Method for producing silylphosphine compound and silylphosphine compound

Abstract

The method for producing a silylphosphine compound of the present invention comprises: a first step of mixing a solvent having a relative dielectric constant of 4 or less, a basic compound, a silanizing agent and a phosphine to obtain a solution containing the silylphosphine compound; a second step of removing the solvent from the solution containing the silylphosphine compound to obtain a concentrated solution of the silylphosphine compound; and a third step of distilling the concentrated solution of the silylphosphine compound to obtain the silylphosphine compound. The silylphosphine compound of the present invention is a silylphosphine compound represented by the following general formula (1), and the content of the compound represented by the following general formula (2) is 0.5 mol% or less (for comments in the formula, see the specification).

Description

[0001] This case is filed on September 19, 2017 、Application number is 201780056268.9 (PCT / JP2017 / 033724) , invention names are "Method for producing silylphosphine compounds" and "divisional application for silylphosphine compounds". Technical Field

[0002] The present invention relates to a method for producing a silylphosphine compound useful as a raw material for a phosphorus component of indium phosphide quantum dots. Background Art

[0003] In recent years, the development of quantum dots as luminescent materials has been gradually promoted. As a representative quantum dot, the development of cadmium-based quantum dots such as CdSe, CdTe, and CdS has been gradually promoted due to their excellent optical properties. However, cadmium has high toxicity and environmental burden, so the development of cadmium-free quantum dots is expected.

[0004] As one of the cadmium-free quantum dots, indium phosphide (InP) can be cited. When manufacturing indium phosphide, its phosphorus component mostly uses silylphosphine compounds such as tri(trimethylsilyl)phosphine as raw materials. Silylphosphine compounds such as tri(trimethylsilyl)phosphine can be used in a solid state or a liquid state dissolved in a solvent, so they can also be used as a phosphorus source for organic synthesis under conditions where a gaseous phosphorus source (phosphine, etc.) cannot be used. As a method for manufacturing silylphosphine compounds such as tri(trimethylsilyl)phosphine, several schemes have been proposed (for example, Patent Document 1 and Non-Patent Documents 1 to 3).

[0005] In the production method of silylphosphine compounds, the production method using a silylating agent such as phosphine or trimethylsilyl trifluoride and a basic compound described in Patent Document 1 and Non-Patent Document 1 is considered to be particularly useful in industrial production from the viewpoints of reaction rate, purity of the product, etc. In these Patent Documents 1 and Non-Patent Document 1, ethers are used as solvents used in the reaction.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: German Patent Publication No. 274626

[0009] Non-patent literature

[0010] Non-patent document 1: Z. anorg. Allg. Chem. 576 (1989) 281-283

[0011] Non-patent document 2: Acta Crystallographica Section C, (1995), C51, 1152-1155

[0012] Non-patent document 3: J. Am. Chem. Soc., 1959, 81(23), 6273-6275 Summary of the invention

[0013] However, the methods for producing silylphosphine compounds described in Patent Document 1 and Non-Patent Document 1 have problems with purity and yield. In addition, in the method of obtaining a silylphosphine compound by reacting a phosphine, a silylating agent and a basic compound in the presence of a solvent, the safety of the solvent volatilized when the reaction mixture is distilled is considered to be a problem.

[0014] Therefore, an object of the present invention is to provide a method for producing a silylphosphine compound which is highly safe, can improve the reaction rate, and can obtain a high-purity silylphosphine compound.

[0015] In order to solve the above problems, the inventors of the present invention conducted intensive research and found that by using a reaction solvent with a specific dielectric constant, not only the safety of production can be improved, but also the reaction rate can be increased to obtain a high-purity silylphosphine compound, thereby completing the present invention.

[0016] That is, the present invention provides a method for producing a silylphosphine compound, which comprises: a first step of mixing a solvent having a relative dielectric constant of 4 or less, a basic compound, a silanizing agent and a phosphine to obtain a solution containing the silylphosphine compound; a second step of removing the solvent from the solution containing the silylphosphine compound to obtain a concentrated solution of the silylphosphine compound; and a third step of obtaining the silylphosphine compound by distilling the concentrated solution of the silylphosphine compound.

[0017] The present invention also provides a silylphosphine compound represented by the following general formula (1), wherein the content of the compound represented by the following general formula (2) is 0.5 mol% or less.

[0018]

[0019] (R is independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.)

[0020]

[0021] (R has the same meaning as in the general formula (1).) BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The recovered product obtained in Example 1 31 P-NMR spectrum.

[0023] Figure 2This is a gas chromatogram of the recovered product obtained in Example 1. DETAILED DESCRIPTION

[0024] The preferred embodiments of the production method and the preferred embodiments of the silylphosphine compound of the present invention are described below. The target silylphosphine compound in the production method is a tertiary phosphine compound, i.e., a compound having three silyl groups bonded to the phosphorus atom, preferably a compound represented by the following general formula (1).

[0025]

[0026] (R is independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.)

[0027] Examples of the alkyl group having 1 to 5 carbon atoms represented by R include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, and tert-pentyl.

[0028] Examples of the aryl group having 6 to 10 carbon atoms represented by R include phenyl, tolyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, sec-butylphenyl, tert-butylphenyl, isobutylphenyl, methylethylphenyl and trimethylphenyl.

[0029] These alkyl groups and aryl groups may have one or more substituents. Examples of the substituents of the alkyl group include hydroxyl groups, halogen atoms, cyano groups, and amino groups. Examples of the substituents of the aryl group include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups, halogen atoms, cyano groups, and amino groups. When the aryl group is substituted with an alkyl group and / or an alkoxy group, the number of carbon atoms of the aryl group includes the number of carbon atoms of the alkyl group and / or the alkoxy group.

[0030] The multiple R's in the general formula (1) may be the same or different (the same applies to the general formula (I) and the general formulas (2) to (7) described later). In addition, the three silyl groups (-SiR3) present in the general formula (1) may be the same or different. As the silylphosphine compound represented by the general formula (1), from the viewpoint of excellent reactivity with other molecules as a phosphorus source during the synthesis reaction, R is preferably an alkyl group having 1 to 4 carbon atoms, or a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, and a trimethylsilyl group is particularly preferred.

[0031] This manufacturing method includes a first step, a second step, and a third step. First, the first step will be described.

[0032] (First process)

[0033] In this step, a silanizing agent, a basic compound, a solvent having a relative dielectric constant of 4 or less, and a phosphine are mixed to obtain a solution containing a silylphosphine compound. In particular, from the viewpoint of ease of mixing of the components, workability, and safety, it is preferred to mix a mixed solution containing a silanizing agent, a basic compound, and a solvent having a relative dielectric constant of 4 or less with a phosphine to obtain a solution containing a silylphosphine compound. It is particularly preferred to introduce a phosphine into the mixed solution and mix the mixed solution with the phosphine to obtain a solution containing a silylphosphine compound.

[0034] As the silanizing agent, from the viewpoint of reactivity with phosphine, for example, a compound represented by the following general formula (I) is preferred.

[0035]

[0036] (R has the same meaning as in the general formula (1), and X is at least one selected from the group consisting of a fluorosulfonic acid group, a fluoroalkanesulfonic acid group, an alkanesulfonic acid group, and a perchloric acid group.)

[0037] An example of the reaction according to the present embodiment when the silanizing agent is a compound represented by the general formula (I) is represented by the following reaction formula.

[0038]

[0039] (In the above formula, R and X have the same meanings as in the general formula (I), B A It is a univalent base.)

[0040] The fluorinated sulfonic acid group represented by X can also be represented by "-OSO2F". Examples of the fluorinated alkane sulfonic acid group represented by X include perfluoroalkane sulfonic acid groups. Examples thereof include trifluoromethanesulfonic acid group (-OSO2CF3), pentafluoroethanesulfonic acid group (-OSO2C2F5), heptafluoropropanesulfonic acid group (-OSO2C3F7), nonafluorobutanesulfonic acid group (-OSO2C4F9), undecafluoropentanesulfonic acid group (-OSO2C5F 11 ) etc. Examples of the alkanesulfonic acid group represented by X include methanesulfonic acid group (-OSO2CH3), ethanesulfonic acid group (-OSO2C2H5), propanesulfonic acid group (-OSO2C3H7), butanesulfonic acid group (-OSO2C4H9), pentanesulfonic acid group (-OSO2C5H 11 ) etc. The perchloric acid group represented by X is also represented by "-OClO3". In these formulas, "-" represents a valence bond.

[0041] As the silanizing agent, from the viewpoint of excellent reactivity, it is preferred that R is an alkyl group having 1 to 5 carbon atoms, or a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 5 carbon atoms. In addition, a silanizing agent in which X is a perfluoroalkanesulfonic acid group, particularly a trifluoromethanesulfonic acid group, is also preferred due to its excellent separation from the silyl group. From these viewpoints, as the silanizing agent, it is particularly preferred to use one or more selected from trimethylsilyl trifluoromethanesulfonate, triethylsilyl trifluoromethanesulfonate, tributylsilyl trifluoromethanesulfonate, triisopropylsilyl trifluoromethanesulfonate, and triphenylsilyl trifluoromethanesulfonate.

[0042] From the viewpoint of effectively suppressing impurities, especially suppressing the generation of secondary silylphosphine and primary silylphosphine, in addition to using the specific solvent described later, it is also preferred that the silanizing agent in the mixed solution is a specific amount. The ratio of the silanizing agent to the phosphine introduced into the mixed solution is preferably above the reaction equivalent, that is, more than 3 times the mole of the phosphine, more preferably more than 3 times the mole, further preferably more than 3.01 times the mole, and particularly preferably more than 3.05 times the mole. From the viewpoint of reducing the residual amount of the remaining silanizing agent to improve the purity and the viewpoint of reducing the manufacturing cost, the silanizing agent in the mixed solution is preferably more than the reaction equivalent with the phosphine but not to the extent of excess. From this viewpoint, the silanizing agent in the mixed solution is preferably less than 2 times the reaction equivalent, that is, less than 6 times the mole, particularly preferably less than 4 times the mole, and most preferably less than 3.5 times the mole.

[0043] The secondary silylphosphine as an impurity is represented by, for example, the following general formula (2).

[0044]

[0045] (R has the same meaning as in the general formula (1).)

[0046] The primary silylphosphine as an impurity is represented by, for example, the following general formula (3).

[0047]

[0048] (R has the same meaning as in the general formula (1).)

[0049] Basic compounds include not only bases in a narrow sense that provide hydroxide ions when dissolved in water, but also bases in a broad sense such as substances that accept protons and substances that provide electron pairs. From the viewpoint of being able to suppress side reactions with phosphine, basic compounds are particularly preferably amines. As amines, primary alkylamines, secondary alkylamines or tertiary alkylamines; anilines; toluidine; piperidine; pyridines, etc. can be listed. As primary alkylamines, secondary alkylamines or tertiary alkylamines, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, diisopropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, etc. can be listed. As anilines, aniline, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, etc. can be listed. As pyridines, pyridine, 2,6-di-tert-butylpyridine, etc. can be listed. They can be used alone or in combination of two or more.

[0050] Among these, from the viewpoint of allowing the reaction to proceed efficiently, it is particularly preferred to use one or more selected from methylamine, dimethylamine, trimethylamine, ethylamine, dimethylamine, triethylamine, ethylenediamine, aniline, toluidine, pyridine and piperidine.

[0051] From the viewpoint of effectively suppressing impurities, especially suppressing the generation of secondary silylphosphine and primary silylphosphine, in addition to using a specific solvent, it is preferred that the alkaline compound is a specific amount. For example, the ratio of the alkaline compound in the mixed solution to the phosphine introduced into the mixed solution is preferably above the reaction equivalent, for example, when the alkaline compound is a monovalent base, it is preferably 3 times more than the phosphine mole, more preferably more than 3 times, further preferably 3.3 times more than the phosphine mole, and particularly preferably 3.5 times more than the phosphine mole. From the viewpoint of improving the purity of the target product and reducing the manufacturing cost, the alkaline compound in the mixed solution is preferably not too excessive, and more preferably a large amount that cannot be regarded as excessive. From this viewpoint, the alkaline compound in the mixed solution is preferably less than 2 times the reaction equivalent relative to the phosphine introduced into the mixed solution, for example, preferably less than 6 times the mole, particularly preferably less than 5 times the mole, and most preferably less than 4 times the mole.

[0052] In the mixed solution, the number of moles of the basic compound is preferably greater than the number of moles of the silanizing agent, for example, from 1.01 mol to 2 mol, more preferably from 1.05 mol to 1.5 mol, per 1 mol of the silanizing agent.

[0053] The inventors of the present invention have conducted in-depth research on a method for producing a silylphosphine compound by reacting a silanizing agent, an alkaline compound and a phosphine, which can improve the yield of the silylphosphine compound and obtain a high purity. As a result, as one of the reasons why it is difficult to obtain high purity and high yield in the prior art, it can be considered that a hydrolyzate of the target silylphosphine compound is generated in the existing production method. In-depth research has been conducted and it has been found that the solvent mixed with the silanizing agent and the alkaline compound is crucial for improving purity and yield. Further research has found that when a substance with a relative dielectric constant below a specific value is used, the yield of the target silylphosphine compound can be improved and high purity can be obtained. Specifically, the relative dielectric constant of the solvent used in the present invention is below 4.

[0054] As one of the reasons why the purity of the obtained silylphosphine compound can be increased and the yield can be improved by using a solvent having a relative dielectric constant of 4 or less, the inventors of the present invention believe that by using a solvent that is sparingly soluble in water in the present invention, it is possible to effectively prevent the mixing of water from the atmosphere. It is believed that this can prevent the hydrolysis of the tertiary silylphosphine compound and effectively inhibit the generation of hydrolyzates. Examples of the hydrolyzate of the tertiary silylphosphine compound include the compound represented by the above general formula (2) or the compound represented by the above general formula (3), and the compound represented by the following general formula (4).

[0055]

[0056] (R has the same meaning as in the general formula (1).)

[0057] The inventors of the present invention also believe that the improvement in the miscibility of the silanizing agent, the basic compound and the phosphine by using a solvent having a relative dielectric constant of less than 4 is another reason for the improvement in yield and purity. The improvement in miscibility can increase the reaction efficiency and improve the yield, and can also inhibit the generation of by-products and thus improve the purity.

[0058] In contrast, in the conventional production methods described in Non-Patent Document 1 and Patent Document 1, ether is used as a solvent, and the relative dielectric constant of ether, for example, diethyl ether is 4.3, and the relative dielectric constant of cyclopentyl methyl ether is 4.8 (see Table 1 below), and the relative dielectric constant exceeds 4. When these solvents having a relative dielectric constant exceeding 4 are used, it is difficult to obtain a tertiary silylphosphine compound with high purity and high yield, as shown in Comparative Examples 1 and 2 described below.

[0059] In addition, since ether is flammable and sometimes generates hydroperoxides which are explosive substances, when the solvent is volatilized by the distillation process in the third step, temperature management and atmosphere management are difficult. In particular, silylphosphine compounds are sometimes self-igniting and thus have a high risk problem. In contrast, for solvents with a relative dielectric constant exceeding 4, this risk is low and management is easy.

[0060] Relative dielectric constant refers to the ratio of the dielectric constant of the substance to the dielectric constant of a vacuum. Generally, as the polarity of the solvent increases, the relative dielectric constant increases. As the relative dielectric constant of the solvent in the present embodiment, the value recorded in "Chemical Handbook Basics 5th Revised Edition" (Chemical Handbook Basics Revised 5th Edition) (edited by the Chemical Society of Japan, published on February 20, 2001, pages II-620 to II-622) can be used.

[0061] The solvent with a relative dielectric constant of 4 or less is usually an organic solvent, and hydrocarbons are preferably cited. As specific examples of solvents with a relative dielectric constant of 4 or less, non-cyclic or cyclic aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds can be cited. As non-cyclic aliphatic hydrocarbon compounds, compounds with a carbon number of 5 or more and 10 or less are preferably cited, and as particularly preferred compounds, for example, pentane (relative dielectric constant 1.8371), n-hexane (relative dielectric constant 1.8865), n-heptane (relative dielectric constant 1.9209), n-octane (relative dielectric constant 1.948), n-nonane (relative dielectric constant 1.9722), and n-decane (relative dielectric constant 1.9853) can be cited. In addition, as cyclic aliphatic hydrocarbon compounds, compounds with a carbon number of 5 or more and 8 or less are preferably cited, and as particularly preferred compounds, for example, cyclohexane (relative dielectric constant 2.0243) and cyclopentane (relative dielectric constant 1.9687) can be cited. Preferred aromatic hydrocarbon compounds include compounds having 6 to 10 carbon atoms, and particularly preferred compounds include benzene (relative dielectric constant 2.2825), toluene (relative dielectric constant 2.379), and p-xylene (relative dielectric constant 2.2735).

[0062] The lower limit of the relative dielectric constant of the solvent having a relative dielectric constant of 4 or less is preferably 0.5 or more, and more preferably 1 or more, from the viewpoint of the ease of the reaction in the above reaction formula. The upper limit is more preferably 3.5 or less, and even more preferably 3 or less.

[0063] In order to easily remove the solvent from the target product in the second and third steps described below, the boiling point of the solvent having a relative dielectric constant of 4 or less is preferably 200°C or less, and more preferably 40°C or more and 120°C or less.

[0064] The method for preparing the mixed solution of the solvent, the alkaline compound and the silanizing agent is not limited, and the three materials may be added to the reaction vessel at the same time, or any one or two of them may be added first and then the remaining components may be added. Preferably, when the silanizing agent and the alkaline compound are mixed in the solvent added in advance, the miscibility of the silanizing agent and the alkaline compound is easily improved, and thus it is preferred.

[0065] In order to prevent the decomposition of the silylphosphine compound caused by reaction with water and the generation of impurities, the solvent is preferably dehydrated before use. The amount of water in the solvent is preferably less than 20 ppm by mass, and more preferably less than 10 ppm. The amount of water can be measured by the method described in the examples described later. In addition, it is also preferred that the solvent is degassed before use to remove oxygen. Degassing can be implemented by any method such as replacing the reactor with an inert atmosphere.

[0066] The amount of the solvent having a relative dielectric constant of 4 or less is not limited, but is preferably set to, for example, 100 to 300 parts by mass, particularly 120 to 200 parts by mass, relative to 100 parts by mass of the silanizing agent, from the viewpoint of efficient reaction.

[0067] Phosphine is introduced into the obtained mixed solution. Phosphine is a gas represented by the molecular formula PH3. In order to prevent the mixing of oxygen and the generation of the following oxides represented by the following general formula (5) and the following compound represented by the general formula (6) due to the reaction of oxygen and the silylphosphine compound, it is preferred to set the reaction system in which the phosphine, the silanizing agent and the alkaline compound react to an inert atmosphere. Examples of the inert gas include nitrogen, helium, argon and other rare gases.

[0068]

[0069] (R has the same meaning as in the general formula (1).)

[0070]

[0071] (R has the same meaning as in the general formula (1).)

[0072] The liquid temperature of the mixed solution during the introduction of phosphine is preferably 20°C or higher from the viewpoint of improving the reaction rate and yield, and preferably 85°C or lower from the viewpoint of preventing decomposition of the target product. From these viewpoints, the liquid temperature of the mixed solution is more preferably 25°C or higher and 70°C or lower.

[0073] The obtained solution is preferably aged before being provided to the solvent removal in the second step. From the viewpoint of improving the reaction rate and yield, the aging is preferably carried out at a temperature of 20°C to 60°C, more preferably at a temperature of 20°C to 50°C. The aging time is preferably 1 hour to 48 hours, more preferably 2 hours to 24 hours. The aging is preferably carried out under an inert atmosphere.

[0074] Through the above-described first step, a solution containing a silylphosphine compound is obtained.

[0075] Further, the second step is performed to remove (separate) at least a portion of the solvent from the solution containing the silylphosphine compound to obtain a concentrated solution of the silylphosphine compound. By removing the solvent by concentration in the second step before distillation, the amount of solvent distilled off in the third step described later can be reduced, and the yield of the silylphosphine compound can be prevented from being reduced due to the distillation of the solvent during distillation, and the thermal denaturation or decomposition of the target silylphosphine compound can be prevented.

[0076] It is preferred to remove the by-product salt HB after the first step, preferably after the above-mentioned aging treatment and before the second step. A + X – processing.

[0077] Specifically, the solution containing the silylphosphine compound obtained in the first step (preferably including the aging step) is allowed to stand, so that the layer containing the silylphosphine compound and the layer containing HB are separated. A + X – The latter is removed by liquid separation, thereby enabling HB A + X – The standing time is preferably 0.5 to 48 hours, more preferably 1 to 24 hours. The separation is preferably performed under an inert atmosphere.

[0078] (Second process)

[0079] As a method for removing the solvent in the second step, there can be cited a method in which a solution containing a silylphosphine compound is heated under reduced pressure under conditions in which the target silylphosphine compound is substantially left, thereby evaporating the solvent. This treatment can be carried out, for example, using any distiller for removing the solvent, such as a rotary evaporator. From the viewpoint of efficiently removing the solvent and preventing the decomposition or modification of the silylphosphine compound, the liquid temperature when the solution containing the silylphosphine compound is heated under reduced pressure in the second step is preferably a maximum liquid temperature of 20°C to 140°C, and more preferably 25°C to 90°C. From the same viewpoint, the pressure (minimum pressure) during reduced pressure is preferably 2 kPa to 20 kPa, and more preferably 5 kPa to 10 kPa, based on absolute pressure. Concentration is preferably carried out under an inert atmosphere.

[0080] The amount of the silylphosphine compound in the solution containing the silylphosphine compound after the second step is preferably reduced by 5% by mass or less, more preferably by 1% by mass or less, relative to the amount of the silylphosphine compound in the solution at the time of starting the second step. 31 P-NMR measurement. The mass of the concentrated solution obtained in the second step is preferably 10% or more of the mass of the solution containing the silylphosphine compound obtained in the first step from the viewpoint of improving the yield; and is preferably less than 50% from the viewpoint of reducing the amount of residual solvent in the subsequent third step to improve the purity.

[0081] (Third process)

[0082] Next, the concentrated liquid obtained in the second step is distilled in the third step. The distillation conditions are conditions under which the silylphosphine compound is vaporized. From the viewpoint of excellent separation of the target compound, the distillation temperature (tower top temperature) is preferably 50°C or higher. From the viewpoint of suppressing decomposition of the target compound and maintaining quality, the distillation temperature is preferably 150°C or lower. From these viewpoints, the distillation temperature is preferably 50°C or higher and 150°C or lower, and more preferably 70°C or higher and 120°C or lower.

[0083] From the viewpoint of being able to recover the target compound of high purity with good efficiency, the pressure during distillation is preferably above 0.01 kPa based on the absolute pressure. In addition, from the viewpoint of being able to suppress the decomposition and modification of the silylphosphine compound and easily obtain the silylphosphine compound with high purity and high yield, the pressure during distillation is preferably below 5 kPa based on the absolute pressure. From these viewpoints, the pressure during distillation is preferably above 0.01 kPa and below 5 kPa, and more preferably above 0.1 kPa and below 4 kPa. The distillation is preferably carried out under an inert atmosphere.

[0084] The primary fraction contains a solvent, a basic compound, a silanizing agent, or trace amounts of decomposition products of each component, and the like. Therefore, by removing these, the purity can be improved.

[0085] After the third step, the amount of the silylphosphine compound in the distillation residue after the silylphosphine compound is vaporized is reduced by preferably 90% by mass or more, more preferably 95% by mass or more, relative to the amount of the silylphosphine compound in the solution containing the silylphosphine compound at the time of starting the third step. 31 P-NMR determination.

[0086] In this step, the compound represented by the following general formula (7) can be removed. The compound represented by the general formula (7) is a byproduct of the reaction between the silanizing agent and the phosphine, and is removed as a high boiling point component by the distillation in the third step.

[0087]

[0088] (R has the same meaning as in the general formula (1).)

[0089] The target silylphosphine compound is obtained by the third step. The obtained silylphosphine compound is in a solid state such as a powder, and is stored in a liquid or solid state in an environment that avoids contact with oxygen, moisture, etc. as much as possible, or in a dispersion state dispersed in an appropriate solvent. A dispersion also includes a solution.

[0090] The solvent for dispersing the silylphosphine compound is an organic solvent, and non-polar solvents are particularly preferred from the viewpoint of preventing the mixing of water and the decomposition of the silylphosphine compound. For example, as non-polar solvents, saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, aromatic hydrocarbon compounds, trialkylphosphines, etc. can be listed. As saturated aliphatic hydrocarbons, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-hexadecane, and n-octadecane can be listed. As unsaturated aliphatic hydrocarbons, 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene, etc. can be listed. As aromatic hydrocarbons, benzene, toluene, xylene, styrene, etc. can be listed. As trialkylphosphines, triethylphosphine, tributylphosphine, tridecylphosphine, trihexylphosphine, trioctylphosphine, tri-dodecylphosphine, tri-dodecylphosphine, etc. can be listed. When the boiling point of the organic solvent for dispersing the silylphosphine compound is high, operations such as storage and transportation of the silylphosphine compound with pyrophoricity can be stably performed, so it is preferred. The boiling point of the organic solvent is preferably 50° C. or higher, more preferably 60° C. or higher. The upper limit of the boiling point of the organic solvent is preferably 270° C. or lower (absolute pressure 0.1 kPa) from the viewpoint of the effect on the physical properties of organic synthetic products and quantum dots produced using the organic solvent as a raw material.

[0091] In order to prevent the decomposition of the silylphosphine compound and the generation of impurities due to the reaction with water, the solvent is preferably fully dehydrated before dispersing the silylphosphine compound. The water content in the solvent is preferably less than 20 ppm by mass, and more preferably less than 10 ppm. The water content can be measured by the method described in the examples described below.

[0092] To achieve such conditions, for example, the solvent is degassed and dehydrated while being heated under reduced pressure or vacuum conditions, and then mixed with the silylphosphine compound under a nitrogen atmosphere and filled in an airtight container.

[0093] By these treatments, a dispersion of a silylphosphine compound in which impurities are sufficiently reduced can be easily obtained.

[0094] In the dispersion of the silylphosphine compound, the proportion of the silylphosphine compound is preferably from 3 mass % to 50 mass %, and more preferably from 8 mass % to 30 mass %.

[0095] Next, the silylphosphine compound of the present invention is described.

[0096] The silylphosphine compound of the present invention is a compound containing a very small amount of the compound represented by the general formula (2), which is an impurity that is difficult to remove in the prior art. Specifically, in the silylphosphine compound of the present invention, the content of the compound represented by the general formula (2) is less than 0.5 mol%, and more preferably less than 0.3 mol%. The silylphosphine compound of the present invention reduces the amount of impurities that are difficult to remove by the existing manufacturing method, and can effectively prevent the disadvantages of damaging the physical properties of organic synthetic products or quantum dots obtained using it as a raw material, or damaging the physical properties of the obtained product. In order to make the compound represented by the general formula (2) below the above-mentioned upper limit, the compound represented by the general formula (1) is manufactured according to the above-mentioned manufacturing method of the present invention, and the ratio of the amount of the silanizing agent to the phosphine is adjusted. The content of the compound represented by the general formula (2) is the ratio relative to the compound represented by the general formula (1). The content of the compound represented by the general formula (1) and the compound represented by the general formula (2) can be adjusted by utilizing 31 The P-NMR analysis is measured, for example, by the method described in Examples below.

[0097] Furthermore, as a raw material for quantum dots or chemical synthesis, the silylphosphine compound of the present invention preferably contains extremely small amounts of other impurities that are difficult to remove in the prior art.

[0098] Specifically, the content of the compound represented by the general formula (3) is preferably below 0.1 mol%, more preferably below 0.08 mol%, and particularly preferably below 0.05 mol%. In this case, the silylphosphine compound of the present invention can more effectively prevent the above-mentioned disadvantages because it reduces the amount of other impurities that are difficult to remove in the prior art. In order to make the compound represented by the general formula (3) below the above-mentioned upper limit, the compound represented by the general formula (1) is manufactured according to the above-mentioned manufacturing method of the present invention, and the amount ratio of the silanizing agent to the phosphine is adjusted. The content of the compound represented by the general formula (3) is the ratio relative to the compound represented by the general formula (1). The content of the compound represented by the general formula (3) can be adjusted by utilizing 31 The P-NMR analysis is measured, for example, by the method described in Examples below.

[0099] The content of the silyl ether compound represented by the above-mentioned general formula (4) in the silyl phosphine compound of the present invention is preferably less than 0.50 mol %, more preferably less than 0.30 mol %, and further preferably less than 0.15 mol %. By reducing the amount of impurities that are difficult to remove in the prior art in this way, the above-mentioned disadvantages can be more effectively prevented. The content of the compound represented by the general formula (4) is a ratio relative to the compound represented by the general formula (1). In order to make the compound represented by the general formula (4) below the above-mentioned upper limit, the compound represented by the general formula (1) can be manufactured according to the above-mentioned manufacturing method of the present invention. The content of the compound represented by the general formula (4) can be determined by analysis using gas chromatography, for example, according to the method described in the examples described later.

[0100] The content of the compound represented by the general formula (5) in the silylphosphine compound of the present invention is preferably less than 0.30 mol%, more preferably less than 0.15 mol%, and particularly preferably less than 0.05 mol%. The content of the compound represented by the general formula (5) is a ratio relative to the compound represented by the general formula (1). In order to make the compound represented by the general formula (5) below the above upper limit, the first step to the third step in the production of the compound represented by the general formula (1) can be carried out under an inert atmosphere according to the production method of the present invention. The content of the compound represented by the general formula (5) can be adjusted by using 31 The P-NMR analysis is measured, for example, by the method described in Examples below.

[0101] The content of the compound represented by the general formula (6) in the silylphosphine compound of the present invention is preferably less than 0.30 mol%, more preferably less than 0.15 mol%, and particularly preferably less than 0.05 mol%. In order to make the compound represented by the general formula (6) below the above upper limit, the first step to the third step in the production of the compound represented by the general formula (1) can be carried out under an inert atmosphere according to the production method of the present invention. The content of the compound represented by the general formula (6) is a ratio relative to the compound represented by the general formula (1). The content of the compound represented by the general formula (6) can be determined by using 31 The P-NMR analysis is measured, for example, by the method described in Examples below.

[0102] The content of the compound represented by the general formula (7) in the silylphosphine compound of the present invention is preferably less than 1.0 mol%, more preferably less than 0.5 mol%, and particularly preferably less than 0.2 mol%. In order to make the compound represented by the general formula (7) below the above upper limit, the high boiling point component can be separated according to the above-mentioned production method of the present invention. The content of the compound represented by the general formula (7) is a ratio relative to the compound represented by the general formula (1). The content of the compound represented by the general formula (7) can be determined by using 31 The P-NMR analysis is measured, for example, by the method described in Examples below.

[0103] The content of the compound represented by the general formula (1) in the silylphosphine compound of the present invention is preferably 99.0 mol% or more, more preferably 99.3 mol% or more, and particularly preferably 99.5 mol% or more. The amount of the compound represented by the general formula (1) can be adjusted by using 31 The P-NMR analysis is measured, for example, by the method described in Examples below.

[0104] The preferred ratio of the compounds represented by the above formulae (2) to (7) to the compound represented by the formula (1) is applicable both when the silylphosphine compound is in a solid state such as a powder and when it is dispersed in a solvent. That is, in the former case, the preferred molar ratio of the compounds represented by the above formulae (2) to (7) means the molar ratio of the compounds represented by the formulae (2) to (7) to the compound represented by the formula (1) in a solid such as a powder composed of the silylphosphine compound. In the latter case, the preferred molar ratio means the molar ratio of the compounds represented by the formulae (2) to (7) to the compound represented by the formula (1) in a dispersion in which the silylphosphine compound is dispersed.

[0105] As described above, in the silylphosphine compound obtained by the production method of the present invention and the silylphosphine compound of the present invention, the mixing of impurities is suppressed as much as possible, and coloration or decomposition is prevented. Therefore, when the silylphosphine compound is used as a raw material for organic synthesis (for example, the production of phosphinine, etc.) or indium phosphide, adverse effects such as interference with the production reaction or reduction in yield, and reduction in the physical properties of the obtained organic compound or indium phosphide can be effectively prevented.

[0106] Example

[0107] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0108] <Example 1>

[0109] After adding 189.8 kg of degassed and dehydrated toluene (water content of 20 ppm or less based on mass) to the reaction container, 82 kg of triethylamine and 149.5 kg of trimethylsilyl trifluoromethanesulfonate were added, the reaction container was replaced with nitrogen, and the liquid temperature was adjusted to 30°C.

[0110] 7.4 kg of phosphine gas was added to the reaction container over 3 hours, and the liquid temperature was adjusted to 35° C., followed by aging for 4 hours.

[0111] The obtained reaction solution of 424.9 kg was separated into two layers. In order to utilize the upper layer, the lower layer was separated after standing for 12 hours. For the upper layer, in order to remove the low-boiling components, it was concentrated under reduced pressure using a concentration tank until the final pressure reached 6.3 KPa based on the absolute pressure standard and the liquid temperature reached 70°C, obtaining 60.1 kg of concentrated liquid. The amount of silyl phosphine compound in the solution containing silyl phosphine compound after the second step was reduced by 3.2% by mass relative to the amount of silyl phosphine compound in the above solution at the time of starting the second step.

[0112] The obtained concentrated liquid was distilled under a reduced pressure of 0.5 KPa at a tower top temperature of 85° C., and after removing the initial fraction, 49.3 kg of the main fraction was recovered to obtain a recovered product. After the third step, the amount of the silyl phosphine compound in the distillation residue after the silyl phosphine compound was vaporized was reduced by 93% by mass relative to the amount of the silyl phosphine compound in the solution containing the silyl phosphine compound at the start of the third step.

[0113] Use under the following conditions 31 The P-NMR analysis confirmed that the recovered product (liquid) was tris(trimethylsilyl)phosphine (TMSP), and its purity and yield were measured. The results are shown in Table 1 below. 31 The spectrum obtained by P-NMR analysis is shown in Figure 1 .exist Figure 1 In the experiment, the peak of the target compound TMSP was observed at δ-251.225ppm. Figure 1 No peaks of the compounds represented by formula (2) to (7) were observed, but under the above conditions, 31 In the P-NMR analysis, the peak position of the compound represented by the above formula (2) (R is a methyl group) is usually δ-237.4 (d, J = 186 Hz) ppm, the peak position of the compound represented by the above formula (3) (R is a methyl group) is δ-239±2.0 (q, J = 180 Hz), the peak position of the compound represented by the above formula (5) (R is a methyl group) is 115.1 ppm, the peak position of the compound represented by the above formula (6) (R is a methyl group) is 24.2 ppm, and the peak position of the compound represented by the above formula (7) (R is a methyl group) is -244.1 ppm.

[0114] Based on the above spectrum, by using 31 The contents of the compounds represented by the above formulae (2), (3), (5), (6) and (7) (R in each case is a methyl group) in tris(trimethylsilyl)phosphine were measured by P-NMR analysis. The results are shown in Table 2 below.

[0115] In addition, the content of the compound represented by formula (4) (R is methyl) in tri(trimethylsilyl)phosphine was measured by gas chromatography. The results are shown in Table 2 below. In addition, the spectrum obtained by gas chromatography is shown in Figure 2 Among them Figure 2 Among them, the peak numbered 1 is derived from the compound represented by formula (4).

[0116] 31 P-NMR measurement conditions:

[0117] A sample to be measured was dissolved in deuterated benzene at 20 mass %, and the obtained solution was measured using JNM-ECA500 manufactured by JEOL Ltd. under the following conditions.

[0118] Observation frequency: 202.4MHz, pulse: 45 degrees, capture time: 5 seconds, accumulation times: 256 times, measurement temperature: 22°C, standard substance: 85 mass% phosphoric acid

[0119] Gas chromatography conditions:

[0120] The measurement sample was dispensed into a container with a septum cap under an inert gas atmosphere, 0.2 μL of the measurement sample was injected into a gas chromatograph (“GC-2010” manufactured by Shimadzu Corporation) using a syringe, and measurement was performed under the following conditions.

[0121] · Column: Agilent J&W, "DB1" (inner diameter 0.25 mm, length 30 m) · Injection temperature: 250°C, detection temperature: 300°C

[0122] Detector: FID, carrier gas: He (100kPa pressure)

[0123] Divide ratio: 1:100

[0124] Heating conditions: maintain 50°C for 3 minutes → increase the temperature to 200°C at a rate of 10°C / min → increase the temperature to 300°C at a rate of 50°C / min → maintain 300°C for 10 minutes

[0125] <Example 2>

[0126] After adding 144.1 g of degassed and dehydrated n-hexane (water content on a mass basis: 10 ppm or less) to the reaction container, 82 g of triethylamine and 149.5 g of trimethylsilyl trifluoromethanesulfonate were added, the reaction container was replaced with nitrogen, and the liquid temperature was adjusted to 30°C.

[0127] 7.4 g of phosphine gas was added to the reaction container over 3 hours, and the liquid temperature was adjusted to 35° C., followed by aging for 4 hours.

[0128] The obtained reaction solution 380g was separated into two layers. In order to use the upper layer, the lower layer was separated after standing for 12 hours. As for the upper layer, in order to remove the low boiling components, it was concentrated under reduced pressure in a concentration tank until the final pressure reached 2.2KPa and the liquid temperature reached 70°C, and 58.4g of concentrated liquid was obtained.

[0129] The obtained concentrated liquid was distilled under a reduced pressure of 0.5 KPa at a tower top temperature of 85°C, and after removing the initial fraction, 49.4 g of the main fraction was recovered.

[0130] By using the above conditions 31 The P-NMR analysis confirmed that the recovered product (liquid) was tris(trimethylsilyl)phosphine, and the purity and yield thereof were measured. The results are shown in Table 1.

[0131] Furthermore, the contents of the compounds of formulae (2) to (7) were measured in the same manner as in Example 1. Table 2 shows the results.

[0132] Comparative Example 1 described below is a comparative example in which the same operation as in Example 2 was performed except that the solvent was diethyl ether as in Non-Patent Document 1.

[0133] <Comparative Example 1>

[0134] After adding 156.9 g of degassed and dehydrated diethyl ether (water content is 10 ppm or less based on mass) to the reaction container, 82 g of triethylamine and 149.5 g of trimethylsilyl trifluoromethanesulfonate were added, the reaction container was replaced with nitrogen, and the liquid temperature was adjusted to 30°C.

[0135] 7.4 g of phosphine gas was added to the reaction container over 3 hours, and the liquid temperature was adjusted to 35° C., followed by aging for 4 hours.

[0136] The obtained reaction solution 424.9 g was separated into two layers. In order to use the upper layer, the lower layer was separated after standing for 12 hours. The upper layer was concentrated under reduced pressure in a concentration tank to remove low-boiling components until the final pressure reached 2.2 KPa and the liquid temperature reached 70°C, obtaining 59.1 g of concentrated liquid.

[0137] The obtained concentrate was distilled under a reduced pressure of 0.5 KPa at a tower top temperature of 85°C, and after removing the initial fraction, 49.9 g of the main fraction was recovered.

[0138] By using the above conditions 31 The purity and yield of tris(trimethylsilyl)phosphine in the recovered product were measured by P-NMR analysis. The results are shown in Table 1. In addition, the contents of the compounds of formulae (2) to (7) were measured in the same manner as in Example 1. The results are shown in Table 2.

[0139] The following Comparative Example 2 is a comparative example in which the same operation as Example 2 was performed except that the solvent was cyclopentyl methyl ether.

[0140] <Comparative Example 2>

[0141] After adding 2150 g of degassed and dehydrated cyclopentyl methyl ether (water content is 10 ppm or less based on mass) to the reaction container, 121.4 g of triethylamine and 280 g of trimethylsilyl trifluoromethanesulfonate were added, the reaction container was replaced with nitrogen, and the liquid temperature was adjusted to 30°C.

[0142] 14.4 g of phosphine gas was added to the reaction container over 15 minutes, and the liquid temperature was adjusted to 35° C., followed by aging for 4 hours.

[0143] The obtained reaction solution 2480.66g was separated into two layers. In order to use the upper layer, the lower layer was separated after standing for 12 hours. The upper layer was concentrated in a concentration tank to remove low-boiling components until the final pressure reached 2.2KPa and the liquid temperature reached 70°C, obtaining 110g of concentrated liquid.

[0144] The obtained concentrated liquid was distilled under a reduced pressure of 0.5 KPa at a tower top temperature of 85°C, and after removing the initial fraction, 97.3 g of the main fraction was recovered.

[0145] By using the above conditions 31 The purity and yield of tris(trimethylsilyl)phosphine in the recovered product were measured by P-NMR analysis. The results are shown in Table 1. In addition, the contents of the compounds of formulae (2) to (7) were measured in the same manner as in Example 1. The results are shown in Table 2.

[0146] [Table 1]

[0147]

[0148] [Table 2]

[0149]

[0150] ND: Below the detection limit (detection limit: less than 0.05 mol%)

[0151] As shown in Tables 1 and 2, silylphosphine compounds were obtained with high purity of 99% or more and high yield of 90% or more in Examples 1 and 2. Comparative Examples 1 and 2 showed that although the yields were comparable to those in Examples 1 and 2, the purity was poor.

[0152] Furthermore, it was shown that the amount of the compounds represented by the general formulae (2) to (7) as impurities in Examples 1 and 2 was extremely small, while the amount in Comparative Examples 1 and 2 was significantly reduced.

[0153] <Example 3>

[0154] As an organic solvent, 1-octadecene (water content of 5.4 ppm on a mass basis) which was degassed and dehydrated by heating under vacuum conditions was used. 89.2 parts by mass of the organic solvent and 10.8 parts by mass of the silylphosphine compound obtained in Example 1 were mixed in a closed space under a nitrogen atmosphere to obtain a silylphosphine compound solution. The mixture was directly filled in a closed container, and after 12 hours, the amount of the compound of formula (2) to (7) in the obtained solution was determined according to the following method. The results are shown in Table 3. The water content was measured using a Karl Fischer moisture meter (MKC610 produced by Kyoto Electronics).

[0155] Moisture content determination method:

[0156] Reagents used: Add AQUAMICRON AS (generator solution) and AQUAMICRON CXU (counter electrode solution) to the measuring cell and allow them to fully stabilize. After stabilization, take 5 g of liquid into a nitrogen-purged 5 ml or larger airtight syringe and introduce it into the generator solution for measurement.

[0157] (Method for measuring the amount of the compound of formula (2) to (7) in the solution)

[0158] By utilizing 31 The P-NMR analysis was used to measure the contents of the compounds represented by the above formulae (1), (2), (3), (5), (6) and (7) in the solution. 31 The measurement conditions of P-NMR were as follows: the sample was prepared as follows. 31 The analysis conditions of P-NMR are the same. The ratios of the compounds of formulae (2), (3), (5), (6) and (7) (R is methyl group in all) to the compound represented by formula (1) are shown in Table 3 below.

[0159] ( 31 Preparation method of sample for P-NMR measurement)

[0160] Under an inert gas atmosphere, 0.4 ml of the solution and 0.2 ml of deuterated benzene were mixed to prepare a sample tube.

[0161] Furthermore, the contents of the compounds represented by formula (1) and formula (4) (R is a methyl group) in the solution were determined by gas chromatography. The conditions for the gas chromatography determination were the same as those for the gas chromatography analysis of the TMSP liquid described above, except that the sample preparation method and the injection volume were changed as described below. The ratio of the compound represented by formula (4) to the compound represented by formula (1) is shown in Table 3 below.

[0162] (Method for preparing sample for gas chromatography measurement)

[0163] In an inert gas atmosphere, 1 ml of the TMSP dilution solution was mixed with 10 mL of dehydrated grade hexane to prepare a solution, and 1.0 μL of the measurement sample was injected into the gas chromatograph using a syringe for measurement.

[0164] <Example 4>

[0165] As an organic solvent, trioctylphosphine (water content of 5 ppm or less based on mass basis) which had been degassed and dehydrated by distillation was used. In addition, the silylphosphine compound obtained in Example 2 was used instead of the silylphosphine compound obtained in Example 1. Except for these, the same operation as in Example 3 was carried out to obtain a silylphosphine compound solution. The ratio of the compounds of formulae (2) to (7) to the compound of formula (1) in the obtained solution was measured in the same manner as in Example 3, and the results are shown in Table 3.

[0166] <Reference Example 1>

[0167] As an organic solvent, 1-octadecene (water content of 40 ppm based on mass) which had not been degassed or dehydrated was used. The same operation as in Example 3 was performed to obtain a silylphosphine compound solution. The ratio of the compounds of formulae (2) to (7) to the compound of formula (1) in the obtained solution was determined in the same manner as in Example 3, and the results are shown in Table 3.

[0168] [Table 3]

[0169]

[0170] As shown in Table 3, it is clear that by mixing a silylphosphine compound in an organic solvent having a reduced water content, the amount of the compound represented by the general formulae (2) to (7) in the solution can be maintained at a low level.

[0171] Industrial Applicability

[0172] The manufacturing method of the silylphosphine compound of the present invention is not only highly safe, but also can improve the reaction rate and effectively suppress the generation of impurities. Therefore, the present manufacturing method can utilize an industrially advantageous method to manufacture a silylphosphine compound useful as a raw material for indium phosphide quantum dots and chemical synthesis. In addition, the silylphosphine compound of the present invention is useful as a raw material for indium phosphide quantum dots and chemical synthesis.

Claims

1. A composition, characterized in that: It is a composition obtained by the following manufacturing method, the manufacturing method comprising: A first step of mixing a solvent having a relative dielectric constant of 4 or less, a basic compound, a silanizing agent and a phosphine to obtain a solution containing a silylphosphine compound; a second step of removing the solvent from the solution containing the silylphosphine compound to obtain a concentrated solution of the silylphosphine compound; and A third step of obtaining a silylphosphine compound by distilling the concentrated solution of the silylphosphine compound, The solvent having a relative dielectric constant of less than 4 is one or more selected from pentane, n-hexane, n-heptane, n-octane, cyclohexane, benzene, toluene and p-xylene. The silanizing agent is a compound represented by the following general formula (I): In the composition, The content of the silylphosphine compound represented by the following general formula (1) is 99.0 mol % or more, The content of the compound represented by the following general formula (2) is 0.3 mol% or less, The content of the compound represented by the following general formula (3) is 0.1 mol % or less, The content of the compound represented by the following general formula (4) is 0.5 mol% or less, The content of the compound represented by the following general formula (5) is 0.05 mol% or less, The content of the compound represented by the following general formula (6) is 0.05 mol% or less, The content of the compound represented by the following general formula (7) is 0.5 mol% or less, In the general formula (1), R is independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. In the general formula (2), R has the same meaning as in the general formula (1). In the general formula (3), R has the same meaning as in the general formula (1). In the general formula (4), R has the same meaning as in the general formula (1). In the general formula (5), R has the same meaning as in the general formula (1). In the general formula (6), R has the same meaning as in the general formula (1). In the general formula (7), R has the same meaning as in the general formula (1). In the general formula (I), R has the same meaning as in the general formula (1), and X is at least one group selected from the group consisting of a fluorosulfonic acid group, a fluoroalkanesulfonic acid group and a perchloric acid group.

2. The composition according to claim 1, characterized in that: The composition exists in a state of being dispersed in an organic solvent.

3. Use of the composition according to claim 1 or 2 as a raw material for indium phosphide.

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