JP7392927B2 - Method for producing silicon-containing iron-platinum nanoparticle catalyst - Google Patents

Description

The present disclosure relates to a method for producing a silicon-containing iron-platinum nanoparticle catalyst.

Reactions that form carbon-silicon bonds are useful reactions in the organosilicon chemical industry. Among these, hydrosilylation reaction is one of the most important reactions for producing industrially useful organosilicon compounds such as silicone resins and silane coupling agents. Metal catalysts have mainly been used as catalysts for hydrosilylation reactions.

For example, Non-Patent Document 1 discloses a method for obtaining alkyltrialkoxysilanes by reacting alkenes and trialkoxysilanes in the presence of Karstedt's catalyst. However, Karstedt's catalyst is an expensive platinum complex catalyst and is difficult to recover after the reaction, making it difficult to reduce costs.
Furthermore, Non-Patent Document 1 discloses a method for obtaining alkyltrialkoxysilanes by reacting alkenes and trialkoxysilanes in the presence of an iron complex. However, the iron complex is unstable in air and is therefore difficult to handle. Also, similar to Karstedt's catalyst, it is difficult to recover after the reaction.

In view of these circumstances, the present applicant has previously proposed a platinum nanoparticle catalyst or a mixture of a platinum nanoparticle catalyst and an iron nanoparticle catalyst (Patent Document 1) and iron and iron as catalysts for the hydrosilylation reaction of alkenes. discloses a nanoparticle catalyst (Non-Patent Document 2). Since these catalysts are in particulate form, they can be easily recovered by filtration or the like, and manufacturing costs can be reduced.

International Publication No. 2018/131430

Tondreau, A. M., et. al., Science, 2012, 335, 567-570 Yasushi Obora, et.al., ChemCatChem, 2018, 10, 2378-2382

However, when using the catalyst described in Patent Document 1, in order to obtain a hydrosilylated product in high yield, an excess of 6 molar equivalents of hydrosilanes is required relative to the alkenes, which increases the raw material cost. In addition to this point, there is room for improvement in that it is difficult to implement on an industrial scale because a large amount of silane gas is generated due to the disproportionation of hydrosilanes used in excess. Further, the catalyst described in Non-Patent Document 2 still has a problem in that the catalytic reaction does not proceed sufficiently when trialkoxysilanes are used as the hydrosilanes.

Therefore, the object of the present invention is to provide a method that can be recovered after the catalytic reaction, can be handled in air, does not require a large amount of substrate in the catalytic reaction, and can also be used as a catalyst in the hydrosilylation reaction using trialkoxysilanes. An object of the present invention is to provide a method for producing an active catalyst.

The present inventors conducted extensive studies to solve the above problems. As a result, it was discovered that the above problems could be solved by heating iron nanoparticles coordinated with a coordinating organic solvent and platinum nanoparticles coordinated with a coordinating organic solvent together with hydrosilanes, and the present invention was completed. Ta. That is, the gist of the present invention is as follows.

（式（Ａ）中、Ｒ^１は、それぞれ独立して、ハロゲン原子、置換基を有していてもよい炭素数１～２０の脂肪族炭化水素基、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、置換基を有していてもよい炭素数３～２０の芳香族複素環基又は置換基を有していてもよい炭素数１～２０のアルコキシ基を表し；ｎは、１～３の整数を表す。）
［３］
前記混合物が、さらに第１のアルケン類を含む、［１］又は［２］に記載の含ケイ素鉄－白金ナノ粒子触媒の製造方法。
［４］
前記第１のアルケン類が、式（Ｂ）で表される化合物である、［３］記載の含ケイ素鉄－白金ナノ粒子触媒の製造方法。

（式（Ｂ）中、Ｒ^２～Ｒ^５は、それぞれ独立して、水素原子、ハロゲン原子、置換基を有していてもよい炭素数１～２０の脂肪族炭化水素基、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基又は置換基を有していてもよい炭素数３～２０の芳香族複素環基を表す。）
［５］
前記第１の配位性有機溶媒及び前記第２の配位性有機溶媒が、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）である、［１］～［４］の何れかに記載の含ケイ素鉄－白金ナノ粒子触媒の製造方法。
［６］
前記混合物において、前記表面に第２の配位性有機溶媒が配位した白金ナノ粒子に対する前記表面に第１の配位性有機溶媒が配位した鉄ナノ粒子の金属換算での混合比（モル比）が、０．１以上１０．０以下である、［１］～［５］の何れかに記載の含ケイ素鉄－白金ナノ粒子触媒の製造方法。
［７］
［１］～［６］の何れかに記載の製造方法により含ケイ素鉄－白金ナノ粒子触媒を製造する触媒製造工程と、
前記含ケイ素鉄－白金ナノ粒子触媒の存在下で、第２のアルケン類と第２のヒドロシラン類とを反応させるヒドロシリル化工程と、
を含む、有機ケイ素化合物の製造方法。
［８］
［１］～［６］の何れかに記載の製造方法により得られる含ケイ素鉄－白金ナノ粒子触
媒の存在下で、第２のアルケン類と第２のヒドロシラン類とを反応させるヒドロシリル化工程を含む、有機ケイ素化合物の製造方法。
［９］
前記第２のアルケン類が、式（Ｃ）で表される化合物である、［７］又は［８］に記載の有機ケイ素化合物の製造方法。

（式（Ｃ）中、Ｒ^６～Ｒ^９は、それぞれ独立して、水素原子、ハロゲン原子、置換基を有していてもよい炭素数１～２０の脂肪族炭化水素基、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基又は置換基を有していてもよい炭素数３～２０の芳香族複素環基を表す。）
［１０］
前記第２のヒドロシラン類が、式（Ｄ）で表される化合物である、［７］～［９］の何れかに記載の有機ケイ素化合物の製造方法。

（式（Ｄ）中、Ｒ^１０は、それぞれ独立して、ハロゲン原子、置換基を有していてもよい炭素数１～２０の脂肪族炭化水素基、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、置換基を有していてもよい炭素数３～２０の芳香族複素環基又は置換基を有していてもよい炭素数１～２０のアルコキシ基を表し；ｍは、１～３の整数を表す。）
［１１］
前記ヒドロシリル化反応が、不活性雰囲気下で行われる、［７］～［１０］の何れかに記載の有機ケイ素化合物の製造方法。
［１２］
前記ヒドロシリル化工程において、前記第２のアルケン類に対する第２のヒドロシラン類の量が、１．０モル当量以上６．０モル当量未満である、［７］～［１１］の何れかに記載の有機ケイ素化合物の製造方法。 [1]
A heating step of heating a mixture containing iron nanoparticles whose surface is coordinated with a first coordinating organic solvent, platinum nanoparticles whose surface is coordinated with a second coordinating organic solvent, and a first hydrosilane. A method for producing a silicon-containing iron-platinum nanoparticle catalyst, comprising:
[2]
The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to [1], wherein the first hydrosilane is a compound represented by formula (A).

(In formula (A), R ¹ is each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituent) An aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. (Representation; n represents an integer from 1 to 3.)
[3]
The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to [1] or [2], wherein the mixture further contains a first alkene.
[4]
The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to [3], wherein the first alkene is a compound represented by formula (B).

(In formula (B), R ² to R ⁵ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent-bearing aliphatic hydrocarbon group) represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent.)
[5]
The silicon-containing iron according to any one of [1] to [4], wherein the first coordinating organic solvent and the second coordinating organic solvent are N,N-dimethylformamide (DMF). Method for producing platinum nanoparticle catalyst.
[6]
In the mixture, the mixing ratio (in terms of metal) of iron nanoparticles whose surface is coordinated with the first coordinating organic solvent to platinum nanoparticles whose surface is coordinated with the second coordinating organic solvent is The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to any one of [1] to [5], wherein the ratio) is 0.1 or more and 10.0 or less.
[7]
A catalyst production step of producing a silicon-containing iron-platinum nanoparticle catalyst by the production method according to any one of [1] to [6];
a hydrosilylation step of reacting a second alkene and a second hydrosilane in the presence of the silicon-containing iron-platinum nanoparticle catalyst;
A method for producing an organosilicon compound, comprising:
[8]
A hydrosilylation step in which the second alkenes and the second hydrosilanes are reacted in the presence of a silicon-containing iron-platinum nanoparticle catalyst obtained by the production method according to any one of [1] to [6]. A method for producing an organosilicon compound.
[9]
The method for producing an organosilicon compound according to [7] or [8], wherein the second alkene is a compound represented by formula (C).

(In formula (C), R ⁶ to R ⁹ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a substituent-bearing aliphatic hydrocarbon group) represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent.)
[10]
The method for producing an organosilicon compound according to any one of [7] to [9], wherein the second hydrosilane is a compound represented by formula (D).

(In formula (D), R ¹⁰ is each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituent) An aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. (Representation; m represents an integer from 1 to 3.)
[11]
The method for producing an organosilicon compound according to any one of [7] to [10], wherein the hydrosilylation reaction is performed in an inert atmosphere.
[12]
In the hydrosilylation step, the amount of the second hydrosilanes relative to the second alkenes is 1.0 molar equivalent or more and less than 6.0 molar equivalents, according to any one of [7] to [11]. Method for producing organosilicon compounds.

According to the present invention, it can be recovered after the catalytic reaction, it can be handled in air, it does not require a large amount of substrate in the catalytic reaction, and it has catalytic activity even in the hydrosilylation reaction using trialkoxysilanes. It is possible to provide a method for producing a catalyst having the following.

This is a STEM image of the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (photograph substituted for a drawing). This is an elemental mapping image of silicon in the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (photograph substituted for a drawing). This is an elemental mapping image of iron in the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (photograph substituted for a drawing). This is an elemental mapping image of platinum in the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (photograph substituted for a drawing).

In explaining the details of the present invention, specific examples will be given and explained, but the present invention is not limited to the following content as long as it does not depart from the spirit of the present invention, and the present invention can be implemented with appropriate changes.

1. Method for producing silicon-containing iron-platinum nanoparticle catalyst The first embodiment of the present invention is a method for producing a silicon-containing iron-platinum nanoparticle catalyst, in which iron whose surface is coordinated with a first coordinating organic solvent The method includes a heating step of heating a mixture containing nanoparticles, platinum nanoparticles whose surfaces are coordinated with a second coordinating organic solvent, and a first hydrosilane.

The silicon-containing iron-platinum nanoparticle catalyst obtained by the production method according to the present embodiment is capable of forming carbon-silicon bonds such as hydrosilylation reactions of alkynes or alkenes; coupling reactions of aryl halides and hydrosilanes; It can be effectively used as a reaction catalyst. Further, the silicon-containing iron-platinum nanoparticle catalyst can be recovered after the reaction and reused as a catalyst. Furthermore, the silicon-containing iron-platinum nanoparticle catalyst has high stability against oxygen and moisture, and can be easily handled in an air atmosphere.

1-1. Heating process [iron nanoparticles with first coordinating organic solvent coordinated on the surface]
As used herein, "iron nanoparticles" refer to particles containing iron as a constituent element. Therefore, the specific composition is not particularly limited as long as it contains iron; in addition to nanoparticles of simple iron, nanoparticles of iron alloys; nanoparticles of simple iron and other atoms such as oxygen atoms and carbon atoms. Also included are doped nanoparticles; nanoparticles of inorganic iron compounds such as iron oxide; and the like.

It is preferable that the iron nanoparticles contain oxygen atoms in addition to iron. Specifically, iron nanoparticles doped with oxygen atoms, iron nanoparticles doped with oxygen atoms, or iron oxide nanoparticles are preferable, and α-Fe ₂ O ₃ particles are more preferable.

The particle size (cumulative median diameter) of the iron nanoparticles is not particularly limited as long as it is in the range of 0.3 nm or more and 200 nm or less, but is preferably 0.5 nm or more, more preferably 1 nm or more, and preferably is 100 nm or less, more preferably 50 nm or less, even more preferably 10 nm or less. Note that the cumulative median diameter (median diameter) can be measured with a transmission electron microscope (TEM).

Moreover, "the first coordinating organic solvent is coordinated to the surface" means that molecules of the first coordinating organic solvent are coordinated to the surface of the iron nanoparticle.
The first coordinating organic solvent that coordinates to the iron nanoparticles can be appropriately selected depending on the desired catalytic reaction. In addition, regarding whether or not the first coordinating organic solvent is coordinated to the iron nanoparticles, it is possible to determine whether the iron nanoparticle catalyst is in the first coordinating organic solvent without performing surface treatment with a dispersant or the like. This can be determined by whether or not it is stably dispersed. That is, for example, an iron nanoparticle catalyst coordinated with N,N-dimethylformamide (DMF) as the first coordinating organic solvent can be stably dispersed in a coordinating organic solvent that has an affinity for DMF. .

Examples of the first coordinating organic solvent include amide solvents such as dimethylacetamide (DMA), N,N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP); sulfoxide solvents such as dimethylsulfoxide (DMSO); Solvents; ether solvents such as 1,4-dioxane and tetrahydrofuran (THF); alcohol solvents such as ethylene glycol and propylene glycol; and the like. Among these, DMF acts as a first coordinating organic solvent, a reaction solvent, and a reducing agent in the production of iron nanoparticles whose surface is coordinated with a first coordinating organic solvent, and is used in one step. It is particularly suitable because it can be manufactured.

The method for producing iron nanoparticles having the first coordinating organic solvent coordinated on the surface is not particularly limited, but can be produced according to a known production method. As a known production method, for example, as described in JP 2015-129103, International Publication No. 2018/131430, etc., a precursor containing an iron element is heated in a first coordinating organic solvent. An example is a method of refluxing.

[Platinum nanoparticles with second coordinating organic solvent coordinated on the surface]
As used herein, "platinum nanoparticles" refer to particles containing elemental platinum as a constituent element. Therefore, the specific composition is not particularly limited as long as it contains platinum; in addition to nanoparticles of simple platinum, nanoparticles of platinum alloys; nanoparticles of simple platinum containing other atoms such as oxygen atoms and carbon atoms. Also included are doped nanoparticles; nanoparticles of inorganic platinum compounds such as platinum oxide; and the like.

The particle diameter (cumulative median diameter) of the platinum nanoparticles is not particularly limited as long as it is in the range of 0.3 nm or more and 200 nm or less, but is preferably 0.5 nm or more, more preferably 1 nm or more, and preferably is 100 nm or less, more preferably 50 nm or less, even more preferably 10 nm or less. Note that the cumulative median diameter (median diameter) can be measured with a transmission electron microscope (TEM).

Moreover, "the second coordinating organic solvent is coordinated to the surface" means that the molecules of the second coordinating organic solvent are coordinated to the surface of the platinum nanoparticle.
The second coordinating organic solvent that coordinates to the platinum nanoparticles can be appropriately selected depending on the desired catalytic reaction. Further, whether or not the second coordinating organic solvent is coordinated to the platinum nanoparticles can be determined using the same method as used to determine whether or not the first coordinating organic solvent is coordinated to the iron nanoparticles. It can be determined by

Examples of the second coordinating organic solvent include the same solvents as the first coordinating organic solvent, and preferred embodiments are also the same. The second coordinating organic solvent may be the same as or different from the first coordinating organic solvent, but is preferably the same.

The method for producing platinum nanoparticles having a surface coordinated with a second coordinating organic solvent is not particularly limited, but can be produced according to a known production method. Known production methods include, for example, a method of heating and refluxing a precursor containing a platinum element in a second coordinating organic solvent, as described in International Publication No. 2018/131430.

[First hydrosilane]
The specific type of the first hydrosilanes is not particularly limited, and examples include compounds represented by the following formula (A) (hereinafter sometimes referred to as "hydrosilanes (A)"). Note that the first hydrosilanes are known or can be easily produced by a method similar to a known production method.

(R ¹ )
In formula (A), R ¹ is each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent. Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. .

Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, the halogen atom is preferably a fluorine atom or a chlorine atom.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group. group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n- Straight chain or branched alkyl groups such as octadecyl group and n-eicosyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, 1-adamantyl group and 2-adamantyl group; and the like.
Among these, the aliphatic hydrocarbon group is preferably a straight-chain or branched alkyl group, more preferably a straight-chain alkyl group. Further, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

The aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ¹ includes phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, fluoranthenyl group. group, triphenylenyl group, perylenyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 18 or less, more preferably 16 or less, and still more preferably 10 or less.

Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ¹ include pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, and benzothienyl group. , indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group, and the like. The number of carbon atoms in the aromatic heterocyclic group is preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less.

The alkoxy group having 1 to 20 carbon atoms represented by R ¹ includes methoxy group, ethoxy group, n-propyloxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group , n-pentyloxy group, isopentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyl Examples include straight-chain or branched alkoxy groups such as oxy, n-hexadecyloxy, n-octadecyloxy, and n-eicosyloxy groups.
Among these, the alkoxy group is preferably a straight-chain alkyl group. Further, the number of carbon atoms in the alkoxy group is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less.

An aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, represented by R ¹ may have a substituent or may be unsubstituted. Substituents include deuterium atom; hydroxyl group; carboxyl group; vinyl group; mercapto group; amino group; ureido group; isocyanate group; thioisocyanate group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; Methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, glycidyloxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-hexyloxy group, etc. with 1 to 6 carbon atoms Alkoxy groups; alkenylcarbonyloxy groups such as methacryloyloxy and acryloyloxy groups; cyclic ether groups such as oxiranyl, oxetanyl and tetrahydrofuryl groups; aryloxy groups such as phenyloxy and tolyloxy groups; benzyloxy and phenethyl Arylalkyloxy groups such as oxy groups; dialkylamino groups such as dimethylamino group, diethylamino group, dibutylamino group; pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, indolyl group and aromatic heterocyclic groups having 3 to 12 carbon atoms such as carbazolyl groups;
In ^addition , an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, or an aromatic heterocyclic group having 1 to 20 carbon atoms, represented by R 1 When the alkoxy group has a substituent, the number of carbon atoms is the total number of carbon atoms of the substituent and the number of carbon atoms of the aliphatic hydrocarbon group, aromatic hydrocarbon group, aromatic heterocyclic group, or alkoxy group. means.

(n)
In formula (A), n represents an integer of 1 to 3. n is preferably 2 or 3, more preferably 3.

Silicon-containing iron-platinum nanoparticle catalysts exhibit activity in reactions between hydrosilanes and alkenes, alkynes, aryl halides, and the like. Here, the first hydrosilanes may be the same compound as the hydrosilanes that are the substrates for the catalytic reaction, or may be different compounds, but it is preferable to select the same compounds.
Therefore, specific hydrosilanes (A) include, for example, the same compounds as the second hydrosilanes exemplified in the description of the method for producing an organosilicon compound according to the second embodiment of the present invention.

[First alkenes]
In this step, the mixture may further contain a first alkene. For example, when producing a silicon-containing iron-platinum nanoparticle catalyst for use in a hydrosilylation reaction of alkenes, a first alkene is added to the mixture from the viewpoint of improving catalytic activity and stabilizing the catalyst during the reaction. It is preferable to include it.
The specific type of the first alkenes is not particularly limited, and examples include compounds represented by the following formula (B) (hereinafter sometimes referred to as "alkenes (B)"). Note that the first alkenes are known or can be easily produced by a method similar to a known production method.

(R ² to R ⁵ )
In formula (B), R ² to R ⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent.

The halogen atom, aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, or aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ² to R ⁵ include: Those similar to the halogen atom, aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, or aromatic heterocyclic group having 3 to 20 carbon atoms, respectively, represented by R ¹ can be mentioned.

When R ² to R ⁵ are aliphatic hydrocarbon groups having 1 to 20 carbon atoms, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 18 or less, More preferably it is 15 or less, and still more preferably 12 or less.
When R ² to R ⁵ are aromatic hydrocarbon groups having 6 to 20 carbon atoms, the number of carbon atoms is preferably 18 or less, more preferably 16 or less, and even more preferably 10 or less.
When R ² to R ⁵ are aromatic heterocyclic groups having 3 to 20 carbon atoms, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, or aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ² to R ⁵ has a substituent. or may be unsubstituted. Examples of the substituent include an aliphatic hydrocarbon group having ¹ to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, or an aromatic heterocyclic group having 1 to 20 carbon atoms, represented by R 1 -20 The same substituents as the alkoxy group may have are mentioned.
Note that an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ² to R ⁵ has a substituent. When it has, the number of carbon atoms means the total number of carbon atoms of the substituent and the number of carbon atoms of the aliphatic hydrocarbon group, aromatic hydrocarbon group, or aromatic heterocyclic group.

When the silicon-containing iron-platinum nanoparticle catalyst is used in the hydrosilylation reaction of alkenes, the first alkene may be the same compound as the alkene that is the substrate, or may be a different compound. , are preferably the same compound.
Therefore, specific examples of alkenes (B) include compounds similar to the second alkenes exemplified in the explanation of the method for producing an organosilicon compound according to the second embodiment of the present invention.

[Organic solvent]
In this step, the mixture may further contain an organic solvent. Here, the organic solvent is an organic compound that exists in a liquid state at the heating temperature in the heating step, and does not include the first hydrosilanes and the first alkenes.
When neither the first hydrosilanes nor the first alkenes exist in a liquid state during the heating step, it is preferable that the mixture contains an organic solvent.

The organic solvent is not particularly limited, and can be appropriately selected depending on the heating temperature and the like. The organic solvent may be, for example, an inert solvent or a third coordinating organic solvent.
Examples of inert solvents include hydrocarbon solvents such as n-hexane, benzene, toluene, and xylene.
Examples of the third coordinating organic solvent include the same organic solvents as the first coordinating organic solvent or the second coordinating organic solvent, and preferred embodiments are also the same. The third coordinating organic solvent may be the same as or different from the first coordinating organic solvent or the second coordinating organic solvent, but from the viewpoint of dispersibility of each nanoparticle. Therefore, it is preferable that the first to third coordinating organic solvents are all the same coordinating organic solvent.
Note that these organic solvents are not limited to one type, and may be a mixed solvent of two or more types.

[Mixing ratio]
The mixing ratio of the iron nanoparticles with the first coordinating organic solvent on the surface and the platinum nanoparticles with the second coordinating organic solvent on the surface is not particularly limited. The mixing ratio (molar ratio) of the iron nanoparticles whose surface is coordinated with the first coordinating organic solvent to the platinum nanoparticles whose surface is coordinated with the first coordinating organic solvent (molar ratio) is usually 0.1 or more and 10 .0 or less. The mixing ratio may be appropriately selected within the above range depending on the desired catalytic reaction, substrate, etc. For example, it may be 0.2 or more, 0.5 or more, or 1.0 or more, and may be 5.0 or less, 3.0 or less, or 2.0 or less.

The amount of the first hydrosilanes to be mixed is a portion of the surface of iron nanoparticles whose surface is coordinated with the first coordinating organic solvent and platinum nanoparticles whose surface is coordinated with the second coordinating organic solvent. There is no particular restriction as long as the first hydrosilane or the silicon-containing compound derived from the first hydrosilane can be physically or chemically bonded to the whole. Usually, the total metal equivalent of iron nanoparticles whose surface is coordinated with a first coordinating organic solvent and platinum nanoparticles whose surface is coordinated with a second coordinating organic solvent (total of iron equivalent and platinum equivalent) The first hydrosilane is mixed in an equal amount, preferably in excess, for example, 10 molar equivalents or more, 100 molar equivalents or more, 200 molar equivalents or more, or 300 molar equivalents or more. Alternatively, based on the first hydrosilanes, iron nanoparticles with a first coordinating organic solvent on the surface and platinum nanoparticles with a second coordinating organic solvent on the surface are combined with a total metal In terms of (total of iron equivalent and platinum equivalent), usually 1.7 mmol% or more, preferably 5.0 mmol% or more, more preferably 8.3 mmol% or more, even more preferably 17 mmol% or more, and usually 833 mmol% or less, The content is preferably 333 mmol% or less, more preferably 167 mmol% or less, even more preferably 83 mmol% or less.

The amount of the first alkenes to be mixed is not particularly limited. For example, based on the first alkenes, iron nanoparticles having the first coordinating organic solvent on the surface and iron nanoparticles having the second coordinating organic solvent on the surface. The platinum nanoparticles coordinated with the organic solvent are usually 0.01 mol% or more, preferably 0.03 mol% or more, more preferably 0.05 mol% or more, in terms of total metal (total of iron equivalent and platinum equivalent). The amount is more preferably 0.1 mol% or more, and usually 5.0 mol% or less, preferably 2.0 mol% or less, more preferably 1.0 mol% or less, and even more preferably 0.5 mol% or less. In addition, when the first alkene exists as a gas under heating conditions, it may be contained in the mixture by circulating the first alkene in the reaction system.

[Heating temperature and heating time]
The heating temperature may be appropriately selected depending on the composition of the mixture, heating time, etc., and is usually 70°C or higher, preferably 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, and usually The temperature is 150°C or lower, preferably 140°C or lower, more preferably 130°C or lower, even more preferably 120°C or lower.
The heating time may be appropriately selected depending on the composition of the mixture, heating temperature, etc., and is usually 1 hour or more, preferably 5 hours or more, more preferably 10 hours or more, even more preferably 15 hours or more, and usually 48 hours. The time period is preferably 42 hours or less, more preferably 36 hours or less, and still more preferably 30 hours or less.
By setting the heating temperature and heating time within the above ranges, iron nanoparticles with the first coordinating organic solvent coordinated on the surface and platinum nanoparticles with the second coordinating organic solvent coordinating on the surface. It is possible to efficiently generate catalytically active species different from a mixture of the above.

[Atmospheric gas, etc.]
This step may be performed under normal pressure or under increased pressure.
In addition, in this embodiment, not only iron nanoparticles whose surface is coordinated with a first coordinating organic solvent and platinum nanoparticles whose surface is coordinated with a second coordinating organic solvent are manufactured. Since the silicon-containing iron-platinum nanoparticle catalyst also has high stability against oxygen and moisture, this step can be performed in an air atmosphere. In addition to the air atmosphere, this step may be performed in an atmosphere containing oxygen or moisture, or in an inert atmosphere such as nitrogen or argon.

1-2. Other Steps The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to this embodiment may include any steps such as a purification step in addition to the catalyst heating step described above. Specific purification methods include methods of removing organic solvents, unreacted first hydrosilanes, disproportionated products of first hydrosilanes, etc. by filtration, washing, drying under reduced pressure, and the like.

2. Method for producing an organosilicon compound Next, a method for producing an organosilicon compound according to the second embodiment of the present invention will be described. The method for producing an organosilicon compound according to the present embodiment includes a process in which a second alkene and a second hydrosilane are combined in the presence of a silicon iron-platinum nanoparticle catalyst obtained by the production method according to the first embodiment of the present invention. It includes a hydrosilylation step of reacting with
The manufacturing method according to the present embodiment may include a catalyst manufacturing step of obtaining a silicon iron-platinum nanoparticle catalyst by the manufacturing method according to the first embodiment of the present invention.

2-1. Organosilicon compound The organosilicon compound produced by the production method according to the present embodiment is a compound obtained by reacting alkenes and hydrosilanes, and has at least one alkyl group on at least one silicon atom in the molecule. The specific structure is not particularly limited, and a wide range of organosilicon compounds may be used as long as the compound is bonded with. Specifically, organosilicon compounds represented by formula (E1) or (E2) (hereinafter sometimes referred to as "organosilicon compound (E1)" or "organosilicon compound (E2)") can be mentioned. .

(R ⁶ to R ⁹ )
In formulas (E1) and (E2), R ⁶ to R ⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a group or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent.

Examples of the halogen atom represented by R ⁶ to R ⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, the halogen atom is preferably a fluorine atom or a chlorine atom.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ⁶ to R ⁹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group , n-octadecyl group, n-eicosyl group, etc.; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group; and the like.
Among these, the aliphatic hydrocarbon group is preferably a straight-chain or branched alkyl group, more preferably a straight-chain alkyl group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 or more, more preferably 4 or more, even more preferably 6 or more, and preferably 18 or less, more preferably 15 or less, and even more preferably 12 or less.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ⁶ to R ⁹ include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, Examples include fluoranthenyl group, triphenylenyl group, perylenyl group, and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably 18 or less, more preferably 16 or less, and still more preferably 10 or less.

Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ⁶ to R ⁹ include pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, Examples include a benzothienyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, and a carbolinyl group. The number of carbon atoms in the aromatic heterocyclic group is preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, or aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ⁶ to R ⁹ have a substituent. or may be unsubstituted. Substituents include deuterium atom; hydroxyl group; carboxyl group; vinyl group; mercapto group; amino group; ureido group; isocyanate group; thioisocyanate group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; Methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, glycidyloxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-hexyloxy group, etc. with 1 to 6 carbon atoms Alkoxy groups; alkenylcarbonyloxy groups such as methacryloyloxy and acryloyloxy groups; cyclic ether groups such as oxiranyl, oxetanyl and tetrahydrofuryl groups; aryloxy groups such as phenyloxy and tolyloxy groups; benzyloxy and phenethyl Arylalkyloxy groups such as oxy groups; dialkylamino groups such as dimethylamino group, diethylamino group, dibutylamino group; pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, indolyl group and aromatic heterocyclic groups having 3 to 12 carbon atoms such as carbazolyl groups;
Note that when an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ⁶ to R ⁹ has a substituent, When it has, the number of carbon atoms means the total number of carbon atoms of the substituent and the number of carbon atoms of the aliphatic hydrocarbon group, aromatic hydrocarbon group, or aromatic heterocyclic group.

R ⁶ to R ⁹ are each independently preferably a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; -20 aliphatic hydrocarbon groups are more preferred.
Particularly preferred embodiments of R ⁶ to R ⁹ include embodiments in which R ⁷ to R ⁹ are all hydrogen atoms; and R ⁶ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms; Examples include embodiments in which all of ⁷ to R ⁹ are hydrogen atoms.

( ^R10 )
In formulas (E1) and (E2), R ¹⁰ each independently has a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 1 to 20 carbon atoms which may have a substituent. Represents an alkoxy group.

The halogen atom, aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, or aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ¹⁰ are each represented by R Similar to the halogen atom, aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, or aromatic heterocyclic group having 3 to 20 carbon atoms represented by ⁶ to R ⁹ can be mentioned.

When R ¹⁰ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms is preferably 1
It is 0 or less, more preferably 5 or less, even more preferably 3 or less.
When R ¹⁰ is an aromatic hydrocarbon group having 6 to 20 carbon atoms, the number of carbon atoms is preferably 18 or less, more preferably 16 or less, and even more preferably 10 or less.
When R ¹⁰ is an aromatic heterocyclic group having 3 to 20 carbon atoms, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by ^R10 include methoxy group, ethoxy group, n-propyloxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group , n-pentyloxy group, isopentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyl Examples include straight-chain or branched alkoxy groups such as oxy, n-hexadecyloxy, n-octadecyloxy, and n-eicosyloxy groups.
Among these, the alkoxy group is preferably a straight-chain alkyl group. Further, the number of carbon atoms in the alkoxy group is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less.

An aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, represented by R ¹⁰ may have a substituent or may be unsubstituted. As a substituent, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ⁶ to R ⁹ is used. The same substituents as the substituents that may be included are mentioned.
In addition, an ^aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, or an aromatic heterocyclic group having 1 to 20 carbon atoms, represented by R10. When the alkoxy group has a substituent, the number of carbon atoms is the total number of carbon atoms of the substituent and the number of carbon atoms of the aliphatic hydrocarbon group, aromatic hydrocarbon group, aromatic heterocyclic group, or alkoxy group. means.

R ¹⁰ is preferably each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms is more preferable, and an alkoxy group having 1 to 20 carbon atoms is even more preferable.
Furthermore, when there is a plurality of R ^10s in formulas (E1) and (E2), R ^10s may be the same or different, but are preferably the same.

(m)
In formulas (E1) and (E2), m represents an integer of 1 to 3. m is preferably 2 or 3, more preferably 3.

In this embodiment, the silicon-containing iron-platinum nanoparticle catalyst used as a catalyst for the hydrosilylation reaction contains alkenes and dialkoxysilanes, which have been difficult to obtain activity with conventional catalysts (for example, the catalyst described in Non-Patent Document 2). It also shows high catalytic activity in reactions with trialkoxysilanes. Therefore, the production method according to this embodiment is an organosilicon compound (E1) or (E2) in which m is 2 and two R ^10s are alkoxy groups; m is 3 and three R ^10s are alkoxy groups. or an organosilicon compound (E1) or (E2) in which m is 3 and two of ^R10 are alkoxy groups and one is an alkyl group; Are suitable. Industrially, it is useful for producing dialkoxy-type or trialkoxy-type silane coupling agents. When producing a silane coupling agent, its raw material, or its intermediate by the production method according to the present embodiment, preferable examples of R ¹⁰ include a methyl group, a methoxy group, and an ethoxy group.

2-2. Catalyst Production Process The catalyst production process is a process of producing a silicon-containing iron-platinum nanoparticle catalyst by the production method according to the first embodiment of the present invention.
In this step, the first alkenes or first hydrosilanes used for producing the silicon-containing iron-platinum nanoparticle catalyst may be the same as the second alkenes or second hydrosilanes, respectively, which will be described later. They may be different, but preferably the same.

In this embodiment, the mixing ratio (in terms of metal) of iron nanoparticles whose surface is coordinated with a first coordinating organic solvent to platinum nanoparticles whose surface is coordinated with a second coordinating organic solvent is ratio) is usually 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, even more preferably 1.0 or more, and usually 10.0 or less, preferably 5.0 or less, more preferably is 3.0 or less, more preferably 2.0 or less.

The silicon-containing iron-platinum nanoparticle catalyst produced in this process exhibits high catalytic activity in the hydrosilylation reaction of alkenes, and the reaction can proceed smoothly even when trialkoxysilanes are used as hydrosilanes. can. The present inventors speculate as follows about the difference in catalytic activity between a conventional catalyst, which cannot obtain sufficient activity when trialkoxysilanes are used, and a silicon-containing iron-platinum nanoparticle catalyst. That is, hydrosilanes are physically or chemically bonded to the surfaces of iron nanoparticles whose surfaces are coordinated with a first coordinating organic solvent and platinum nanoparticles whose surfaces are coordinated with a second coordinative organic solvent. By doing so, a catalytically active species different from a mere mixture of iron nanoparticles whose surface is coordinated with a first coordinating organic solvent and platinum nanoparticles whose surface is coordinated with a second coordinating organic solvent is generated. It is assumed that

2-3. Hydrosilylation Step The hydrosilylation step is a step of obtaining an organosilicon compound by reacting a second alkene with a second hydrosilane in the presence of a silicon-containing iron-platinum nanoparticle catalyst.
The substrate and reaction conditions for the hydrosilylation reaction in this step will be described in detail below.

[Silicon-containing iron-platinum nanoparticle catalyst]
The silicon-containing iron-platinum nanoparticle catalyst is obtained by the manufacturing method according to the first embodiment of the present invention, and its detailed description can be found in the description of the manufacturing method according to the first embodiment of the present invention and The description of the catalyst manufacturing process in this embodiment will be referred to.

[Second alkenes]
The specific type of alkene used as a substrate is not particularly limited, and can be appropriately selected depending on the organosilicon compound to be produced. Examples of the second alkenes include compounds represented by the following formula (C) (hereinafter sometimes referred to as "alkenes (C)"). Note that the second alkenes are known or can be easily produced by a method similar to a known production method.

In formula (C), R ⁶ to R ⁹ are defined in the same manner as R ⁶ to R ⁹ in formula (E1) or (E2), and preferred embodiments are also the same.

Specific alkenes (C) include 1-propene, 1-heptene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 1-octene, 1-decene, 1-dodecene, 4 -Phenyl-1-butene, 6,6-dimethyl-1-heptene, 4,4-dimethyl-1-hexene, styrene, allyl glycidyl ether, allyl methacrylate, allyl acrylate, allylamine, allyl urea, allyl mercaptan, etc. Examples include α-olefins. Among these, 1-dodecene is preferred. Also preferred are alkenes that can be used as raw materials for silane coupling agents, such as allyl glycidyl ether, allyl methacrylate, allyl acrylate, allylamine, allyl urea, and allyl mercaptan.
In addition, regarding alkenes (C) having multiple alkenyl groups in one molecule, such as the above-mentioned allyl glycidyl ether, allyl methacrylate, allyl acrylate, etc., hydrosilylation can proceed in any alkenyl group. However, due to the high catalytic activity of the silicon-containing iron-platinum nanoparticle catalyst, the desired hydrosilylation product (a compound in which only the allyl group is hydrosilylated) can be obtained in a considerable yield.

[Second hydrosilanes]
The specific type of the second hydrosilane used as the substrate is not particularly limited, and can be appropriately selected depending on the organosilicon compound to be produced. Examples of the second hydrosilanes include compounds represented by the following formula (D) (hereinafter sometimes referred to as "hydrosilanes (D)"). Note that the second hydrosilanes are known or can be easily produced by a method similar to a known production method.

In formula (D), R ¹⁰ and m are defined similarly to R ¹⁰ and m in formula (E1) or (E2), respectively, and preferred embodiments are also the same.

Specific hydrosilanes (D) include monoalkylsilanes such as methylsilane, ethylsilane, and propylsilane; dialkylsilanes such as dimethylsilane, diethylsilane, and ethylmethylsilane; and trialkylsilanes such as trimethylsilane and triethylsilane. ; Monoarylsilanes such as phenylsilane and naphthylsilane; Diarylsilanes such as diphenylsilane and dinaphthylsilane; Triarylsilanes such as triphenylsilane and trinaphthylsilane; Monoarylsilanes such as methoxysilane, ethoxysilane, and propoxysilane Alkoxysilanes; dialkoxysilanes such as dimethoxysilane, diethoxysilane, ethoxymethoxysilane, dipropoxysilane; trialkoxysilanes such as trimethoxysilane, triethoxysilane, diethoxymethoxysilane; methyldimethoxysilane, methyldimethoxysilane; Examples include alkyldialkoxysilanes such as ethoxysilane; dialkylalkoxysilanes such as dimethylmethoxysilane and dimethylethoxysilane; and the like.

Among these, the hydrosilanes (D) are preferably dialkoxysilanes, trialkoxysilanes or alkyldialkoxysilanes, and more preferably trialkoxysilanes. That is, the hydrosilanes (D) have an embodiment in which m is 2 and two R ^10s are alkoxy groups; an embodiment in which m is 3 and three R ^10s are alkoxy groups; or m is 3 and, An embodiment in which two of R ¹⁰ are an alkoxy group and one is an alkyl group is preferable, and an embodiment in which three R ¹⁰ are an alkoxy group is more preferable.

[Amount of silicon-containing iron-platinum nanoparticle catalyst]
The amount of the silicon-containing iron-platinum nanoparticle catalyst used in the hydrosilylation reaction is not particularly limited, but is usually 0.01 mol% or more, preferably 0.01 mol% or more in terms of total metal (total of iron equivalent and platinum equivalent) based on the alkenes. .03 mol% or more, more preferably 0.05 mol% or more, even more preferably 0.1 mol% or more, and usually 5.0 mol% or less, preferably 2.0 mol% or less, more preferably 1.0 mol% or less, and Preferably it is 0.5 mol% or less. By controlling the amount of catalyst within the above range, the conversion rate of the substrate, the yield of the organosilicon compound, the ease of purification of the organosilicon compound, etc. can be improved.

[Molar ratio of substrate]
In the hydrosilylation step, the amount of the second hydrosilane relative to the second alkene is not particularly limited, but is usually 1.0 molar equivalent or more and less than 6.0 molar equivalent. From the viewpoint of suppressing the amount of silane gas produced, the amount of the second hydrosilanes relative to the second alkenes is preferably 5.0 molar equivalents or less, more preferably 4.0 molar equivalents or less, and even more preferably 3.0 molar equivalents. It is less than the molar equivalent. Further, from the viewpoint of improving the yield of the organosilicon compound, the amount of the second hydrosilane relative to the second alkene is preferably 1.5 molar equivalent or more, more preferably 2.0 molar equivalent or more.
In this embodiment, by using a silicon-containing iron-platinum nanoparticle catalyst as a catalyst for the hydrosilylation reaction, the hydrosilylation reaction can be smoothly carried out even when the amount of hydrosilanes (the amount charged) is smaller than when using a conventional catalyst. The organic silicon compound can be produced efficiently.

[Atmospheric gas, etc.]
The hydrosilylation step may be performed under normal pressure or under increased pressure.
In addition, conventional catalysts for hydrosilylation reactions (catalysts described in Patent Document 1) require oxygen for activation and cannot obtain sufficient catalytic activity in an inert atmosphere, whereas silicon-containing iron-platinum nanoparticle catalysts shows high catalytic activity even under an inert atmosphere. Therefore, in the production method according to the present embodiment, the hydrosilylation reaction can be carried out not only in an oxygen-containing atmosphere such as oxygen or air, but also in an inert atmosphere such as nitrogen or argon. .
In this embodiment, the hydrosilylation reaction is preferably performed under an inert atmosphere. Carrying out the hydrosilylation reaction in an inert atmosphere has the advantage that disproportionation of hydrosilanes is suppressed, and as a result, generation of silane gas is suppressed.

[Reaction solvent]
The hydrosilylation step may be carried out without a solvent or in a reaction solvent, but it is preferably carried out without a solvent. In this specification, "solvent-free" means that no reaction solvent is intentionally added to the reaction system, and does not mean that no solvent is present in the reaction system.
The reaction solvent is not particularly limited, and includes, for example, hydrocarbon solvents such as hexane, benzene, and toluene; ether solvents such as diethyl ether, 1,4-dioxane, diglyme, cyclopentyl methyl ether (CPME), and tetrahydrofuran (THF); acetic acid. Ester solvents such as ethyl and butyl acetate; halogenated hydrocarbon solvents such as 1,2-dichloroethane and chloroform; nitrile solvents such as acetonitrile and benzonitrile; protic polar solvents such as acetic acid, ethanol, butanol, ethylene glycol, and glycerin; Examples include aprotic polar solvents such as acetone, dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethylsulfoxide (DMSO). These reaction solvents are not limited to one type, and may be a mixed solvent of two or more types. Further, the reaction solvent is preferably used after being dehydrated and deoxygenated.

[Reaction temperature]
The reaction temperature may be appropriately selected depending on the reaction conditions such as the type of catalyst, the reactivity of the substrate, the type of reaction solvent, and the reaction time, and is usually 70°C or more and 150°C or less. From the viewpoint of reaction rate, the lower limit of the reaction temperature is preferably 80°C or higher, more preferably 90°C or higher, and still more preferably 100°C or higher. Further, the upper limit of the reaction temperature is preferably 140°C or less, more preferably 130°C or less, and still more preferably 120°C or less, from the viewpoint of suppressing disproportionation of hydrosilanes.

[Reaction time]
The reaction time may be appropriately selected depending on the reaction conditions such as the type of catalyst, the reactivity of the substrate, the type of reaction solvent, and the reaction temperature, and is usually 1 hour or more and 48 hours or less. From the viewpoint of improving the yield of the organosilicon compound, the lower limit of the reaction time is preferably 4 hours or more, more preferably 10 hours or more, and still more preferably 15 hours or more. Further, from the viewpoint of facilitating purification, the upper limit of the reaction time is preferably 42 hours or less, more preferably 36 hours or less, and still more preferably 30 hours or less.

2-4. Other Steps The method for producing an organosilicon compound according to this embodiment may include any other steps in addition to the catalyst production step and hydrosilylation step. The optional step includes a purification step to increase the purity of the organosilicon compound. In the purification step, purification methods commonly used in the field of organic synthesis, such as filtration, adsorption, column chromatography, and distillation, can be employed.

The present invention will be described in more detail with reference to Examples below, but changes can be made as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below.
In addition, the measurement method of gas chromatography (GC) in Examples is as follows.

<GC measurement conditions>
Equipment name: GC-2025 (Shimadzu Corporation)
Column: BP-5 (Trajan Scientific and Medical)
Carrier gas: nitrogen

<Synthesis of silicon-containing iron-platinum nanoparticle catalyst>
(Synthesis Example 1: Preparation of dispersion of iron nanoparticles with DMF coordinated on the surface)
Add 0.1 mmol of Fe(OAc) ₂ and 1 mL of ethanol to a screw tube, and
By allowing the mixture to stand until (OAc) ₂ became highly dispersed, a Fe(OAc) ₂ dispersion was obtained. Next, 50 mL of DMF weighed out under an air atmosphere was added to a three-necked round bottom flask that had been co-washed with DMF, and the DMF was preheated at 140° C. for 10 minutes while stirring at 1500 rpm. Subsequently, 500 μL of the Fe(OAc) ₂ dispersion was added to the three-necked round-bottomed flask and heated under reflux for 8 hours to produce iron nanoparticles (hereinafter sometimes referred to as “FeNPs”) whose surfaces were coordinated with DMF. ) was obtained.
Assuming that all Fe(OAc) ₂ is converted into iron oxide nanoparticles, the concentration of elemental iron in the resulting dispersion is 1.0 mmol/L.

(Synthesis Example 2: Preparation of a dispersion of platinum nanoparticles with DMF coordinated on the surface)
Add 0.1 mmol of H ₂ PtCl _{6.6H 2} O and 1 mL of DMF to a screw tube,
A H ₂ PtCl _{6.6H 2} O dispersion was obtained by allowing the mixture to stand until H ₂ PtCl _{6.6H 2} O became highly dispersed. Next, 50 mL of DMF weighed out under an air atmosphere was added to a three-necked round bottom flask that had been co-washed with DMF, and the DMF was preheated at 140° C. for 10 minutes while stirring at 1500 rpm. Next, 500 μL of the H ₂ PtCl _{6.6H 2} O dispersion was added to the three-necked round-bottomed flask and heated under reflux for 10 hours to form platinum nanoparticles (hereinafter referred to as "PtNPs") with DMF coordinated on the surface. ) was obtained.
Assuming that all H ₂ PtCl ₆ is converted into metallic platinum nanoparticles, the concentration of elemental platinum in the resulting dispersion will be 1.0 mmol/L.

(Synthesis Example 3: Synthesis of silicon-containing iron-platinum nanoparticle catalyst)
250 μL (0.25 μmol in terms of Fe) of the dispersion obtained in Synthesis Example 1 and 250 μL (0.25 μmol in terms of Pt) of the dispersion obtained in Synthesis Example 2 were added to a Schlenk tube, and DMF was distilled off under vacuum. Next, 0.5 mmol of 1-dodecene and 3.0 mmol of triethoxysilane were placed in a Schlenk tube, and the mixture was stirred at 100° C. for 24 hours in an air atmosphere. The resulting reaction solution was cooled to room temperature. Subsequently, 8 mL of hexane and 2 mL of DMF were added to the Schlenk tube, stirred, and allowed to stand, and then the supernatant liquid was removed with a Pasteur pipette. Further, 8 mL of hexane was added to the Schlenk tube, stirred, and left to stand, and then the supernatant liquid was removed with a Pasteur pipette. By drying the precipitate under vacuum, a silicon-containing iron-platinum nanoparticle catalyst (hereinafter sometimes referred to as "Fe-Pt-Si") was obtained.

The obtained silicon-containing iron-platinum nanoparticle catalyst was observed using a scanning transmission electron microscope (STEM). The results are shown in Figure 1. Furthermore, elemental mapping images of silicon (Si), iron (Fe), and platinum (Pt) in the silicon-containing iron-platinum nanoparticle catalyst are shown in FIGS. 2 to 4, respectively.

(Synthesis Example 4: Synthesis of silicon-containing iron-platinum nanoparticle catalyst)
500 μL (0.5 μmol in terms of Fe) of the dispersion obtained in Synthesis Example 1 and 500 μL (0.5 μmol in terms of Pt) of the dispersion obtained in Synthesis Example 2 were added to a Schlenk tube, and DMF was distilled off under vacuum. Next, 3.0 mmol of triethoxysilane was added to the Schlenk tube, and the mixture was stirred at 100° C. for 10 hours in an air atmosphere. Thereafter, by distilling off volatile components such as unreacted triethoxysilane from the reaction solution under vacuum, a silicon-containing iron-platinum nanoparticle catalyst (hereinafter referred to as "Fe-Pt-[Si]") is removed. ) was obtained.

<Production of organosilicon compound 1>

(Example 1)
The interior of the Schlenk tube containing the silicon-containing iron-platinum nanoparticle catalyst (0.25 μmol in terms of Fe, 0.25 μmol in terms of Pt) obtained in Synthesis Example 3 was replaced with argon. 1.0 mmol (0.168 g) of 1-dodecene and 1.0 mmol (0.164 g) of triethoxysilane were added to a Schlenk tube, and the mixture was stirred for 24 hours while heating in an oil bath set at 100°C. After cooling the reaction solution in an ice bath, about 10 mL of hexane and nonane as an internal reference substance were added to the reaction solution, and GC measurement was performed. Table 1 shows the substrate conversion rate and product yield calculated from the GC measurement results.

(Example 2)
A hydrosilylation reaction was carried out in the same manner as in Example 1, except that the reaction conditions were as shown in Table 1. Table 1 shows the substrate conversion rate and product yield calculated from the GC-MS measurement results.

(Comparative example 1)
Add 250 μL of the dispersion obtained in Synthesis Example 1 (0.25 μmol in terms of Fe) and 250 μL of the dispersion obtained in Synthesis Example 2 (0.25 μmol in terms of Pt) to a Schlenk tube, and add the dispersion medium while stirring under vacuum. By distilling off, a FeNPs-PtNPs mixed catalyst was obtained.
A hydrosilylation reaction was carried out in the same manner as in Example 1, except that the catalyst was replaced with a FeNPs-PtNPs mixed catalyst (0.25 μmol in terms of Fe, 0.25 μmol in terms of Pt). Table 1 shows the substrate conversion rate and product yield calculated from the GC-MS measurement results.

(Comparative example 2)
A hydrosilylation reaction was carried out in the same manner as in Comparative Example 1, except that the reaction conditions were as shown in Table 1. Table 1 shows the substrate conversion rate and product yield calculated from the GC-MS measurement results.
Note that Table 1 also shows the results of Example 18 of International Publication No. 2018/131430 for reference.

From the results shown in Table 1, when FeNPs-PtNPs mixed catalyst is used as a catalyst (Comparative Examples 1 and 2), when the amount of hydrosilanes is 1.0 molar equivalent or 2.0 molar equivalent relative to alkenes, However, the desired organosilicon compound was obtained only in low yield. Therefore, in order to obtain organosilicon compounds in high yield, it is necessary to use a large amount of hydrosilanes, about 6 molar equivalents relative to alkenes, as shown in Example 18 of International Publication No. 2018/131430. It can be said that there is.

On the other hand, when silicon-containing iron-platinum nanoparticle catalysts were used as catalysts (Examples 1 and 2), when the amount of hydrosilanes was 1.0 molar equivalent to alkenes, organosilicon was produced with a yield of 33%. It was found that when a compound was obtained and the molar equivalent was 2.0, an organosilicon compound could be obtained with a high yield of 82%. In other words, in the presence of a silicon-containing iron-platinum nanoparticle catalyst, the hydrosilylation reaction of alkenes can be suppressed even if the amount of hydrosilane used is about one-sixth to one-third of that when using a conventional catalyst. It was shown that the process proceeded smoothly.
It was also shown that by using a silicon-containing iron-platinum nanoparticle catalyst as a catalyst, hydrosilylation proceeded smoothly even under an inert atmosphere.
Furthermore, in Examples 1 and 2, silane gas was not detected in the GC measurement.

<Production of organosilicon compound 2>

(Example 3)
The interior of the Schlenk tube containing the silicon-containing iron-platinum nanoparticle catalyst (0.25 μmol in terms of Fe, 0.25 μmol in terms of Pt) obtained in Synthesis Example 4 was replaced with argon. 0.5 mmol (0.084 g) of 1-dodecene and 3.0 mmol (0.493 g) of triethoxysilane were added to a Schlenk tube, and the mixture was stirred for 14 hours while heating in an oil bath set at 100°C. After cooling the reaction solution in an ice bath, about 10 mL of hexane and nonane as an internal reference substance were added to the reaction solution, and GC measurement was performed. Table 2 shows the substrate conversion rate and product yield calculated from the GC measurement results.

(Example 4)
A hydrosilylation reaction was carried out in the same manner as in Example 3, except that the amount of triethoxysilane was changed as shown in Table 2. Table 2 shows the substrate conversion rate and product yield calculated from the GC-MS measurement results.

The silicon-containing iron-platinum nanoparticle catalysts used in Examples 3 and 4 differ from the catalysts used in Examples 1 and 2 in that they were synthesized in the absence of the first alkenes. From Examples 3 and 4, it was found that even by using this silicon-containing iron-platinum nanoparticle catalyst, the hydrosilylation of alkenes proceeded rapidly in an inert atmosphere.
Furthermore, by using the silicon-containing iron-platinum nanoparticle catalyst, the amount of hydrosilanes relative to alkenes was not only reduced to 6.0 molar equivalents (Example 3) but also reduced to 5.0 molar equivalents. It was shown that even in the case (Example 4), the desired organosilicon compound could be obtained in high yield.

According to the present invention, it can be recovered after the catalytic reaction, can be handled in air, does not require a large amount of substrate in the catalytic reaction, and has catalytic activity for hydrosilylation reactions using trialkoxysilanes. A silicon-containing iron-platinum nanoparticle catalyst can be produced.
Further, according to the present invention, by using a silicon-containing iron-platinum nanoparticle catalyst, the reaction between alkenes and hydrosilanes proceeds even under an inert atmosphere without requiring an excessive amount of hydrosilanes, and is efficient. Desired organosilicon compounds can be produced in a controlled manner. This catalytic reaction does not use a large amount of hydrosilanes, so the atomic efficiency of the reaction is high, and less silane gas, which is a disproportionate product of hydrosilanes, is generated, so it is useful for industrial implementation. Furthermore, the catalytic reaction proceeds smoothly even when trialkoxysilanes are used as the hydrosilanes, making it particularly effective for producing trialkoxy-type silane coupling agents, raw materials thereof, or intermediates thereof. It can be used.

Claims (10)

A heating step of heating a mixture containing iron nanoparticles whose surface is coordinated with a first coordinating organic solvent, platinum nanoparticles whose surface is coordinated with a second coordinating organic solvent, and a first hydrosilane. A method for producing a silicon-containing iron-platinum nanoparticle catalyst, including (excluding those carried out in the presence of an alkene) . The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to claim 1, wherein the first hydrosilane is a compound represented by formula (A).

(In formula (A), R ¹ is each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituent) An aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. (Representation; n represents an integer from 1 to 3.) The silicon-containing iron-platinum nanoparticle catalyst according to claim 1 or 2 , wherein the first coordinating organic solvent and the second coordinating organic solvent are N,N-dimethylformamide (DMF). Production method. In the mixture, the mixing ratio (in terms of metal) of iron nanoparticles whose surface is coordinated with the first coordinating organic solvent to platinum nanoparticles whose surface is coordinated with the second coordinating organic solvent is The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to any one of claims 1 to 3 , wherein the ratio) is 0.1 or more and 10.0 or less. A catalyst production step of producing a silicon-containing iron-platinum nanoparticle catalyst by the production method according to any one of claims 1 to 4 ;
a hydrosilylation step of reacting a second alkene and a second hydrosilane in the presence of the silicon-containing iron-platinum nanoparticle catalyst;
A method for producing an organosilicon compound, comprising: A hydrosilylation step in which the second alkenes and the second hydrosilanes are reacted in the presence of the silicon-containing iron-platinum nanoparticle catalyst obtained by the production method according to any one of claims 1 to 4 . A method for producing an organosilicon compound. The method for producing an organosilicon compound according to claim 5 or 6 , wherein the second alkene is a compound represented by formula (C).

(In formula (C), R ⁶ to R ⁹ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a substituent-bearing aliphatic hydrocarbon group) represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent.) The method for producing an organosilicon compound according to any one of claims 5 to 7 , wherein the second hydrosilane is a compound represented by formula (D).

(In formula (D), R ¹⁰ is each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituent) An aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. (Representation; m represents an integer from 1 to 3.) The method for producing an organosilicon compound according to any one of claims 5 to 8 , wherein the hydrosilylation step is performed under an inert atmosphere. According to any one of claims 5 to 9 , in the hydrosilylation step, the amount of the second hydrosilanes relative to the second alkenes is 1.0 molar equivalent or more and less than 6.0 molar equivalents. A method for producing an organosilicon compound.

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