JP6699003B2 - Method for producing allylsilane compound - Google Patents

Description

  The present invention relates to a method for producing an allylsilane compound, and more particularly to a method for producing an allylsilane compound using nanoparticles containing palladium element.

  Allylsilane is a raw material compound in the Hosomi-Sakurai reaction, Hiyama cross-coupling reaction, allylfluoride synthesis and the like, and is a useful building block in organic synthesis. As a method for synthesizing allylsilane, a method using a Grignard reagent (see Non-Patent Document 1), a method using an organic-copper reagent (see Non-Patent Document 2), a method using an allyl ester (see Non-Patent Document 3), etc. Various methods have been reported.

  On the other hand, it has been reported that nanoparticles of gold, platinum, palladium or the like having a particle size of about 2 nm or less can be easily synthesized in a large amount by reducing a metal chloride or the like in dimethylformamide (DMF). . Such nanoparticles have the excellent property that they can be uniformly dispersed in various media without surface treatment with a dispersant, etc. Is being promoted. For example, a cross coupling reaction using platinum or palladium nanoparticles as a catalyst has been reported (see Patent Document 1).

JP2012-000593A

H. Gilman, et al., J. Am. Chem. Soc., 1959, 81, 5925. J. G. Smith, et al., J. Org. Chem., 1984, 49, 4112. H. URATA, et al., Bull. Chem. Soc. Jpn., 57, 607, 1984.

The conventional method for synthesizing allylsilane has problems that the reagents used are unstable, the process is complicated, and the usable substrates are limited.
An object of the present invention is to provide a method for producing an allylsilane compound that can efficiently produce an allylsilane compound.

  As a result of repeated intensive studies to solve the above problems, the present inventors have reacted with a halogenated allyl compound and a disilane compound in the presence of palladium element-containing nanoparticles in which a solvent is coordinated on the surface, and an allylsilane compound is obtained. The inventors have found that they can be efficiently generated, and have completed the present invention.

That is, the present invention is as follows.
<1> A method for producing an allylsilane compound, which comprises a reaction step of reacting an allyl halide compound with a disilane compound in the presence of palladium-containing nanoparticles having a solvent coordinated on the surface to produce an allylsilane compound. ..
<2> The method for producing an allylsilane compound according to <1>, which produces an allylsilane compound represented by the following formula (A).

(In the formula (A), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, an oxygen atom, a silicon atom, or sulfur. Atom, and a hydrocarbon group having 1 to 20 carbon atoms, which may include at least one selected from the group consisting of a halogen atom, R ^{4 to} R ⁶ are each independently a hydrogen atom, a halogen atom, or a carbon atom. It represents a hydrocarbon group of the number 1 to 20.)
<3> The solvent is at least one compound selected from the group consisting of dimethylacetamide (DMA), 1,4-dioxane, N,N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP). The method for producing an allylsilane compound according to <1> or <2>, which comprises:
<4> The method for producing an allylsilane compound according to any one of <1> to <3>, in which the cumulative median diameter (Median diameter) of the palladium element-containing nanoparticles is 0.5 to 100 nm.

  According to the present invention, an allylsilane compound can be efficiently produced.

It is a measurement result of the particle size distribution of the dispersion liquid obtained in Synthesis Example 1 by a dynamic light scattering method (DLS). It is an observation result of the high-resolution transmission electron microscope (HRTEM) of the solid obtained in Synthesis Example 1 (drawing-substituting photograph).

  In describing the details of the present invention, specific examples will be described, but the present invention is not limited to the following contents without departing from the gist of the present invention, and various modifications can be appropriately made and implemented.

<Method for producing allylsilane compound>
The method for producing an allylsilane compound that is one embodiment of the present invention (hereinafter, may be abbreviated as “the production method of the present invention”) includes “a palladium element-containing nanoparticle having a solvent coordinated on the surface (hereinafter, “PdNCs”). In the presence of ")." in the presence of "allyl halide compound" and "disilane compound" to produce an allylsilane compound (hereinafter, may be abbreviated as "reaction step"). It is characterized by including.
The present inventors have conducted extensive studies for a method capable of efficiently producing an allylsilane compound, and as a result, an allyl halide compound and a disilane compound are present in the presence of palladium element-containing nanoparticles in which a solvent is coordinated on the surface. It was found that they reacted and the allylsilane compound was efficiently produced. Although the mechanism of such a reaction has not been sufficiently clarified, it is considered that, for example, when allyl chloride and hexamethyldisilane are used, the reaction proceeds by the catalytic cycle represented by the following formula.

The PdNCs used in the production method of the present invention can be recovered and reused as a catalyst after being used in the production of the allylsilane compound. Generally, complex catalysts are inactivated or decomposed after completion of the reaction, making reuse difficult. However, since the surface of PdNCs is protected by a solvent, they are less likely to deteriorate and have poor catalytic activity. It is considered to be easy to maintain. Further, since the production method of the present invention performs silylation using disilane, it can be said that this is an excellent technique that leads to a reduction in the amount of the organometallic reagent such as Grignard reagent used.
The "palladium element-containing nanoparticles" mean particles having a particle diameter (cumulative median diameter (Median diameter)) of 0.5 to 100 nm and containing palladium element as a constituent element. Therefore, the specific composition is not particularly limited as long as it contains a palladium element, in addition to metal palladium particles, alloy particles of palladium and other metals, metal palladium particles containing other atoms such as oxygen atoms and carbon atoms. It means that particles doped with, or inorganic compound particles containing a palladium element such as palladium oxide are also included.
In addition, "the solvent is coordinated on the surface" means that the solvent molecules are coordinated on the surface of the palladium element-containing nanoparticles. The "solvent" coordinated with the palladium element-containing nanoparticles is not limited to a specific type and can be substituted, and thus can be appropriately selected according to the intended reaction. In addition, whether or not the “solvent” is coordinated with the palladium element-containing nanoparticles can be judged by whether or not the “solvent” is stably dispersed, without performing surface treatment with a dispersant or the like. it can. That is, for example, palladium element-containing nanoparticles in which N,N-dimethylformamide (DMF) is coordinated can be stably dispersed in a “solvent” having an affinity for DMF.
The “halogenated allyl compound” means a compound in which the carbon atoms at the β and γ positions of the halogen atom are double bonds. The “disilane compound” means a compound having at least one silicon-silicon bond (Si—Si). The “allylsilane compound” means a compound in which the carbon atoms at the β and γ positions of the silicon atom are double bonds.
Therefore, examples of the reaction between the "allyl halide compound" and the "disilane compound" include the reactions represented by the following formulas ("allyl halide compound" is "cinnamyl chloride", and "disilane compound" is "Hexamethyldisilane").

(Allylsilane compound)
The allylsilane compound produced by the production method of the present invention is not particularly limited in other structures as long as the bonds of the carbon atoms at the β and γ positions of the silicon atom are double bonds, and a wide range of allylsilane compounds. Can be applied to.
Specific examples include an allylsilane compound represented by the following formula (A).

(In the formula (A), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, an oxygen atom, a silicon atom, or sulfur. Atom, and a hydrocarbon group having 1 to 20 carbon atoms, which may include at least one selected from the group consisting of a halogen atom, R ^{4 to} R ⁶ are each independently a hydrogen atom, a halogen atom, or a carbon atom. It represents a hydrocarbon group of the number 1 to 20.)
R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. It represents a hydrocarbon group having 1 to 20 carbon atoms which may include at least one selected from the group consisting of "from a group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. “It may contain at least one selected” means a chloro group (—Cl), a fluoro group (—F), an amino group (—NH ₂ ), a nitro group (—NO ₂ ), an epoxy group, a hydroxyl group. (-OH), an carbonyl group (-C (= O) -) , tert- butyldimethylsilyl group (-SiBuMe _2), nitrogen atom, oxygen atom, such as azide group (-N _3), a silicon atom, a sulfur atom , Or a functional group containing a halogen atom may be included, and a nitrogen atom such as an ether group (—O—) and a thioether group (—S—), an oxygen atom, a silicon atom, a sulfur atom, or This means that a linking group containing a halogen atom may be contained inside or at the end of the carbon skeleton. Therefore, examples of the hydrocarbon group “which may contain at least one selected from the group consisting of nitrogen atom, oxygen atom, silicon atom, sulfur atom, and halogen atom” include —CH ₂ —CH ₂ —OH. hydrocarbon group of 2 carbon atoms containing hydroxyl group such as _a hydrocarbon group of 2 carbon atoms containing an ether group such as -CH 2 -O-CH ₃ in the interior of the carbon skeleton, and -O-CH ₂ - It includes a hydrocarbon group having a carbon number of 2, such as CH ₃ having an ether group at the end of the carbon skeleton. Further, the “hydrocarbon group” is not limited to a linear saturated hydrocarbon group, but means that it may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure.
When R ¹ is a hydrocarbon group, the number of carbon atoms is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 19 or less, more preferably 17 or less, still more preferably 15 or less. is there.
R ¹ is a hydrogen atom, a methyl group (—CH ₃ , —Me), an ethyl group (—C ₂ H ₅ , —Et), an n-propyl group ( ^—n C ₃ H ₇ , ^—n Pr), i. - propyl _{^{(- i C 3 H 7,}} - i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t- butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl _{^{(- c C 6 H 11,}} -Cy), phenyl group (-C ₆ H _5, -Ph), and the like. Among these, a phenyl group and a hydrogen atom are particularly preferable.
When R ² is a hydrocarbon group, the number of carbon atoms is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 19 or less, more preferably 17 or less, still more preferably 15 or less. is there.
R ² is a hydrogen atom, a methyl group (—CH ₃ , —Me), an ethyl group (—C ₂ H ₅ , —Et), an n-propyl group ( ^—n C ₃ H ₇ , ^—n Pr), i. - propyl _{^{(- i C 3 H 7,}} - i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t- butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl _{^{(- c C 6 H 11,}} -Cy), phenyl group (-C ₆ H _5, -Ph), and the like. Among these, a hydrogen atom and a phenyl group are particularly preferable.
When R ³ is a hydrocarbon group, the carbon number is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 19 or less, more preferably 17 or less, still more preferably 15 or less. is there.
As R ^3, a hydrogen atom, a methyl group _(-CH 3, -Me), ethyl _{(-C 2 H 5, -Et)} , n- propyl _{^{(- n C 3 H 7,}} - n Pr), i - propyl _{^{(- i C 3 H 7,}} - i Pr), n- butyl _{^{(- n C 4 H 9,}} - n Bu), t- butyl _{^{(- t C 4 H 9,}} - t Bu), n- pentyl _{^{(- n C 5 H 11)}} , n- hexyl group _{^{(- n C 6 H 13,}} - n Hex), cyclohexyl _{^{(- c C 6 H 11,}} -Cy), phenyl group (-C ₆ H _5, -Ph), and the like. Among these, a hydrogen atom and the like are particularly preferable.

R ^{4 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. However, when R ^{4 to} R ⁶ are hydrocarbon groups, the number of carbon atoms is It is preferably 12 or less, more preferably 9 or less, and further preferably 6 or less.
R ^{4 to} R ⁶ are hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group (—CH ₃ , —Me), ethyl group (—C ₂ H ₅ , —Et), n-propyl. group _{^{(- n C 3 H 7,}} - n Pr), i- propyl _{^{(- i C 3 H 7,}} - i Pr), t- butyl _{^{(- t C 4 H 9,}} - t Bt), a phenyl group _(-C 6 _H 5, -Ph), and the like. Among these, a methyl group, a t-butyl group, a phenyl group and the like are particularly preferable.

Examples of the allylsilane compound include compounds represented by the following formula.

(Allyl halide compound)
The type of the allyl halide compound is not particularly limited, and should be appropriately selected based on the allylsilane compound that is the production purpose.
Basically, an allyl halide compound having a structure common to the allylsilane compound which is the object of production should be selected, and examples thereof include compounds represented by the following formula (a).

(In the formula (a), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, an oxygen atom, a silicon atom, or sulfur. An atom and a hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one selected from the group consisting of halogen atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom.)
X represents a chlorine atom, a bromine atom, or an iodine atom, but a chlorine atom is preferable.
Specific examples of the allyl halide compound include allyl chloride, cinnamyl chloride, 1-chloro-2-pentene, and the like.

(Disilane compound)
The type of the disilane compound is not particularly limited, and should be appropriately selected based on the allylsilane compound that is the production purpose.
A disilane compound having a structure that is basically the same as that of the allylsilane compound that is the object of production should be selected, and examples thereof include compounds represented by the following formula (s).

(In the formula (s), R ^{4 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.)
Specific disilane compounds include hexamethyldisilane, hexaethyldisilane, hexaphenyldisilane, hexahydrodisilane, 1,1,2,2-tetramethyl-1,2-diphenyldisilane, 1,2-dimethyl-1, 1,2,2-tetraphenyldisilane, 1,2-di(t-butyl)-1,1,2,2-tetramethyldisilane and the like can be mentioned.

  The amount of the disilane compound used in the production method of the present invention is not particularly limited, but is usually 0.2 times or more, preferably 1 time or more in terms of the amount of substance ([mol]) with respect to the amount of the allyl halide compound used, It is more preferably 2 times or more, usually 20 times or less, preferably 10 times or less, more preferably 8 times or less. Within the above range, the allylsilane compound can be produced with higher yield.

(Palladium element-containing nanoparticles with a solvent coordinated on the surface)
The solvent-coordinated palladium element-containing nanoparticles are not particularly limited as long as they correspond to the palladium element-containing nanoparticles described above, the specific type of solvent, the composition of the palladium element-containing nanoparticles, the physical properties, etc. ..
The solvent for coordinating the palladium element-containing nanoparticles can be appropriately selected according to the intended reaction as described above, but specifically, a hydrocarbon solvent such as hexane, benzene, toluene, diethyl ether, 1 , 4-dioxane, ether solvent such as tetrahydrofuran (THF), halogen solvent such as 1,2-dichloroethane and chloroform, protic polar solvent such as ethanol, ethylene glycol and glycerin, acetone, dimethylacetamide (DMA), N , N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO) and the like aprotic polar solvents.
The solvent coordinated with the palladium element-containing nanoparticles can be appropriately replaced. For example, DMF is distilled off from a DMF dispersion of metal palladium nanoparticles coordinated with DMF using a rotary evaporator or the like to obtain metal palladium nanoparticles as a solid. Then, the solid matter is brought into contact with another solvent such as THF and stirred to make the mixture fit to obtain metal palladium nanoparticles in which THF is coordinated. Moreover, the solvent to be contacted is not limited to one type, and may be a mixed solvent in which two or more types are mixed.
Palladium element-containing nanoparticles, the specific composition is not particularly limited as long as it contains a palladium element as a constituent element as described above, it is preferable to contain an oxygen element in addition to the palladium element, the oxygen atom is doped More preferable are metal palladium particles or palladium alloy particles, or palladium oxide particles.
The particle size of the palladium element-containing nanoparticles (cumulative median size (Median size)) is not particularly limited as long as it is in the range of 0.5 to 100 nm as described above, but preferably 0.8 nm or more, more preferably 1 nm. It is above, preferably 50 nm or less, more preferably 10 nm or less, and further preferably 5 nm or less. The cumulative median diameter (Median diameter) can be measured with a transmission electron microscope (TEM).

The method for preparing the palladium element-containing nanoparticles in which the solvent is coordinated on the surface is not particularly limited, and examples thereof include a method in which a precursor containing the palladium element is heated and refluxed in a polar solvent.
Hereinafter, the conditions and the like in the method of heating and refluxing the precursor containing the palladium element in the polar solvent will be described in detail.
The type of the precursor containing the palladium element is not particularly limited, but palladium (II) chloride (PdCl ₂ ), palladium (II) bromide (PdBr ₂ ), palladium acetate (II) (Pd(CH ₃ CO ₂ )) is used. ₂ ), palladium (II) trifluoroacetate (Pd(CF ₃ CO ₂ ) ₂ ) and the like. Among these, palladium(II) chloride is particularly preferable. By using palladium(II) chloride, it becomes easy to prepare the palladium element-containing nanoparticles having excellent catalytic activity.
The type of polar solvent is not particularly limited, and examples thereof include ethylene glycol, dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethylsulfoxide (DMSO). Among these, N,N-dimethylformamide is particularly preferable. Use of N,N-dimethylformamide facilitates preparation of palladium element-containing nanoparticles having excellent catalytic activity.
The temperature condition to be set should be selected according to the polar solvent used and is not particularly limited.
The reflux is preferably performed while stirring with a stir bar or the like. The rotation speed of the stirrer is usually 500 rpm or higher, preferably 800 rpm or higher, more preferably 1000 rpm or higher, and usually 2000 rpm or lower, preferably 1800 rpm or lower, more preferably 1700 rpm or lower. Within the above range, it becomes easy to prepare palladium element-containing nanoparticles having excellent catalytic activity.
The reflux time is usually 1 hour or longer, preferably 3 hours or longer, more preferably 6 hours or longer, and usually 24 hours or shorter, preferably 12 hours or shorter, more preferably 10 hours or shorter. Within the above range, it becomes easy to prepare palladium element-containing nanoparticles having excellent catalytic activity.
Reflux may be performed under an inert atmosphere such as nitrogen or argon, or may be performed under an air atmosphere. From the viewpoint of preparing metal palladium particles or palladium alloy particles, palladium oxide particles, etc., which are doped with oxygen atoms, it is preferably carried out in an air atmosphere.

The amount of the palladium element-containing nanoparticles in which the solvent is coordinated to the surface in the production method of the present invention is not particularly limited, but is the amount of the palladium element ([mol]) relative to the amount of the allyl halide compound used. It is usually 0.5 times or less, preferably 0.1 times or less, more preferably 0.05 times or less, usually 0.0001 times or more, preferably 0.0005 times or more, more preferably 0.001 times or more. is there. Within the above range, the allylsilane compound can be produced with higher yield.
The palladium element-containing nanoparticles in which the solvent is coordinated on the surface may be put into the reaction container as a solid substance, or may be put into the reaction container as a dispersion liquid dispersed in the solvent. By storing and using as a dispersion liquid, deterioration of the palladium element-containing nanoparticles can be suppressed and the operation can be simplified.

  The type of solvent in the production method of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Specific examples include hydrocarbon solvents such as hexane, benzene and toluene, diethyl ether, and 1,4-dioxane. , Ether solvent such as tetrahydrofuran (THF), halogen solvent such as 1,2-dichloroethane and chloroform, protic polar solvent such as ethanol, ethylene glycol and glycerin, acetone, dimethylacetamide (DMA), N,N-dimethyl Examples include aprotic polar solvents such as formamide (DMF), N-methylpyrrolidone (NMP), and dimethylsulfoxide (DMSO). Further, the solvent is not limited to one type, and may be a mixed solvent in which two or more types are mixed. Among these, dimethylacetamide (DMA), 1,4-dioxane, N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) and the like are particularly preferable.

(Reaction conditions)
Reaction conditions such as reaction temperature and reaction time in the reaction step are not particularly limited.
The reaction temperature is usually 25°C or higher, preferably 50°C or higher, more preferably 80°C or higher, and usually 200°C or lower, preferably 150°C or lower, more preferably 130°C or lower. Within the above range, the allylsilane compound can be produced in higher yield.
The reaction time is usually 1 hour or longer, preferably 2 hours or longer, more preferably 6 hours or longer, and usually 72 hours or shorter, preferably 48 hours or shorter, more preferably 24 hours or shorter.
The reaction is usually performed under an inert atmosphere such as nitrogen or argon.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

<Synthesis of palladium element-containing nanoparticles in which solvent is coordinated on the surface>
In a 100-mL three-necked flask connected to a Dimroth condenser, 15 mL of dehydrated N,N-dimethylformamide (DMF) was put under an air atmosphere, immersed in an oil bath heated to 140° C., and an agitator was placed under an air atmosphere. Pre-heating was performed for about 10 minutes under reflux conditions while rotating at 1500 rpm. Then, 150 μl of a 0.1 molar (0.1 M) aqueous solution of palladium(II) chloride (PdCl ₂ ) was added using a microsyringe in an air atmosphere, and the mixture was heated under reflux at 140° C. for 10 hours while stirring. .. After the lapse of 10 hours, it was cooled to room temperature to obtain a dispersion liquid. The particle size distribution of the obtained dispersion liquid was measured by the dynamic light scattering method (DLS), and the result is shown in FIG.

Further, DMF was distilled off from the dispersion liquid using a rotary evaporator (conditions: 10 hPa, 40° C.), and after sufficiently dried, the solid substance was observed by a high resolution transmission electron microscope (HRTEM). The results are shown in Figure 2.
From these results, it can be confirmed that palladium element-containing nanoparticles having a particle diameter of several nm and coordinated with a solvent are formed.

<Production of allylsilane compound>
(Example 1)
0.5 mmol of cinnamyl chloride, 2.0 mmol of hexamethyldisilane, synthesized palladium element-containing nanoparticles (amount of palladium element: 0.001 mmol, amount of palladium element relative to cinnamyl chloride: 0.2 mol%) ) And 1 mL of dimethylacetamide were charged, and the mixture was heated and stirred at 100° C. for 16 hours to carry out the reaction. ^From the measurement results of ¹ H NMR, ¹³ C NMR, and GC, it was confirmed that the compound represented by the following formula was produced in the ratios shown in Table 1.

(Comparative Example 1)
The reaction was performed in the same manner as in Example 1 except that the palladium element-containing nanoparticles were changed to bis(dibenzylideneacetone)palladium (Pd(dba) ₂ , 0.0075 mmol, 5 mol%). The results are shown in Table 1.

(Comparative example 2)
The reaction was performed in the same manner as in Example 1 except that the palladium element-containing nanoparticles were changed to bis(triphenylphosphine)palladium dichloride (PdCl ₂ (PPh ₃ ) ₂ , 0.0075 mmol, 5 mol%). The results are shown in Table 1.

(Comparative example 3)
The reaction was carried out by the same method as in Example 1 except that the palladium element-containing nanoparticles were not added. The results are shown in Table 1.

(Example 2)
The reaction was performed in the same manner as in Example 1 except that the amount of the palladium element-containing nanoparticles was changed to 0.0005 mmol (0.1 mol%). The results are shown in Table 2.

(Example 3)
The reaction was carried out in the same manner as in Example 1 except that the amount of the palladium element-containing nanoparticles was changed to 0.005 mmol (1.0 mol%). The results are shown in Table 2.

(Example 4)
The reaction was carried out by the same method as in Example 1 except that the input amount of hexamethyldisilane was changed to 0.5 mmol. The results are shown in Table 3.

(Example 5)
The reaction was carried out by the same method as in Example 1 except that the input amount of hexamethyldisilane was changed to 1.0 mmol. The results are shown in Table 3.

(Example 6)
The reaction was carried out in the same manner as in Example 1 except that the input amount of hexamethyldisilane was changed to 3.0 mmol. The results are shown in Table 3.

(Example 7)
The reaction was carried out by the same method as in Example 1 except that dimethylacetamide was changed to dioxane. The results are shown in Table 4.

(Example 8)
The reaction was carried out by the same method as in Example 1 except that dimethylacetamide was changed to N,N-dimethylformamide (DMF). The results are shown in Table 4.

(Example 9)
The reaction was performed by the same method as in Example 1 except that dimethylacetamide was changed to N-methylpyrrolidone (NMP). The results are shown in Table 4.

(Example 10)
The reaction was carried out by the same method as in Example 1 except that the atmosphere in the Schlenk was changed from argon to oxygen substitution. The results are shown in Table 5.

  The allylsilane compound produced by the production method of the present invention can be used for the production of pharmaceuticals and the like through the Hosomi-Sakurai reaction, the Hiyama cross coupling reaction and the like.

Claims (4)

The presence of a palladium element-containing nanoparticles solvent is coordinated to the surface, by reacting a halogenated allyl compound and the disilane compound saw including a reaction step of producing allyl silane compound,
The method for producing an allylsilane compound , wherein the solvent is N,N-dimethylformamide (DMF) . The method for producing an allylsilane compound according to claim 1, wherein the allylsilane compound represented by the following formula (A) is produced.
(In the formula (A), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, an oxygen atom, a silicon atom, or sulfur. Atom, and a hydrocarbon group having 1 to 20 carbon atoms, which may include at least one selected from the group consisting of a halogen atom, R ^{4 to} R ⁶ are each independently a hydrogen atom, a halogen atom, or a carbon atom. It represents a hydrocarbon group of the number 1 to 20.) Method for producing a cumulative median diameter of the palladium element-containing nanoparticles (Median diameter) is 0.5 to 100 nm, allylsilane compound according to claim 1 or 2. The amount of the palladium element-containing nanoparticles used is 0.0001 times or more and 0.002 times or less in terms of the amount of the palladium element substance ([mol]) with respect to the amount of the allyl halide compound used. method for producing allyl silane compound according to any one of 1-3.