Tooth-shaped metal complex and preparation method thereof, and preparation method of alpha and beta alkenyl silane compound

Abstract

The invention relates to a tooth-shaped metal complex and a preparation method thereof, and a preparation method of alpha and beta alkenyl silane compounds. The invention relates to a preparation method of alpha and beta alkenyl silane compounds, which comprises the following steps: under the condition of nitrogen protection, mixing silane, alkyne, a tooth-shaped metal complex, an additive and a solvent, reacting at room temperature for 6-24 hours, concentrating, and carrying out silica gel column chromatography separation to respectively obtain the alpha and beta alkenyl silane compounds. According to the tooth-shaped metal complex, the preparation method thereof and the preparation method of the alpha and beta alkenyl silane compound, bidentate cobalt and tridentate iron pyridine imine complexes are used as alkyne hydrosilylation reaction catalysts and are used for preparing the alpha and beta alkenyl silane compound; the method has the advantages of simplicity and convenience in operation, mild conditions, wide substrate universality, high reaction selectivity and high catalytic efficiency, so that the method has the characteristics of simplicity and convenience in synthesis and relatively high applicability in synthesis.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a toothed metal complex and a preparation method thereof, and a preparation method of α and β alkenyl silane compounds. Background Art

[0002] Alkynes are an important class of organic compounds with rich chemical reactivity and diverse structures. They can be converted into organic compounds such as olefins or cycloalkanes through hydrosilylation reactions, thus expanding the application range of alkynes. Through the hydrosilylation reaction of alkynes, a variety of organic compounds with biological activity or industrial uses, such as drugs, pesticides, polymer materials, etc., can be synthesized.

[0003] As the reaction progresses, the hydrosilylation reaction of alkynes has achieved great success. Although traditional catalysts have good catalytic effects, they are expensive and difficult to recycle; or they are cheap but have poor catalytic effects. Therefore, there is a problem of difficulty in balancing the catalytic effect and price of traditional catalysts, which limits the further development of the hydrosilylation reaction of alkynes.

[0004] Cobalt and iron, as a cheap and environmentally friendly transition metal, have been reported many times in hydrosilylation reactions in recent years. They have good catalytic activity, high catalytic efficiency, good stability, and the catalyzed hydrosilylation reactions have good chemical selectivity and regioselectivity.

[0005] In view of this, the present invention provides a dentate metal complex and a preparation method thereof, and a preparation method of α- and β-vinylsilane compounds. The method can simultaneously obtain α- and β-vinylsilane compounds, and has the advantages of mild conditions, wide substrate universality, high reaction selectivity, and high catalytic efficiency. Summary of the invention

[0006] The object of the present invention is to provide a dentate metal complex, which is a bidentate cobalt and tridentate iron pyridine imine complex, is an effective cobalt and iron catalyst, can be used for alkyne hydrosilylation reaction, and has the advantages of wide substrate universality, high reaction selectivity and high catalytic efficiency.

[0007] In order to achieve the above purpose, the technical solution adopted is:

[0008] A dentate metal complex is a bidentate cobalt complex or a tridentate iron complex, and its general chemical structure is:

[0009]

[0010] Wherein, X is a halogen element.

[0011] Furthermore, in the chemical structure formula of the toothed metal complex, R8, R9, R10 It is selected from one of H, Me, iPr, and tBu groups, and X is Cl or Br.

[0012] Another object of the present invention is to provide a method for preparing the above-mentioned tooth-shaped metal complex, which is simple.

[0013] In order to achieve the above purpose, the technical solution adopted is:

[0014] The preparation method of the above-mentioned tooth-shaped metal complex, the chemical reaction formula of the preparation method is:

[0015]

[0016] Another object of the present invention is to provide a method for preparing α and β alkenyl silane compounds. The method uses the above-mentioned toothed metal complex. The method is simple to operate and has mild conditions, and can simultaneously obtain α and β alkenyl silane compounds.

[0017] In order to achieve the above purpose, the technical solution adopted is:

[0018] A method for preparing α and β alkenyl silane compounds, comprising:

[0019] Under nitrogen protection, silane, alkyne, dentate metal complex, additive and solvent are mixed, reacted at room temperature for 6-24 hours, concentrated, and separated by silica gel column chromatography to obtain α and β alkenyl silane compounds respectively;

[0020] The toothed metal complex is the toothed metal complex described above;

[0021] Further, the molar ratio of the alkyne, silane, dentate metal complex, and additive is 1:1.0-2.0:005-0.03:0.01-0.05;

[0022] The volume of the solvent and the molar amount of the alkyne are between 0.5-2mL:1mmol.

[0023] Further, the structural formula of the alkyne is Wherein R1 and R2 are selected from one of aryl, heteroaryl, alkyl and hydrogen.

[0024] Furthermore, the structural formula of the silane is R3R4R5SiH, wherein R3, R4, and R5 are selected from one of hydrogen, alkyl, alkoxy, and aryl.

[0025] Furthermore, the solvent is selected from at least one of tetrahydrofuran, ether, benzene, toluene, ethyl acetate, dichloromethane, acetonitrile, petroleum ether, n-hexane, and N,N-dimethylformamide;

[0026] The additive is sodium triethylborohydride or sodium tert-butoxide.

[0027] Furthermore, petroleum ether is used as eluent during the silica gel column chromatography separation process.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. In the technical solution of the present invention, an effective cobalt and iron tooth-shaped complex is prepared, which can be used to catalyze the hydrosilylation reaction of alkynes to prepare α and β alkenyl silane compounds. Compared with the traditional hydrosilylation reaction, α and β alkenyl silane compounds can be obtained at the same time.

[0030] 2. In the technical solution of the present invention, an effective cobalt and iron tooth-shaped complex is prepared, which can be used to catalyze the hydrosilylation reaction of alkynes. It has the advantages of simple operation, mild conditions, wide substrate universality, high reaction selectivity, and high catalytic efficiency, and thus has high applicability. DETAILED DESCRIPTION

[0031] In order to further explain the tooth-shaped metal complex and its preparation method, and the preparation method of α and β alkenyl silane compounds of the present invention, and to achieve the intended purpose of the invention, the tooth-shaped metal complex and its preparation method, and the preparation method of α and β alkenyl silane compounds proposed by the present invention are described in detail below in combination with the preferred embodiments. In the following description, different "one embodiment" or "embodiment" does not necessarily refer to the same embodiment. In addition, specific features, structures or characteristics in one or more embodiments may be combined in any suitable form.

[0032] The following will further introduce the toothed metal complex and its preparation method, and the preparation method of α and β alkenyl silane compounds of the present invention in detail with reference to specific embodiments:

[0033] The technical scheme of the present invention is: under the condition of nitrogen protection, silane, alkyne, synthesized metal complex (respectively bidentate cobalt complex and tridentate iron complex further synthesized with bidentate ligand as raw material), additives and reaction solvent are mixed, reacted at room temperature for 6-24h, and then treated to obtain α and β alkenyl silane compounds respectively. The present invention utilizes bidentate cobalt and tridentate iron pyridine imine complexes obtained by a simple route, thereby providing an effective method for preparing α and β alkenyl silane compounds by alkyne hydrosilylation reaction catalyzed by cobalt and iron. Compared with the existing method, it is characterized in that a method is used to obtain metal complexes of different tooth types, which can be used to prepare α and β alkenyl silane compounds at the same time, and has the advantages of simple operation, mild conditions, wide substrate universality, high reaction selectivity, and high catalytic efficiency. It has the characteristics of simple synthesis and high applicability in synthesis. The technical scheme of the present invention is:

[0034] A dentate metal complex is a bidentate cobalt complex or a tridentate iron complex, and its general chemical structure is:

[0035]

[0036] Wherein, X is a halogen element.

[0037] Preferably, in the chemical structure formula of the toothed metal complex, R8, R9, R 10 It is selected from one of H, Me, iPr, and tBu groups, and X is Cl or Br.

[0038] The preparation method of the above-mentioned tooth-shaped metal complex, the chemical reaction formula of the preparation method is:

[0039]

[0040] In the above technical solution, the structural formula of the pyridine imine ligand is (i.e. bidentate ligand 1), R6 is an aryl group, and R7 is Br or pyrazole. The aniline form of the aryl group is represented by: R8, R9, R 10 One selected from H, Me, iPr, tBu groups.

[0041] By further adding metal salt to the synthesized bidentate ligand 1 and tridentate ligand 2, a bidentate cobalt complex 3 and a tridentate iron complex 4 can be obtained.

[0042] A method for preparing α and β alkenyl silane compounds, comprising:

[0043] Under nitrogen protection, silane, alkyne, dentate metal complex, additive and solvent are mixed, reacted at room temperature for 6-24 hours, concentrated, and separated by silica gel column chromatography to obtain α and β alkenyl silane compounds respectively;

[0044] The toothed metal complex is the toothed metal complex described above;

[0045] Preferably, the molar ratio of the alkyne, silane, dentate metal complex and additive is 1:1.0-2.0:005-0.03:0.01-0.05;

[0046] The volume of the solvent and the molar amount of the alkyne are between 0.5-2mL:1mmol.

[0047] Preferably, the structural formula of the alkyne is Wherein R1 and R2 are selected from one of aryl, heteroaryl, alkyl and hydrogen.

[0048] Preferably, the structural formula of the silane is R3R4R5SiH, wherein R3, R4, and R5 are selected from one of hydrogen, alkyl, alkoxy, and aryl. Further preferably, the silane is phenylsilane or diphenylsilane.

[0049] Preferably, the solvent is selected from at least one of tetrahydrofuran, ether, benzene, toluene, ethyl acetate, dichloromethane, acetonitrile, petroleum ether, n-hexane, and N,N-dimethylformamide;

[0050] The additive is sodium triethylborohydride or sodium tert-butoxide.

[0051] Preferably, petroleum ether is used as eluent during the silica gel column chromatography separation process.

[0052] Example 1: Synthesis of toothed complexes

[0053] The reaction formula is as follows:

[0054]

[0055] In the reaction formula, R8, R9, R 10 It is selected from one of H, Me, iPr, and tBu groups, and X is Cl or Br.

[0056] The specific steps are as follows:

[0057] (1) Take 5 mmol of 2-bromo-6-acetylpyridine and 7.5 mmol of aniline with different substituents, add 20 ml of methanol as the reaction solvent, and 0.1 ml of formic acid as the catalyst, and carry out amine-aldehyde condensation reaction under reflux conditions for 24 hours. The product is separated by a chromatographic column, concentrated and purified to obtain the bidentate ligand 1.

[0058] (2) The obtained bidentate ligand 1 and pyrazole were reacted with CuI and K2CO3 as co-catalysts, DMSO as the reaction solvent, and the reaction temperature was 120°C. The tridentate ligand 2 was obtained after the reaction for 24 hours.

[0059] (3) Take 1 mmol of the above-mentioned bidentate ligand 1 or tridentate ligand 2 and 1.1 mmol of the corresponding metal salt (tridentate ligand 2 reacts with FeCl2, and bidentate ligand 1 reacts with CoX2), use THF as the reaction solvent, stir at room temperature for 24 hours, filter the precipitate, and you can get complex 3 or 4, that is, the bidentate cobalt complex or tridentate iron complex.

[0060] Example 2.

[0061] The method of Example 1 was used to prepare complex A and complex B, and their structural formulas are shown below:

[0062]

[0063] Specific:

[0064] In the preparation process of complex A: R8, R9, R 10 are iPr, iPr, H respectively, and X is Cl.

[0065] In the preparation process of complex B: R8, R9, R 10 They are iPr, iPr, and H respectively.

[0066] Example 3-4.

[0067] The complex A prepared in Example 2 was used for the synthesis of α-vinylsilane compounds, and the complex B was used for the synthesis of β-vinylsilane compounds.

[0068] Example 3: Markovnikov hydrosilation reaction of alkynes and phenylsilane catalyzed by bidentate cobalt complex A The specific operation steps are as follows:

[0069] Under nitrogen atmosphere, 0.01mmol (0.004g) of cobalt complex, 1.0mmol of alkyne substrate, 1.0mmol of phenylsilane, 2mL of THF solution, and 0.05mmol of sodium triethylborohydride were added to the reaction tube in sequence, and the obtained mixture was stirred at room temperature for 12h. Then, the reaction solution was concentrated, and the crude product was quickly subjected to silica gel column chromatography. The silica gel column chromatography was separated using petroleum ether as the eluent, and the eluent containing the target compound was collected, the solvent was evaporated and dried to obtain the final product.

[0070] The reactants and products are shown in Table 1.

[0071] Table 1

[0072]

[0073] Specific:

[0074] Product 1: phenyl (1-phenylvinyl) silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.61 (dt, J = 6.8, 3.4Hz, 2H), 7.43-7.26 (m, 8H), 6.30-6.20 (m, 1H), 5.89-5.80 (m, 1H), 4.86 (s, 2H).

[0075] Product 2: Phenyl (1- (o-tolyl) vinyl) silane, its NMR data is: 1 H NMR(400MHz, CDCl3)δ7.56(dd,J=7.9,1.5Hz,2H),7.43-7.34(m,3H),7.18-7.11(m,3H) ),7.02-6.96(m,1H),5.96-5.91(m,1H),5.90-5.81(m,1H),4.72(s,2H),2.26(s,3H).

[0076] Product 3: Phenyl (1- (m-tolyl) vinyl) silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.64-7.58(m,2H),7.44-7.35(m,3H),7.24-7.16(m,3H),7.08(d ,J=6.9Hz,1H),6.24(d,J=2.1Hz,1H),5.82(d,J=2.3Hz,1H),4.85(s,2H),2.35(s,3H).

[0077] Product 4: phenyl(1-(p-tolyl)vinyl)silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.60 (dt, J=5.4, 2.6Hz, 2H), 7.41-7.36 (m, 3H), 7.30 (d, J=8.1Hz, 2H), 7.1 3(d,J=7.3Hz,2H),6.23(dd,J=8.0,2.3Hz,1H),5.80(t,J=3.3Hz,1H),4.84(s,2H),2.34(s,3H).

[0078] Product 5: (1-(4-methoxyphenyl)vinyl)(phenyl)silane, its NMR data is: 1H NMR (400MHz, CDCl3) δ7.63-7.58(m,2H),7.44-7.30(m,5H),6.89-6.81(m,2H),6.22-6.16(m,1H),5.79-5.73(m,1H),4.83(s,2H),3.80(s,3H).

[0079] Product 6: (1-(4-fluorophenyl)vinyl)(phenyl)silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.61-7.56(m,2H),7.43-7.31(m,5H),7.03-6.96(m,2H),6.21-6.17(m,1H),5.85-5.80(m,1H),4.82(s,2H).

[0080] Product 7: (E)-(1,2-diphenylvinyl)(phenyl)silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.57 (dd, J=7.8, 1.4Hz, 2H), 7.37 (ddd, J=20.7, 9.9, 4.7Hz, 3H), 7.24 (dd, J=5.2, 2.3 Hz,2H),7.21-7.16(m,1H),7.13-7.09(m,3H),7.08-7.04(m,3H),7.02(dd,J=6.8,2.9Hz,2H),4.78(s,2H).

[0081] Example 4: Anti-Markovnikov hydrosilation of alkynes and phenylsilane catalyzed by tridentate iron complex B

[0082] The specific steps are as follows:

[0083] Under nitrogen atmosphere, 0.03mmol (0.012g) of iron complex, 1.0mmol of alkyne substrate, 2.0mmol of phenylsilane, 2mL of THF solution, and 0.01mmol of sodium tert-butoxide were added to the reaction tube in sequence, and the obtained mixture was stirred at room temperature for 6h. The reaction solution was then concentrated, and the crude product was subjected to rapid silica gel column chromatography. The silica gel column chromatography was separated using petroleum ether as the eluent, and the eluent containing the target compound was collected, the solvent was evaporated and dried to obtain the final product.

[0084] The reactants and products are shown in Table 2.

[0085] Table 2

[0086]

[0087] Specific:

[0088] Product 8: (E)-phenyl(styryl)silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.65 (dt, J=10.4, 4.1Hz, 2H), 7.48 (dd, J=9.4, 2.3Hz, 2H), 7.43-7 .31(m,6H),7.20(t,J=11.7Hz,1H),6.53(dt,J=19.0,3.3Hz,1H),4.72(d,J=3.3Hz,2H).

[0089] Product 9: (E)-(3-methylphenylvinyl)(phenyl)silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.75-7.71(m,2H),7.55-7.45(m,4H),7.39-7.32(m,3H),7.21(d,J =5.6Hz,1H),6.59(dt,J=19.0,3.3Hz,1H),4.80(d,J=3.2Hz,2H),2.45(d,J=6.2Hz,3H).

[0090] Product 10: (E)-(2-([1,1'-biphenyl]-4-yl)vinyl)(phenyl)silane, its NMR data are: 1 HNMR(400MHz, CDCl3)δ7.65(dd,J=7.6,1.7Hz,2H),7.62-7.58(m,4H),7.54(d,J=8.4Hz,2H),7 .47-7.35(m,6H),7.19(t,J=12.0Hz,1H),6.56(dt,J=19.0,3.3Hz,1H),4.73(d,J=3.2Hz,2H).

[0091] Product 11: (E)-(4-fluorophenylvinyl)(phenyl)silane, its NMR data is: 1 H NMR (400MHz, CDCl3) δ7.63 (dt, J=7.6, 3.7Hz, 2H), 7.43 (dt, J=9.9, 5.9Hz, 5H), 7.17- 7.12(m,1H),7.07-6.99(m,2H),6.43(dt,J=19.0,3.2Hz,1H),4.71(d,J=3.2Hz,2H).

[0092] Product 12: (E)-phenyl(2-(thiophen-3-yl)vinyl)silane, its NMR data is: 1H NMR (400MHz, CDCl3) δ7.61 (dt, J=4.5, 2.2Hz, 2H), 7.41-7.36 (m, 3H), 7.26 (ddd, J=7.3, 3.9, 1.7Hz, 3H), 7.13 (d, J=18.9Hz, 1H), 6.27 (ddd, J=8.8, 6.5, 3.2Hz, 1H), 4.67 (d, J=3.2Hz, 2H).

[0093] It can be seen from Examples 3-4 that the dentate metal complex prepared in the present invention is used to catalyze the hydrosilylation reaction of alkynes, and has the advantages of high reaction selectivity and high catalytic efficiency.

[0094] Example 5.

[0095] The specific steps are as follows:

[0096] (1) The bidentate cobalt complex was prepared by the method of Example 1, wherein R8, R9, R 10 They are Me, H, Me respectively, and X is Br.

[0097] (2) Under nitrogen atmosphere, 0.005 mmol (0.002 g) of the bidentate cobalt complex prepared in step (1), 1.0 mmol of alkyne substrate (CH3C≡CH), 1.5 mmol of silane (CH3O-SiH2-C6H5), 1.5 mL of ether solution, and 0.01 mmol of sodium triethylborohydride were added to the reaction tube in sequence, and the obtained mixture was stirred at room temperature for 24 h. Then, the reaction solution was concentrated, and the crude product was quickly subjected to silica gel column chromatography. The silica gel column chromatography was separated using petroleum ether as the eluent, and the eluent containing the target compound was collected, the solvent was evaporated and dried to obtain the final product. According to nuclear magnetic resonance determination, alkenyl silane compounds were also obtained. The product yields were all greater than 75%.

[0098] Example 6.

[0099] The specific steps are as follows:

[0100] (1) The bidentate cobalt complex was prepared by the method of Example 1, wherein R8, R9, R 10 They are H, tBu, tBu respectively, and X is Cl.

[0101] (2) Under nitrogen atmosphere, 0.01 mmol (0.004 g) of the bidentate cobalt complex prepared in step (1), 1.0 mmol of alkyne substrate (CH3C≡CCH3), 2.0 mmol of diphenylsilane (C6H5-SiH2-C6H5), 0.5 mL of benzene solution, 1.0 mL of toluene solution, and 0.02 mmol of sodium triethylborohydride were added to the reaction tube in sequence, and the obtained mixture was stirred at room temperature for 18 h. Then, the reaction solution was concentrated, and the crude product was quickly subjected to silica gel column chromatography. The silica gel column chromatography was separated using petroleum ether as the eluent, and the eluent containing the target compound was collected, the solvent was evaporated and dried to obtain the final product. According to nuclear magnetic resonance determination, alkenyl silane compounds were also obtained. The product yields were all greater than 72%.

[0102] Example 7.

[0103] The specific steps are as follows:

[0104] (1) The method of Example 1 was used to prepare a tridentate iron complex, wherein R8, R9, R 10 They are Me, H, and Me respectively.

[0105] (2) Under nitrogen atmosphere, 0.005 mmol (0.002 g) of the tridentate iron complex prepared in step (1), 1.0 mmol of alkyne substrate (C6H5C≡CH), 1.0 mmol of silane (CH3-SiH2-C6H5), 0.5 mL of N,N dimethylformamide solution, and 0.01 mmol of sodium tert-butoxide were added to the reaction tube in sequence, and the obtained mixture was stirred at room temperature for 18 h. Then, the reaction solution was concentrated, and the crude product was quickly subjected to silica gel column chromatography. The silica gel column chromatography was separated using petroleum ether as the eluent, and the eluent containing the target compound was collected, the solvent was evaporated and dried to obtain the final product. According to nuclear magnetic resonance determination, alkenyl silane compounds were also obtained. The product yields were all greater than 70%.

[0106] Example 8.

[0107] The operating steps of Example 8 are the same as the method for producing Product 1 in Example 3, except that ethyl acetate, dichloromethane, acetonitrile, petroleum ether, and n-hexane are used as solvents, respectively.

[0108] The final products were subjected to nuclear magnetic resonance analysis to obtain vinyl silane compounds, and the product yields were all greater than 80%.

[0109] The above is only a preferred embodiment of the embodiment of the present invention, and does not impose any form of limitation on the embodiment of the present invention. Any simple modification, equivalent changes and modifications made to the above embodiment based on the technical essence of the embodiment of the present invention are still within the scope of the technical solution of the embodiment of the present invention.

Claims

1. A toothed metal complex, characterized in that: The dentate metal complex is a bidentate cobalt complex or a tridentate iron complex, and its general chemical structure is: Wherein, X is a halogen element.

2. The toothed metal complex according to claim 1, characterized in that: In the chemical structure formula of the toothed metal complex, R8, R9, R 10 It is selected from one of H, Me, iPr, and tBu groups, and X is Cl or Br.

3. The method for preparing the toothed metal complex according to any one of claims 1 to 2, characterized in that: The chemical reaction formula of the preparation method is:

4. A method for preparing α and β alkenyl silane compounds, characterized in that: The preparation method is: Under nitrogen protection, silane, alkyne, dentate metal complex, additive and solvent are mixed, reacted at room temperature for 6-24 hours, concentrated, and separated by silica gel column chromatography to obtain α and β alkenyl silane compounds respectively; The toothed metal complex is the toothed metal complex according to any one of claims 1 to 2.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the alkyne, silane, toothed metal complex and additive is 1:1.0-2.0:005-0.03:0.01-0.05; The volume of the solvent and the molar amount of the alkyne are between 0.5-2mL:1mmol.

6. The preparation method according to claim 4, characterized in that: The structural formula of the alkyne is Wherein R1 and R2 are selected from one of aryl, heteroaryl, alkyl and hydrogen.

7. The preparation method according to claim 4, characterized in that: The structural formula of the silane is R3R4R5SiH, wherein R3, R4, and R5 are selected from one of hydrogen, alkyl, alkoxy, and aryl.

8. The preparation method according to claim 4, characterized in that: The solvent is selected from at least one of tetrahydrofuran, ether, benzene, toluene, ethyl acetate, dichloromethane, acetonitrile, petroleum ether, n-hexane, and N,N-dimethylformamide.

9. The preparation method according to claim 4, characterized in that: The additive is sodium triethylborohydride or sodium tert-butoxide.

10. The preparation method according to claim 4, characterized in that: In the silica gel column chromatography separation process, petroleum ether is used as the eluent.

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