JP2020132553A - Method for producing allylsilane compound utilizing palladium nanoparticle catalyst - Google Patents

Abstract

To provide a method for efficiently producing an allylsilane compound from a substrate being inexpensive and capable of being easily handled in one step without using a large amount of a metal catalyst.SOLUTION: The method for producing an allylsilane compound represented by formula (C) includes a reaction step of reacting an allyl alcohol compound represented by formula (A) and a disilane compound represented by formula (B) in the presence of a palladium nanoparticle catalyst having a coordinating organic compound coordinated to the surface of a palladium nanoparticle and a co-catalyst. (In formulae (A) to (C), Rto Reach independently represent a hydrogen atom, a 1-20C aliphatic hydrocarbon group, a 6-20C aromatic hydrocarbon group or a 3-20C aromatic heterocyclic group; Rand Reach independently represent a hydrogen atom, 1-20C aliphatic hydrocarbon group, a 6-20C aromatic hydrocarbon group or a 3-20C aromatic heterocyclic group; and Rto Reach independently represent a hydrogen atom, a halogen atom, a 1-20C aliphatic hydrocarbon group or a 6-20C aromatic hydrocarbon group.)SELECTED DRAWING: None

Description

The present invention relates to a method for producing an allylsilane compound using a palladium nanoparticle catalyst.

The allylsilane compound is known as an allylating agent in an asymmetric allylation reaction of, for example, a carbonyl compound and an imine compound, and is used in the synthesis of pharmaceuticals and pharmaceutical intermediates. Allylsilane compounds are less toxic and more stable to water and air than allylating agents such as allylmagnesium halides and allyllithium. Therefore, allylsilane compounds are in high demand as useful organic synthetic reagents, and their production methods have been actively developed.

For example, Non-Patent Document 1 describes an ester obtained by reacting an allyl alcohol compound with trifluoroacetic acid anhydride in the presence of N, N-dimethylaminopyridine (DMAP) to synthesize a trifluoroacetic acid ester of an allyl alcohol compound as an intermediate. A method comprising a chemicalization step and a silylation step of reacting the synthesized intermediate with a disilane compound in the presence of bis (dibenzilidenacetone) palladium (0) is disclosed. However, in this method, the allyl substrate undergoes two steps, an esterification step and a silylation step, resulting in a decrease in yield and an increase in production cost.
Non-Patent Document 2 discloses a method for reacting an allyl alcohol compound with a disilane compound in the presence of a catalyst, tetrakis (acetonitrile) palladium (II) bis (tetrafluoroborate). This method requires as much as 5 mol% of catalyst with respect to the substrate, and there is a problem that the yield decreases when the amount of catalyst is reduced. Therefore, further improvement is desired from the viewpoint of manufacturing cost and environmental compatibility.
Non-Patent Document 3 discloses a method for reacting an allyl halide compound with trimethylsilyl copper. In this method, in order to obtain trimethylsilyl copper as a substrate, it is necessary to react hexamethyldisilane with methyllithium to obtain trimethylsilyllithium, which is further reacted with copper (I) iodide. As described above, methyllithium, which is unstable to water or air, must be used for the synthesis of the substrate, and the number of steps is large, so that method is not suitable as an industrial production method.
Non-Patent Document 4 discloses a method for reacting allylmagnesium bromide with triphenylsilane. However, since an organometallic that is highly reactive and unstable to water and air is used, it is difficult to control the reaction, and a large amount of organometallic reagent is required, which causes problems in workability, manufacturing cost, and environment. It is left.
Further, Patent Document 1 discloses a method of reacting an allyl halide compound with a disilane compound in the presence of palladium element-containing nanoparticles in which a solvent is coordinated on the surface. In this method, since the allyl halide compound used as a substrate is expensive, there is room for improvement in terms of production cost.

Japanese Unexamined Patent Publication No. 2017-088756

Yuan Ma, Heteroatom Chemistry, 2002, 13, 310-315 Nicklas Selander, et al., J. Am. Chem. Soc. 2011, 133, 3, 409-411 Janice Gorzynski Smith, et al., J. Org. Chem. 1984, 49, 22, 4112-4120 Henry Gilman, et al., J. Am. Chem. Soc. 1959, 81, 22, 5925-5928

An object of the present invention is to provide a method for efficiently producing an allylsilane compound from an inexpensive and easy-to-handle substrate in one step without using a large amount of metal catalyst.

The present inventors have made diligent studies to solve the above problems. As a result, it was found that the silylation of the allyl alcohol compound proceeds in the presence of the palladium nanoparticle catalyst and the co-catalyst to produce allylsilane, and the present invention has been completed.

（式（Ａ）〜（Ｃ）中、Ｒ^１〜Ｒ^３は、それぞれ独立して水素原子、炭素数１〜２０の脂肪族炭化水素基、炭素数６〜２０の芳香族炭化水素基又は炭素数３〜２０の芳香族複素環基を表し；Ｒ^４、Ｒ^５は、それぞれ独立して水素原子、炭素数１〜２０の脂肪族炭化水素基、炭素数６〜２０の芳香族炭化水素基又は炭素数３〜２０の芳香族複素環基を表し；Ｒ^６〜Ｒ^８は、それぞれ独立して水素原子、ハロゲン原子、炭素数１〜２０の脂肪族炭化水素基又は炭素数６〜２０の芳香族炭化水素基を表す。）
（２）
前記共触媒が、トリフルオロ酢酸である、（１）に記載のアリルシラン化合物の製造方法。
（３）
配位性有機溶媒が、エチレングリコール、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルピロリドン（ＮＭＰ）及びジメチルスルホキシド（ＤＭＳＯ）からなる群より選択される１以上の有機化合物である、（１）又は（２）に記載のアリルシラン化合物の製造方法。
（４）
前記反応が、反応溶媒中で行われる、（１）〜（３）の何れかに記載のアリルシラン化合物の製造方法。
（５）
前記反応溶媒が、１，４−ジオキサン、ジグリム、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、酢酸、トルエン、シクロペンチルメチルエーテル（ＣＰＭＥ）及びベンゾニトリルからなる群より選択される１以上の反応溶媒である、（４）に記載のアリルシラン化合物の製造方法。 That is, the present invention is as follows.
(1)
An allyl alcohol compound represented by the formula (A) and a disilane represented by the formula (B) in the presence of a palladium nanoparticle catalyst and a co-catalyst in which a coordinating organic solvent is coordinated on the surface of the palladium nanoparticles. A method for producing an allylsilane compound represented by the formula (C), which comprises a silylation step of reacting with the compound.

(In formulas (A) to (C), R ^{1 to} R ³ are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or carbons. Represents an aromatic heterocyclic group having a number of 3 to 20; R ⁴ and R ⁵ are independent hydrogen atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, respectively. Alternatively, it represents an aromatic heterocyclic group having 3 to 20 carbon atoms; R ^{6 to} R ⁸ independently have a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group having 6 to 20 carbon atoms. Represents an aromatic hydrocarbon group.)
(2)
The method for producing an allylsilane compound according to (1), wherein the cocatalyst is trifluoroacetic acid.
(3)
One or more organics selected from the group consisting of ethylene glycol, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) as the coordinating organic solvent. The method for producing an allylsilane compound according to (1) or (2), which is a compound.
(4)
The method for producing an allylsilane compound according to any one of (1) to (3), wherein the reaction is carried out in a reaction solvent.
(5)
The reaction solvent is one or more reaction solvents selected from the group consisting of 1,4-dioxane, diglyme, N, N-dimethylformamide (DMF), acetic acid, toluene, cyclopentyl methyl ether (CPME) and benzonitrile. , (4). The method for producing an allylsilane compound.

According to the production method of the present invention, an allylsilane compound can be efficiently produced in one step from an inexpensive and easy-to-handle allyl alcohol compound in the presence of a small amount of palladium nanoparticle catalyst.

In explaining the details of the present invention, specific examples will be given, but the contents are not limited to the following as long as they do not deviate from the gist of the present invention, and they can be modified as appropriate.

<1. Allylsilane compound>
According to the production method according to the present embodiment, an allylsilane compound represented by the formula (C) (sometimes referred to as "allylsilane compound (C)") is provided.

(R ^{1 to} R ³ )
R ^{1 to} R ³ independently form a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Represent.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 to} R ³ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and an iso. Alkyl groups such as −butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neopentyl group, n-hexyl group, n-octyl group; cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group Cycloalkyl groups such as groups; alkenyl groups such as vinyl groups, allyl groups, isopropenyl groups, 2-butenyl groups, 3-pentenyl groups; and the like.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^{1 to} R ³ 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 and a pyrenyl group. Examples thereof include a fluoranthenyl group, a triphenylenyl group and a peryleneyl group.

Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms represented by R ^{1 to} R ³ 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 indolyl 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 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 may have a substituent and is unsubstituted. It may be. Substituents include dear hydrogen atom; amino group; methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n- Alkyloxy group having 1 to 6 carbon atoms such as hexyloxy group; aryloxy group such as phenyloxy group and triloxy group; arylalkyloxy group such as benzyloxy group and phenethyloxy group; dimethylamino group, diethylamino group and dibutylamino Basic dialkylamino groups: Aromatic heterocyclic groups such as pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, indolyl group, carbazolyl group; and the like.
When an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms has a substituent, the carbon number is substituted. It means the total number of carbon atoms of the carbon number of the group and the carbon number of the aliphatic hydrocarbon group, the aromatic hydrocarbon group or the aromatic heterocyclic group.

Hereinafter, preferred embodiments of R ^{1 to} R ³ will be described.
When R ^{1 to} R ³ are aliphatic hydrocarbon groups having 1 to 20 carbon atoms, the number of carbon atoms is preferably 15 or less, more preferably 12 or less, still more preferably 10 or less, and particularly preferably 6 or less. ..
When R ^{1 to} R ³ are aromatic hydrocarbon groups having 6 to 20 carbon atoms, the number of carbon atoms is preferably 18 or less, more preferably 16 or less, still more preferably 10 or less.
When R ^{1 to} R ³ are aromatic heterocyclic groups having 3 to 20 carbon atoms, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.
More specifically, as R ¹ , a hydrogen atom, a methyl group, a 4-methyl-3-penten-1-yl group or a phenyl group is preferable, and a 4-methyl-3-penten-1-yl group or a phenyl group is preferable. More preferred.
As R ² , a hydrogen atom, a methyl group or a phenyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
As R ^3, a hydrogen atom is preferred.

(R ⁴ , R ⁵ )
R ⁴ and R ⁵ independently form a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Represent.

The above-mentioned R ¹ is used as an aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ , an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. ~ R ³ is the same as the group shown as an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Can be mentioned. Further, these groups may have a substituent or may be unsubstituted. Examples of the substituent include the same substituents that R ^{1 to} R ³ may have.

Hereinafter will be described a preferred embodiment of R ^4.
When R ⁴ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, still more preferably less, and particularly preferably 5 or less.
When R ⁴ 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, still more preferably 10 or less.
More particularly, the R ^4, a hydrogen atom, preferably a methyl group or a phenyl group, more preferably a hydrogen atom or a phenyl group.

(R ^{6 to} R ⁸ )
R ^{6 to} R ⁸ independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the halogen atom represented by R ^{6 to} R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ^{6 to} R ⁸ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and an iso. Alkyl groups such as -butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neopentyl group, n-hexyl group, n-octyl group; cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group. Cycloalkyl groups such as groups; alkenyl groups such as vinyl groups, allyl groups, isopropenyl groups, 2-butenyl groups; and the like.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^{6 to} R ⁸ 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, and a pyrenyl group. Examples thereof include a fluoranthenyl group, a triphenylenyl group and a peryleneyl group.

Hereinafter, preferred embodiments of R ^{6 to} R ⁸ will be described.
When R ^{6 to} R ⁸ are aliphatic hydrocarbon groups having 1 to 20 carbon atoms, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less. ..
When R ^{6 to} R ⁸ are aromatic hydrocarbon groups having 6 to 20 carbon atoms, the number of carbon atoms is preferably 18 or less, more preferably 16 or less, still more preferably 10 or less.
When R ^{6 to} R ⁸ are aromatic heterocyclic groups having 3 to 20 carbon atoms, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.
More specifically, as R ^{6 to} R ⁸ , a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group and a phenyl group are preferable, and a methyl group is more preferable.
Further, R ^{6 to} R ⁸ may be the same as or different from each other, but are preferably the same.

Specific examples of the allylsilane compound (C) include the following allylsilane compounds.

<2. Method for producing allylsilane compound>
The method for producing the allylsilane compound (C) according to the present embodiment is referred to as palladium nanoparticle catalysts (“PdNPs”) in which a coordinating organic solvent is coordinated on the surface of palladium nanoparticles, as shown in the following scheme. In the presence of (there is) and a co-catalyst, an allyl alcohol compound represented by the formula (A) (sometimes referred to as "allyl alcohol compound (A)") and a disilane compound represented by the formula (B) ("disilane compound (" disilane compound (" B) ”is sometimes included) and a silylation step is included.

(In formulas (A) to (C), R ^{1 to} R ³ are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or carbons. Represents an aromatic heterocyclic group having a number of 3 to 20; R ⁴ and R ⁵ are independent hydrogen atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, respectively. Alternatively, it represents an aromatic heterocyclic group having 3 to 20 carbon atoms; R ^{6 to} R ⁸ independently have a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group having 6 to 20 carbon atoms. Represents an aromatic hydrocarbon group.)

<2-1. Substrate>
(Allyl alcohol compound)
The specific type of the allyl alcohol compound (A) used as the substrate is not particularly limited, and can be appropriately selected depending on the allyl silane compound (C) to be produced. Further, the allyl alcohol compound (A) is known or can be easily produced by a method according to a known production method.

R ^{1 to} R ⁵ each represent the same group as R ^{1 to} R ⁵ in the formula (C), and the preferred embodiment is also the same.

Specific examples of the allyl alcohol compound (A) include the following allyl alcohol compounds.

(Disilane compound)
The specific type of the disilane compound (B) used as the substrate is not particularly limited, and can be appropriately selected depending on the allylsilane compound (C) to be produced. Further, the disilane compound (B) is known or can be easily produced by a method according to a known production method.

R ^{6 to} R ⁸ each represent the same group as R ^{6 to} R ⁸ in the formula (C), and the preferred embodiment is also the same. R ^{6 to} R ⁸ may be the same or different from each other, but are preferably the same. Also, disilane compound (B) in a molecule, each other R ⁶ present two each, R ⁷ s or R ⁸ each other, but may be the same or different from each other, but are preferably the same ..

Specific examples of the disilane compound (B) include the following disilane compounds.

<2-2. Palladium nanoparticle catalyst>
The palladium nanoparticle catalyst in the present embodiment is a catalyst in which a coordinating organic solvent is coordinated on the surface of the palladium nanoparticles. The palladium nanoparticle catalyst has an advantage that it can be recovered and reused as a catalyst after being used in the silylation step. Further, it is considered that the coordinating organic solvent coordinating the surface of the palladium nanoparticles protects the palladium nanoparticles from deterioration and maintains the catalytic activity.

“Palladium nanoparticles” means particles containing a palladium element as a constituent element. Therefore, the specific composition is not particularly limited as long as it contains palladium, and in addition to metallic palladium particles, palladium alloy particles, particles in which other atoms such as oxygen atoms and carbon atoms are doped in metallic palladium particles, Alternatively, inorganic palladium compound particles such as palladium oxide are also included.

Palladium nanoparticles preferably contain an oxygen atom in addition to palladium. Specifically, metallic palladium particles doped with oxygen atoms, palladium alloy particles doped with oxygen atoms, or palladium oxide particles are preferable.

The particle size (cumulative median diameter) of the palladium nanoparticles is not particularly limited as long as it is in the range of 0.5 nm or more and 100 nm or less, but is preferably 0.8 nm or more, more preferably 1 nm or more, and is preferable. Is 50 nm or less, more preferably 10 nm or less, still more preferably 5 nm or less. The cumulative median diameter (Median diameter) can be measured with a transmission electron microscope (TEM).

Further, "the coordinating organic solvent is coordinated on the surface" means that the molecule of the coordinating organic solvent is coordinated on the surface of the palladium nanoparticles.
The coordinating organic solvent that coordinates the palladium nanoparticles can be appropriately selected according to the desired reaction. Regarding whether or not the coordinating organic solvent is coordinated with the palladium nanoparticles, the palladium nanoparticles catalyst is stably dispersed in the coordinating organic solvent without subjecting the surface treatment with a dispersant or the like. It can be judged by whether or not. That is, for example, a palladium nanoparticle catalyst coordinated with N, N-dimethylformamide (DMF) as a coordinating organic solvent can be stably dispersed in a coordinating organic solvent having an affinity for DMF.

Examples of the coordinating organic solvent include ethylene glycol and dimethylacetamide (DMA).
), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO) and the like. Of these, N, N-dimethylformamide (DMF) is particularly preferable from the viewpoint of catalytic activity.

The method for preparing the palladium nanoparticle catalyst is not particularly limited, and examples thereof include a method of heating and refluxing a precursor containing a palladium element in a polar solvent. Specifically, the palladium nanoparticle catalyst can be prepared by the method described in Japanese Patent No. 6459126 or Japanese Patent Application Laid-Open No. 2017-0887576.

<2-3. Co-catalyst>
The silylation step is carried out in the presence of a co-catalyst in addition to the palladium nanoparticle catalyst. The cocatalyst is not particularly limited as long as it promotes the catalytic silylation reaction of the allyl alcohol compound. In addition, to promote the catalytic silylation reaction of the allyl alcohol compound, specifically, it is coordinated with palladium of the palladium nanoparticles catalyst to improve the catalytic activity, or it acts on the hydroxyl group of the allyl alcohol compound. It is to increase the desorption ability of the hydroxyl group and enhance the reactivity of the allyl alcohol compound.

Examples of the co-catalyst include trifluoroacetic acid; acetic acid; potassium tetrafluoroborate; potassium fluoride; Lewis acid such as iron (III) chloride and aluminum chloride; and the like. Of these, trifluoroacetic acid is particularly preferable from the viewpoint of improving the catalytic activity, suppressing side reactions, and improving the reactivity of the allyl alcohol compound.

<2-4. Reaction conditions in the silylation step>
The silylation step is carried out by reacting the allyl alcohol compound (A) with the disilane compound (B) in the presence of a palladium nanoparticle catalyst and a co-catalyst.

(Amount of palladium nanoparticle catalyst)
The amount of the palladium nanoparticle catalyst used in the silylation step is not particularly limited, but is usually 0.01 mol% or more, preferably 0.05 mol% or more, in terms of the amount of substance of the palladium element with respect to the allyl alcohol compound (A). It is preferably 0.1 mol% or more, usually 5.0 mol% or less, more preferably 3.0 mol% or less, still more preferably 1.0 mol% or less.

(Amount of co-catalyst)
The amount of the co-catalyst used in the silylation step depends on the amount of the palladium nanoparticle catalyst, the reaction concentration and the like, but is usually 1 mol% or more and 150 mol% or less with respect to the allyl alcohol compound (A). From the viewpoint of the yield of the allylsilane compound (C), the lower limit of the amount of the cocatalyst is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, based on the allyl alcohol compound (A). As mentioned above, it is particularly preferably 20 mol% or more. From the viewpoint of easiness of purification, the upper limit of the amount of the cocatalyst is preferably 120 mol% or less, more preferably 100 mol% or less, still more preferably 50 mol% or less with respect to the allyl alcohol compound (A). ..
Specifically, for example, when 0.5 mmol of allyl alcohol compound (A) is reacted in 0.4 mL of 1,4-dioxane in the presence of 1 μmol of a palladium nanoparticle catalyst, the amount of cocatalyst is the allyl alcohol compound (A). It is preferably about 20 mol%.

(Mole ratio of substrate)
In the silylation step, the amount of the disilane compound (B) with respect to the allyl alcohol compound (A) is not particularly limited, but is usually 1.0 equivalent or more and 6.0 equivalent with respect to 1.0 equivalent of the allyl alcohol compound (A). It is as follows. From the viewpoint of suppressing side reactions and easiness of purification, the amount of disilane compound (B) with respect to 1.0 equivalent of allyl alcohol compound (A) is preferably 4.0 equivalents or less, more preferably 3.0 equivalents or less. , More preferably 2.0 equivalents or less.

(Reaction solvent)
The silylation step may be carried out without a solvent or in a reaction solvent. From the viewpoint of suppressing side reactions, it is preferable to carry out without a solvent, and from the viewpoint of the yield of the allylsilane compound (C), it is preferably carried out in a reaction solvent.

The reaction solvent is not particularly limited, and is, for example, a hydrocarbon solvent such as hexane, benzene and toluene; an ether solvent such as diethyl ether, 1,4-dioxane, diglyme, cyclopentylmethyl ether (CPME) and tetrahydrofuran (THF); acetic acid. Ester solvents such as ethyl and butyl acetate; halogenated hydrocarbon solvents such as 1,2-dichloroethane and chloroform; nitrile solvents such as acetonitrile and benzonitrile; protic polar solvents such as acetic acid, ethanol, butanol, ethylene glycol and glycerin; 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. The reaction solvent is preferably dehydrated and deoxidized before use.

Of these reaction solvents, 1,4-dioxane, diglyme, N, N-dimethylformamide (DMF), acetic acid, toluene, cyclopentyl methyl ether (CPME) or benzonitrile are preferable. In particular, from the viewpoint of the yield of the allylsilane compound (C), 1,4-dioxane is more preferable, and from the viewpoint of suppressing side reactions, diglyme, N, N-dimethylformamide (DMF), acetic acid, toluene or benzonitrile Is more preferable.

(Reaction temperature)
The reaction temperature is not particularly limited, but is usually 70 ° C. or higher and 150 ° C. or lower. The lower limit of the reaction temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, from the viewpoint of the yield of the allylsilane compound (C). The upper limit of the reaction temperature is preferably 145 ° C. or lower, more preferably 140 ° C. or lower, from the viewpoint of suppressing side reactions. In particular, setting the reaction temperature to around 130 ° C. is preferable in that the yield of the allylsilane compound (C) is improved and side reactions are suppressed.

(Reaction time)
The reaction time is not particularly limited, but is usually 1 hour or more and 24 hours or less. From the viewpoint of improving the yield of the allylsilane compound (C) and suppressing side reactions, 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, the upper limit of the reaction time is preferably 22 hours or less, more preferably 20 hours or less in terms of facilitating purification.

(Atmospheric gas, etc.)
The silylation step may be carried out under normal pressure or under pressure. The silylation step does not require strict water-reactive conditions, but is usually carried out in an inert atmosphere such as nitrogen or argon.

<2-5. Other processes>
The method for producing the allylsilane compound (C) according to the present embodiment may include any step in addition to the above-mentioned silylation step. An optional step includes a purification step for increasing the purity of the allylsilane compound (C). 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 without departing from the spirit 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-MS) in the examples is as follows.

<Measurement method of GC-MS>
(GC-MS measurement conditions)
Gas chromatograph: GC2010 GC-MS QP2010 (Manufacturer: Shimadzu Corporation)
Column: BP5 (Manufacturer: SGE Analytical Science, inner diameter: 0.22 mm, film thickness: 0.25 μm, length: 25 m)
Carrier gas: He (column flow rate 0.98 mL / min)
Column temperature condition: Hold at 40 ° C for 4 minutes, then raise to 280 ° C at 15 ° C / min Ion source temperature: 200 ° C
Interface temperature: 280 ° C
Injection temperature: 280 ° C
Injection volume: 1.0 μL
Injection mode: Split ionization method: EI method Internal standard substance: Undecane Detector: Secondary electron doubling tube with conversion dynode

<Synthesis of palladium nanoparticle catalyst>
(Synthesis Example 1)
In a 100 mL three-necked flask connected with a Dimroth condenser, 15 mL of dehydrated N, N-dimethylformamide (DMF) was placed in an air atmosphere, immersed in an oil bath heated to 140 ° C., and the stirrer was placed in an air atmosphere. Preheating 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 under an air atmosphere, and the mixture was heated under reflux at 140 ° C. for 10 hours with stirring. .. After 10 hours, the mixture was cooled to room temperature to obtain a dispersion.

DMF was distilled off from the obtained dispersion by a rotary evaporator, and the mixture was sufficiently dried (conditions: 10 hPa, 40 ° C.). As a result, a palladium nanoparticle catalyst was obtained.

<Manufacturing of allylsilane compound>
(Experimental Example 1-1: Examination of catalyst)

2 μmol (0.4 mol% with respect to cinnamyl alcohol) of the palladium nanoparticle catalyst obtained in Synthesis Example 1 was placed in a branched Schlenk flask, and the inside of the branched Schlenk flask was replaced with argon. Next, 0.5 mmol of cinnamyl alcohol and 1 mL of 1,4-dioxane were added to the palladium nanoparticle catalyst and stirred for 20 minutes to obtain a dispersion liquid in which the palladium nanoparticle catalyst was uniformly dispersed.
To the obtained dispersion, 1.5 mmol of hexamethyldisilane and 0.5 mmol of trifluoroacetic acid (100 mol% with respect to cinnamyl alcohol) were sequentially added to obtain a reaction solution. Subsequently, the obtained reaction solution was stirred while heating in an oil bath at 130 ° C. When 15 hours had passed from the start of heating, a sample was taken from the reaction solution, and the progress of the reaction was confirmed by GC-MS. Table 1 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. Then, the reaction solution was cooled, and 10 mL of diethyl ether was added to the cooled reaction solution to obtain a reaction mixture.
The resulting reaction mixture was filtered and concentrated on an evaporator. The residue obtained by concentration was purified by medium pressure silica gel chromatography (equipment: SP1-A1A0 manufactured by Biotage, column: SNAP Ultra 10 g manufactured by Biotage, developing solvent: hexane / ethyl acetate = 100/0), and allylsilane. The compound was obtained as a colorless liquid.

(Experimental Example 1-2-2 Experimental Example 1-6: Examination of catalyst)
The reaction was carried out in the same manner as in Experimental Example 1-1 except that the palladium nanoparticle catalyst and its amount were changed 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.

From the results shown in Table 1, only a small amount of allylsilane compound was obtained from the allyl alcohol compound and the disilane compound without the reaction catalyst.
Further, in the presence of a palladium catalyst other than the palladium nanoparticle catalyst, the allyl alcohol compound 1 and the disilane compound 2 both showed sufficient conversion rates, but the yield of the allylsilane compound 3 was small.
On the other hand, in the presence of the palladium nanoparticle catalyst, the reaction between the allyl alcohol compound 1 and the disilane compound 2 proceeded, and the allylsilane compound 3 was obtained. Further, in the presence of the palladium nanoparticle catalyst, although the by-product 4 was also produced, the ratio of the yield of the allylsilane compound 3 to the yield of the by-product 4 (sometimes referred to as "reaction selectivity") is It was 2 or more. That is, according to the production method according to the present embodiment, it was shown that the side reaction was suppressed and the desired silylation proceeded selectively.

(Experimental Example 2-1: Examination of the amount of palladium nanoparticle catalyst)

1 μmol of the palladium nanoparticle catalyst obtained in Synthesis Example 1 (0.2 mol% with respect to cinnamyl alcohol) was placed in a branched Schlenk flask, and the inside of the branched Schlenk flask was replaced with argon. Next, 0.5 mmol of cinnamyl alcohol and 1 mL of 1,4-dioxane were added to the palladium nanoparticle catalyst and stirred for 20 minutes to obtain a dispersion liquid in which the palladium nanoparticle catalyst was uniformly dispersed.
Hexamethyldisilane (3 mmol) and trifluoroacetic acid (0.5 mmol) (100 mol% with respect to cinnamyl alcohol) were sequentially added to the obtained dispersion to obtain a reaction solution. Subsequently, the obtained reaction solution was stirred while heating in an oil bath at 130 ° C. When 15 hours had passed from the start of heating, a sample was taken from the reaction solution, and the progress of the reaction was confirmed by GC-MS. Table 2 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. Then, the reaction solution was cooled, and 10 mL of diethyl ether was added to the cooled reaction solution to obtain a reaction mixture.
The obtained reaction mixture was purified by the same method as in Experimental Example 1-1 to obtain an allylsilane compound as a colorless liquid.

(Experimental Example 2-2-2 Experimental Example 2-3: Examination of the amount of palladium nanoparticle catalyst)
The reaction was carried out in the same manner as in Experimental Example 2-1 except that the amount of the palladium nanoparticle catalyst was changed 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.

From the results shown in Table 2, when the amount of palladium nanoparticle catalyst was changed in the range of 0.2 to 0.4 mol% with respect to allyl alcohol compound 1 in silylation, the amount of palladium nanoparticle catalyst was increased. It was found that the conversion rate of the allyl alcohol compound 1, which is a substrate, was improved. Further, even if the amount of the palladium nanoparticle catalyst was changed within the above range, neither the yield of the allylsilane compound 3 nor the yield of the by-product 4 was significantly changed.
That is, according to the production method according to the present embodiment, even if the amount of the palladium nanoparticle catalyst is 0.2 mol% with respect to the substrate allyl alcohol compound 1, high catalytic activity and high reaction selectivity are exhibited. I understand.

(Experimental Example 3-1: Examination of base mass)

1 μmol of the palladium nanoparticle catalyst obtained in Synthesis Example 1 (0.2 mol% with respect to cinnamyl alcohol) was placed in a branched Schlenk flask, and the inside of the branched Schlenk flask was replaced with argon. Next, 0.5 mmol of cinnamyl alcohol and 1 mL of 1,4-dioxane were added to the palladium nanoparticle catalyst and stirred for 20 minutes to obtain a dispersion liquid in which the palladium nanoparticle catalyst was uniformly dispersed.
Hexamethyldisilane 0.5 mmol and trifluoroacetic acid 0.5 mmol (100 mol% with respect to cinnamyl alcohol) were sequentially added to the obtained dispersion to obtain a reaction solution. Subsequently, the obtained reaction solution was stirred while heating in an oil bath at 130 ° C. When 15 hours had passed from the start of heating, a sample was taken from the reaction solution, and the progress of the reaction was confirmed by GC-MS. Table 3 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. Then, the reaction solution was cooled, and 10 mL of diethyl ether was added to the cooled reaction solution to obtain a reaction mixture.
The obtained reaction mixture was purified by the same method as in Experimental Example 1-1 to obtain an allylsilane compound as a colorless liquid.

(Experimental Example 3-2 to Experimental Example 3-5: Examination of base mass)
The reaction was carried out in the same manner as in Experimental Example 3-1 except that the amount of hexamethyldisilane was changed as shown in Table 3. Table 3 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.

From the results shown in Table 3, when the amount of disilane compound 2 is varied in the range of 0.5 to 3 mmol (that is, 1 to 6 equivalents with respect to allyl alcohol compound 1), the amount of disilane compound 2 is increased. It was found that the conversion rate of disilane compound 2 decreased, but the yield of allylsilane compound 1 was not significantly affected. It was also found that when the disilane compound 2 is used in an excess amount with respect to the allyl alcohol compound 1, the yield of the by-product 4 increases, so that the reaction selectivity tends to decrease.

(Experimental Example 4-1: Examination of co-catalyst)

2 μmol (0.4 mol% with respect to cinnamyl alcohol) of the palladium nanoparticle catalyst obtained in Synthesis Example 1 was placed in a branched Schlenk flask, and the inside of the branched Schlenk flask was replaced with argon. Next, 0.5 mmol of cinnamyl alcohol and 1 mL of 1,4-dioxane were added to the palladium nanoparticle catalyst and stirred for 20 minutes to obtain a dispersion liquid in which the palladium nanoparticle catalyst was uniformly dispersed.
Hexamethyldisilane (3 mmol) and trifluoroacetic acid (0.15 mmol) (30 mol% with respect to cinnamyl alcohol) were sequentially added to the obtained dispersion to obtain a reaction solution. Subsequently, the obtained reaction solution was stirred while heating in an oil bath at 130 ° C. When 15 hours had passed from the start of heating, a sample was taken from the reaction solution, and the progress of the reaction was confirmed by GC-MS. Table 4 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. Then, the reaction solution was cooled, and 10 mL of diethyl ether was added to the cooled reaction solution to obtain a reaction mixture.
The obtained reaction mixture was purified by the same method as in Experimental Example 1-1 to obtain an allylsilane compound as a colorless liquid.

(Experimental Examples 4-2 to 4-5: Examination of cocatalyst)
The reaction was carried out in the same manner as in Experimental Example 4-1 except that the cocatalyst was changed as shown in Table 4. Table 4 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.

From the results shown in Table 4, it was found that the silylation reaction did not proceed when the cocatalyst was not added to the reaction system. It was also shown that when trifluoroacetic acid was used as the co-catalyst, the allylsilane compound 3 was obtained in a higher yield than when other co-catalysts were used.

(Experimental Example 5-1: Examination of reaction solvent)

2 μmol (0.4 mol% with respect to cinnamyl alcohol) of the palladium nanoparticle catalyst obtained in Synthesis Example 1 was placed in a branched Schlenk flask, and the inside of the branched Schlenk flask was replaced with argon. Next, 0.5 mmol of cinnamyl alcohol and 1 mL of diglyme were added to the palladium nanoparticle catalyst, and the mixture was stirred for 20 minutes to obtain a dispersion liquid in which the palladium nanoparticle catalyst was uniformly dispersed.
Hexamethyldisilane (3 mmol) and trifluoroacetic acid (0.5 mmol) (100 mol% with respect to cinnamyl alcohol) were sequentially added to the obtained dispersion to obtain a reaction solution. Subsequently, the obtained reaction solution was stirred while heating in an oil bath at 130 ° C. When 15 hours had passed from the start of heating, a sample was taken from the reaction solution, and the progress of the reaction was confirmed by GC-MS. Table 5 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. Then, the reaction solution was cooled, and 10 mL of diethyl ether was added to the cooled reaction solution to obtain a reaction mixture.
The obtained reaction mixture was purified by the same method as in Experimental Example 1-1 to obtain an allylsilane compound as a colorless liquid.

(Experimental Example 5-2 to Experimental Example 5-9: Examination of reaction solvent)
The reaction was carried out in the same manner as in Experimental Example 5-1 except that the reaction solvent was changed as shown in Table 5. Table 5 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.

From the results shown in Table 5, it was found that the allylsilane compound 3 can be obtained in a high yield by using 1,4-dioxane as the reaction solvent.
Further, when diglycim, N, N-dimethylformamide, acetic acid, toluene or benzonitrile, particularly acetic acid, toluene or benzonitrile is used as the reaction solvent, or when the reaction solvent is not used, the yield of allylsilane compound 3 is not high. It was found that the progress of side reactions was effectively suppressed and high reaction selectivity was exhibited.

(Experimental Example 6-1: Examination of reaction temperature)

2 μmol (0.4 mol% with respect to cinnamyl alcohol) of the palladium nanoparticle catalyst obtained in Synthesis Example 1 was placed in a branched Schlenk flask, and the inside of the branched Schlenk flask was replaced with argon. Next, 0.5 mmol of cinnamyl alcohol and 1 mL of 1,4-dioxane were added to the palladium nanoparticle catalyst and stirred for 20 minutes to obtain a dispersion liquid in which the palladium nanoparticle catalyst was uniformly dispersed.
To the obtained dispersion, 1.5 mmol of hexamethyldisilane and 0.5 mmol of trifluoroacetic acid (100 mol% with respect to cinnamyl alcohol) were sequentially added to obtain a reaction solution. Subsequently, the obtained reaction solution was stirred while heating in an oil bath at 100 ° C. When 15 hours had passed from the start of heating, a sample was taken from the reaction solution, and the progress of the reaction was confirmed by GC-MS. Table 6 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. Then, the reaction solution was cooled, and 10 mL of diethyl ether was added to the cooled reaction solution to obtain a reaction mixture.
The obtained reaction mixture was purified by the same method as in Experimental Example 1-1 to obtain an allylsilane compound as a colorless liquid.

(Experimental Examples 6-2 to 6-5: Examination of reaction temperature)
The reaction was carried out in the same manner as in Experimental Example 6-1 except that the reaction temperature was changed as shown in Table 6. Table 6 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.

From the results in Table 6, it was found that the yield and reaction selectivity of the allylsilane compound 3 became the highest when the reaction temperature was around 130 ° C., and gradually decreased as the reaction temperature became higher or lower than 130 ° C.

(Experimental Example 7-1: Examination of reaction time)

2 μmol (0.4 mol% with respect to cinnamyl alcohol) of the palladium nanoparticle catalyst obtained in Synthesis Example 1 was placed in a branched Schlenk flask, and the inside of the branched Schlenk flask was replaced with argon. Next, 0.5 mmol of cinnamyl alcohol and 1 mL of 1,4-dioxane were added to the palladium nanoparticle catalyst and stirred for 20 minutes to obtain a dispersion liquid in which the palladium nanoparticle catalyst was uniformly dispersed.
To the obtained dispersion, 1.5 mmol of hexamethyldisilane and 0.5 mmol of trifluoroacetic acid (100 mol% with respect to cinnamyl alcohol) were sequentially added to obtain a reaction solution. Subsequently, the obtained reaction solution was stirred while heating in an oil bath at 130 ° C. When 4 hours had passed from the start of heating, a sample was taken from the reaction solution, and the progress of the reaction was confirmed by GC-MS. Table 7 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. Then, the reaction solution was cooled, and 10 mL of diethyl ether was added to the cooled reaction solution to obtain a reaction mixture.
The obtained reaction mixture was purified by the same method as in Experimental Example 1-1 to obtain an allylsilane compound as a colorless liquid.

(Experimental Example 7-2 to Experimental Example 7-5: Examination of reaction time)
The reaction was carried out in the same manner as in Experimental Example 7-1 except that the reaction time was changed as shown in Table 7. Table 7 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS.

From the results shown in Table 7, it was found that the longer the reaction time, the higher the conversion rate of the allyl alcohol compound 1 and the higher the yield of the allyl silane compound 3. Further, as the reaction time became longer, the yield of the by-product 4 also increased slightly, but the yield of the allylsilane compound 3 increased to a higher degree, and as a result, the longer the reaction time, the higher the reaction selectivity. It was found that it showed a tendency to become.

(Experimental Examples 8-1 to 8-2: Examination of substrate type)

The reaction was carried out in the same manner as in Experimental Example 1-1 except that the cinnamyl alcohol was changed to the allyl alcohol compound 5 shown in Table 8. Table 8 shows the conversion rate of the substrate and the yield of the product calculated from the measurement results of GC-MS. For comparison, the results of Experimental Example 1-1 are also shown in Table 8.

From the results in Table 8, it was found that in the allyl alcohol compound 5, the phenyl group was bonded to the carbon to which the OH group was bonded, so that high reaction selectivity was exhibited and the allylsilane compound 6 could be efficiently obtained. ..

According to the present invention, the silylation reaction of an inexpensive and easy-to-handle allyl alcohol compound proceeds in the presence of a small amount of palladium nanoparticle catalyst, and the allylsilane compound can be efficiently produced in one step. The allylsilane compound produced by the production method of the present invention can be used as a useful allylating agent, for example, in the organosilicon chemical industry.

Claims (5)

An allyl alcohol compound represented by the formula (A) and a disilane represented by the formula (B) in the presence of a palladium nanoparticle catalyst and a co-catalyst in which a coordinating organic solvent is coordinated on the surface of the palladium nanoparticles. A method for producing an allylsilane compound represented by the formula (C), which comprises a silylation step of reacting with the compound.

(In formulas (A) to (C), R ^{1 to} R ³ are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or carbons. Represents an aromatic heterocyclic group having a number of 3 to 20; R ⁴ and R ⁵ are independent hydrogen atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, respectively. Alternatively, it represents an aromatic heterocyclic group having 3 to 20 carbon atoms; R ^{6 to} R ⁸ independently have a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aliphatic hydrocarbon group having 6 to 20 carbon atoms. Represents an aromatic hydrocarbon group.) The method for producing an allylsilane compound according to claim 1, wherein the cocatalyst is trifluoroacetic acid. One or more organics selected from the group consisting of ethylene glycol, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) as the coordinating organic solvent. The method for producing an allylsilane compound according to claim 1 or 2, which is a compound. The method for producing an allylsilane compound according to any one of claims 1 to 3, wherein the reaction is carried out in a reaction solvent. The reaction solvent is one or more reaction solvents selected from the group consisting of 1,4-dioxane, diglyme, N, N-dimethylformamide (DMF), acetic acid, toluene, cyclopentyl methyl ether (CPME) and benzonitrile. , The method for producing an allylsilane compound according to claim 4.