JP7716051B2 - Method for producing organosilane compounds using manganese nanoparticle catalyst - Google Patents

Description

The present invention relates to a method for producing organosilane compounds using a manganese nanoparticle catalyst.

The hydrosilylation reaction, which forms carbon-silicon bonds, is one of the most important organic chemical reactions and is widely used industrially. Typically, platinum catalysts, ruthenium catalysts (see Patent Document 1), etc. are used for hydrosilylation reactions. However, the use of catalysts containing such expensive noble metals makes it difficult to reduce production costs. Therefore, in recent years, catalysts containing general-purpose metals have been developed as catalysts for hydrosilylation reactions.

For example, Non-Patent Document 1 discloses a technique in which a manganese complex is preactivated with a base such as sodium tert-butoxide and then used as a catalyst for the hydrosilylation reaction of an alkene with a hydrosilane. Also, Non-Patent Document 2 discloses a technique in which a manganese complex is preactivated with a reducing agent such as sodium triethylborohydride and then used as a catalyst for the hydrosilylation reaction.
Furthermore, Patent Document 2 and Non-Patent Document 3 disclose a method for producing an organosilane by carrying out a hydrosilylation reaction between an alkene and a hydrosilane in the presence of iron-containing nanoparticles having a solvent coordinated to the surface.

Japanese Patent Application Laid-Open No. 2021-123545 JP 2015-129103 A

Stephen P. Thomas, et.al., Angew. Chem., Int. Ed., 2018, 57, 10620-10624 Ryan J. Trovitch, et.al., Chem. Sci., 2018, 9, 7673-7680 Yasushi Obora, et.al., ChemCatChem, 2018, 10, 2378-2382

However, in the hydrosilylation reactions described in Non-Patent Documents 1 and 2, the base or reducing agent used for preactivation of the manganese complex may cause side reactions, resulting in a decrease in the yield of the target product. In addition, the manganese complex before preactivation has a complex structure, which poses a problem in that its production requires complicated procedures.
Furthermore, the iron catalysts described in Patent Document 2 and Non-Patent Document 3 have problems such as a low yield when a secondary hydrosilane is used as the hydrosilane compound, and the reaction hardly proceeds when a tertiary hydrosilane is used, and therefore there is room for improvement.

Therefore, an object of the present invention is to provide a method for efficiently producing an organosilane compound from an alkene compound and a hydrosilane compound without using a noble metal catalyst or a metal complex that requires a complicated production procedure.

The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that a hydrosilylation reaction between an alkene compound and a hydrosilane compound proceeds in the presence of a manganese nanoparticle catalyst in which a coordinating organic solvent is coordinated to the surface of manganese-containing nanoparticles, thereby producing an organosilane compound. This finding led to the completion of the present invention. That is, the gist of the present invention is as follows.

[1]
a hydrosilylation step of reacting an alkene compound with a hydrosilane compound in the presence of a hydrosilylation catalyst,
The method for producing an organosilane compound, wherein the hydrosilylation catalyst is a manganese nanoparticle catalyst in which a coordinating organic solvent is coordinated to the surface of manganese-containing nanoparticles.
[2]
The method for producing an organosilane compound according to [1], wherein the alkene compound is a compound represented by general formula (A):
(In general formula (A), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms; when R ¹ and R ² are both the hydrocarbon group, R ¹ and R ² may be bonded to each other to form a ring; when R ³ and R ⁴ are both the hydrocarbon group, R ³ and R ⁴ may be bonded to each other to form a ring.)
[3]
The method for producing an organosilane compound according to [1] or [2], wherein the hydrosilane compound is a compound represented by general formula (B):
Si(R ⁶ ) _n H _4-n (B)
(In general formula (B), each ^R6 independently represents a substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms or a substituted or unsubstituted hydrocarbonoxy group having from 1 to 40 carbon atoms; n represents an integer of from 0 to 3; when n is 2 or 3, ^R6s may be linked to each other to form a ring.)
[4]
[5] The method for producing an organosilane compound according to [3], wherein n in the general formula (B) is 3.
The method for producing an organosilane compound according to any one of [1] to [4], wherein the coordinating organic solvent is at least one selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,4-dioxane, diglyme, tetrahydrofuran, ethylene glycol, and propylene glycol.
[6]
The method for producing an organosilane compound according to any one of [1] to [5], wherein the reaction is carried out in an ether solvent or without a solvent.

The present invention provides a method for efficiently producing organosilane compounds from alkene compounds and hydrosilane compounds without using precious metal catalysts or metal complexes that require complicated production procedures.

FIG. 1 is a diagram showing the results of XPS measurement of the manganese nanoparticle catalyst obtained in the examples. 1 is a STEM image (photograph as a substitute for a drawing) of a manganese nanoparticle catalyst obtained in an example. FIG. 1 is a diagram showing the results of thermogravimetry of the manganese nanoparticle catalyst obtained in the examples.

In explaining the details of the present invention, specific examples will be given, but the present invention is not limited to the following content and can be implemented with appropriate modifications as long as it does not deviate from the spirit of the present invention.
In this specification, when a numerical range is described with a lower limit and an upper limit separately, the numerical range can be a combination of any of the lower limit and upper limit values.

A method for producing an organosilane compound according to one embodiment of the present invention includes a hydrosilylation step in which an alkene compound is reacted with a hydrosilane compound (hydrosilylation reaction) in the presence of a hydrosilylation catalyst.

1. Hydrosilylation Step 1-1. Manganese Nanoparticle Catalyst In the production method according to this embodiment, the hydrosilylation reaction is carried out in the presence of a manganese nanoparticle catalyst (hereinafter, sometimes simply referred to as "manganese nanoparticle catalyst") in which a coordinating organic solvent is coordinated to the surface of manganese-containing nanoparticles.

In this specification, the phrase "the coordinating organic solvent is coordinated to the surface of the nanoparticles" means that molecules of the coordinating organic solvent are coordinated to the surface of the manganese-containing nanoparticles.
The coordinating organic solvent that coordinates with the manganese-containing nanoparticles can be appropriately selected depending on the target catalytic reaction. Whether or not a coordinating organic solvent is coordinated with the manganese-containing nanoparticles can be determined by whether or not the manganese nanoparticle catalyst can be stably dispersed in the coordinating organic solvent or another coordinating organic solvent that has affinity with the coordinating organic solvent without surface treatment with a dispersant or the like. That is, for example, a manganese nanoparticle catalyst in which N,N-dimethylformamide (DMF) is coordinated to the surface of the manganese-containing nanoparticles can be stably dispersed in a coordinating organic solvent that has affinity with DMF.

There are no particular limitations on the specific composition of manganese-containing nanoparticles, as long as they contain manganese as a constituent element. Examples include nanoparticles of pure manganese, as well as nanoparticles of manganese alloys; nanoparticles in which pure manganese nanoparticles are doped with other atoms such as oxygen atoms or carbon atoms; and nanoparticles of inorganic manganese compounds such as manganese oxide. One type of manganese-containing nanoparticle may be used alone, or two or more types may be used in any combination and ratio.

Examples of coordinating organic solvents include amide solvents such as N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP); sulfoxide solvents such as dimethyl sulfoxide (DMSO); ether solvents such as 1,4-dioxane, diglyme, and tetrahydrofuran (THF); and alcohol solvents such as ethylene glycol and propylene glycol. Among these, DMF is particularly suitable for producing manganese nanoparticle catalysts because it functions as a coordinating organic solvent, reaction solvent, and reducing agent, enabling production in a single step. Coordinating organic solvents may be used alone, or two or more may be used in any combination and ratio.

The particle size of the manganese nanoparticle catalyst is not particularly limited, but is usually 0.3 nm or more, preferably 0.5 nm or more, and more preferably 0.8 nm or more. It is also usually 200 nm or less, preferably 100 nm or less, more preferably 50 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less. In this specification, the particle size of the manganese nanoparticle catalyst refers to the arithmetic mean diameter based on the number of particles, and can be measured using an annular dark-field scanning transmission electron microscope (ADF-STEM). Specifically, the manganese nanoparticle catalyst is photographed using ADF-STEM, and approximately 100 particles (e.g., 95 to 105 particles) are randomly selected from the obtained image, their particle sizes are measured, and the arithmetic mean value is taken as the particle size of the manganese nanoparticle catalyst.

The manganese nanoparticle catalyst contains low-toxicity manganese, is particulate, and is stable against air and water. Therefore, the manganese nanoparticle catalyst is easy to handle and can be easily recovered by filtration or other methods after the reaction. The recovered manganese nanoparticle catalyst can then be reused as a hydrosilylation catalyst. Therefore, the production method according to this embodiment is both safe and environmentally friendly.

Furthermore, because the manganese nanoparticle catalyst itself is active as a hydrosilylation catalyst between an alkene compound and a hydrosilane compound, preactivation using a base, a reducing agent, or the like prior to the hydrosilylation reaction is not required. In addition, in the hydrosilylation step of this embodiment, additives such as co-catalysts may be added as long as they do not impair the effects of the present invention. However, because the manganese nanoparticle catalyst alone exhibits high catalytic activity, the addition of such additives is not necessary. Therefore, the operating procedure for the hydrosilylation step of this embodiment can be simplified.

In this embodiment, the manganese nanoparticle catalyst serving as the hydrosilylation catalyst does not contain precious metals such as platinum or ruthenium. In this specification, "free of precious metals" means that the hydrosilylation catalyst does not intentionally contain precious metals, and does not exclude the hydrosilylation catalyst containing trace amounts of precious metals as impurities. The term "trace amount" as used herein refers to an amount preferably of 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less, relative to the mass of the manganese nanoparticle catalyst.

The method for producing the manganese nanoparticle catalyst is not particularly limited, but can be, for example, a production method similar to the methods described in JP 2015-129103 A, WO 2018/131430 A, etc. Specifically, the manganese nanoparticle catalyst can be produced by mixing a precursor containing elemental manganese with a solvent containing a coordinating organic solvent and heating under reflux.

1-2. Alkene Compound The specific type of alkene compound is not particularly limited, and examples thereof include a compound represented by the following general formula (A) (hereinafter, sometimes referred to as "alkene compound (A)"). The alkene compound is either publicly known or can be easily produced by a method similar to a publicly known production method.

(R ¹ to R ⁴ )
In general formula (A), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms. When ^{R 1} and R ² are both the hydrocarbon group, R ¹ and R ² may be bonded to each other to form a ring. When R ³ and R ⁴ are both the hydrocarbon group, R ³ and R ⁴ may be bonded to each other to form a ring.

In this specification, the term "hydrocarbon group" includes aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Aliphatic hydrocarbon groups are not limited to linear hydrocarbon groups, but may have a branched structure, a carbon-carbon unsaturated bond, or a cyclic structure. Aromatic hydrocarbon groups may be monocyclic, polycyclic, or fused-ring, or may be heterocyclic aromatic hydrocarbon groups.

Examples of the halogen atom represented by R ¹ to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of carbon atoms in the hydrocarbon group represented by R ¹ to R ⁴ is not particularly limited, but when the hydrocarbon group is an aliphatic hydrocarbon group, it is usually 1 or more and usually 40 or less, preferably 32 or less, more preferably 24 or less, and even more preferably 16 or less. When the hydrocarbon group is an aromatic hydrocarbon group, it is usually 3 or more and usually 40 or less, preferably 32 or less, more preferably 24 or less, and even more preferably 16 or less. In this specification, when the hydrocarbon group has a substituent, the number of carbon atoms in the hydrocarbon group includes the number of carbon atoms in the substituent.

Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms represented by R ¹ to R ⁴ 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, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecanyl group, an n-isopropyl methyl ... Examples of the alkyl group include linear or branched saturated aliphatic hydrocarbon groups such as an n-octadecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; saturated aliphatic hydrocarbon groups having a cyclic structure such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group; and unsaturated aliphatic hydrocarbon groups such as a vinyl group and an allyl group.

Examples of the unsubstituted aromatic hydrocarbon group having 3 to 40 carbon atoms represented by R ¹ to R ⁴ include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a fluorenyl group, an indenyl group, a fluoranthenyl group, a triphenylenyl group, a perylenyl group, a pyrrolyl group, a pyridyl group, a pyrimidyl group, a triazinyl group, a carbazolyl group, a furyl group, a dibenzofuranyl group, a thiophenyl group, a dibenzothiophenyl group, etc. The positions of the bonds in these groups are not particularly limited.

When the hydrocarbon group having 1 to 40 carbon atoms represented by R ¹ to R ⁴ has a substituent, the substituent may be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, or an n-hexyl group; or an alkyl group having 3 to 6 carbon atoms such as a vinyl group, an allyl group, or a 3-butenyl group. alkenyl groups such as those listed below; cycloalkyl groups having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups; aryl groups such as phenyl and tolyl groups; arylalkyl groups such as benzyl and phenethyl groups; methoxy, ethoxy, n-propyloxy, isopropyloxy, glycidyloxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, and n-hexyloxy groups. aryloxy groups such as phenyloxy group and tolyloxy group; arylalkyloxy groups such as benzyloxy group and phenethyloxy group; α,β-unsaturated carbonyloxy groups such as acryloxy group and methacryloxy group; primary to tertiary amino groups such as amino group, dimethylamino group, diethylamino group and dibutylamino group; heterocyclic groups having 3 to 12 carbon atoms such as pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, quinolyl group, isoquinolyl group, indolyl group, carbazolyl group, morpholino group, oxiranyl group, oxetanyl group, tetrahydrofuryl group, furyl group and thienyl group; and the like.

When ^R1 and ^R2 are linked to each other to form a ring, and when ^R3 and ^R4 are linked to each other to form a ring, these groups may be linked by a direct bond or via a linking group. Examples of the linking group include -S-, -O-, -CO-, -COO-, -OCO-, _-SO2- , ^-NR5- , ^-CONR5- , ^-NR5CO- , and ^-OCONR5- . Each ^R5 independently represents a hydrogen atom or a hydrocarbon group having from 1 to 8 carbon atoms. Examples of the hydrocarbon group having from 1 to 8 carbon atoms include those having from 1 to 8 carbon atoms among the hydrocarbon groups represented by ^R1 to ^R4 .

R ¹ to R ⁴ are preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, and even more preferably a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 24 carbon atoms.
The alkene compound (A) is preferably a terminal alkene, and therefore, it is preferred that ^R1 and ^R2 are both hydrogen atoms and/or that ^R3 and ^R4 are both hydrogen atoms.

Specific examples of the alkene compound (A) 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, and N,N-dimethylallylamine.

1-3. Hydrosilane Compound The specific type of hydrosilane compound is not particularly limited and can be appropriately selected depending on the organosilane compound to be produced. Examples of the hydrosilane compound include a compound represented by the following general formula (B) (hereinafter, sometimes referred to as "hydrosilane compound (B)"). The hydrosilane compound is either known or can be easily produced by a method similar to a known production method.
Si(R ⁶ ) _n H _4-n (B)

(n)
In formula (B), n represents an integer of 0 or more and 3 or less. n is preferably an integer of 1 or more and 3 or less, more preferably 2 or 3, and even more preferably 3. In the present embodiment, even when n is 3, i.e., when the hydrosilyl compound is a tertiary hydrosilane compound, the hydrosilylation reaction proceeds rapidly, and an industrially useful tertiary organosilane compound can be efficiently produced.

(R ⁶ )
In general formula (B), R ⁶ is independently a substituted or unsubstituted group having 1 to 40 carbon atoms.
represents the following hydrocarbon group or a substituted or unsubstituted hydrocarbonoxy group having from 1 to 40 carbon atoms: When n is 2 or 3, ^R6s may be linked to each other to form a ring.

The substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms represented by ^R6 is defined in the same manner as the substituted or unsubstituted hydrocarbon groups having 1 to 40 carbon atoms represented by ^R1 to ^R4 (excluding groups containing an aliphatic double bond).
Furthermore, the substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms in the substituted or unsubstituted hydrocarbonoxy group having from 1 to 40 carbon atoms represented by ^R6 is defined in the same manner as the substituted or unsubstituted hydrocarbon groups having from 1 to ⁴⁰ carbon atoms represented by ^R1 to R4 (excluding groups containing an aliphatic double bond).

When ^R6 's are linked to each other to form a ring, ^R6 's may be linked to each other by a direct bond or via a linking group. As the linking group, the same linking group as the linking group for linking ^R1 and ^R2 (excluding groups containing an aliphatic double bond) can be used.

Each ^R6 is preferably a substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms, and more preferably a substituted or unsubstituted aliphatic hydrocarbon group having from 1 to 40 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having from 3 to 40 carbon atoms.

Specific examples of the hydrosilane compound (B) include monoalkylsilane compounds such as methylsilane, ethylsilane, and propylsilane; dialkylsilane compounds such as dimethylsilane, diethylsilane, and ethylmethylsilane; trialkylsilane compounds such as trimethylsilane and triethylsilane; monoarylsilane compounds such as phenylsilane and naphthylsilane; diarylsilane compounds such as diphenylsilane and dinaphthylsilane; triarylsilane compounds such as triphenylsilane and trinaphthylsilane; diarylalkylsilane compounds such as diphenylmethylsilane and diphenylethylsilane; and aryldialkylsilane compounds such as phenyldimethylsilane and phenyldiethylsilane.
Of these, the hydrosilane compound (B) is preferably a trialkylsilane compound, a triarylsilane compound, a diarylalkylsilane compound, or an aryldialkylsilane compound, and more preferably a diarylalkylsilane compound.

1-4. Organosilane Compound The organosilane compound produced by the production method according to this embodiment is not particularly limited in terms of its specific structure, and a wide variety of organosilane compounds may be used, as long as the organosilane compound is a hydrosilylation reaction product of an alkene compound and a hydrosilane compound. Specific examples include organosilane compounds represented by general formula (C1) or general formula (C2) obtained by reacting an alkene compound (A) with a hydrosilane compound (B) (hereinafter, these may be referred to as "organosilane compound (C1)" or "organosilane compound (C2)").

In general formulas (C1) and (C2), R ¹ to R ⁴ have the same meanings as R ¹ to R ⁴ in general formula (A), respectively. In addition, in general formulas (C1) and (C2), R ⁶ and n have the same meanings as R ⁶ and n in formula (B), respectively.

1-5. Reaction conditions (catalytic amount)
The amount (charge amount) of the manganese nanoparticle catalyst used in the hydrosilylation step is not particularly limited, but because the manganese nanoparticle catalyst has a high catalyst turnover number, sufficient catalytic activity can be ensured even with a small amount.
Specifically, the amount of the manganese nanoparticle catalyst used is, in terms of total metal (manganese equivalent), usually 0.001 mol% or more, preferably 0.005 mol% or more, more preferably 0.01 mol% or more, even more preferably 0.03 mol% or more, and particularly preferably 0.05 mol% or more, relative to the aliphatic double bonds of the alkene compound, and is usually 5.0 mol% or less, preferably 1.0 mol% or less, more preferably 0.5 mol% or less, even more preferably 0.1 mol% or less, and particularly preferably 0.08 mol% or less.

(molar ratio of substrate)
The amount of the hydrosilane compound used (charge amount) relative to the amount of the alkene compound used (charge amount) is not particularly limited, but is usually 1.0 equivalent or more, preferably 2.0 equivalents or more, more preferably 3.0 equivalents or more, and even more preferably 5.0 equivalents or more, relative to the aliphatic double bond of the alkene compound, and is usually 50.0 equivalents or less, preferably 20 equivalents or less, and more preferably 10.0 equivalents or less. By setting the amount of the hydrosilane compound used relative to the aliphatic double bond of the alkene compound within the above range, the yield of the organosilane compound can be improved and post-reaction purification can be facilitated.

(Reaction Solvent)
The hydrosilylation step may be carried out without a solvent, or may be carried out in a reaction solvent. The reaction solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as hexane, benzene, toluene, and xylene; ether solvents such as diethyl ether, 1,4-dioxane, diglyme, cyclopentyl methyl ether (CPME), and tetrahydrofuran (THF); ester solvents such as ethyl acetate 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; and aprotic polar solvents such as acetone, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). The reaction solvent may be used alone, or two or more types may be mixed in any combination and ratio.

From the viewpoint of improving the conversion rate of the hydrosilane compound and the yield of the organosilane, the hydrosilylation step is preferably carried out in an ether solvent or without a solvent, and more preferably in diglyme or without a solvent. It is also preferable to dehydrate and deoxygenate the reaction solvent before use.

(Reaction temperature)
The reaction temperature may be appropriately selected depending on reaction conditions such as the heat resistance of the catalyst, the reactivity of the substrate, the type of reaction solvent, and the reaction time. Specifically, the lower limit of the reaction temperature is preferably 50°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher, from the viewpoint of the yield of the organosilane compound. The upper limit of the reaction temperature is preferably 180°C or lower, more preferably 160°C or lower, and even more preferably 140°C or lower, from the viewpoint of suppressing decomposition or inactivation of the catalyst.

(Reaction time)
The reaction time is not particularly limited and may be appropriately selected depending on reaction conditions such as the type of catalyst, the reactivity of the substrate, the type of reaction solvent, and the reaction temperature. Specifically, from the viewpoint of improving the yield of the organosilane compound, the reaction time is preferably 4 hours or more, more preferably 10 hours or more, and even more preferably 15 hours or more. Furthermore, from the viewpoint of suppressing side reactions, the reaction time is preferably 60 hours or less, more preferably 48 hours or less, and even more preferably 36 hours or less.

(Atmospheric gas, etc.)
The hydrosilylation step may be carried out under normal pressure or under increased pressure.
The hydrosilylation step does not require strict water-free conditions. Therefore, the hydrosilylation step may be carried out in an air atmosphere or in an inert atmosphere such as nitrogen or argon, but is preferably carried out in an inert atmosphere. These inert gases may be used alone or in any combination and ratio of two or more.

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

The present invention will be explained in more detail below using examples, but modifications can be made as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below.

<GC measurement>
The conditions for measuring the conversion rate of the alkene compound, the conversion rate of the hydrosilane compound, and the yield of the organosilane compound by gas chromatography (GC) are as follows.
Device name: GC-2010 (Shimadzu Corporation)
Detector: FID (Flame Ionization Detector)
Column: BP-5 (Trajan Scientific and Medical)
Carrier gas: Nitrogen Data processing: Analysis data system Lab Solutions LC/GC Ver.5.99 (Shimadzu Corporation)

<XPS Measurement>
The analysis conditions for the manganese nanoparticle catalyst by X-ray photoelectron spectroscopy (XPS) are as follows.
Device name: Ulvac-PHI 5000 VersaProbe III (ULVAC-PHI, Inc.)
Radiation source: Al Kα radiation Sample mount: Ag plate (Nilaco Corporation, plate thickness 0.2 mm)

<Particle size measurement>
The particle size of the manganese nanoparticle catalyst was measured using an annular dark-field scanning transmission electron microscope (ADF-STEM) under the following conditions:
Device name: JEM-ARM200F (JEOL Ltd.)
Accelerating voltage: 200 kV

<Thermogravimetric measurement>
The conditions for thermogravimetry (TG) of the manganese nanoparticle catalyst were as follows.
Device name: TGA 4000 (PerkinElmer)
Measurement temperature: 50℃~500℃
Heating rate: 10℃/1min
Holding time: 10min
Atmosphere: Nitrogen

Synthesis Example 1: Synthesis of hydrosilylation catalyst
1.0 mmol (0.1258 g) of manganese chloride tetrahydrate, 9.0 mL of water, and 1.0 mL of 36% hydrochloric acid were added to a screw tube, and the mixture was allowed to stand until the manganese chloride tetrahydrate was completely dissolved, thereby obtaining an aqueous manganese chloride solution.
Next, 50 mL of DMF was added to a three-necked round-bottom flask equipped with a stirrer, and the DMF was preheated at 140° C. for 5 minutes while stirring at 1500 rpm. At this time, the three-necked flask, stirrer, and other equipment were washed with DMF before use.
Next, 500 μL of an aqueous manganese chloride solution was added to a three-necked round-bottom flask and heated under reflux for 24 hours to obtain a dispersion of manganese nanoparticle catalyst (hereinafter sometimes referred to as "Mn NPs"). Assuming that all of the manganese chloride was converted to manganese nanoparticles, the concentration of manganese element in the obtained dispersion would be 1.0 mmol/L.

The dispersion medium was removed from the resulting manganese nanoparticle catalyst dispersion under vacuum. The resulting residue was then dried under vacuum at 80°C to thoroughly remove any DMF not coordinated to the manganese nanoparticles, yielding a sample for measuring the physical properties of the manganese nanoparticle catalyst. This sample was used to perform XPS measurement, particle size measurement, and thermogravimetry of the manganese nanoparticle catalyst.

The results of XPS measurement of the manganese nanoparticle catalyst are shown in Figure 1. In Figure 1, a main peak and satellite peaks attributed to MnO can be seen. This suggests that manganese chloride was converted to manganese oxide during the production process of the manganese nanoparticle catalyst.

The results of observation using an annular dark-field scanning transmission electron microscope (ADF-STEM) are shown in Figure 2. The average particle diameter of the manganese nanoparticle catalyst (average value of 98 particles) calculated using ADF-STEM was approximately 2.9 nm.

The results of thermogravimetry of the manganese nanoparticle catalyst are shown in Figure 3. Figure 3 shows that the manganese nanoparticle catalyst has a 5% weight loss temperature of 137°C, demonstrating its high heat resistance.

<Production of Organosilane Compound>
(Example 1-1: Study of reaction solvent)

50 μL (0.05 μmol in terms of Mn) of the manganese nanoparticle catalyst dispersion obtained in Synthesis Example 1 was added to the Schlenk flask, and the dispersion medium was distilled off under vacuum. To thoroughly remove any DMF not coordinated to the manganese nanoparticles, the resulting residue was further dried under vacuum at 80°C to obtain a manganese nanoparticle catalyst.

A stirrer was placed in the Schlenk tube containing the manganese nanoparticle catalyst, and the Schlenk tube was sealed with a two-way stopcock and a rubber stopper. After purging the Schlenk tube with argon, 1 mL of diglyme, 0.5 mmol (0.0842 g) of 1-dodecene, and 2.5 mmol (0.496 g) of diphenylmethylsilane were added to the Schlenk tube. The reaction mixture was stirred for 24 hours while heated at 130°C, and the resulting reaction mixture was cooled in an ice bath and mixed with 10 mL of hexane to terminate the reaction.

GC measurements were then performed using nonane as an internal standard. The substrate conversion rate and product yield calculated from the GC measurement results are shown in Table 1.

(Examples 1-2 to 1-4: Examination of reaction solvents)
A hydrosilylation reaction was carried out in the same manner as in Example 1-1, except that the reaction solvent was changed as shown in Table 1. The conversion of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 1.

Table 1 shows that the conversion rate of the alkene compound and the yield of the organosilane compound improved when diglyme was used as the reaction solvent (Example 1-1) and when no reaction solvent was used (Example 1-4). It also shows that when the reaction was carried out in diglyme solvent (Example 1-1), the organosilane compound was obtained in particularly high yield. On the other hand, when p-xylene or DMF was used as the reaction solvent (Examples 1-2 and 1-3), the conversion rate of the alkene compound and the yield of the organosilane compound were lower than in Examples 1-1 and 1-4, but it was confirmed that the hydrosilylation reaction proceeded.

(Example 2-1: Study of reaction atmosphere)

First, a manganese nanoparticle catalyst was obtained in a Schlenk flask in the same manner as in Example 1-1. Next, a stirrer was placed in the Schlenk flask containing the manganese nanoparticle catalyst, and the Schlenk flask was sealed with a two-way stopcock and rubber stopper. 1 mL of diglyme, 0.5 mmol (0.0842 g) of 1-dodecene, and 2.5 mmol (0.496 g) of diphenylmethylsilane were added to the Schlenk flask. The reaction solution was stirred for 24 hours while heated at 130°C, and then the resulting reaction mixture was cooled in an ice bath and mixed with 10 mL of hexane to terminate the reaction.

GC measurements were then performed using nonane as an internal standard. The substrate conversion rate and product yield calculated from the GC measurement results are shown in Table 2.

(Example 2-2: Study of reaction atmosphere)
The hydrosilylation reaction was carried out in the same manner as in Example 2-1, except that the Schlenk flask was not sealed. The conversion of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 2.

(Example 2-3: Study of reaction atmosphere)
A hydrosilylation reaction was carried out in the same manner as in Example 2-1, except that the atmosphere in the Schlenk tube was replaced with argon before adding diglyme, 1-dodecene, and diphenylmethylsilane to the Schlenk tube. The conversion of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 2.

Table 2 shows that the hydrosilylation reaction proceeds in both air and inert atmospheres, and that organosilane compounds can be obtained in particularly high yields when the hydrosilylation reaction is carried out in an inert atmosphere.

(Example 3-1: Study of reaction time)

First, a manganese nanoparticle catalyst was obtained in a Schlenk flask in the same manner as in Example 1-1. Next, a stirrer was placed in the Schlenk flask containing the manganese nanoparticle catalyst, and the Schlenk flask was sealed with a two-way stopcock and a rubber stopper. After purging the atmosphere in the Schlenk flask with argon, 0.5 mmol (0.0842 g) of 1-dodecene and 2.5 mmol (0.496 g) of diphenylmethylsilane were added to the Schlenk flask. The reaction mixture was stirred for 16 hours while heated at 130°C, and then the resulting reaction mixture was cooled in an ice bath and mixed with 10 mL of hexane to terminate the reaction.

GC measurements were then performed using nonane as an internal standard. The substrate conversion rate and product yield calculated from the GC measurement results are shown in Table 3.

(Example 3-2: Study of reaction time)
The hydrosilylation reaction was carried out in the same manner as in Example 3-1, except that the reaction time was changed as shown in Table 3. The conversion of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 3.

Table 3 shows that at a reaction temperature of 130°C, the reaction does not stop due to catalyst decomposition, and the substrate conversion rate and organosilane compound yield improve over reaction time.

(Example 4-1: Study of reaction temperature)

First, a manganese nanoparticle catalyst was obtained in a Schlenk flask in the same manner as in Example 1-1. Next, a stirrer was placed in the Schlenk flask containing the manganese nanoparticle catalyst, and the Schlenk flask was sealed with a two-way stopcock and rubber stopper. After purging the atmosphere in the Schlenk flask with argon, 0.5 mmol (0.0842 g) of 1-dodecene and 2.5 mmol (0.496 g) of diphenylmethylsilane were added to the Schlenk flask. The reaction mixture was stirred for 24 hours while heated at 100°C, and then the resulting reaction mixture was cooled in an ice bath and mixed with 10 mL of hexane to terminate the reaction.

GC measurements were then performed using nonane as an internal standard. The substrate conversion rate and product yield calculated from the GC measurement results are shown in Table 4.

(Example 4-2: Study of reaction temperature)
The hydrosilylation reaction was carried out in the same manner as in Example 4-1, except that the reaction temperature was changed as shown in Table 4. The conversion of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 4.

Table 4 shows that increasing the reaction temperature from 100°C to 130°C increases the reaction rate, improving the substrate conversion rate and the yield of organosilane compounds.

According to the present invention, an organosilane compound can be efficiently produced from an alkene compound and a hydrosilane compound in the presence of a manganese nanoparticle catalyst.
The production method according to the present invention does not require the use of a noble metal catalyst. Furthermore, the manganese nanoparticle catalyst used in the hydrosilylation reaction between an alkene compound and a hydrosilane compound does not have a complex structure like conventional manganese complex catalysts. Therefore, it can be easily produced, has high catalytic activity, and can be easily recovered and reused after the reaction. Therefore, the production method according to the present invention can reduce the production cost of organosilane compounds, simplify the production procedure, and is an environmentally friendly method.

Furthermore, the organosilane compounds produced by this manufacturing method can be used in a variety of applications, including industrial chemical products such as paints and silicone oils, pharmaceuticals, and cosmetics.

Claims (6)

a hydrosilylation step of reacting an alkene compound with a hydrosilane compound in the presence of a hydrosilylation catalyst,
The method for producing an organosilane compound, wherein the hydrosilylation catalyst is a manganese nanoparticle catalyst in which a coordinating organic solvent is coordinated to the surface of manganese-containing nanoparticles. The method for producing an organosilane compound according to claim 1 , wherein the alkene compound is a compound represented by general formula (A):
(In general formula (A), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms; when R ¹ and R ² are both the hydrocarbon group, R ¹ and R ² may be bonded to each other to form a ring; when R ³ and R ⁴ are both the hydrocarbon group, R ³ and R ⁴ may be bonded to each other to form a ring.) 3. The method for producing an organosilane compound according to claim 1, wherein the hydrosilane compound is a compound represented by general formula (B):
Si(R ⁶ ) _n H _4-n (B)
(In general formula (B), each ^R6 independently represents a substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms or a substituted or unsubstituted hydrocarbonoxy group having from 1 to 40 carbon atoms; n represents an integer of from 0 to 3; when n is 2 or 3, ^R6s may be linked to each other to form a ring.) The method for producing an organosilane compound according to claim 3, wherein n in general formula (B) is 3. The method for producing an organosilane compound according to any one of claims 1 to 4, wherein the coordinating organic solvent is one or more selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,4-dioxane, diglyme, tetrahydrofuran, ethylene glycol, and propylene glycol. The method for producing an organosilane compound according to any one of claims 1 to 5, wherein the reaction is carried out in an ether solvent or without a solvent.