JP2021115497A - Method for producing silicon-containing iron-platinum nanoparticle catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a catalyst which can be recovered after a catalytic reaction, can be handled in air, does not require a large amount of substrate in the catalytic reaction, and has catalytic activity of a hydrosilylation reaction using trialkoxysilanes. Provide a method.
SOLUTION: A mixture containing iron nanoparticles in which a first coordinating organic solvent is coordinated on the surface, platinum nanoparticles in which a second coordinating organic solvent is coordinated on the surface, and first hydrosilanes. A method for producing a silicon-containing iron-platinum nanoparticle catalyst, which comprises a heating step of heating.
[Selection diagram] Fig. 1

Description

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

The reaction of forming a carbon-silicon bond is a useful reaction in the organosilicon chemical industry. Among them, the hydrosilylation reaction is one of the most important reactions for producing an industrially useful organosilicon compound such as a silicone resin and a silane coupling agent. As a catalyst for the hydrosilylation reaction, a metal catalyst has been mainly used.

For example, Non-Patent Document 1 discloses a method for obtaining alkyltrialkoxysilanes by reacting alkenes with trialkoxysilanes in the presence of a Karstedt's catalyst. However, the Karstedt's catalyst is an expensive platinum complex catalyst, and it is difficult to recover it after the reaction, so that there is a problem that it is difficult to reduce the cost.
Further, Non-Patent Document 1 discloses a method of reacting alkenes with trialkoxysilanes in the presence of an iron complex to obtain alkyltrialkoxysilanes. However, since the iron complex is unstable in air, it is difficult to handle. Also, like the Karstedt's catalyst, it is difficult to recover after the reaction.

In view of these circumstances, the applicant has previously described a platinum nanoparticle catalyst or a mixture of a platinum nanoparticle catalyst and an iron nanoparticle catalyst as a catalyst for the hydrosilylation reaction of alkenes (Patent Document 1) and iron iron. A nanoparticle catalyst (Non-Patent Document 2) is disclosed. Since these catalysts are in the form of particles, they can be easily recovered by filtration or the like, and the manufacturing cost 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 the catalyst described in Patent Document 1 is used, in order to obtain a hydrosilylation product in high yield, 6 molar equivalents and an excess amount of hydrosilanes are required with respect to alkenes, and the raw material cost is high. 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 excessively. Further, the catalyst described in Non-Patent Document 2 has a problem in that the catalytic reaction does not proceed sufficiently when trialkoxysilanes are used as the hydrosilanes.

Therefore, the subject of the present invention is that 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 is also a catalyst in the hydrosilylation reaction using trialkoxysilanes. The purpose is to provide a method for producing an active catalyst.

The present inventors have made diligent studies to solve the above problems. As a result, they found that the above problems could be solved by heating the iron nanoparticles coordinated with the coordinating organic solvent and the platinum nanoparticles coordinated with the coordinating organic solvent together with the hydrosilanes, and completed the present invention. rice field. 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 coordinated with a first coordinating organic solvent on the surface, platinum nanoparticles coordinated with a second coordinating organic solvent on the surface, and first hydrosilanes. A method for producing a silicon-containing iron-platinum nanoparticle catalyst, which comprises.
[2]
The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to [1], wherein the first hydrosilane is a compound represented by the formula (A).

(In the formula (A), R ¹ independently has a halogen atom and an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a carbon which may have a substituent. An aromatic hydrocarbon group having a number of 6 to 20, 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 of 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 the formula (B).

(In the formula (B), R ^{2 to} R ⁵ each independently have an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a hydrogen atom, a halogen atom and a substituent. It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent.
[5]
The silicon-containing iron-containing 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). A method for producing a platinum nanoparticle catalyst.
[6]
In the mixture, the mixing ratio (mol) of the iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface with respect to the platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface. 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 manufacturing step of manufacturing a silicon-containing iron-platinum nanoparticle catalyst by the manufacturing method according to any one of [1] to [6].
A hydrosilylation step of reacting a second alkene with a second hydrosilane in the presence of the silicon-containing iron-platinum nanoparticle catalyst.
A method for producing an organosilicon compound, which comprises.
[8]
A hydrosilylation step of reacting a second alkene with a second hydrosilane 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, which comprises.
[9]
The method for producing an organosilicon compound according to [7] or [8], wherein the second alkene is a compound represented by the formula (C).

(In the formula (C), R ^{6 to} R ⁹ each independently have an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a hydrogen atom, a halogen atom and a substituent. It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms 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 the formula (D).

In the formula (D), R ¹⁰ independently has a halogen atom and an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a carbon which may have a substituent. An aromatic hydrocarbon group having a number of 6 to 20, 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 of 1 to 3)
[11]
The method for producing an organosilicon compound according to any one of [7] to [10], wherein the hydrosilylation reaction is carried out in an inert atmosphere.
[12]
The method according to any one of [7] to [11], wherein 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.

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 even in a hydrosilylation reaction using trialkoxysilanes. A method for producing a catalyst having a catalyst can be provided.

It is a STEM image of the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (drawing substitute photograph). It is an element mapping image of silicon in the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (drawing substitute photograph). It is an element mapping image of iron in the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (drawing substitute photograph). It is an element mapping image of platinum in the silicon-containing iron-platinum nanoparticle catalyst obtained in Synthesis Example 3 (drawing substitute photograph).

In explaining the details of the present invention, specific examples will be given, but the present invention is not limited to the following contents as long as it does not deviate from the gist of the present invention, and can be appropriately modified and carried out.

1. 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, wherein a first coordinating organic solvent is coordinated on the surface of iron. It comprises a heating step of heating a mixture containing nanoparticles, platinum nanoparticles having a second coordinating organic solvent coordinated on the surface, and first hydrosilanes.

The silicon-containing iron-platinum nanoparticle catalyst obtained by the production method according to the present embodiment can form a carbon-silicon bond such as a hydrosilylation reaction of alkynes or alkenes; a coupling reaction between aryl halides and hydrosilanes; It can be effectively used as a catalyst for the reaction. In addition, 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 is highly stable against oxygen and moisture and can be easily handled in an air atmosphere.

1-1. Heating step [Iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface]
As used herein, the term "iron nanoparticles" means particles containing an iron element as a constituent element. Therefore, the specific composition is not particularly limited as long as it contains iron, and in addition to the nanoparticles of elemental iron, the nanoparticles of iron alloy; the nanoparticles of elemental iron contain other atoms such as oxygen atoms and carbon atoms. Dope nanoparticles; nanoparticles of inorganic iron compounds such as iron oxide; and the like are also included.

The iron nanoparticles preferably 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 is preferable. Is 100 nm or less, more preferably 50 nm or less, still more preferably 10 nm or less. The cumulative median diameter can be measured with a transmission electron microscope (TEM).

Further, "the first coordinating organic solvent is coordinated on the surface" means that the molecules of the first coordinating organic solvent are coordinated on the surface of the iron nanoparticles.
The first coordinating organic solvent that coordinates the iron nanoparticles can be appropriately selected according to the desired catalytic reaction. Regarding whether or not the first coordinating organic solvent is coordinated to the iron nanoparticles, the iron nanoparticles catalyst is contained in the first coordinating organic solvent without surface treatment with a dispersant or the like. It can be judged whether or not it is stably dispersed. That is, for example, the iron nanoparticle catalyst in which N, N-dimethylformamide (DMF) is coordinated as the first coordinating organic solvent can be stably dispersed in the coordinating organic solvent having 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); and sulfoxide solvents such as dimethyl sulfoxide (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 in which the first coordinating organic solvent is coordinated on the surface, and in one step. It is particularly suitable because it can be manufactured.

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

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

The particle size (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 is preferable. Is 100 nm or less, more preferably 50 nm or less, still more preferably 10 nm or less. The cumulative median diameter can be measured with a transmission electron microscope (TEM).

Further, "the second coordinating organic solvent is coordinated on the surface" means that the molecule of the second coordinating organic solvent is coordinated on the surface of the platinum nanoparticles.
The second coordinating organic solvent that coordinates the platinum nanoparticles can be appropriately selected according to the desired catalytic reaction. Further, whether or not the second coordinating organic solvent is coordinated to the platinum nanoparticles is the same method as determining whether or not the first coordinating organic solvent is coordinated to the iron nanoparticles. Can be judged by.

Examples of the second coordinating organic solvent include the same solvent as the first coordinating organic solvent, and the preferred embodiment is 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 the platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface is not particularly limited, but the platinum nanoparticles can be produced according to a known production method. As a known production method, for example, as described in International Publication No. 2018/131430, a method of heating and refluxing a precursor containing a platinum element in a second coordinating organic solvent can be mentioned.

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

(R ¹ )
In the formula (A), R ¹ independently has a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent. It represents an aromatic hydrocarbon group of 6 to 20, 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. Of 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group and a 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- Linear 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.
Of these, the aliphatic hydrocarbon group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ¹ include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, an indenyl group, a pyrenyl group and a fluoranthenyl group. Examples thereof include a group, a triphenylenyl group, a peryleneyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 18 or less, more preferably 16 or less, and further preferably 10 or less.

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

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, and a 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 thereof include linear or branched alkoxy groups such as an oxy group, an n-hexadecyloxy group, an n-octadecyloxy group and an n-eicosyloxy group.
Of these, the alkoxy group is preferably a linear alkyl group. The number of carbon atoms of 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 represented by R ¹ , 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. May have a substituent or may be unsubstituted. Substituents include dear hydrogen atom; hydroxyl group; carboxyl group; vinyl group; mercapto group; amino group; ureido group; isocyanate group; thioisocyanate group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; 1 to 6 carbon atoms of 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. Alkoxy group; alkenylcarbonyloxy group such as methacryloyloxy group, acryloyloxy group; cyclic ether group such as oxylanyl group, oxetanyl group and tetrahydrofuryl group; aryloxy group such as phenyloxy group and triloxy group; benzyloxy group 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, frill group, pyrrolyl group, quinolyl group, isoquinolyl group, indrill An aromatic heterocyclic group having 3 to 12 carbon atoms such as a group and a carbazolyl group; and the like can be mentioned.
An aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , 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. When the alkoxy group has a substituent, the carbon number is the total carbon number of the carbon number of the substituent and the carbon number of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, the aromatic heterocyclic group or the alkoxy group. means.

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

The silicon-containing iron-platinum nanoparticle catalyst exhibits activity in the reaction of hydrosilanes with alkenes, alkynes, aryl halides and the like. Here, the first hydrosilanes may be the same compound as the hydrosilanes which are the substrates of the catalytic reaction, or may be different compounds, but it is preferable to select the same compound.
Therefore, specific examples of the hydrosilanes (A) include compounds similar to 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 the first alkenes. For example, in the case of producing a silicon-containing iron-platinum nanoparticle catalyst used for the hydrosilylation reaction of alkenes, the first alkenes are added to the mixture from the viewpoints of improving catalytic activity and stabilizing the catalyst during the reaction. It is preferable to include it.
The specific type of the first alkene is not particularly limited, and examples thereof include a compound represented by the following formula (B) (hereinafter, may be referred to as "alkene (B)"). The first alkenes are known or can be easily produced by a method according to a known production method.

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

Halogen atom represented by R ² to R ^5, the aliphatic hydrocarbon group having 1 to 20 carbon atoms, and aromatic heterocyclic group of aromatic hydrocarbon group or a 3 to 20 carbon atoms having 6 to 20 carbon atoms, Similar to the halogen atom represented by R ¹ , the aliphatic hydrocarbon group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 20 carbon atoms, or the aromatic heterocyclic group having 3 to 20 carbon atoms, respectively. Can be mentioned.

If R ² to R ⁵ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, more preferably 6 or more, preferably 18 or less, It is more preferably 15 or less, still more preferably 12 or less.
If R ² to R ⁵ 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, more preferably 10 or less.
When R ^{2 to} R ⁵ are aromatic heterocyclic groups having 3 to 20 carbon atoms, the carbon number thereof is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.

R ² to R ⁵ carbon atoms represented by 1-20 aliphatic hydrocarbon group, an aromatic heterocyclic group of the aromatic hydrocarbon group or a 3 to 20 carbon atoms having 6 to 20 carbon atoms, have a substituent It may be or is not substituted. Examples of the substituent include ^{an aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 1} , an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, or 1 carbon group. Examples thereof include substituents that may be possessed by ~ 20 alkoxy groups.
An aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ^{2 to} R ⁵ , an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms serves as a substituent. When possessed, the carbon number means the total carbon number of the carbon number of the substituent and the carbon number of the aliphatic hydrocarbon group, the aromatic hydrocarbon group or the aromatic heterocyclic group.

When a silicon-containing iron-platinum nanoparticle catalyst is used for the hydrosilylation reaction of alkenes, the first alkenes may be the same compound as the substrate alkenes or may be different compounds. , It is preferable that they are the same compound.
Therefore, specific alkenes (B) include, for example, compounds similar to the second alkenes exemplified in the description 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 contain the first hydrosilanes and the first alkenes.
When neither the first hydrosilanes nor the first alkenes are present in the liquid state in the heating step, it is preferable to include an organic solvent in the mixture.

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 the inert solvent include hydrocarbon solvents such as n-hexane, benzene, toluene and xylene.
Examples of the third coordinating organic solvent include the first coordinating organic solvent and the same organic solvent as the second coordinating organic solvent, and the preferred embodiment is 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.
The organic solvent is not limited to one type, and may be a mixed solvent in which two or more types are combined.

[Mixing ratio]
The mixing ratio of the iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and the platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface is not particularly limited, but the second on the surface. The metal-equivalent mixing ratio (molar ratio) of the iron nanoparticles coordinated with the first coordinating organic solvent on the surface with respect to the platinum nanoparticles coordinated with the coordinating organic solvent is usually 0.1 or more and 10 It is less than or equal to 0.0. The mixing ratio may be appropriately selected within the above range according to the desired catalytic reaction, substrate and the like. 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 mixed amount of the first hydrosilanes is a part of the surface of the iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and the platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface. Alternatively, there is no particular limitation as long as the first hydrosilanes or the silicon-containing compound derived from the first hydrosilanes can be physically or chemically bonded to the whole. Usually, the total metal equivalent of iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface (total of iron equivalent and platinum equivalent). An equal amount, preferably an excess amount, for example, 10 molar equivalents or more, 100 molar equivalents or more, 200 molar equivalents or 300 molar equivalents or more of the first hydrosilanes are mixed. Alternatively, the iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and the platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface are all metals based on the first hydrosilanes. In terms of conversion (total of iron conversion and platinum conversion), it is usually 1.7 mmol% or more, preferably 5.0 mmol% or more, more preferably 8.3 mmol% or more, still more preferably 17 mmol% or more, and usually 833 mmol% or less. Mixing is preferably 333 mmol% or less, more preferably 167 mmol% or less, still more preferably 83 mmol% or less.

The mixing amount of the first alkene is not particularly limited, and for example, based on the first alkene, the iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and the second coordination on the surface. Platinum nanoparticles coordinated with a sex 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, usually 5.0 mol% or less, preferably 2.0 mol% or less, more preferably 1.0 mol% or less, still more preferably 0.5 mol% or less. When the first alkenes are present as a gas under heating conditions, the first alkenes may be contained in the mixture by circulating the first alkenes in the reaction system.

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

[Atmospheric gas, etc.]
This step may be performed under normal pressure or under pressure.
Further, in the present embodiment, not only iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface are produced. Since the silicon-containing iron-platinum nanoparticle catalyst is also highly stable 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 humidity, or may be performed 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 the present embodiment may include an arbitrary step such as a purification step in addition to the above catalyst heating step. Specific examples of the purification method include a method of removing an organic solvent, unreacted first hydrosilanes, disproportionates of the first hydrosilanes, and the like by filtration, washing, drying under reduced pressure, and the like.

2. Method for Producing Organosilicon Compound Next, a method for producing the 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 is a second alkene and a second hydrosilane in the presence of the silicon iron-platinum nanoparticle catalyst obtained by the production method according to the first embodiment of the present invention. Includes a hydrosilylation step that reacts with the class.
The production method according to the present embodiment may include a catalyst production step for obtaining a silicon iron-platinum nanoparticle catalyst by the production 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 alkens with hydrosilanes, and has at least one alkyl group on at least one silicon atom in the molecule. As long as it is a compound to which is bonded, the specific structure is not particularly limited, and a wide range of organosilicon compounds may be used. Specific examples thereof include an organosilicon compound represented by the formula (E1) or (E2) (hereinafter, may be referred to as "organosilicon compound (E1)" or "organosilicon compound (E2)"). ..

(R ^{6 to} R ⁹ )
In formulas (E1) and (E2), R ^{6 to} R ⁹ are independently substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom, a halogen atom and a substituent. It 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. Of 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and an 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 and other linear or branched alkyl groups; cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group and other cycloalkyl groups; and the like.
Of these, the aliphatic hydrocarbon group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, preferably 18 or less, more preferably 15 or less, still 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 a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group, a fluorenyl group, an indenyl group and a pyrenyl group. Examples thereof include a fluoranthenyl group, a triphenylenyl group, a peryleneyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 18 or less, more preferably 16 or less, and further preferably 10 or less.

Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ^{6 to} R ⁹ include a pyridyl group, a pyrimidinyl group, a triazinyl group, a thienyl group, a furyl group, a pyrrolyl group, a quinolyl group, an isoquinolyl group and a benzofuranyl group. Examples thereof include a benzothienyl group, an indrill group, a carbazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzoimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group and a carborinyl group. The number of carbon atoms of the aromatic heterocyclic group is preferably 15 or less, more preferably 10 or less, and further preferably 5 or less.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ^{6 to} R ⁹ , the aromatic hydrocarbon group having 6 to 20 carbon atoms, or the aromatic heterocyclic group having 3 to 20 carbon atoms has a substituent. It may be or is not substituted. Substituents include dear hydrogen atom; hydroxyl group; carboxyl group; vinyl group; mercapto group; amino group; ureido group; isocyanate group; thioisocyanate group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; 1 to 6 carbon atoms of 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. Alkoxy group; alkenylcarbonyloxy group such as methacryloyloxy group, acryloyloxy group; cyclic ether group such as oxylanyl group, oxetanyl group and tetrahydrofuryl group; aryloxy group such as phenyloxy group and triloxy group; benzyloxy group 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, frill group, pyrrolyl group, quinolyl group, isoquinolyl group, indrill An aromatic heterocyclic group having 3 to 12 carbon atoms such as a group and a carbazolyl group; and the like can be mentioned.
An aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ^{6 to} R ⁹ , an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms serves as a substituent. When possessed, the carbon number means the total carbon number of the carbon number of the substituent and the carbon number of the aliphatic hydrocarbon group, the aromatic hydrocarbon group or the aromatic heterocyclic group.

Each of R ^{6 to} R ⁹ is 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, and is preferably a hydrogen atom or an aromatic hydrocarbon group having 1 carbon atom. More preferably, it is an aliphatic hydrocarbon group of ~ 20.
Further, as a particularly preferable embodiment of ^{R 6 to} R ^{9 , all of R 7 to} R ⁹ are hydrogen atoms; and R ⁶ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and R. ^{An embodiment in which all 7 to} R ⁹ are hydrogen atoms; can be mentioned.

(R ¹⁰ )
In the formulas (E1) and (E2), R ¹⁰ independently has a halogen atom and an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It may have 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 represented by R 10} , the aliphatic hydrocarbon group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 20 carbon atoms, or the aromatic heterocyclic group having 3 to 20 carbon atoms are R. ^{Similar to halogen atoms represented by 6 to} R ⁹ , aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or aromatic heterocyclic groups having 3 to 20 carbon atoms. Can be mentioned.

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

The alkoxy group having 1 to 20 carbon atoms represented by R ¹⁰ includes a methoxy group, an ethoxy group, an n-propyloxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, and a 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 thereof include linear or branched alkoxy groups such as an oxy group, an n-hexadecyloxy group, an n-octadecyloxy group and an n-eicosyloxy group.
Of these, the alkoxy group is preferably a linear alkyl group. The number of carbon atoms of 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 represented by R ¹⁰ , 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. May have a substituent or may be unsubstituted. Examples of the substituent include ^{an aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 6 to} R ⁹ , an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Examples include those similar to the substituents that may have.
An aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ , 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. When the alkoxy group has a substituent, the carbon number is the total carbon number of the carbon number of the substituent and the carbon number of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, the aromatic heterocyclic group or the alkoxy group. means.

Each of R ¹⁰ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or 1 carbon atom. It is more preferably an alkoxy group of ~ 20, and even more preferably an alkoxy group having 1 to 20 carbon atoms.
Also, if there are a plurality of R ¹⁰ s in the formula (E1) and (E2), R ¹⁰ may be identical to each other, may be different, but are preferably the same.

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

In the present embodiment, the silicon-containing iron-platinum nanoparticle catalyst used as a catalyst for the hydrosilylation reaction includes alkenes and dialkoxysilanes whose activity has been difficult to obtain with conventional catalysts (for example, the catalyst described in Non-Patent Document 2). It also exhibits high catalytic activity in the reaction with trialkoxysilanes. Therefore, in the production method according to the present embodiment, the 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. For the production of an organosilicon compound (E1) or (E2); or an organosilicon compound (E1) or (E2) in which m is 3 and ^{two of R 10} are alkoxy groups and one is an alkyl group. Is suitable. Industrially, it is useful for producing dialkoxy-type or trialkoxy-type silane coupling agents. The manufacturing method according to this embodiment, silane coupling agent, when producing the raw material or the intermediate is a preferred R ^10, a methyl group, a methoxy group or an ethoxy group.

2-2. Catalyst manufacturing step The catalyst manufacturing step is a step of manufacturing a silicon-containing iron-platinum nanoparticle catalyst by the manufacturing method according to the first embodiment of the present invention.
In this step, even if the first alkene or the first hydrosilane used for producing the silicon-containing iron-platinum nanoparticle catalyst is the same as the second alkene or the second hydrosilane described later, respectively. It may be different, but preferably the same.

In the present embodiment, the mixing ratio (molar) of the iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface with respect to the platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface in terms of metal. The ratio) is usually 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, still 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 step shows 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 the difference in catalytic activity between the conventional catalyst in which sufficient activity cannot be obtained when trialkoxysilanes are used and the silicon-containing iron-platinum nanoparticle catalyst as follows. That is, hydrosilanes are physically or chemically bonded to the surfaces of iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface. By doing so, a catalytically active species different from a simple mixture of iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface and platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface is generated. It is presumed that it is.

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 production method according to the first embodiment of the present invention, and detailed description thereof includes the description of the production method according to the first embodiment of the present invention and the detailed description thereof. The description of the catalyst manufacturing process in this embodiment is incorporated.

[Second alkenes]
The specific types of alkenes used as the substrate are not particularly limited, and can be appropriately selected depending on the organosilicon compound to be produced. Examples of the second alkene include a compound represented by the following formula (C) (hereinafter, may be referred to as "alkene (C)"). The second alkenes are known or can be easily produced by a method according 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 so are preferred embodiments.

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, allylglycidyl ether, allyl methacrylate, allyl acrylate, allylamine, allylurea, allyl mercaptan, etc. Examples include α-olefins. Of these, 1-dodecene is preferable. 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 are also preferable.
For alkenes (C) having a plurality of alkenyl groups in one molecule, such as the above-mentioned allyl glycidyl ether, allyl methacrylate, allyl acrylate, etc., hydrosilylation can proceed in any of the alkenyl groups. However, due to the high catalytic activity of the silicon-containing iron-platinum nanoparticles 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 hydrosilanes 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, may be referred to as “hydrosilanes (D)”). The second hydrosilanes are known or can be easily produced by a method according to a known production method.

In formula (D), R ^{10 and m are defined in the same manner as 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; trialkylsilanes such as trimethylsilane and triethylsilane. Monoarylsilanes such as phenylsilane and naphthylsilane; Diarylsilanes such as diphenylsilane and dinaphthylsilane; Triarylsilanes such as triphenylsilane and trinaphthylsilane; Alkoxysilanes; Dialkoxysilanes such as dimethoxysilane, diethoxysilane, ethoxymethoxysilane, dipropoxysilane; Trialkoxysilanes such as trimethoxysilane, triethoxysilane, diethoxymethoxysilane; methyldimethoxysilane, methyldi Alkyldialkoxysilanes such as ethoxysilane; dialkylalkoxysilanes such as dimethylmethoxysilane and dimethylethoxysilane; and the like.

Of 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; or an embodiment in which m is 3 and three ^{R 10s are alkoxy groups; or m is 3 and.} two of R ¹⁰ one alkoxy group but embodiments an alkyl group; is preferably, and more preferably three R ¹⁰ is embodiment is an alkoxy group.

[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 in total metal equivalent (total of iron equivalent and platinum equivalent) with respect to alkenes. 0.03 mol% or more, more preferably 0.05 mol% or more, further 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, further It is preferably 0.5 mol% or less. By setting the amount of the 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 and the like can be improved.

[Mole ratio of substrate]
In the hydrosilylation step, the amount of the second hydrosilanes relative to the second alkenes is not particularly limited, but is usually 1.0 molar equivalent or more and less than 6.0 molar equivalents. 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, still more preferably 3.0. It is less than or equal to the molar equivalent. From the viewpoint of improving the yield of the organosilicon compound, the amount of the second hydrosilanes relative to the second alkenes is preferably 1.5 molar equivalents or more, more preferably 2.0 molar equivalents or more.
In the present 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 if the amount of hydrosilanes (charged amount) is smaller than that when a conventional catalyst is used. It can be advanced and an organosilicon compound can be efficiently produced.

[Atmospheric gas, etc.]
The hydrosilylation step may be carried out under normal pressure or under pressure.
Further, the conventional catalyst for the hydrosilylation reaction (catalyst described in Patent Document 1) requires oxygen for activation, and sufficient catalytic activity cannot be obtained in an inert atmosphere. Therefore, a silicon-containing iron-platinum nanoparticle catalyst is used. Shows high catalytic activity even in 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 and air, but also in an inert atmosphere such as nitrogen and argon. ..
In the present embodiment, the hydrosilylation reaction is preferably carried out in an inert atmosphere. By carrying out the hydrosilylation reaction in an inert atmosphere, the disproportionation of hydrosilanes is suppressed, and as a result, the generation of silane gas is suppressed.

[Reaction solvent]
The hydrosilylation step may be carried out without a solvent or in a reaction solvent, but is preferably carried out without a solvent. In the present specification, "solvent-free" means that the reaction solvent is not 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 is, for example, a hydrocarbon solvent such as hexane, benzene, toluene; an ether solvent such as diethyl ether, 1,4-dioxane, diglyme, cyclopentylmethyl ether (CPME), 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; protonic polar solvents such as acetic acid, ethanol, butanol, ethylene glycol and glycerin; Aprotic polar solvents such as acetone, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO); and the like. These reaction solvents are not limited to one type, and may be a mixed solvent in which two or more types are combined. Moreover, it is preferable that the reaction solvent is dehydrated and deoxidized before use.

[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 higher and 150 ° C. or lower. From the viewpoint of the reaction rate, the lower limit of the reaction temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher. The upper limit of the reaction temperature is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 120 ° C. or lower, from the viewpoint of suppressing disproportionation of hydrosilanes.

[Reaction time]
The reaction time may be appropriately selected according to 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, still more preferably 15 hours or more. Further, in terms of facilitating purification, the upper limit of the reaction time is preferably 42 hours or less, more preferably 36 hours or less, still more preferably 30 hours or less.

2-4. Other Steps The method for producing an organosilicon compound according to the present embodiment may include any step in addition to the catalyst manufacturing step and the hydrosilylation step. An optional step includes a purification step for increasing the purity of the organosilicon compound. In the purification step, purification methods usually performed in the field of organic synthesis such as filtration, adsorption, column chromatography, and distillation can be adopted.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention can be appropriately modified as long as it does not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.
The method for measuring gas chromatography (GC) in the examples is as follows.

<GC measurement conditions>
Device 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)
The _Fe (OAc) 2 _0.1mmol and ethanol 1mL in addition to a screw tube, Fe
_{(OAc) 2} is that to stand until a highly dispersed state, to give a Fe _{(OAc) 2} dispersion. Next, 50 mL of DMF weighed in an air atmosphere was added to a three-necked round bottom flask co-washed with DMF, and the DMF was preheated at 140 ° C. for 10 minutes while stirring at 1500 rpm. _{Subsequently, 500 μL of Fe (OAc) 2} dispersion liquid is added to the three-necked round-bottom flask, and the mixture is heated under reflux for 8 hours, whereby iron nanoparticles in which DMF is coordinated on the surface (hereinafter, referred to as “FeNPs”) may be referred to. ) Was obtained.
Assuming that all Fe (OAc) ₂ is converted into iron oxide nanoparticles, the concentration of iron element in the obtained dispersion is 1.0 mmol / L.

(Synthesis Example 2: Preparation of dispersion of platinum nanoparticles with DMF coordinated on the surface)
The _{H 2 PtCl 6 · 6H 2 O} 0.1mmol and DMF1mL addition to a screw tube,
By H ₂ PtCl ₆ · 6H ₂ O is allowed to stand until a highly dispersed _state, to obtain a H ₂ PtCl ₆ · 6H 2 O dispersion. Next, 50 mL of DMF weighed in an air atmosphere was added to a three-necked round bottom flask co-washed with DMF, and the DMF was preheated at 140 ° C. for 10 minutes while stirring at 1500 rpm. Then, the _{H 2} PtCl ₆ · 6H 2 O dispersion 500μL was added to the three-necked round-bottomed flask by heating under reflux for 10 hours, the platinum nanoparticles DMF on the surface is coordinated (hereinafter referred to as "PtNPs" ) Was obtained.
Assuming that all of H ₂ PtCl ₆ has been converted into metallic platinum nanoparticles, the concentration of platinum element in the obtained dispersion is 1.0 mmol / L.

(Synthesis Example 3: Synthesis of Silicon-Containing Iron-Platinum Nanoparticle Catalyst)
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) were added to the 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 under an air atmosphere. The obtained reaction solution was cooled to room temperature. Subsequently, 8 mL of hexane and 2 mL of DMF were added to the Schlenk tube, stirred, allowed to stand, and then the supernatant was removed with a Pasteur pipette. Further, 8 mL of hexane was added to the Schlenk tube, and the mixture was stirred, allowed to stand, and then the supernatant was removed with a Pasteur pipette. The precipitate was dried under vacuum to obtain a silicon-containing iron-platinum nanoparticle catalyst (hereinafter, may be referred to as "Fe-Pt-Si").

The obtained silicon-containing iron-platinum nanoparticle catalyst was observed with a scanning transmission electron microscope (STEM). The results are shown in FIG. In addition, 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 of the dispersion obtained in Synthesis Example 1 (0.5 μmol in terms of Fe) and 500 μL of the dispersion obtained in Synthesis Example 2 (0.5 μmol in terms of Pt) were added to the 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. Then, by distilling off unreacted volatile components such as triethoxysilane from the reaction solution under vacuum, it is referred to as a silicon-containing iron-platinum nanoparticle catalyst (hereinafter referred to as "Fe-Pt- [Si]"). There is.)

<Manufacturing of organosilicon compounds 1>

(Example 1)
The inside of the Schlenk tube containing the silicon-containing iron-platinum nanoparticle catalyst (0.25 μmol in Fe conversion and 0.25 μmol in Pt conversion) 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 the 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 conversion rate of the substrate and the yield of the product calculated from the GC measurement results.

(Example 2)
The 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 conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.

(Comparative Example 1)
250 μL of the dispersion obtained in Synthesis Example 1 (0.25 μmol in Fe conversion) and 250 μL of the dispersion obtained in Synthesis Example 2 (0.25 μmol in terms of Pt) were added to the Schlenk tube, and the dispersion medium was added while stirring under vacuum. By distilling off, a FeNPs-PtNPs mixed catalyst was obtained.
The 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 and 0.25 μmol in terms of Pt). Table 1 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.

(Comparative Example 2)
The 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 conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.
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 a FeNPs-PtNPs mixed catalyst is used as the catalyst (Comparative Examples 1 and 2), the amount of hydrosilanes relative to alkenes is assumed to be 1.0 molar equivalent or 2.0 molar equivalent. , The desired organosilicon compound was obtained only in low yield. Therefore, in order to obtain an organosilicon compound in a high yield, it is necessary to use a large amount of hydrosilanes of about 6 molar equivalents with respect 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 a silicon-containing iron-platinum nanoparticle catalyst is used as the catalyst (Examples 1 and 2), if the amount of hydrosilanes relative to alkenes is 1.0 molar equivalent, the yield of organosilicon is 33%. It was found that an organosilicon compound was obtained in a high yield of 82% when the compound was obtained and the equivalent was 2.0 molar equivalents. That is, in the presence of a silicon-containing iron-platinum nanoparticle catalyst, the hydrosilylation reaction of alkenes can be carried out even if the amount of hydrosilanes used is about 1/6 to 1/6 of that when a conventional catalyst is used. It was shown to proceed smoothly.
It was also shown that by using a silicon-containing iron-platinum nanoparticle catalyst as a catalyst, hydrosilylation proceeds smoothly even in an inert atmosphere.
Furthermore, in Examples 1 and 2, no silane gas was detected in the GC measurement.

<Manufacturing of organosilicon compounds 2>

(Example 3)
The inside of the Schlenk tube containing the silicon-containing iron-platinum nanoparticle catalyst (0.25 μmol in Fe conversion and 0.25 μmol in Pt conversion) 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 the 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 conversion rate of the substrate and the yield of the product calculated from the GC measurement results.

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

The silicon-containing iron-platinum nanoparticle catalysts used in Examples 3 and 4 are different 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 the hydrosilylation of alkenes proceeded rapidly in an inert atmosphere also by using this silicon-containing iron-platinum nanoparticle catalyst.
Further, by using the silicon-containing iron-platinum nanoparticle catalyst, the amount of hydrosilanes relative to alkenes was reduced to 5.0 molar equivalents, not to mention the case of 6.0 molar equivalents (Example 3). Even in the case (Example 4), it was shown that the desired organosilicon compound can be obtained in a 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 a hydrosilylation reaction using trialkoxysilanes. A silicon-containing iron-platinum nanoparticle catalyst can be produced.
Further, according to the present invention, by using the silicon-containing iron-platinum nanoparticle catalyst, the reaction between the alkenes and the hydrosilanes proceeds even in an inert atmosphere without requiring an excessive amount of hydrosilanes, and the efficiency is increased. The desired organosilicon compound can be produced. Since a large amount of hydrosilanes is not used in this catalytic reaction, the atomic efficiency of the reaction is high and the generation of silane gas, which is a disproportionate of hydrosilanes, is small, which is useful for industrial implementation. Furthermore, since the catalytic reaction proceeds smoothly even when trialkoxysilanes are used as the hydrosilanes, it is particularly effective in producing a trialkoxy-type silane coupling agent, a raw material thereof, or an intermediate thereof. Can be used.

Claims (12)

A heating step of heating a mixture containing iron nanoparticles coordinated with a first coordinating organic solvent on the surface, platinum nanoparticles coordinated with a second coordinating organic solvent on the surface, and first hydrosilanes. A method for producing a silicon-containing iron-platinum nanoparticle catalyst, which comprises. The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to claim 1, wherein the first hydrosilane is a compound represented by the formula (A).

(In the formula (A), R ¹ independently has a halogen atom and an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a carbon which may have a substituent. An aromatic hydrocarbon group having a number of 6 to 20, 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 of 1 to 3) The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to claim 1 or 2, wherein the mixture further contains the first alkene. The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to claim 3, wherein the first alkene is a compound represented by the formula (B).

(In the formula (B), R ^{2 to} R ⁵ each independently have an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a hydrogen atom, a halogen atom and a substituent. It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent. The silicon-containing iron-containing according to any one of claims 1 to 4, wherein the first coordinating organic solvent and the second coordinating organic solvent are N, N-dimethylformamide (DMF). A method for producing a platinum nanoparticle catalyst. In the mixture, the mixing ratio (mol) of the iron nanoparticles in which the first coordinating organic solvent is coordinated on the surface with respect to the platinum nanoparticles in which the second coordinating organic solvent is coordinated on the surface. The method for producing a silicon-containing iron-platinum nanoparticle catalyst according to any one of claims 1 to 5, wherein the ratio) is 0.1 or more and 10.0 or less. A catalyst manufacturing step of manufacturing a silicon-containing iron-platinum nanoparticle catalyst by the manufacturing method according to any one of claims 1 to 6.
A hydrosilylation step of reacting a second alkene with a second hydrosilane in the presence of the silicon-containing iron-platinum nanoparticle catalyst.
A method for producing an organosilicon compound, which comprises. A hydrosilylation step of reacting a second alkene with a second hydrosilane in the presence of a silicon-containing iron-platinum nanoparticle catalyst obtained by the production method according to any one of claims 1 to 6. A method for producing an organosilicon compound, which comprises. The method for producing an organosilicon compound according to claim 7 or 8, wherein the second alkene is a compound represented by the formula (C).

(In the formula (C), R ^{6 to} R ⁹ each independently have an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a hydrogen atom, a halogen atom and a substituent. It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms 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 7 to 9, wherein the second hydrosilane is a compound represented by the formula (D).

In the formula (D), R ¹⁰ independently has a halogen atom and an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a carbon which may have a substituent. An aromatic hydrocarbon group having a number of 6 to 20, 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 of 1 to 3) The method for producing an organosilicon compound according to any one of claims 7 to 10, wherein the hydrosilylation reaction is carried out in an inert atmosphere. The method according to any one of claims 7 to 11, wherein 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.

Images