Preparation method of dialkynyl silane compound

Abstract

The invention discloses a preparation method of a dialkynyl silane compound, which belongs to the technical field of organic synthesis and comprises the following steps: sequentially adding a reducing agent, an organic solvent, alkynyl bromide and chlorosilane into a reaction container, and reacting at 20-60 DEG C for 6-36 hours to obtain a mixture A; wherein R1 is allyl, alkyl or aryl; wherein R2 is allyl, alkyl or aryl; wherein R3 is an alkenyl group, an alkyl group, an alkoxy group or a silicon group; wherein R is halogen, alkyl, aryl, alkoxy, ester group, cyano or carbonyl; diluting the mixture A with ethyl acetate, adding silica gel powder, and performing vacuum concentration to remove the reaction solvent to obtain a mixture B; and separating the mixture B through thin-layer chromatography or column chromatography to obtain the target product dialkynyl silane compound. According to the method, dialkynyl silane substituted by different alkynyl groups can be obtained at the same time, the chemical selectivity is good, and dialkynyl silane which is not easy to obtain by other methods can be synthesized.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of organic synthesis, in particular to a preparation method of a diacetylsilyl compound. BACKGROUND

[0002] As a frequently used synthon in organic synthetic chemistry, the core value of organosilane is first reflected in the aspect of bond construction: from the perspective of classic construction of carbon-carbon bond, Hiyama coupling, Kumada coupling, Peterson olefin synthesis and Saegusa oxidation reaction all take it as a key participant, becoming the mainstream strategy for building carbon skeleton. On this basis, the functional value of organosilane is more prominent--introducing silicon atoms into material or drug molecules can often specifically regulate the electrochemical stability, solubility and pharmacokinetic properties of the compounds, providing the possibility of precise modification for the design of functional molecules. Acetylsilyl is an indispensable important branch, and diacetylsilyl is more concerned as a key precursor of aggregation-induced emission (AIE) material. However, its synthesis has long been a challenge: the traditional method relies on the reaction of Grignard reagent (R-M, M=Mg, Li) and dichlorosilane (R1R2SiCl2) under low temperature (-78 DEG C) conditions, which not only needs a strict waterless and oxygenless atmosphere, but also has poor compatibility with ester groups, cyano groups, carbonyl groups and the like, greatly limiting the application scenarios. In order to break through this limitation, synthetic chemists turn to the cross-coupling strategy of double electrophilic reagents: using electrophilic reagents (R-X, X=Cl, Br, I) such as aryl, alkyl or acetylene to directly couple with chlorosilane to generate acetylsilyl. Compared with the traditional method, the strategy significantly improves the mildness of the reaction conditions and the applicability of the functional groups. However, the existing cross-coupling strategy still has shortcomings: not only does it need metal catalysts, reducing agents and ligands to participate together, but also the product is mostly limited to monochlorosilane. Therefore, developing a new synthesis strategy without metal catalysts, under mild conditions and compatible with dichlorosilane has become a core direction that needs to be overcome in the current field, and it has attracted more and more attention. Therefore, the application provides a preparation method of a diacetylsilyl compound. SUMMARY

[0003] Therefore, the technical problem to be solved by the application is that the existing cross-coupling strategy needs metal catalysts, reducing agents and ligands to participate together, and the product is mostly limited to monochlorosilane.

[0004] To solve the above technical problems, the application provides a preparation method of a diacetylsilyl compound, which comprises the following steps: Step one: sequentially adding a reducing agent, an organic solvent, an acetylene bromide and a chlorosilane into a reaction container, and reacting at 20-60 DEG C for 6-36 h to obtain a mixture A; The structure of the chlorosilane is:

[0005] wherein R1 is allyl, alkyl or aryl; wherein R2 is allyl, alkyl or aryl; The structure of the alkynyl bromide is: or

[0006] wherein R3 is alkenyl, alkyl, alkoxy or silyl; wherein R is halogen, alkyl, aryl, alkoxy, ester, cyano or carbonyl; Step two: dilute mixture A with ethyl acetate, add silica gel powder, and remove the reaction solvent under reduced pressure to obtain mixture B; Step three: separate mixture B by thin layer chromatography or column chromatography to obtain the target product di-alkynyl silyl compound.

[0007] Preferably, the molar ratio of the reducing agent, alkynyl bromide and chlorosilane is 2.5-3.5:2.0-3.0:0.8-1.2, and the corresponding organic solvent for each mole of chlorosilane is 1-3 L.

[0008] Preferably, in step one, the molar ratio of the reducing agent, alkynyl bromide and chlorosilane is 3.0:2.5:1.0, and the corresponding organic solvent for each mole of chlorosilane is 1-2 L.

[0009] Preferably, the organic solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, 1,2-dichloroethane, toluene, 1,4-dioxane, acetonitrile, ethylene glycol dimethyl ether, methyl tert-butyl ether, polyethylene glycol dimethyl ether and ethylene glycol diethyl ether.

[0010] Preferably, the organic solvent is tetrahydrofuran and acetonitrile.

[0011] Preferably, the reaction temperature in step one is 35-45℃.

[0012] Preferably, the reaction time in step one is 24 h.

[0013] Preferably, the reducing agent is Zn powder, Mn powder or Fe powder.

[0014] Preferably, the alkyl of R is methyl, n-butyl, cyclopropyl; 3,3,3-trifluoropropyl, 1-chloro-propyl, phenethyl or cyclohexylmethyl.

[0015] Preferably, the halogen is fluorine, chlorine or bromine.

[0016] The technical scheme of the present application has the following advantages: 1. The application can obtain different alkynyl-substituted di-alkynylsilanes simultaneously, has good chemical selectivity, and can synthesize di-alkynylsilanes that are not easy to obtain by other methods. 2. The method has high yield, mild reaction conditions, simple operation steps, wide substrate range, simple and green post-treatment. DETAILED DESCRIPTION

[0017] The following examples are provided to better further understand the application, and are not limited to the best mode, and do not constitute a limitation on the content and protection scope of the application, and any person under the inspiration of the application or the combination of the application with other prior art features obtains any product same or similar to the application, which falls within the protection scope of the application.

[0018] The specific experimental steps or conditions are not indicated in the examples, and can be operated according to the conventional experimental steps described in the literature in the art or the operation or conditions. The reagents or instruments used are not indicated by the manufacturer, and are conventional reagent products that can be obtained by market purchase.

[0019] The reaction equation of the application is as follows: Example 1

[0020] Preparation of dimethyl 4,4'-((dimethylsilanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0021] In a glove box (nitrogen atmosphere), Zn powder 0.6mmol, acetonitrile 2mL, 4-(bromoethynyl)benzoic acid methyl ester 0.5mmol, dimethyldichlorosilane 0.2mmol were added to an 8mL reaction bottle with a magnetic stirrer, after addition, the reaction bottle was sealed and taken out of the glove box, and reacted at 40℃ for 24h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and 3g of silica gel was added, and the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 67.7mg of the target product, with a yield of 90%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.1 Hz, 4H), 7.57 (d, J = 8.0Hz, 4H), 3.92 (s, 6H), 0.51 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 166.4, 132.0,130.1, 129.4, 127.1, 105.0, 93.5, 52.2, 0.2. Example 2

[0022] Preparation of dimethyl 4,4'-((diphenylsilanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0023] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, methyl 4-(bromoethynyl)benzoate 0.5 mmol, diphenyldichlorosilane 0.2 mmol were added to a 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 50.0 mg of the target product, the yield was 50%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.0 Hz, 1H), 7.91 – 7.82 (m,1H), 7.65 (d, J = 8.0 Hz, 1H), 7.46 (q, J = 6.9 Hz, 1H), 3.92 (s, 1H). 13 C NMR(101 MHz, CDCl3) δ 166.3, 134.9, 132.3, 132.0, 130.5, 130.4, 129.4, 128.21126.8, 107.7, 90.6, 52.5. Example 3

[0024] Preparation of dimethyl 4,4'-((cyclopropyl(phenyl)silanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0025] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, methyl 4-(bromoethynyl)benzoate 0.5 mmol, dichloro(cyclopropyl)(phenyl)silane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and the reaction was carried out at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 65.0 mg of the target product, the yield was 70%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.1 Hz, 4H),7.92 –7.85 (m, 2H), 7.60 (d, J = 8.1 Hz, 4H), 7.50 – 7.42 (m, 3H), 3.91 (s, 6H),0.88 – 0.82 (m, 2H), 0.76 – 0.68 (m, 2H), 0.16 – 0.05 (m, 1H). 13 C NMR (101MHz, CDCl3) δ 166.3, 134.5, 132.6, 132.2, 130.4, 130.2, 129.3, 128.1, 126.8,106.4, 90.4, 52.2, 2.3, -6.0. Example 4

[0026] Preparation of dimethyl 4,4'-((butyl(phenyl)silanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0027] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, methyl 4-(bromoethynyl)benzoate 0.5 mmol, butyldichloro(phenyl)silane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and the reaction was carried out at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 65.0 mg of the target product, the yield was 70%. The nuclear magnetic resonance characterization of the compound is as follows: 1H NMR (600 MHz, CDCl3) δ 8.05 - 7.99 (m, 4H), 7.89 - 7.80 (m, 2H), 7.64 - 7.58 (m, 4H), 7.50 - 7.41 (m, 3H), 3.92 (s, 6H), 1.65 - 1.56 (m, 2H), 1.46 (h, J = 7.3 Hz, 2H), 1.18 - 1.10 (m, 2H), 0.93 (t, J = 7.3 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 166.4, 134.4, 132.6, 132.2, 130.3, 130.2, 129.4, 128.1, 127.0, 106.7, 91.4, 52.3, 25.9, 25.6, 15.5, 13.7. Example 5

[0028] Preparation of dimethyl 4,4'-(((3-chloropropyl)(methyl)silanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0029] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, methyl 4-(bromoethynyl)benzoate 0.5 mmol, dichloro(3-chloropropyl)(phenyl)silane 0.2 mmol were added to a 8 mL reaction bottle equipped with a magnetic, after adding, the reaction bottle was sealed and taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 63.0 mg of the target product, yield 72%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 8.1 Hz, 4H), 7.58(d, J = 8.1 Hz, 4H), 3.92 (s, 6H), 3.65 (t, J = 6.8 Hz, 2H), 2.22 - 1.99 (m, 2H), 1.25 - 0.87 (m, 2H), 0.51 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 166.3, 132.0, 130.2, 129.3, 126.8, 105.8, 92.0, 52.2, 47.2, 27.2, 13.6, -1.5. Example 6

[0030] Preparation of dimethyl 4,4'-((phenyl(3,3,3-trifluoropropyl)silanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0031] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, methyl 4-(bromoethynyl)benzoate 0.5 mmol, dichloro(phenyl)(3,3,3- trifluoropropyl)silane 0.2 mmol were added to a 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and the reaction was carried out at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed under reduced pressure, and the mixture was purified by silica gel column chromatography to obtain 98.8 mg of the target product, yield 95%. The nuclear magnetic characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.2 Hz, 3H), 7.82 (dd, J = 7.1, 2.1 Hz, 2H), 7.64 (s, 4H), 7.57 - 7.42 (m, 3H), 3.92 (s, 6H), 2.46 - 2.26 (m, 2H), 1.39 - 1.32 (m, 2H). 13 C NMR (101 MHz, CDCl3) δ 166.2, 134.3, 132.2, 130.9, 130.7, 130.6, 129.5, 128.4, 127.4 (q, J = 277.2 Hz), 126.4, 107.78, 89.3, 52.3, 28.5 (q, J = 30.5 Hz), 8.3 (q, J = 2.3 Hz). Example 7

[0032] Preparation of dimethyl 4,4'-((allyl(phenyl)silanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0033] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, methyl 4-(bromoethynyl)benzoate 0.5 mmol, allyldichloro(phenyl)silane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and brought out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 83.5 mg of the target product, yield 90%. The nuclear magnetic characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 8.1 Hz, 4H), 7.87 – 7.81(m, 2H), 7.61 (d, J = 8.1 Hz, 4H), 7.50 – 7.39 (m, 3H), 5.94 (ddt, J = 17.7,9.9, 7.8 Hz, 1H), 5.19 – 4.99 (m, 2H), 3.91 (s, 6H), 2.14 (d, J = 7.9 Hz,2H). 13 C NMR (101 MHz, CDCl3) δ 166.2, 134.4, 132.2, 131.7, 131.6, 130.4,130.3, 129.3, 128.1, 126.7, 116.0, 107.2, 90.5, 52.2, 23.3. Example 8

[0034] Preparation of dimethyl 4,4'-((methyl(thiophen-2-yl)silanediyl)bis(ethyne-2,1-diyl))dibenzoate

[0035] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, methyl 4-(bromoethynyl)benzoate 0.5 mmol, dichloro(methyl)(thiophen-2-yl)silane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and brought out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 66.6 mg of the target product, yield 75%. The nuclear magnetic characterization of the compound is as follows: 1H NMR (400 MHz, CDC13) δ 8.00 (d, J = 8.0 Hz, 4H), 7.73 (d, J = 4.6 Hz, 1H), 7.65 - 7.56 (m, 5H), 7.26 (dd, J = 4.7, 3.2 Hz, 1H), 3.91 (s, 6H), 0.79 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 166.3, 136.8, 132.7, 132.5, 132.1, 130.4, 129.4, 128.5 126.72, 106.3, 91.6, 52.3, 0.8. Example 9

[0036] Preparation of dimethylbis(phenylethynyl)silane

[0037] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, (bromoethynyl)benzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction bottle equipped with a magnetic, after adding, sealing the reaction bottle, and taking it out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and added 3 g of silica gel, concentrated under reduced pressure to remove the solvent, the mixture was purified by silica gel column chromatography to obtain 35.4 mg of the target product, yield 68%. The nuclear magnetic characterization of the compound is as follows: 1 H NMR (400 MHz, CDC13) δ 8.00 (d, J = 8.0 Hz, 4H), 7.73 (d, J = 4.6 Hz, 1H), 7.65 - 7.56 (m, 5H), 7.26 (dd, J = 4.7, 3.2 Hz, 1H), 3.91 (s, 6H), 0.79 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 166.3, 136.8, 132.7, 132.5, 132.1, 130.4, 129.4, 128.5 126.72, 106.3, 91.6, 52.3, 0.8. Example 10

[0038] Preparation of bis((4-fluorophenyl)ethynyl)dimethylsilane

[0039] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1- (bromoethynyl)-4-fluorobenzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 47.4 mg of the target product, yield 80%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.62 – 7.34 (m, 4H), 7.00 (t, J = 8.7 Hz,4H), 0.47 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 162.8 (d, J = 250.6 Hz), 134.1(d, J = 8.6 Hz), 118.7 (d, J = 3.6 Hz), 115.5 (d, J = 22.1 Hz), 104.8, 90.3,0.4. Example 11

[0040] Preparation of bis((4-chlorophenyl)ethynyl)dimethylsilane

[0041] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1- (bromoethynyl)-4-fluorobenzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 47.4 mg of the target product, yield 80%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.43 (d, J = 8.5 Hz, 4H), 7.28 (d,J = 8.5 Hz, 4H), 0.48 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 135.0, 133.3, 128.6,121.1, 104.7, 91.6, 0.3. Example 12

[0042] Preparation of bis((4-bromophenyl)ethynyl)dimethylsilane

[0043] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1- bromo-4-(bromoethynyl)benzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 49.9 mg of the target product, with a yield of 60%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.48 – 7.42 (m, 4H), 7.40 – 7.33 (m, 4H),0.47 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 133.6, 131.6, 123.3, 121.6, 104.8,91.8, 0.3. Example 13

[0044] Preparation of dimethylbis(o-tolylethynyl)silane

[0045] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1- bromo-4-(bromoethynyl)benzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 49.9 mg of the target product, with a yield of 60%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 7.6 Hz, 2H), 7.25 – 7.16 (m,4H), 7.15 – 7.08 (m, 2H), 2.46 (s, 6H), 0.50 (d, J = 1.3 Hz, 6H). 13C NMR (101 MHz, CDC13) δ 140.9, 132.2, 129.4, 128.8, 125.4, 122.5, 104.8, 94.8, 20.60, 0.6, 0.6. Example 14

[0046] Preparation of bis((4-(tert-butyl)phenyl)ethynyl)dimethylsilane

[0047] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1-(bromoethynyl)-4-tert-butylbenzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction bottle with a magnetic, after adding, sealing the reaction bottle, and take it out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and add 3 g of silica gel, remove the solvent under reduced pressure, the mixture was purified by silica gel column chromatography to obtain 52.1 mg of the target product, yield 70%. The nuclear magnetic characterization of the compound is as follows: 1 H NMR (400 MHz, CDC13) δ 7.44 (d, J = 8.0 Hz, 4H), 7.31 (d, J = 8.1 Hz, 4H), 1.30 (s, 24H), 0.47 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 152.1, 131.9, 125.2, 119.7, 106.1, 90.0, 34.8, 31.1, 0.6, 0.6. Example 15

[0048] Preparation of bis([1,1'-biphenyl]-4-ylethynyl)dimethylsilane

[0049] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 4-(bromoethynyl)-1,1'-biphenyl 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction bottle with a magnetic, after adding, sealing the reaction bottle, and take it out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and add 3 g of silica gel, remove the solvent under reduced pressure, the mixture was purified by silica gel column chromatography to obtain 75.8 mg of the target product, yield 92%. The nuclear magnetic characterization of the compound is as follows: 1H NMR (400 MHz, CDC13) δ 8.30 - 7.06 (m, 18H), 0.52 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 141.5, 140.1, 132.6, 128.8, 127.7, 127.0, 126.8, 121.5, 105.8, 91.3, 0.5. Example 16

[0050] Preparation of bis((4-methoxyphenyl)ethynyl)dimethylsilane

[0051] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1- (bromoethynyl)-4-methoxybenzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to a 8 mL reaction bottle equipped with a magnetic, after adding, the reaction bottle was sealed, and it was taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 59.5 mg of the target product, yield 93%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDC13) δ 7.44 (d, J = 8.4 Hz, 4H), 6.81 (d, J = 8.4 Hz, 4H), 3.78 (s, 6H), 0.46 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 159.9, 133.6, 114.7, 113.8, 105.9, 89.2, 55.2, 0.6. Example 17

[0052] Preparation of bis((3,5-dimethoxyphenyl)ethynyl)dimethylsilane

[0053] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1-(bromoethynyl)-3,5-dimethoxybenzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 57.0 mg of the target product, yield 75%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 6.66 (d, J = 2.4 Hz, 2H), 6.46 (d, J =2.4 Hz, 4H), 3.77 (s, 12H), 0.49 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 160.4,123.8, 109.7, 105.8, 102.6, 90.1, 55.4, 0.4. Example 18

[0054] Preparation of 1,1'-(((dimethylsilanediyl)bis(ethyne-2,1-diyl))bis(4,1-phenylene))bis(ethan-1-one)

[0055] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1-(bromoethynyl)-3,5-dimethoxybenzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 57.0 mg of the target product, yield 75%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.5 Hz, 1H), 7.60 (d, J = 8.5Hz, 1H), 2.61 (s, 2H), 0.52 (s, 2H). 13 C NMR (101 MHz, CDCl3) δ 197.3, 136.7,132.3, 128.1, 127.3, 104.9, 93.9, 26.7, 0.17. Example 19

[0056] Preparation of 4,4'-((dimethylsilanediyl)bis(ethyne-2,1-diyl))dibenzonitrile

[0057] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 4- (bromoethynyl)benzonitrile 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction bottle with a magnetic, after adding, sealing the reaction bottle, and take it out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and add 3 g of silica gel, remove the solvent under reduced pressure, the mixture was purified by silica gel column chromatography to obtain 37.2 mg of the target product, yield 60%. The nuclear magnetic characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.70 – 7.56 (m, 8H), 0.53 (s, 6H). 13 C NMR (101MHz, CDCl3) δ 132.6, 131.9, 127.2, 118.2, 112.3, 104.0, 94.9, -0.1. Example 20

[0058] Preparation of dimethylbis(naphthalen-1-ylethynyl)silane

[0059] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 4- (bromoethynyl)benzonitrile 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction bottle with a magnetic, after adding, sealing the reaction bottle, and take it out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and add 3 g of silica gel, remove the solvent under reduced pressure, the mixture was purified by silica gel column chromatography to obtain 37.2 mg of the target product, yield 60%. The nuclear magnetic characterization of the compound is as follows: 1 HNMR (400 MHz, CDCl3) δ 8.43 (d, J = 8.3 Hz, 2H), 7.86 – 7.79 (m, 4H), 7.79 –7.73 (m, 2H), 7.60 – 7.53 (m, 2H), 7.52 – 7.47 (m, 2H), 7.43 – 7.36 (m, 2H),0.65 (s, 6H). 13C NMR (101 MHz, CDC13) δ 133.5, 133.0, 131.1, 129.4, 128.3, 127.0, 126.5, 126.2, 125.1, 120.3, 104.1, 96.0, 0.7. Example 21

[0060] Preparation of bis(cyclohex-1-en-1-ylethynyl)dimethylsilane

[0061] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 1- (bromoethynyl)cyclohex-1-ene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction bottle with a magnetic, after adding, the reaction bottle was sealed, and it was taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 42.9 mg of the target product, the yield was 80%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDC13) δ 6.45 - 5.83 (m, 2H), 2.26 - 1.95 (m, 8H), 1.77 - 1.53 (m, 8H), 0.50 - 0.21 (m, 6H). 13 C NMR (101 MHz, CDC13) δ 137.0, 120.6, 107.8, 87.7, 28.8, 25.6, 22.1, 21.3, 0.7. Example 22

[0062] Preparation of dimethylbis((triisopropylsilyl)ethynyl)silane

[0063] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, (bromoethynyl)triisopropylsilane 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction bottle with a magnetic, after adding, the reaction bottle was sealed, and it was taken out of the glove box, 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, the mixture was purified by silica gel column chromatography to obtain 58.8 mg of the target product, the yield was 70%. The nuclear magnetic resonance characterization of the compound is as follows: 1H NMR (400 MHz, CDC13) δ 1.20 - 0.98 (m, 42H), 0.32 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 42.5, 41.4, -51.5, -58.9, -69.6. Example 23

[0064] Preparation of bis(3-cyclohexylprop-1-yn-1-yl)dimethylsilane

[0065] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, (3- bromoprop-2-yn-1-yl)cyclohexane 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to a 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 39.0 mg of the target product, yield 65%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDC13) δ 2.13 (d, J = 6.7 Hz, 4H), 1.86 - 1.76 (m, 4H), 1.76 - 1.59 (m, 6H), 1.55 - 1.42 (m, 2H), 1.35 - 1.09 (m, 6H), 1.05 - 0.90 (m, 4H), 0.28 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 107.2, 82.6, 37.1, 32.6, 27.7, 26.2, 26.1, 0.9. Example 24

[0066] Preparation of dimethylbis(4-phenylbut-1-yn-1-yl)silane

[0067] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, (4- bromobut-3-yn-1-yl)benzene 0.5 mmol, dichlorodimethylsilane 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 56.9 mg of the target product, the yield was 90%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.32 – 7.24 (m, 4H), 7.20 (d, J = 7.1 Hz,6H), 2.84 (t, J = 7.7 Hz, 4H), 2.51 (t, J = 7.7 Hz, 4H), 0.27 (s, 6H). 13 C NMR(101 MHz, CDCl3) δ 140.4, 128.5, 128.3, 126.3, 107.4, 82.4, 34.8, 22.2, 0.6. Example 25

[0068] Preparation of bis(3-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-yn-1-yl)dimethylsilane

[0069] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 2,6- dimethyl-8-(prop-2-yn-1-yloxy)oct-2-ene and 8-((3-bromoprop-2-yn-1-yl)oxy)-2,6- dimethyloct-2-ene (1 / 1) 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 62.2 mg of the target product, the yield was 70%. The nuclear magnetic resonance characterization of the compound is as follows: 1H NMR (400 MHz, CDC13) δ 5.10 (t, J = 7.3 Hz, 2H), 4.14 (s, 4H), 3.63 - 3.46 (m, 4H), 1.98 (tq, J = 15.6, 7.5 Hz, 4H), 1.78 - 1.51 (m, 16H), 1.49 - 1.26 (m, 4H), 1.23 - 1.09 (m, 2H), 0.90 (d, J = 6.5 Hz, 6H), 0.34 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 131.12, 124.75, 103.00, 87.41, 68.48, 58.74, 37.17, 36.37, 29.43, 25.68, 25.41, 19.40, 17.60, 0.10. Example 26

[0070] Preparation of (dimethylsilanediyl)bis(prop-2-yne-3, 1-diyl) bis(4-(N,N- dipropylsulfamoyl)benzoate)

[0071] In the glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 3-bromoprop-2-yne-l-yl 4-(N,N-dipropylsulfamoyl)benzoate 0.2 mmol were added to an 8 mL reaction bottle equipped with a magnetic, after adding, the reaction bottle was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction liquid was diluted with ethyl acetate and added with 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 63.2 mg of the target product, with a yield of 45%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDC13) δ 8.28 - 8.15 (m, 4H), 7.95 - 7.84 (m, 4H), 4.98 (s, 4H), 3.57 - 2.92 (m, 8H), 1.63 - 1.48 (m, 8H), 0.87 (t, J = 7.4 Hz, 16H), 0.39 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 164.4, 144.6, 132.6, 130.5, 127.0, 99.8, 88.7, 53.5, 49.9, 21.9, 11.1, -0.2. Example 27

[0072] Preparation of (dimethylsilanediyl)bis(prop-2-yne-3,1-diyl) (2R,2'R)-bis(2-(6- methoxynaphthalen-2-yl)propanoate)

[0073] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 3- bromoprop-2-yne-1-yl (R)-2-(6-methoxynaphthalen-2-yl)propanoate 0.2 mmol were added to a 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and reacted at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added with 3 g of silica gel, the solvent was removed by reduced pressure concentration, and the mixture was purified by silica gel column chromatography to obtain 59.2 mg of the target product, with a yield of 50%. The nuclear magnetic characterization of this compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.71 - 7.62 (m, 6H), 7.38 (dd, J = 8.4, 1.9 Hz, 2H), 7.18 - 7.06 (m, 4H), 4.96 - 4.45 (m, 4H), 3.95 - 3.83 (m, 8H), 1.58 (d, J = 7.2 Hz, 6H), 0.26 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 173.7, 157.6, 135.1, 133.7, 129.2, 128.9, 127.2, 126.1, 125.97, 119.0, 105.5, 100.2, 88.1, 55.2, 52.8, 45.1, 18.6, -0.3. Example 28

[0074] (dimethylsilanediyl)bis(prop-2-yne-3,1-diyl) (2R,2'R)-bis(2-(4-isobutylphenyl)propanoate)

[0075] In a glove box (nitrogen atmosphere), Zn powder 0.6 mmol, acetonitrile 2 mL, 3-bromoprop-2-yn-l-yl 2-(4-isobutylphenyl)propanoate 0.2 mmol were added to an 8 mL reaction vial equipped with a magnetic stir bar, after addition, the reaction vial was sealed and taken out of the glove box, and the reaction was carried out at 40 °C for 24 h; cooled to room temperature, the reaction solution was diluted with ethyl acetate and added 3 g of silica gel, the solvent was removed under reduced pressure, and the mixture was purified by silica gel column chromatography to obtain 50.0 mg of the target product, yield 45%. The nuclear magnetic resonance characterization of the compound is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.20 (d, J = 8.0 Hz, 4H), 7.09 (d, J = 8.0 Hz,4H), 4.86 – 4.52 (m, 4H), 3.74 (q, J = 7.1 Hz, 2H), 2.44 (d, J = 7.2 Hz, 4H),1.84 (dp, J = 13.5, 6.7 Hz, 2H), 1.49 (d, J = 7.2 Hz, 6H), 0.89 (d, J = 6.7Hz, 12H), 0.30 (d, J = 1.5 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 173.8, 140.6,137.2, 129.3, 127.1, 100.3, 88.0, 52.8, 45.0, 44.8, 30.1, 22.4, 18.6, -0.3. Obviously, the above examples are only examples for the sake of clarity, and are not limited to the embodiments. Based on the above description, other different forms of changes or variations can also be made by those of ordinary skill in the art. Here, it is not necessary and impossible to exhaust all embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A method for preparing a diynylsilane compound, characterized in that, Includes the following steps: Step 1: Add reducing agent, organic solvent, alkynyl bromide and chlorosilane to the reaction vessel in sequence, and react at 20~60℃ for 6~36h to obtain mixture A; The structural formula of the chlorosilane is: Wherein R1 is allyl, alkyl, or aryl; wherein R2 is allyl, alkyl, or aryl; The structural formula of the alkynyl bromide is: or Where R3 is alkenyl, alkyl, alkoxy, or silyl; where R is halogen, alkyl, aryl, alkoxy, ester, cyano, or carbonyl. Step 2: Dilute mixture A with ethyl acetate, add silica gel powder, and then concentrate under reduced pressure to remove the reaction solvent, obtaining mixture B; Step 3: Separate mixture B by thin-layer chromatography or column chromatography to obtain the target product, diynylsilane compound.

2. The method for preparing the diynylsilane compound according to claim 1, characterized in that: The molar ratio of the reducing agent, alkynyl bromide, and chlorosilane is 2.5~3.5:2.0~3.0:0.8~1.2, and the organic solvent corresponding to each mole of chlorosilane is 1~3L.

3. The method for preparing the diynylsilane compound according to claim 2, characterized in that: In step one, the molar ratio of the reducing agent, alkynyl bromide, and chlorosilane is 3.0:2.5:1.0, and the organic solvent corresponding to each mole of chlorosilane is 1~2L.

4. The method for preparing the diynylsilane compound according to claim 1, characterized in that: The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, 1,2-dichloroethane, toluene, 1,4-dioxane, acetonitrile, ethylene glycol dimethyl ether, methyl tert-butyl ether, polyethylene glycol dimethyl ether, and ethylene glycol diethyl ether.

5. The method for preparing the diynylsilane compound according to claim 4, characterized in that: The organic solvent is tetrahydrofuran and acetonitrile.

6. The method for preparing the diynylsilane compound according to claim 1, characterized in that: The reaction temperature in step one is 35~45℃.

7. The method for preparing the diynylsilane compound according to claim 1, characterized in that: The reaction time in step one is 24 hours.

8. The method for preparing a diynylsilane compound according to claim 1, characterized in that: The reducing agent is Zn powder, Mn powder, or Fe powder.

9. The method for preparing a diynylsilane compound according to claim 1, characterized in that: The alkyl group of R is methyl, n-butyl, cyclopropyl, 3,3,3-trifluoropropyl, 1-chloropropyl, phenethyl, or cyclohexylmethyl.

10. The method for preparing a diynylsilane compound according to claim 1, characterized in that: The halogen is fluorine, chlorine, or bromine.

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