Organometallic complex catalyst for olefin metathesis reaction

Abstract

To provide an organometallic complex catalyst with enhanced water resistance in olefin metathesis reactions compared to conventional catalysts.SOLUTION: The present invention provides an organometallic complex catalyst for olefin metathesis reactions with a chemical structure represented by the formula (1) below.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an organometallic complex catalyst for use in olefin metathesis reactions, more particularly to an organometallic complex catalyst having a ligand containing a nitrogen-containing heterocyclic carbene structure and a ruthenium coordination center for use in olefin metathesis reactions. [Background technology]

[0002] Olefin metathesis reactions, such as ring-opening metathesis polymerization of olefin compounds, ring-closing metathesis reactions, cross metathesis reactions of acyclic olefins, homometathesis reactions, and metathesis polymerization of acyclic dienes, are industrially useful reactions.

[0003] Known catalysts for use in olefin metathesis reactions include the second generation Hoveyda-Grubbs catalyst disclosed in Patent Document 1 (JP-A-2004-506755), and the first generation Grubbs catalyst shown in the comparative example.

[0004] In response to this, as disclosed in Patent Document 2 (WO 2023-048084), the present applicant has conducted intensive research, particularly from the viewpoint of obtaining a high yield of the target product in a ring-closing olefin metathesis reaction, and has invented and filed a patent application for a so-called phosphine-type organometallic complex catalyst for olefin metathesis reactions represented by the following formula (3). [ka]

[0005] In addition, in the formula (3), Me represents a methyl group, Ph represents a phenyl group, and PCy3 represents tricyclohexylphosphine. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2004-506755 A [Patent Document 2] International Publication No. 2023-048084 Summary of the Invention [Problem to be solved by the invention]

[0007] However, from the viewpoint of being less susceptible to decomposition even in the presence of minute amounts of water containing a solvent and having excellent water resistance, the present inventors have found that there is still room for improvement even in the prior art catalyst of the above-mentioned formula (3). The present invention has been made in view of the above technical circumstances, and has an object to provide an organometallic complex catalyst which has superior water resistance to conventional catalysts in an olefin metathesis reaction. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that an organometallic complex catalyst having a structure represented by the following formula (1), in which a coordination center M and a phenyl group form a cyclic structure in the complex portion, is effective.

[0009] More specifically, the present invention comprises the following technical features. That is, the present invention provides 1. An organometallic complex catalyst for use in an olefin metathesis reaction, comprising: It has a chemical structure represented by the following formula (1): An organometallic complex catalyst for olefin metathesis reactions is provided. [ka]

[0010] In the formula (1), M is a coordination center and represents a Ru atom or an ion thereof. Also, R 1 , R 2 and R 3may be the same or different and each is at least one substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, and an aryl group.

[0011] Furthermore, R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 may be the same or different, and each is at least one substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, a hydroxylate group, a thiocarboxy group, a dithiocarboxy group, a sulfo group, a sulfino group, an oxycarbonyl group, a carbamoyl group, a hydrazinocarbonyl group, an amidino group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, an oxo group, a thioformyl group, a thioxo group, a mercapto group, an amino group, an imino group, a hydrazino group, an aryloxy group, a sulfide group, a nitro group, and a silyl group.

[0012] In addition, in the formula (1), X represents a halogen atom capable of coordinating to the coordination center M. Furthermore, R 8 ~R 13 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, a hydroxylate group, a thiocarboxy group, a dithiocarboxy group, a sulfo group, a sulfino group, an oxycarbonyl group, a carbamoyl group, a hydrazinocarbonyl group, an amidino group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, an oxo group, a thioformyl group, a thioxo group, a mercapto group, an amino group, an imino group, a hydrazino group, an aryloxy group, a sulfidokyl group, an alkoxy group, an alkenyl group, an alkynyl group, and an aryl group.

[0013] The organometallic complex catalyst of the present invention having the above-mentioned structure has better water resistance in olefin metathesis reactions than the conventional catalysts (e.g., Grubbs' catalyst) exemplified in the prior art documents mentioned above. Moreover, the organometallic complex catalyst of the present invention is suitably used in homometathesis reactions of acyclic olefin compounds.

[0014] Although the detailed mechanism by which the organometallic complex catalyst of the present invention has excellent water resistance has not been elucidated, the present inventors speculate as follows. That is, the present inventors have found that while conventional catalysts have a structure in which a hydrogen atom is bonded to the 4th or 5th backbone carbon in the NHC structure of the imidazole ring (IPr ligand structure), the organometallic complex catalyst of the present invention has the above-mentioned silyl group (-SiR 1 R 2 R 3 ) is believed to contribute to improving the yield of the desired product.

[0015] In addition, the organometallic complex catalyst of the present invention has a silyl group (-SiR 1 R 2 R 3 ) is thought to contribute to improving the yield of the desired product.

[0016] Furthermore, from the viewpoint of more reliably obtaining the effects of the present invention, the organometallic complex catalyst for olefin metathesis reaction of the present invention preferably has a structure represented by the following formula (2). [ka]

[0017] In the formula (2), Me represents a methyl group.

[0018] In order to more reliably obtain the effects of the present invention, the organometallic complex catalyst of the present invention is preferably used in the homometathesis reaction of a non-cyclic olefin compound.

[0019] The organometallic complex catalyst of the present invention, unlike the second generation Grubbs catalyst, has a silyl group (-SiR 1 R 2 R 3 ) is further bonded, and it can be applied to olefin metathesis reactions using the second generation Grubbs catalyst. In addition, it has a structure that incorporates the structure of the first generation Grubbs catalyst, and therefore it can be said that it can be applied to olefin metathesis reactions using the first generation Grubbs catalyst. Effect of the Invention

[0020] According to the present invention, there is provided an organometallic complex catalyst which is more water resistant than conventional catalysts in an olefin metathesis reaction. [Brief description of the drawings]

[0021] [Figure 1] 1 is a graph showing the 1H NMR spectrum obtained for the organometallic complex catalyst {TMSIPrRu} of Example 1. [Diagram 2] 1 is a graph showing the 13C NMR spectrum obtained for the organometallic complex catalyst {TMSIPrRu} of Example 1. [Diagram 3] 1 is a graph showing the 29Si NMR spectrum obtained for the organometallic complex catalyst {TMSIPrRu} of Example 1. [Figure 4] 1 is a graph showing the results of GC measurements obtained for the organometallic complex catalyst {TMSIPrRu} of Example 1 and the catalyst (HG) of Comparative Example 1. [Diagram 5] FIG. 2 is a graph showing the results of evaluation of water resistance for the organometallic complex catalysts of Example 1 and Comparative Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Preferred embodiments of the present invention will now be described in detail.

[0023] <Constitution of organometallic complex catalyst for olefin metathesis reaction> The organometallic complex catalyst for olefin metathesis reaction of the present embodiment is an organometallic complex catalyst used in an olefin metathesis reaction, preferably a homometathesis reaction of a non-cyclic olefin compound, and has a structure represented by the following formula (1). [ka]

[0024] In the formula (1), M is a coordination center and represents a Ru atom or an ion thereof. Also, R 1 , R 2 and R 3 may be the same or different and each is at least one substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, and an aryl group.

[0025] Furthermore, R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 may be the same or different, and each is at least one substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, a hydroxylate group, a thiocarboxy group, a dithiocarboxy group, a sulfo group, a sulfino group, an oxycarbonyl group, a carbamoyl group, a hydrazinocarbonyl group, an amidino group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, an oxo group, a thioformyl group, a thioxo group, a mercapto group, an amino group, an imino group, a hydrazino group, an aryloxy group, a sulfide group, a nitro group, and a silyl group.

[0026] In addition, in the formula (1), X represents a halogen atom capable of coordinating to the coordination center M. Furthermore, R 10 ~R 15 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, a hydroxylate group, a thiocarboxy group, a dithiocarboxy group, a sulfo group, a sulfino group, an oxycarbonyl group, a carbamoyl group, a hydrazinocarbonyl group, an amidino group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, an oxo group, a thioformyl group, a thioxo group, a mercapto group, an amino group, an imino group, a hydrazino group, an aryloxy group, a sulfidokyl group, an alkoxy group, an alkenyl group, an alkynyl group, and an aryl group.

[0027] The organometallic complex catalyst for olefin metathesis reaction of the present embodiment, which contains the ligand of the present embodiment having the above-mentioned configuration as a constituent material, can obtain a higher yield of the target product in an olefin metathesis reaction than a conventional Grubbs catalyst, and also has excellent water resistance.

[0028] Although the detailed mechanism by which the organometallic complex catalyst for olefin metathesis reaction of the present embodiment can provide a high yield of the target product has not been elucidated, the present inventors speculate as follows. That is, the present inventors have found that while conventional catalysts have a structure in which a hydrogen atom is bonded to the backbone carbon at the 4th or 5th position in the NHC structure of the imidazole ring (the structure of the IPr ligand (formula (P1))), the organometallic complex catalyst of the present invention has the above-mentioned silyl group (-SiR 1 R 2 R 3 ) is believed to contribute to improving the yield of the desired product.

[0029] Here, the coordination center M is a Ru atom or ion. R1 , R 2 and R 3 From the viewpoint of more reliably obtaining the effects of the present invention, at least one of the groups is preferably an alkyl group or an alkoxy group, and more preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms. R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 From the viewpoint of more reliably obtaining the effects of the present invention, it is preferable that at least one of the groups is an alkyl group having 1 to 3 carbon atoms.

[0030] From the viewpoint of more reliably obtaining the effects of the present invention and from the viewpoint of easy availability of raw materials, X is preferably Cl among halogen atoms. R 10 ~R 15 From the viewpoint of more reliably obtaining the effects of the present invention, is preferably a substituent having 3 to 10 carbon atoms and having a π bond capable of coordinating to the coordination center M, and more preferably a substituent having 3 to 9 carbon atoms and having a π bond capable of coordinating to a preferred coordination center Ru.

[0031] Furthermore, from the viewpoint of more reliably obtaining the effects of the present invention, the organometallic complex catalyst for olefin metathesis reaction of the present invention preferably has a structure represented by the following formula (2). [ka]

[0032] In the formula (2), Me represents a methyl group.

[0033] According to the present embodiment, there is provided an organometallic complex catalyst capable of obtaining a higher yield of the target product in an olefin metathesis reaction than conventional catalysts. In order to obtain the effects of the present invention more reliably, the organometallic complex catalyst of the present invention is preferably used in the metathesis reaction of a non-cyclic olefin compound.

[0034] Furthermore, the organometallic complex catalyst of the present invention has a silyl group (-SiR) at the 4- or 5-position backbone carbon of the IPr ligand, unlike the second generation Grubbs catalyst. 1 R 2 R 3 ) is further bonded, and it can be applied to olefin metathesis reactions using the second generation Grubbs catalyst. In addition, it has a structure that incorporates the structure of the first generation Grubbs catalyst, and therefore it can be said that it can be applied to olefin metathesis reactions using the first generation Grubbs catalyst.

[0035] <Preferred embodiment of the method for producing an organometallic complex catalyst> The organometallic complex catalyst for olefin metathesis reaction of the present embodiment is not particularly limited, and can be produced by combining and optimizing known methods for synthesizing ligands and known methods for synthesizing complex catalysts.

[0036] The method for producing an organometallic complex catalyst for olefin metathesis reaction according to the present embodiment includes the steps of: A first step of synthesizing a ligand having an NHC structure represented by the following formula (4): In the above formula (1), the coordination center M, the halogen X, and the substituent R 8 A second step of synthesizing a complex comprising a third step of reacting the ligand having an NHC structure obtained in the first step with the complex obtained in the second step to synthesize an organometallic complex catalyst for olefin metathesis reaction of the present embodiment; Includes. [ka]

[0037] Here, in formula (4), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is R in formula (1). 1 , R 2 , R 3 , R4 , R 5 , R 6 , R 7 , R 8 and R 9 The same substituents as those shown in the above formula are shown.

[0038] The coordination center M, halogen X, and substituent R in formula (1) used in the second step 8 As the complex containing the above, a first generation Hoveyda-Grubbs catalyst represented by (dichloro 2-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II) represented by the following formula (HG1) can be used. [ka]

[0039] Furthermore, the method for producing the organometallic complex catalyst for olefin metathesis reaction of the present embodiment may further include a fourth step of purifying the organometallic complex catalyst for olefin metathesis reaction of the present embodiment obtained after the third step. The purification method in the fourth step may be a known purification method. For example, a recrystallization method using a predetermined solvent may be used.

[0040] According to the method for producing an organometallic complex catalyst for olefin metathesis reactions of the present embodiment, it is possible to reliably produce an organometallic complex catalyst for olefin metathesis reactions that uses the ligand and has high water resistance and is capable of obtaining a higher yield of the target product in an olefin metathesis reaction than conventional catalysts.

[0041] Furthermore, according to the production method of the present embodiment, it is possible to more easily and reliably produce an organometallic complex catalyst for olefin metathesis reaction of the present embodiment, which uses the ligand of the present embodiment and has high water resistance and is capable of obtaining a higher yield of the target product in an olefin metathesis reaction than conventional catalysts.

[0042] Conventionally, the synthesis of a ligand having an NHC structure in which hydrogen on the backbone carbon is replaced with another substituent required multiple synthetic steps, but the production method of the present invention makes it possible to synthesize in high yield a ligand in which a silyl group is bonded to the backbone carbon at position 4 or 5 with relatively few synthetic steps and under relatively mild conditions, based on a ligand in which hydrogen is bonded to the backbone carbon at position 4 or 5. Moreover, in the production method of the present invention, by changing the silicon reagent used as the raw material, various types of silyl groups can be introduced to the hydrogen moiety bonded to the backbone carbon at position 4 or 5.

[0043] For example, according to the production method of this embodiment, as exemplified by the following formulas (C1) and (C2), the number of synthesis steps required to obtain a final product (an organoRu complex catalyst having a ligand in which hydrogen on a backbone carbon of a ligand having an NHC structure is substituted with a silyl group) from IPr can be reduced to a relatively small number of three steps. [ka] [ka]

[0044] Here, in formula (C1), n BuLi represents CH3CH2CH2CH2Li, THF represents tetrahydrofuran, Me represents a methyl group, Ph represents a phenyl group, and PCy3 represents tricyclohexylphosphine.

[0045] The synthesis method shown in formula (C1) is described, for example, in the non-patent literature: "Wang, Y et al., J. Am. Chem. Soc., 2010, 132, 14370." On the other hand, the synthesis method of formula (C2) is a simple synthesis method discovered by the present inventors. For example, a commercially available first generation Hoveyda-Grubbs catalyst can be used. EXAMPLES

[0046] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0047] (Description of the analysis device) The following instruments were used for the analyses performed in synthesizing the organometallic complex catalysts in the Examples and Comparative Examples described below. [NMR Spectrum] 1 H NMR, 13 C NMR spectrum and 29 The Si NMR measurements were performed using a Bruker Biospin Avance400 (400 MHz) manufactured by Bruker. Dehydrated heavy solvents were used for all ligand measurements to prevent decomposition of the ligands.

[0048] [Example 1] The organometallic complex catalyst shown in the above formula (2) (hereinafter, as necessary, TMS (hereinafter referred to as "IPrRu" or "TMS-IPrRu") was synthesized according to the following procedure.

[0049] [Example 1, Step 1-1] Synthesis of ligand "IPr" having an NHC structure Starting from 2,6-diisopropylaniline, we synthesized the ligand "IPr" {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene} having an NHC structure. Specifically, the compound was synthesized through the three steps shown in the following reaction schemes (R1) to (R3) by referring to the methods described in academic papers (Tang, P., Wang, W., Ritter, TJ Am. Chem. Soc. 2011, 133, 11482, and Pompeo, M., Froese, RDJ, Hadei, N., Organ, MG Angew. Chem. Int. Ed. 2012, 51, 11354). 1 Identification was performed using 1 H NMR to confirm that IPr and intermediate products had been synthesized. [ka] In formula (R1), MeOH represents methanol, and HOAc represents acetic acid.

[0050] The synthesis procedure of intermediate product 1 in formula (R1) will be described. 6.00g (33.8mmol) of 2,6-diisopropylaniline, 30mL of methanol, and 0.31mL (3.5mol%) of acetic acid were added to a 50mL eggplant flask and heated to 50℃. Next, a mixed solution of 2.40g (0.5eq.) of 40% aq. of glyoxal and 10mL of methanol was added dropwise. As the mixed solution was added dropwise, it changed from a colorless transparent solution to a yellow transparent solution. After stirring at 50℃ for 15 minutes, it was returned to room temperature and stirred for another 11 hours. When it cooled to room temperature, a yellow solid precipitated. After the reaction was completed, it was filtered using a membrane filter and the solid was washed with methanol. When washing, a small amount of the target intermediate product 1 was dissolved in methanol, so the filtrate was collected and the solvent was removed, and the obtained solid was washed again with a small amount of methanol and filtered. The yellow solid obtained in the first and second times was combined and dried. The amount of intermediate product 1 (yellow powder solid) in formula (R1) was 5.49 g, and the yield was 86.0%. [ka]

[0051] In formula (R2), TMSCl represents chlorotrimethylsilane, and EtOAc represents ethyl acetate.

[0052] The synthetic procedure of intermediate product 2 in formula (R2) will be described. In a 500 mL recovery flask, 3.80 g (10.08 mmol) of (1E,2E)-1,2-bis(2,6-diisopropylphenylimino)ethane, 0.32 g (10.66 mmol) of paraformaldehyde, and 83 mL of ethyl acetate were added and heated to 70°C. The mixture was in a yellow slurry state. Next, a mixed solution of 0.34 mL (10.66 mmol) of chlorotrimethylsilane and 8 mL of ethyl acetate was added dropwise over 20 minutes. The mixture was then stirred at 70°C for 2 hours. The color of the solvent changed from yellow to orange. After the reaction was completed, the mixture was placed in ice water and cooled to 0°C. After cooling, the mixture was filtered through a membrane filter and the solid was washed with ethyl acetate. It was then vacuum dried to obtain a light pink powder solid. The amount of intermediate product 2 (white powder solid) in formula (R2) was 3.96 g, the yield was 92.5%. [ka]

[0053] In formula (R3), t BuOK refers to (CH3)3COK, and THF refers to tetrahydrofuran.

[0054] The synthesis procedure of the product 3 "IPr" in formula (R3) will be described. Under an inert gas atmosphere, 0.43 g (1.01 mmol) of 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride was added to a 25 mL Schlenk flask. t 0.14 g (1.21 mmol) of BuOK and 5 mL of dehydrated THF were added and stirred at room temperature for 3.5 hours. The solution changed from white to brown. After the reaction was completed, the solvent was removed, 5 mL of dehydrated toluene was added, and the solid was dissolved by heating and stirring at 50°C. Then, 5 mL of dehydrated hexane was added. In order to remove the salt (KCl) in the solution, celite filtration was performed in a glove box. A brown, transparent solution was obtained. The solvent was removed and the solution was dried in vacuum to obtain a brown powder solid. The yield of product 3 "IPr" (brown powder solid) in formula (R3) was 0.30 g, the yield was 78.0%.

[0055] 1 Identification was performed using 1 H NMR, and it was confirmed that IPr and intermediate products (intermediate product 1 in formula (R1) and intermediate product 2 in formula (R2)) had been synthesized. For each of the ligands having the NHC structure shown in reaction formulas (R1) to (R3), 1 The H NMR spectrum was measured and confirmed. 1 For H NMR spectroscopy, CDCl3 was used as a deuterated solvent. 1 CD3CN was used as a deuterated solvent for H NMR spectroscopy. 1 For 1 H NMR spectroscopy, C6D6 was used as a deuterated solvent.

[0056] The measurement results of intermediate product 1 are shown below. 1 H NMR (CDCl3, 400 MHz): δ8.10 (s, 2H), 7.20-7.13 (m, 6H), 2.94 (m, 4H), 1.21 (d, 24H, J = 6.8 Hz)

[0057] The measurement results of intermediate product 2 are shown below. 1 H NMR (CD3CN, 400 MHz): δ9.35 (s, 1H), 7.87 (s, 2H), 7.65 (t, 2H, J = 7.5 Hz), 7.47 (d, 4H, J = 7.7 Hz), 2.41 (m, 4H), 1.26 (d, 12H, J = 6.8 Hz), 1.20 (d, 12H, J = 6.8 Hz)

[0058] The measurement results for product 3 "IPr" are shown below. 1H NMR (C6D6, 400 MHz): δ7.31-7.27 (m, 2H), 7.19-7.17 (m, 4H), 6.61 (s, 2H), 2.96 (m, 4H), 1.29 (d, 12H, J = 6.8 Hz), 1.18 (d, 12H, J = 7.0Hz)

[0059] [Example 1, Step 1-2] Synthesis of a ligand having a trimethylsilyl group bonded to the 4-carbon in the NHC structure of IPr Using the ligand IPr obtained in the above-mentioned first step-1, a ligand having an NHC structure represented by the following formula (4-1) was synthesized. [ka]

[0060] Specifically, the method described in the academic paper (Wang, Y., Xie, Yaming., Abraham, MY, Wei, P., Schaeferlll, HF, Schleyer, PR, Robinson, GHJ Am. Chem. Soc. 2010, 132, 14370) was improved to obtain a ligand represented by formula (4-1) {hereinafter, as necessary, "TMS group") in which a trimethylsilyl group (-SiMe3, hereinafter, as necessary, "TMS group") is bonded to the 4-position carbon in the NHC structure of IPr (reactant 3) through the two steps shown in the following reaction formula (R4). TMS We synthesized a compound called "IPr." [ka]

[0061] In formula (R4), n BuLi refers to CH3CH2CH2CH2Li, and THF refers to tetrahydrofuran.

[0062] The synthesis procedure of intermediate product 4 (Li-IPr) in formula (R4) will be described. First, in a glove box, 10.79 g (27.62 mmol) of IPr (reactant 3) and 100 mL of dehydrated hexane were added to a 300 mL recovery flask, and the resulting liquid was stirred at room temperature for 30 minutes. n BuLi was slowly added dropwise, and the mixture was allowed to react at room temperature overnight with stirring. The mixture changed from a light brown slurry-like solution to a yellow slurry-like solution. After the reaction was completed, the mixture was filtered through a membrane filter and washed with dehydrated hexane. The resulting yellow powder solid {intermediate product 4 in formula (R4) (lithiated product: Li-IPr)} was dried. The amount of intermediate product 4 (yellow powder solid) in formula (R4) was 10.0 g, and the yield was 92.0%.

[0063] Next, the product 5( TMS The synthesis procedure for IPr is explained below. First, 0.78 g (1.98 mmol) of intermediate product 4 (Li-IPr) and 25 mL of dehydrated THF were added to a 50 mL Schlenk in a glove box and dissolved. Next, 0.26 mL (2.04 mmol) of chlorotrimethylsilane (ClSiMe3, hereinafter referred to as "ClTMS" as necessary) was slowly added dropwise and reacted for 25 minutes. After the reaction was completed, the solvent was removed. In a glove box, 10 mL of dehydrated toluene was added to the solid product to dissolve it, and the resulting liquid was transferred to a centrifuge tube. The liquid in the centrifuge tube was centrifuged at 4000 rpm for 6 minutes at room temperature to separate the salt (LiCl). The resulting filtrate was then passed through a filter (Advantec, 0.2 μm) and separated in a 50 mL Schlenk filter. The solvent was then removed to leave a yellow powder solid ( TMS IPr, i.e., the desired ligand 5), was obtained. Product 5 in formula (R4) TMS The yield of "IPr" (yellow powder solid) was 0.901 g, and the yield was 98.9%.

[0064] 1 Identification was performed using H NMR, and it was found that the lithiation of the hydrogen atom bonded to the 4-carbon in the NHC structure of IPr (reactant 3) had progressed. TMSIt was confirmed that IPr (the desired ligand 5) was synthesized.

[0065] Product 5' TMS The measurement results of "IPr" (target ligand 5) are shown below. 1 H NMR (C6D6, 400 MHz): δ=7.33-7.27 (m, 2H), 7.21-7.17 (m, 4H), 6.89 (s, 2H), 3.04 (m, 2H), 2.84 (m, 2H), 1.40 (d, 6H, J = 6.8 Hz), 1.28 (d, 12H, J =6.8 Hz, 6.9 Hz), 1.18 (d, 6H, J = 6.9 Hz), 0.05 ppm (s, 9H).

[0066] 1 The results of H NMR showed that the TMS group was bonded to the 4-carbon in the NHC structure of IPr (reactant 3). i It was confirmed that the proton peak derived from -CH of the Pr group became asymmetric and was split into two.

[0067] In addition, the consumption of the raw material was confirmed, and a peak due to the methyl group of the TMS group was observed around 0 ppm. The chemical shift and integral values ​​were consistent with those in the literature. TMS It was confirmed that IPr (target ligand 5) was synthesized. n It was confirmed that the lithiation of IPr (reactant 3) with BuLi had proceeded sufficiently.

[0068] [Example 1, Step 2] A commercially available first generation Hoveyda-Grubbs catalyst represented by the above-mentioned formula (HG1) (manufactured by Aldrich Chemical Company, trade name "Hoveyda-Grubbs M700") was prepared.

[0069] [Example 1, Step 3] Reaction of the NHC ligand obtained in the first step with the first generation Hoveyda-Grubbs catalyst prepared in the second step. The organometallic complex catalyst “TMSIPrRu” of Example 1 was synthesized by carrying out the reaction shown in the following reaction formula (R5) using the ligand having an NHC structure (TMSIPr) obtained in the first step and the first-generation Hoveyda-Grubbs catalyst prepared in the second step. The present inventors independently investigated the reaction conditions for this third step. [ka]

[0070] In a glove box, the ligand ( TMS IPr) (116 mg, 0.250 mmol) was placed in a 30 mL Schlenk flask and dehydrated toluene (7 mL) was added. In another vial, the first generation Hoveyda-Grubbs catalyst: (dichloro 2-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II) (HG1) (150 mg, 0.25 mmol) was weighed and dissolved in dehydrated toluene (3 mL). The first generation Hoveyda-Grubbs / toluene solution was added dropwise to the Schlenk flask and stirred at room temperature overnight.

[0071] After the reaction was completed, toluene was distilled off and the mixture was dried under vacuum for 30 minutes. The obtained solid was dissolved in dehydrated hexane, then placed in a 13.5 mL vial and recrystallized at -40°C. After recrystallization, the mixture was filtered using a membrane filter to obtain the target product, a dull yellow powder. TMS IPrRu was obtained (485 mg, 62% yield).

[0072] [Example 1 Identification] TMS Identification of IPrRu 1 H NMR, 13 C NMR, 29 The results were confirmed by Si NMR. C6D6 was used as the deuterated solvent in these three NMR measurements. FIG. 1 shows the organometallic complex catalyst of Example 1. TMS IPrRu} was obtained. 1 The H NMR spectrum of the organometallic complex catalyst { TMSIPrRu} was obtained. 13 The C NMR spectrum of the organometallic complex catalyst { TMS IPrRu} was obtained. 29 The Si NMR spectrum is shown.

[0073] 1 H NMR (400MHz, C6D6): δ(ppm)= 16.64 (s, Ru=CH, 1H), 7.46-7.20 (m, H Ar , 6H), 7.20-7.00 (m, H Ar , 2H), 6.69 (t, J = 5.0 Hz, H Ar , 1H), 6.33 (d, J = 5.5 Hz, H Ar , 1H), 4.46 (sept, J = 4.1 Hz, OCH(CH3)2, 1 H), 3.65 (sept, J = 4.5 Hz, CH(CH3)2, 2H), 3.12 (sept, J = 4.5 Hz, CH(CH3)2, 2H), 1.72 (d, J = 4.5 Hz, CH(CH3)2, 6 H), 1.40 (d, J = 4.1 Hz, OCH(CH3)2, 6 H), 1.14 -1.13 (m, CH(CH3)2, 12 H), 1.08 (d, J = 4.5 Hz, CH(CH3)2, 6 H), -0.05 (s, 9H)

[0074] 13 C NMR (100 MHz, C6D6): δ(ppm) = δ= 283.55 (Ru=C), 181.70 (C NHC ), 153.51, 149.41, 148.65, 145.32, 139.60, 138.23, 138.15, 136.09, 135.92, 131.21, 130.73, 129.66, 128.79,126.03, 125.29, 124.29, 122.69, 122.27, 113.63, 75.60, 30.17, 28.71, 27.73, 25.49, 25.08, 23.34, 22.12, 0.53 (SiMe3)

[0075] 29 Si NMR (119.2 MHz, C6D6): δ(ppm) = -9.40

[0076] From the results of Figures 1, 2 and 3, TMS It was determined that IPrRu had been synthesized.

[0077] [Comparative Example 1] As shown in the following reaction formula R6, the ligand ( TMS A second-generation Hoveyda-Grubbs catalyst represented by formula (HG2) was synthesized in the same manner as in Example 1, except that IPr was changed to IPr having no silyl group. [ka]

[0078] [Comparative Examples 2 and 3] A commercially available first generation Hoveyda-Grubbs catalyst represented by the above-mentioned formula (HG1) (manufactured by Aldrich Chemical Company, trade name "Hoveyda-Grubbs M700") was prepared. In addition, as a so-called phosphine-type organometallic complex catalyst for olefin metathesis reactions represented by the above formula (3) based on the above Patent Document 2, an organometallic complex catalyst manufactured by NECHEMCAT under the product name "MTMS-RUA" was prepared.

[0079] <Evaluation of catalytic activity by olefin metathesis reaction> Using the organometallic complex catalysts of Example 1, Comparative Example 1, and Comparative Example 2, an olefin metathesis reaction (homometathesis reaction of 5-hexenyl acetate) represented by the following reaction formula (R7) was carried out. [ka]

[0080] Example 1 TMSIPrRu (5.3 mg, 6.88 μmol) was placed in a 4 cc vial, and toluene-d8 (0.86 mL) was added. TMS A IPrRu / toluene-d8 solution (8.0 μM) was prepared. In a glove box, 5-hexenyl acetate (32.0 μL, 0.20 mmol) and an internal standard substance (1,3,5-trimethylbenzene, 13.8 μL, 0.10 mmol) were placed in a 10 mL round-bottom flask, and toluene (1.0 mL) was added as a solvent. Next, add the mixture: TMS IPrRu / toluene-d8 solution (250 μL, TMS IPrRu: 2.0 μmol, 1.0 mol%) was added, and the homometathesis reaction shown in the above reaction formula (R7) was carried out at room temperature. The conversion rate of 5-hexenyl acetate was determined by gas chromatography measurement 240 minutes after the start of the reaction. The results are shown in Table 1.

[0081] The homometathesis reaction represented by the above reaction formula (R7) was carried out at room temperature using the organometallic complex catalyst of Comparative Example 1 (the second-generation Hoveyda-Grubbs catalyst represented by formula (HG2)) under the same conditions and procedures as those in the above-mentioned reaction evaluation test. The conversion rate of 5-hexenyl acetate was determined by GC measurement 240 minutes after the start of the reaction. The results are shown in Table 1.

[0082] A homometathesis reaction was carried out at room temperature according to reaction formula (R7) using the organometallic complex catalyst of Comparative Example 2 (the first generation Hoveyda-Grubbs catalyst represented by formula (HG1)) under the same conditions and procedures as those used in the above-mentioned reaction evaluation test. The conversion rate of 5-hexenyl acetate was determined by GC measurement 60 minutes and 240 minutes after the start of the reaction. The results are shown in Table 2. [Table 1]

[0083] The results shown in Table 2 reveal that, compared with the organometallic complex catalysts of Comparative Example 1 and Comparative Example 2, which are conventional Hoveyda-Grubbs catalysts, when the organometallic complex catalyst of Example 1 satisfying the configuration of the present invention is used, the target product can be obtained in a very high yield in an olefin metathesis reaction (homometathesis reaction of 5-hexenyl acetate).

[0084] Next, using the organometallic complex catalysts of Example 1, Comparative Example 1, and Comparative Example 2, an olefin metathesis reaction (mixed metathesis reaction of 5-hexenyl acetate and methyl acrylate) represented by the following reaction formula (R8) was carried out. [ka]

[0085] Example 1 TMS IPrRu (5.3 mg, 6.88 μmol) was placed in a 4 cc vial, and toluene-d8 (0.86 mL) was added. TMS A IPrRu / toluene-d8 solution (8.0 μM) was prepared. In a glove box, 5-hexenyl acetate (32.0 μL, 0.20 mmol), methyl acrylate (18.0 μL, 0.20 mmol), and an internal standard substance (1,3,5-trimethylbenzene, 13.8 μL, 0.10 mmol) were placed in a 10 mL round-bottom flask, and toluene (1.0 mL) was added as a solvent. Next, add the mixture: TMS IPrRu / toluene-d8 solution (250 μL, TMS IPrRu: 2.0 μmol, 1.0 mol%) was added, and the homometathesis reaction shown in the above reaction formula (R8) was carried out at room temperature. 180 minutes after the start of the reaction, the GC area ratio (= [GC peak area of ​​product] / [GC peak area of ​​internal standard substance]) of the homometathesis (HM) product and the cross metathesis (CM) product was determined by gas chromatography (GC) measurement (Shimadzu GC-2014). The results are shown in Table 2.

[0086] The cross-metathesis reaction shown in reaction formula (R4) was carried out at room temperature using the organometallic complex catalyst of Comparative Example 1 (the second-generation Hoveyda-Grubbs catalyst shown in formula (HG2)) under the same conditions and procedures as those in the above-mentioned reaction evaluation test. The conversion rate of 5-hexenyl acetate was determined by GC measurement 240 minutes after the start of the reaction. The results are shown in Table 2 and Figure 4. [Table 2]

[0087] The results shown in Table 2 and FIG. 4 demonstrate that, compared with the organometallic complex catalyst of Comparative Example 1, which is a conventional Hoveyda-Grubbs catalyst, when the organometallic complex catalyst of Example 1 satisfying the configuration of the present invention is used, the reactivity to methyl acrylate in an olefin metathesis reaction (cross-metathesis reaction of 5-hexenyl acetate and methyl acrylate) is reduced, and it is possible to selectively accelerate the homometathesis reaction of 5-hexenyl acetate.

[0088] <Water resistance evaluation> The NMR spectra of the organometallic complex catalysts of Example 1 and Comparative Example 3 were observed over time in a heavy solvent (C6D6) containing water. The results are shown in FIG. As can be seen from the results shown in FIG. 5, for the organometallic complex catalyst of Example 1, a peak was still observed even after 7 days had passed, and no decomposition was confirmed, whereas for the organometallic complex catalyst of Comparative Example 3, the peak disappeared after 7 days had passed, and decomposition was confirmed. [Industrial Applicability]

[0089] The catalyst of the present invention can obtain a higher yield of the target product in an olefin metathesis reaction than conventional catalysts. Therefore, the present invention contributes to the development of mass production technology in the fields of medicine, agricultural chemicals, and electronic materials, in which olefin metathesis reactions can be used to synthesize target products (e.g., aromatic amines).

Claims

1. 1. An organometallic complex catalyst for use in an olefin metathesis reaction, comprising: It has a chemical structure represented by the following formula (1): Organometallic complex catalyst for olefin metathesis reactions. 【Chemistry 1】 [In formula (1), M is a coordination center and represents a Ru atom or an ion thereof; R １ , R ２ and R ３ may be the same or different, and each represents at least one substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, and an aryl group, R ４ , R ５ , R ６ , R ７ , R ８ , and R ９ may be the same or different, and each is at least one substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, a hydroxylate group, a thiocarboxy group, a dithiocarboxy group, a sulfo group, a sulfino group, an oxycarbonyl group, a carbamoyl group, a hydrazinocarbonyl group, an amidino group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, an oxo group, a thioformyl group, a thioxo group, a mercapto group, an amino group, an imino group, a hydrazino group, an aryloxy group, a sulfide group, a nitro group, and a silyl group; X represents a halogen atom capable of coordinating to the coordination center M; R １０ R １５ may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, a hydroxylate group, a thiocarboxy group, a dithiocarboxy group, a sulfur group, It represents an aryl group, a sulfino group, an oxycarbonyl group, a carbamoyl group, a hydrazinocarbonyl group, an amidino group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, an oxo group, a thioformyl group, a thioxo group, a mercapto group, an amino group, an imino group, a hydrazino group, an aryloxy group, a sulfidoxy group, an alkoxy group, an alkenyl group, an alkynyl group, and an aryl group.

2. It has a chemical structure represented by the following formula (2): The organometallic complex catalyst for olefin metathesis reactions according to claim 1 . 【Chemistry 2】

3. Used in homometathesis reactions of acyclic olefins. The organometallic complex catalyst for olefin metathesis reactions according to claim 1 or 2.

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