JP2018039754A - Method for producing n-silylaminoalkylsilane compounds - Google Patents

Abstract

A method for producing an N-silylaminoalkylsilane compound is provided. A method for producing an N-silylaminoalkylsilane compound by reacting an aminoalkylsilane compound and a monochlorosilane compound using an aprotic polar solvent in the presence of a tertiary amine compound. A method for producing an N-silylaminoalkylsilane compound, wherein the aminoalkylsilane compound is, for example, a compound represented by formula (1), and the aprotic polar solvent is, for example, 1,2-dimethoxyethane. (R1 is C1-5 alkyl; R2 is H, phenyl or 2-aminoethyl; m is an integer of 1 to 5; n is an integer of 0 to 2) [Selection] 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 can produce an N-silylaminoalkylsilane compound by reacting an aminoalkylsilane compound and a monochlorosilane compound in the presence of a tertiary amine compound by using an aprotic polar solvent. The present invention has been completed.

  The advantage of the present invention is that the target product N-silylaminoalkylsilane compound can be obtained in 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 using an aprotic polar solvent in the presence of a tertiary amine compound.

式（１）において、
Ｒ^１は炭素数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 alkyl having 1 to 5 carbons; R ² is hydrogen, phenyl, or 2-aminoethyl; m is 1, 2, 3, 4, or 5; 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 aprotic polar solvent is a solution miscible with water.

  Item 5. Item 5. The method for producing an N-silylaminoalkylsilane compound according to any one of Items 1 to 4, wherein the aprotic polar solvent is a compound having an ether bond.

  Item 6. Item 6. The method for producing an N-silylaminoalkylsilane compound according to any one of Items 1 to 5, wherein the aprotic polar solvent is 1,2-dimethoxyethane.

  Item 7. Item 7. The method for producing an N-silylaminoalkylsilane compound according to any one of Items 1 to 6, 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 8. Item 8. A method for producing an N-silylaminoalkylsilane compound according to any one of Items 1 to 7, 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 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 alkyl having 1 to 5 carbons; R ² is hydrogen, phenyl, or 2-aminoethyl; m is 1, 2, 3, 4, or 5; 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).

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, an aprotic polar solvent is used. As the solvent, the aprotic polar solvent preferably has a property of being miscible with water. Examples of the aprotic polar solvent include ether solvents, amide solvents, and urea solvents. A preferred aprotic polar solvent is an ether solvent.

Examples of ether solvents include THF, DME (1,2-dimethoxyethane), and 1,4-dioxane.
Examples of amide or urea solvents include DMF (N, N-dimethylformamide), N, N-dimethylacetamide, N-methyl-2-pyrrolidine, 1,1,3,3-tetramethylurea, DMI (1 , 3-dimethyl-2-imidazolidianone) and DMPU (N, N′-dimethylpropylene urea).

  The amount of the solvent is preferably such an amount that the slurry concentration of the hydrochloride of amine produced in the reaction system is less than 40%. In the ether system, the generated amine hydrochloride is hardly soluble, and therefore it is necessary to add a solvent so that the slurry concentration of the amine hydrochloride is less than 40%. In addition, a solvent having a high ability to dissolve amine hydrochloride such as DMF can reduce the amount of the solvent because the slurry concentration is decreased by the solubility of amine hydrochloride.

  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 an aprotic polar solvent. In order to proceed while controlling the reaction suitably, it is possible to dissolve the monochlorosilane compound and the tertiary amine compound in an aprotic polar solvent, bring the reaction temperature to a predetermined temperature, and then drop the aminoalkylsilane compound dropwise. preferable.

  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 a compound represented by formula (3), formula (4), or formula (5) is used as a target product.

In Formula (3), Formula (4), and Formula (5),
R ¹ is 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 sample was filtered with a 0.5 μm syringe filter, and 1 μl of the filtrate was injected into the sample vaporizing chamber. For the recorder, a GCsolution system manufactured by Shimadzu Corporation was used.

[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 100 mL four-necked flask with nitrogen, 17.4 g of DME (1,2-dimethoxyethane), 10.4 g (69 mmol) of DBU, and 7.3 g (67 mmol) of trimethylchlorosilane were added at room temperature. Prepared. While stirring, the mixture was heated to 50 ° C., and 5.0 g (26.5 mmol) 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. Gas chromatographic analysis was conducted to obtain the target product N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane with a GC yield of 99.9% or more.

The following solvents including DME used in Example 1 are designated as Solvents 1-7.

The solubility of solvents 1 to 7 in water was obtained from the solvent handbook (Kodansha Publishing).

[Examples 2 to 4]
Instead of DME (solvent 1) used in Example 1, solvents 2 to 4 were used, and aminosilane, chlorosilane, and DBU used were the same as those in Example 1, and the same molar ratio of raw materials and the like as in Example 1 The production reaction was carried out using a reaction apparatus and a reaction method.

[Comparative Examples 1-3]
Instead of DME (solvent 1) used in Example 1, solvents 5 to 7 were used, and the aminosilane, chlorosilane, and DBU used were the same as in Example 1, and the same moles of raw materials and the like as in Example 1 The production reaction was carried out by ratio, reactor and reaction method.

  Depending on the reaction, as a by-product, cyclized product (1-trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane), mono product (N-trimethylsilyl-3-aminopropylmethyldiethoxylane) was gotten. The composition after reaction of Examples 1-4 and Comparative Examples 1-3 is shown. The composition is expressed as a percentage of each component based on the total of GC% of the raw material aminosilane, target product, cyclized product, and mono product.

  In Comparative Examples 1 to 3, a large amount of unreacted aminosilane remained at 5% or more. In contrast, Examples 1 to 4 were able to obtain the target product N, N- (bistrimethylsilyl) -3-aminopropylmethyldiethoxylane in good yield.

  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 (8)

A method for producing an N-silylaminoalkylsilane compound by reacting an aminoalkylsilane compound and a monochlorosilane compound using an aprotic polar solvent 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 alkyl having 1 to 5 carbons; R ² is hydrogen, phenyl, or 2-aminoethyl; m is 1, 2, 3, 4, or 5; 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 aprotic polar solvent is a solution miscible with water.   The method for producing an N-silylaminoalkylsilane compound according to any one of claims 1 to 4, wherein the aprotic polar solvent is a compound having an ether bond.   The method for producing an N-silylaminoalkylsilane compound according to any one of claims 1 to 5, wherein the aprotic polar solvent is 1,2-dimethoxyethane.   The method for producing an N-silylaminoalkylsilane compound according to any one of claims 1 to 6, 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 7, 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 alkyl having 1 to 5 carbons; m is 1, 2, 3, 4, or 5; n is 0, 1, or 2.