preferably 0.1 to 1 k
Pa.

The tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide thus obtained has a sufficiently high purity and can be used as it is as a polymerization catalyst for an alkylene oxide compound. Can be further purified as necessary. The method of purification is not particularly limited, but usually, evaporation,
General purification methods such as distillation, recrystallization, and adsorption treatment can be used.

[0027]

The present invention will be described in more detail with reference to the following examples. However, the present embodiment specifically describes the present invention, and the present invention is not limited to only these embodiments.

Example 1 115.85 g of iminotris (dimethylamino) phosphorane was placed in a 500 ml glass reactor under a nitrogen atmosphere.
(650 mmol) and 132.22 g of n-heptane
Was charged. A mixture of 15.50 g (100 mmol) of phosphorus oxychloride and 15.86 g of n-heptane was added to 50 parts.
The mixture was added dropwise at 1 ° C. over 1 hour. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 6.5. After completion of the dropwise addition, stirring was continued at 90 ° C. for 4 hours to obtain a white slurry liquid. A part of this reaction solution was collected. From the results of HPLC quantitative analysis using toluene as a solvent and ethyl acetate as an internal standard compound (the yield and purity were analyzed by this method in the following), tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide Was 85.8% based on phosphorus oxychloride (hereinafter simply referred to as yield).

After the reaction, the white slurry obtained is filtered under a nitrogen stream to obtain aminotris (dimethylamino).
The phosphonium chloride and by-products insoluble in the solvent were simultaneously removed, and the residue was washed with a small amount of n-heptane to obtain a filtrate. The filtrate was removed with n-heptane using an evaporator to obtain a concentrated solution containing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. Further, excess iminotris (dimethylamino) phosphorane was removed from the concentrate using a thin film evaporator,
Tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide was obtained. The purity of the thus obtained tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide was 99.2% by weight, and the yield was 85.1%.

Example 2 142.57 g of iminotris (dimethylamino) phosphorane was placed in a 500 ml glass reactor under a nitrogen atmosphere.
(800 mmol) and 162.72 g of n-heptane
Was charged. A mixture of 15.50 g (100 mmol) of phosphorus oxychloride and 15.86 g of n-heptane was added to 70
The mixture was added dropwise at 1 ° C. over 1 hour. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 8.0. After completion of the dropwise addition, stirring was continued at 70 ° C. for 6 hours to obtain a white slurry liquid. As a result of collecting and analyzing a part of this reaction solution, the yield of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide with respect to phosphorus oxychloride was 83.1%.

After the reaction, the obtained white slurry was treated in the same manner as in Example 1 to obtain tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. The thus obtained tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide had a purity of 98.4% by weight and a yield of 82.1%.

Example 3 115.85 g of iminotris (dimethylamino) phosphorane was placed in a 500 ml glass reactor under a nitrogen atmosphere.
(650 mmol) and 162.72 g of n-decane. A mixed solution of 15.50 g (100 mmol) of phosphorus oxychloride and 15.86 g of n-decane was added dropwise at 50 ° C. over 1 hour. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 6.
5 After completion of the dropwise addition, stirring was continued at 120 ° C. for 2 hours to obtain a white slurry liquid. As a result of collecting and analyzing a part of this reaction solution, the yield of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide based on phosphorus oxychloride was 83.4%.

After the reaction, the obtained white slurry was treated in the same manner as in Example 1 to obtain tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. The purity of the thus obtained tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide was 98.1% by weight and the yield was 82.6%.

Example 4 124.75 g of iminotris (dimethylamino) phosphorane was placed in a 500 ml glass reactor under a nitrogen atmosphere.
(700 mmol) and 142.38 cyclohexane.
g. A mixture of 15.50 g (100 mmol) of phosphorus oxychloride and 15.86 g of cyclohexane was added dropwise at 50 ° C. over 1 hour. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 7.0. After completion of the dropwise addition, stirring was continued at 81 ° C. (reflux) for 4 hours to obtain a white slurry liquid. As a result of collecting and analyzing a part of the reaction solution, the yield of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide with respect to phosphorus oxychloride was 84.4%.

After the reaction, the obtained white slurry was treated in the same manner as in Example 1 to obtain tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. The purity of the thus obtained tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide was 98.7% by weight, and the yield was 83.9%.

Example 5 The same reaction as in Example 4 was carried out. After the reaction, the obtained white slurry was filtered under a nitrogen stream to obtain aminotris (dimethylamino) phosphonium chloride and by-products insoluble in the solvent. And the residue was washed with a small amount of cyclohexane to obtain a filtrate. Cyclohexane and excess iminotris (dimethylamino) phosphorane were simultaneously removed from the filtrate using a thin film evaporator. The purity of the thus obtained tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide is 96.0.
% By weight, and the yield was 84.4%.

Example 6 Under a nitrogen atmosphere, 15.50 g (100 mmol) of phosphorus oxychloride and 15.86 g of n-heptane were charged into a 500 ml glass reactor. A mixture of 115.85 g (650 mmol) of iminotris (dimethylamino) phosphorane and 132.22 g of n-heptane was added to 60
The mixture was added dropwise at 1 ° C. over 1 hour. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 6.5. After completion of the dropwise addition, stirring was continued at 80 ° C. for 5 hours to obtain a white slurry liquid. As a result of collecting and analyzing a part of this reaction solution, the yield of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide with respect to phosphorus oxychloride was 85.2%.

After the reaction, the obtained white slurry was treated in the same manner as in Example 1 to obtain tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. The purity of the thus obtained tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide was 98.9% by weight, and the yield was 84.8%.

Comparative Example 1 G. N. It carried out by the method based on the method of the literature of Koidan et al. Under a nitrogen atmosphere, a 3.5 ml glass reactor was charged with 53.5 g (300 mmol) of iminotris (dimethylamino) phosphorane and 200 ml of dry petroleum ether (the concentration of the phosphorane was 29% by weight). A mixture of 7.67 g (50.0 mmol) of phosphorus oxychloride and 25 ml of dry petroleum ether (concentration of phosphorus oxychloride is 32% by weight) was added thereto while stirring and controlling the internal temperature to 20 ° C. It was added dropwise over 30 minutes. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 6.0. At this point, a part of the reaction solution was collected, and almost no desired product was produced. For this reason, the temperature was raised to a temperature at which the reaction liquid was refluxed (about 40 ° C.), and the reaction was continued.
After 24 and 48 hours the yield was 59.8% and 7
3.0%. Thus, in the method described in the document,
Clearly the reaction was slow and the yield was low.

Comparative Example 2 G. N. The reaction was carried out from a reaction solution obtained by a method according to the method described in Koidan et al.'S document (the reaction solution obtained in Comparative Example 1) by a method according to the purification method described in the document. The white slurry of petroleum ether obtained in the reaction solution of Comparative Example 1 was filtered, and the solid was washed twice with 50 ml of petroleum ether.
The obtained filtrate was washed at 30 ° C. and 20 kPa (150 mmH
g) and concentrated to dryness. 21.5 g of a slightly yellowish white solid were obtained, to which 6.0 g of petroleum ether (only 28% by weight based on the solid) was added and almost dissolved at a temperature of 25 ° C. This solution was filtered, and the filtrate was cooled to precipitate crystals. However, when the temperature was lowered to −10 ° C., only a small amount of precipitate was observed. Further cooling to −20 ° C. finally allowed a certain amount of crystals to precipitate. This was quickly filtered through a -20 ° C cold filter,
About 3 g of petroleum ether cooled to −30 ° C.
And 5.89 g of white crystals were obtained. These crystals are 98.2% by weight of tris [tris (dimethylamino)].
Phosphoranylideneamino] phosphine oxide, but the yield was only 20.0%. Although recrystallization was carried out with such a small amount of solvent, extremely low temperature was required for crystallization, and the yield of crystals was low.

Comparative Example 3 In the method of Comparative Example 1, the amount of iminotris (dimethylamino) phosphorane used was changed to 57.9 g (325 mmol), and the reaction was carried out at a temperature at which the reaction solution was refluxed (about 40 ° C.). The reaction was carried out exactly in the same manner as in Comparative Example 1 except that the time was changed to 30 hours, and the purification was carried out at −20 ° C. in the same manner as in Comparative Example 2. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 6.5 (more than stoichiometric). The yield after the reaction was 75.3%.
The reaction rate was clearly improved only by increasing the amount of the phosphorane used in comparison with the results of the above. After recrystallization, 6.57
g of white crystals were obtained. These crystals have a purity of 91.1% by weight.
The yield was 20.7%, and the purity was insufficient even when the recrystallization operation was performed. About 2% by weight of iminotris (dimethylamino) phosphorane was observed in the crystals together with unknown impurities. The phosphorane used in excess of the stoichiometric amount in the reaction could not be sufficiently removed by this method, resulting in remaining in the crystals of the target product precipitated by the recrystallization operation.

Comparative Example 4 Under a nitrogen atmosphere, 15.4 g (100 mmol) of phosphorus oxychloride and 154 g of dried o-dichlorobenzene were charged into a 500 ml glass reactor. While stirring, while controlling the internal temperature to 70 ° C. or lower, 116 g (651 mmol) of iminotris (dimethylamino) phosphorane was added dropwise thereto over 1 hour. The molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is 6.5. After completion of the dropwise addition, stirring was continued at 70 ° C. for 1 hour to obtain a white slurry. As a result of collecting and analyzing a part of the reaction solution, the yield of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide with respect to phosphorus oxychloride was 85.4%.

After the reaction, the obtained white slurry was filtered, and the residue was washed with a small amount of o-dichlorobenzene to obtain 266 g of a filter wash. Using a thin film evaporator, o-dichlorobenzene and excess iminotris (dimethylamino) phosphorane were simultaneously removed from the filtrate to obtain tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. The purity was 95.2% by weight and the yield was 83.3%. To the thus obtained tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide, 10-fold by weight of n-hexane was added and stirred for 40 minutes to dissolve, and a solid insoluble in n-hexane remained. The solution was filtered to remove a solid, washed with a small amount of n-hexane, and dried. The weight of the solid was 1.9 g, which was 3.8% by weight based on the total weight before dissolving n-hexane. Was. Also, the purity of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide obtained by combining the filtrate obtained at the time of filtration of the n-hexane insoluble solid and the washing solution and concentrating to dryness was 99.2% by weight. The yield was 83.1%. As described above, when an aromatic hydrocarbon is used as the reaction solvent, the purity of tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide is reduced due to contamination of the reaction by-product. After removing the aliphatic hydrocarbons, a purification step is required in which purification using an aliphatic hydrocarbon solvent is performed to remove by-products insoluble in the aliphatic hydrocarbons.

[0044]

According to the method of the present invention, in a method for producing tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide by reacting iminotris (dimethylamino) phosphorane with phosphorus oxychloride, a simple purification method is provided. Process, the stoichiometric amount of the phosphorane can be used, and tris [tris (dimethylamino)
Phosphoranylideneamino] phosphine oxide can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shiro Honma, 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. 72) Inventor Naoto Ito 30 No. Asamata-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. F-term (reference) 4H050 AD11 AD17 BA90 BB11 BC10 BC19 BD80 WA12 WA15 WA27

Claims (5)

[Claims] In producing a tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide by reacting iminotris (dimethylamino) phosphorane with phosphorus oxychloride, an aliphatic hydrocarbon is used as a solvent, and iminotris ( The molar ratio of dimethylamino) phosphorane to phosphorus oxychloride is more than 6 and 10 or less and the reaction temperature is from 40 ° C. to 180 ° C., and is co-produced at the same time as tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide. A reaction solution containing solid aminotris (dimethylamino) phosphonium chloride is obtained, and aminotris (dimethylamino) phosphonium chloride and by-products insoluble in a solvent are simultaneously removed from the reaction solution by solid-liquid separation. Solvent and imino in excess Tris [tris (dimethylamino) phosphorane is removed by distillation to obtain tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide.
Method for producing phosphoranylideneamino] phosphine oxide. 2. The method according to claim 1, wherein the aliphatic hydrocarbon is an aliphatic hydrocarbon selected from aliphatic hydrocarbons having 6 to 10 carbon atoms. 3. The method according to claim 1, wherein the molar ratio of iminotris (dimethylamino) phosphorane to phosphorus oxychloride is from 6.1 to 8.0. 4. The reaction temperature of iminotris (dimethylamino) phosphorane with phosphorus oxychloride is 50 ° C. to 120 ° C.
The method according to any one of claims 1 to 3, wherein the temperature is ° C. 5. The method according to claim 1, wherein the solvent contained in the solution obtained by the solid-liquid separation is removed by distillation, if necessary, and then the excess iminotris (dimethylamino) phosphorane contained is removed by thin-film evaporation. A method according to any of claims 1 to 4, characterized in that: