JP6578211B2 - Method for producing solid catalyst by adding metal oxide to metal complex - Google Patents

Description

The present invention relates to a solid catalyst and a method for producing an iridium catalyst eluting from a solid catalyst into a solution, a method for producing a silyl group-substituted unsaturated compound using a catalyst, and more particularly to a method for producing a silyl group-substituted unsaturated compound using an iridium catalyst. is there.
The present invention also relates to a method for recovering and reusing an iridium catalyst.

A method for producing silylalkenes, which are industrially important basic compounds as raw materials for various organosilicon polymers and as raw materials for synthesis of unsaturated compounds, by dehydrogenation silylation reaction using hydrosilanes and alkenes as raw materials, hydrosilanes and It is an excellent technique with high atomic efficiency that does not require prior activation of alkenes.

  The catalyst in the organic synthesis reaction is largely divided into a homogeneous catalyst and a heterogeneous catalyst. A complex catalyst, which is a typical homogeneous catalyst, has an advantage that it is easy to realize a highly efficient and highly selective reaction, and is therefore often used for organic synthesis that requires precise control. A method for producing silylalkenes utilizing a homogeneous rhodium complex catalyst (Non-patent Documents 1 and 2) or a palladium complex catalyst (Non-patent Document 3) has already been found and reported. 1) The catalyst manufacturing process is complicated, high environmental impact and high cost, 2) separation and recovery and reuse of the catalyst are difficult, and metal contamination into the product becomes a problem 3) Generally chemical and heat There are serious and essential problems in industrialization such as being unstable and difficult to handle. Furthermore, this reaction is essentially accompanied by a by-product of silylalkane by a hydrosilylation reaction, and it is necessary to suppress the by-product of silylalkane in order to selectively obtain the desired silylalkene. Therefore, it is indispensable to use harmful phosphine or expensive 1,10-phenanthroline derivative as a ligand or additive that is difficult to separate and recover after the reaction. However, especially when dimethylphenylsilane is used as a raw material. Byproduct of silylalkane is remarkable, and it is extremely difficult to selectively obtain silylalkene.

  On the other hand, among the heterogeneous catalysts, oxide-supported catalysts are often inferior in activity and selectivity, but compared with homogeneous catalysts, 1) the catalyst can be easily separated and recovered and reused. The development of solid catalysts with low activity and selectivity comparable to complex catalysts has been proposed, including the low risk of contamination of metal species into materials, 3) high stability to heat and air, and easy handling. Essential from a chemistry perspective.

From this viewpoint, Wada et al. Developed a cerium oxide-supported ruthenium (Ru / CeO ₂ ) catalyst and an iridium (Ir / CeO ₂ ) catalyst, and found that these are effective for various organic synthesis reactions. -3 and Non-Patent Documents 4-10. These are all a group of catalysts that fall under the category of “metal oxide-supported catalyst”, and the catalyst is calcined to be converted into a metal oxide and used in that form.

WO2014 / 133031 JP2010-189313 JP2010-184881

Activation of the Vinylic d C-H Bond of Styrene by a Rhodium-Siloxide Complex: The Key Step in the Silylative Coupling of Styrene with Vinylsilanes, Marciniec, B .; Walczuk-Gusciora, E .; Pietraszuk, C. Organometallics 2001, 20 , 3423-3428. Cationic Rhodium Complex-Catalyzed Highly Selective Dehydrogenative Silylation of Styrene, Takeuchi, R .; Yasue, H. Organometallics 1996, 15, 2098-2102. Mechanistic Studies of Palladium (II) -Catalyzed Hydrosilation and Dehydrogenative Silation Reactions, LaPointe, A. M .; Rix, F. C .; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906-917. Ruthenium-catalyzed Intermolecular Hydroacylation of Internal Alkynes: The Use of Ceria-supported Catalyst facilitates the Catalyst RecyclingMiura, H .; Wada, K .; Hosokawa, S .; Inoue, M. Chem. Eur. J. 2013, 19, 861- 864 .. Highly Selective Linear Dimerization of Styrenes by Ceria-Supported Ruthenium CatalystsShimura, S .; Miura, H .; Tsukada, S .; Wada, K .; Hosokawa, S .; Inoue, M. ChemCatChem 2012, 4, 2062-2067. Active Ruthenium Catalysts Based on Phosphine-modified Ru / CeO2 for the Selective Addition of Carboxylic Acids to Terminal AlkynesNishiumi, M .; Miura, H .; Wada, K .; Hosokawa, S .; Inoue, M.ACS Catalysis 2012, 2, 1753-1759. Development of Ceria-supported Ruthenium Catalysts for Green Organic Transformation Processes Wada, K .; Miura, H .; Hosokawa, S .; Inoue, M.J. Jpn. Petro. Inst. 2013, 56, 69-79 .. "Development of supported ruthenium catalyst for green molecular conversion process" Kenji Wada; Taiki Miura, Chemical Engineering 2012, 57, 679-684. “Development of effective supported iridium catalyst for selective dehydrogenation silylation reaction to alkene” Fuka Tsukada, Kenji Wada, Saburo Hosokawa, Ryu Abe, 112th Catalysis Conference, 1I30, September 18-20, 2013 Sun (September 18), Akita University Handprint Campus, Akita City (Oral) Fukashi Tsudada Department of Industrial Chemistry, Faculty of Engineering, Kyoto University 2011 Graduation Thesis

  The present invention does not require the use of harmful substances such as phosphine, which are difficult to recover and reuse, and expensive ligands such as 1,10-phenanthroline, and is a solid catalyst and solid composite that are extremely simple to prepare and easy to regenerate It is an object of the present invention to provide a method for producing a silyl group-substituted unsaturated compound using a catalyst that elutes into a solution.

The present inventors have found a method for producing silylalkenes that are remarkably highly efficient and have a low environmental impact by using a wide range of iridium complexes or iridium salts and rare earth metal oxides such as cerium oxide. It was.
The present invention provides the following iridium catalyst production method, iridium catalyst, silyl group-substituted unsaturated compound production method using the iridium catalyst, and iridium catalyst recovery and reuse method.
Item 1. A method for producing an iridium catalyst, comprising treating an oxide containing a rare earth metal and an iridium compound in a solvent.
Item 2. Item 2. The iridium catalyst according to Item 1, wherein the iridium compound and the hydrosilane are added to the solvent and heated, and then the oxide containing the rare earth metal is added to treat the iridium compound and the hydrosilane in the solvent. Production method.
Item 3. Item 3. The method for producing an iridium catalyst according to Item 1 or 2, wherein the treatment is mixing an oxide containing a rare earth metal and an iridium compound in a solvent.
Item 4. Item 3. The method for producing an iridium catalyst according to Item 1 or 2, wherein the treatment is impregnating or immersing an oxide containing a rare earth metal in a solvent solution of an iridium compound.
Item 5. Item 3. The method for producing an iridium catalyst according to Item 1 or 2, wherein the oxide containing the rare earth metal and the iridium compound are treated in a solvent and heated.
Item 6. Item 6. The method for producing an iridium catalyst according to any one of Items 1 to 5, wherein the oxide containing a rare earth metal is a rare earth metal oxide or a complex oxide containing a rare earth metal.
Item 7. Item 7. The method for producing an iridium catalyst according to any one of Items 1 to 6, wherein the oxide is cerium oxide.
Item 8. Item 8. The method for producing an iridium catalyst according to any one of Items 1 to 7, wherein the iridium compound is an iridium complex or an iridium salt.
Item 9. Item 8. The iridium compound is IrCl ₃ .xH ₂ O (x = 0 to 3), triacetylacetonatoiridium, Ir ₄ (CO) ₁₂ , bis (cyclopentadienyliridium dichloride) The manufacturing method of iridium catalyst of description.
Item 10. Item 10. An iridium catalyst for producing a silyl group-substituted unsaturated compound obtained by the production method according to any one of items 1 to 9.
Item 11. Item 11. A process for producing a silane compound represented by the general formula (I), comprising reacting the silane compound (1) and the unsaturated compound (2) in the presence of the iridium catalyst according to item 10:

(In the formula, R ¹ represents an R ^1a R ^1b R ^1c Si group, and R ² represents an alkyl group, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a substituted group. A heteroarylalkyl group which may have a group and an aralkyl group which may have a substituent are shown.
R ^1a , R ^1b and R ^1c each independently represent an alkyl group, an alkoxy group, an aryl group which may have a substituent, or a halogen atom. )
Item 12. Add oxide and iridium compound containing rare earth metal in solvent and prepare iridium catalyst by heating if necessary, and use the obtained iridium catalyst for dehydrogenation silylation reaction using hydrosilanes and alkenes as raw materials And collecting the iridium catalyst from the reaction solution by filtration, and further using the collected iridium catalyst for the next dehydrogenation silylation reaction at least once.
Item 13. The first iridium catalyst was prepared by adding an iridium compound, hydrosilanes, and an oxide containing a rare earth metal to the solvent and heating. Hereinafter, at least the recovery of the iridium catalyst and its reuse in the dehydrogenation silylation reaction were performed. Item 13. The method for recovering and reusing an iridium catalyst in the dehydrogenation silylation reaction according to Item 12, which is performed once.
Item 14. An iridium compound, hydrosilanes, alkene and oxide containing rare earth metal are added to the solvent and heated, and the initial iridium catalyst preparation and dehydrogenation silylation reaction are performed simultaneously. Item 13. A method for recovering and reusing an iridium catalyst in a dehydrogenation silylation reaction according to Item 12, wherein the iridium catalyst is reused at least once.
Item 15. The first iridium catalyst was prepared by adding an iridium compound and hydrosilane to the solvent and heating, and further adding an oxide containing a rare earth metal and heating, and in the presence of the obtained iridium catalyst and alkene. Item 15. The dehydrogenated silyl according to any one of Items 12 to 14, wherein a dehydrogenated silylation reaction is performed, and thereafter, the recovery of the iridium catalyst and the reuse for the dehydrogenated silylation reaction are performed at least once. For recovering and reusing an iridium catalyst in an oxidation reaction.

The present invention provides a method for producing silylalkenes, which are industrially important basic compounds as raw materials for various organosilicon polymers and as raw materials for unsaturated compound synthesis, by a dehydrogenation silylation reaction using hydrosilanes and alkenes as raw materials. It is to provide. The method of the present invention is an excellent technique with high atomic efficiency that does not require prior activation of hydrosilanes and alkenes.

The catalyst of the present invention desirably contains no alkali metal such as sodium or potassium in the metal oxide (an alkali metal-free catalyst), and preferably contains no alkaline earth metal.

In the present invention, various iridium complexes or iridium salts that are relatively inexpensive and easily available for the silyl coupling reaction, and a catalyst that elutes into the solution from the solid complex is used in the reaction system. Can do.

  According to the production method of the present invention, it is not necessary to use harmful phosphine, so that phosphine is not mixed into the product.

  Further, the catalyst of the present invention does not require regeneration treatment and can be used repeatedly in batch, semi-batch or continuous reactions.

Furthermore, by using the catalyst of the present invention, the production process of the product can be simplified or omitted by preventing iridium species from being mixed into the produced silylalkene.
The catalyst of the present invention has a remarkably high activity for the dehydrogenation silylation reaction, can be reused without deteriorating the catalytic activity, and is generated with the use of a homogeneous complex catalyst. The problem can be solved.

(A) Effect of addition of metal oxide to Ir (acac) ₃ (B) Effect of addition of metal oxide to Ir (acac) ₃ . (A) Effect of addition of cerium oxide on Ir ₄ (CO) ₁₂ . (B) Effect of addition of cerium oxide on IrCl ₃ xH ₂ O Effect of cerium oxide addition to Ir (acac) _{3 at} high substrate / catalyst ratio Examination of reusability of the catalyst of the present invention

The iridium catalyst of the present invention can be produced by treating an oxide containing a rare earth metal (hereinafter sometimes referred to as “rare earth metal oxide”) and an iridium compound in a solvent. The oxide containing the rare earth metal and the iridium compound may be mixed, or the rare earth metal oxide may be impregnated or immersed in the solvent solution of the iridium compound. The treatment may be performed under heating, or may be performed after the treatment.

The iridium catalyst of the present invention can be produced by treating a rare earth metal oxide and an iridium compound in a solvent, but without adding an alkene, heating a mixture of hydrosilanes, iridium compound and rare earth metal oxide in a solvent. However, a highly active iridium solid catalyst can be obtained. For example, an iridium catalyst can be obtained in a solvent by adding hydrosilanes to an oxide containing a rare earth metal and an iridium compound in a solvent and heating. A mixture of hydrosilanes, an iridium compound and a rare earth metal oxide is heated in a solvent to prepare an iridium catalyst, and a dehydrogenation silylation reaction can also be performed by adding an alkene. In a preferred embodiment of the present invention, a highly active iridium catalyst can be obtained by adding hydrosilanes and an iridium compound to a solvent and pretreating with heating, adding a rare earth metal oxide thereto and heating. Thus, the iridium catalyst of the present invention can be prepared using two components of an iridium compound and a rare earth metal oxide, or can be prepared using three components of an iridium compound, a rare earth metal oxide, and hydrosilanes. it can. When three components are used, any two components (for example, iridium compound and hydrosilane) are added first, and then the remaining one component (for example, rare earth metal oxide) is added regardless of the order of addition to the solvent. In particular, it is preferable to pre-treat with hydrosilanes and an iridium compound, and then to allow the rare earth metal oxide to act.

In this specification, examples of the “oxide containing a rare earth metal” include a rare earth metal oxide such as cerium oxide or a composite oxide containing a rare earth metal and a non-rare earth metal. In this specification, these oxides and composite oxides may be referred to as “rare earth metal-containing oxides”. Preferred oxides containing rare earth metals are cerium oxide, praseodymium oxide, terbium oxide, ytterbium oxide, yttrium oxide, cerium and praseodymium composite oxide, cerium and terbium composite oxide, cerium and ytterbium composite oxide, cerium and It is a complex oxide of yttrium.

In this specification, the “iridium compound” is an excellent iridium catalyst for producing silylalkenes by dehydrogenation silylation reaction using hydrosilanes and alkenes as raw materials by reacting with oxides containing rare earth metals. Which can be at least partially dissolved in a solvent and brought into contact with an oxide containing a rare earth metal to ultimately become the iridium catalyst of the present invention. The iridium compound includes an iridium salt and an iridium complex.

In the present invention, by mixing an oxide containing a rare earth metal and an iridium compound, a catalyst exhibiting catalytic activity and selectivity far exceeding those of a conventional iridium complex, an iridium compound such as an iridium salt, or a rare earth metal oxide-supported iridium. Can be manufactured.

The iridium complex of the present invention may be prepared in a reaction system for producing a silylalkene by a dehydrogenation silylation reaction using hydrosilanes and an alkene as raw materials. It can also be added. The iridium catalyst recovered from the reaction system can be used repeatedly.

Iridium catalyst production method Oxides / complex oxides containing rare earth metals added together with iridium compounds such as iridium complexes and iridium salts generally have high mechanical strength, and wear and powder of the catalyst when used as a catalyst. It is possible to avoid disadvantages such as loss due to chemicalization and product contamination, easy preparation of a catalyst having high activity, high thermal and chemical stability, and other by-products From the point of not producing a product, a rare earth metal oxide or a composite oxide containing these is given.

Examples of rare earth metals include cerium, praseodymium, terbium, ytterbium, yttrium, and the like. These rare earth metal oxides may be used alone or in combination of two or more rare earth metals. Among these metal oxides, cerium oxide or a composite oxide containing the same is preferable from the viewpoints of availability, cost, catalytic activity, and the like.

  Further, the rare earth metal-containing oxide may be a composite oxide with other metal oxides. Here, the “composite oxide” means a composite of a rare earth metal oxide and another metal (especially a transition metal) oxide. The other metal preferably does not contain an alkali metal, and more preferably contains neither an alkali metal nor an alkaline earth metal. Examples of the metal oxide other than the rare earth metal include titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, and copper oxide.

  In the case of using the composite oxide, the content ratio of the metal oxide other than the rare earth metal oxide is not particularly limited as long as the function as a catalyst can be expressed. For example, in the composite oxide, the content is 50% by mass or less. It is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

  Rare earth metal-containing oxides use as their precursors metal salts such as nitrates, oxynitrates, carbonates, oxalates, acetates, etc., and are calcined in the air after hydrolysis or directly pyrolyzed. can get. Preferably, the rare earth metal-containing oxide is obtained by adding a precipitating agent to a solution of a rare earth metal nitrate, oxynitrate, carbonate, oxalate, acetate or the like and firing the resulting precipitate. Can do. Precipitating agents include alkali metal hydroxides such as ammonia, sodium hydroxide, potassium hydroxide, and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrogen carbonates such as sodium bicarbonate and potassium bicarbonate. Examples include salts, amines such as ethylamine, diethylamine, triethylamino, monoethanolamine, diethanolamine, and triethanolamine. The firing temperature for obtaining the rare earth metal-containing oxide is preferably 200 to 700 ° C, more preferably about 300 to 500 ° C.

  As a method for producing the catalyst, "treatment of an oxide containing a rare earth metal and an iridium compound in a solvent" may be performed, and then heating may be performed as necessary. For example, an iridium compound and a rare earth metal-containing oxide are both put in a solvent and mixed, and if necessary, heated in a solvent, or the rare earth metal-containing oxide is impregnated or immersed in an iridium compound solution in a solvent. The iridium catalyst can be produced by heating as necessary. These mixing, impregnation and immersion all correspond to “treating an oxide containing a rare earth metal and an iridium compound in a solvent”. Preferred examples of the solvent include solvents for producing silylalkenes (I) by a dehydrogenation silylation reaction using hydrosilanes (1) and alkenes (2) as raw materials, specifically benzene, toluene, xylene. , Aromatic hydrocarbons such as mesitylene, aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane, nitriles such as acetonitrile, heteroaromatic compounds such as pyridine and imidazole, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as trichloroethane and tetrachloroethane, water, lower alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran and ether Ethers such as diisopropyl ether, glycols such as ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, alkylene glycol mono / dialkyl ethers such as ethylene glycol diethyl ether, glycerin, dioxane Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetic acid and the like. The iridium catalyst used in the present invention can be prepared in a reaction system for producing an unsaturated silane compound represented by the general formula (I), and the solvent used in such a reaction is preferably exemplified as the solvent. .

  In another embodiment of the present invention, the iridium catalyst of the present invention can be obtained by adding an oxide containing an iridium compound, a hydrosilane, and a rare earth metal to a solvent.

  In yet another embodiment of the present invention, an iridium compound, a hydrosilane, an alkene, an oxide containing a rare earth metal, and an alkene compound are added to a solvent, and an iridium catalyst is generated in the reaction system while simultaneously performing a dehydrogenation silylation reaction. You may go.

  Examples of the iridium compound include iridium salts and iridium complexes. Specifically, IrCl_Four, IrCl_Three, IrCl₂, IrBr_Four, IrBr_Three, IrBr₂, IrI_Four, IrI_Three, IrI₂, Iridium salts such as iridium acetate, hexachloroiridic acid [H₂IrCl₆], (NH_Four)₂IrCl₆, (NH_Four)₂IrBr₆, [Ir (CO)₂I]₂, [Ir (CO)₂Cl]₂, [Ir (CO)₂Br]₂, [Ir (CO)₂I₂]^-H⁺, [Ir (CO)₂Br₂]^-H⁺, [Ir (CO)₂I _Four]^-H⁺, [Ir (CH_Three) I_Three(CO)₂]^-H⁺, Ir_Four(CO)₁₂, Ir (acac) (CO)₂, Ir (acac)_Three(“Acac” is acetylacetonato), iridium complexes such as bis (cyclopentadienyliridium dichloride) and the like, and these iridium compounds may be hydrates. Preferred iridium compounds are IrCl_ThreeXH₂O (x = 0-3), triacetylacetonatoiridium, Ir₄(CO)₁₂, Bis (cyclopentadienyliridium dichloride).

  The iridium catalyst of the present invention can be produced by treating (mixing, impregnating, immersing) a rare earth metal-containing oxide in a solvent solution of an iridium compound, but preferably by further heating in a solvent. Can do.

  The ratio of the iridium compound such as an iridium complex or an iridium salt (the amount of the iridium compound added to the solvent) is preferably about 0.001 to 20% by mass based on the addition amount of the rare earth metal-containing oxide. About 1-5 mass% is more preferable, and about 0.08-0.2 mass% is still more preferable. Such a range is preferable in order to reduce the cost of the catalyst and at the same time prevent the catalyst rotational speed from decreasing.

  In a preferred embodiment of the present invention, the iridium compound added together with the rare earth metal-containing oxide is mixed and heated in a solvent (in the preferred embodiment, the raw material and solvent for dehydrogenation silylation), and the iridium catalyst of the present invention is produced. Can be done.

  The iridium compound and the rare earth metal-containing oxide are mixed in a solvent, and then heated as necessary. When not heating, the catalyst of this invention can be obtained by making it react for that much time. The reaction temperature is preferably room temperature or higher, more preferably about 40 to 200 ° C, still more preferably about 80 to 170 ° C, and particularly preferably about 120 to 140 ° C. This reaction temperature is applicable to both iridium catalyst production and dehydrogenation silylation reactions. When preparing an iridium catalyst in a dehydrogenation silylation reaction system using hydrosilanes and alkenes as raw materials, the time required for catalyst synthesis and dehydrogenation silylation reaction should be shortened if the reaction temperature is 40 ° C or higher. Can do. Moreover, the loss of the component with a comparatively low boiling point can be suppressed by setting reaction temperature to 200 degrees C or less. By carrying out the reaction at such a temperature, a highly active iridium catalyst can be obtained. The reaction time required for dehydrogenation silylation is about 30 minutes to 48 hours, preferably about 1 to 24 hours.

  The mixing of the rare earth metal-containing oxide and the iridium compound and the reaction step at the reaction temperature can be performed in air, but may be performed in an inert gas atmosphere. Examples of the inert gas include argon, nitrogen, helium and the like.

  The iridium catalyst supported on the metal oxide produced as described above should be used for the next reaction without separation and recovery after washing, if necessary, after producing the compound of formula (I). Can do.

  Although it does not specifically limit as a cleaning agent used for washing | cleaning, For example, THF, diethyl ether, methanol, ethanol, water, hexane, petroleum ether, or these mixtures etc. are mentioned.

  The iridium catalyst obtained in the present invention may be used as it is as a catalyst when it is generated in a reaction system for producing silylalkenes by a dehydrogenation silylation reaction using hydrosilanes and alkenes as raw materials. In the case of recovering / reusing the catalyst, the temperature of the reaction system is lowered (for example, room temperature), and the oxide containing the rare earth metal may be filtered off in that state. By lowering the temperature of the reaction system, the iridium component is almost completely adsorbed by the oxide containing rare earth metal, so that only iridium below the detection limit exists in the solution, so that the loss of iridium is minimized. It can be recovered and the iridium content in the product can be reduced as much as possible.

  The iridium compound is at least partially dissolved in the solvent, and the oxide containing the rare earth metal exists as an insoluble substance. When these compounds are reacted in a solvent to generate an active iridium compound and filtered, the catalytic activity can be confirmed in both the filtrate and the insoluble matter to be filtered off. Although not wishing to be bound by theory, catalytically active iridium in the filtrate is suitable for dehydrogenation silylation reaction using hydrosilanes and alkenes as raw materials by contacting with oxides containing rare earth metals. The present inventor believes that it has been converted to a catalyst. On the other hand, most of such catalytically active iridium exists in a form adsorbed on the surface of the solvent-insoluble rare earth metal-containing oxide, and when this insoluble matter is added to the reaction system for producing the unsaturated silane compound, In this reaction system, the present inventor believes that a small amount of catalytically active iridium is liberated in the solvent or acts as a highly selective iridium catalyst while adsorbed on the surface of an oxide containing a rare earth metal. Therefore, the iridium catalyst obtained by the method for producing a catalyst of the present invention may be in a form dissolved in a solvent or in a form insoluble in a solvent.

Method for Producing Compound of Formula (I) The present invention relates to a method for producing compound (I) comprising a step of reacting compound (1) and compound (2) in the presence of an iridium catalyst obtained by the above production method. Also related.
The production method of compound (I) is shown in Scheme 1.

（式中、Ｒ^１、Ｒ^２は、前記に定義されるとおりである）

(Wherein R ¹ and R ² are as defined above)

  When the compound of formula (I) is produced in the presence of a solvent, the solvent is a nonpolar solvent such as mesitylene, xylene, toluene, benzene, hexane, n-octane, n-decane; N-methyl-2-pyrrolidone (Hereinafter also referred to as NMP), polar solvents such as N, N-dimethylformamide, THF, dioxane, methylene chloride and the like. Among these, the yield of the compound of formula (I) is improved. A nonpolar solvent is preferable, and specifically, toluene, mesitylene and the like are particularly preferable.

  In the method for producing the compound of formula (I), the reaction temperature is preferably about 40 to 200 ° C, more preferably about 80 to 150 ° C. The reaction time is about 30 minutes to 48 hours, preferably about 1 to 24 hours.

  In the process for producing the compound of formula (I), compound (2) is used in an amount of about 0.5 mol to 10 mol, preferably about 1.6 mol to 2.4 mol, per 1 mol of compound (1).

  The iridium catalyst used in the present invention is a solid catalyst in which an iridium species is adsorbed on a rare earth metal-containing oxide and an iridium species that elutes from the solid into a solution. Performed in a liquid phase process. Therefore, for example, the iridium catalyst supported on the rare earth metal-containing oxide of the present invention is packed in a column or the like, and a starting material or the like is flowed (circulated as necessary) to obtain a compound (I) continuously. It is possible to apply to a method of performing the above, a method of dispersing in a solution and separating a catalyst and a product by filtration or a gradient method after the reaction.

  The compound (I) produced by the production method of the present invention is useful as an organosilicon polymer raw material. In the current process using a homogeneous catalyst, the environmental and energy load is high in the stage of removing the catalyst component from the product. On the other hand, according to the production method using the catalyst of the present invention, it is possible to reduce the cost for removing the catalyst component, no regeneration step is required, and a phosphorus compound such as triphenylphosphine, Since it is not necessary to use an expensive ligand such as 10-phenanthroline, useful utilization can be expected.

  Hereinafter, the present invention will be described in more detail with reference to Reference Examples, Examples and Test Examples, but these do not limit the present invention.

Example 1
1． Experiment 1.1) Catalyst preparation
(Preparation of cerium oxide) 12.6 g of cerium (III) nitrate hexahydrate (29.0 mmol manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 400 mL of ion-exchanged water, and 35 mL of 28% aqueous ammonia was added dropwise and stirred at room temperature for 2 hours. did. After standing for 1 hour or more, the resulting purple precipitate was washed with ion-exchanged water, dried at 80 ° C. overnight, heated in air at 10 ° C./min, and calcined at a predetermined temperature for 30 minutes to obtain cerium oxide. It was. The cerium oxide thus obtained is expressed as, for example, CeO ₂ (NH ₃ , 400) when calcined at 400 ° C. with ammonia water as a precipitant. Moreover, when using sodium hydroxide aqueous solution as a precipitant, 40 mL of 3.0M sodium hydroxide aqueous solution was used instead of ammonia water. The cerium oxide obtained at this time is expressed as, for example, CeO ₂ (NaOH, 400). When NaOH is used as the precipitating agent, a trace amount of Na is contained in cerium oxide.

(Preparation of catalyst of the present invention and comparative catalyst)
To 125 mg of cerium oxide prepared above, triacetylacetonatoiridium (Ir (acac) _3, manufactured by Aldrich, 13 to 0.625 μmol as iridium) is added to a 20 mL reaction container made of Pyrex (registered trademark), and the reaction described below It was subjected to a silyl compound synthesis reaction under conditions.

The comparative catalyst (Ir / CeO ₂ ) was prepared by dissolving triacetylacetonatoiridium (manufactured by Aldrich) in about 10 mL of methanol so that the supported amount was 0.2 to 2% by mass, and adding 1.0 g of cerium oxide at room temperature. It was impregnated, evaporated to dryness, and calcined in air at 300 ° C. for 30 minutes to obtain an iridium (Ir / CeO ₂ ) catalyst supported on cerium oxide. Other supported catalysts were synthesized in the same manner.

1.2) Examination of catalyst A predetermined amount of CeO ₂ (NH ₃ , 400) and triacetylacetonatoiridium were added to a 20 mL Pyrex (registered trademark) reaction vessel containing a magnetic rotor, and after substitution with argon, dimethyl 1.0 mmol of phenylsilane (1a), 3.0 mmol of styrene (1b), tetradecane (C ₁₄ H ₃₀ ) as an internal standard, and 2.0 mL of toluene as a solvent were added, and a reflux cooling device was provided in an argon atmosphere. Reaction was carried out on a hot plate maintained at 120 ° C. for 3 hours to synthesize silylstyrene together with ethylbenzene. Note that a rubber balloon filled with argon was attached to the reaction vessel. The qualitative and quantitative properties of the obtained compound are NMR (EX-400 manufactured by JEOL Ltd.), GC-MS (Parvum2 manufactured by Shimadzu Corporation) and GC (GC14APF manufactured by Shimadzu Corporation). It measured using.

The catalyst and reaction temperature were changed as shown in the following chart, and the dehydrogenation silylation reaction was performed in the same manner.

1.3) Hot filtration test for solid components For the solid catalyst prepared in the reaction system according to this formulation, either the metal species eluted from the solid surface into the solution or the metal species immobilized on the solid surface has catalytic activity. A hot filtration test was conducted to see if it functions as a seed. After reaction for a predetermined time under the conditions shown in 1.2), the suspension being heated was collected with a syringe, and the catalyst was filtered using a syringe filter. At that time, the filtrate was added to the reaction vessel that had been heated in advance, and the reaction was again carried out. Thereafter, the change over time was continued by the same operation as in 1.2).

1.4) Recovery and reuse of solid components
After the reaction under the conditions shown in 1.2), the solid component was collected by centrifugation, washed three times with diethyl ether, dried overnight at 80 ° C. in a vacuum dryer, and then again as a catalyst. Used for the reaction under the conditions shown in 2).

2. Results and discussion (addition effect of metal oxide on Ir (acac) ₃ )
The results of studies using the catalyst of the present invention (Ir (acac) ₃ + CeO ₂ ) and the comparative catalyst (Ir (acac) ₃ ) for the dehydrogenation-type silylation reaction of styrene with dimethylphenylsilane are shown in Formula 1 and FIG. . Here, the amount of Ir in each catalyst is 0.013 mmol (1.3% with respect to the raw material), and the target product in this reaction is Iaa and the by-product is IIaa. CeO ₂ (NH ₃ , 400) was used as cerium oxide unless otherwise specified. According to Non-Patent Document 2, dimethylphenylsilane is the raw material for which the hydrosilylation reaction is most likely to proceed and the development of a catalyst capable of selectively producing only Iaa is required.

When a comparative catalyst (Ir (acac) ₃ only) was used, Iaa was produced in a yield of about 60% and IIaa was produced in a yield of about 10% 3 hours after the start of the reaction, whereas the catalyst of the present invention was used. Markedly improved activity and selectivity, and the yields of Iaa and by-product IIaa 3 hours after the start were 86% and 3%, respectively. On the other hand, when other oxides such as titanium oxide and magnesium oxide and solid bases such as sodium carbonate are added, Iaa selectivity is not improved, and Iaa yield is also significantly improved. No effect was observed. In this reaction, formation of an equivalent amount of ethylbenzene relative to the target product Iaa has been confirmed, and it has been found that the reaction proceeds with hydrogen transfer from the iridium hydride species to styrene. From the above results, it was shown that iridium species having high activity and high selectivity are generated by the specific interaction between Ir (acac) ₃ and cerium oxide.

  The influence of the calcination temperature of cerium oxide added in the catalyst of the present invention was examined. It has been found that the activity and selectivity of the catalyst of the present invention are affected by the firing temperature, and the firing temperature of cerium oxide is more preferably about 400 ° C. When baked at a lower temperature, the activity tended to decrease, and when baked at a higher temperature, the activity was slightly improved, while the Iaa selectivity tended to decrease.

(Additional effect of cerium oxide on various iridium complexes and iridium salts)
The effect of adding cerium oxide on various iridium complexes and iridium salts such as Ir ₄ (CO) ₁₂ and IrCl ₃ .xH ₂ O was examined. The results are shown in FIG. None of the iridium complexes showed any activity in this reaction as they were, but exhibited excellent catalytic activity in the presence of cerium oxide, and Iaa was selectively obtained. In particular, when cerium oxide was added to the Ir ₄ (CO) ₁₂ catalyst, the activity was higher than that of the impregnated supported Ir / CeO ₂ catalyst. On the other hand, IrCl ₃ · xH ₂ is O to use impregnation Ir / CeO ₂ catalyst precursor when IIaa-production of was observed, and this is In the co-existence of cerium oxide IrCl ₃ · xH ₂ O IIaa by-product was significantly suppressed. Thus, the effect of addition of cerium oxide was recognized for a wide range of iridium complexes, and in particular, performance superior to the conventional solid catalyst (impregnated supported Ir / CeO ₂ catalyst) shown in Non-Patent Paper 10 was shown. It was.

(Additional effect of cerium oxide at high substrate / catalyst ratio)
  Ir (acac) in the presence of cerium oxide (125 mg)₃As a result of examining the effect of the amount of catalyst, the catalyst rotation frequency became maximum at around 0.625 μmol. The substrate / catalyst ratio at this time is 1600. FIG. 3 shows the catalyst of the present invention and the comparative catalyst (Ir (acac)) under these conditions. ₃) Shows the results of the study. Ir / CeO impregnated with the same amount of iridium₂The results when using a catalyst are also shown. As shown in FIG. 3, the catalyst of the present invention showed high catalytic activity and superior selectivity over the comparative catalyst group. Thus, it has been found that the catalyst of the present invention maintains excellent selectivity and activity even at a practically high substrate / catalyst ratio. Further, after completion of the reaction, the solid was filtered at room temperature, and the amount of iridium contained in the filtrate was measured with an ICP emission analyzer (iCAP6300 manufactured by Thermo Fisher Scientific Co., Ltd.). It was found that the iridium component was almost completely adsorbed by the oxide containing the rare earth metal by lowering the temperature of.

(Results of hot filtration test of the catalyst of the present invention)
With respect to the catalyst of the present invention (iridium amount 0.625 μmol), the solid was filtered 1 hour after the start of the reaction, and the filtrate was heated again. As a result, the reaction did not stop and almost no by-product IIaa was observed. From this, it is considered that the form of iridium species changes in the initial stage of the reaction due to the interaction between Ir (acac) ₃ and cerium oxide, and these iridium species are eluted into the liquid phase and function as a catalyst.

(Reuse test result of the catalyst of the present invention)
In the study using the catalyst of the present invention (iridium amount 0.625 μmol), the solid after the reaction was recovered, washed and dried, and used again as a catalyst. As shown in FIG. 4, the activity and selectivity decreased. The reaction proceeded smoothly with little to no. Furthermore, it was confirmed that it can be used at least three times without a decrease in activity. That is, it has been found that most iridium species are adsorbed on the surface of cerium oxide after the catalytic reaction and show high activity and selectivity when used again as a solid catalyst in the reaction.

(Influence of alkali metals)
When cerium oxide prepared using NaOH as a precipitant was used, by-product IIaa was hardly suppressed. Thus, when NaCl or KCl was added to the catalyst of the present invention (CeO ₂ (using NH ₃ , 400)) and studied, by-product IIaa was observed in any case. From this, it is considered that the presence of alkali metal promotes the by-production of IIaa, and it has been found that it is more desirable to use cerium oxide containing no alkali metal.

(Examination of application range of raw materials)
Table 1 shows the results of examining the substrate application range in the cross-coupling reaction with dimethylvinylphenylsilane using various styrene derivatives and alkenes.
The reaction with the styrene derivative shown here proceeded smoothly at a reaction temperature of 130 ° C. regardless of these structures and substituents. Although accurate quantification has not been achieved at the present time, it was estimated from the results of GC-MS measurement that the target product was produced in good yield ((). Thus, it was shown that a wide variety of styrene derivatives are applicable. Furthermore, the reaction with the acrylic acid derivative also proceeded (◯). The present inventor confirmed that the reaction between alkene compound and triethylsilane (product: Iba) proceeds in good yield (◎).

(Effect of hydrosilane pretreatment)
In the presence of toluene solvent (2.0 mL) and 1.0 mmol of dimethylphenylsilane (1a), Ir (acac) ₃ (iridium content: 1.25 μmol) was pretreated at 130 ° C. for 90 minutes in an argon atmosphere. When the reaction was carried out by adding 3.0 mmol of styrene (1b) as a substrate and 125 mg of CeO ₂ , a short induction period was observed at the initial stage of the reaction, but the subsequent reaction was smooth without any by-product of IIaa. The yield of Iaa reached 77% 1 hour after the start of the reaction. Thus, it has been found that the catalytic activity is remarkably improved by subjecting the iridium complex to a heat pretreatment in the presence of hydrosilane and then adding CeO ₂ .

Predetermined amounts of CeO ₂ (NH ₃ , 400) and triacetylacetonatoiridium are added to a 20 mL Pyrex (registered trademark) reaction vessel containing a magnetic rotor, and after substitution with argon, dimethylphenylsilane (1a) is 1 1.0 mmol, 3.0 mmol of styrene (1b), tetradecane (C ₁₄ H ₃₀ ) as an internal standard, and 2.0 mL of toluene as a solvent, and a hot plate maintained at 120 ° C. equipped with a reflux cooling device in an argon atmosphere The reaction was carried out for 3 hours above, and silylstyrene was synthesized together with ethylbenzene. Note that a rubber balloon filled with argon was attached to the reaction vessel. The qualitative and quantitative properties of the obtained compound are NMR (EX-400 manufactured by JEOL Ltd.), GC-MS (Parvum2 manufactured by Shimadzu Corporation) and GC (GC14APF manufactured by Shimadzu Corporation). It measured using.

The catalyst obtained by the production method of the present invention does not require the addition of harmful substances such as phosphine and expensive ligands such as 1,10-phenanthroline, can suppress the mixing of iridium species into the product, and has an activity. Since it can be reused repeatedly without losing it, the use of this catalyst solves various problems in the production of silylalkenes possessed by conventional complex catalysts and supported iridium catalysts already reported by the present inventors. Is done.

  It is used as an efficient and low environmental impact manufacturing method for organosilicon polymer raw materials, organic inorganic composite porous material raw materials, pharmaceutical raw materials, agricultural chemical raw materials, liquid crystal materials, electronic materials, etc., but in the current process using homogeneous catalysts The environmental and energy load during the removal of catalyst components from the product is large. In particular, when used as a polymer material for medical use, it is extremely difficult to remove heavy metal species incorporated into the polymer, and future utilization of the present invention that can minimize the mixing of metal species into the product can be expected.

Claims (15)

A method for producing an iridium catalyst for producing a non-fired silyl group-substituted unsaturated compound , comprising treating an oxide containing a rare earth metal and an iridium compound in a solvent to prepare an iridium catalyst in the solvent. The silyl group according to claim 1, wherein the iridium compound and the hydrosilane are added to the solvent and heated, and then the oxide containing the rare earth metal is added to treat the iridium compound and the hydrosilane in the solvent. A method for producing an iridium catalyst for producing a substituted unsaturated compound . The method for producing an iridium catalyst for producing a silyl group-substituted unsaturated compound according to claim 1 or 2, wherein the treatment is mixing an oxide containing a rare earth metal and an iridium compound in a solvent. The method for producing an iridium catalyst for producing a silyl group-substituted unsaturated compound according to claim 1 or 2, wherein the treatment is impregnating or immersing an oxide containing a rare earth metal in a solvent solution of an iridium compound. The method for producing an iridium catalyst for producing a silyl group-substituted unsaturated compound according to claim 1 or 2, wherein the oxide containing the rare earth metal and the iridium compound are treated in a solvent and heated. The method for producing an iridium catalyst for producing a silyl group-substituted unsaturated compound according to any one of claims 1 to 5, wherein the oxide containing a rare earth metal is a rare earth metal oxide or a complex oxide containing a rare earth metal. The method for producing an iridium catalyst for producing a silyl group-substituted unsaturated compound according to any one of claims 1 to 6, wherein the oxide is cerium oxide. The method for producing an iridium catalyst for producing a silyl group-substituted unsaturated compound according to any one of claims 1 to 7, wherein the iridium compound is an iridium complex or an iridium salt. The iridium compound is IrCl ₃ · xH ₂ O (x = 0 to 3), triacetylacetonatoiridium, Ir ₄ (CO) ₁₂ , or bis (cyclopentadienyliridium dichloride). The manufacturing method of the iridium catalyst for silyl group substituted unsaturated compound manufacture of description. The iridium catalyst for silyl group substituted unsaturated compound manufacture obtained by the manufacturing method in any one of Claims 1-9. A process for producing a silane compound represented by the general formula (I), wherein the silane compound (1) and the unsaturated compound (2) are reacted in the presence of the iridium catalyst according to claim 10:

(In the formula, R ¹ represents an R ^1a R ^1b R ^1c Si group, and R ² represents an alkyl group, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a substituted group. A heteroarylalkyl group which may have a group and an aralkyl group which may have a substituent are shown.
R ^1a , R ^1b and R ^1c each independently represent an alkyl group, an alkoxy group, an aryl group which may have a substituent, or a halogen atom. ) Add an oxide containing a rare earth metal and an iridium compound in a solvent, heat as necessary to prepare an iridium catalyst in the solvent, and use the resulting non-fired iridium catalyst as a raw material from hydrosilanes and alkenes The iridium catalyst is recovered from the reaction solution by filtration using the dehydrogenation silylation reaction, and the recovered non-calcined iridium catalyst is further used for the next dehydrogenation silylation reaction at least once. To recover and reuse iridium catalyst. The first iridium catalyst was prepared by adding an iridium compound, hydrosilanes, and an oxide containing a rare earth metal to the solvent and heating. Hereinafter, at least the recovery of the iridium catalyst and its reuse in the dehydrogenation silylation reaction were performed. The method for recovering and reusing an iridium catalyst in the dehydrogenation silylation reaction according to claim 12, wherein the method is performed once. An iridium compound, hydrosilanes, alkene and oxide containing rare earth metal are added to the solvent and heated, and the initial iridium catalyst preparation and dehydrogenation silylation reaction are performed simultaneously. The method for recovering and reusing an iridium catalyst in a dehydrogenation silylation reaction according to claim 12, wherein the recycle to the hydration reaction is performed at least once. The first iridium catalyst was prepared by adding an iridium compound and hydrosilane to the solvent and heating, and further adding an oxide containing a rare earth metal and heating, and in the presence of the obtained iridium catalyst and alkene. The dehydrogenation silylation reaction is performed, and the dehydrogenation according to any one of claims 12 to 14, wherein the recovery of the iridium catalyst and the reuse for the dehydrogenation silylation reaction are performed at least once. A method for recovering and reusing an iridium catalyst in a silylation reaction.

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