Method for producing organosilane compounds using manganese nanoparticle catalyst

Abstract

To provide a method for efficiently producing an organic silane compound from an alkene compound and a hydrosilane compound without using a noble metal catalyst or a metal complex requiring a complicated production procedure.SOLUTION: A method for producing an organic silane compound includes a hydrosilylation step of reacting an alkene compound with a hydrosilane compound in the presence of a hydrosilylation catalyst, wherein the hydrosilylation catalyst is a manganese nanoparticle catalyst including a coordinating organic solvent coordinated on a surface of manganese nanoparticles.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an organosilane compound using a manganese nanoparticle catalyst.

Background Art

[0002] The hydrosilylation reaction is one of the most important organic chemical reactions for forming a carbon-silicon bond and is widely used industrially. Generally, platinum catalysts, ruthenium catalysts (see Patent Document 1), etc. are used in the hydrosilylation reaction. However, when using catalysts containing such expensive noble metals, there is a problem that it is difficult to reduce the production cost. Therefore, in recent years, catalysts containing general metals have been developed as catalysts for the hydrosilylation reaction.

[0003] For example, Non-Patent Document 1 discloses a technique of pre-activating a manganese complex with a base such as sodium tert-butoxide and using it as a catalyst for the hydrosilylation reaction of an alkene and a hydrosilane. Further, Non-Patent Document 2 discloses a technique of pre-activating a manganese complex with a reducing agent such as sodium triethylborohydride and using it as a catalyst for the hydrosilylation reaction. Furthermore, Patent Document 2 and Non-Patent Document 3 disclose a method for producing an organosilane by performing a hydrosilylation reaction of an alkene and a hydrosilane in the presence of iron element-containing nanoparticles coordinated with a solvent on the surface.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0005]

Non-Patent Document 1

[0006] However, in the hydrosilylation reactions in Non-Patent Documents 1 and 2, the base or reducing agent used for the preliminary activation of the manganese complex may cause side reactions, leading to a reduction in the yield of the target product. In addition, the manganese complex before preliminary activation has a complex complex structure, so there is also a problem that its production requires complicated procedures. In addition, the iron catalysts described in Patent Document 2 and Non-Patent Document 3 have problems that the yield is low when a secondary hydrosilane is used as the hydrosilane compound, and the reaction hardly proceeds when a tertiary hydrosilane is used, and there is room for improvement.

[0007] 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 and a metal complex that requires a complicated production procedure. [Means for Solving the Problems]

[0008] The present inventors conducted intensive studies to solve the above problems. As a result, a manganese element-containing In the presence of a manganese nanoparticle catalyst in which a coordinating organic solvent is coordinated on the surface of the nanoparticles, it has been found that a hydrosilylation reaction between an alkene compound and a hydrosilane compound proceeds to obtain an organosilane compound, and the present invention has been completed. That is, the gist of the present invention is as follows.

[0009] 〔1〕 A hydrosilylation step of reacting an alkene compound with a hydrosilane compound in the presence of a hydrosilylation catalyst, wherein the hydrosilylation catalyst is a manganese nanoparticle catalyst in which a coordinating organic solvent is coordinated on the surface of manganese element-containing nanoparticles, a method for producing an organosilane compound. 〔2〕 The method for producing an organosilane compound according to [1], wherein the alkene compound is a compound represented by the general formula (A).

Chemical formula

[0010] According to the present invention, it is possible to provide a method for efficiently producing an organosilane compound from an alkene compound and a hydrosilane compound without using a noble metal catalyst and a metal complex that requires a complicated production procedure. [Brief Description of the Drawings]

[0011]

Figure 1

Figure 2

Figure 3

[0012] 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.

[0013] A method for producing an organosilane compound according to one embodiment of the present invention includes a hydrosilylation step of reacting an alkene compound with a hydrosilane compound (hydrosilylation reaction) in the presence of a hydrosilylation catalyst.

[0014] 1. Hydrosilylation process 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.

[0015] 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 coordinated to the manganese-containing nanoparticles can be appropriately selected depending on the target catalytic reaction. Whether or not the coordinating organic solvent is coordinated to 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.

[0016] The manganese-containing nanoparticles are not particularly limited in specific composition as long as they contain manganese as a constituent element, and include nanoparticles of manganese alone, nanoparticles of manganese alloys, nanoparticles in which manganese nanoparticles are doped with other atoms such as oxygen atoms or carbon atoms, nanoparticles of inorganic manganese compounds such as manganese oxide, etc. The manganese-containing nanoparticles may be used alone or in any combination and ratio of two or more types.

[0017] 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 acts as a coordinating organic solvent, reaction solvent, and reducing agent, allowing for one-step production. The coordinating organic solvents may be used alone, or two or more may be used in any combination and ratio.

[0018] 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, and is usually 200 nm or less, preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 10 nm or less. It is preferably 0.01 to 0.1 nm, 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.

[0019] 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 the like after the reaction. The recovered manganese nanoparticle catalyst can be reused as a hydrosilylation catalyst. Therefore, the production method according to this embodiment is excellent in safety and environmental friendliness.

[0020] Furthermore, since 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 a co-catalyst may be added within a range that does not impair the effects of the present invention. However, since the manganese nanoparticle catalyst alone exhibits high catalytic activity, the addition of such additives is not necessary. Therefore, the operating procedure of the hydrosilylation step of this embodiment can be simplified.

[0021] In this embodiment, the manganese nanoparticle catalyst serving as the hydrosilylation catalyst does not contain a precious metal such as platinum or ruthenium. In this specification, "no precious metal" means that the hydrosilylation catalyst does not intentionally contain a precious metal, and does not exclude the hydrosilylation catalyst containing a trace amount of precious metal as an impurity. The term "trace amount" as used herein refers to a content of preferably 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.

[0022] The method for producing the manganese nanoparticle catalyst is not particularly limited, and can be, for example, a production method based on the methods described in JP 2015-129103 A, WO 2018 / 131430, etc. Specifically, the manganese nanoparticle catalyst can be produced by mixing a precursor containing manganese element with a solvent containing a coordinating organic solvent and heating under reflux.

[0023] 1-2. Alkene compounds 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.

[0024] [ka]

[0025] (R 1 ~R 4 ) In general formula (A), R 1 ~R 4 are each independently a hydrogen atom, a halogen atom, or a substituent. R represents a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms. 1 and R 2 are both hydrocarbon groups, R 1 and R 2 may be linked to each other to form a ring. 3 and R 4 are both hydrocarbon groups, R 3 and R 4 may be linked to each other to form a ring.

[0026] In this specification, the term "hydrocarbon group" includes aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group is not limited to a linear hydrocarbon group, but may have a branched structure, a carbon-carbon unsaturated bond, or a cyclic structure. The aromatic hydrocarbon group may be a monocyclic, polycyclic, or fused ring type, or may be a heterocyclic aromatic hydrocarbon group.

[0027] R 1 ~R 4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0028] R 1 ~R 4 The number of carbon atoms in the hydrocarbon group represented by the formula (I) 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 is meant to include the number of carbon atoms in the substituent.

[0029] R 1 ~R 4 Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and represented by the formula (I) 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 group, an ethyl ... Examples of such saturated aliphatic hydrocarbon groups include linear or branched saturated aliphatic hydrocarbon groups such as n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups; saturated aliphatic hydrocarbon groups having a cyclic structure such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and cyclododecyl groups; and unsaturated aliphatic hydrocarbon groups such as vinyl and allyl groups.

[0030] R 1 ~R 4Examples of the unsubstituted aromatic hydrocarbon group having 3 to 40 carbon atoms represented by include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, fluorenyl group, indenyl group, fluoranthenyl group, triphenylenyl group, perylenyl group, pyrrolyl group, pyridyl group, pyrimidyl group, triazinyl group, carbazolyl group, furyl group, dibenzofuranyl group, thiophenyl group, dibenzothiophenyl group and the like. The position of the bond in these groups is not particularly limited.

[0031] R 1 ~R 4 When the hydrocarbon group having 1 to 40 carbon atoms represented by has a substituent, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl group; alkenyl groups having 3 to 6 carbon atoms such as vinyl group, allyl group and 3-butenyl group; cycloalkyl groups having 3 to 6 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; arylalkyl groups such as benzyl group and phenethyl group; methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, glycidyloxy group, n-butoxy group, sec-butoxy group, iso-isobutoxy group, tert-butoxy an alkoxy group having 1 to 6 carbon atoms such as a methyl group, an n-hexyloxy group; an alkenyloxy group having 3 to 6 carbon atoms such as a vinyloxy group, an allyloxy group, a 3-butenyloxy group; a cycloalkyloxy group having 3 to 6 carbon atoms such as a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group; an aryloxy group such as a phenyloxy group, a tolyloxy group; an arylalkyloxy group such as a benzyloxy group, a phenethyloxy group; an α,β-unsaturated carbonyloxy group such as an acryloxy group, a methacryloxy group; a primary to tertiary amino group such as an amino group, a dimethylamino group, a diethylamino group, a dibutylamino group; a heterocyclic group having 3 to 12 carbon atoms such as a pyridyl group, a pyrimidinyl group, a triazinyl group, a pyrrolyl group, a quinolyl group, an isoquinolyl group, an indolyl group, a carbazolyl group, a morpholino group, an oxiranyl group, an oxetanyl group, an oxiranyl group, a tetrahydrofuryl group, a furyl group, a thienyl group; etc. are mentioned.

[0032] R 1 and R 2 when they are linked to each other to form a ring, and R 3 and R 4 when they are linked to each other to form a ring, these groups may be linked by a direct bond or may be linked via a linking group. Examples of the linking group include -S-, -O-, -CO-, -COO-, -OCO-, -SO2-, -NR 5 -, -CONR 5 -, -NR 5 CO-, -OCONR 5 - etc. are mentioned. R 5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms include those shown as the hydrocarbon groups represented by R 1 ~R 4 among them, those having 1 to 8 carbon atoms are mentioned.

[0033] R 1 ~R 4is 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. In addition, the alkene compound (A) is preferably a terminal alkene. 1 and R 2 are both hydrogen atoms, and / or R 3 and R 4 are preferably all hydrogen atoms.

[0034] 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.

[0035] 1-3. Hydrosilane compounds 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 compounds represented by the following general formula (B) (hereinafter, sometimes referred to as "hydrosilane compound (B)"). The hydrosilane compound is either publicly known or can be easily produced by a method similar to a publicly known production method. Si(R 6 ) n H 4-n (B)

[0036] (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, that is, when the hydrosilyl compound is a tertiary hydrosilane compound, the hydrosilylation reaction proceeds rapidly, and it is possible to efficiently produce a tertiary organic silane compound having high industrial utility.

[0037] (R 6 ) In general formula (B), R 6 each independently represents a substituted or unsubstituted hydrocarbon group having 1 or more and 40 or less carbon atoms or a substituted or unsubstituted hydrocarbon oxy group having 1 or more and 40 or less carbon atoms. When n is 2 or 3, R 's may be linked to each other to form a ring. 6

[0038] The substituted or unsubstituted hydrocarbon group having 1 or more and 40 or less carbon atoms represented by R 6 is defined in the same manner as the substituted or unsubstituted hydrocarbon group having 1 or more and 40 or less carbon atoms represented by R 1 ~R 4 (however, excluding groups containing aliphatic double bonds). Further, the substituted or unsubstituted hydrocarbon group having 1 or more and 40 or less carbon atoms in the substituted or unsubstituted hydrocarbon oxy group having 1 or more and 40 or less carbon atoms represented by R 6 is defined in the same manner as the substituted or unsubstituted hydrocarbon group having 1 or more and 40 or less carbon atoms represented by R 1 ~R 4 (however, excluding groups containing aliphatic double bonds).

[0039] R 6 When's are linked to each other to form a ring, R 6 's may be directly linked or linked via a linking group. As the linking group, the same ones as the linking group for linking R 1 and R 2 (however, excluding groups containing aliphatic double bonds) can be adopted.

[0040] R 6 are each independently preferably a substituted or unsubstituted hydrocarbon group having from 1 to 40 carbon atoms, 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.

[0041] 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.

[0042] 1-4.Organosilane compounds The organosilane compound produced by the production method according to this embodiment is not particularly limited in structure, and may be a wide variety of organosilane compounds, as long as it 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) (hereinafter, sometimes referred to as "organosilane compound (C1)" or "organosilane compound (C2)") obtained by the reaction of an alkene compound (A) with a hydrosilane compound (B).

[0043] [ka]

[0044] In general formulas (C1) and (C2), R 1 ~R 4 is synonymous with R 1 ~R 4 in general formula (A), respectively. Also, in general formulas (C1) and (C2), R 6 and n are synonymous with R 6 and n in formula (B), respectively.

[0045] 1 - 5. Reaction Conditions (Catalyst Amount) The amount (charged amount) of the manganese nanoparticle catalyst used in the hydrosilylation step is not particularly limited. However, since the catalyst turnover number of the manganese nanoparticle catalyst is high, sufficient catalytic activity can be ensured even with a small amount. Specifically, the usage amount of the manganese nanoparticle catalyst is usually 0.001 mol% or more, preferably 0.005 mol% or more, more preferably 0.01 mol% or more, still more preferably 0.03 mol% or more, particularly preferably 0.05 mol% or more in terms of total metal conversion (manganese conversion) with respect to the aliphatic double bond of the alkene compound. Also, it is usually 5.0 mol% or less, preferably 1.0 mol% or less, more preferably 0.5 mol% or less, still more preferably 0.1 mol% or less, and particularly preferably 0.08 mol% or less.

[0046] (Molar Ratio of Substrates) The usage amount (charged amount) of the hydrosilane compound with respect to the usage amount (charged amount) of the alkene compound is not particularly limited. However, it is usually 1.0 equivalent or more, preferably 2.0 equivalents or more, more preferably 3.0 equivalents or more, still more preferably 5.0 equivalents or more with respect to the aliphatic double bond of the alkene compound. Also, it is usually 50.0 equivalents or less, preferably 20 equivalents or less, more preferably 10.0 equivalents or less. By setting the usage amount of the hydrosilane compound with respect to the aliphatic double bond of the alkene compound within the above range, the yield of the organosilane compound can be improved, and purification after the reaction becomes easy.

[0047] (Reaction Solvent) The hydrosilylation step may be carried out in a solventless reaction, or 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 in any combination and ratio of two or more.

[0048] 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, more preferably in diglyme or without a solvent. It is also preferable to dehydrate and deoxygenate the reaction solvent before use.

[0049] (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.

[0050] (Reaction time) The reaction time is not particularly limited and may be appropriately selected depending on the reaction conditions such as the type of catalyst, the reactivity of the substrate, the type of reaction solvent, the reaction temperature, etc. Specifically, the reaction time is From the viewpoint of improving the yield, the reaction time is preferably 4 hours or more, more preferably 10 hours or more, and even more preferably 15 hours or more. 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.

[0051] (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.

[0052] 2. Other processes The method for producing an organosilane compound according to this embodiment may include any other step in addition to the hydrosilylation step. The optional step may include a purification step for increasing the purity of the organosilane compound. In the purification step, a purification method commonly used in the field of organic synthesis, such as filtration, adsorption, column chromatography, or distillation, may be used. [Example]

[0053] The present invention will be explained in more detail below by way of 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 construed as being limited by the specific examples shown below.

[0054] <GC測定> 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)

[0055] <XPS測定> 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)

[0056] <Particle size measurement> The conditions for measuring the particle size of the manganese nanoparticle catalyst using an annular dark-field scanning transmission electron microscope (ADF-STEM) are as follows. Device name: JEM-ARM200F (JEOL Ltd.) Accelerating voltage: 200 kV

[0057] <Thermogravimetry> 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

[0058] <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 stir bar, and this DMF was preheated at 140 °C for 5 minutes while stirring at 1500 rpm. At this time, instruments such as the three-necked flask and the stir bar were used after co-washing with DMF. Subsequently, 500 μL of an aqueous manganese chloride solution was added to the three-necked round-bottom flask, and the mixture was heated under reflux for 24 hours to obtain a dispersion of a manganese nanoparticle catalyst (hereinafter sometimes referred to as "Mn NPs"). Assuming that all of the manganese chloride was converted into manganese nanoparticles, the concentration of the manganese element in the obtained dispersion was 1.0 mmol / L.

[0059] From the obtained dispersion of the manganese nanoparticle catalyst, the dispersion medium was distilled off under vacuum. The obtained residue was further dried under vacuum at 80 °C to strictly remove DMF not coordinated to the manganese nanoparticles, thereby obtaining a sample for measuring the physical properties of the manganese nanoparticle catalyst. Using this sample, XPS measurement, particle size measurement, and thermogravimetric measurement of the manganese nanoparticle catalyst were performed.

[0060] The results of the XPS measurement of the manganese nanoparticle catalyst are shown in Fig. 1. In Fig. 1, the main peak and satellite peak attributed to MnO can be confirmed. From this, it is considered that manganese chloride was converted into manganese oxide during the production process of the manganese nanoparticle catalyst.

[0061] The results of the observation by annular dark-field scanning transmission electron microscope (ADF-STEM) are shown in Fig. 2. The average particle size (average value of 98 particles) of the manganese nanoparticle catalyst calculated by ADF-STEM was about 2.9 nm.

[0062] The results of the thermogravimetric measurement of the manganese nanoparticle catalyst are shown in Fig. 3. From Fig. 3, it was found that the manganese nanoparticle catalyst had a 5% weight loss temperature of 137 °C and had high heat resistance.

[0063] <Production of Organosilane Compound> (Example 1-1: Examination of Reaction Solvent)

Chemical Formula

[0064] To a Schlenk tube, 50 μL of the manganese nanoparticle catalyst dispersion liquid obtained in Synthesis Example 1 (0.05 μmol in terms of Mn) was added, and the dispersion medium was distilled off under vacuum. In order to strictly remove DMF not coordinated to the manganese nanoparticles, the obtained residue was further dried under vacuum at 80 °C to obtain a manganese nanoparticle catalyst.

[0065] A stir bar was placed in the Schlenk tube containing the manganese nanoparticle catalyst, and the Schlenk tube was sealed with a two-way cock and a rubber stopper. After replacing 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 solution was heated at 130 °C and stirred for 24 hours After stirring, the obtained reaction mixture was cooled in an ice bath and mixed with 10 mL of hexane to stop the reaction.

[0066] Thereafter, GC measurement was performed using nonane as an internal standard substance. The conversion rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 1.

[0067] (Examples 1-2 to 1-4: Investigation of reaction solvents) The 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 rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 1.

[0068]

Table 1

[0069] Table 1 shows that the conversion 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 the organosilane compound was obtained in particularly high yield when the reaction was carried out in diglyme solvent (Example 1-1). On the other hand, when p-xylene or DMF was used as the reaction solvent (Examples 1-2 and 1-3), the conversion of the alkene compound and the yield of the organosilane compound were lower than those in Examples 1-1 and 1-4, but it was confirmed that the hydrosilylation reaction proceeded.

[0070] (Example 2-1: Study of reaction atmosphere) [ka]

[0071] First, a manganese nanoparticle catalyst was obtained in a Schlenk tube in the same manner as in Example 1-1. Next, 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. To this Schlenk tube, 1 mL of diglyme, 0.5 mmol (0.0842 g) of 1-dodecene, and 2.5 mmol (0.496 g) of diphenylmethylsilane were added. The reaction mixture 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.

[0072] Then, GC measurement was performed using nonane as an internal standard. The conversion rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 2.

[0073] (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 results of GC measurement are shown in Table 2.

[0074] (Example 2-3: Study of reaction atmosphere) The hydrosilylation reaction was carried out in the same manner as in Example 2-1, except that the Schlenk tube was purged with argon before adding diglyme, 1-dodecene, and diphenylmethylsilane to the Schlenk tube. The conversion rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 2.

[0075]

Table 2

[0076] From Table 2, it was found that the hydrosilylation reaction proceeds both in an air atmosphere and in an inert atmosphere, and in particular, when the hydrosilylation reaction is carried out in an inert atmosphere, an organosilane compound can be obtained in a high yield.

[0077] (Example 3-1: Examination of reaction time)

Chemical formula

[0078] First, manganese nanoparticle catalyst was obtained in a Schlenk tube in the same manner as in Example 1-1. Next, a stir bar was placed in the Schlenk tube containing the manganese nanoparticle catalyst, and the Schlenk tube was sealed with a two-way cock and a rubber stopper. After purging the Schlenk tube 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 tube. The reaction solution was stirred for 16 hours while heating at 130 °C, and then the obtained reaction mixture was cooled in an ice bath and mixed with 10 mL of hexane to stop the reaction.

[0079] Thereafter, GC measurement was carried out using nonane as an internal standard substance. The conversion rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 3.

[0080] (Example 3-2: Examination 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 rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 3.

[0081]

Table 3

[0082] From Table 3, it can be seen that at a reaction temperature of 130 °C, the reaction does not stop due to the decomposition of the catalyst, and the conversion rate of the substrate and the yield of the organosilane compound improve with the passage of the reaction time.

[0083] (Example 4-1: Examination of reaction temperature)

Chemical formula

[0084] First, manganese nanoparticle catalyst was obtained in a Schlenk tube in the same manner as in Example 1-1. Next, a stir bar was placed into the Schlenk tube containing the manganese nanoparticle catalyst, and the Schlenk tube was sealed with a two-way cock and a rubber stopper. After replacing the Schlenk tube 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 tube. After stirring the reaction solution at 100 °C for 24 hours while heating, the obtained reaction mixture was cooled in an ice bath and the reaction was stopped by mixing with 10 mL of hexane.

[0085] Thereafter, GC measurement was performed using nonane as an internal standard substance. The conversion rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 4.

[0086] (Example 4-2: Examination 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 rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 4.

[0087]

Table 4

[0088] From Table 4, it can be seen that increasing the reaction temperature from 100°C to 130°C increases the reaction rate, and improves the conversion rate of the substrate and the yield of the organosilane compound. [Industrial Applicability]

[0089] According to the present invention, a method for hydrosilation of an alkene compound in the presence of a manganese nanoparticle catalyst is disclosed. From the mixture, an organosilane compound can be efficiently produced. 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.

[0090] Furthermore, the organosilane compounds produced by this production method can be used in a variety of applications, including industrial chemical products such as paints and silicone oils, pharmaceuticals, and cosmetics.

Claims

1. comprising a hydrosilylation step of reacting an alkene compound with a hydrosilane compound in the presence of a hydrosilylation catalyst, wherein the hydrosilylation catalyst is a manganese nanoparticle catalyst in which a coordinating organic solvent is coordinated on the surface of manganese element-containing nanoparticles, and a method for producing an organosilane compound.

2. The method for producing an organosilane compound according to claim 1, wherein the alkene compound is a compound represented by the general formula (A). 【Chemical 1】 (In general formula (A), R １ ~R ４ each independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms; when both R １ and R ２ are the hydrocarbon groups, R １ and R ２ may be linked to each other to form a ring; when both R ３ and R ４ are the hydrocarbon groups, R ３ and R ４ may be linked to each other to form a ring.)

3. The method for producing an organosilane compound according to claim 1 or 2, wherein the hydrosilane compound is a compound represented by the general formula (B). Si(R ６ ) ｎ H ４－ｎ (B) (In general formula (B), R ６ each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms or a substituted or unsubstituted hydrocarbon oxy group having 1 to 40 carbon atoms; n represents an integer of 0 or more and 3 or less; when n is 2 or 3, R ６ s may be linked to each other to form a ring.)

4. The method for producing an organosilane compound according to claim 3, wherein n in the general formula (B) is 3.

5. The method for producing an organosilane compound according to any one of claims 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 claims 1 to 5, wherein the reaction is carried out in an ether solvent or without a solvent.

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