JP2018070488A - Method for producing n-silyl-aminoalkylsilane compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing N-silyl-aminoalkylsilane compounds.SOLUTION: Provided are: a method for producing N-silyl-aminoalkylsilane compounds by reacting aminoalkylsilane compounds and monochlorosilane compounds by using acetonitrile in the presence of a tertiary amine compound; the method for producing N-silyl-aminoalkylsilane compounds, wherein the aminoalkylsilane compound is a compound represented by the formula (1); and the method for producing N-silyl-aminoalkylsilane compounds, wherein the tertiary amine compound preferably has an acid dissociation constant (pKa) of 7 or more and, more preferably, is 1,8-diazabicyclo[5.4.0]undec-7-ene. (In the formula, R's are each independently a C1-5 alkyl; Ris H, phenyl, or 2-aminoethyl; m is an integer of 1 to 5; and n is an integer of 0 to 2.)SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an N-silylaminoalkylsilane compound.

In Patent Document 1, N, N-bis (trimethylsilyl) aminopropylsilane is synthesized by hydrosilylation reaction of N, N-bis (trimethylsilyl) allylamine and methyldialkoxysilane, but N, N-bis (trimethylsilyl) is synthesized. ) Allylamine, which is a raw material for allylamine, is highly toxic and requires the use of an expensive platinum catalyst.
In Patent Document 2, aminopropylsilane and trimethylchlorosilane are reacted in the presence of triethylamine. However, in order to obtain an N-silylaminopropylsilane compound, it is necessary to react at room temperature for a long time. When heated to advance the reaction quickly, a side reaction occurs, a trimethylsilane cyclic compound or the like is generated, and an N-silylaminopropylsilane compound is hardly obtained.
Therefore, a method for producing an efficient N-silylaminoalkylsilane compound with a short reaction time is desired.

Japanese Patent Laid-Open No. 10-17579 JP 2009-24931 A

  An object of the present invention is to provide a method for producing an N-silylaminoalkylsilane compound that solves the problems of the prior art and is suitable for industrial production.

  The present inventors have found that by using acetonitrile, an N-silylaminoalkylsilane compound can be produced by reacting an aminoalkylsilane compound and a monochlorosilane compound in the presence of a tertiary amine compound. Completed the invention.

  The merit of the present invention is that the amine hydrochloride formed as a by-product is completely dissolved in a small amount of solvent, and the acetonitrile layer of the amine hydrochloride and the target N-silylaminoalkylsilane compound layer are separated into two layers. In other words, it can be obtained efficiently by a liquid separation operation and in a high yield.

  The present invention includes the following items. In the chemical formula, “Me” is methyl and “Ph” is phenyl.

  Item 1. A method for producing an N-silylaminoalkylsilane compound by reacting an aminoalkylsilane compound and a monochlorosilane compound with acetonitrile in the presence of a tertiary amine compound.

式（１）において、
Ｒ^１は独立して、炭素数１から５のアルキルであり；Ｒ^２は、水素、フェニル、または２−アミノエチルであり；ｍは、１、２、３、４、または５であり；ｎは、０、１、または２である。 Item 2. Item 2. The method for producing an N-silylaminoalkylsilane compound according to Item 1, wherein the aminoalkylsilane compound is a compound represented by Formula (1).

In equation (1),
R ¹ is independently alkyl having 1 to 5 carbons; R ² is hydrogen, phenyl, or 2-aminoethyl; m is 1, 2, 3, 4, or 5; n Is 0, 1, or 2.

Item 3. Tertiary amine compounds, acid dissociation constant (pKa) of is not less than 7, and polar surface area (PSA) is the 12A ² or more, a method for producing a N- silyl aminoalkyl silane compound according to claim 1 or 2.

  Item 4. Item 4. The method for producing an N-silylaminoalkylsilane compound according to any one of Items 1 to 3, wherein the tertiary amine compound is 1,8-diazabicyclo [5.4.0] undec-7-ene.

式（３）、式（４）、および式（５）において、
Ｒ^１は独立して、炭素数１から５のアルキルであり；ｍは、１、２、３、４、または５であり；ｎは、０、１、または２である。 Item 5. Item 5. A method for producing an N-silylaminoalkylsilane compound according to any one of Items 1 to 4, wherein the target compound is the compound represented by Formula (3), Formula (4), or Formula (5).

In Formula (3), Formula (4), and Formula (5),
R ¹ is independently alkyl having 1 to 5 carbons; m is 1, 2, 3, 4, or 5; n is 0, 1, or 2.

式（１）において、
Ｒ^１は独立して炭素数１から５のアルキルであり；Ｒ^２は、水素、フェニル、または２−アミノエチルであり；ｍは、１、２、３、４、または５であり；ｎは、０、１、または２である。 The aminoalkylsilane compound which is a raw material of the present invention is preferably a compound represented by the formula (1).

In equation (1),
R ¹ is independently alkyl having 1 to 5 carbons; R ² is hydrogen, phenyl, or 2-aminoethyl; m is 1, 2, 3, 4, or 5; n is , 0, 1, or 2.

  Examples of the compound represented by the formula (1) include 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-anilinopropyl. Methyldiethoxysilane, 3-anilinopropyltriethoxysilane, 3-anilinopropylmethyldimethoxysilane, 3-anilinopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 1-aminomethylmethyldiethoxysilane, 1-aminomethyltriethoxysilane, 2-aminoethylmethyldiethoxysilane, 2-aminoethyltriethoxysilane, etc. Can be mentioned.

式（６）において、
Ｒ^３は、水素、炭素数１から５のアルキル、またはフェニルである。 A monochlorosilane compound is used as the other raw material. A preferred monochlorosilane compound is a compound represented by the formula (6).

In equation (6),
R ³ is hydrogen, alkyl having 1 to 5 carbons, or phenyl.

Examples of the monochlorosilane compound include trimethylchlorosilane, dimethylchlorosilane, ethyldimethylchlorosilane, vinyldimethylchlorosilane, and phenyldimethylchlorosilane.
The amount of the monochlorosilane compound added to the reaction is preferably equal to or greater than the mole of hydrogen in the amine in the aminopropylsilane compound. More preferably, it is in the range of 1-fold mole to 3-fold mole, and even more preferably in the range of 1-fold mole to 2-fold mole.

Since the tertiary amine compound used in the present invention is used as a dehydrochlorinating agent, it needs to be a base and is preferably a stronger base. Accordingly, it is preferable that the acid dissociation constant (pKa) is 7 or more and the polar surface area (PSA) is 12A ² or more. In order to avoid the substitution reaction of the amine compound of the strong base, it is preferable that there is no hydrogen directly bonded to the nitrogen of the amine, so that the tertiary amine is obtained.

  The acid dissociation constant (pKa) and polar surface area (PSA) can be calculated by Advanced Chemistry Development (ACD / Labs) Software V11.02 (c1994-2016 ACD / Labs). For example, each value can be obtained from the database SciFinder (registered trademark).

The base acid dissociation constant (pKa) and polar surface area (PSA) values were obtained from the database SciFinder®.

A tertiary amine compound having an acid dissociation constant (pKa) of 7 or more and a polar surface area (PSA) of 12A ² or more is an amine compound having at least one oxygen, or a conjugated amine having at least two nitrogens A compound is preferred.

The amine compound having at least one oxygen is preferably 4-methylmorpholine.

Examples of the conjugated amine compound having at least two nitrogens include heterocyclic compounds and DMAP (N, N-dimethyl-4-aminopyridine).

式（２）において、
Ｒ^ａ、Ｒ^ｃ、およびＲ^ｄは独立して、炭素数１から５のアルキルまたは炭素数１から５のアルケニルであり；Ｒ^ｂは、水素、炭素数１から５のアルキル、炭素数１から５のアルケニル、または２つの水素が炭素数１から５のアルキルで置き換えられたアミノであり；
Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ、およびＲ^ｄから選ばれた２つは、お互いに結合して、環を形成してもよい。 The conjugated amine compound having at least two nitrogen atoms that is a tertiary amine used as a dehydrochlorinating agent is preferably a compound having an amidine skeleton. As the compound having an amidine skeleton, a compound represented by the formula (2) is preferable.

In equation (2),
R ^a , R ^c , and R ^d are independently alkyl having 1 to 5 carbons or alkenyl having 1 to 5 carbons; R ^b is hydrogen, alkyl having 1 to 5 carbons, and 1 to C carbons 5 alkenyl, or amino in which two hydrogens are replaced by alkyl having 1 to 5 carbons;
Two selected from R ^a , R ^b , R ^c and R ^d may be bonded to each other to form a ring.

Examples of the compound represented by the formula (2) include the following compounds.

最も好ましい脱塩化水素剤は、ＤＢＵである。 More preferably, the dehydrochlorinating agent is a heterocyclic compound. Examples of the heterocyclic compound include DBU (1,8-diazabicyclo [5.4.0] undec-7-ene), DBN (1,5-diazabicyclo [4.3.0] non-5-ene), and the like. Can be mentioned.

The most preferred dehydrochlorinating agent is DBU.

Added to the reaction, the acid dissociation constant (pKa) of is not less than 7, and the amount of the amine compound is a polar surface area (PSA) is 12A ² or more, with respect to hydrogen in the amine of the aminopropyl silane compound, magnification It is preferable that it is more than mol. More preferably, it is in the range of 1-fold mole to 3-fold mole, and more preferably in the range of 1-fold mole to 2-fold mole.

  In the reaction of the present invention, acetonitrile is used as a solvent.

  The amount of acetonitrile as a solvent is preferably an amount that completely dissolves the hydrochloride of amine produced in the reaction system. Since the solubility of amine hydrochloride increases by raising the temperature, the amount of solvent can be reduced. Acetonitrile is preferably used in an amount of 15 to 50% by weight as a proportion of the entire reaction system. More preferably, acetonitrile is used in an amount of 20% to 35% by weight as a proportion of the entire reaction system. By making acetonitrile 15 wt% or more as a proportion of the whole reaction system, it becomes easy to completely dissolve the hydrochloride of amine. Moreover, volume efficiency after reaction and liquid separation improves by making acetonitrile into 50 weight% or less as a ratio of the whole reaction system.

In the production method of the present invention, the reaction proceeds by charging and stirring an aminoalkylsilane compound, a monochlorosilane compound, a tertiary amine compound, and acetonitrile. In order to proceed while controlling the reaction suitably, it is preferable that the monochlorosilane compound and the tertiary amine compound are dissolved in acetonitrile and brought to a predetermined reaction temperature, and then the aminoalkylsilane compound is dropped.
After completion of the reaction, the amine hydrochloride is dissolved in acetonitrile. Thus, by liquid-liquid separation, the acetonitrile layer containing the lower amine hydrochloride is extracted and separated to obtain the target N-silylaminoalkylsilane compound layer. It is possible.

  The reaction temperature is preferably in the range of 0 ° C to 100 ° C. More preferably, it is in the range of 10 ° C to 80 ° C. More preferably, it is the range of 20 to 60 degreeC. After accelerating the reaction at high temperature, it can be aged at low temperature

The pressure of the reaction is not particularly limited. However, when the pressure is reduced, the low-boiling monochlorosilane compound is likely to be volatilized, and therefore, normal pressure or higher is preferable.
The reaction is preferably performed in a dry air or dry nitrogen stream for the purpose of preventing moisture from entering. In the reaction, combustible materials are handled, and therefore, an inert atmosphere, for example, an environment of nitrogen or argon is preferable.

式（３）、式（４）、および式（５）において、
Ｒ^１は独立して炭素数１から５のアルキルであり；ｍは、１、２、３、４、または５であり；ｎは、０、１、または２である。 The reaction of the present invention can be suitably used when the compounds represented by formula (3), formula (4), and formula (5) are intended.

In Formula (3), Formula (4), and Formula (5),
R ¹ is independently alkyl having 1 to 5 carbons; m is 1, 2, 3, 4, or 5; n is 0, 1, or 2.

In the compound represented by the formula (1), when R ² is hydrogen, the compound represented by the formula (3) is the target product. When R ² is phenyl, the compound represented by formula (4) is the target product. When R ² is 2-aminoethyl, the compound represented by the formula (5) is the target product.

  The invention is explained in more detail by means of examples. The invention is not limited by these examples.

  The compound was synthesized by the following procedure. The synthesized compound was identified by NMR analysis and quantified by gas chromatography analysis.

NMR analysis: ECP400 manufactured by JEOL was used for measurement. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent of CDCl ₃ and measured under conditions of room temperature, 400 MHz, and the number of integrations of 32 times. Chloroform was used as an internal standard. ^In the measurement of ¹³ C-NMR, CDCl ₃ was used as an internal standard, and the integration was performed 14 times. In the description of the nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, quin is a quintet, and m is a multiplet.

For example, spectral data of N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, which is one of the objects, are shown.

  Gas chromatographic analysis: A GC-2014 gas chromatograph manufactured by Shimadzu Corporation was used for measurement. As the column, packed column inner diameter 2.6 mm, length 3 m, packing material, SE-30 10% 60/80, Shimalite WAW was used. Helium (20 ml / min) was used as the carrier gas. The temperature of the sample vaporization chamber was set to 250 ° C., and the temperature of the detector (TCD) portion was set to 250 ° C. The upper layer solution or filtrate as a sample was added with 0.1 g of pseudocumene as an internal standard substance to 1 g of the sample, and 1 μl was injected into the sample vaporizing chamber. The recorder was quantified by an internal standard method using a GCsolution system manufactured by Shimadzu Corporation.

[Example 1]

The molar ratio of the aminoalkylsilane compound, the monochlorosilane compound, and the dehydrochlorinating agent was 1: 2.5: 2.6.
After replacing the inside of the 1 L four-neck flask with nitrogen, 228 g of acetonitrile, 207 g of DBU (1.36 mol), and 142 g (1.31 mol) of trimethylchlorosilane were charged at room temperature. While stirring, 100 g (0.52 mol) of 3-aminopropylmethyldiethoxysilane (APMS-E) was added at room temperature. Heat to 50 ° C. and stir for 1 hour. Thereafter, the mixture was cooled to room temperature and transferred to a 1 L separatory funnel to obtain 201 g of the upper layer and 473 g of the lower layer. The upper layer was analyzed by gas chromatography and contained 79.0% by weight of the target product N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, yield 159 g (0.47 mol), yield 90. Obtained at 4%.

Including acetonitrile used in Example 1, the following solvents are designated as solvents 1 to 3.

[Example 2]
After replacing the inside of the 1 L jacketed bottom flask with nitrogen, 228 g of acetonitrile (solvent 1), 207 g of DBU (1.36 mol) and 142 g of trimethylchlorosilane (1.31 mol) were charged at room temperature. While stirring, the mixture was heated to 50 ° C. and 100 g (0.52 mol) of 3-aminopropylmethyldiethoxysilane (APMS-E) was added. After stirring for 1 hour, heating to 60 ° C. and stirring were stopped, and a liquid separation operation was performed. 193 g of the upper layer and 367 g of the lower layer were obtained. The upper layer was analyzed by gas chromatography and contained 81.1% by weight of the target product N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, yield 157 g (0.46 mol), yield 89. Obtained at 3%.

[Comparative Example 1]
Instead of acetonitrile (solvent 1) used in Example 1, toluene of solvent 2 was used, and aminosilane, chlorosilane, and DBU used were the same as those in Example 1, and the same moles of raw materials and the like as in Example 1 The production reaction was carried out by the ratio and reactor.
After replacing the inside of the 1 L four-necked flask with nitrogen, 312 g of toluene, 186 g of DBU (1.22 mol), and 129 g of trimethylchlorosilane (1.19 mol) were charged at room temperature. While stirring, the mixture was heated to 50 ° C., and 90 g (0.47 mol) of 3-aminopropylmethyldiethoxysilane (APMS-E) was added. Then, it heated at 60 degreeC at 50 degreeC for 1 hour, and also stirred for 3 hours. Thereafter, it was cooled to room temperature and aged for about 20 hours. The filtrate was transferred to a 1 L pressure filter and filtered to obtain 419 g of filtrate. The filtrate was analyzed by gas chromatography. It contained 26.2% by weight of the target product N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, and was obtained in a yield of 110 g (0.33 mol) and a yield of 70.2%.

[Comparative Example 2]
In the filter after filtration of Comparative Example 1, the residue was washed twice with 210 g / times of toluene, which was the solvent used in the reaction, to obtain 822 g of a crude liquid that was the combined filtrate and washing liquid. This crude liquid was analyzed by gas chromatography. The target product, N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, contained 16.2% by weight, and was obtained in a yield of 133 g (0.40 mol) and a yield of 84.3%.

[Comparative Example 3]
Instead of toluene (solvent 2) used in Comparative Example 1, 1,2-dimethoxyethane (DME) as solvent 3 was used, and aminosilane, chlorosilane, and DBU used were the same as in Example 1, and Example 1 The production reaction was carried out using the same molar ratio of raw materials and the like as in the above.
After replacing the inside of the 1 L four-neck flask with nitrogen, 312 g of DME, 186 g (1.22 mol) of DBU, and 129 g (1.19 mol) of trimethylchlorosilane were charged at room temperature. While stirring, the mixture was heated to 50 ° C., and 90 g (0.47 mol) of 3-aminopropylmethyldiethoxysilane (APMS-E) was added. Stir at 50 ° C. for 1 hour. Thereafter, it was cooled to room temperature, transferred to a 1 L pressure filter, and filtered to obtain 414 g of filtrate. The filtrate was analyzed by gas chromatography. It contained 26.8% by weight of the target product N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, and was obtained in a yield of 111 g (0.33 mol) and a yield of 70.2%.

[Comparative Example 4]
In the filter after the filtration of Comparative Example 3, the residue was washed twice with 210 g / dose of DME, which was the solvent used in the reaction, to obtain 820 g of a crude liquid in which the filtrate and the washing solution were combined. The filtrate was subjected to gas chromatographic analysis, and contained 16.3% by weight of the target product N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, yield 134 g (0.40 mol), yield 85 Obtained at 0.0%.

Examples 1-2 and Comparative Examples 1-4 show the type and amount of solvent used, the ratio of the solvent in the reaction solution, the reaction time and temperature.

The post-process after the reaction of Examples 1-2 and Comparative Examples 1-4, a crude liquid composition, and the yield of a target object are shown.

In Comparative Examples 1 to 4, the amount of solvent during the reaction was large, and a filtration step was required as a post-treatment to separate the amine hydrochloride and the target product. The filtration step is troublesome to operate and causes a decrease in the yield of the target product. The reason why the yield of the target product is poor as in Comparative Example 1 and Comparative Example 3 is that the target product adheres to the residue of the filtration step. Therefore, as in Comparative Example 2 and Comparative Example 4, in the filtration step, a washing operation with the solvent used in the reaction is required. Although the yield of the target product could be increased to some extent by this washing, the content of the target product in the crude liquid was lowered, and the volumetric efficiency was deteriorated.
On the other hand, Example 1 and Example 2 do not require a filtration step, and only N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane, which is the target product, can be obtained by a liquid separation operation. The yield was good and the volumetric efficiency was good.

  The N-silylaminoalkylsilane compound that can be produced in the present invention is a useful compound as a raw material for producing aminoalkyl-modified silicone, a silane coupling agent for a fuel-efficient tire, a surface treatment agent, and various silane coupling agent raw materials.

Claims (5)

A method for producing an N-silylaminoalkylsilane compound by reacting an aminoalkylsilane compound and a monochlorosilane compound with acetonitrile in the presence of a tertiary amine compound. The method for producing an N-silylaminoalkylsilane compound according to claim 1, wherein the aminoalkylsilane compound is a compound represented by the formula (1).

In equation (1),
R ¹ is independently alkyl having 1 to 5 carbons; R ² is hydrogen, phenyl, or 2-aminoethyl; m is 1, 2, 3, 4, or 5; n Is 0, 1, or 2. The method for producing an N-silylaminoalkylsilane compound according to claim 1 or 2, wherein the tertiary amine compound has an acid dissociation constant (pKa) of 7 or more and a polar surface area (PSA) of 12A ² or more. .   The method for producing an N-silylaminoalkylsilane compound according to any one of claims 1 to 3, wherein the tertiary amine compound is 1,8-diazabicyclo [5.4.0] undec-7-ene. . The method for producing an N-silylaminoalkylsilane compound according to any one of claims 1 to 4, wherein the target compound is the compound represented by formula (3), formula (4), or formula (5). .

In Formula (3), Formula (4), and Formula (5),
R ¹ is independently alkyl having 1 to 5 carbons; m is 1, 2, 3, 4, or 5; n is 0, 1, or 2.