A method for synthesizing arylstannane compounds by ZnO@GO piezoelectric catalysis

Abstract

The present invention discloses a method for synthesizing arylstannane compounds using ZnO@GO piezoelectric catalysis. The method uses an aryl diazonium salt and a simple stannane compound as substrates, a ZnO@GO composite material as a piezoelectric catalyst, and a common solvent as an auxiliary grinding agent. The synthesis of the arylstannane compound is piezoelectrically driven by the mechanical force provided by a ball mill at room temperature. The method of the present invention utilizes a wide range of raw materials and is low in cost. The method uses only trace amounts of organic solvents, conforming to the principles of green chemistry. The reaction can be carried out at room temperature under mild conditions. The method uses only a small amount of catalyst to achieve a high conversion rate. The method has the advantages of being simple to operate, conforming to the principles of green chemistry, and being highly practical.

Description

Technical Field

[0001] The present invention relates to the technical field of organic catalysis, and in particular to a method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO. Background Art

[0002] The cross-coupling reaction involving organotin reagents, namely the Stille coupling reaction, has been recognized as one of the most important methods for forming CC bonds in organic synthesis. In addition, Ar-Sn bonds can also be used for the transformation of various functional groups, such as the formation of CN, CF, CB, C-OCF3, and CP bonds (Lam PY S, et al. Tetrahedron Letters, 2002, 43: 3091-3094; Makaravage KJ, et al. Organic Letters, 2016, 18(20): 5440-5443; Britovsek GJP, et al. American Chemical Society, 2005, 24: 1685-1691; Huang C, et al. Journal of the American Chemical Society, 2011, 133(34): 13308-13310; Zhang Z, et al. Chemical Science, 2023, 14(11): 2990-2998.).

[0003] The traditional method for preparing aryltin alkylates is to react an air-sensitive organometallic reagent with trialkyltin chloride (Qiu D, et al. Angewandte Chemie International Edition, 2013, 52(44): 11581-11584). In recent years, many researchers have proposed new synthetic strategies for organotin derivatives, including the metal-free BF3·OEt2-catalyzed cross-coupling reaction of (SnMe3)2 with aryl triazene; the successful tin alkylation reaction of aryl acyl fluoride decarbonylation using a small amount of palladium catalyst; and the direct photoinduced reaction of aryl azosulfone with (SnMe3)2 under catalyst-free and additive-free conditions (Mao S, et al. The Journal of Organic Chemistry, 2018, 84(1): 463-471; Kayumov M, Advanced Synthesis & Catalysis, 2019, 362(4): 776-781; Lian C, Organic Letters, 2019, 21(13): 5187-5191.). Aromatic diazonium salts (Ar–N2 +) is a widely used structural unit in modern organic synthesis. It can be synthesized from the corresponding aniline through simple experimental operations and has good reactivity and low redox potential. As early as 2014, Qiu et al. successfully developed a new route for preparing aryltin compounds by Sandmeyer-type transformation (Qiu D, et al. Angewandte Chemie International Edition, 2013, 52(44):11581-11584.), that is, aromatic amine compounds are directly converted into arylstannanes under solvent phase and metal-free conditions. This is an innovative development in the synthesis of arylstannane compounds.

[0004] Unfortunately, the above methods are difficult to synthesize arylstannanes on a large scale, which limits the application of organotin derivatives in the field of fine chemicals. The main reasons are as follows: First, some reactions require transition metal catalysts, which greatly increases the reaction cost; second, the reaction needs to be carried out in excess organic solvent, which is not in line with the concept of green environmental protection; in addition, some reactions require excessive reaction time, heating treatment, or being carried out under an inert gas atmosphere, which is complex and consumes a lot of energy. Therefore, establishing a new, greener method for the alkylation of arylstannanes and developing its safe conversion process are key to achieving high-value-added large-scale conversion of organotin derivatives.

[0005] Piezoelectric catalysis is a new catalytic conversion technology. Piezoelectric materials are a class of materials with non-centrosymmetry, such as BaTiO3, ZnO, MoS2, g-C3N4, etc. (Amiri O, et al. RSC Advances, 2021, 11(59): 37138-37149; Ding C, et al. Chinese Journal of Chemistry, 2023, 41(20): 2691-2696; Yue J, et al. Applied Surface Science, 2023, 623: 157033-157042; Yan C, et al. Composites Communications, 2023, 37: 101466-101473.); when stimulated by external mechanical forces, these materials will produce piezoelectric polarization. When the surface Gibbs free energy reaches the necessary level, the field energy promotes the recombination of surface charges and triggers redox reactions on the catalyst surface, thereby realizing piezoelectric catalysis of the entire system (Dong H, et al. Chemical Engineering Journal, 2024, 487: 150480-150495; Liu J, et al. Angewandte Chemie International Edition, 2022, 62 (5): 202213927-202213952.). In 2019, Kubota and Ito et al. (Kubota K, et al. Science 2019, 366: 1500-1504.) for the first time used the mechanical force provided by the ball mill instead of light and heat as the only stimulus source to induce the production of aromatic radicals and realize the arylation and borylation reactions of the substrate. This achieved a major breakthrough in the field of piezoelectric catalysis and opened a new chapter in the field of piezoelectric catalysis in organic synthesis. However, the piezoelectric potential provided by a single piezoelectric material is limited, and its electron transport performance is not enough to expand the reaction system, which makes a single piezoelectric material have certain limitations in practical applications. Therefore, the rational design of composite catalysts is particularly important in promoting the application of piezoelectric catalysis.

[0006] ZnO is a non-ferroelectric piezoelectric and wide-bandgap semiconductor material with the advantages of large photoelectric coupling coefficient, high chemical stability, excellent optical, electrical and piezoelectric properties, non-toxicity and low cost. It has been widely used in photocatalysis (Weerathunga H, et al. Journal of Colloid and Interface Science, 2022, 606: 588-599.), piezoelectric catalysis (Wang B, et al. Journal of Energy Chemistry, 2022, 65: 304-311.) and piezoelectric-photocatalysis (Bettini S, et al. Surfaces and Interfaces, 2023, 36: 102581-102589.). The surface of graphene oxide (GO) is rich in hydroxyl and carboxyl functional groups. These inherent active oxygen functional groups provide an effective platform for the anchoring and epitaxy of various substances. Moreover, the unique amphiphilic properties of GO make GO and its related composite materials have better dispersibility in aqueous and organic solvents, so the active sites of GO-based composite catalysts can be effectively dispersed (Ahmad H, et al. Composites Part B: Engineering, 2018, 145: 270-280.). In addition, graphene oxide can be hybridized with other hexagonal nanoparticles, such as ZnO, BaTiO3, TiO2 and SnO2. The synergistic effect of the two can greatly promote the separation and migration of electrons and holes (Ma W, et al. Journal of Environmental Chemical Engineering, 2022, 10 (3): 107840-107851.), which can improve the piezoelectric catalytic performance to a certain extent. Since 2017, many researchers have prepared composite materials of piezoelectric materials and GO to degrade pollutants and achieve antibacterial disinfection of microorganisms. Characterization and experiments have shown that the piezoelectric potential of the composite material is improved to a certain extent compared with that of a single piezoelectric material, and the piezoelectric catalytic performance is better (Ma W, et al. Journal of Environmental Chemical Engineering, 2022, 10(3): 107840-107851; Kavinkumar T, et al. Journal of the European Ceramic Society, 2017, 37(4): 1401-1409; Pan M, et al. Environmental Science & Technology, 2019, 53(14): 8342-8351.). Summary of the Invention

[0007] The problem solved by the present invention is to provide a method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO, wherein the ZnO@GO composite catalyst has good activity and stability and is suitable for large-scale production of arylstannane compounds.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] A method for synthesizing arylstannane compounds using ZnO@GO piezoelectric catalysis, comprising placing an aryldiazo compound and a stanane compound in a reaction tank, and performing a piezoelectric catalytic reaction in a ball mill to obtain the arylstannane compound.

[0010] In terms of mass percentage, the graphene oxide in the ZnO@GO accounts for 5 to 70%.

[0011] The ZnO@GO is obtained by dispersing graphene oxide in a zinc acetate dihydrate system, fully stirring, adjusting the pH to 7-11, heating to 90-140° C. and reflux for 3-10 hours, and cooling to room temperature.

[0012] Furthermore, the ZnO@GO is prepared as follows:

[0013] GO was dispersed in deionized water and ultrasonicated for 10 to 60 minutes, then mixed with an aqueous solution of zinc acetate dihydrate and stirred for 0.5 to 3 hours. Ammonia was added to adjust the pH to 7 to 11. In a reflux reaction apparatus, the temperature was raised to 90 to 140°C and refluxed for 3 to 10 hours. After the reaction, the mixture was cooled to room temperature. The product was thoroughly washed several times until the washing effluent was neutral, and the product was dried at 60 to 90°C for 6 to 24 hours to obtain a ZnO@GO piezoelectric catalyst.

[0014] Furthermore, an auxiliary grinding agent is placed in the reaction tank; the frequency of the ball mill is 5 to 50 Hz; and the reaction is carried out in the ball mill at room temperature for 0.5 to 12 hours.

[0015] The auxiliary grinding agent is one or more of 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, water, dichloroethane, ether, and acetone.

[0016] The aromatic diazonium compound is benzenediazonium tetrafluoroborate, benzenediazonium tetrafluoroboric acid, or benzenesulfonic acid diazonium salt.

[0017] The stannane compound is hexamethyltin ditin, trimethyltin chloride, hexaethyltin ditin or triethyltin chloride.

[0018] Furthermore, the molar ratio of the aryldiazo compound to the stannane compound is 1:(0.5-5);

[0019] The mass ratio of aromatic diazo compounds to ZnO@GO is 1:(0.02~0.5).

[0020] Furthermore, the reaction tank is an agate ball mill tank with a volume of 10 to 250 mL, in which agate balls with a diameter of 6 to 20 mm are placed, and the number of the agate balls is 1 to 15.

[0021] Compared with the prior art, the present invention has the following beneficial technical effects:

[0022] This method uses aryldiazo compounds and stannane compounds as substrates, a ZnO@GO composite material as a piezoelectric catalyst, and a common solvent as an auxiliary grinding agent. The mechanical force provided by a ball mill is piezoelectrically driven at room temperature to synthesize arylstannane compounds. This method utilizes a wide range of raw materials and is low-cost. It uses only trace amounts of organic solvents, aligning with the principles of green chemistry. The reaction can be carried out at room temperature under mild conditions. It uses only a small amount of catalyst to achieve high conversion rates. This method offers the advantages of simple operation, adherence to the principles of green chemistry, and strong practicality.

[0023] The present invention uses ZnO@GO as a composite piezoelectric catalytic system. When ZnO@GO is stimulated by the mechanical force provided by a ball mill, piezoelectric polarization occurs, inducing the generation of aromatic free radicals, thereby achieving the stannanation of aromatic diazonium salts. This method is a heterogeneous catalytic system, and the catalyst can be recovered and reused by simple centrifugal separation, with good stability. The method is widely applicable and can be applied to different types of aromatic diazonium salt substrates. In addition, the method can be used for large-scale experiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is the XRD pattern of GO prepared by the Hummers method in the present invention;

[0025] Figure 2 Figure 2 is the XRD pattern of ZnO@GO with different GO contents, where ZnO@GO-10 is the composite catalyst with a GO content of 10 wt%, and the other catalysts are named similarly;

[0026] Figure 3 FT-IR spectra of GO, ZnO in the present invention and ZnO@GO-20 in Example 1.

[0027] Figure 4 This is the SEM image of ZnO@GO-20 in Example 1 of the present invention.

[0028] Figure 5 This is the H NMR spectrum of ethyl 4-(trimethyltinyl)benzoate in Example 2 of the present invention. DETAILED DESCRIPTION

[0029] In order to deepen the understanding of the present invention, the present invention will be further described below with reference to the embodiments. The embodiments are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0030] The present invention provides a method for synthesizing aryl stannane compounds using ZnO@GO piezoelectric catalysis, wherein ZnO@GO is used as a piezoelectric catalyst, an aryl diazo compound and a stannane compound are placed in a reaction tank, and a piezoelectric catalytic reaction is carried out in a ball mill to obtain the aryl stannane compound;

[0031] In terms of mass percentage, the graphene oxide in the ZnO@GO accounts for 5 to 70%.

[0032] The ZnO@GO is obtained by dispersing graphene oxide in a zinc acetate dihydrate system, fully stirring, adjusting the pH to 7-11, heating to 90-140° C. and reflux for 3-10 hours, and cooling to room temperature.

[0033] Furthermore, the ZnO@GO is prepared as follows:

[0034] GO was dispersed in deionized water and ultrasonicated for 10 to 60 minutes, then mixed with an aqueous solution of zinc acetate dihydrate and stirred for 0.5 to 3 hours. Ammonia was added to adjust the pH to 7 to 11. In a reflux reaction apparatus, the temperature was raised to 90 to 140°C and refluxed for 3 to 10 hours. After the reaction was completed, the reaction was cooled to room temperature. The product was thoroughly washed several times until the washing effluent was neutral, and the product was dried in an oven at 60 to 90°C for 6 to 24 hours to obtain a ZnO@GO piezoelectric catalyst.

[0035] Furthermore, an auxiliary grinding agent is placed in the reaction tank; the frequency of the ball mill is 5 to 50 Hz; and the reaction is carried out at room temperature for 0.5 to 12 hours.

[0036] Furthermore, the molar ratio of the aryldiazo compound to the stannane compound is 1:(0.5-5);

[0037] The mass ratio of aromatic diazo compounds to ZnO@GO is 1:(0.02~0.5).

[0038] Furthermore, the reaction tank is an agate ball mill tank with a volume of 10 to 250 mL, in which agate balls with a diameter of 6 to 20 mm are placed, and the number of the agate balls is 1 to 15.

[0039] Specifically, the aromatic diazonium salt compounds are 4-ethoxybenzenediazonium tetrafluoroborate, 4-nitrobenzenediazonium tetrafluoroborate, 3-nitrobenzenediazonium tetrafluoroboric acid, 2-nitrobenzenediazonium tetrafluoroboric acid, 2,4-dichlorobenzenediazonium tetrafluoroborate, 4-chlorobenzenediazonium tetrafluoroborate, 4-methylbenzenesulfonic acid benzene diazonium salt, 3-cyanobenzenediazonium tetrafluoroborate, 4-cyanobenzenediazonium tetrafluoroborate, and the like.

[0040] The stannane compounds are hexamethyltin ditin, trimethyltin chloride, hexaethyltin ditin, and triethyltin chloride.

[0041] The auxiliary grinding agents are 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, water, dichloroethane, diethyl ether, and acetone.

[0042] The following are specific examples.

[0043] Example 1

[0044] Synthesis of ZnO@GO-20 composite catalyst:

[0045] GO was synthesized according to the traditional Hummers method (Jr WSH, et al. American Chemical Society, 1958, 80: 1339.);

[0046] Disperse 100 mg of GO in 30 mL of deionized water and sonicate for 30 minutes. Simultaneously, weigh 1.0789 g of zinc acetate dihydrate and 250 mL of deionized water into a beaker and stir until the solid is completely dissolved. Once the GO is dispersed, pour it into the beaker containing the zinc acetate dihydrate and stir for 1 hour. Ammonia is then added to adjust the pH to 10. The mixture is then poured into a round-bottom flask, and the reaction system is heated to 120°C and refluxed for 4 hours. After the reaction is complete, cool the mixture to room temperature. Finally, wash the mixture several times with deionized water by centrifugation until neutral. The resulting product is dried in an oven at 60°C for 12 hours to obtain the ZnO@GO-20 composite catalyst.

[0047] The present invention characterized the structure and morphology of the ZnO@GO composite catalyst by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM).

[0048] like Figure 1 As shown in the XRD pattern of GO, a characteristic diffraction peak of the GO sample corresponding to the (002) crystal plane is observed at about 2θ of 10°, and a weak and broad diffraction peak is formed at about 2θ of 21°, which indicates that the order of graphite is significantly reduced in the process of graphene being transformed into GO.

[0049] Figure 2The XRD pattern of ZnO@GO is shown. The characteristic peaks at 2θ values ​​of 31.8, 34.4, 36.3, 47.5, 56.6, 62.9, 67.9, and 69.1 correspond to the (100), (002), (101), (102), (110), (103), (112), and (201) crystal planes, respectively, which correspond exactly to the ZnO standard card NO.36-1451.

[0050] Figure 3 Shown are the FT-IR spectra of GO, ZnO, and ZnO@GO-20. The characteristic peaks shown indicate the successful preparation of ZnO@GO composite materials.

[0051] Figure 4 Shown is the SEM image of ZnO@GO-20, in which ZnO nanorods grow on the GO surface in different directions, and some nanorods are embedded between GO layers. The composite of the two effectively avoids the self-aggregation of ZnO nanorods and does not have any effect on their rod-like structure.

[0052] Example 2

[0053]

[0054] Synthesis of ethyl 4-(trimethyltinyl)benzoate:

[0055] 4-Ethoxybenzodiazonium tetrafluoroborate (0.2 mmol), hexamethyltin disulfide, ZnO@GO-20, and ethanol (EtOH) were weighed (measured) in sequence and added to an agate jar containing an agate ball. The molar ratio of 4-Ethoxybenzodiazonium tetrafluoroborate to hexamethyltin disulfide was 1:1.1; the mass ratio of 4-Ethoxybenzodiazonium tetrafluoroborate to ZnO@GO-20 was 1:0.19; the auxiliary grinding agent EtOH was used at a dosage of 3 μL / mg. The agate ball mill had a volume of 10 mL, a diameter of 10 mm, and one agate ball.

[0056] The system was placed in a planetary ball mill, set to a frequency of 30 Hz, and reacted at room temperature for 1 hour. When the ZnO@GO was stimulated by the mechanical force provided by the ball mill, piezoelectric polarization occurred, inducing the generation of aryl radicals, thereby achieving stannanylation of the aryl diazonium salt.

[0057] After the reaction is completed, the mixture is diluted with dichloromethane, separated by suction filtration, the filtrate is concentrated under reduced pressure, and finally the product is separated by thin layer chromatography using ethyl acetate and petroleum ether as a mixed developing solvent to purify and separate the product. The isolation yield of the target compound is 83%.

[0058] Figure 5The H NMR spectrum of the product prepared in Example 2 is shown, and the results show that it is consistent with the H NMR spectrum of ethyl 4-(trimethyltinyl)benzoate.

[0059] Example 3

[0060]

[0061] Gram-scale synthesis of ethyl 4-(trimethyltinyl)benzoate:

[0062] 4-Ethoxybenzodiazonium tetrafluoroborate (4 mmol), hexamethyltin disulfide, ZnO@GO-20, and ethanol (EtOH) were weighed (measured) in sequence and added to an agate jar containing agate balls. The molar ratio of 4-Ethoxybenzodiazonium tetrafluoroborate to hexamethyltin disulfide was 1:1.1; the mass ratio of 4-Ethoxybenzodiazonium tetrafluoroborate to ZnO@GO-20 was 1:0.19; the auxiliary grinding agent EtOH was used at a dosage of 0.3 μL / mg. The agate ball mill had a volume of 50 mL, and the agate balls had a diameter of 10 mm and a total of 6 agate balls.

[0063] The system was placed in a planetary ball mill set to 30 Hz and reacted at room temperature for 1 hour. After the reaction, the mixture was diluted with dichloromethane and separated by filtration. The filtrate was concentrated under reduced pressure, and the product was purified by column chromatography using 300-400 mesh silica gel as the stationary phase and a mixed eluent of ethyl acetate and petroleum ether. The yield of the target compound was 54%.

[0064] Example 4

[0065]

[0066] Synthesis of (4-nitro)trimethyltin:

[0067] 4-Nitrobenzenediazonium tetrafluoroborate (0.2 mmol), hexamethyltin disulfide, ZnO@GO-20, and ethanol (EtOH) were weighed (measured) in sequence and added to an agate jar containing an agate ball. The molar ratio of 4-nitrobenzenediazonium tetrafluoroborate to hexamethyltin disulfide was 1:1.1; the mass ratio of 4-nitrobenzenediazonium tetrafluoroborate to ZnO@GO-20 was 1:0.21. The auxiliary grinding agent, EtOH, was used at a dosage of 3 μL / mg. The agate ball mill had a volume of 10 mL, a diameter of 10 mm, and one agate ball.

[0068] The system was placed in a planetary ball mill set to 30 Hz and reacted at room temperature for 1 hour. After the reaction, the mixture was diluted with dichloromethane and separated by filtration. The filtrate was concentrated under reduced pressure, and the product was purified by thin-layer chromatography using a mixed developing solvent of ethyl acetate and petroleum ether. The yield of the target compound was 80%.

[0069] Example 5

[0070]

[0071] Synthesis of (2,4-dichlorophenyl)trimethylstannane:

[0072] 2,4-Dichlorobenzenediazonium tetrafluoroborate (0.2 mmol), hexamethyltin disulfide, ZnO@GO-20, and ethanol (EtOH) were weighed (measured) in sequence and added to an agate jar containing an agate ball. The molar ratio of 2,4-Dichlorobenzenediazonium tetrafluoroborate to hexamethyltin disulfide was 1:1.1; the mass ratio of 2,4-Dichlorobenzenediazonium tetrafluoroborate to ZnO@GO-20 was 1:0.19. The auxiliary grinding agent EtOH was used at a dosage of 3 μL / mg. The agate ball mill had a volume of 10 mL, a diameter of 10 mm, and one agate ball.

[0073] The system was placed in a planetary ball mill set to 30 Hz and reacted at room temperature for 1 hour. After the reaction, the mixture was diluted with dichloromethane and separated by filtration. The filtrate was concentrated under reduced pressure, and the product was purified by thin-layer chromatography using a mixed developing solvent of ethyl acetate and petroleum ether. The yield of the target compound was 50%.

[0074] Example 6

[0075]

[0076] Synthesis of trimethylphenylstannane:

[0077] 4-Methylbenzenesulfonate benzene diazonium salt (0.2 mmol), trimethyltin chloride, ZnO@GO-30, and 1,2-dichloroethane (DCE) were weighed (measured) in sequence and added to an agate jar containing an agate ball. The molar ratio of 4-Methylbenzenesulfonate benzene diazonium salt to trimethyltin chloride was 1:2; the mass ratio of 4-Methylbenzenesulfonate benzene diazonium salt to ZnO@GO-30 was 1:0.3; the auxiliary grinding agent (DCE) was used at a dosage of 3 μL / mg. The agate ball mill had a volume of 10 mL, a diameter of 8 mm, and one agate ball.

[0078] The system was placed in a planetary ball mill at 40 Hz and allowed to react at room temperature for 1 hour. After the reaction was complete, the mixture was diluted with dichloromethane and separated by filtration. The filtrate was concentrated under reduced pressure, and the product was purified by thin-layer chromatography using a mixed developing solvent of ethyl acetate and petroleum ether.

[0079] Example 7

[0080]

[0081] Synthesis of (4-chlorophenyl)triethyltin:

[0082] 4-Chlorobenzenediazonium tetrafluoroborate (0.2 mmol), hexaethyltin ditin, ZnO@GO-40, and methanol (MeOH) were weighed (measured) in sequence and added to an agate jar containing agate balls. The molar ratio of 4-chlorobenzenediazonium tetrafluoroborate to hexaethyltin ditin was 1:1.5; the mass ratio of 4-chlorobenzenediazonium tetrafluoroborate to ZnO@GO-40 was 1:0.22. The auxiliary grinding agent, MeOH, was used at a dosage of 2 μL / mg. The agate ball mill had a volume of 10 mL, a diameter of 10 mm, and one agate ball.

[0083] The system was placed in a planetary ball mill at 30 Hz and allowed to react at room temperature for 2 hours. After the reaction was complete, the mixture was diluted with dichloromethane and separated by filtration. The filtrate was concentrated under reduced pressure, and the product was purified by thin-layer chromatography using a mixed developing solvent of ethyl acetate and petroleum ether.

[0084] Example 8

[0085]

[0086] Synthesis of (3-cyanophenyl)triethyltin:

[0087] 3-Cyanobenzenediazonium tetrafluoroborate (0.2 mmol), triethyltin chloride, ZnO@GO-20, and ethanol (EtOH) were weighed (measured) in sequence and added to an agate jar containing an agate ball. The molar ratio of 3-Cyanobenzenediazonium tetrafluoroborate to triethyltin chloride was 1:3; the mass ratio of 3-Cyanobenzenediazonium tetrafluoroborate to ZnO@GO-20 was 1:0.4. The auxiliary grinding agent EtOH was used at a dosage of 2 μL / mg. The agate ball mill had a volume of 10 mL, a diameter of 10 mm, and one agate ball.

[0088] The system was placed in a planetary ball mill at 20 Hz and allowed to react at room temperature for 5 hours. After the reaction was complete, the mixture was diluted with dichloromethane and separated by filtration. The filtrate was concentrated under reduced pressure, and the product was purified by thin-layer chromatography using a mixed developing solvent of ethyl acetate and petroleum ether.

[0089] The above examples show that the method of the present invention can be carried out at room temperature using only a trace amount of organic solvent, and a high conversion rate can be achieved using only a small amount of catalyst.

[0090] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, improvements and modifications can be made without departing from the core technology of the present invention. These improvements and modifications should also fall within the scope of patent protection of the present invention.

Claims

1. A method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO, characterized in that: Using ZnO@GO as a piezoelectric catalyst, aromatic diazo compounds and stannane compounds are placed in a reaction tank and subjected to piezoelectric catalytic reaction in a ball mill to obtain aromatic stannane compounds. In terms of mass percentage, the graphene oxide in the ZnO@GO accounts for 5 to 70%; The preparation of the ZnO@GO is as follows: GO was dispersed in deionized water and ultrasonicated for 10 to 60 minutes, then mixed with an aqueous solution of zinc acetate dihydrate and stirred for 0.5 to 3 hours. Ammonia was added to adjust the pH to 7 to 11. In a reflux reactor, the temperature was raised to 90 to 140°C and refluxed for 3 to 10 hours. After the reaction was completed, the reaction was cooled to room temperature. The product was thoroughly washed several times until the washing effluent was neutral, and the product was dried at 60 to 90°C for 6 to 24 hours to obtain a ZnO@GO piezoelectric catalyst. The aromatic diazonium compound is benzene diazonium tetrafluoroborate or benzene diazonium benzenesulfonate; The stannane compound is hexamethyltin ditin, trimethyltin chloride, hexaethyltin ditin or triethyltin chloride.

2. The method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO according to claim 1, wherein: Auxiliary grinding agents are also placed in the reaction tank; the frequency of the ball mill is 5 to 50 Hz; and the reaction is carried out in the ball mill at room temperature for 0.5 to 12 hours.

3. The method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO as claimed in claim 2, characterized in that: The auxiliary grinding agent is 1,2-dichloroethane, acetonitrile, N,N - one or more of dimethylformamide, dimethyl sulfoxide, methanol, ethanol, water, ethylene dichloride, ether, and acetone.

4. The method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO according to claim 1, wherein: The molar ratio of the aromatic diazo compound to the stannane compound is 1:(0.5-5); The mass ratio of aromatic diazo compounds to ZnO@GO is 1:(0.02~0.5).

5. The method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO as claimed in claim 1, characterized in that: The reaction tank is an agate ball mill tank with a volume of 10 to 250 mL, in which agate balls with a diameter of 6 to 20 mm are placed, and the number of the agate balls is 1 to 15.

6. The method for synthesizing arylstannane compounds by piezoelectric catalysis using ZnO@GO as claimed in claim 2, characterized in that: The amount of auxiliary grinding agent used is 0.1-10 μL / mg based on the mass of the aromatic diazo compound.

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