A process for the synthesis of vinylsilanes from acetylene and hydrosilane hydrosilanes

Abstract

The application discloses a method for synthesizing vinylsilane by acetylene and hydrogen silane hydrosilication; the method is prepared by heating reaction under the action of a solvent, a cobalt catalyst and a ligand, or under the action of the solvent, the cobalt catalyst, the ligand and an additive, and the raw materials are acetylene and hydrogen silane; wherein m is an integer of 1-3, n is 4-m; y is an integer of 1-m, and x is m-y; R is independently selected from C1-C18 alkyl, substituted C1-C6 alkyl, benzofuranyl, benzothiophenyl, thiophenyl, benzyl or C1-C6 alkoxy. The raw material source of the preparation method is simple, the substrate range is wide, the operation is simple, the condition is mild, the production can be scaled up, and the demand of research and development and production in the fields of organic, chemical, medicine, material and the like can be met.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for the hydrosilylation of acetylene and hydrosilane to synthesize vinylsilane. Background Technology

[0002] Organosilicon compounds play an important role in organic synthesis, biomedicine, and materials science. Monovinylsilanes and polyvinylsilanes are a unique class of organosilicon compounds in which a single or multiple vinyl groups are directly bonded to silicon atoms. They can be used as monomers for synthesizing multifunctional silicon-containing polymers [(a) M. Tsumura, T. Iwahara, T. Hirose, Polym. J. 1995, 27, 1048–1053; (b) M. Itoh, K. Iwata, M. Kobayashi, R. Takeuchi, T. Kabeya, Macromolecules 1998, 31, 5609–5615], and are important crosslinking agents in materials design [(a) PEPlueddemann, Silane Coupling Agents, Plenum Press, New Zealand]. York, 1991; (b)LD de Almeida, H. Wang, K. Junge, X. Cui, M. Beller, Angew. Chem. Int. Ed. 2021, 60, 550–565.], and can also serve as unique π-electron accepting ligands in organometallic catalysts (ASChang, KE Kawamura, HSHenness, VMSalpino, JC Greene, LN Zakharov, AK Cook, ACS Catal. 2022, 12, 11002–11014, etc.

[0003] Traditionally, vinylsilanes and polyvinylsilanes are prepared by nucleophilic substitution reactions of hazardous and water-sensitive polychlorinated silanes with stoichiometric vinyl Grignard reagents [(a) JJ Eisch, JTTrainor, J. Org. Chem. 1963, 28, 487–492; (b) B. Boury, RJP Corriu, R. [Chem. Mater. 1998, 10, 1795–1804.]. However, the drawback of this method is the difficulty in precisely controlling the amount of the pre-synthesized, air- and moisture-sensitive vinyl Grignard reagent, which may lead to multiple nucleophilic substitution reactions, resulting in the formation of various vinylsilane compounds that are difficult to separate.

[0004] In 2023, Wu et al. employed a photocatalytic strategy to rapidly and selectively generate bromosilanes (substitutes for chlorosilanes) by reacting dihydrosilanes or trihydrosilanes with dibromomethane in a continuous-flow microfluidic reactor. This was then quenched with a slightly excess of vinyl Grignard reagent, allowing for the controllable preparation of various vinylsilanes (X. Fan, M. Zhang, Y. Gao, Q. Zhou, Y. Zhang, J. Yu, W. Xu, J. Yan, H. Liu, Z. Lei, YCTer, S. Chanmungkalakul, Y. Lum, X. Liu, G. Cui, J. Wu, Nat. Chem. 2023, 15, 666–676.). However, this method also requires pre-synthesized vinyl Grignard reagents, necessitates large quantities of metal reagents, suffers from low atom economy, and has high production costs.

[0005] Transition metal-catalyzed hydrosilylation of acetylene is one of the most direct and economical methods for synthesizing vinylsilanes (T. Zhang, M. Li, P. Zheng, J. Li, J. Gao, H. He, F. Gu, W. Chen, Y. Ji, Z. Zhong, D. Bai, G. Xu, F. Su, Ind. Eng. Chem. Res. 2022, 61, 18703–18711.). Compared to substituted alkynes (aryl or alkyl substituted), acetylene, as a gaseous substance, has lower reactivity. Catalyzing the hydrosilylation of acetylene and silanes to prepare vinylsilane typically requires Group VIII noble metals such as Ru, Rh, Pd, and Pt, resulting in higher production costs [(a) H. Watanabe, M. Asami, Y. Nagai, J. Organomet. Chem. 1980, 195, 363-373; (b) V. Gevorgyan, L. Borisova, J. Popelis, E.Lukevics,Z.Foltynowicz,J.Gulinski,B.Marciniec,J.Organomet.Chem.1992,424,15-22; (c)M.Voronkov, V. Pukhnarevich, I. Tsykhanskaya, N. Ushakova, Yu. Gaft, I. Zakharova, Inorg. Chim. Acta. 1983, 68, 103-105.]. In addition, in industry, vinylsilanes are mainly synthesized by the hydrosilylation of acetylene with tertiary silanes (especially alkoxy-substituted hydrosilanes) using highly active but expensive platinum-based Karstedt catalysts [(a) W. Yang, Ritscher, S. James, US5041595A, 1991; (b) T. Preiss, H. Friedrich, J. Henkelmann, EP1174433, 2002]. However, due to the high reactivity of the catalysts, the hydrosilylation of acetylene with primary silanes (RSiH3) and secondary silanes (RR'SiH2) results in complete hydrosilylation without retaining Si-H, thus making the selective synthesis of monovinylsilanes with acetylene still very challenging (H. Yamashita, Y. Uchimaru, Chem. Commun. 1999, 1763–1764.).

[0006] Recently, the inexpensive cobalt-catalyzed hydrosilylation of alkynes to prepare vinylsilanes has attracted much attention due to its low cost, sustainability, and low toxicity. However, due to the low reactivity of cobalt metal catalysts, most silanes used for the hydrosilylation of alkynes are limited to primary and secondary silanes. Tertiary silanes with large steric hindrance and low reactivity are generally unsuitable for cobalt metal catalysts [(a) Z. Zuo, J. Yang, Z. Huang, Angew. Chem. Int. Ed. 2016, 55, 10839–10843; (b) J. Guo, Z. Lu, Angew. Chem. Int. Ed. 2016, 55, 10835–10838; (c) WJ Teo, C. Wang, YWTan, S. Ge, Angew. Chem. Int. Ed. 2017, 56, 4328–4332; (d) YB Kim, D. Kim, SUDighe, S. Chang, J.-W. Park, ACS Catal.2021,11,1548–1553; (e)D.Wang,Y.Lai,P.Wang,X.Leng,J.Xiao,L.Deng,J.Am.Chem.Soc.2021,143,12847–12 856; (f) Z. Cheng, M. Li, X.-Y. Zhang, Y. Sun, Q.-L. Yu, X.-H. Zhang, Z. Lu, Angew. Chem. Int. Ed. 2023, 62, e202215029]. Summary of the Invention

[0007] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane using an inexpensive cobalt catalyst.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane includes the following steps:

[0010] Vinylsilane is prepared by heating a reaction using hydrosilane and acetylene as raw materials, in the presence of solvent, cobalt catalyst and ligand, or in the presence of solvent, cobalt catalyst, ligand and additive.

[0011]

[0012] Where m is an integer from 1 to 3, n is 4-m; y is an integer from 1 to m, and x is my;

[0013] R is selected independently from each of the following. C1-C18 alkyl, substituted C1-C6 alkyl, benzofuranyl, benzothiophenyl, thiophenyl, benzyl, or C1-C6 alkoxy; wherein R 9 R 10 Each of the substituents is independently selected from one or more substituents on the benzene ring and the naphthalene ring, and each substituent is independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, trifluoromethyl, trifluoromethoxy, methylenedioxy, morpholino or phenyl; the substituent of the substituted C1-C6 alkyl is a benzene ring.

[0014] Preferably, the cobalt catalyst is selected from at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8;

[0015] Preferably, the ligand is selected from at least one of bisphosphine ligands and bipyridine ligands;

[0016] More preferably, the ligand is selected from PPh3, dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, Dpephos, Binap, phen, bpy, 6-Me bpy and 4-tBu,6-Me At least one of bpy.

[0017] Preferably, the molar ratio of the hydrosilane, cobalt catalyst, and ligand is 1:(0.01-0.5):(0.015-0.55);

[0018] Preferably, the pressure of the acetylene is 1 to 10 atm;

[0019] Preferably, the solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water;

[0020] Preferably, the concentration of the hydrosilane in the solvent is 0.25M to 1.0M;

[0021] Preferably, post-processing is performed after the reaction;

[0022] More preferably, the post-processing includes the following steps: solvent removal, extraction, and column chromatography.

[0023] Preferably, the additive is selected from NaBHEt3, Zn powder, Fe powder, Mn powder, and R. 12 2SiH2 and R12 At least one of SiH3, wherein R 12 Each is independently selected from C6-C20 aryl and C1-C18 alkyl groups;

[0024] Preferably, the molar ratio of the hydrosilane to the additive is 1:(0 to 1.0).

[0025] Preferably, the reaction temperature is room temperature to 100°C; the reaction time is 12 to 72 hours.

[0026] Preferably, the method for hydrosilylating acetylene and hydrosilane to synthesize vinylsilane includes the following six schemes;

[0027] Technical Solution 1:

[0028] Selective hydrosilylation of acetylene and secondary hydrosilanes of formula (I-2) to prepare monovinylsilanes of formula (II);

[0029] Using secondary hydrogen silane as shown in formula (I-2) and acetylene as raw materials, monovinyl silane as shown in formula (II) was prepared by heating reaction under the action of solvent, cobalt catalyst and ligand I;

[0030]

[0031] Technical Solution Two:

[0032] Selective hydrosilylation of acetylene and secondary hydrosilanes of formula (I-2) to prepare divinylsilanes of formula (III);

[0033] Using secondary hydrogen silane as shown in formula (I-2) and acetylene as raw materials, the divinylsilane as shown in formula (III) was prepared by heating reaction under the action of solvent, cobalt catalyst and ligand II.

[0034]

[0035] Technical Solution 3:

[0036] Selective hydrosilylation of acetylene and primary hydrosilane of formula (I-1) to prepare monovinylsilane of formula (IV);

[0037] Using primary hydrogen silane as shown in formula (I-1) and acetylene as raw materials, monovinyl silane as shown in formula (IV) was prepared by heating reaction under the action of solvent, cobalt catalyst and ligand I.

[0038]

[0039] Technical Solution Four:

[0040] Selective hydrosilylation of acetylene and primary hydrosilane of formula (I-1) to prepare divinylsilane of formula (V);

[0041] Using primary hydrogen silane of formula (I-1) and acetylene as raw materials, a heating reaction is carried out in the presence of a solvent, a cobalt catalyst, and ligand III to prepare divinylsilane of formula (V); wherein ligand III is selected from at least one of ligand I and ligand II.

[0042]

[0043] Technical Solution 5:

[0044] Selective hydrosilylation of acetylene and primary hydrosilane of formula (I-1) to prepare trivinylsilane of formula (VI);

[0045] Using primary hydrogen silane as shown in formula (I-1) and acetylene as raw materials, trivinylsilane as shown in formula (VI) is prepared by heating reaction under the action of solvent, cobalt catalyst and ligand II.

[0046]

[0047] Technical Solution Six:

[0048] Selective hydrosilylation of acetylene and tertiary hydrosilanes of formula (I-3) to prepare monovinylsilanes of formula (VII);

[0049] Using tertiary hydrosilanes and acetylenes as raw materials, monovinylsilanes as shown in formula (VII) are prepared by heating reaction under the action of solvent, cobalt catalyst, ligand II and additives.

[0050]

[0051] Among them, R 3 Each independently selected C1-C18 alkyl or substituted C1-C6 alkyl; the R 7 R 8 It is one or more substituents on the benzene ring and the naphthalene ring, each substituent being independently selected from hydrogen atoms, C1-C6 alkyl groups, and C1-C6 alkoxy groups; the substituents of the substituted C1-C6 alkyl groups are benzene rings;

[0052] R 1 and R 2 Each independently selected C1-C8 alkyl, benzofuranyl, benzothiophenyl, thiophenyl; the R 9 R 10 Each of the substituents is independently selected from one or more substituents on the benzene ring and the naphthalene ring, and each substituent is independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, trifluoromethyl, trifluoromethoxy, methylenedioxy, morpholino or phenyl;

[0053] R 4 R 5 and R 6 Each independently selected Thiophene, benzyl, C1-C6 alkyl, and C1-C6 alkoxy; the R 11 It is one or more substituents on the benzene ring, each substituent being independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 alkoxy or trifluoromethyl;

[0054] The ligand I is selected from at least one of PPh3, dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, Dpephos and Binap;

[0055] The ligand II is selected from phen, bpy, 6-Me bpy and 4-tBu,6-Me At least one of bpy.

[0056] The hydrosilane raw materials of the present invention (including primary hydrosilanes shown in formula (I-1), secondary hydrosilanes shown in formula (I-2), and tertiary hydrosilanes shown in formula (I-3)) can be prepared by reacting trichlorosilane or phenyltrichlorosilane with Grignard reagents according to the methods described in the literature [(a) S. Chang, KE Kawamura, HSHenness, VMSalpino, JC Greene, LN Zakharov, AK Cook, ACS Catal. 2022, 12, 11002–11014; (b) NTTran, T. Min, AK Franz, Chem.–Eur. J 2011, 17, 9897–9900] or by reducing substituted trichlorosilanes with LiAlH4.

[0057] Substituent definition and general terminology:

[0058] The term "halogen" used in this invention refers to fluorine, chlorine, bromine, and iodine.

[0059] The term "alkyl" as used in this invention refers to a straight-chain, branched, or cyclic hydrocarbon group containing 1 to 18 carbon atoms.

[0060] The term "C1-C18" used in this invention refers to containing 1 to 18 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18) carbon atoms.

[0061] The term "C1 to C6" used in this invention refers to the presence of 1 to 6 (1, 2, 3, 4, 5, 6) carbon atoms.

[0062] The term "C1 to C8" used in this invention refers to the presence of 1 to 8 (1, 2, 3, 4, 5, 6, 7, 8) carbon atoms.

[0063] In technical solution one,

[0064] Preferably, the structural formula of the monovinylsilane shown in formula (II) is as follows:

[0065]

[0066]

[0067] Preferably, the cobalt catalyst includes, but is not limited to, at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8.

[0068] More preferably, the cobalt catalyst is at least one of Co(OAc)2, Co(OTf)2, CoBr2, and CoCl2; more preferably, the cobalt catalyst is Co(OAc)2.

[0069] Preferably, the ligand I is at least one of PPh3, dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, Dpephos, and Binap.

[0070]

[0071] More preferably, the ligand I is at least one of dppe, dppp, Xantphos, and Dpephos; more preferably, the ligand I is Xantphos.

[0072] Preferably, the molar ratio of the secondary silane, catalyst, and ligand I shown in formula (I-2) is 1:(0.02-0.5):(0.03-0.55).

[0073] More preferably, the molar ratio of the secondary silane, catalyst and ligand I shown in formula (I-2) is 1:(0.02-0.05):(0.03-0.06); more preferably, the molar ratio of the secondary silane, catalyst and ligand I shown in formula (I-2) is 1:0.02:0.03.

[0074] Preferably, the solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water; more preferably, the solvent is tetrahydrofuran or water.

[0075] Preferably, the concentration of the secondary silane shown in formula (I-2) in the solvent is 0.25M to 0.5M.

[0076] Acetylene can be supplied by an acetylene pressure vessel or generated on-site by calcium carbide.

[0077] Preferably, the pressure range of the acetylene is 1 to 10 atm; more preferably, the pressure range of the acetylene is 1 to 3 atm.

[0078] Preferably, the reaction temperature is room temperature to 120°C; more preferably, the reaction temperature is 45°C to 60°C; even more preferably, the reaction temperature is 45°C.

[0079] Preferably, the reaction time is 12 to 24 hours; more preferably, the reaction time is 12 hours.

[0080] Preferably, the reaction is followed by post-processing, which includes the following steps: solvent removal, extraction, and column chromatography.

[0081] In technical solution two,

[0082] Preferably, the structural formula of the divinylsilane shown in formula (III) is as follows:

[0083]

[0084] Preferably, the cobalt catalyst includes, but is not limited to, at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8.

[0085] More preferably, the cobalt catalyst is at least one of Co(OAc)2, Co(OTf)2, CoBr2, and CoCl2; more preferably, the cobalt catalyst is Co(OAc)2.

[0086] Preferably, the ligand II is phen, bpy, or phen. 6-Me bpy and 4-tBu,6-Me At least one of bpy.

[0087] More preferably, the ligand II is6-Me bpy, 4-tBu,6-Me At least one of bpy; more preferably, the ligand II is 6-Me bpy.

[0088]

[0089] Preferably, the molar ratio of the secondary silane, catalyst and ligand II shown in formula (I-2) is 1:(0.02-0.5):(0.03-0.55).

[0090] More preferably, the molar ratio of the secondary silane, catalyst and ligand II shown in formula (I-2) is 1:(0.02-0.05):(0.003-0.06); more preferably, the molar ratio of the secondary silane, catalyst and ligand II shown in formula (I-2) is 1:0.05:0.06.

[0091] Preferably, the solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water; more preferably, the solvent is tetrahydrofuran.

[0092] Preferably, the concentration of the secondary silane shown in formula (I-2) in the solvent is 0.25M to 0.1M; more preferably, the concentration of the secondary silane shown in formula (I-2) in the solvent is 0.5M.

[0093] Acetylene can be supplied by an acetylene pressure vessel or generated on-site by calcium carbide.

[0094] Preferably, the pressure range of the acetylene is 1 to 10 atm; more preferably, the pressure range of the acetylene is 1 to 3 atm.

[0095] Preferably, the reaction temperature is 45–100°C; the reaction time is 12–24 hours.

[0096] More preferably, the temperature and time procedure for the reaction is as follows: react at 45°C for 2 to 5 hours, then raise the temperature to 80 to 100°C and react for 10 to 24 hours.

[0097] More preferably, the temperature and time operation procedure of the reaction is as follows: react at 45°C for 2 hours, and then raise the temperature to 100°C for 10 hours.

[0098] Preferably, the reaction is followed by post-processing, which includes the following steps: solvent removal, extraction, and column chromatography.

[0099] Technical Solution 3:

[0100] Preferably, the monovinylsilane shown in formula (IV) has the following structural formula:

[0101]

[0102] Preferably, the cobalt catalyst includes, but is not limited to, at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8.

[0103] More preferably, the cobalt catalyst is at least one of Co(OAc)2, Co(OTf)2, CoBr2, and CoCl2; more preferably, the cobalt catalyst is Co(OAc)2.

[0104] Preferably, the ligand I is at least one of PPh3, dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, Dpephos, and Binap.

[0105] More preferably, the ligand I is at least one of dppe, dppp, Xantphos, and Dpephos; more preferably, the ligand I is Xantphos.

[0106] Preferably, the molar ratio of the primary hydrosilane, catalyst, and ligand I shown in formula (I-1) is 1:(0.02-0.5):(0.03-0.55).

[0107] More preferably, the molar ratio of the primary hydrosilane, catalyst, and ligand I shown in formula (I-1) is 1:(0.02-0.05):(0.03-0.06).

[0108] Preferably, the solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water; more preferably, the solvent is tetrahydrofuran.

[0109] Preferably, the concentration of the primary hydrosilane shown in formula (I-1) in the solvent is 0.25M to 0.5M.

[0110] Acetylene can be supplied by an acetylene pressure vessel or generated on-site by calcium carbide.

[0111] Preferably, the pressure range of the acetylene is 1 to 10 atm; more preferably, the pressure range of the acetylene is 1 to 3 atm.

[0112] Preferably, the reaction temperature is 45–100°C; more preferably, the reaction temperature is 45–80°C.

[0113] Preferably, the reaction time is 12 to 48 hours; more preferably, the reaction time is 12 to 24 hours.

[0114] Preferably, the reaction is followed by post-processing, which includes the following steps: solvent removal, extraction, and column chromatography.

[0115] Technical Solution Four:

[0116] Preferably, the structural formula of the divinylsilane shown in formula (V) is as follows:

[0117]

[0118] Preferably, the cobalt catalyst includes, but is not limited to, at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8.

[0119] More preferably, the cobalt catalyst is at least one of Co(OAc)2, Co(OTf)2, CoBr2, and CoCl2; more preferably, the cobalt catalyst is Co(OAc)2.

[0120] Preferably, the ligand III is PPh3, dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, Dpephos, phen, Binap, bpy, 6-Me bpy and 4-tBu,6-Me At least one of bpy.

[0121] More preferably, if R 3 Selected from The R 7 R 8 It is one or more substituents on the benzene ring and the naphthalene ring, each substituent being independently selected from hydrogen atom, C1-C6 alkyl, C1-C6 alkoxy; the ligand III is selected from ligand I, namely at least one of dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, and Dpephos; more preferably, the ligand III is Xantphos.

[0122] More preferably, if R 3The ligand is selected from C1-C18 alkyl groups or substituted C1-C6 alkyl groups, wherein the substituent of the substituted C1-C6 alkyl group is a benzene ring; the ligand III is selected from ligand II, namely phen, bpy, ... 6-Me bpy and 4-tBu,6-Me At least one of bpy; more preferably, ligand III is 6-Me bpy.

[0123] Preferably, the molar ratio of the primary silane, catalyst, and ligand III shown in formula (I-1) is 1:(0.02-0.5):(0.03-0.55).

[0124] More preferably, the molar ratio of the primary silane, catalyst, and ligand III shown in formula (I-1) is 1:(0.02-0.05):(0.03-0.06).

[0125] Preferably, the solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water; more preferably, the solvent is tetrahydrofuran.

[0126] Preferably, the concentration of the primary silane shown in formula (I-1) in the solvent is 0.25M to 0.5M.

[0127] Acetylene can be supplied by an acetylene pressure vessel or generated on-site by calcium carbide.

[0128] Preferably, the pressure range of the acetylene is 1 to 10 atm; more preferably, the pressure range of the acetylene is 1 to 3 atm.

[0129] Preferably, the reaction temperature is 45–100°C; the reaction time is 12–48 hours.

[0130] More preferably, the temperature and time procedure for the reaction is to react at 45°C for 2 to 5 hours, and then raise the temperature to 80 to 100°C for 10 to 24 hours.

[0131] More preferably, if R 3 Selected from The R 7 R 8 The reaction consists of one or more substituents on the benzene ring and the naphthalene ring, each substituent being independently selected from hydrogen atoms, C1-C6 alkyl groups, and C1-C6 alkoxy groups; the temperature and time procedure for the reaction is 45-100°C for 12-48 hours.

[0132] More preferably, if R 3The reaction mixture is selected from C1-C18 alkyl groups or substituted C1-C6 alkyl groups, wherein the substituent of the substituted C1-C6 alkyl groups is a benzene ring; the temperature and time procedure of the reaction is to react at 45°C for 2-5 hours, and then raise the temperature to 80-100°C for 10-24 hours; more preferably, the temperature and time procedure of the reaction is to react at 45°C for 2 hours, and then raise the temperature to 100°C for 10 hours.

[0133] Preferably, the reaction is followed by post-processing, which includes the following steps: solvent removal, extraction, and column chromatography.

[0134] In technical solution five,

[0135] Preferably, the structural formula of the trivinylsilane shown in formula (VI) is as follows:

[0136]

[0137] Preferably, the cobalt catalyst includes, but is not limited to, at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8.

[0138] More preferably, the cobalt catalyst is at least one of Co(OAc)2, Co(OTf)2, CoBr2, and CoCl2; more preferably, the cobalt catalyst is Co(OAc)2.

[0139] Preferably, the ligand II is phen, bpy, or phen. 6-Me bpy and 4-tBu,6-Me At least one of bpy.

[0140] More preferably, the ligand II is 6-Me bpy, 4-tBu,6-Me At least one of bpy; more preferably, the ligand II is 6-Me bpy.

[0141] Preferably, the molar ratio of the primary silane, catalyst and ligand II shown in formula (I-1) is 1:(0.02-0.5):(0.03-0.55).

[0142] More preferably, the molar ratio of the primary silane, catalyst and ligand II shown in formula (I-1) is 1:(0.02-0.05):(0.03-0.06); more preferably, the molar ratio of the primary silane, catalyst and ligand II shown in formula (I-1) is 1:0.05:0.06.

[0143] Preferably, the solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water; more preferably, the solvent is tetrahydrofuran.

[0144] Preferably, the concentration of the primary silane shown in formula (I-1) in the solvent is 0.25M to 0.1M; more preferably, the concentration of the primary silane shown in formula (I-1) in the solvent is 0.5M.

[0145] Acetylene can be supplied by an acetylene pressure vessel or generated on-site by calcium carbide.

[0146] Preferably, the pressure range of the acetylene is 1 to 10 atm; more preferably, the pressure range of the acetylene is 1 to 3 atm.

[0147] Preferably, the reaction temperature is 45–100°C; the reaction time is 12–24 hours.

[0148] More preferably, the temperature and time procedure for the reaction is to react at 45°C for 2 to 5 hours, and then raise the temperature to 80 to 100°C for 10 to 24 hours.

[0149] More preferably, the temperature and time procedure for the reaction is to react at 45°C for 2 hours, and then raise the temperature to 100°C for 10 hours.

[0150] Preferably, the reaction is followed by post-processing, which includes the following steps: solvent removal, extraction, and column chromatography.

[0151] In technical solution six,

[0152] Preferably, the structural formula of the monovinylsilane shown in formula (VII) is as follows:

[0153]

[0154] Preferably, the cobalt catalyst includes, but is not limited to, at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8.

[0155] More preferably, the cobalt catalyst is at least one of Co(OAc)2, Co(OTf)2, CoBr2, and CoCl2; more preferably, the cobalt catalyst is Co(OAc)2.

[0156] Preferably, the ligand II is phen, bpy, or phen. 6-Me bpy and 4-tBu,6-Me At least one of bpy.

[0157] More preferably, the ligand II is 6-Me bpy, 4-tBu,6-Me At least one of bpy

[0158] Preferably, the additive is NaBHEt3, Zn powder, Fe powder, Mn powder, R 12 2SiH2 and R 12 At least one of SiH3, wherein R 12 Each is independently selected from C6-C20 aryl and C1-C18 alkyl groups;

[0159] More preferably, the additive is R 12 2SiH2 and R 12 At least one of SiH3; more preferably, the additive is at least one of Ph2SiH2 and PhSiH3; more preferably PhSiH3.

[0160] Preferably, the molar ratio of the tertiary silane, catalyst, and ligand II shown in formula (I-3) is 1:(0.05~0.5):(0.06~0.55).

[0161] More preferably, the molar ratio of the tertiary silane, catalyst, and ligand II shown in formula (I-3) is 1:(0.05~0.1):(0.06~0.11).

[0162] Preferably, the molar ratio of the tertiary silane and the additive shown in formula (I-3) is 1:(0.06~1.0);

[0163] More preferably, the molar ratio of the tertiary silane and the additive shown in formula (I-3) is 1:(0.2-0.3).

[0164] Preferably, the solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water; more preferably, the solvent is tetrahydrofuran.

[0165] Preferably, the concentration of the tertiary silane shown in formula (I-3) in the solvent is 0.25M to 1.0M; more preferably, the concentration of the tertiary silane shown in formula (I-3) in the solvent is 0.25M to 0.5M; more preferably, the concentration of the tertiary silane shown in formula (I-3) in the solvent is 0.5M.

[0166] Acetylene can be supplied by an acetylene pressure vessel or generated on-site by calcium carbide.

[0167] Preferably, the pressure range of the acetylene is 1 to 10 atm; more preferably, the pressure range of the acetylene is 1 to 3 atm.

[0168] Preferably, the reaction temperature is 45–100°C; more preferably, the reaction temperature is 100°C.

[0169] Preferably, the reaction time is 12 to 72 hours; more preferably, the reaction time is 48 to 72 hours.

[0170] Preferably, the reaction is followed by post-processing, which includes the following steps: solvent removal, extraction, and column chromatography.

[0171] Compared with the prior art, the beneficial effects of the present invention are:

[0172] (1) This invention provides a method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane using a non-precious metal cobalt catalyst.

[0173] (2) This invention provides a method for the selective synthesis of monovinyl, divinyl, and trivinylsilanes from acetylene and primary, secondary, and tertiary silanes. The method utilizes readily available and inexpensive commercial cobalt metal and ligands, undergoing a catalytic hydrosilylation reaction to synthesize specific monovinyl, divinyl, and trivinylsilanes with high selectivity and high yield. This method has a broad substrate range (including tertiary silanes with low reactivity), some reactions can be carried out using water as a solvent, the operation is simple, the raw materials are inexpensive and readily available, and it is easily scaled up, meeting the research and production needs of organic, chemical, pharmaceutical, and materials fields. Detailed Implementation

[0174] The present invention is further described below, but the embodiments do not limit the invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field, and can be purchased directly or synthesized by methods known in the literature.

[0175] Example 1

[0176] This embodiment provides a method for preparing diphenylvinylsilane (II-1) (THF as solvent), and the reaction equation is as follows:

[0177]

[0178] The procedure was as follows: Co(OAc)₂ (0.01 mmol, 2 mol%) and ligand Xantphos (0.015 mmol, 3 mol%) were added sequentially to the reaction flask. The flask was then sealed with a rubber stopper, an acetylene balloon was inserted, and the atmosphere was evacuated five times using a vacuum pump. 2.0 mL of THF was added using a syringe, and the mixture was stirred at room temperature for 1 minute. Diphenylsilane (I-2-1, 0.5 mmol) was then added, and the reaction was carried out at 45 °C for 12 hours. After the reaction was complete, the metal catalyst was filtered off, and the residual liquid in the reaction flask was washed with ethyl acetate. The filtrate was concentrated under vacuum and then purified by column chromatography (eluent: petroleum ether) to obtain diphenylvinylsilane (II-1, 95.6 mg, yield 91%). 1 H NMR(500MHz,Chloroform-d)δ7.67(dd,J=7.8,1.6Hz,4H),7.52-7.44(m,6H),6.55(ddd,J=20.2,1 4.5, 3.1Hz, 1H), 6.35 (dd, J=14.5, 3.6Hz, 1H), 6.01 (dd, J=20.2, 3.6Hz, 1H), 5.22 (d, J=3.1Hz, 1H). 13 C NMR (126MHz, Chloroform-d) δ137.07,135.54,133.40,132.77,129.82,128.11.

[0179] Example 2

[0180] This embodiment provides a method for preparing diphenylvinylsilane (II-1) (using water as a solvent), and the reaction equation is as follows:

[0181]

[0182] The procedure was as follows: Co(OAc)₂ (0.01 mmol, 2 mol%) and ligand Xantphos (0.015 mmol, 3 mol%) were added sequentially to the reaction flask. The flask was then sealed with a rubber stopper, an acetylene balloon was inserted, and the atmosphere was evacuated five times using a vacuum pump. 2.0 mL of water (0.25 M) was added using a syringe, and the mixture was stirred at room temperature for 1 minute. Diphenylsilane (I-2-1, 0.5 mmol) was then added, and the reaction was carried out at 45 °C for 12 hours. After the reaction was complete, the reaction solution was extracted with ethyl acetate. The extract was concentrated under vacuum and then purified by column chromatography (eluent: petroleum ether) to obtain diphenylvinylsilane (II-1, 88.6 mg, yield 85%).

[0183] Examples 3-7

[0184] This example provides a series of diphenylsilanes (I-2-1) under the same operating method, solvent, temperature, and reaction time as in Example 1, using a 5 mol% Co(OAc)2 catalyst and 6 mol% different ligands, to compare the selectivity of diphenylvinylsilane (II-1) and diphenyldivinylsilane (III-1). The specific results are shown in Table 1:

[0185] Table 1 Examples 3-7

[0186] Example ligands II-1 Yield % III-1 Yield % 3 dppe 21 Not detected 4 Xantphos 98 Not detected 5 Dpephos 15 Not detected 6 bpy 24 3 7 terpy 43 8 8 ligand-free Not detected Not detected

[0187] Examples 9-13

[0188] This example provides a series of diphenylsilanes (I-2-1) under the same operating method, solvent (THF), temperature, and reaction time as in Example 1, using 5 mol% of different catalysts and 6 mol% of different Xantphos ligands, to compare the selectivity of diphenylvinylsilane (II-1) and diphenyldivinylsilane (III-1). The specific results are shown in Table 2:

[0189] Table 2 Examples 9-13

[0190] Example catalyst II-1 Yield % III-1 Yield % 9 <![CDATA[Co(OAc)2·4H2O]]> 91 Not detected 10 <![CDATA[Co(PPh3)3Cl]]> 96 Not detected 11 <![CDATA[Co2(CO)8]]> 23 38 12 <![CDATA[Fe(OAc)2]]> Not detected Not detected 13 <![CDATA[Ni(OAc)2·2H2O]]> 4 Not detected

[0191] Examples 14-18

[0192] This example provides a series of diphenylsilanes (I-2-1) under the same operating method, solvent (H2O), temperature, and reaction time as in Example 2, using 5 mol% of different catalysts and 6 mol% of different Xantphos ligands, to compare the selectivity of diphenylvinylsilane (II-1) and diphenyldivinylsilane (III-1). The specific results are shown in Table 3.

[0193] Table 3 Examples 14-18

[0194] Example catalyst II-1 Yield % III-1 Yield % 14 <![CDATA[Co(acac)2]]> 73 Not detected 15 <![CDATA[Co(acac)3]]> 84 Not detected 16 <![CDATA[Co(OTf)2]]> 89 Not detected 17 <![CDATA[CoBr2]]> 89 Not detected 18 <![CDATA[CoCl2·6H2O]]> 88 Not detected

[0195] Examples 19-43

[0196] This embodiment provides a method for preparing a series of monovinylsilanes by hydrosilylation of the secondary silane described in formula (I-2) and acetylene. The feeding and operation are the same as in Example 1 or Example 2. The raw materials, products and corresponding yields are shown in Table 4.

[0197] Table 4 Examples 19-43

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] Example 44

[0205] This embodiment provides a method for preparing diphenyldivinylsilane (III-1), and the reaction equation is as follows:

[0206]

[0207] The procedure is as follows: Add Co(OAc)₂ (0.0125 mmol, 5 mol%) and ligand sequentially to a Shrek tube. 6-Me bpy (0.015 mmol, 6 mol%) was added, the container was then sealed, and acetylene gas was purged five times using a vacuum pump. 1.0 mL of THF (0.5 M) was added, and the mixture was stirred at room temperature for 1 minute before adding diphenylsilane (I-2-1, 0.25 mmol). The reaction was then carried out at 45 °C for 2 hours, followed by a further heating to 100 °C and a reaction time of 10 hours. After the reaction was complete, the metal catalyst was filtered off, and the residual liquid in the reaction flask was washed with ethyl acetate. The filtrate was concentrated under vacuum and then purified by column chromatography (eluent: petroleum ether) to obtain diphenyldivinylsilane (III-1, 44.3 mg, yield 75%). 1 H NMR(400MHz,Chloroform-d)δ7.65(dd,J=7.6,1.7Hz,4H),7.51–7.43(m,6H),6.60( dd,J=20.2,14.6Hz,2H), 6.36(dd,J=14.6,3.7Hz,2H), 5.91(dd,J=20.2,3.7Hz,2H). 13 C NMR (101MHz, Chloroform-d) δ136.60,135.60,134.32,133.89,129.60,127.95.

[0208] Examples 45-48

[0209] This embodiment provides a series of diphenylsilanes (I-2-1) obtained by using the same operating method, catalyst, ligand, temperature, and reaction time as in Example 44, with a reaction concentration of 0.25M and different solvents, resulting in diphenyldivinylsilane (III-1). The specific results are shown in Table 5.

[0210] Table 5 Examples 45-48

[0211] Example solvent III-1 Yield % 45 <![CDATA[ 2-Me THF]]> 60 46 EtOAc 60 47 MeCN 64 48 <![CDATA[H2O]]> 42

[0212] Examples 49-50

[0213] This embodiment provides a series of diphenylsilanes (I-2-1) obtained by using different reaction concentrations under the same operating method, catalyst, solvent, ligand, temperature, and reaction time as in Example 44. The specific results are shown in Table 6.

[0214] Table 6 Examples 49-50

[0215] Example reaction concentration III-1 Yield % 49 0.25M 65 50 1.0M 64

[0216] Examples 51-67

[0217] This embodiment provides a method for preparing a series of divinylsilanes by hydrosilylation of the secondary silane described in formula (I-2) and acetylene. The feeding and operation are the same as in Example 44, and the raw materials, products and corresponding yields are shown in Table 7:

[0218] Table 7 Examples 51-67

[0219]

[0220]

[0221]

[0222]

[0223]

[0224] Example 68

[0225] This embodiment provides a method for preparing (6-phenylhexyl)(vinyl)silane (IV-1), and the reaction equation is as follows:

[0226]

[0227] The procedure was the same as in Example 1 to obtain (6-phenylhexyl)(vinyl)silane (IV-1, 41.5 mg, yield 38%). 1HNMR(400MHz,Chloroform-d)δ7.35-7.29(m,2H),7.25-7.20(m,3H),6.21-6.07(m,2H),5.93(dd,J=17.0,6.9Hz,1H), 3.96(q,J=3.0Hz,2H),2.69-2.61(m,2H),1.66(p,J=7.6Hz,2H),1.49-1.37(m,6H),0.80(ddt,J=9.1,7.1,3.5Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ142.88,135.61,131.77,128.43,128.26,125.61,36.01,32.67,31.42,28.99,25.07,9.36.HRMS(ESI)m / z:[M+Na] + calcd for C 11 H 16 SiNa + 241.1381; found 241.1389.

[0228] Example 69

[0229] This embodiment provides a method for preparing octadecyl(vinyl)silane (IV-2), and the reaction equation is as follows:

[0230]

[0231] The procedure was the same as in Example 1, yielding octadecyl (vinyl)silane (IV-2, 69.8 mg, 45% yield). 1 H NMR(400MHz Chloroform-d)δ6.22-6.03(m,2H),5.90(dd,J=17.5,6.5Hz,1H),3.93(q,J=3.4 Hz,2H),1.28(s,32H),0.91(t,J=6.8Hz,3H),0.78(ddt,J=10.0,6.3,3.2Hz,2H). 13 CNMR(101MHz,Chloroform-d)δ135.50,131.82,32.82,31.95,29.72,29.70,29.56,29.39,29.31,25.12,22.71,14.13,9.33.HRMS(ESI)m / z:[M+H] + calcd for C 20 H 43 Si +311.3129; found 311.3129.

[0232] Example 70

[0233] This embodiment provides a method for preparing (2,4,6-trimethylphenyl)(vinyl)silane (IV-3), and the reaction equation is as follows:

[0234]

[0235] The procedure was the same as in Example 1, but the reaction temperature and time were changed to: react at 80°C for 24 hours to obtain (2,4,6-trimethylphenyl)(vinyl)silane (IV-3, 79.3 mg, yield 90%). 1 H NMR(400MHz,Chloroform-d)δ6.93(s,2H),6.27(ddt,J=19.4,14.2,2.5Hz,1H),6.13(dd,J=14 .2,3.9Hz,1H),5.90(dd,J=19.8,4.4Hz,1H),4.70(d,J=2.2Hz,2H),2.50(s,6H),2.34(s,3H). 13 C NMR(101MHz,Chloroform-d)δ144.95,139.89,135.79,131.06,128.25,125.86,23.64,21.26.HRMS(ESI)m / z:[M+Na] + calcd for C 11 H 16 SiNa + 199.0913; found 199.0914.

[0236] Examples 71-74

[0237] This embodiment provides a method for preparing a series of divinylsilanes by hydrosilylation of the primary silane described in formula (I-1) and acetylene. The feeding and operation are the same as in Example 1, and the raw materials, products and corresponding yields are shown in Table 8:

[0238] Table 8 Examples 71-74

[0239]

[0240]

[0241] Example 75

[0242] This embodiment provides a method for preparing (6-phenylhexyl)bis(vinyl)silane (V-5), and the reaction equation is as follows:

[0243]

[0244] The procedure was the same as in Example 44, yielding (6-phenylhexyl)bis(vinyl)silane (V-5, 27.6 mg, 45% yield). 1 HNMR(400MHz,Chloroform-d)δ7.34-7.28(m,2H),7.24-7.18(m,3H),6.23-6.14(m,2H),6.11(dd,J=14.7,5.2Hz,2 H),5.80(dd,J=19.0,5.2Hz,2H),2.70-2.58(m,2H),1.68-1.59(m,2H),1.37(d,J=15.8Hz,6H),0.83–0.68(m,2H). 13 C NMR(101MHz,Chloroform-d)δ142.93,134.92,134.29,128.42,128.24,125.58,36.03,33.42,31.45,28.99,23.58,12.68.HRMS(ESI)m / z:[M+H] + calcd for C 16 H 25 Si + 245.1720; found 245.1719.

[0245] Example 76

[0246] This embodiment provides a method for preparing octadecyldis(vinyl)silane (V-6), and the reaction equation is as follows:

[0247]

[0248] The procedure was the same as in Example 44, yielding octadecyldis(vinyl)silane (V-6, 39.1 mg, yield 47%). 1 HNMR(400MHz,Chloroform-d)δ6.27-6.05(m,4H),5.79(dd,J=19.1,5.0Hz,2H),1.28(s,32H),0.91(t,J=6.8Hz,3H),0.81-0.68(m,2H). 13 C NMR(101MHz,Chloroform-d)δ134.96,134.20,33.57,31.95,29.72,29.60,29.39,29.31,23.64,22.71,14.13,12.66.HRMS(ESI)m / z:[M+Na] +calcd for C 22 H 44 SiNa + 359.3106; found 359.3106.

[0249] Example 77

[0250] This embodiment provides a method for preparing phenyltrisylsilane (VI-1), and the reaction equation is as follows:

[0251]

[0252] The procedure was the same as in Example 44, yielding phenyltris(vinyl)silane (VI-1, 29.2 mg, yield 31%). 1 H NMR(400MHz,Chloroform-d)δ7.60(dd,J=6.9,2.0Hz,2H),7.42(d,J=6.7Hz,3H),6.38 (dd,J=20.0,14.7Hz,3H),6.25(dd,J=14.7,4.0Hz,3H),5.87(dd,J=20.0,4.0Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ135.97,135.10,134.46,133.83,129.46,127.88.

[0253] Example 78

[0254] This embodiment provides a method for preparing 4-methoxyphenyltrisylsilane (VI-2), and the reaction equation is as follows:

[0255]

[0256] The procedure was the same as in Example 44, yielding 4-methoxyphenyltris(vinyl)silane (VI-2, 41.4 mg, yield 38%). 1 H NMR(400MHz,Chloroform-d)δ7.52(d,J=8.6Hz,2H),6.98(d,J=8.6Hz,2H),6.37(dd,J=20 .0,14.6Hz,3H),6.24(dd,J=14.6,4.1Hz,3H),5.86(dd,J=20.0,4.1Hz,3H),3.86(s,3H). 13 C NMR (101MHz, Chloroform-d) δ160.80,136.62,135.73,134.23,125.05,113.71,55.06.

[0257] Example 79

[0258] This embodiment provides a method for preparing triphenylvinylsilane (VII-1), and the reaction equation is as follows:

[0259]

[0260] The procedure is as follows: Add Co(OAc)₂ (0.0125 mmol, 5 mol%) and ligand sequentially to a Shrek tube. 6-Me bpy (0.015 mmol, 6 mol%) was added, then the container was stoppered, and the acetylene gas was purged five times using a vacuum pump. 0.5 mL of THF (0.5 M) was added, and the mixture was stirred at room temperature for 1 minute. PhSiH3 (0.05 mmol, 20 mol%) and triphenylsilane (I-3-1, 0.25 mmol) were then added sequentially, and the reaction was carried out at 100 °C for 48 hours. After the reaction, the metal catalyst was filtered off, and the residual liquid in the reaction flask was washed with ethyl acetate. The filtrate was concentrated under vacuum and then purified by column chromatography (eluent: petroleum ether / ethyl acetate = 100 / 1) to obtain triphenylvinylsilane (VII-1, 64.4 mg, yield 91%). 1 H NMR(400MHz,Chloroform-d)δ7.66(dd,J=7.8,1.5Hz,6H),7.54-7.43(m,9H),6.82( dd,J=20.2,14.6Hz,1H), 6.43(dd,J=14.6,3.6Hz,1H), 5.93(dd,J=20.2,3.6Hz,1H). 13 C NMR (101MHz, Chloroform-d) δ136.95,136.07,134.29,133.97,129.68,127.99.

[0261] Examples 80-87

[0262] This embodiment provides a comparison of a series of triphenylsilanes (I-3-1) obtained by hydrosilylation with acetylene to obtain triphenylvinylsilane (VII-1) under the same operating method, solvent, and temperature as in Example 79, using different additives and their amounts, and reaction times. The specific results are shown in Table 9:

[0263] Table 9 Examples 80-87

[0264] Example Time / hour additive VII-1 Yield % 80 24 No additives 0 81 24 <![CDATA[Ph2SiH2(20mol%)]]> 77 82 24 <![CDATA[PhSiH3(20mol%)]]> 81 83 24 <![CDATA[NaBHEt3(20mol%)]]> 85 84 48 <![CDATA[PhSiH3(15mol%)]]> 83 85 48 <![CDATA[PhSiH3(10mol%)]]> 68 86 48 <![CDATA[PhSiH3(6mol%)]]> 28 87 48 Zn powder (100 mol%) 20

[0265] Examples 88-102

[0266] This embodiment provides a method for preparing a series of monovinylsilanes by hydrosilylation of the tertiary silanes described in formula (I-3) and acetylene. The feeding and operation are the same as in Example 79, and the raw materials, products and corresponding yields are shown in Table 10:

[0267] Table 10 Examples 88-102

[0268]

[0269]

[0270]

[0271]

[0272]

[0273] Example 103

[0274] This embodiment provides a scaled-up preparation method for diphenylvinylsilane (II-1).

[0275] The procedure was as follows: Co(OAc)₂ (0.12 mmol, 2 mol%) and ligand Xantphos (1.18 mmol, 3 mol%) were added sequentially to the reaction flask. The flask was then sealed with a rubber stopper, fitted with an acetylene balloon, and evacuated five times using a vacuum pump. 24 mL of water was added, and the mixture was stirred at room temperature for 10 minutes. Diphenylsilane (I-2-1, 6 mmol) was then added, and the reaction was carried out at 45 °C for 12 hours. After the reaction was complete, the reaction solution was extracted with ethyl acetate. The extract was concentrated under vacuum and then purified by column chromatography (eluent: petroleum ether) to obtain diphenylvinylsilane (II-1, 1.29 g, yield 96%).

[0276] Example 104

[0277] This embodiment provides a scaled-up preparation method for diphenylvinylsilane (II-1).

[0278] The procedure was as follows: Co(OAc)₂ (1.0 mmol, 2 mol%) and ligand Xantphos (1.5 mmol, 3 mol%) were added sequentially to the reaction flask. The flask was then sealed with a rubber stopper, fitted with an acetylene balloon, and evacuated five times using a vacuum pump. 200 mL of water was added, and the mixture was stirred at room temperature for 10 minutes. Diphenylsilane (I-2-1, 50 mmol) was then added, and the reaction was carried out at 45 °C for 12 hours. After the reaction was complete, the reaction solution was extracted with ethyl acetate. The extract was concentrated under vacuum and then purified by column chromatography (eluent: petroleum ether) to obtain diphenylvinylsilane (II-1, 10.01 g, yield 82%).

[0279] Example 105

[0280] This embodiment provides a scaled-up preparation method for diphenyldivinylsilane (III-1).

[0281] The procedure is as follows: Add Co(OAc)₂ (2.5 mmol, 5 mol%) and ligand sequentially to a reaction flask equipped with a reflux condenser. 6-Me bpy (3.0 mmol, 6 mol%) was then capped and fitted with an acetylene balloon. The acetylene gas was purged five times using a vacuum pump. 100 mL of 1,4-dioxane was added, and the mixture was stirred at room temperature for 10 minutes. Diphenylsilane (I-2-1, 50 mmol) was then added, and the mixture was reacted at 45 °C for 2 hours, followed by a further reaction at 100 °C for 10 hours. After the reaction, the metal catalyst was filtered off, and the residual liquid in the reaction flask was washed with ethyl acetate. The filtrate was concentrated under vacuum and then purified by column chromatography (eluent: petroleum ether) to give diphenyldivinylsilane (III-1, 6.56 g, 65% yield).

[0282] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane, characterized in that, Includes the following steps: Vinylsilane is prepared by heating a reaction using hydrosilane and acetylene as raw materials, in the presence of solvent, cobalt catalyst and ligand, or in the presence of solvent, cobalt catalyst, ligand and additive. Where m is an integer from 1 to 3, n is 4-m; y is an integer from 1 to m, and x is my; R is selected independently from each of the following. C1-C18 alkyl, substituted C1-C6 alkyl, benzofuranyl, benzothiophenyl, thiophenyl, benzyl, or C1-C6 alkoxy; wherein R 9 R 10 Each of the substituents is independently selected from one or more substituents on the benzene ring and the naphthalene ring, and each substituent is independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, trifluoromethyl, trifluoromethoxy, methylenedioxy, morpholino or phenyl; the substituent of the substituted C1-C6 alkyl is a benzene ring.

2. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, The cobalt catalyst is selected from at least one of Co(OAc)2, Co(acac)2, Co(acac)3, Co(OTf)2, CoBr2, CoCl2, CoI2, Co(BF4)2, Co(PPh3)2Cl2, Co(dppe)Cl2, Co(PPh3)3Cl and Co2(CO)8; The ligand is selected from at least one of bisphosphine ligands and bipyridine ligands; The molar ratio of the hydrosilane, cobalt catalyst, and ligand is 1:(0.01~0.5):(0.015~0.55); The pressure of the acetylene is 1–10 atm; The solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, toluene, N,N-dimethylformamide, acetone, ethyl acetate, n-hexane, toluene, and water; The concentration of the hydrosilane in the solvent is 0.25M to 1.0M; The reaction is followed by post-processing, which includes the following steps: solvent removal, extraction, and column chromatography. The additives are selected from NaBHEt3, Zn powder, Fe powder, Mn powder, and R. 12 2SiH2 and R 12 At least one of SiH3, wherein R 12 Each is independently selected from C6-C20 aryl and C1-C18 alkyl groups; The molar ratio of the hydrosilane to the additive is 1:(0 to 1.0).

3. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 2, characterized in that, The ligands are selected from PPh3, dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, Dpephos, Binap, phen, bpy. 6-Me bpy and 4-tBu,6-Me At least one of bpy.

4. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, The following six options are included; Technical Solution 1: Using secondary hydrogen silane as shown in formula (I-2) and acetylene as raw materials, monovinyl silane as shown in formula (II) was prepared by heating reaction under the action of solvent, cobalt catalyst and ligand I; Technical Solution Two: Using secondary hydrogen silane as shown in formula (I-2) and acetylene as raw materials, the divinylsilane as shown in formula (III) was prepared by heating reaction under the action of solvent, cobalt catalyst and ligand II. Technical Solution 3: Using primary hydrogen silane as shown in formula (I-1) and acetylene as raw materials, monovinyl silane as shown in formula (IV) was prepared by heating reaction under the action of solvent, cobalt catalyst and ligand I. Technical Solution Four: Using primary hydrogen silane (I-1) and acetylene as raw materials, a heating reaction was carried out in the presence of solvent, cobalt catalyst and ligand III to prepare divinylsilane (V). The ligand III is selected from at least one of ligand I and ligand II; Technical Solution 5: Using primary hydrogen silane as shown in formula (I-1) and acetylene as raw materials, trivinylsilane as shown in formula (VI) is prepared by heating reaction under the action of solvent, cobalt catalyst and ligand II. Technical Solution Six: Using tertiary hydrosilanes and acetylenes as raw materials, monovinylsilanes as shown in formula (VII) are prepared by heating reaction under the action of solvent, cobalt catalyst, ligand II and additives. Among them, R 3 Each independently selected C1-C18 alkyl or substituted C1-C6 alkyl; the R 7 R 8 It is one or more substituents on the benzene ring and the naphthalene ring, each substituent being independently selected from hydrogen atoms, C1-C6 alkyl groups, and C1-C6 alkoxy groups; the substituents of the substituted C1-C6 alkyl groups are benzene rings; R 1 and R 2 Each independently selected C1-C8 alkyl, benzofuranyl, benzothiophenyl, thiophenyl; the R 9 R 10 Each of the substituents is independently selected from one or more substituents on the benzene ring and the naphthalene ring, and each substituent is independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, trifluoromethyl, trifluoromethoxy, methylenedioxy, morpholino or phenyl; R 4 R 5 and R 6 Each independently selected Thiophene, benzyl, C1-C6 alkyl, and C1-C6 alkoxy; the R 11 It is one or more substituents on the benzene ring, each substituent being independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 alkoxy or trifluoromethyl; The ligand I is selected from at least one of PPh3, dppe, dppp, dppb, dpppe, dppf, dppbz, Xantphos, Dpephos and Binap; The ligand II is selected from phen, bpy, 6-Me bpy and 4-tBu,6-Me At least one of bpy.

5. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, In technical solution one, The reaction temperature is between room temperature and 120°C; the reaction time is between 12 and 24 hours. The structural formula of the monovinylsilane shown in formula (II) is as follows:

6. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, In technical solution two, The reaction temperature is 45–100°C; the reaction time is 12–24 hours. The structural formula of the divinylsilane shown in formula (III) is as follows:

7. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, In technical solution three, The reaction temperature is 45–100°C; the reaction time is 12–48 hours. The structural formula of the monovinylsilane shown in formula (IV) is as follows:

8. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, In technical solution four, The reaction temperature is 45–100°C; the reaction time is 12–48 hours. If R 3 Selected from The R 7 R 8 It consists of one or more substituents on the benzene ring and the naphthalene ring, each substituent being independently selected from hydrogen atoms, C1-C6 alkyl groups, and C1-C6 alkoxy groups; ligand III is selected from ligand I. If R 3 The ligand is selected from C1-C18 alkyl groups or substituted C1-C6 alkyl groups, wherein the substituent of the substituted C1-C6 alkyl group is a benzene ring; the ligand III is selected from ligand II; The structural formula of the divinylsilane shown in formula (V) is as follows:

9. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, In technical solution five, the reaction temperature is 45–100°C; the reaction time is 12–24 hours. The structural formula of the trivinylsilane shown in formula (VI) is as follows:

10. The method for synthesizing vinylsilane by hydrosilylation of acetylene and hydrosilane according to claim 1, characterized in that, In technical solution six, the reaction temperature is 45–100°C; the reaction time is 12–72 hours. The concentration of the tertiary silane shown in formula (I-3) in the solvent is 0.25M to 0.5M; The molar ratio of the tertiary silane and additives shown in formula (I-3) is 1:(0.06~1.0); The structural formula of the monovinylsilane shown in formula (VII) is as follows:

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