Silaindene compound as well as preparation method and application thereof

Abstract

The invention discloses a silaindene compound as well as a preparation method and application thereof. The structural formula of the silaindene compound is shown in the specification, and in the formula, R is selected from-H, methyl, ethyl, n-butyl or halogen. The preparation method of the silaindene compound comprises the following steps: dispersing a dimethyl (2-(phenylethynyl) phenyl) (vinyl) silane compound, a cobalt catalyst, an organic ligand, an additive and a reducing agent in an organic solvent for reaction. The silaindene compound disclosed by the invention has potential application value in the fields of medicinal chemistry, photoelectric devices, fluorescent probes, chemical sensing and the like, and the preparation method has the advantages of simplicity in operation, cheap and easily available raw materials, mild reaction conditions, high atom economy, wide substrate adaptability, easiness in product purification, low production cost, greenness, safety and the like; the method is suitable for large-scale industrial production and application.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, specifically to a silane-indene compound, its preparation method, and its application. Background Technology

[0002] Benzosilane heterocyclic compounds, possessing π-conjugated systems and silicon-based hyperconjugation effects, have become important building blocks for numerous functional molecular materials, demonstrating enormous application potential. Studies have shown that introducing silicon into the carbon framework can significantly enhance the bioactivity, photophysical properties, and electronic characteristics of organosilicon molecules. Therefore, developing diverse synthetic strategies for benzosilane heterocyclic frameworks has become a core issue in medicinal chemistry and materials science.

[0003] Currently, the synthesis of benzo[a]silane heterocyclic compounds mostly requires the use of precious metal catalysts such as palladium and rhodium. Not only is the production cost of the catalyst high, but each reaction system can usually only synthesize one type of compound, resulting in poor substrate adaptability and failing to meet the needs of practical applications.

[0004] Therefore, it is of great significance to develop a method for preparing benzo[a]silane heterocyclic compounds that is simple to operate, uses inexpensive and readily available raw materials, has mild reaction conditions, high atom economy, broad substrate adaptability, easy product purification, low production cost, and is green and safe, and to prepare a variety of novel benzo[a]silane heterocyclic compounds. Summary of the Invention

[0005] The purpose of this invention is to provide a silicon-indene compound, its preparation method, and its application.

[0006] The technical solution adopted in this invention is:

[0007] A silicon-based indene compound has the following structural formula: In the formula, R is selected from -H, methyl, ethyl, n-butyl or halogen.

[0008] A method for preparing the silicon-indene compound as described above includes the following steps: A dimethyl (2-(phenylethynyl)phenyl)(vinyl)silane compound, a cobalt catalyst, an organic ligand, an additive, and a reducing agent are dispersed in an organic solvent for reaction. The dimethyl (2-(phenylethynyl)phenyl)(vinyl)silane compound is... Silica-indene compounds were obtained.

[0009] The synthesis reactions of silane-indene compounds are as follows: .

[0010] Preferably, the ratio of the dimethyl (2-(phenylethynyl)phenyl)(vinyl)silane compound, cobalt catalyst, organic ligand, additive, and reducing agent is 1:0.1-0.2:0.1-0.2:0.1-0.5:0.2-1.0.

[0011] Preferably, the cobalt catalyst is at least one of cobalt acetate and cobalt iodide.

[0012] More preferably, the cobalt catalyst is cobalt acetate tetrahydrate.

[0013] Preferably, the organic ligand is at least one selected from 1,2-bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, and 1,2-bis(diphenylphosphine)propane.

[0014] More preferably, the organic ligand is 1,2-bis(diphenylphosphine)methane.

[0015] Preferably, the additive is zinc halide.

[0016] More preferably, the additive is at least one of zinc chloride, zinc bromide, and zinc iodide.

[0017] More preferably, the additive is zinc iodide.

[0018] Preferably, the reducing agent is at least one of zinc powder, manganese powder, and magnesium powder.

[0019] More preferably, the reducing agent is zinc powder.

[0020] Preferably, the organic solvent is at least one of dichloromethane, trichloromethane, and chlorobenzene.

[0021] Preferably, the reaction is carried out at a temperature of 60℃ to 120℃ for a reaction time of 2h to 12h.

[0022] Preferably, the reaction is carried out in an argon atmosphere.

[0023] Preferably, after the reaction is completed, product separation and purification operations are also performed.

[0024] Preferably, the product separation and purification includes the following steps: filtering the reaction solution, concentrating the filtrate, and then performing column chromatography.

[0025] Preferably, the eluent used in the column chromatography is petroleum ether.

[0026] Application of a silicon-indene compound as described above in the preparation of pharmaceuticals, optoelectronic devices, fluorescent probes, or chemical sensors.

[0027] The beneficial effects of this invention are: the silicon-indene compounds of this invention have potential application value in the fields of medicinal chemistry, optoelectronic devices, fluorescent probes and chemical sensing, and their preparation method has the advantages of simple operation, inexpensive and readily available raw materials, mild reaction conditions, high atom economy, wide substrate adaptability, easy product purification, low production cost, green and safe, etc., making them suitable for large-scale industrial production and application. Attached Figure Description

[0028] Figure 1 The image shows the 1H NMR spectrum of the silicon-indene compound from Example 1.

[0029] Figure 2 The image shows the carbon NMR spectrum of the silicon-indene compound from Example 1.

[0030] Figure 3 The image shows the 1H NMR spectrum of the silicon-indene compound from Example 2.

[0031] Figure 4 The image shows the carbon NMR spectrum of the silicon-indene compound from Example 2.

[0032] Figure 5 The image shows the 1H NMR spectrum of the silicon-indene compound from Example 3.

[0033] Figure 6 The image shows the carbon NMR spectrum of the silicon-indene compound from Example 3.

[0034] Figure 7 The image shows the hydrogen nuclear magnetic resonance spectrum of the silicon-indene compound in Example 4.

[0035] Figure 8 The image shows the carbon NMR spectrum of the silicon-indene compound in Example 4.

[0036] Figure 9 The image shows the 1H NMR spectrum of the silicon-indene compound from Example 5.

[0037] Figure 10 The image shows the carbon NMR spectrum of the silicon-indene compound from Example 5.

[0038] Figure 11 The 1H NMR spectrum of 1,2-diphenyl-1,3-butadiene is shown in the example.

[0039] Figure 12 The image shows the carbon NMR spectrum of 1,2-diphenyl-1,3-butadiene as an application example. Detailed Implementation

[0040] The present invention will be further explained and described below with reference to specific embodiments.

[0041] Example 1: A silicon-based indene compound, the preparation method of which is as follows: 0.20 mmol of dimethyl(2-(phenylethynyl)phenyl)(vinyl)silane, 0.02 mmol of cobalt acetate tetrahydrate, 0.02 mmol of 1,2-bis(diphenylphosphine)methane, 0.04 mmol of zinc iodide, and 0.1 mmol of zinc powder were dispersed in 2 mL of dichloromethane. The mixture was then stirred at 100 °C for 2 h under an argon atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated under reduced pressure and then subjected to column chromatography using petroleum ether as the eluent. This yielded 38 mg of a silane-indene compound (pale yellow liquid; yield: 73%).

[0042] The 1H NMR spectrum of the silicon-indene compound in this embodiment is shown below. Figure 1 As shown, the carbon NMR spectrum is as follows: Figure 2 As shown.

[0043] Spectral analysis: 1 H NMR (400 MHz, Chloroform-d): δ 7.80 (d, J = 8.0 Hz, 0.88H), 7.63 (ddd, J = 7.2, 1.5, 0.7 Hz, 1H), 7.57 - 7.52 (m, 1.78H), 7.46 (ddd, J = 8.2,7.3, 1.4 Hz, 1H), 7.39 - 7.30 (m, 3.4H), 7.28 - 7.21 (m, 1.14H), 7.16 (s,0.87H), 7.10 (ddd, J = 8.6, 7.3, 1.4 Hz, 0.17H), 7.02 (s, 0H), 6.28 (d, J =1.9 Hz, 0.14H), 6.01 (dd, J = 2.5, 0.7 Hz, 0.86H), 5.60 (dd, J = 2.6, 0.8 Hz, 0.86H), 5.53 (d, J = 1.9 Hz, 0.14H), 0.44 (d, J = 4.0 Hz, 6H).

[0044] 13 C NMR (101 MHz, Chloroform-d): δ 149.89, 148.07, 142.43, 139.04,138.39, 132.53, 130.13, 129.03, 128.25, 127.35, 126.80, 126.54, 122.45,121.25, -2.48.

[0045] HR-MS: Theoretical value [M+H] + :C 18 H 19 Si: 263.1251, Measured value: 263.1256.

[0046] In summary, the structural formula of the silicon-indene compound in this embodiment is as follows: .

[0047] Example 2: A silicon-based indene compound, the preparation method of which is as follows: 0.20 mmol of (2-((4-methylphenyl)ethynyl)phenyl)dimethyl(vinyl)silane, 0.02 mmol of cobalt acetate tetrahydrate, 0.02 mmol of 1,2-bis(diphenylphosphine)methane, 0.04 mmol of zinc iodide, and 0.1 mmol of zinc powder were dispersed in 2 mL of dichloromethane. The mixture was then stirred at 100 °C for 2 h under an argon atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated under reduced pressure and then subjected to column chromatography using petroleum ether as the eluent. This yielded 40 mg of a silane-indene compound (pale yellow liquid; yield: 74%).

[0048] The 1H NMR spectrum of the silicon-indene compound in this embodiment is shown below. Figure 3 As shown, the carbon NMR spectrum is as follows: Figure 4 As shown.

[0049] Spectral analysis: 1H NMR (500 MHz, Chloroform-d): δ 7.73 (d, J = 8.0 Hz, 0.74H), 7.55 (t, J = 6.5 Hz, 1H), 7.53 - 7.49 (m, 0.33H), 7.42 - 7.36 (m, 2.34H), 7.32 (d,J = 7.5 Hz,0.27H), 7.27 (dd, J = 7.5, 4.3 Hz, 1.23H), 7.18 - 7.13 (m, 0.74H),7.11 (dd, J = 7.9, 4.2 Hz, 1.83H), 7.07 (s, 0.74H), 6.93 (s, 7.26H), 6.20 (d,J = 1.8 Hz, 0.26H), 6.01 (d, J = 2.6 Hz, 0.74H), 5.55 (d, J = 2.6 Hz, 0.74H), 5.46 (d, J = 1.8 Hz, 0.36H), 2.36 (s, 1H), 2.34 (s, 2H), 0.38 (d, J = 4.0 Hz, 6H).

[0050] 13 C NMR (126 MHz, Chloroform-d): δ 155.10, 152.52, 150.69, 149.61,144.36, 143.55, 141.37, 140.88, 138.96, 138.74, 138.00, 137.73, 134.97,134.87, 134.05, 134.00, 131.66, 131.61, 131.42, 131.40, 130.90, 130.81,129.66, 129.04, 125.00, 124.23, 123.64, 120.64.

[0051] HR-MS: Theoretical value [M+H] + :C 19 H 21 Si: 277.1407, Measured value: 277.1399.

[0052] In summary, the structural formula of the silicon-indene compound in this embodiment is as follows: .

[0053] Example 3: A silicon-based indene compound, the preparation method of which is as follows: 0.20 mmol of (2-((4-ethylphenyl)ethynyl)phenyl)dimethyl(vinyl)silane, 0.02 mmol of cobalt acetate tetrahydrate, 0.02 mmol of 1,2-bis(diphenylphosphine)methane, 0.04 mmol of zinc iodide, and 0.1 mmol of zinc powder were dispersed in 2 mL of dichloromethane. The mixture was then stirred at 100 °C for 2 h under an argon atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated under reduced pressure and then subjected to column chromatography using petroleum ether as the eluent. This yielded 39 mg of a silane-indene compound (pale yellow liquid; yield: 68%).

[0054] The 1H NMR spectrum of the silicon-indene compound in this embodiment is shown below. Figure 5 As shown, the carbon NMR spectrum is as follows: Figure 6 As shown.

[0055] Spectral analysis: 1 H NMR (400 MHz, Chloroform-d): δ 7.73 (d, J = 8.0 Hz, 1H), 7.56 (d, J= 7.0 Hz, 1H), 7.40 (dd, J = 17.3, 7.9 Hz, 3H), 7.32 - 7.22 (m, 2H), 7.14 (d,J = 7.9 Hz, 2H), 7.08 (s, 1H), 6.94 (s, 0H), 6.20 (s, 0H), 6.02 (t, J = 2.0Hz, 1H), 5.55 (t, J = 2.0 Hz, 1H), 5.46 (s, 0H), 2.64 (q, J = 7.6 Hz, 2H),1.25 (t, J = 7.2 Hz, 5H), 0.38 (d, J = 1.6 Hz, 5H).

[0056] 13 C NMR (101 MHz, Chloroform-d): δ 142.69, 141.87, 138.90, 135.50,132.46, 130.07, 128.96, 127.69, 127.16, 126.50, 122.57, 121.16, 28.64, 15.48,-2.51.

[0057] HR-MS: Theoretical value [M+H] + :C 20 H 23 Si: 291.1564, Measured value: 291.1568.

[0058] In summary, the structural formula of the silicon-indene compound in this embodiment is as follows: .

[0059] Example 4: A silicon-based indene compound, the preparation method of which is as follows: 0.20 mmol of (2-((4-n-butylphenyl)ethynyl)phenyl)dimethyl(vinyl)silane, 0.02 mmol of cobalt acetate tetrahydrate, 0.02 mmol of 1,2-bis(diphenylphosphine)methane, 0.04 mmol of zinc iodide, and 0.1 mmol of zinc powder were dispersed in 2 mL of dichloromethane. The mixture was then stirred at 100 °C for 2 h under an argon atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated under reduced pressure and then subjected to column chromatography using petroleum ether as the eluent. This yielded 44 mg of a silane-indene compound (pale yellow liquid; yield: 70%).

[0060] The 1H NMR spectrum of the silicon-indene compound in this embodiment is shown below. Figure 7 As shown, the carbon NMR spectrum is as follows: Figure 8 As shown.

[0061] Spectral analysis: 1 H NMR (400 MHz, Chloroform-d): δ 7.78 (dt, J = 8.1, 0.9 Hz, 1H), 7.61 (ddd, J = 7.2, 1.4, 0.7 Hz, 1H), 7.49 - 7.41 (m, 3H), 7.34 - 7.28 (m, 1H),7.18 - 7.15 (m, 2H), 7.12 (s, 1H), 6.06 (d, J = 2.6 Hz, 1H), 5.60 (d, J = 2.6Hz, 1H), 2.68 - 2.63 (m, 2H), 1.66 (tt, J = 9.1, 6.9 Hz, 2H), 1.41 (dt, J =14.6, 7.3 Hz, 3H), 0.98 (t, J = 7.3 Hz, 3H), 0.42 (s, 6H).

[0062] 13C NMR (101 MHz, Chloroform-d): δ 150.11, 148.24, 141.83, 141.39,138.89, 135.46, 132.49, 130.09, 128.89, 128.27, 127.17, 126.52, 122.61,121.18, 35.47, 33.61, 22.43, 14.01, -2.48.

[0063] HR-MS: Theoretical value [M+H] + :C 22 H 27 Si: 319.1877, Measured value: 319.1869.

[0064] In summary, the structural formula of the silicon-indene compound in this embodiment is as follows: .

[0065] Example 5: A silicon-based indene compound, the preparation method of which is as follows: 0.20 mmol of (2-((4-chlorophenyl)ethynyl)phenyl)dimethyl(vinyl)silane, 0.02 mmol of cobalt acetate tetrahydrate, 0.02 mmol of 1,2-bis(diphenylphosphine)methane, 0.04 mmol of zinc iodide, and 0.1 mmol of zinc powder were dispersed in 2 mL of dichloromethane. The mixture was then stirred at 100 °C for 2 h under an argon atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated under reduced pressure and then subjected to column chromatography using petroleum ether as the eluent. This yielded 38 mg of a silane-indene compound (pale yellow liquid; yield: 65%).

[0066] The 1H NMR spectrum of the silicon-indene compound in this embodiment is shown below. Figure 9 As shown, the carbon NMR spectrum is as follows: Figure 10 As shown.

[0067] Spectral analysis: 1H NMR (400 MHz, Chloroform-d): δ 7.77 (d, J = 8.0 Hz, 0.75H), 7.63 (d, J = 7.2 Hz, 1H), 7.52 - 7.42 (m, 2.48H), 7.36 - 7.30 (m, 3.44H), 7.16 -7.11 (m, 0.25H), 7.05 (s, 0.75H), 6.90 (s, 0.25H), 6.25 (d, J = 1.8 Hz,0.25H), 6.01 (d, J = 2.5 Hz, 0.75H), 5.62 (d, J = 2.6 Hz, 0.75H), 5.53 (d, J= 1.8 Hz, 0.25H), 0.44 (d, J = 2.6 Hz, 6H).

[0068] 13 C NMR (101 MHz, Chloroform-d): δ 154.83, 151.89, 150.41, 148.92,145.53, 145.34, 143.70, 141.43, 139.39, 139.09, 135.14, 134.87, 134.42,133.94, 131.34, 131.00, 130.75, 129.85, 129.35, 128.74, 123.54, 123.26,122.51, 120.92, -0.00, -0.23.

[0069] HR-MS: Theoretical value [M+H] + :C 18 H 18 ClSi: 297.0861, Measured value: 297.0846.

[0070] In summary, the structural formula of the silicon-indene compound in this embodiment is as follows: .

[0071] Application example: A method for preparing 1,2-diphenyl-1,3-butadiene (a key raw material for synthesizing light guide plates, see patent: CN 104101939A) is as follows: 0.2 mmol of the silane-indene compound from Example 1, 0.02 mmol of palladium acetate (Pd(OAc)2), 0.02 mmol of 1,4-bis(diphenylphosphine)butane (DPPB), and 0.4 mmol of tetrabutylammonium fluoride (TBAF) were dispersed in 2 mL of tetrahydrofuran (THF). The mixture was stirred at room temperature for 12 h. The reaction solution was then concentrated by vacuum evaporation and column chromatography using petroleum ether as the eluent to obtain 7.5 mg of 1,2-diphenyl-1,3-butadiene (colorless transparent liquid; yield: 19%).

[0072] The synthesis reaction of 1,2-diphenyl-1,3-butadiene in this application example is as follows: .

[0073] The 1H NMR spectrum of 1,2-diphenyl-1,3-butadiene in this application example is as follows: Figure 11 As shown, the carbon NMR spectrum is as follows: Figure 12 As shown.

[0074] Spectral analysis: 1 H NMR (500 MHz, Chloroform-d): δ 7.40 - 7.24 (m, 7H), 7.13 - 7.06 (m,1H), 7.04 - 6.92 (m, 1.42H), 6.82 (dd, J = 7.2, 2.6 Hz, 1H), 6.67 (dd, J =17.2, 10.5 Hz, 0.58H), 6.53 (d, J = 4.5 Hz, 1H), 5.29 (d, J = 11.0 Hz,0.58H), 5.16 (dd, J = 17.5, 1.6 Hz, 0.58H), 5.09 (d, J = 10.4 Hz, 0.42H),4.77 (d, J = 17.2 Hz, 0.42H).

[0075] 13 C NMR (126 MHz, Chloroform-d): δ 141.78, 141.76, 137.9, 137.3, 136.7,134.7, 131.5, 130.9, 129.60, 129.4, 129.2, 128.8, 128.2, 128.1, 128.0, 127.4,127.3, 127.1, 126.9, 119.7, 116.5.

[0076] In summary, the structural formula of 1,2-diphenyl-1,3-butadiene in this application example is as follows: .

[0077] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A silicon-indene compound, characterized in that, The structure is as follows: In the formula, R is selected from -H, methyl, ethyl, n-butyl or halogen.

2. A method for preparing the silicon-indene compound as described in claim 1, characterized in that, Includes the following steps: A dimethyl (2-(phenylethynyl)phenyl)(vinyl)silane compound, a cobalt catalyst, an organic ligand, an additive, and a reducing agent are dispersed in an organic solvent for reaction. The dimethyl (2-(phenylethynyl)phenyl)(vinyl)silane compound is... Silica-indene compounds were obtained.

3. The preparation method according to claim 2, characterized in that: The ratio of the dimethyl (2-(phenylethynyl)phenyl)(vinyl)silane compound, cobalt catalyst, organic ligand, additive, and reducing agent is 1:0.1-0.2:0.1-0.2:0.1-0.5:0.2-1.

0.

4. The preparation method according to claim 2 or 3, characterized in that: The cobalt catalyst is at least one of cobalt acetate and cobalt iodide.

5. The preparation method according to claim 2 or 3, characterized in that: The organic ligand is at least one of 1,2-bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, and 1,2-bis(diphenylphosphine)propane.

6. The preparation method according to claim 2 or 3, characterized in that: The additive is zinc halide.

7. The preparation method according to claim 2 or 3, characterized in that: The reducing agent is at least one of zinc powder, manganese powder, and magnesium powder.

8. The preparation method according to claim 2, characterized in that: The organic solvent is at least one of dichloromethane, trichloromethane, and chlorobenzene.

9. The preparation method according to any one of claims 2, 3 and 8, characterized in that: The reaction was carried out at a temperature of 60℃ to 120℃ for a time of 2h to 12h.

10. The use of a silicon-indene compound as described in claim 1 in the preparation of pharmaceuticals, optoelectronic devices, fluorescent probes, or chemical sensors.

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