WO2010016416A1 - Catalyst for hydrosilylation reaction, and process for producing organic silicon compound using the catalyst - Google Patents
Catalyst for hydrosilylation reaction, and process for producing organic silicon compound using the catalyst Download PDFInfo
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- WO2010016416A1 WO2010016416A1 PCT/JP2009/063498 JP2009063498W WO2010016416A1 WO 2010016416 A1 WO2010016416 A1 WO 2010016416A1 JP 2009063498 W JP2009063498 W JP 2009063498W WO 2010016416 A1 WO2010016416 A1 WO 2010016416A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Definitions
- the present invention relates to a novel catalyst for hydrosilylation reaction and a method for producing an organosilicon compound using the same.
- Si—C bonds are used for functional compounds, but especially compounds having Si—C bonds are often used. Examples include silane coupling agents, rubber, release paper, adhesives, mold taking agents, LIMS molding agents and the like.
- Si—C bond formation includes a method using an organometallic compound such as magnesium and lithium, and a hydrosilylation reaction between a silicon hydride compound and an unsaturated compound.
- the former method has a wide range of synthesis and is suitable for the synthesis of special compounds, but has a complicated process and is not suitable for industrial mass production.
- hydrosilylation reactions are used for industrial mass production because they have few by-products and are easy to react.
- Examples of the hydrosilylation catalyst include transition metals such as platinum, palladium, rhodium, and ruthenium.
- platinum is generally used because of its yield and ease of operation (Non-Patent Documents 1 to 3).
- Non-Patent Documents 1 to 3 Non-Patent Documents 1 to 3).
- the rise in metal prices due to the increase in demand for rare metals has been remarkable.
- platinum has a high rate of price increase because it has many uses.
- 92% of platinum produced worldwide is limited to South Africa and the Russian Federation. Therefore, there is great concern about stable supply.
- the present invention has been made in view of the above circumstances, and a novel hydrosilyl capable of reacting a ⁇ Si—H group and a carbon-carbon multiple bond group to form a ⁇ Si—C bond using an iron compound catalyst. It is an object of the present invention to provide a catalyst for an oxidation reaction and a method for producing an organosilicon compound using the catalyst.
- the present inventors have found that when a platinum catalyst is used when an ⁇ Si—H group is reacted with a carbon-carbon multiple bond group using an iron complex compound as a catalyst. It was found that ⁇ Si—C bonds can be formed in the same manner as described above, and the present invention has been made.
- Claim 1 A catalyst for hydrosilylation reaction comprising an iron complex compound represented by the following general formula (1).
- R 1 is a hydrogen atom, an unsubstituted or substituted alkyl or aryl group having 1 to 10 carbon atoms, or a ligand that affects the oxidation number of an iron atom formed from a SiR 3 group;
- s is 0 ⁇ s ⁇ 3
- R represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or alkoxy group, a halogen atom, or a siloxane residue.
- X is a ligand that affects the oxidation number of the iron atom, and is an unsubstituted or substituted cyclic compound having a C 4-10 aliphatic unsaturated group, trispirazolyl borate, tetrafluoroborate, hexafluorophosphate , And porphine and phthalocyanine.
- t is 0 ⁇ t ⁇ 2.
- Y is a ligand that does not affect the oxidation number of iron atoms formed from ammonia molecules, carbonyl molecules, oxygen atoms, oxygen molecules, amine molecules, phosphine molecules, or phosphite molecules, and u is 0 ⁇ u ⁇ 12.
- Claim 2 The hydrosilylation catalyst comprising an iron complex compound according to claim 1, wherein the iron complex compound is a compound represented by the following general formula (2).
- Claim 3 The catalyst for hydrosilylation reaction comprising the iron complex compound according to claim 2, wherein the iron complex compound is a compound represented by the following general formula (3).
- Claim 4 A silicon compound having a ⁇ Si-H group and an organic compound having a carbon-carbon multiple bond group as raw materials, and in the presence of a hydrosilylation reaction catalyst comprising an iron complex compound according to any one of claims 1 to 3, A method for producing an organic compound having an Si-C bond, wherein an organic compound having an Si-C bond is obtained by a hydrosilylation reaction in the presence or absence of an organic solvent.
- Claim 5 5.
- Claim 6 6.
- an ⁇ Si—H group and a carbon-carbon multiple bond group are reacted using the iron complex compound of the formula (1) of the present invention, an ⁇ Si—C bond can be formed in the same manner as when a platinum catalyst is used. Is possible. According to the present invention, a useful siloxane or silane compound can be produced in a high yield, and a compound having a ⁇ Si—C bond useful as a functional compound material can be produced at a low cost.
- the novel catalyst for hydrosilylation reaction of the present invention is a compound represented by the following general formula (1), particularly a II-valent or IV-valent complex.
- R 1 is independently a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a phenyl group or a pyridyl group, or a part of hydrogen atoms bonded to a carbon atom of these groups ( 1 or 2 or more) or all of them are selected from a hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, a 3,3,3-trifluoropropyl group, etc. substituted with a hydroxy group, a cyano group, a halogen atom, etc.
- R independently represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group, a halogen atom, or a siloxane residue.
- examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, the alkoxy group, and the halogen atom include those similar to R 6 in the formula (5) described later.
- Examples of the siloxane residue include a group in which one hydrogen atom bonded to a silicon atom is eliminated in formula (4) described later.
- X is cyclopentadiene, cyclohexadiene, cyclooctatetraene or a part (one or two or more) or all of hydrogen atoms bonded to carbon atoms of these groups by hydroxy group, cyano group, halogen atom, etc.
- a ligand formed from an anion, porphine, or phthalocyanine that forms a salt such as a cyclic product, trispyrazolyl borate, tetrafluoroborate, hexafluorophosphate.
- cyclopentadienyl anion is preferable.
- Y affects the oxidation number of iron atoms selected from ammonia molecules, carbonyl molecules, oxygen atoms, oxygen molecules, amine molecules, phosphine molecules such as triphenylphosphine, phosphite molecules such as triethyl phosphite and triphenyl phosphite. It is a ligand that does not give.
- s, t, and u are 0 ⁇ s ⁇ 3, 0 ⁇ t ⁇ 2, and 0 ⁇ u ⁇ 12.
- s is greater than 0 and t and u are 0 or more, but s, t and u are numbers that make the entire metal salt neutral, and s and t are divalent or 4 oxidation numbers of iron atoms. It is a number that gives a value.
- R 1 is a hydrogen atom, or a methyl group, an ethyl group, a phenyl group, an alkyl group or an aryl group having 1 to 8 carbon atoms such as a pyridyl group
- X is denoted by C 5 R 2 5
- R 2 is hydrogen
- Y is a carbonyl molecule or a phosphine molecule such as triphenylphosphine.
- (A) is a catalyst precursor, and the actual catalytically active species is considered to be (B). It is considered that (B) is formed by reacting (A) with the starting complex and hydrosilane, and olefin and hydrosilane are sequentially reacted with this to cause a hydrosilylation reaction.
- (B) is formed by reacting (A) with, for example, 2 equivalents of hydrosilane, a complex (C) is formed, and when this complex is heated in solution, the silyl group and hydride are reductively eliminated from the iron to yield (B). Therefore, (C) is also a catalyst precursor for the hydrosilylation reaction of olefin, and complex (C) is an IV valent iron complex.
- an organic compound having a Si—C bond by a hydrosilylation reaction according to the present invention, a silicon compound having an ⁇ Si—H group, an organic compound having a carbon-carbon multiple bond group, a general formula as a catalyst for a hydrosilylation reaction
- an organic compound having a Si—C bond can be produced.
- Each component for producing an organic compound having a Si—C bond more suitably by a hydrosilylation reaction is described below.
- silicon compounds having ⁇ Si—H groups include the following components (A) and (B).
- Component (A) is an organohydrogenpolysiloxane represented by the following general formula (4).
- R 4 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and does not have an aliphatic unsaturated bond, such as an alkyl group such as a methyl group, an ethyl group, or a propyl group. Groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, and halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl groups.
- R 5 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond.
- Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, and a propyl group. And an alkyl group such as a phenyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and a halogen-substituted alkyl group such as a 3,3,3-trifluoropropyl group.
- g, h, i, and j are 0 or a positive number, but any one of g, h, and i must be a positive number, and g + h + i + j ⁇ 2 and at least one Si—H group in one molecule. It is what you have. More preferably, 2 ⁇ g + h + i + j ⁇ 1,000, still more preferably 2 ⁇ g + h + i + j ⁇ 100, and the number of Si is preferably 2 to 1,000, particularly 2 to 100.
- the Si—H number is preferably 1 or more, particularly 2 to 100.
- the amount of hydrogen polysiloxane blended is such that the number of moles of hydrogen atoms bonded to silicon atoms is 0.3 to 10 times the mole of the total number of alkenyl groups of the compound having a carbon-carbon multiple bond. It is sufficient if it is a mass part corresponding to 0.5 to 5 moles. If the blending amount is less than 0.3 times mole, it is not practical because the remaining amount of the organic compound having a carbon-carbon multiple bond group, which is the other reaction raw material of the hydrosilylation reaction, increases, and it exceeds 10 times mole. Even if used, the yield of the hydrosilylation reaction is not improved.
- Component (B) is a silane compound having an ⁇ Si—H group represented by the following composition formula (5).
- R 6 is independently a hydrogen atom, An alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group or a biphenyl group; or one of hydrogen atoms bonded to a carbon atom of these groups. 1 to 10 carbon atoms of unsubstituted or substituted selected from trifluoromethyl group, hydroxypropyl group, cyanoethyl group, etc., wherein part (one or two or more) or all are substituted with hydroxy group, cyano group, halogen atom, etc.
- the amount of the silane compound used is such that the number of moles of hydrogen atoms bonded to the silicon atom is 0.3 parts by weight corresponding to the total number of alkenyl groups of the compound having a carbon-carbon multiple bond.
- the mass part may correspond to 0.5 to 5 times mol. If the blending amount is less than 0.3 times mol, the remaining amount of the organic compound having a carbon-carbon multiple bond group, which is another reaction raw material of the hydrosilylation reaction, is not practical, and more than 10 times mol. Even if used, the yield of the hydrosilylation reaction is not improved.
- an organic compound represented by the following composition formula (6) can be exemplified as the component (C).
- R 7 is independently a hydrogen atom, Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, aryl groups such as phenyl group, naphthyl group, biphenyl group, vinyl group, allyl group, butenyl group, etc. Alkenyl groups, or trifluoromethyl groups, hydroxypropyl groups, cyanoethyl groups, in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with hydroxy groups, cyano groups, epoxy groups, halogen atoms, etc.
- Alkyl groups such as methyl group, ethyl group, propyl group, butyl group
- cycloalkyl groups such as cyclopentyl group, cyclohexyl group
- aryl groups such as phenyl group, naphthy
- An unsubstituted or substituted alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group;
- Halogen atoms such as acrylic group, fluorine, chlorine, bromine, iodine, Examples include polyether-containing groups.
- an acetylene structure in which R 7 groups on different carbon atoms at the 1 and 2 positions are small, or R 7 may be bonded to each other to form a cyclic structure.
- cyclopentene, cyclohexene, norbornene, Norbornadiene, bicyclo [2,2,2] octene, indene and the like, and a part (one or two or more) or all of hydrogen atoms bonded to carbon atoms of these cyclic structures are further methyl group, ethyl group Alkyl groups such as propyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group, naphthyl group and biphenyl group, alkenyl groups such as vinyl group, allyl group and butenyl group, or Some or all of the hydrogen atoms bonded to the carbon atom are replaced with hydroxy groups, cyano groups, epoxy groups
- Those substituted with 10 alkoxycarbonyl groups, and those further substituted with acrylic groups, halogen atoms such as fluorine, chlorine, bromine and iodine, polyether-containing groups and the like are also included.
- an alkenyl group, an alkyl group, an aryl group, and an alkoxy group are preferable, and an alkenyl group, an alkyl group, and an alkoxy group are more preferable.
- the substitution pattern of the carbon-carbon multiple bond is preferably disubstituted, monosubstituted, more preferably monosubstituted olefin.
- Component (D) is a novel catalyst for hydrosilylation reaction, and is an iron complex represented by the above general formula (1).
- the above iron catalyst can be suitably used in an amount of 0.0001 to 10-fold mol, preferably 0.001 to 1-fold mol based on the total number of alkenyl groups in component (C).
- an organic solvent can be optionally used for the production of an organic compound having a Si—C bond.
- the organic solvent is an organic solvent that does not participate in the hydrosilylation reaction, preferably a hydrocarbon type, more preferably heptane, octane, or toluene.
- the production of the organic compound having an Si—C bond by the hydrosilylation reaction is 20 to 150 ° C., preferably 50 to 120 ° C. as the reaction temperature.
- Example 1 The Schlenk tube was placed under a nitrogen atmosphere, C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron] 23 mg (0.119 mmol), 1-hexene 1.47 mL (11.88 mmol), pentamethyl 1 mL of toluene was added to 0.584 mL (2.97 mmol) of disiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure.
- the obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane), and 244 mg of the product 2,2,4,4-tetramethyl-3-oxa-2,4-disiladecane (7) was obtained. (1.04 mmol) was obtained.
- Example 2 The Schlenk tube was placed under a nitrogen atmosphere, 20.7 mg (0.107 mmol) of C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron], 1.67 mL (10.67 mmol) of 1-octene, 1 mL of toluene was added to 0.524 mL (2.67 mmol) of pentamethyldisiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure.
- the obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane) to obtain 621 mg of the product 2,2,4,4-tetramethyl-3-oxa-2,4-disiladodecane (8). (2.66 mmol) was obtained.
- Example 3 The Schlenk tube was placed under a nitrogen atmosphere, 21.1 mg (0.109 mmol) of C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron], 0.311 mL (2.72 mmol) of styrene, pentamethyl 1 mL of toluene was added to 0.533 mL (2.71 mmol) of disiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure.
- the obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane), and the product 2,2,4,4-tetramethyl-6-phenyl-3-oxa-2,4-disilahexane ( 9) and 2,2,4,4-tetramethyl-6-phenyl-3-oxa-2,4-disilahex-5-ene (10) 308 mg were obtained.
Abstract
A catalyst for a hydrosilylation reaction, which comprises an iron complex compound represented by general formula (1):Xt-Fe-R1
s(Yu) (1)[wherein R1 represents H, an alkyl group, an aryl group, or a ligand that is formed by a group SiR3 and can influence on the oxidation number of the iron atom; s represents a number of greater than 0 and not greater than 3 (i.e., 0<s≤3); R represents H, an alkoxy group, a halogen atom, or a siloxane residue; X represents a ligand which can influence on the oxidation number of the iron atom and is selected from a cyclic structure having an aliphatic unsaturated C4-10 group, a trispyrazolylborate, a tetrafluoroborate, a hexafluorophosphate, a porphine and a phthalocyanine; t represents a number of not less than 0 and less than 2 (i.e., 0≤t<2); Y represents a ligand formed by an ammonia molecule, a carbonyl molecule, an oxygen atom, an oxygen molecule, an amine molecule, a phosphine molecule or a phosphite molecule and does not influence on the oxidation number of the iron atom; and u represents a number of 0 to 12 inclusive (i.e., 0≤u≤12); provided that s represents a number of greater than 0, t and u independently represent a number of 0 or greater, s, t and u independently represent such a number that a metal salt becomes neutral as a whole, and s and t independently represent such a number that the oxidation number of the iron atom becomes 2 or 4].
Description
本発明は、新規なヒドロシリル化反応用触媒、及びこれを用いた有機ケイ素化合物の製造方法に関するものである。
The present invention relates to a novel catalyst for hydrosilylation reaction and a method for producing an organosilicon compound using the same.
機能性化合物には様々な結合形式が用いられているが、特にＳｉ－Ｃ結合を有する化合物は多く使用されている。例として、シランカップリング剤、ゴム、剥離紙、接着剤、型取り剤、ＬＩＭＳ成形剤などが挙げられる。一般にＳｉ－Ｃ結合形成には、マグネシウム、リチウムなどの有機金属化合物を用いた方法と、水素化ケイ素化合物と不飽和化合物のヒドロシリル化反応がある。前者の方法は、合成の範囲が広く、特殊な化合物の合成には適するが、工程が複雑であり、工業的大量生産には不適である。一方、ヒドロシリル化反応は副生成物が少なく、反応も容易であることから、工業的大量生産に利用されている。ヒドロシリル化反応の触媒としては遷移金属である白金、パラジウム、ロジウム、ルテニウムなどが挙げられるが、特に白金は収率、操作の簡便性などから一般的に使用されている（非特許文献１～３）。しかし、近年はレアメタルの需要増加による金属価格上昇が顕著であり、特に白金は使用用途が多いため価格上昇の割合が高い。加えて白金は世界で産出される９２％が南アフリカ共和国とロシア連邦に限られている。従って安定的供給に大きな不安を抱えている。そこで高価でかつ安定的供給に問題のある白金を用いず、安価で安定供給が可能な金属触媒を用いてＳｉ－Ｃ結合が形成可能であれば、有機ケイ素化合物を得る方法として非常に有用である。
Various types of bonds are used for functional compounds, but especially compounds having Si—C bonds are often used. Examples include silane coupling agents, rubber, release paper, adhesives, mold taking agents, LIMS molding agents and the like. In general, Si—C bond formation includes a method using an organometallic compound such as magnesium and lithium, and a hydrosilylation reaction between a silicon hydride compound and an unsaturated compound. The former method has a wide range of synthesis and is suitable for the synthesis of special compounds, but has a complicated process and is not suitable for industrial mass production. On the other hand, hydrosilylation reactions are used for industrial mass production because they have few by-products and are easy to react. Examples of the hydrosilylation catalyst include transition metals such as platinum, palladium, rhodium, and ruthenium. In particular, platinum is generally used because of its yield and ease of operation (Non-Patent Documents 1 to 3). ). However, in recent years, the rise in metal prices due to the increase in demand for rare metals has been remarkable. In particular, platinum has a high rate of price increase because it has many uses. Additionally, 92% of platinum produced worldwide is limited to South Africa and the Russian Federation. Therefore, there is great concern about stable supply. Therefore, if a Si—C bond can be formed using a metal catalyst that is inexpensive and can be stably supplied without using platinum that is expensive and has a problem with stable supply, it is very useful as a method for obtaining an organosilicon compound. is there.
本発明は、上記事情に鑑みなされたもので、鉄化合物触媒を用いて、≡Ｓｉ－Ｈ基と炭素－炭素多重結合基を反応させ、≡Ｓｉ－Ｃ結合を形成させることができる新規なヒドロシリル化反応用触媒、及び同触媒を用いた有機ケイ素化合物の製造方法を提供することを目的とする。
The present invention has been made in view of the above circumstances, and a novel hydrosilyl capable of reacting a ≡Si—H group and a carbon-carbon multiple bond group to form a ≡Si—C bond using an iron compound catalyst. It is an object of the present invention to provide a catalyst for an oxidation reaction and a method for producing an organosilicon compound using the catalyst.
本発明者らは、上記目的を達成するため鋭意検討を重ねた結果、触媒として鉄錯体化合物を用いて≡Ｓｉ－Ｈ基を炭素－炭素多重結合基と反応させると、白金触媒を用いたときと同様に≡Ｓｉ－Ｃ結合を形成させることができることを見出し、本発明をなすに至ったものである。
As a result of intensive investigations to achieve the above object, the present inventors have found that when a platinum catalyst is used when an ≡Si—H group is reacted with a carbon-carbon multiple bond group using an iron complex compound as a catalyst. It was found that ≡Si—C bonds can be formed in the same manner as described above, and the present invention has been made.
即ち、下記一般式（１）の鉄化合物触媒を用いると、≡Ｓｉ－Ｈ基と炭素－炭素多重結合基のヒドロシリル化反応が進行し、白金触媒を用いたときと同様に≡Ｓｉ－Ｃ結合が形成される。特に、ジカルボニルシクロペンタジエニルメチル鉄［以後、Ｃ5Ｈ5－Ｆｅ－ＣＨ3（ＣＯ）2と記載］のようなＩＩ価又はＩＶ価の錯体化合物を用いるとヒドロシリル化反応が容易に進行することを見出した。本反応では、このような鉄錯体化合物が加熱されることにより、鉄錯体に結合した配位子が脱離するか、あるいはＣＯ挿入反応が起こり、鉄錯体に空配位座が発生する。この空配座に≡Ｓｉ－Ｈ基もしくは炭素－炭素多重結合基が配位し、ヒドロシリル化反応が進行すると考えられる。
That is, when an iron compound catalyst of the following general formula (1) is used, the hydrosilylation reaction of ≡Si—H group and carbon-carbon multiple bond group proceeds, and ≡Si—C bond is the same as when a platinum catalyst is used. Is formed. In particular, when a II-valent or IV-valent complex compound such as dicarbonylcyclopentadienylmethyliron [hereinafter referred to as C 5 H 5 —Fe—CH 3 (CO) 2 ] is used, the hydrosilylation reaction proceeds easily. I found out. In this reaction, when such an iron complex compound is heated, a ligand bonded to the iron complex is eliminated or a CO insertion reaction occurs, and an vacant coordination site is generated in the iron complex. It is considered that a ≡Si—H group or a carbon-carbon multiple bond group is coordinated to this vacant conformation and the hydrosilylation reaction proceeds.
従って、本発明は、下記新規なヒドロシリル化反応用触媒、及び同触媒を用いた有機ケイ素化合物の製造方法を提供する。
請求項１：
下記一般式（１）に示す鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｘt－Ｆｅ－Ｒ1 s（Ｙu） （１）
（式中、Ｒ1は水素原子、非置換もしくは置換の炭素数１～１０のアルキル基又はアリール基、又はＳｉＲ3基から形成される鉄原子の酸化数に影響を与える配位子であり、ｓは０＜ｓ≦３である。Ｒは水素原子、非置換又は置換の炭素数１～１０の１価炭化水素基又はアルコキシ基、ハロゲン原子、又はシロキサン残基を示す。
Ｘは鉄原子の酸化数に影響を与える配位子であって、非置換又は置換の炭素数４～１０の脂肪族不飽和基を有する環状体、トリスピラゾリルボレート，テトラフルオロボレート，ヘキサフルオロホスフェート、及びポルフィン、フタロシアニンから選ばれる。ｔは０≦ｔ＜２である。
Ｙはアンモニア分子、カルボニル分子、酸素原子、酸素分子、アミン分子、ホスフィン分子、又はホスファイト分子から形成される鉄原子の酸化数に影響を与えない配位子であり、ｕは０≦ｕ≦１２である。
ｓは０より大きく、ｔ、ｕは０以上であるが、ｓ、ｔ、ｕは金属塩全体が中性となるような数で、更にｓ、ｔは鉄原子の酸化数が２価又は４価となるような数である。）
請求項２：
上記鉄錯体化合物が、下記一般式（２）で表される化合物である請求項１記載の鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｃ5Ｒ2 5－Ｆｅ－Ｒ3 s（ＣＯ）u （２）
（式中、Ｒ2は水素原子又は炭素数１～６の１価炭化水素基、Ｒ3は水素原子、炭素数１～８のアルキル基又はアリール基、又はＳｉＲ3基（Ｒは上記の通り）を示す。ｓ、ｕは上記の通り。）
請求項３：
上記鉄錯体化合物が、下記一般式（３）で表される化合物である請求項２記載の鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｃ5Ｈ5－Ｆｅ－ＣＨ3（ＣＯ）2 （３）
請求項４：
≡Ｓｉ－Ｈ基を持つケイ素化合物と炭素－炭素多重結合基を持つ有機化合物を原料とし、請求項１～３のいずれか１項記載の鉄錯体化合物からなるヒドロシリル化反応用触媒の存在下、有機溶媒の存在又は不存在の条件で、ヒドロシリル化反応によりＳｉ－Ｃ結合を有する有機化合物を得ることを特徴とするＳｉ－Ｃ結合を有する有機化合物の製造方法。
請求項５：
≡Ｓｉ－Ｈ基を持つケイ素化合物がシラン化合物又はポリシロキサンであることを特徴とする請求項４記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。
請求項６：
炭素－炭素多重結合基を持つ有機化合物が、炭化水素基を有する有機化合物から選択されることを特徴とする請求項４又は５記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。
請求項７：
有機溶剤が炭化水素系有機化合物である請求項４～６のいずれか１項記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。 Therefore, the present invention provides the following novel hydrosilylation catalyst and a method for producing an organosilicon compound using the catalyst.
Claim 1:
A catalyst for hydrosilylation reaction comprising an iron complex compound represented by the following general formula (1).
X t —Fe—R 1 s (Y u ) (1)
(In the formula, R 1 is a hydrogen atom, an unsubstituted or substituted alkyl or aryl group having 1 to 10 carbon atoms, or a ligand that affects the oxidation number of an iron atom formed from a SiR 3 group; s is 0 <s ≦ 3 R represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or alkoxy group, a halogen atom, or a siloxane residue.
X is a ligand that affects the oxidation number of the iron atom, and is an unsubstituted or substituted cyclic compound having a C 4-10 aliphatic unsaturated group, trispirazolyl borate, tetrafluoroborate, hexafluorophosphate , And porphine and phthalocyanine. t is 0 ≦ t <2.
Y is a ligand that does not affect the oxidation number of iron atoms formed from ammonia molecules, carbonyl molecules, oxygen atoms, oxygen molecules, amine molecules, phosphine molecules, or phosphite molecules, and u is 0 ≦ u ≦ 12.
s is greater than 0 and t and u are 0 or more, but s, t and u are numbers that make the entire metal salt neutral, and s and t are divalent or 4 oxidation numbers of iron atoms. It is a number that gives a value. )
Claim 2:
The hydrosilylation catalyst comprising an iron complex compound according to claim 1, wherein the iron complex compound is a compound represented by the following general formula (2).
C 5 R 2 5 -Fe-R 3 s (CO) u (2)
(Wherein R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R 3 is a hydrogen atom, an alkyl group or aryl group having 1 to 8 carbon atoms, or a SiR 3 group (R is as defined above) S and u are as described above.)
Claim 3:
The catalyst for hydrosilylation reaction comprising the iron complex compound according to claim 2, wherein the iron complex compound is a compound represented by the following general formula (3).
C 5 H 5 —Fe—CH 3 (CO) 2 (3)
Claim 4:
A silicon compound having a ≡Si-H group and an organic compound having a carbon-carbon multiple bond group as raw materials, and in the presence of a hydrosilylation reaction catalyst comprising an iron complex compound according to any one of claims 1 to 3, A method for producing an organic compound having an Si-C bond, wherein an organic compound having an Si-C bond is obtained by a hydrosilylation reaction in the presence or absence of an organic solvent.
Claim 5:
5. The method for producing an organic compound having a Si—C bond according to claim 4, wherein the silicon compound having a ≡Si—H group is a silane compound or polysiloxane.
Claim 6:
6. The method for producing an organic compound having an Si—C bond according to claim 4, wherein the organic compound having a carbon-carbon multiple bond group is selected from organic compounds having a hydrocarbon group.
Claim 7:
The method for producing an organic compound having a Si-C bond according to any one of claims 4 to 6, wherein the organic solvent is a hydrocarbon organic compound.
請求項１：
下記一般式（１）に示す鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｘt－Ｆｅ－Ｒ1 s（Ｙu） （１）
（式中、Ｒ1は水素原子、非置換もしくは置換の炭素数１～１０のアルキル基又はアリール基、又はＳｉＲ3基から形成される鉄原子の酸化数に影響を与える配位子であり、ｓは０＜ｓ≦３である。Ｒは水素原子、非置換又は置換の炭素数１～１０の１価炭化水素基又はアルコキシ基、ハロゲン原子、又はシロキサン残基を示す。
Ｘは鉄原子の酸化数に影響を与える配位子であって、非置換又は置換の炭素数４～１０の脂肪族不飽和基を有する環状体、トリスピラゾリルボレート，テトラフルオロボレート，ヘキサフルオロホスフェート、及びポルフィン、フタロシアニンから選ばれる。ｔは０≦ｔ＜２である。
Ｙはアンモニア分子、カルボニル分子、酸素原子、酸素分子、アミン分子、ホスフィン分子、又はホスファイト分子から形成される鉄原子の酸化数に影響を与えない配位子であり、ｕは０≦ｕ≦１２である。
ｓは０より大きく、ｔ、ｕは０以上であるが、ｓ、ｔ、ｕは金属塩全体が中性となるような数で、更にｓ、ｔは鉄原子の酸化数が２価又は４価となるような数である。）
請求項２：
上記鉄錯体化合物が、下記一般式（２）で表される化合物である請求項１記載の鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｃ5Ｒ2 5－Ｆｅ－Ｒ3 s（ＣＯ）u （２）
（式中、Ｒ2は水素原子又は炭素数１～６の１価炭化水素基、Ｒ3は水素原子、炭素数１～８のアルキル基又はアリール基、又はＳｉＲ3基（Ｒは上記の通り）を示す。ｓ、ｕは上記の通り。）
請求項３：
上記鉄錯体化合物が、下記一般式（３）で表される化合物である請求項２記載の鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｃ5Ｈ5－Ｆｅ－ＣＨ3（ＣＯ）2 （３）
請求項４：
≡Ｓｉ－Ｈ基を持つケイ素化合物と炭素－炭素多重結合基を持つ有機化合物を原料とし、請求項１～３のいずれか１項記載の鉄錯体化合物からなるヒドロシリル化反応用触媒の存在下、有機溶媒の存在又は不存在の条件で、ヒドロシリル化反応によりＳｉ－Ｃ結合を有する有機化合物を得ることを特徴とするＳｉ－Ｃ結合を有する有機化合物の製造方法。
請求項５：
≡Ｓｉ－Ｈ基を持つケイ素化合物がシラン化合物又はポリシロキサンであることを特徴とする請求項４記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。
請求項６：
炭素－炭素多重結合基を持つ有機化合物が、炭化水素基を有する有機化合物から選択されることを特徴とする請求項４又は５記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。
請求項７：
有機溶剤が炭化水素系有機化合物である請求項４～６のいずれか１項記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。 Therefore, the present invention provides the following novel hydrosilylation catalyst and a method for producing an organosilicon compound using the catalyst.
Claim 1:
A catalyst for hydrosilylation reaction comprising an iron complex compound represented by the following general formula (1).
X t —Fe—R 1 s (Y u ) (1)
(In the formula, R 1 is a hydrogen atom, an unsubstituted or substituted alkyl or aryl group having 1 to 10 carbon atoms, or a ligand that affects the oxidation number of an iron atom formed from a SiR 3 group; s is 0 <s ≦ 3 R represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or alkoxy group, a halogen atom, or a siloxane residue.
X is a ligand that affects the oxidation number of the iron atom, and is an unsubstituted or substituted cyclic compound having a C 4-10 aliphatic unsaturated group, trispirazolyl borate, tetrafluoroborate, hexafluorophosphate , And porphine and phthalocyanine. t is 0 ≦ t <2.
Y is a ligand that does not affect the oxidation number of iron atoms formed from ammonia molecules, carbonyl molecules, oxygen atoms, oxygen molecules, amine molecules, phosphine molecules, or phosphite molecules, and u is 0 ≦ u ≦ 12.
s is greater than 0 and t and u are 0 or more, but s, t and u are numbers that make the entire metal salt neutral, and s and t are divalent or 4 oxidation numbers of iron atoms. It is a number that gives a value. )
Claim 2:
The hydrosilylation catalyst comprising an iron complex compound according to claim 1, wherein the iron complex compound is a compound represented by the following general formula (2).
C 5 R 2 5 -Fe-R 3 s (CO) u (2)
(Wherein R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R 3 is a hydrogen atom, an alkyl group or aryl group having 1 to 8 carbon atoms, or a SiR 3 group (R is as defined above) S and u are as described above.)
Claim 3:
The catalyst for hydrosilylation reaction comprising the iron complex compound according to claim 2, wherein the iron complex compound is a compound represented by the following general formula (3).
C 5 H 5 —Fe—CH 3 (CO) 2 (3)
Claim 4:
A silicon compound having a ≡Si-H group and an organic compound having a carbon-carbon multiple bond group as raw materials, and in the presence of a hydrosilylation reaction catalyst comprising an iron complex compound according to any one of claims 1 to 3, A method for producing an organic compound having an Si-C bond, wherein an organic compound having an Si-C bond is obtained by a hydrosilylation reaction in the presence or absence of an organic solvent.
Claim 5:
5. The method for producing an organic compound having a Si—C bond according to claim 4, wherein the silicon compound having a ≡Si—H group is a silane compound or polysiloxane.
Claim 6:
6. The method for producing an organic compound having an Si—C bond according to claim 4, wherein the organic compound having a carbon-carbon multiple bond group is selected from organic compounds having a hydrocarbon group.
Claim 7:
The method for producing an organic compound having a Si-C bond according to any one of claims 4 to 6, wherein the organic solvent is a hydrocarbon organic compound.
本発明の式（１）の鉄錯体化合物を用いて≡Ｓｉ－Ｈ基と炭素－炭素多重結合基を反応させると、白金触媒を用いたときと同様に≡Ｓｉ－Ｃ結合を形成させることが可能である。本発明によれば、有用なシロキサン又はシラン化合物を高収率で製造することができ、機能性化合物の素材として有用な≡Ｓｉ－Ｃ結合を有する化合物を、安価に製造することができる。
When an ≡Si—H group and a carbon-carbon multiple bond group are reacted using the iron complex compound of the formula (1) of the present invention, an ≡Si—C bond can be formed in the same manner as when a platinum catalyst is used. Is possible. According to the present invention, a useful siloxane or silane compound can be produced in a high yield, and a compound having a ≡Si—C bond useful as a functional compound material can be produced at a low cost.
本発明の新規なヒドロシリル化反応用触媒は、下記一般式（１）で示される化合物で、特にＩＩ価又はＩＶ価の錯体である。
Ｘt－Ｆｅ－Ｒ1 s（Ｙu） （１） The novel catalyst for hydrosilylation reaction of the present invention is a compound represented by the following general formula (1), particularly a II-valent or IV-valent complex.
X t —Fe—R 1 s (Y u ) (1)
Ｘt－Ｆｅ－Ｒ1 s（Ｙu） （１） The novel catalyst for hydrosilylation reaction of the present invention is a compound represented by the following general formula (1), particularly a II-valent or IV-valent complex.
X t —Fe—R 1 s (Y u ) (1)
Ｒ1は独立に水素原子、又はメチル基、エチル基、プロピル基等のアルキル基、フェニル基、ピリジル基等のアリール基、又はこれらの基の炭素原子に結合している水素原子の一部（１個又は２個以上）又は全部をヒドロキシ基、シアノ基、ハロゲン原子などで置換したヒドロキシプロピル基、シアノエチル基、１－クロロプロピル基、３，３，３－トリフルオロプロピル基などから選択される非置換又は置換の炭素数１～１０のアルキル基又はアリール基、又はＳｉＲ3で示される基である。Ｒは独立に水素原子、非置換又は置換の炭素数１～１０の１価炭化水素基又はアルコキシ基、ハロゲン原子、又はシロキサン残基を示す。この場合、非置換又は置換の炭素数１～１０の１価炭化水素基、アルコキシ基、ハロゲン原子としては、後述する式（５）のＲ6と同様のものが例示される。シロキサン残基としては、後述する式（４）において、これからケイ素原子に結合する水素原子が１個脱離した基を挙げることができる。Ｘはシクロペンタジエン、シクロヘキサジエン、シクロオクタテトラエン又はこれらの基の炭素原子に結合している水素原子の一部（１個又は２個以上）又は全部をヒドロキシ基、シアノ基、ハロゲン原子などで置換したヒドロキシプロピル基、シアノエチル基、１－クロロプロピル基、３，３，３－トリフルオロプロピル基などから選択される基で置換した又は非置換の炭素数４～１０の脂肪族不飽和基を有する環状体、トリスピラゾリルボレート、テトラフルオロボレート、ヘキサフルオロホスフェートなどの塩を形成する陰イオン、ポルフィン、又はフタロシアニンから形成される配位子である。中でも、シクロペンタジエニル陰イオンが好ましい。Ｙはアンモニア分子、カルボニル分子、酸素原子、酸素分子、アミン分子、トリフェニルホスフィンなどのホスフィン分子、トリエチルホスファイト、トリフェニルホスファイトなどのホスファイト分子から選択される鉄原子の酸化数に影響を与えない配位子である。
ｓ、ｔ、ｕは、０＜ｓ≦３、０≦ｔ＜２、０≦ｕ≦１２である。ｓは０より大きく、ｔ、ｕは０以上であるが、ｓ、ｔ、ｕは金属塩全体が中性となるような数で、更にｓ、ｔは鉄原子の酸化数が２価又は４価となるような数である。好ましくは、Ｒ1が水素原子、又はメチル基、エチル基、フェニル基、ピリジル基などの炭素数１～８のアルキル基又はアリール基、ＸはＣ5Ｒ2 5で表記され、Ｒ2は水素原子、メチル基、エチル基等の炭素数１～６の１価炭化水素基、Ｙはカルボニル分子、又はトリフェニルホスフィンなどのホスフィン分子である。 R 1 is independently a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a phenyl group or a pyridyl group, or a part of hydrogen atoms bonded to a carbon atom of these groups ( 1 or 2 or more) or all of them are selected from a hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, a 3,3,3-trifluoropropyl group, etc. substituted with a hydroxy group, a cyano group, a halogen atom, etc. An unsubstituted or substituted alkyl group or aryl group having 1 to 10 carbon atoms, or a group represented by SiR 3 . R independently represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group, a halogen atom, or a siloxane residue. In this case, examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, the alkoxy group, and the halogen atom include those similar to R 6 in the formula (5) described later. Examples of the siloxane residue include a group in which one hydrogen atom bonded to a silicon atom is eliminated in formula (4) described later. X is cyclopentadiene, cyclohexadiene, cyclooctatetraene or a part (one or two or more) or all of hydrogen atoms bonded to carbon atoms of these groups by hydroxy group, cyano group, halogen atom, etc. A substituted or unsubstituted aliphatic unsaturated group having 4 to 10 carbon atoms, which is substituted or unsubstituted with a group selected from a substituted hydroxypropyl group, cyanoethyl group, 1-chloropropyl group, 3,3,3-trifluoropropyl group, etc. A ligand formed from an anion, porphine, or phthalocyanine that forms a salt such as a cyclic product, trispyrazolyl borate, tetrafluoroborate, hexafluorophosphate. Of these, cyclopentadienyl anion is preferable. Y affects the oxidation number of iron atoms selected from ammonia molecules, carbonyl molecules, oxygen atoms, oxygen molecules, amine molecules, phosphine molecules such as triphenylphosphine, phosphite molecules such as triethyl phosphite and triphenyl phosphite. It is a ligand that does not give.
s, t, and u are 0 <s ≦ 3, 0 ≦ t <2, and 0 ≦ u ≦ 12. s is greater than 0 and t and u are 0 or more, but s, t and u are numbers that make the entire metal salt neutral, and s and t are divalent or 4 oxidation numbers of iron atoms. It is a number that gives a value. Preferably, R 1 is a hydrogen atom, or a methyl group, an ethyl group, a phenyl group, an alkyl group or an aryl group having 1 to 8 carbon atoms such as a pyridyl group, X is denoted by C 5 R 2 5, R 2 is hydrogen An atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, and Y is a carbonyl molecule or a phosphine molecule such as triphenylphosphine.
ｓ、ｔ、ｕは、０＜ｓ≦３、０≦ｔ＜２、０≦ｕ≦１２である。ｓは０より大きく、ｔ、ｕは０以上であるが、ｓ、ｔ、ｕは金属塩全体が中性となるような数で、更にｓ、ｔは鉄原子の酸化数が２価又は４価となるような数である。好ましくは、Ｒ1が水素原子、又はメチル基、エチル基、フェニル基、ピリジル基などの炭素数１～８のアルキル基又はアリール基、ＸはＣ5Ｒ2 5で表記され、Ｒ2は水素原子、メチル基、エチル基等の炭素数１～６の１価炭化水素基、Ｙはカルボニル分子、又はトリフェニルホスフィンなどのホスフィン分子である。 R 1 is independently a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a phenyl group or a pyridyl group, or a part of hydrogen atoms bonded to a carbon atom of these groups ( 1 or 2 or more) or all of them are selected from a hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, a 3,3,3-trifluoropropyl group, etc. substituted with a hydroxy group, a cyano group, a halogen atom, etc. An unsubstituted or substituted alkyl group or aryl group having 1 to 10 carbon atoms, or a group represented by SiR 3 . R independently represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group, a halogen atom, or a siloxane residue. In this case, examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, the alkoxy group, and the halogen atom include those similar to R 6 in the formula (5) described later. Examples of the siloxane residue include a group in which one hydrogen atom bonded to a silicon atom is eliminated in formula (4) described later. X is cyclopentadiene, cyclohexadiene, cyclooctatetraene or a part (one or two or more) or all of hydrogen atoms bonded to carbon atoms of these groups by hydroxy group, cyano group, halogen atom, etc. A substituted or unsubstituted aliphatic unsaturated group having 4 to 10 carbon atoms, which is substituted or unsubstituted with a group selected from a substituted hydroxypropyl group, cyanoethyl group, 1-chloropropyl group, 3,3,3-trifluoropropyl group, etc. A ligand formed from an anion, porphine, or phthalocyanine that forms a salt such as a cyclic product, trispyrazolyl borate, tetrafluoroborate, hexafluorophosphate. Of these, cyclopentadienyl anion is preferable. Y affects the oxidation number of iron atoms selected from ammonia molecules, carbonyl molecules, oxygen atoms, oxygen molecules, amine molecules, phosphine molecules such as triphenylphosphine, phosphite molecules such as triethyl phosphite and triphenyl phosphite. It is a ligand that does not give.
s, t, and u are 0 <s ≦ 3, 0 ≦ t <2, and 0 ≦ u ≦ 12. s is greater than 0 and t and u are 0 or more, but s, t and u are numbers that make the entire metal salt neutral, and s and t are divalent or 4 oxidation numbers of iron atoms. It is a number that gives a value. Preferably, R 1 is a hydrogen atom, or a methyl group, an ethyl group, a phenyl group, an alkyl group or an aryl group having 1 to 8 carbon atoms such as a pyridyl group, X is denoted by C 5 R 2 5, R 2 is hydrogen An atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, and Y is a carbonyl molecule or a phosphine molecule such as triphenylphosphine.
鉄錯体化合物として、下記一般式（２）
Ｃ5Ｒ2 5－Ｆｅ－Ｒ3 s（ＣＯ）u （２）
（Ｒ2、ｓ、ｕは上記の通り、Ｒ3は水素原子、炭素数１～８のアルキル基又はアリール基、又はＳｉＲ3（Ｒは上記の通り）を示す。）
で示されるものが特に好ましく、更に好ましくは、下記一般式（３）
Ｃ5Ｈ5－Ｆｅ－ＣＨ3（ＣＯ）2 （３）
で示されるジカルボニルシクロペンタジエニルメチル鉄である。或いは下記一般式（４）
Ｃ5Ｈ5－Ｆｅ－（ＳｉＲ3）2（Ｈ）（ＣＯ） （４）
（Ｒは上記の通りであるが、特にトリアルキルシリル基、とりわけトリメチルシリル基が好ましい。）
で示されるものである。 As an iron complex compound, the following general formula (2)
C 5 R 2 5 -Fe-R 3 s (CO) u (2)
(R 2 , s and u are as described above, R 3 is a hydrogen atom, an alkyl or aryl group having 1 to 8 carbon atoms, or SiR 3 (R is as described above).)
Particularly preferred are those represented by the following general formula (3):
C 5 H 5 —Fe—CH 3 (CO) 2 (3)
It is dicarbonylcyclopentadienylmethyliron shown by these. Or the following general formula (4)
C 5 H 5 —Fe— (SiR 3 ) 2 (H) (CO) (4)
(R is as described above, and a trialkylsilyl group, particularly a trimethylsilyl group is particularly preferable.)
It is shown by.
Ｃ5Ｒ2 5－Ｆｅ－Ｒ3 s（ＣＯ）u （２）
（Ｒ2、ｓ、ｕは上記の通り、Ｒ3は水素原子、炭素数１～８のアルキル基又はアリール基、又はＳｉＲ3（Ｒは上記の通り）を示す。）
で示されるものが特に好ましく、更に好ましくは、下記一般式（３）
Ｃ5Ｈ5－Ｆｅ－ＣＨ3（ＣＯ）2 （３）
で示されるジカルボニルシクロペンタジエニルメチル鉄である。或いは下記一般式（４）
Ｃ5Ｈ5－Ｆｅ－（ＳｉＲ3）2（Ｈ）（ＣＯ） （４）
（Ｒは上記の通りであるが、特にトリアルキルシリル基、とりわけトリメチルシリル基が好ましい。）
で示されるものである。 As an iron complex compound, the following general formula (2)
C 5 R 2 5 -Fe-R 3 s (CO) u (2)
(R 2 , s and u are as described above, R 3 is a hydrogen atom, an alkyl or aryl group having 1 to 8 carbon atoms, or SiR 3 (R is as described above).)
Particularly preferred are those represented by the following general formula (3):
C 5 H 5 —Fe—CH 3 (CO) 2 (3)
It is dicarbonylcyclopentadienylmethyliron shown by these. Or the following general formula (4)
C 5 H 5 —Fe— (SiR 3 ) 2 (H) (CO) (4)
(R is as described above, and a trialkylsilyl group, particularly a trimethylsilyl group is particularly preferable.)
It is shown by.
即ち、下記式（Ａ）、（Ｃ）で示されるものが特に有効に用いられる。
That is, those represented by the following formulas (A) and (C) are particularly effectively used.
ここで、以下の理論に限定されるものではないが、（Ａ）は触媒前駆体であり、実際の触媒活性種は（Ｂ）であると思われる。（Ａ）を出発錯体としてこれとヒドロシランが反応して（Ｂ）が生成し、これにオレフィンとヒドロシランが順次反応してヒドロシリル化反応が起こっていると考えられる。一方、（Ａ）に例えばヒドロシランを２当量反応させると錯体（Ｃ）が生成し、この錯体は溶液中で加熱すると鉄上からシリル基とヒドリドが還元的脱離して（Ｂ）を生じるもので、従って（Ｃ）もオレフィンのヒドロシリル化反応の触媒前駆体となり、錯体（Ｃ）はＩＶ価鉄錯体である。
Here, although not limited to the following theory, (A) is a catalyst precursor, and the actual catalytically active species is considered to be (B). It is considered that (B) is formed by reacting (A) with the starting complex and hydrosilane, and olefin and hydrosilane are sequentially reacted with this to cause a hydrosilylation reaction. On the other hand, when (A) is reacted with, for example, 2 equivalents of hydrosilane, a complex (C) is formed, and when this complex is heated in solution, the silyl group and hydride are reductively eliminated from the iron to yield (B). Therefore, (C) is also a catalyst precursor for the hydrosilylation reaction of olefin, and complex (C) is an IV valent iron complex.
本発明に係るヒドロシリル化反応によるＳｉ－Ｃ結合を有する有機化合物の製造においては、≡Ｓｉ－Ｈ基を持つケイ素化合物、炭素－炭素多重結合基を持つ有機化合物、ヒドロシリル化反応用触媒として一般式（１）で示される鉄錯体化合物を用い、必要に応じて有機溶媒を用いることで、Ｓｉ－Ｃ結合を有する有機化合物の製造が可能である。より好適にヒドロシリル化反応によりＳｉ－Ｃ結合を有する有機化合物を製造するための各成分を下記に記載する。
In the production of an organic compound having a Si—C bond by a hydrosilylation reaction according to the present invention, a silicon compound having an ≡Si—H group, an organic compound having a carbon-carbon multiple bond group, a general formula as a catalyst for a hydrosilylation reaction By using the iron complex compound represented by (1) and using an organic solvent as necessary, an organic compound having a Si—C bond can be produced. Each component for producing an organic compound having a Si—C bond more suitably by a hydrosilylation reaction is described below.
≡Ｓｉ－Ｈ基を持つケイ素化合物としては、以下に示す成分（Ａ）、（Ｂ）を例示することができる。
成分（Ａ）は、下記一般式（４）で示されるオルガノハイドロジェンポリシロキサンである。
Examples of silicon compounds having ≡Si—H groups include the following components (A) and (B).
Component (A) is an organohydrogenpolysiloxane represented by the following general formula (4).
成分（Ａ）は、下記一般式（４）で示されるオルガノハイドロジェンポリシロキサンである。
Component (A) is an organohydrogenpolysiloxane represented by the following general formula (4).
Ｒ4は独立に水素原子、又は非置換もしくは置換の炭素数１～１０の１価炭化水素基であり、脂肪族不飽和結合を有さない、例えばメチル基、エチル基、プロピル基等のアルキル基、フェニル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基、３，３，３－トリフルオロプロピル基等のハロゲン置換アルキル基などが挙げられる。Ｒ5は独立に非置換又は置換の炭素数１～１０の１価炭化水素基であり、脂肪族不飽和結合を有さないもので、１価炭化水素基としてはメチル基、エチル基、プロピル基等のアルキル基、フェニル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基、３，３，３－トリフルオロプロピル基等のハロゲン置換アルキル基などが挙げられる。また、ｇ、ｈ、ｉ、ｊは０又は正の数であるが、ｇ、ｈ、ｉのいずれかは必ず正の数で、ｇ＋ｈ＋ｉ＋ｊ≧２かつＳｉ－Ｈ基を１分子中に１個以上有するものである。より好ましくは２≦ｇ＋ｈ＋ｉ＋ｊ≦１，０００であり、更に好ましくは２≦ｇ＋ｈ＋ｉ＋ｊ≦１００であり、Ｓｉ数は２～１，０００、特に２～１００であることが好ましい。また、Ｓｉ－Ｈ数は１以上、特に２～１００であることが好ましい。
R 4 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and does not have an aliphatic unsaturated bond, such as an alkyl group such as a methyl group, an ethyl group, or a propyl group. Groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, and halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl groups. R 5 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, and a propyl group. And an alkyl group such as a phenyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and a halogen-substituted alkyl group such as a 3,3,3-trifluoropropyl group. In addition, g, h, i, and j are 0 or a positive number, but any one of g, h, and i must be a positive number, and g + h + i + j ≧ 2 and at least one Si—H group in one molecule. It is what you have. More preferably, 2 ≦ g + h + i + j ≦ 1,000, still more preferably 2 ≦ g + h + i + j ≦ 100, and the number of Si is preferably 2 to 1,000, particularly 2 to 100. The Si—H number is preferably 1 or more, particularly 2 to 100.
このハイドロジェンポリシロキサンの配合量は、ケイ素原子に結合した水素原子のモル数が炭素－炭素多重結合を有する化合物のアルケニル基の総数に対して０．３～１０倍モルに相当する質量部になるようにすればよく、好ましくは０．５～５倍モルに相当する質量部であればよい。配合量が０．３倍モル未満では、ヒドロシリル化反応のもう一方の反応原料である炭素－炭素多重結合基を持つ有機化合物の残存量が多くなるため実用的ではなく、また１０倍モルを超えて用いても、ヒドロシリル化反応の収率は向上しない。
The amount of hydrogen polysiloxane blended is such that the number of moles of hydrogen atoms bonded to silicon atoms is 0.3 to 10 times the mole of the total number of alkenyl groups of the compound having a carbon-carbon multiple bond. It is sufficient if it is a mass part corresponding to 0.5 to 5 moles. If the blending amount is less than 0.3 times mole, it is not practical because the remaining amount of the organic compound having a carbon-carbon multiple bond group, which is the other reaction raw material of the hydrosilylation reaction, increases, and it exceeds 10 times mole. Even if used, the yield of the hydrosilylation reaction is not improved.
成分（Ｂ）は、下記組成式（５）で示される≡Ｓｉ－Ｈ基を持つシラン化合物である。
Component (B) is a silane compound having an ≡Si—H group represented by the following composition formula (5).
Ｒ6は独立に水素原子、
メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基、ビフェニル基などのアリール基、又はこれらの基の炭素原子に結合している水素原子の一部（１個又は２個以上）又は全部をヒドロキシ基、シアノ基、ハロゲン原子などで置換したトリフルオロメチル基、ヒドロキシプロピル基、シアノエチル基などから選択される非置換又は置換の炭素数１～１０の１価炭化水素基、
メトキシ基、エトキシ基、イソプロポキシ基などの非置換又は置換の炭素数１～１０のアルコキシ基、
フッ素、塩素、臭素、ヨウ素などのハロゲン原子
などが挙げられる。反応性の面からアルキル基、アリール基、アルコキシ基が好ましく、更に好ましくはアルキル基、アルコキシ基である。 R 6 is independently a hydrogen atom,
An alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group or a biphenyl group; or one of hydrogen atoms bonded to a carbon atom of these groups. 1 to 10 carbon atoms of unsubstituted or substituted selected from trifluoromethyl group, hydroxypropyl group, cyanoethyl group, etc., wherein part (one or two or more) or all are substituted with hydroxy group, cyano group, halogen atom, etc. A monovalent hydrocarbon group of
An unsubstituted or substituted alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group;
And halogen atoms such as fluorine, chlorine, bromine and iodine. From the viewpoint of reactivity, an alkyl group, an aryl group, and an alkoxy group are preferable, and an alkyl group and an alkoxy group are more preferable.
メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基、ビフェニル基などのアリール基、又はこれらの基の炭素原子に結合している水素原子の一部（１個又は２個以上）又は全部をヒドロキシ基、シアノ基、ハロゲン原子などで置換したトリフルオロメチル基、ヒドロキシプロピル基、シアノエチル基などから選択される非置換又は置換の炭素数１～１０の１価炭化水素基、
メトキシ基、エトキシ基、イソプロポキシ基などの非置換又は置換の炭素数１～１０のアルコキシ基、
フッ素、塩素、臭素、ヨウ素などのハロゲン原子
などが挙げられる。反応性の面からアルキル基、アリール基、アルコキシ基が好ましく、更に好ましくはアルキル基、アルコキシ基である。 R 6 is independently a hydrogen atom,
An alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group or a biphenyl group; or one of hydrogen atoms bonded to a carbon atom of these groups. 1 to 10 carbon atoms of unsubstituted or substituted selected from trifluoromethyl group, hydroxypropyl group, cyanoethyl group, etc., wherein part (one or two or more) or all are substituted with hydroxy group, cyano group, halogen atom, etc. A monovalent hydrocarbon group of
An unsubstituted or substituted alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group;
And halogen atoms such as fluorine, chlorine, bromine and iodine. From the viewpoint of reactivity, an alkyl group, an aryl group, and an alkoxy group are preferable, and an alkyl group and an alkoxy group are more preferable.
このシラン化合物の使用量は、ケイ素原子に結合した水素原子のモル数が炭素－炭素多重結合を有する化合物のアルケニル基の総数に対して０．３～１０倍モルに相当する質量部になるようにすればよく、好ましくは０．５～５倍モルに相当する質量部であればよい。配合量が０．３倍モル未満では、ヒドロシリル化反応のもう一方の反応原料である炭素－炭素多重結合基を持つ有機化合物の残存量が多くなるため実用的ではなく、また１０倍モルを超えて用いても、ヒドロシリル化反応の収率は向上しない。
The amount of the silane compound used is such that the number of moles of hydrogen atoms bonded to the silicon atom is 0.3 parts by weight corresponding to the total number of alkenyl groups of the compound having a carbon-carbon multiple bond. Preferably, the mass part may correspond to 0.5 to 5 times mol. If the blending amount is less than 0.3 times mol, the remaining amount of the organic compound having a carbon-carbon multiple bond group, which is another reaction raw material of the hydrosilylation reaction, is not practical, and more than 10 times mol. Even if used, the yield of the hydrosilylation reaction is not improved.
炭素－炭素多重結合を持つ有機化合物としては、成分（Ｃ）として、下記組成式（６）で示される有機化合物を例示することができる。
As an organic compound having a carbon-carbon multiple bond, an organic compound represented by the following composition formula (6) can be exemplified as the component (C).
Ｒ7は独立に水素原子、
メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロペンチル基、シクロヘキシル基などのシクロアルキル基、フェニル基、ナフチル基、ビフェニル基などのアリール基、ビニル基、アリル基、ブテニル基などのアルケニル基、又はこれらの基の炭素原子に結合している水素原子の一部又は全部をヒドロキシ基、シアノ基、エポキシ基、ハロゲン原子などで置換したトリフルオロメチル基、ヒドロキシプロピル基、シアノエチル基、３，４－エポキシシクロヘキシル基などから選択される非置換又は置換の炭素数１～１０の１価炭化水素基、
メトキシ基、エトキシ基、イソプロポキシ基などの非置換又は置換の炭素数１～１０のアルコキシ基、
メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基などの非置換又は置換の炭素数１～１０のアルコキシカルボニル基、
アクリル基、フッ素、塩素、臭素、ヨウ素などのハロゲン原子、
ポリエーテル含有基などが挙げられる。 R 7 is independently a hydrogen atom,
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, aryl groups such as phenyl group, naphthyl group, biphenyl group, vinyl group, allyl group, butenyl group, etc. Alkenyl groups, or trifluoromethyl groups, hydroxypropyl groups, cyanoethyl groups, in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with hydroxy groups, cyano groups, epoxy groups, halogen atoms, etc. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms selected from a 3,4-epoxycyclohexyl group and the like;
An unsubstituted or substituted alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group;
An unsubstituted or substituted alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group;
Halogen atoms such as acrylic group, fluorine, chlorine, bromine, iodine,
Examples include polyether-containing groups.
メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロペンチル基、シクロヘキシル基などのシクロアルキル基、フェニル基、ナフチル基、ビフェニル基などのアリール基、ビニル基、アリル基、ブテニル基などのアルケニル基、又はこれらの基の炭素原子に結合している水素原子の一部又は全部をヒドロキシ基、シアノ基、エポキシ基、ハロゲン原子などで置換したトリフルオロメチル基、ヒドロキシプロピル基、シアノエチル基、３，４－エポキシシクロヘキシル基などから選択される非置換又は置換の炭素数１～１０の１価炭化水素基、
メトキシ基、エトキシ基、イソプロポキシ基などの非置換又は置換の炭素数１～１０のアルコキシ基、
メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基などの非置換又は置換の炭素数１～１０のアルコキシカルボニル基、
アクリル基、フッ素、塩素、臭素、ヨウ素などのハロゲン原子、
ポリエーテル含有基などが挙げられる。 R 7 is independently a hydrogen atom,
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, aryl groups such as phenyl group, naphthyl group, biphenyl group, vinyl group, allyl group, butenyl group, etc. Alkenyl groups, or trifluoromethyl groups, hydroxypropyl groups, cyanoethyl groups, in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with hydroxy groups, cyano groups, epoxy groups, halogen atoms, etc. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms selected from a 3,4-epoxycyclohexyl group and the like;
An unsubstituted or substituted alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group;
An unsubstituted or substituted alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group;
Halogen atoms such as acrylic group, fluorine, chlorine, bromine, iodine,
Examples include polyether-containing groups.
また、１，２位の異なる炭素原子上のＲ7基が１個ずつ少ないアセチレン構造を形成したり、Ｒ7同士が結合して環状構造を形成してもよく、例えばシクロペンテン、シクロヘキセン、ノルボルネン、ノルボルナジエン、ビシクロ［２，２，２］オクテン、インデン等が挙げられ、これらの環状構造の炭素原子に結合した水素原子の一部（１個又は２個以上）又は全部が更にメチル基、エチル基、プロピル基等のアルキル基、シクロペンチル基、シクロヘキシル基などのシクロアルキル基、フェニル基、ナフチル基、ビフェニル基などのアリール基、ビニル基、アリル基、ブテニル基などのアルケニル基、又はこれらの基の炭素原子に結合している水素原子の一部又は全部をヒドロキシ基、シアノ基、エポキシ基、ハロゲン原子などで置換したトリフルオロメチル基、ヒドロキシプロピル基、シアノエチル基、３，４－エポキシシクロヘキシル基などから選択される非置換又は置換の炭素数１～１０の１価炭化水素基などで置換されたもの、メトキシ基、エトキシ基、イソプロポキシ基などの非置換又は置換の炭素数１～１０のアルコキシ基などで置換されたもの、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基などの非置換又は置換の炭素数１～１０のアルコキシカルボニル基などで置換されたもの、更にアクリル基、フッ素、塩素、臭素、ヨウ素などのハロゲン原子、ポリエーテル含有基などで置換されたものも含む。
In addition, an acetylene structure in which R 7 groups on different carbon atoms at the 1 and 2 positions are small, or R 7 may be bonded to each other to form a cyclic structure. For example, cyclopentene, cyclohexene, norbornene, Norbornadiene, bicyclo [2,2,2] octene, indene and the like, and a part (one or two or more) or all of hydrogen atoms bonded to carbon atoms of these cyclic structures are further methyl group, ethyl group Alkyl groups such as propyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group, naphthyl group and biphenyl group, alkenyl groups such as vinyl group, allyl group and butenyl group, or Some or all of the hydrogen atoms bonded to the carbon atom are replaced with hydroxy groups, cyano groups, epoxy groups, halogen atoms, etc. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms selected from a trifluoromethyl group, a hydroxypropyl group, a cyanoethyl group, a 3,4-epoxycyclohexyl group, a methoxy group, An unsubstituted or substituted alkoxy group having 1 to 10 carbon atoms such as an ethoxy group or an isopropoxy group, an unsubstituted or substituted carbon atom having 1 to 10 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group; Those substituted with 10 alkoxycarbonyl groups, and those further substituted with acrylic groups, halogen atoms such as fluorine, chlorine, bromine and iodine, polyether-containing groups and the like are also included.
反応性の面からアルケニル基、アルキル基、アリール基、アルコキシ基が好ましく、更に好ましくはアルケニル基、アルキル基、アルコキシ基である。また炭素－炭素多重結合の置換様式は、好ましくは二置換、一置換、更に好ましくは一置換オレフィンが好適である。
From the viewpoint of reactivity, an alkenyl group, an alkyl group, an aryl group, and an alkoxy group are preferable, and an alkenyl group, an alkyl group, and an alkoxy group are more preferable. The substitution pattern of the carbon-carbon multiple bond is preferably disubstituted, monosubstituted, more preferably monosubstituted olefin.
成分（Ｄ）は、新規なヒドロシリル化反応用触媒であり、上記一般式（１）で示される鉄錯体である。
上記の鉄触媒は、成分（Ｃ）中のアルケニル基総数に対して０．０００１～１０倍モル、好ましくは０．００１～１倍モルが好適に使用できる。 Component (D) is a novel catalyst for hydrosilylation reaction, and is an iron complex represented by the above general formula (1).
The above iron catalyst can be suitably used in an amount of 0.0001 to 10-fold mol, preferably 0.001 to 1-fold mol based on the total number of alkenyl groups in component (C).
上記の鉄触媒は、成分（Ｃ）中のアルケニル基総数に対して０．０００１～１０倍モル、好ましくは０．００１～１倍モルが好適に使用できる。 Component (D) is a novel catalyst for hydrosilylation reaction, and is an iron complex represented by the above general formula (1).
The above iron catalyst can be suitably used in an amount of 0.0001 to 10-fold mol, preferably 0.001 to 1-fold mol based on the total number of alkenyl groups in component (C).
またＳｉ－Ｃ結合を有する有機化合物の製造に関しては、任意で有機溶剤を使用することができる。有機溶剤としてはヒドロシリル化反応に関与しない有機溶剤、好ましくは炭化水素系、更に好ましくはヘプタン、オクタン、トルエンである。
Also, an organic solvent can be optionally used for the production of an organic compound having a Si—C bond. The organic solvent is an organic solvent that does not participate in the hydrosilylation reaction, preferably a hydrocarbon type, more preferably heptane, octane, or toluene.
上記のヒドロシリル化反応によるＳｉ－Ｃ結合を有する有機化合物の製造は、反応温度として２０～１５０℃、好ましくは５０～１２０℃である。
The production of the organic compound having an Si—C bond by the hydrosilylation reaction is 20 to 150 ° C., preferably 50 to 120 ° C. as the reaction temperature.
以下、実施例を示し、本発明を具体的に説明するが、本発明はこれによって限定されるものではない。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
［新規なヒドロシリル化反応用触媒を用いた有機ケイ素化合物の製造］
下記に新規なヒドロシリル化反応用触媒を用いた有機ケイ素化合物の製造について記載する。 [Production of organosilicon compound using novel hydrosilylation catalyst]
The production of an organosilicon compound using a novel hydrosilylation reaction catalyst is described below.
下記に新規なヒドロシリル化反応用触媒を用いた有機ケイ素化合物の製造について記載する。 [Production of organosilicon compound using novel hydrosilylation catalyst]
The production of an organosilicon compound using a novel hydrosilylation reaction catalyst is described below.
［実施例１］
シュレンク管を窒素雰囲気下にし、Ｃ5Ｈ5Ｆｅ（ＣＯ）2ＣＨ3［ジカルボニルシクロペンタジエニルメチル鉄］２３ｍｇ（０．１１９ｍｍｏｌ）、１－ヘキセン１．４７ｍＬ（１１．８８ｍｍｏｌ）、ペンタメチルジシロキサン０．５８４ｍＬ（２．９７ｍｍｏｌ）にトルエン１ｍＬを添加し、８０℃で４８時間撹拌した。冷却後、反応混合物を減圧濃縮した。得られた残渣をカラムクロマトグラフィー（充填剤：シリカゲル、展開溶媒：ヘキサン）で精製し、生成物２，２，４，４－テトラメチル－３－オキサ－２，４－ジシラデカン（７）を２４４ｍｇ（１．０４ｍｍｏｌ）得た。 [Example 1]
The Schlenk tube was placed under a nitrogen atmosphere, C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron] 23 mg (0.119 mmol), 1-hexene 1.47 mL (11.88 mmol), pentamethyl 1 mL of toluene was added to 0.584 mL (2.97 mmol) of disiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure. The obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane), and 244 mg of the product 2,2,4,4-tetramethyl-3-oxa-2,4-disiladecane (7) was obtained. (1.04 mmol) was obtained.
シュレンク管を窒素雰囲気下にし、Ｃ5Ｈ5Ｆｅ（ＣＯ）2ＣＨ3［ジカルボニルシクロペンタジエニルメチル鉄］２３ｍｇ（０．１１９ｍｍｏｌ）、１－ヘキセン１．４７ｍＬ（１１．８８ｍｍｏｌ）、ペンタメチルジシロキサン０．５８４ｍＬ（２．９７ｍｍｏｌ）にトルエン１ｍＬを添加し、８０℃で４８時間撹拌した。冷却後、反応混合物を減圧濃縮した。得られた残渣をカラムクロマトグラフィー（充填剤：シリカゲル、展開溶媒：ヘキサン）で精製し、生成物２，２，４，４－テトラメチル－３－オキサ－２，４－ジシラデカン（７）を２４４ｍｇ（１．０４ｍｍｏｌ）得た。 [Example 1]
The Schlenk tube was placed under a nitrogen atmosphere, C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron] 23 mg (0.119 mmol), 1-hexene 1.47 mL (11.88 mmol), pentamethyl 1 mL of toluene was added to 0.584 mL (2.97 mmol) of disiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure. The obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane), and 244 mg of the product 2,2,4,4-tetramethyl-3-oxa-2,4-disiladecane (7) was obtained. (1.04 mmol) was obtained.
収率３０％。
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝０．０３（ｓ，６Ｈ，Ｓｉ（ＣＨ 3）2）、０．０６（ｓ，９Ｈ，Ｓｉ（ＣＨ 3）3）、０．５０（ｍ，２Ｈ，Ｓｉ（ＣＨ 2））、０．８８（ｔ，3ＪHH＝６．４Ｈｚ，３Ｈ，ＣＨ 3ＣＨ2）、１．２９（ｍ，８Ｈｚ，（ＣＨ 2）4）． Yield 30%.
1 H NMR (400 MHz, CDCl 3 ) δ = 0.03 (s, 6H, Si (C H 3 ) 2 ), 0.06 (s, 9H, Si (C H 3 ) 3 ), 0.50 (m , 2H, Si (C H 2 )), 0.88 (t, 3 J HH = 6.4 Hz, 3H, C H 3 CH 2 ), 1.29 (m, 8 Hz, (C H 2 ) 4 ).
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝０．０３（ｓ，６Ｈ，Ｓｉ（ＣＨ 3）2）、０．０６（ｓ，９Ｈ，Ｓｉ（ＣＨ 3）3）、０．５０（ｍ，２Ｈ，Ｓｉ（ＣＨ 2））、０．８８（ｔ，3ＪHH＝６．４Ｈｚ，３Ｈ，ＣＨ 3ＣＨ2）、１．２９（ｍ，８Ｈｚ，（ＣＨ 2）4）． Yield 30%.
1 H NMR (400 MHz, CDCl 3 ) δ = 0.03 (s, 6H, Si (C H 3 ) 2 ), 0.06 (s, 9H, Si (C H 3 ) 3 ), 0.50 (m , 2H, Si (C H 2 )), 0.88 (t, 3 J HH = 6.4 Hz, 3H, C H 3 CH 2 ), 1.29 (m, 8 Hz, (C H 2 ) 4 ).
［実施例２］
シュレンク管を窒素雰囲気下にし、Ｃ5Ｈ5Ｆｅ（ＣＯ）2ＣＨ3［ジカルボニルシクロペンタジエニルメチル鉄］２０．７ｍｇ（０．１０７ｍｍｏｌ）、１－オクテン１．６７ｍＬ（１０．６７ｍｍｏｌ）、ペンタメチルジシロキサン０．５２４ｍＬ（２．６７ｍｍｏｌ）にトルエン１ｍＬを添加し、８０℃で４８時間撹拌した。冷却後、反応混合物を減圧濃縮した。得られた残渣をカラムクロマトグラフィー（充填剤：シリカゲル、展開溶媒：ヘキサン）で精製し、生成物２，２，４，４－テトラメチル－３－オキサ－２，４－ジシラドデカン（８）を６２１ｍｇ（２．６６ｍｍｏｌ）得た。 [Example 2]
The Schlenk tube was placed under a nitrogen atmosphere, 20.7 mg (0.107 mmol) of C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron], 1.67 mL (10.67 mmol) of 1-octene, 1 mL of toluene was added to 0.524 mL (2.67 mmol) of pentamethyldisiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure. The obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane) to obtain 621 mg of the product 2,2,4,4-tetramethyl-3-oxa-2,4-disiladodecane (8). (2.66 mmol) was obtained.
シュレンク管を窒素雰囲気下にし、Ｃ5Ｈ5Ｆｅ（ＣＯ）2ＣＨ3［ジカルボニルシクロペンタジエニルメチル鉄］２０．７ｍｇ（０．１０７ｍｍｏｌ）、１－オクテン１．６７ｍＬ（１０．６７ｍｍｏｌ）、ペンタメチルジシロキサン０．５２４ｍＬ（２．６７ｍｍｏｌ）にトルエン１ｍＬを添加し、８０℃で４８時間撹拌した。冷却後、反応混合物を減圧濃縮した。得られた残渣をカラムクロマトグラフィー（充填剤：シリカゲル、展開溶媒：ヘキサン）で精製し、生成物２，２，４，４－テトラメチル－３－オキサ－２，４－ジシラドデカン（８）を６２１ｍｇ（２．６６ｍｍｏｌ）得た。 [Example 2]
The Schlenk tube was placed under a nitrogen atmosphere, 20.7 mg (0.107 mmol) of C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron], 1.67 mL (10.67 mmol) of 1-octene, 1 mL of toluene was added to 0.524 mL (2.67 mmol) of pentamethyldisiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure. The obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane) to obtain 621 mg of the product 2,2,4,4-tetramethyl-3-oxa-2,4-disiladodecane (8). (2.66 mmol) was obtained.
収率８９％。
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝－０．０５（ｓ，６Ｈ，Ｓｉ（ＣＨ 3）2）、－０．０３（ｓ，９Ｈ，Ｓｉ（ＣＨ 3）3）、０．４１（ｍ，２Ｈ，Ｓｉ－ＣＨ 2）、０．７９（ｔ，3ＪHH＝６．６Ｈｚ，３Ｈ，ＣＨ 3ＣＨ2）、１．１７（ｍ，１２Ｈｚ，（ＣＨ 2）6）． Yield 89%.
1 H NMR (400 MHz, CDCl 3 ) δ = −0.05 (s, 6H, Si (C H 3 ) 2 ), −0.03 (s, 9H, Si (C H 3 ) 3 ), 0.41 ( M , 2H, Si—C H 2 ), 0.79 (t, 3 J HH = 6.6 Hz, 3H, C H 3 CH 2 ), 1.17 (m, 12 Hz, (C H 2 ) 6 ) .
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝－０．０５（ｓ，６Ｈ，Ｓｉ（ＣＨ 3）2）、－０．０３（ｓ，９Ｈ，Ｓｉ（ＣＨ 3）3）、０．４１（ｍ，２Ｈ，Ｓｉ－ＣＨ 2）、０．７９（ｔ，3ＪHH＝６．６Ｈｚ，３Ｈ，ＣＨ 3ＣＨ2）、１．１７（ｍ，１２Ｈｚ，（ＣＨ 2）6）． Yield 89%.
1 H NMR (400 MHz, CDCl 3 ) δ = −0.05 (s, 6H, Si (C H 3 ) 2 ), −0.03 (s, 9H, Si (C H 3 ) 3 ), 0.41 ( M , 2H, Si—C H 2 ), 0.79 (t, 3 J HH = 6.6 Hz, 3H, C H 3 CH 2 ), 1.17 (m, 12 Hz, (C H 2 ) 6 ) .
［実施例３］
シュレンク管を窒素雰囲気下にし、Ｃ5Ｈ5Ｆｅ（ＣＯ）2ＣＨ3［ジカルボニルシクロペンタジエニルメチル鉄］２１．１ｍｇ（０．１０９ｍｍｏｌ）、スチレン０．３１１ｍＬ（２．７２ｍｍｏｌ）、ペンタメチルジシロキサン０．５３３ｍＬ（２．７１ｍｍｏｌ）にトルエン１ｍＬを添加し、８０℃で４８時間撹拌した。冷却後、反応混合物を減圧濃縮した。得られた残渣をカラムクロマトグラフィー（充填剤：シリカゲル、展開溶媒：ヘキサン）で精製し、生成物２，２，４，４－テトラメチル－６－フェニル－３－オキサ－２，４－ジシラヘキサン（９）と２，２，４，４－テトラメチル－６－フェニル－３－オキサ－２，４－ジシラヘキサ－５－エン（１０）の混合物３０８ｍｇ得た。 [Example 3]
The Schlenk tube was placed under a nitrogen atmosphere, 21.1 mg (0.109 mmol) of C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron], 0.311 mL (2.72 mmol) of styrene, pentamethyl 1 mL of toluene was added to 0.533 mL (2.71 mmol) of disiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure. The obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane), and the product 2,2,4,4-tetramethyl-6-phenyl-3-oxa-2,4-disilahexane ( 9) and 2,2,4,4-tetramethyl-6-phenyl-3-oxa-2,4-disilahex-5-ene (10) 308 mg were obtained.
シュレンク管を窒素雰囲気下にし、Ｃ5Ｈ5Ｆｅ（ＣＯ）2ＣＨ3［ジカルボニルシクロペンタジエニルメチル鉄］２１．１ｍｇ（０．１０９ｍｍｏｌ）、スチレン０．３１１ｍＬ（２．７２ｍｍｏｌ）、ペンタメチルジシロキサン０．５３３ｍＬ（２．７１ｍｍｏｌ）にトルエン１ｍＬを添加し、８０℃で４８時間撹拌した。冷却後、反応混合物を減圧濃縮した。得られた残渣をカラムクロマトグラフィー（充填剤：シリカゲル、展開溶媒：ヘキサン）で精製し、生成物２，２，４，４－テトラメチル－６－フェニル－３－オキサ－２，４－ジシラヘキサン（９）と２，２，４，４－テトラメチル－６－フェニル－３－オキサ－２，４－ジシラヘキサ－５－エン（１０）の混合物３０８ｍｇ得た。 [Example 3]
The Schlenk tube was placed under a nitrogen atmosphere, 21.1 mg (0.109 mmol) of C 5 H 5 Fe (CO) 2 CH 3 [dicarbonylcyclopentadienylmethyliron], 0.311 mL (2.72 mmol) of styrene, pentamethyl 1 mL of toluene was added to 0.533 mL (2.71 mmol) of disiloxane, and the mixture was stirred at 80 ° C. for 48 hours. After cooling, the reaction mixture was concentrated under reduced pressure. The obtained residue was purified by column chromatography (filler: silica gel, developing solvent: hexane), and the product 2,2,4,4-tetramethyl-6-phenyl-3-oxa-2,4-disilahexane ( 9) and 2,2,4,4-tetramethyl-6-phenyl-3-oxa-2,4-disilahex-5-ene (10) 308 mg were obtained.
（９）収率８７％
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝０．０８－０．１２（ｍ，１５Ｈ，Ｓｉ（ＣＨ 3）2，Ｓｉ（ＣＨ 3）3）、０．９０（ｍ，２Ｈ，Ｓｉ－ＣＨ 2）、２．６５（ｍ，２Ｈ，ＰｈＣＨ 2）、７．１５－７．４６（ｍ，５Ｈ，Ｃ6 Ｈ 5）． (9) Yield 87%
1 H NMR (400 MHz, CDCl 3 ) δ = 0.08-0.12 (m, 15 H, Si (C H 3 ) 2 , Si (C H 3 ) 3 ), 0.90 (m, 2H, Si— C H 2 ), 2.65 (m, 2H, PhC H 2 ), 7.15-7.46 (m, 5H, C 6 H 5 ).
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝０．０８－０．１２（ｍ，１５Ｈ，Ｓｉ（ＣＨ 3）2，Ｓｉ（ＣＨ 3）3）、０．９０（ｍ，２Ｈ，Ｓｉ－ＣＨ 2）、２．６５（ｍ，２Ｈ，ＰｈＣＨ 2）、７．１５－７．４６（ｍ，５Ｈ，Ｃ6 Ｈ 5）． (9) Yield 87%
1 H NMR (400 MHz, CDCl 3 ) δ = 0.08-0.12 (m, 15 H, Si (C H 3 ) 2 , Si (C H 3 ) 3 ), 0.90 (m, 2H, Si— C H 2 ), 2.65 (m, 2H, PhC H 2 ), 7.15-7.46 (m, 5H, C 6 H 5 ).
（１０）収率１３％
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝０．０８－０．１２（ｍ，１５Ｈ，Ｓｉ（ＣＨ 3）2，Ｓｉ（ＣＨ 3）3）、６．４２（ｄ，3ＪHH＝１９．６Ｈｚ，１Ｈ，ＣＨ＝ＣＨ）、６．９３（ｄ，3ＪHH＝２２．４Ｈｚ，１Ｈ，ＣＨ＝ＣＨ）、７．１５－７．４６（ｍ，５Ｈ，Ｃ6 Ｈ 5）． (10) Yield 13%
1 H NMR (400 MHz, CDCl 3 ) δ = 0.08-0.12 (m, 15 H, Si (C H 3 ) 2 , Si (C H 3 ) 3 ), 6.42 (d, 3 J HH = 19.6 Hz, 1 H, CH = CH), 6.93 (d, 3 J HH = 22.4 Hz, 1 H, CH = CH), 7.15-7.46 (m, 5 H, C 6 H 5 ).
1Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）δ＝０．０８－０．１２（ｍ，１５Ｈ，Ｓｉ（ＣＨ 3）2，Ｓｉ（ＣＨ 3）3）、６．４２（ｄ，3ＪHH＝１９．６Ｈｚ，１Ｈ，ＣＨ＝ＣＨ）、６．９３（ｄ，3ＪHH＝２２．４Ｈｚ，１Ｈ，ＣＨ＝ＣＨ）、７．１５－７．４６（ｍ，５Ｈ，Ｃ6 Ｈ 5）． (10) Yield 13%
1 H NMR (400 MHz, CDCl 3 ) δ = 0.08-0.12 (m, 15 H, Si (C H 3 ) 2 , Si (C H 3 ) 3 ), 6.42 (d, 3 J HH = 19.6 Hz, 1 H, CH = CH), 6.93 (d, 3 J HH = 22.4 Hz, 1 H, CH = CH), 7.15-7.46 (m, 5 H, C 6 H 5 ).
Claims (7)
- 下記一般式（１）に示す鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｘt－Ｆｅ－Ｒ1 s（Ｙu） （１）
（式中、Ｒ1は水素原子、非置換もしくは置換の炭素数１～１０のアルキル基又はアリール基、又はＳｉＲ3基から形成される鉄原子の酸化数に影響を与える配位子であり、ｓは０＜ｓ≦３である。Ｒは水素原子、非置換又は置換の炭素数１～１０の１価炭化水素基又はアルコキシ基、ハロゲン原子、又はシロキサン残基を示す。
Ｘは鉄原子の酸化数に影響を与える配位子であって、非置換又は置換の炭素数４～１０の脂肪族不飽和基を有する環状体、トリスピラゾリルボレート，テトラフルオロボレート，ヘキサフルオロホスフェート、及びポルフィン、フタロシアニンから選ばれる。ｔは０≦ｔ＜２である。
Ｙはアンモニア分子、カルボニル分子、酸素原子、酸素分子、アミン分子、ホスフィン分子、又はホスファイト分子から形成される鉄原子の酸化数に影響を与えない配位子であり、ｕは０≦ｕ≦１２である。
ｓは０より大きく、ｔ、ｕは０以上であるが、ｓ、ｔ、ｕは金属塩全体が中性となるような数で、更にｓ、ｔは鉄原子の酸化数が２価又は４価となるような数である。） A catalyst for hydrosilylation reaction comprising an iron complex compound represented by the following general formula (1).
X t —Fe—R 1 s (Y u ) (1)
(In the formula, R 1 is a hydrogen atom, an unsubstituted or substituted alkyl or aryl group having 1 to 10 carbon atoms, or a ligand that affects the oxidation number of an iron atom formed from a SiR 3 group; s is 0 <s ≦ 3 R represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or alkoxy group, a halogen atom, or a siloxane residue.
X is a ligand that affects the oxidation number of the iron atom, and is an unsubstituted or substituted cyclic compound having a C 4-10 aliphatic unsaturated group, trispirazolyl borate, tetrafluoroborate, hexafluorophosphate , And porphine and phthalocyanine. t is 0 ≦ t <2.
Y is a ligand that does not affect the oxidation number of iron atoms formed from ammonia molecules, carbonyl molecules, oxygen atoms, oxygen molecules, amine molecules, phosphine molecules, or phosphite molecules, and u is 0 ≦ u ≦ 12.
s is greater than 0 and t and u are 0 or more, but s, t and u are numbers that make the entire metal salt neutral, and s and t are divalent or 4 oxidation numbers of iron atoms. It is a number that gives a value. ) - 上記鉄錯体化合物が、下記一般式（２）で表される化合物である請求項１記載の鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｃ5Ｒ2 5－Ｆｅ－Ｒ3 s（ＣＯ）u （２）
（式中、Ｒ2は水素原子又は炭素数１～６の１価炭化水素基、Ｒ3は水素原子、炭素数１～８のアルキル基又はアリール基、又はＳｉＲ3基（Ｒは上記の通り）を示す。ｓ、ｕは上記の通り。） The hydrosilylation catalyst comprising an iron complex compound according to claim 1, wherein the iron complex compound is a compound represented by the following general formula (2).
C 5 R 2 5 -Fe-R 3 s (CO) u (2)
(Wherein R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R 3 is a hydrogen atom, an alkyl group or aryl group having 1 to 8 carbon atoms, or a SiR 3 group (R is as defined above) S and u are as described above.) - 上記鉄錯体化合物が、下記一般式（３）で表される化合物である請求項２記載の鉄錯体化合物からなるヒドロシリル化反応用触媒。
Ｃ5Ｈ5－Ｆｅ－ＣＨ3（ＣＯ）2 （３） The catalyst for hydrosilylation reaction comprising the iron complex compound according to claim 2, wherein the iron complex compound is a compound represented by the following general formula (3).
C 5 H 5 —Fe—CH 3 (CO) 2 (3) - ≡Ｓｉ－Ｈ基を持つケイ素化合物と炭素－炭素多重結合基を持つ有機化合物を原料とし、請求項１～３のいずれか１項記載の鉄錯体化合物からなるヒドロシリル化反応用触媒の存在下、有機溶媒の存在又は不存在の条件で、ヒドロシリル化反応によりＳｉ－Ｃ結合を有する有機化合物を得ることを特徴とするＳｉ－Ｃ結合を有する有機化合物の製造方法。 A silicon compound having a ≡Si-H group and an organic compound having a carbon-carbon multiple bond group as raw materials, and in the presence of a hydrosilylation reaction catalyst comprising an iron complex compound according to any one of claims 1 to 3, A method for producing an organic compound having an Si-C bond, wherein an organic compound having an Si-C bond is obtained by a hydrosilylation reaction in the presence or absence of an organic solvent.
- ≡Ｓｉ－Ｈ基を持つケイ素化合物がシラン化合物又はポリシロキサンであることを特徴とする請求項４記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。 5. The method for producing an organic compound having an Si—C bond according to claim 4, wherein the silicon compound having an ≡Si—H group is a silane compound or polysiloxane.
- 炭素－炭素多重結合基を持つ有機化合物が、炭化水素基を有する有機化合物から選択されることを特徴とする請求項４又は５記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。 6. The method for producing an organic compound having a Si—C bond according to claim 4, wherein the organic compound having a carbon-carbon multiple bond group is selected from organic compounds having a hydrocarbon group.
- 有機溶剤が炭化水素系有機化合物である請求項４～６のいずれか１項記載のＳｉ－Ｃ結合を有する有機化合物の製造方法。 The method for producing an organic compound having a Si-C bond according to any one of claims 4 to 6, wherein the organic solvent is a hydrocarbon-based organic compound.
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| US8415443B2 (en) | 2009-07-10 | 2013-04-09 | Momentive Performance Materials Inc. | Hydrosilylation catalysts |
| WO2013081794A1 (en) * | 2011-12-01 | 2013-06-06 | Dow Corning Corporation | Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use |
| KR20170042319A (en) | 2014-08-12 | 2017-04-18 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Hydrosilylation reaction catalyst |
| KR20170042681A (en) | 2014-08-19 | 2017-04-19 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Hydrosilylation iron catalyst |
| KR20180030080A (en) | 2015-07-14 | 2018-03-21 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Hydrosilylation reaction catalyst |
| US10000515B2 (en) | 2014-08-12 | 2018-06-19 | Kyushu University, National University Corporation | Hydrosilylation reaction catalyst |
| WO2018159595A1 (en) | 2017-02-28 | 2018-09-07 | 国立大学法人九州大学 | Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction |
| KR20180108656A (en) | 2016-01-22 | 2018-10-04 | 신에쓰 가가꾸 고교 가부시끼가이샤 | The novel isocyanide compound and the hydrosilylation reaction catalyst |
| CN110234679A (en) * | 2016-12-23 | 2019-09-13 | 埃肯有机硅法国简易股份公司 | Can be used as silicon composition hydrosilylation, dehydrogenation it is silylated and crosslinking catalyst cobalt compound |
| FR3126417A1 (en) * | 2021-08-31 | 2023-03-03 | Elkem Silicones France Sas | Hydrosilylation process catalyzed by an iron complex |
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- 2009-07-29 WO PCT/JP2009/063498 patent/WO2010016416A1/en active Application Filing
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| CN103958059A (en) * | 2011-12-01 | 2014-07-30 | 道康宁公司 | Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use |
| JP2015510494A (en) * | 2011-12-01 | 2015-04-09 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use |
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