Method for synthesizing silanol by electrochemically mediating ring opening of cyclobutyl silane

Abstract

The invention relates to a novel method for synthesizing silanol by splitting a Si-C bond of electrochemically mediated cyclobutyl silane, which comprises the following steps of: adding cyclobutyl silane, water, an additive, electrolyte and a solvent into a reaction bottle under the condition of no water and no oxygen, electrifying and stirring for 1.0 hour at normal temperature; according to the present invention, the use of noble metals is mainly avoided, and new organic conversion is developed by using electrons as the redox reagent under the mild condition, such that the stoichiometric oxidizing agent or reducing agent is avoided, and the unnecessary waste is reduced so as to meet the increasing requirements of environmental friendliness and sustainability. The method is simple and easy to operate, the materials required in the method are low in toxicity, safe and environment-friendly, the substrate expansion range is wide, and the yield is high.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic compound synthesis, and relates to a method for electrochemically mediated ring-opening of cyclobutylsilane to synthesize silanols. Background Art

[0002] The ring-opening reaction of cyclobutylsilane to form a silicon-oxygen bond (Si-OH) is an important research direction in organosilicon chemistry. As an important structure, the silicon-oxygen bond has wide application value in the fields of medicine, agrochemistry, and materials science, and is a key intermediate in many organic transformation applications.

[0003] In traditional synthesis methods, strategies such as metal catalysis, photocatalysis, and organocatalysis are usually relied on. Metal-catalyzed methods (such as using metal catalysts like palladium, manganese, rhodium, etc.) are efficient, but suffer from problems such as high catalyst cost, difficulty in removing metal residues, and environmental unfriendliness. Photocatalytic methods utilize light energy to excite catalysts (such as organic dyes or transition metal complexes) to achieve the formation of silicon-oxygen bonds under mild conditions, but their reaction efficiency is limited by the light source intensity and catalyst stability.

[0004] In recent years, organic electrochemistry synthesis, as a green, efficient, and sustainable synthesis method, has shown unique advantages in the reaction of synthesizing silicon-oxygen bonds. Organic electrochemistry synthesis can precisely control the reaction activity and selectivity by adjusting the electrode potential, without the use of expensive metal catalysts or strong oxidants, thus avoiding the problem of metal residues. In addition, organic electrochemistry is usually carried out at room temperature, with low energy consumption and mild reaction conditions, and is suitable for various heat-sensitive and light-sensitive substrates. Based on the above advantages, we have developed a new method for electrochemically mediated ring-opening of cyclobutylsilane to generate Si-OH bonds, which can produce highly active intermediates through anodic oxidation and achieve the efficient construction of Si-OH bonds through intramolecular rearrangement, providing a new idea for the development of environmentally friendly silicon-oxygen bond synthesis strategies and conforming to the development concepts of green chemistry and sustainable chemistry.

[0005] [(a) J. Wang, B. Li, L.-C. Liu, C. Jiang, T. He, W. He, Sci. China Chem., 2018, 61, 1594 - 1599. (b) K. Wang, J. Zhou, Y. Jiang, M. Zhang, C. Wang, D. Xue, W. Tang, H. Sun, J. Xiao, C. Li, Angew. Chem. Int. Ed., 2019, 58, 6380 - 6384. (c) Y. Ge, X. Huang, J. Ke, C. He, Chem. Catal., 2022, 2, 2898 - 2928. (d) H. Li, L. Chen, P. Duan, W. Zhang, ACS Sustainable Chem. Eng, 2022, 10, 4642 - 4649.] Summary of the Invention

[0006] The purpose of this section is to outline some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of the present application, to avoid obscuring the purpose of this section, the abstract, and the title, but such simplifications or omissions shall not be used to limit the scope of the present invention.

[0007] (1) Technical Problem

[0008] The present invention mainly avoids the use of precious metals, stoichiometric oxidants or reductants, and solves the problem of generating unnecessary waste to meet the growing demands for environmental friendliness and sustainability.

[0009] (2) Technical Solution

[0010] The reaction flask is equipped with graphite felt electrodes, which serve as the cathode and anode. Under nitrogen protection, 0.2 mmol of cyclobutylsilane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are successively added to the reaction flask, and stirred at room temperature for 1.0 h with a current of 8 mA.

[0011] The above-mentioned cyclobutasilane is one of 1,1-diphenylsilacyclobutane, 1,1-di(p-tolyl)silacyclobutane, 1,1-di(thiophen-2-yl)silacyclobutane, 1,1-di(4-tert-butylphenyl)silacyclobutane, 1,1-di(4-trifluoromethylphenyl)silacyclobutane, 1-methyl-1-(p-tolyl)silacyclobutane, 1-methyl-1-(naphthalen-1-yl)silacyclobutane, 1-(4-fluorophenyl)-1-methylsilacyclobutane, 1-benzyl-1-methylsilacyclobutane, 7-phenyl-7-methyl-7-silabicyclo[4.2.0]octa-1,3,5-triene; the water is deionized water; the amount of triethylamine is 0.1 mmol; the electrode materials are both graphite felt; the electrolyte is tetrabutylammonium iodide salt; the solvent is acetonitrile.

[0012] The molar ratio of the additive to the cyclobutasilane is 1:2; the amount of deionized water used is 0.4 mL; the amount of the electrolyte used is 0.05 mol / mL; the amount of the solvent used is 4 mL.

[0013] (3) Beneficial effects and innovation

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] The present invention mainly avoids the use of precious metals, and develops new organic transformations by using electrons as redox reagents under mild conditions, thereby avoiding stoichiometric oxidants or reductants, reducing unnecessary wastes, and meeting the growing requirements for environmental friendliness and sustainability.

[0016] The present invention is simple and easy to operate, the items required in the method have low toxicity, are safe and environmentally friendly, have a wide substrate expansion range, and a high yield. Description of the drawings

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained according to these drawings without creative efforts. Among them:

[0018] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the product prepared in Example 1 of the present invention;

[0019] Figure 2 It is the nuclear magnetic resonance carbon spectrum of the product prepared in Example 1 of the present invention. Detailed implementation manners

[0020] To make the above objects, features, and advantages of the present invention more obvious and understandable, the following detailed description of the specific implementation manners of the present invention will be given in conjunction with the embodiments of the specification.

[0021] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, the present invention may be practiced in other ways than those specifically described herein, and those skilled in the art can make similar generalizations without departing from the spirit of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0022] Secondly, as used herein, an "embodiment" or "embodiments" refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor is it an isolated or alternative embodiment that is mutually exclusive of other embodiments.

[0023] Example 1

[0024] Electrochemically catalyze the reaction of 1,1-diphenylsilacyclobutane with deionized water. The reaction process is as follows:

[0025] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1,1-diphenylsilacyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are sequentially added to the reaction flask, and stirred at room temperature with a current of 8 mA for 1.0 h. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, and the solvent is removed using a rotary evaporator to obtain a crude product. The crude product is separated by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents, and finally 45.0 mg of the product is obtained, with a yield of 93%.

[0026] Characterize the product: 1 H NMR (600 MHz, CDCl3): δ 7.61 (dd, J = 7.9, 1.4 Hz, 4H), 7.46 - 7.35 (m, 6H), 1.54 - 1.46 (m, 2H), 1.18 - 1.13 (m, 2H), 1.00 (t, J = 7.3 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 136.44, 134.18, 129.84, 127.90, 77.24, 77.03, 76.82, 18.14, 17.68, 16.65. HRMS (ESI): calculated for C 15 H 19 OSi + [M + H] + : 243.1200; found: 243.1200.

[0027] The structural formula of the product is:

[0028] Example 2

[0029] Electrochemically catalyze the reaction of 1,1 - bis(p - tolyl)silylcyclobutane with deionized water. The reaction process is as follows:

[0030] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1,1 - bis(p - tolyl)silylcyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are successively added to the reaction flask, and stirred at room temperature with a current of 8 mA for 1.0 h. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, the solvent is removed using a rotary evaporator to obtain the crude product, and the crude product is separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents. Finally, 49.7 mg of the product is obtained with a yield of 92%.

[0031] Characterize the product: 1 H NMR(600MHz, CDCl3): δ7.50(d, J = 7.9Hz, 4H), 7.21(d, J = 7.6Hz, 4H), 2.37(s, 6H), 1.56 - 1.42(m, 2H), 1.16 - 1.10(m, 2H), 0.99(t, J = 7.3Hz, 3H). 13 CNMR(151MHz, CDCl3): δ139.72, 134.27, 133.05, 128.71, 21.57, 18.18, 17.83, 16.72. HRMS(ESI): calculated for C 17 H 23 OSi + [M + H] + : 271.1513; found: 271.1516.

[0032] The structural formula of the product is:

[0033] Example 3

[0034] Electrochemically catalyze the reaction of 1,1 - bis(thiophen - 2 - yl)silylcyclobutane with deionized water. The reaction process is as follows:

[0035] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1,1-bis(thiophen-2-yl)silacyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are successively added to the reaction flask, and stirred at room temperature with a current of 8 mA for 1.0 h. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, the solvent is removed using a rotary evaporator to obtain the crude product, and the crude product is separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally 48.3 mg of the product is obtained with a yield of 95%.

[0036] The product was characterized as follows: 1 H NMR (600 MHz, CDCl3): δ 7.64 (d, J = 4.5 Hz, 1H), 7.37 (d, J = 3.2 Hz, 1H), 7.22 (t, J = 3.8 Hz, 1H), 1.51 - 1.46 (m, 2H), 1.00 (t, J = 7.3 Hz, 3H), 0.90 (dd, J = 10.1, 6.3 Hz, 2H), 0.45 (s, 3H). 13 C NMR (151 MHz, CDCl3): δ 137.86, 134.77, 131.08, 128.19, 19.84, 17.98, 16.60, -0.57. HRMS (ESI): calculated for C 11 H 15 OS2Si + [M + H] + : 255.0328; found: 255.0328.

[0037] The structural formula of the product is:

[0038] Example 4

[0039] The electrochemical catalysis reaction of 1,1-bis(4-tert-butylphenyl)silacyclobutane and deionized water is as follows:

[0040] The reaction flask was equipped with graphite felt electrodes, and the graphite felt served as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1,1-bis(4-tert-butylphenyl)silacyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile were successively added to the reaction flask, and stirred at room temperature for 1.0 h with a current of 8 mA. After the reaction was completed, the reaction mixture was filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed using a rotary evaporator to obtain the crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as the eluents, and finally 32.6 mg of the product was obtained with a yield of 46%.

[0041] The product was characterized as follows: 1 H NMR (600 MHz, CDCl3): δ 7.55 (d, J = 8.2 Hz, 4H), 7.41 (d, J = 8.2 Hz, 4H), 1.55 - 1.48 (m, 2H), 1.32 (s, 18H), 1.18 - 1.10 (m, 2H), 1.00 (t, J = 7.3 Hz, 3H). 13 C NMR (151 MHz, CDCl3): 6 152.72, 134.09, 133.14, 124.83, 34.73, 31.23, 18.23, 17.87, 16.72. HRMS (ESI): calculated for C 23 H 35 OSi + [M + H] + : 355.2453; found: 355.2454.

[0042] The structural formula of the product is:

[0043] Example 5

[0044] The reaction of electrochemically catalyzing 1,1-bis(4-trifluoromethylphenyl)silacyclobutane with deionized water was carried out as follows:

[0045] The reaction flask was equipped with graphite felt electrodes, and the graphite felt served as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1,1-bis(4-trifluoromethylphenyl)silacyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile were successively added to the reaction flask, and stirred at room temperature for 1.0 h with a current of 8 mA. After the reaction was completed, the reaction mixture was filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed using a rotary evaporator to obtain the crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as the eluents, and finally 46.1 mg of the product was obtained with a yield of 61%.

[0046] Characterize the product: 1 1H NMR (600 MHz, CDCl3): δ 7.71 (d, J = 7.8 Hz, 4H), 7.64 (d, J = 7.8 Hz, 4H), 1.52 - 1.50 (m, 2H), 1.21 - 1.17 (m, 2H), 1.01 (t, J = 7.3 Hz, 3H). 13 13C NMR (151 MHz, CDCl3): δ 140.42, 134.39, 132.15, 131.93, 124.93, 124.65, 124.63, 124.60, 124.57, 123.13, 17.99, 17.29, 16.44. 19 19F NMR (377 MHz, CDCl3): δ -63.08. HRMS (ESI): calculated for C 17 H 17 F6OSi + [M + H] + : 379.0947; found: 379.0949.

[0047] The structural formula of the product is:

[0048] Example 6

[0049] Electrochemically catalyze the reaction of 1-methyl-1-(p-tolyl)silacyclobutane with deionized water. The reaction process is as follows:

[0050] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1-methyl-1-(p-tolyl)silacyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are successively added to the reaction flask, and stirred at room temperature for 1.0 h with a current of 8 mA. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, the solvent is removed using a rotary evaporator to obtain a crude product, and the crude product is separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally 19.8 mg of the product is obtained with a yield of 55%.

[0051] Characterize the product: 1 1H NMR (600 MHz, CDCl3): δ 7.59 (dd, J = 7.4, 1.9 Hz, 2H), 7.44 - 7.34 (m, 3H), 1.48 - 1.41 (m, 2H), 0.98 (t, J = 7.3 Hz, 3H), 0.88 - 0.83 (m, 2H), 0.39 (s, 3H). 13CNMR (151 MHz, CDCl3): δ 138.55, 133.24, 129.58, 127.88, 19.10, 18.08, 16.66, -1.59. HRMS (ESI): calculated for C 10 H 17 OSi + [M + H] + : 181.1043; found: 181.1039.

[0052] The structural formula of the product is:

[0053] Example 7

[0054] Electrochemically catalyze the reaction of 1 - methyl - 1 - (naphthalen - 1 - yl) silacyclobutane with deionized water. The reaction process is as follows:

[0055] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1 - methyl - 1 - (naphthalen - 1 - yl) silacyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are successively added to the reaction flask, and stirred at room temperature with a current of 8 mA for 1.0 h. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, the solvent is removed using a rotary evaporator to obtain the crude product, and the crude product is separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally 37.7 mg of the product is obtained with a yield of 82%.

[0056] Characterize the product: 1 H NMR (600 MHz, CDCl3): δ 8.26 (d, J = 8.3 Hz, 1H), 7.90 - 7.86 (m, 2H), 7.78 (dd, J = 6.8, 1.3 Hz, 1H), 7.54 - 7.46 (m, 3H), 1.52 - 1.42 (m, 2H), 1.07 - 1.03 (m, 2H). 13 C NMR (151 MHz, CDCl3): δ 136.76, 136.42, 133.48, 133.40, 130.33, 129.02, 128.13, 127.89, 125.98, 125.83, 125.51, 125.03, 20.15, 18.07, 16.88, -0.19. HRMS (ESI): calculated for C 14 H 19 OSi + [M + H] + : 231.1200; found: 231.1203.

[0057] The structural formula of the product is as follows:

[0058] Example 8

[0059] Electrochemically catalyze the reaction of 1-(4-fluorophenyl)-1-methylsilylcyclobutane with deionized water. The reaction process is as follows:

[0060] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1-(4-fluorophenyl)-1-methylsilylcyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are successively added to the reaction flask, and stirred at room temperature for 1.0 h with a current of 8 mA. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, the solvent is removed using a rotary evaporator to obtain the crude product, and the crude product is separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally 32.9 mg of the product is obtained with a yield of 80%.

[0061] Characterize the product: 1 H NMR(600MHz, CDCl3): δ7.55(dd, J = 8.4, 6.3Hz, 2H), 7.07(dd, J = 9.3, 8.6Hz, 2H), 1.45 - 1.39(m, 2H), 0.97(t, J = 7.3Hz, 3H), 0.87 - 0.80(m, 2H), 0.38(s, 3H). 13 C NMR(151MHz, CDCl3): 6164.82, 163.18, 135.28, 135.24, 134.06, 115.08, 114.95, 19.17, 18.03, 16.62, -1.47. 19 F NMR(377MHz, CDCl3): δ - 111.15. HRMS(ESI): calculated for C 10 H16FOSi + [M + H] + : 199.0949; found: 199.0953.

[0062] The structural formula of the product is as follows:

[0063] Example 9

[0064] Electrochemically catalyze the reaction of 1-benzyl-1-methylsilylcyclobutane with ionic water. The reaction process is as follows:

[0065] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 1-benzyl-1-methylsilylcyclobutane, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are successively added to the reaction flask, and stirred at room temperature for 1.0 h with a current of 8 mA. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, the solvent is removed using a rotary evaporator to obtain the crude product, and the crude product is separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally 24.1 mg of the product is obtained with a yield of 62%.

[0066] The product was characterized as follows: 1 H NMR(600 MHz, CDCl3): δ 7.24 (dd, J = 14.8, 7.1 Hz, 2H), 7.10 (t, J = 7.2 Hz, 1H), 7.06 (d, J = 7.4 Hz, 2H), 2.24 - 2.12 (m, 2H), 1.44 - 1.36 (m, 2H), 0.97 (t, J = 7.2 Hz, 3H), 0.62 (td, J = 7.7, 3.3 Hz, 2H), 0.11 (s, 3H). 13 C NMR(151 MHz, CDCl3): δ 139.03, 128.44, 128.19, 124.29, 26.74, 18.34, 18.07, 16.55, -2.24. HRMS(ESI): calculated for C 11 H 19 OSi + [M + H] + : 195.1200; found: 1951200

[0067] The structural formula of the product is:

[0068] Example 10

[0069] The reaction of electrochemically catalyzing 7-phenyl-7-methyl-7-silabicyclo[4.2.0]octa-1,3,5-triene with ionic water is as follows:

[0070] The reaction flask is equipped with graphite felt electrodes, and the graphite felt serves as the cathode and anode. Under nitrogen protection, 0.2 mmol of 7-phenyl-7-methyl-7-silabicyclo[4.2.0]octa-1,3,5-triene, 0.2 mmol of tetrabutylammonium iodide salt, 0.4 ml of deionized water, 0.1 mmol of triethylamine, 4 ml of acetonitrile, and a current of 8 mA are successively added to the reaction flask and stirred at room temperature for 1.0 h. After the reaction is completed, the reaction mixture is filtered through diatomaceous earth, rinsed with ethyl acetate, the organic phases are combined, the solvent is removed using a rotary evaporator to obtain the crude product, and the crude product is separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally 42.0 mg of the product is obtained with a yield of 94%.

[0071] The product was characterized as follows: 1 H NMR (600 MHz, CDCl3): δ 7.62 (d, J = 7.3 Hz, 1H), 7.60 - 7.56 (m, 2H), 7.46 - 7.41 (m, 1H), 7.40 - 7.33 (m, 3H), 7.25 - 7.17 (m, 2H), 2.36 (s, 3H), 0.72 (s, 3H). 13 C NMR (151 MHz, CDCl3): δ 143.85, 137.82, 135.28, 135.21, 133.81, 133.44, 130.23, 130.00, 129.80, 128.51, 128.43, 127.99, 127.90, 125.00, 124.53, 22.99, -0.36. HRMS (ESI): calculated for C 14 H 17 OSi + [M + H] + : 229.1043; found: 229.1046.

[0072] The structural formula of the product is:

[0073] The present invention provides a method for electrochemically mediated ring-opening synthesis of silanols from cyclobutylsilanes

[0074] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. Under anhydrous and oxygen-free conditions, add cyclotetrasilane, water, additives, electrolytes, and solvents into a reaction bottle, and stir the mixture at room temperature for 1.0 hour.

2. The molar ratio of the additive to cyclotetrasilane is 1:2; the amount of water used is 0.4 ml; the amount of the electrolyte used is 0.05 mol per ml; and the amount of the solvent used is 4 ml.

3. The cyclotetrasilane is one of 1,1-diphenylsilylcyclobutane, 1,1-di-p-tolylsilylcyclobutane, 1,1-di(thiophene-2-yl)silylcyclobutane, 1,1-di(4-tert-butylphenyl)silylcyclobutane, 1,1-di(4-trifluoromethylphenyl)silylcyclobutane, 1-methyl-1-(p-tolyl)silylcyclobutane, 1-methyl-1-(naphthalene-1-yl)silylcyclobutane, 1-(4-fluorophenyl)-1-methylsilylcyclobutane, 1-benzyl-1-methylsilylcyclobutane, and 7-phenyl-7-methyl-7-silylbicyclo[4.2.0]octa-1,3,5-triene; the water is deionized water; the triethylamine is 0.1 mmol; the electrode materials are all graphite felt; the electrolyte is tetrabutylammonium iodide salt; and the solvent is acetonitrile.

4. The reaction bottle is equipped with graphite felt electrodes, which are the cathode and anode. Under nitrogen protection, 0.2 mmol of cyclobutanesilane, 0.2 mmol of tetrabutylammonium iodide, 0.4 ml of deionized water, 0.1 mmol of triethylamine, and 4 ml of acetonitrile are added to the reaction bottle in sequence, and the current is 8 mA and stirred at room temperature for 1.0 h.

Images