Organosilane synthesis method based on chlorosilane reductive coupling reaction

Abstract

The invention provides an organosilane synthesis method based on chlorosilane reductive coupling reaction, which comprises the following steps: by taking chlorosilane as a raw material shown in a formula I as a raw material, carrying out reductive coupling reaction on the chlorosilane and aryl halide or heteroaryl halide shown in a formula IV under the action of a reducing agent and the promotion of a pyridine accelerator to generate an aryl organosilicon compound with a structural formula II; or the alkenyl organic silicon compound with the structural formula III is generated through the reduction coupling reaction with the alkenyl halide with the formula V. The method has the advantages of no need of transition metal catalysis, wide raw material source, economical and practical steps, wide substrate applicability, good compatibility of reaction functional groups and the like. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of preparation of organosilane, and in particular to a method for synthesizing organosilane based on a chlorosilane reduction coupling reaction. Background Art

[0002] The construction of aromatic carbon-silicon bonds is one of the most important chemical reactions in the field of organic chemistry. Especially in the field of organosilicon chemistry, it converts the abundant silicon resources on the earth into useful organosilicon compounds. Since silicon and carbon belong to adjacent elements in the same main group in the periodic table, and silicon has a large atomic radius and low electronegativity, organosilicon compounds have unique reactivity. Aromatic silanes have unique C(sp 2 )-Si bonds have biological activity, chemical and physical properties and are widely used in drug synthesis, material science, polymer chemistry and medicinal chemistry. Organosilicon compounds can be used as antipsychotic drugs, anticancer drugs and optoelectronic materials. Organosilicon compounds are also synthetic intermediates with important application value. Direct functionalization of aryl and alkyl silanes through various organic transformations, such as Hiyama coupling reaction and Tamao-Fleming oxidation, are basic research areas for organosilicon applications.

[0003] However, conventional synthetic routes rely heavily on the coupling of organometallic reagents with silicon-based electrophiles or with transition metal catalysts, and the use of highly reactive metal reagents impairs their efficiency and versatility in synthesis. The use of excess organic solvents and expensive metal catalysts increases safety risks and waste. Therefore, further efforts are needed to provide strategic and practical methods for the preparation of organosilanes to meet the exponentially growing demand for functional organosilanes. Summary of the invention

[0004] In view of the defects in the prior art, the purpose of the present invention is to provide a method for synthesizing organosilanes based on the reductive coupling reaction of chlorosilanes, taking chlorosilanes as raw materials, and preparing aryl or heteroaryl silanes or alkenyl silanes through coupling reactions with reaction substrates such as aryl or heteroaryl halides, alkenyl halides (including iodine, bromide and chloride).

[0005] The present invention provides a method for synthesizing an organosilicon compound based on a chlorosilane reduction coupling reaction, which specifically comprises the following steps: using a chlorosilane of formula I as a raw material, and under the action of a reducing agent and the promotion of a pyridine accelerator, a coupling reaction with an aryl or alkenyl halide is performed to generate an organosilicon compound with an aromatic structure of structural formula II or an organosilicon compound with an alkenyl structure of structural formula III.

[0006]

[0007] In the formula: R is any one of halogen, alkyl, cycloalkyl, alkenyl, alkyl containing heteroatoms and heterocyclic aromatic groups, wherein the heteroatoms are at least one of O, S and N; R 1 , R 2 are alkyl, R 3 It is an alkyl group or an alkyl group containing a heteroatom.

[0008] The present invention provides a method for synthesizing an organosilane based on a chlorosilane reduction coupling reaction. The method uses a chlorosilane of formula I as a raw material, and under the action of a reducing agent and the promotion of a pyridine accelerator, generates an aromatic organosilicon compound of structural formula II through a reduction coupling reaction with an aromatic halide or heteroaromatic halide of formula IV; or generates an alkenyl organosilicon compound of structural formula III through a reduction coupling reaction with an alkenyl halide of formula V;

[0009]

[0010] In the above formula, X is any one of Cl, Br and I, R, R 1 , R 2 , R 3 are the same or different, and R is any one of halogen, alkyl, cycloalkyl, alkenyl, alkyl containing heteroatoms, and heterocyclic aromatic groups, wherein the heteroatoms are at least one of O, S, and N; R 1 , R 2 are alkyl, R 3 It is an alkyl group or an alkyl group containing a heteroatom.

[0011] Optionally, the reducing agent is any one of Zn, Mg, Mn, In and Sm. Preferably, the reducing agent is Zn, Mg, Mn, and more preferably, the reducing agent is Zn.

[0012] Optionally, the pyridine accelerator is any one of 4-cyanopyridine, 4-(trifluoromethyl)pyridine, 4-chloropyridine, pyridine, 4-ethylpyridine, 4-tert-butylpyridine, 4-methoxypyridine, 4-pyrrolidinylpyridine and 4-dimethylaminopyridine. Preferably, the pyridine accelerator is 4-ethylpyridine, 4-tert-butylpyridine, 4-methoxypyridine, 4-pyrrolidinylpyridine and 4-dimethylaminopyridine. More preferably, the pyridine accelerator is 4-dimethylaminopyridine.

[0013] Optionally, the amount of the reducing agent added is 0.2-5 equivalents of the molar amount of the reaction substrate, preferably, the amount of the reducing agent added is 1.5-3 equivalents of the molar amount of the reaction substrate, and more preferably, the amount of the reducing agent added is 2.8 equivalents of the molar amount of the reaction substrate.

[0014] Optionally, the amount of the pyridine accelerator added is 0.2-5 equivalents of the molar amount of the reaction substrate, preferably, the amount of the pyridine accelerator added is 1.5-3 equivalents of the molar amount of the reaction substrate, and more preferably, the amount of the pyridine accelerator added is 2.8 equivalents of the molar amount of the reaction substrate.

[0015] Optionally, the amount of chlorosilane added is 1-4 equivalents, preferably 1.1-3 equivalents, based on the molar amount of the reaction substrate.

[0016] Optionally, the reduction coupling reaction temperature is 60-140°C, and the time is 1-24 hours. Preferably, the reduction coupling reaction temperature is 100-135°C, and the time is 12-24 hours. More preferably, the reduction coupling reaction temperature is 135°C, and the time is 12 hours.

[0017] Optionally, the solvent used is any one or more of acetonitrile, ethyl acetate, cyclohexane, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, benzene, fluorobenzene and trifluorotoluene. Preferably, the solvent used is any one or more of 1,4-dioxane, benzene, fluorobenzene and trifluorotoluene. More preferably, the solvent used is trifluorotoluene.

[0018] Compared with the prior art, the present invention has at least one of the following beneficial effects:

[0019] The present invention can conveniently use aryl or alkenyl halides as substrates to prepare RSiR 1 R 2 R 3 This type of organosilicon compound has the advantages of not requiring transition metal catalysis, a wide range of raw material sources, economical and practical steps, wide substrate applicability, and good compatibility of reaction functional groups. DETAILED DESCRIPTION

[0020] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0021] Example 1

[0022] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 4-bromocyclopropylbenzene (78.8 mg) and chloro(dimethyl)phenylsilane (75.1 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 63.5 mg, yield 63%).

[0023]

[0024] The product testing data are as follows:

[0025] 1 H NMR (400MHz, CDCl3) δ7.59–7.50(m,2H),7.48–7.41(m,2H),7.40–7.33(m,3H),7.13–7.05(m,2H ),1.97–1.84(m,1H),1.28(s,1H),1.04–0.93(m,2H),0.78–0.68(m,2H),0.56(d,J=7.8Hz,6H). 13 C NMR (150MHz, CDCl3) δ145.25,138.56,134.57,134.30,134.23,129.08,127.84,125.18,15.46,9.55,-2.24. 29 Si NMR(119MHz,CDCl3)δ-8.28.HRMS(ESI)calcd.for C 17 H 21 Si[M+H] + :253.1407,found:253.1412.

[0026] Example 2

[0027] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 4-bromobenzocyclobutane (73.2 mg) and chloro(dimethyl)phenylsilane (75.1 mg) were added to the reaction tube in sequence, and fluorobenzene was finally injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 58.1 mg, yield 61%).

[0028]

[0029] The product testing data are as follows:

[0030] 1 H NMR (400MHz, CDCl3) δ7.59–7.52(m,2H),7.43–7.33(m,4H),7.24(s,1H),7.08(d,J=7.3Hz,1H),3.20(s,4H),0.56(s,6H). 13 C NMR (150MHz, CDCl3) δ147.32,145.69,138.71,136.32,134.25,132.59,129.07,128.03,127.85,122.04,30.00,29.88,-2.08. 29 SiNMR(119MHz,CDCl3)δ-7.52.HRMS(EI)calcd.for C 16 H 18 Si[M] + :238.1172,found:238.1179.

[0031] Example 3

[0032] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 2,4,6-trifluorobromobenzene (84.4 mg) and chloro(dimethyl)phenylsilane (75.1 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 60.7 mg, yield 57%).

[0033]

[0034] The product testing data are as follows:

[0035] 1 H NMR (600MHz, CDCl3) δ7.58–7.53(m,2H),7.41–7.33(m,3H),6.61–6.54(m,2H),0.65(s,6H). 13C NMR (150MHz, CDCl3) δ168.29 (dd, J=18.8, 14.8Hz), 166.66 (dd, J=18.8, 14.8Hz), 165.54 (t, J=16.1Hz) ,163.88(t,J=16.2Hz),137.41,133.64,129.44,127.90,108.51–107.40(m),100.39–99.89(m),-1.01. 19 F NMR(565MHz, CDCl3)δ-93.19(s,1F),-93.20(s,1F),-106.17(s,1F). 29 Si NMR(119MHz,CDCl3)δ-9.56.HRMS(EI)calcd.forC 14 H 13 F3Si[M] + :266.0733,found:266.0740.

[0036] Example 4

[0037] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), (4-bromophenyl) 2,2-dimethylpropionate (102.8 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 74.9 mg, yield 60%).

[0038]

[0039] The product testing data are as follows:

[0040] 1 H NMR (400MHz, CDCl3) δ7.57–7.51(m,4H),7.40–7.35(m,3H),7.10–7.02(m,2H),1.38(s,9H),0.57(s,6H). 13 C NMR (100MHz, CDCl3) δ179.30,154.35,140.30,137.70,136.47,131.48,130.14,123.21,41.38,29.44,0.00. 29 Si NMR(119MHz,CDCl3)δ-7.84.HRMS(EI)calcd.for C19 H 24 O2Si[M] + :312.1540,found:312.1539.

[0041] Example 5

[0042] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), N-(4-bromophenyl)-N-methyl-2,2-dimethylpropylamine (102.8 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 24 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 63.7 mg, yield 49%).

[0043]

[0044] The product testing data are as follows:

[0045] 1 H NMR (400MHz, CDCl3) δ7.54–7.50(m,4H),7.41–7.34(m,3H),7.20–7.17(m,2H),3.20(s,3H),1.04(s,9H),0.57(s,6H). 13 C NMR (100MHz, CDCl3) δ180.53,148.33,140.60,140.01,137.43,136.48,131.66,130.39,130.27,43.65,43.18,31.87,0.00. 29 Si NMR(119MHz,CDCl3)δ-7.78.HRMS(EI)calcd.for C 20 H 27 NOSi[M] + :325.1856,found:325.1862.

[0046] Example 6

[0047] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 1-bromo-4-(3-butene-1-yloxy)benzene (90.4 mg) and chloro(dimethyl)phenylsilane (88.7 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 77.9 mg, yield 69%).

[0048]

[0049] The product testing data are as follows:

[0050] 1 H NMR (400MHz, CDCl3) δ7.62–7.57(m,2H),7.55–7.48(m,2H),7.41(dq,J=4.9,3.0,2.3Hz,3H),7.02–6.93(m,2 H),6.06–5.90(m,1H),5.30–5.13(m,2H),4.13–4.04(m,2H),2.61(tdd,J=8.4,6.8,2.3Hz,2H),0.60(s,6H). 13 C NMR (100MHz, CDCl3) δ162.02,140.87,137.81,136.60,136.31,131.16,131.13,129.94,119.18,116.37,69.08,35.78,-0.01. 29 Si NMR(119MHz,CDCl3)δ-8.40.HRMS(EI)calcd.for C 18 H 22 OSi[M] + :282.1434,found:282.1429.

[0051] Example 7

[0052] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromobenzothiophene (85.2 mg) and chloro(dimethyl)phenylsilane (75.1 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 72.9 mg, yield 68%).

[0053]

[0054] The product testing data are as follows:

[0055] 1 H NMR(600MHz, CDCl3)δ8.02(s,1H),7.90(d,J=8.0Hz,1H),7.62–7.54(m,2H),7.49(d,J=8 .1Hz,1H),7.43(d,J=5.5Hz,1H),7.41–7.36(m,3H),7.34(d,J=5.4Hz,1H),0.63(s,6H). 13 C NMR (100MHz, CDCl3) δ142.90,141.42,140.49,136.38,135.50,131.96,131.59,131.29,130.00,128.24,126.03,124.16,0.00. 29 Si NMR(119MHz,CDCl3)δ-7.20.HRMS(EI)calcd.for C 16 H 16 SSi[M] + :268.0736,found:268.0735.

[0056] Example 8

[0057] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromobenzofuran (78.8 mg) and chloro(dimethyl)phenylsilane (75.1 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 65.5 mg, yield 65%).

[0058]

[0059] The product testing data are as follows:

[0060] 1H NMR (400MHz, CDCl3) δ7.79(t,J=1.0Hz,1H),7.62(d,J=2.2Hz,1H),7.58–7.55(m,2H),7.54– 7.51(m,1H),7.47(dd,J=8.2,1.2Hz,1H),7.40–7.35(m,3H),6.79–6.74(m,1H),0.61(s,6H). 13 C NMR (100MHz, CDCl3) δ157.78,146.85,140.61,136.21,133.73,132.02,131.09,129.83,129.55,129.31,113.11,108.43,0.00. 29 Si NMR(119MHz,CDCl3)δ-7.31.HRMS(EI)calcd.for C 16 H 16 OSi[M] + :252.0964,found:252.0972.

[0061] Example 9

[0062] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 2-bromo-5-phenylthiophene (95.7 mg) and chloro(dimethyl)phenylsilane (75.1 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 91.8 mg, yield 78%).

[0063]

[0064] The product testing data are as follows:

[0065] 1 H NMR (400MHz, CDCl3) δ7.66–7.60(m,4H),7.47–7.35(m,6H),7.32–7.24(m,2H),0.65(s,6H). 13 C NMR (100MHz, CDCl3) δ151.74,138.98,138.95,137.69,135.62,135.26,130.76,130.17,129.24,128.86,127.35,125.80,0.00. 29Si NMR(119MHz,CDCl3)δ-11.45.HRMS(ESI)calcd.for C 18 H 19 SSi[M+H] + :295.0971,found:295.0964.

[0066] Example 10

[0067] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromothiophene-2-carbonitrile (75.2 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (brown oily liquid, 90.4 mg, yield 93%).

[0068]

[0069] The product testing data are as follows:

[0070] 1 H NMR (600MHz, CDCl3) δ7.65(d,J=3.6Hz,1H),7.56–7.49(m,2H),7.46–7.37(m,3H),7.20(d,J=3.6Hz,1H),0.64(s,6H). 13 C NMR (150MHz, CDCl3) δ148.67,138.08,135.73,135.02,133.90,130.13,128.25,114.72,114.34,-1.59. 29 Si NMR(119MHz,CDCl3)δ-10.34.HRMS(ESI)calcd.for C 13 H 14 NSSi[M+H] + :244.0611,found:244.0612.

[0071] Embodiment 11

[0072] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromothiophene-2-carboxylic acid ethyl ester (94.0 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 96.3 mg, yield 83%).

[0073]

[0074] The product testing data are as follows:

[0075] 1 H NMR(400MHz, CDCl3)δ7.75(d,J=3.6Hz,1H),7.50–7.45(m,2H),7.34–7.27(m,3H) ,7.14(d,J=3.5Hz,1H),4.26(q,J=7.1Hz,2H),1.29(t,J=7.1Hz,3H),0.54(s,6H). 13 CNMR(100MHz, CDCl3)δ163.71,148.53,140.85,138.20,136.93,135.69,135.47,131.30,129.62,62.70,15.95,0.00. 29 Si NMR(119MHz,CDCl3)δ-10.85.HRMS(ESI)calcd.forC 15 H 19 O2SSi[M+H] + :291.0870,found:291.0862.

[0076] Example 12

[0077] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg) were added to the reaction tube in sequence, and then 1-(5-bromo-2-butyl)-2-methyl-1-propanone (92.8 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube, and finally trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 57.6 mg, yield 50%).

[0078]

[0079] The product testing data are as follows:

[0080] 1 H NMR(400MHz, CDCl3)δ7.74(d,J=3.6Hz,1H),7.59–7.52(m,2H),7.42–7.35(m,3H) ),7.24(d,J=3.6Hz,1H),3.41–3.32(m,1H),1.23(d,J=6.9Hz,6H),0.62(s,6H). 13 C NMR (100MHz, CDCl3) δ198.89,150.09,149.75,138.14,137.30,135.51,133.90,131.36,129.67,39.26,21.06,0.00. 29 Si NMR(119MHz,CDCl3)δ-10.69.HRMS(ESI)calcd.forC 16 H 21 OSSi[M+H] + :289.1077,found:289.1078.

[0081] Embodiment 13

[0082] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg) were added to the reaction tube in sequence, and then 5-bromo-N, N-diethyl-2-thiophenecarboxamide (98.0 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube, and finally trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (brown oily liquid, 65.1 mg, yield 54%).

[0083]

[0084] The product testing data are as follows:

[0085] 1 H NMR (400MHz, CDCl3) δ7.60–7.51(m,2H),7.44–7.32(m,3H),7.04(d,J=3.4Hz ,1H),6.69(d,J=3.4Hz,1H),3.51(b,4H),1.20(t,J=7.1Hz,6H),0.56(s,6H). 13C NMR (100MHz, CDCl3) δ160.44,159.79,153.36,136.08,133.89,129.65,127.97,122.08,116.11,42.91,41.37,14.85,12.80,-3.07,-3.35. 29 Si NMR(119MHz,CDCl3)δ-15.08.HRMS(ESI)calcd.for C 17 H 24 NO2Si[M+H] + :302.1571,found:302.1569.

[0086] Embodiment 14

[0087] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 2-(4-bromophenyl)pyridine (93.6 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 64.8 mg, yield 56%).

[0088]

[0089] The product testing data are as follows:

[0090] 1 H NMR (400MHz, CDCl3) δ8.72–8.69(m,1H),8.01–7.94(m,2H),7.78–7.70(m,2H),7.68–7.60(m ,2H),7.58–7.51(m,2H),7.40–7.33(m,3H),7.23(ddd,J=6.7,4.8,2.1Hz,1H),0.59(s,6H). 13 C NMR (100MHz, CDCl3) δ159.80,152.11,142.40,141.50,140.48,139.11,137.06,136.58,131.54,130.22,128.59,124.59,123.02,0.00. 29 Si NMR(119MHz,CDCl3)δ-7.87.HRMS(EI)calcd.for C 19 H 19 NSi[M]+ :289.1281,found:289.1282.

[0091] Embodiment 15

[0092] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 6-bromo-2-methylquinoline (88.8 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product (white solid, 46.6 mg, yield 42%) as shown in the following structural formula.

[0093]

[0094] The product testing data are as follows:

[0095] 1 H NMR (400MHz, CDCl3) δ8.05–7.97 (m, 2H), 7.93 (s, 1H), 7.80 (dd, J = 8.4, 1.5Hz, 1H), 7. 59–7.52(m,2H),7.42–7.33(m,3H),7.28(d,J=8.5Hz,1H),2.75(s,3H),0.64(s,6H). 13 C NMR (100MHz, CDCl3) δ161.85,150.46,140.15,138.77,138.30,136.81,136.59,136.55,131.63,130.27,129.97,128.35,124.44,27.69,0.00. 29 Si NMR(119MHz,CDCl3)δ-7.57.HRMS(EI)calcd.for C 18 H 29 NSi[M] + :277.1281,found:277.1285.

[0096] Example 16

[0097] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 4-bromo-2,6-dimethylpyridine (74.4 mg) and chloro(dimethyl)phenylsilane (102.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 53.1 mg, yield 55%).

[0098]

[0099] The product testing data are as follows:

[0100] 1 H NMR (400MHz, CDCl3) δ7.54–7.45(m,2H),7.38(dtd,J=7.0,5.2,2.2Hz,3H),7.05(s,2H),2.50(s,6H),0.55(s,6H). 13 C NMR (100MHz, CDCl3) δ156.47,148.67,136.71,134.12,129.52,128.02,125.30,24.40,-2.94. 29 Si NMR(119MHz,CDCl3)δ-7.93.HRMS(ESI)calcd.for C 15 H 20 NSi[M+H] + :242.1360,found:242.1351.

[0101] Embodiment 17

[0102] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromothiophene-2-carbonitrile (75.2 mg) and triethylsilyl chloride (78.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 75.9 mg, yield 85%).

[0103]

[0104] The product testing data are as follows:

[0105] 1H NMR (400MHz, CDCl3) δ7.67(dd,J=3.5,1.2Hz,1H),7.20(dd,J=3.5,1.2Hz,1H),0.99(t,J=7.8Hz,9H),0.86–0.81(m,6H). 13 C NMR (100MHz, CDCl3) δ147.31,137.86,134.39,114.44,114.14,7.16,4.15. 29 Si NMR(119MHz,CDCl3)δ1.73.HRMS(ESI)calcd.forC 11 H 18 NSSi[M+H] + :224.0924,found:224.0926.

[0106] Embodiment 18

[0107] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromothiophene-2-carbonitrile (75.2 mg) and tert-butyldimethylsilyl chloride (78.4 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135° C. for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 45.5 mg, yield 51%).

[0108]

[0109] The product testing data are as follows:

[0110] 1 H NMR (400MHz, CDCl3) δ7.67 (d, J = 3.6 Hz, 1H), 7.21 (d, J = 3.6 Hz, 1H), 0.92 (s, 9H), 0.33 (s, 6H). 13 C NMR (100MHz, CDCl3) δ147.73,137.75,134.79,114.37,114.28,26.12,16.79,-5.08. 29 Si NMR(119MHz,CDCl3)δ2.44.HRMS(ESI)calcd.for C 11 H 18 NSSi[M+H] + :224.0924,found:224.0926.

[0111] Embodiment 19

[0112] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromothiophene-2-carbonitrile (75.2 mg) and triisopropylsilyl chloride (100.2 mg) were added to the reaction tube in sequence, and trifluorotoluene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (white solid, 35.0 mg, yield 33%).

[0113]

[0114] The product testing data are as follows:

[0115] 1 H NMR (600MHz, CDCl3) δ7.69 (d, J = 3.5Hz, 1H), 7.23 (d, J = 3.6Hz, 1H), 1.35 (p, J = 7.4Hz, 3H), 1.10 (d, J = 7.5Hz, 18H). 13 C NMR (100MHz, CDCl3) δ144.90,137.65,135.26,114.43,114.18,18.38,11.68. 29 Si NMR(119MHz,CDCl3)δ2.71.HRMS(ESI)calcd.forC 14 H 24 NSSi[M+H] + :266.1393,found:266.1396.

[0116] Embodiment 20

[0117] Zinc powder (71.6 mg), 4-dimethylaminopyridine (136.7 mg), 5-bromothiophene-2-carbonitrile (75.2 mg) and 3-methylacrylate (chlorodimethylsilyl)propyl ester (114.8 mg) were added to the reaction tube in sequence, and benzene was injected into the reaction tube. After reacting at 135°C for 12 hours, the mixture was cooled to room temperature, filtered through a sand core funnel, concentrated, and subjected to silica gel column chromatography (200-300 mesh silica gel) to obtain the target product shown in the following structural formula (colorless oily liquid, 37.5 mg, yield 32%).

[0118]

[0119] The product testing data are as follows:

[0120] 1H NMR (400MHz, CDCl3) δ7.66(d,J=3.6Hz,1H),7.20(d,J=3.6Hz,1H),6.08(d,J=0.8Hz,1H),5.55(t,J=1.6 Hz,1H),4.10(t,J=6.8Hz,2H),1.93(t,J=1.3Hz,3H),1.79–1.46(m,2H),0.89–0.72(m,2H),0.36(s,6H). 13 C NMR (100MHz, CDCl3) δ169.67,150.94,140.29,138.64,136.44,127.67,116.65,116.52,68.86,25.23,20.59,14.50,0.00. 29 SiNMR(119MHz,CDCl3)δ-3.23.HRMS(ESI)calcd.for C 14 H 19 NNaO2SSi[M+Na] + :316.0798,found:316.0801.

[0121] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various modifications or variations within the scope of the claims, which does not affect the essence of the present invention. The above preferred features can be used in any combination without conflicting with each other.

Claims

1. A method for synthesizing an organosilane based on a chlorosilane reduction coupling reaction, characterized in that: The method uses chlorosilane of formula I as a raw material, and generates an aromatic organosilicon compound of structural formula II through a reduction coupling reaction with an aromatic halide or heteroaromatic halide of formula IV under the action of a reducing agent and the promotion of a pyridine accelerator; or generates an alkenyl organosilicon compound of structural formula III through a reduction coupling reaction with an alkenyl halide of formula V; In the above formula, X is any one of Cl, Br and I, R, R 1 , R 2 , R 3 are the same or different, and R is any one of halogen, alkyl, cycloalkyl, alkenyl, or alkyl containing heteroatoms and heterocyclic aromatic groups, wherein the heteroatoms are at least one of O, S and N; R 1 , R 2 are alkyl, R 3 It is an alkyl group or an alkyl group containing a heteroatom.

2. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 1, characterized in that: The reducing agent is any one of Zn, Mg, Mn, In and Sm.

3. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 2, characterized in that: The reducing agent is Zn.

4. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 1, characterized in that: The pyridine accelerator is any one of 4-cyanopyridine, 4-(trifluoromethyl)pyridine, 4-chloropyridine, pyridine, 4-ethylpyridine, 4-tert-butylpyridine, 4-methoxypyridine, 4-pyrrolidinylpyridine and 4-dimethylaminopyridine.

5. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 4, characterized in that: The pyridine accelerator is 4-dimethylaminopyridine.

6. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 1, characterized in that: The amount of the reducing agent added is 0.2-5 equivalents of the molar amount of the reaction substrate.

7. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 1, characterized in that: The amount of the pyridine accelerator added is 0.2-5 equivalents of the molar amount of the reaction substrate.

8. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 1, characterized in that: The amount of the chlorosilane added is 1-4 equivalents of the molar amount of the reaction substrate.

9. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 1, characterized in that: The temperature of the reduction coupling reaction is 60-140° C. and the time is 1-24 hours.

10. The method for synthesizing organosilane based on chlorosilane reduction coupling reaction according to claim 1, characterized in that: The solvent used is any one or more of acetonitrile, ethyl acetate, cyclohexane, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, benzene, fluorobenzene and trifluorotoluene.

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