A method for preparing 1,3-dithiane substituted diene derivatives

Abstract

The present invention belongs to the field of organic chemistry, and provides a method for preparing a conjugated diene compound. That is, using vinyl-1,3-dithiane derivatives and alkyne compounds as raw materials, under the action of iron compounds, 1,3-sulfur migration occurs twice to obtain a conjugated diene compound. The method provided by the present invention uses cheap iron compounds, avoids the use of precious metal catalysts, and has mild reaction conditions, simple operation, wide substrate applicability, does not require anhydrous and oxygen-free operation, and has strong practicality and prospects for industrial application. The method provided by the present invention can be used for the synthesis and late modification of natural products, drug molecules and functional material molecules.

Description

Technical Field

[0001] The invention belongs to the field of organic chemistry, and specifically relates to a method for preparing a 1,3-dithiane substituted diene derivative compound. Background Art

[0002] 1,3-Diene derivatives not only exist in many natural active products and bioactive compounds, but also play an important role in the field of organic synthesis (Advanced Synthesis & Catalysis 2020, 362, 5532-5575.). 1,3-Diene derivatives have been widely used in various chemical materials due to their light weight, temperature resistance, durability and low synthesis cost (Chem. Sci. 2022, 13, 9515.). In addition, due to the special nature of their functional groups, 1,3-Diene derivatives can be easily synthesized into other compound molecules. For example, there are examples of using 1,3-Diene derivatives as substrates to synthesize polysubstituted pyridine compounds (Chemistry 2022, 28, e202201328.). So far, the research on 1,3-Diene derivatives is relatively extensive, and there are many methods for synthesizing 1,3-Diene derivatives. As early as 1979, Suzuki's group discovered that palladium can catalyze the cross-coupling of boronic acid derivatives and vinyl bromide in an alkaline environment to generate 1,3-diene derivatives (Tetrahedron Lett 1979, 36, 3437–3440.). In 2004, Xie's group discovered the dimerization of two molecules of terminal alkynes mediated by metal palladium and copper, and synthesized 1,3-diene derivatives by a regioselective and stereoselective dimerization synthesis method (Journal of organic chemistry 2004, 69, 8125-8127.). In 2018, Qin Huali's group established a palladium-catalyzed, SO2F2-mediated cross-coupling reaction between alcohol and olefin derivatives. This reaction is to construct 1,3-diene derivatives by removing a molecule of water (Org. Chem. Front. 2019, 6, 796). In 2022, Zhu Shoufei's research group reported the generation of 1,3-diene derivatives by terminal alkynes and vinyl zinc under the catalysis of metallic iron (J.Am.Chem.Soc.2022,144,515-526). However, most of the previously reported methods have obvious limitations, such as the activation of the reaction substrate; the use of some relatively expensive precious metals such as ruthenium, rhodium and palladium as catalysts; and the harsh reaction conditions. Therefore, it is extremely necessary to develop a low-cost, mild and easy-to-operate method to synthesize 1,3-diene derivatives and their derivatives. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing a 1,3-dithiane substituted diene derivative compound, that is, adding a vinyl-1,3-dithiane derivative, an alkyne compound, a suitable solvent and a Lewis acid in a reactor in sequence, and reacting at a suitable temperature to obtain a class of 1,3-dithiane substituted diene derivative compounds. The method does not require precious metal catalysis, does not require anhydrous and oxygen-free operation, has mild conditions, wide substrate applicability, and high stereoselectivity.

[0004] The present invention adopts the following technical scheme: under the action of Lewis acid, vinyl-1,3-dithiane derivatives and alkyne compounds are dissolved in an organic solvent, stirred at a specific temperature for a period of time, and separated and purified after the reaction is complete to obtain 1,3-dithiane substituted diene derivative compounds. The chemical reaction equation of the technical scheme is as follows:

[0005]

[0006] In the above technical solution, the Lewis acid is one or more of ferrous chloride tetrahydrate, ferric chloride hexahydrate, anhydrous ferric chloride, and anhydrous ferric bromide.

[0007] In the above technical solution, the organic solvent is one of dichloromethane, chloroform and 1,2-dichloroethane.

[0008] In the above technical solution, the molar ratio of the Lewis acid, the vinyl-1,3-dithiane derivative, and the alkyne compound is 0.5-1.5:1.0:2.0.

[0009] In the above technical scheme, the specific reaction steps include: adding vinyl-1,3-dithiane derivatives, alkyne compounds, suitable solvents and Lewis acids to a reaction flask in sequence, stirring the reaction at 0-60°C for 1-6 hours, monitoring the reaction by thin layer chromatography, and after the vinyl-1,3-dithiane derivatives are completely consumed, adding water to the reaction system, and extracting three times with dichloromethane (15 ml), combining the organic phases, washing the organic phases three times with saturated brine (15 ml), drying over anhydrous sodium sulfate, filtering, removing volatiles under vacuum, and obtaining the product by column chromatography. DETAILED DESCRIPTION

[0010] The following examples can help those skilled in the art to more fully understand the present invention, but they do not limit the present invention in any way. The raw materials used in the present invention are all known compounds, which can be purchased from the market or synthesized using methods known in the art.

[0011] Example 1: Preparation of 4-((1Z,3E)-1-chloro-4-(2-(4-methoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0012] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), ((4-methoxyphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0013] The structure and NMR data of the product 4-((1Z,3E)-1-chloro-4-(2-(4-methoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 1 are as follows:

[0014]

[0015] 1 H NMR(600MHz,Chloroform-d)δ8.02–7.97(m,2H),7.71–7.63(m,4H),7.02–6.9 3(m,2H),6.89–6.84(m,2H),6.23(d,J=14.1Hz,1H),3.89(s,3H),3.77(s,3H). 13 C NMR (151MHz, Chloroform-d) δ166.6,159.4,141.7,141.2,133.0,132.6,130.2,129.8,129.7,126.5,126.3,114.0,58.2,55.4,52.3,28.9,24.5.

[0016] Example 2: Preparation of methyl4-((1Z,3E)-4-(2-(4-butylphenyl)-1,3-dithian-2-yl)-1-chlorobuta-1,3-dien-1-yl)benzoate:

[0017] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), ((4-butylphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0018] The structure and NMR data of the product methyl4-((1Z,3E)-4-(2-(4-butylphenyl)-1,3-dithian-2-yl)-1-chlorobuta-1,3-dien-1-yl)benzoate obtained in Example 2 are as follows:

[0019]

[0020] 1 H NMR(400MHz,Chloroform-d)δ8.03(d,J=8.4Hz,2H),7.73(d,J=8.4Hz,2H),7. 66(d,J=8.3Hz,2H),7.18(d,J=8.3Hz,2H),7.06–6.95(m,2H),6.33–6.22(m,1H ),3.93(s,3H),3.05–2.93(m,2H),2.83–2.72(m,2H),2.61(t,J=7.7Hz,2H),2 .15–1.90(m,2H),1.63–1.54(m,2H),1.41–1.29(m,2H),0.92(t,J=7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ166.6,143.2,141.8,141.2,138.3,132.7,130.3,129. 8,129.7,128.8,128.2,126.6,126.3,58.6,52.3,35.4,33.5,28.8,24.6,22.5,14.1.

[0021] Example 3: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-(4-propylphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0022] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), trimethyl((4-propylphenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0023] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-(4-propylphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 3 are as follows:

[0024]

[0025] 1 H NMR(400MHz,Chloroform-d)δ8.03(d,J=8.6Hz,2H),7.72(d,J=8.6Hz,2H),7.66(d,J=8.4Hz,2H),7.18(d,J=8.4Hz,2H),7.05–6.96(m,2H),6.33 –6.21(m,1H),3.92(s,3H),3.04–2.93(m,2H),2.84–2.72(m,2H),2.61–2 .56(m,3H),2.13–1.90(m,2H),1.69–1.58(m,2H),0.94(t,J=7.3Hz,3H). 13C NMR(101MHz,Chloroform-d)δ166.6,143.0,141.8,141.2,138.3,132.6,130.2,12 9.8,129.7,128.8,128.2,126.6,126.3,58.5,52.3,37.7,28.8,24.6,24.5,13.9.

[0026] Example 4: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-(p-tolyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0027] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), trimethyl(p-tolylethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0028] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-(p-tolyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 4 are as follows:

[0029]

[0030] 1 H NMR(400MHz,Chloroform-d)δ8.03(d,J=8.7Hz,2H),7.72(d,J=8.7Hz,2H),7.69–7.62(m,2H),7.17(d,J=8.1Hz,2H),7. 06–6.95(m,2H),6.33–6.20(m,1H),3.92(s,3H),3.05–2.93(m,2H),2.84–2.71(m,2H),2.34(s,3H),2.12–1.88(m,2H). 13C NMR(101MHz,Chloroform-d)δ166.6,141.7,141.2,138.2,138.1,132.6,130 .2,129.8,129.7,129.4,128.2,126.6,126.3,58.5,52.3,28.8,24.6,21.2.

[0031] Example 5: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-phenyl-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0032] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), trimethyl(phenylethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0033] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-phenyl-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 5 are as follows:

[0034]

[0035] 1 H NMR(400MHz,Chloroform-d)δ8.03(d,J=8.8Hz,2H),7.79(d,J=8.2Hz,2H),7.72(d,J=8.8Hz,2H),7.42–7.35(m,2H),7.33–7 .28(m,1H),7.05–6.93(m,2H),6.28(d,J=14.3Hz,1H),3.93(s,3H),3.06–2.92(m,2H),2.85–2.72(m,2H),2.13–1.91(m,2H). 13CNMR(101MHz,Chloroform-d)δ166.6,141.7,141.1,141.0,132.8,130.3,129.9,128.8,128.5,128.3,126.5,126.3,58.8,52.4,28.8,24.6.

[0036] Example 6: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-(4-fluorophenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0037] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), ((4-fluorophenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0038] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-(4-fluorophenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 6 are as follows:

[0039]

[0040] 1H NMR(400MHz,Chloroform-d)δ7.71–7.62(m,2H),7.47–7.41(m,2H),7.24–7.18(m,2H),7.09–7.02(m,2H),6.87–6.79(m,4H),6.64(dd,J=11.0,0.7Hz ,1H),6.32(dd,J=15.2,11.0Hz,1H),6.02(dd,J=15.0,0.7Hz,1H),3.84(s, 3H),3.80(s,3H),2.88–2.78(m,2H),2.74–2.63(m,2H),2.05–1.87(m,2H). 13 C NMR(101MHz,Chloroform-d)δ159.5,159.2,144.0,141.0,135.4,135.1,133.2,131 .8,131.7,131.6,130.7,129.2,124.5,121.9,113.7,113.5,58.9,55.4,28.7,24.5.

[0041] Example 7: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-(4-chlorophenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0042] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), ((4-chlorophenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0043] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-(4-chlorophenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 7 are as follows:

[0044]

[0045] 1 H NMR(400MHz,Chloroform-d)δ8.03(d,J=8.6Hz,2H),7.77–7.69(m,4H),7.35(d,J=8.7Hz,2H),7.03–6.8 8(m,2H),6.24(d,J=14.2Hz,1H),3.93(s,3H),3.01–2.90(m,2H),2.83–2.70(m,2H),2.15–1.90(m,2H). 13 C NMR(101MHz,Chloroform-d)δ166.6,141.7,140.4,139.8,134.2,133.3,130.4 ,130.1,129.9,128.9,126.4,126.3,77.5,77.2,76.8,58.3,52.4,28.7,24.4.

[0046] Example 8: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-(4-(methoxycarbonyl)phenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0047] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), methyl4-((trimethylsilyl)ethynyl)benzoate (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0048] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-(4-(methoxycarbonyl)phenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 8 are as follows:

[0049]

[0050] 1 H NMR(400MHz,Chloroform-d)δ8.08–8.01(m,4H),7.90(d,J=8.6Hz,2H),7.72(d,J=8.3Hz,2H),7.02–6.8 6(m,2H),6.26(d,J=14.6Hz,1H),3.93(s,6H),3.02–2.92(m,2H),2.82–2.73(m,2H),2.13–1.93(m,2H). 13 C NMR(101MHz,Chloroform-d)δ166.8,166.6,146.2,141.6,140.1,133.4,130.4, 130.2,130.0,130.0,129.9,128.8,126.4,126.3,58.7,52.4,52.3,28.7,24.4.

[0051] Example 9: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-(m-tolyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0052] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), trimethyl(m-tolylethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0053] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-(m-tolyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 9 are as follows:

[0054]

[0055] 1H NMR(400MHz,Chloroform-d)δ8.04(d,J=8.8Hz,2H),7.73(d,J=8.8Hz,2H),7.61–7.54(m,2H),7.29–7.24(m,1H),7.12(d,J=7.0H z,1H),7.08–6.97(m,2H),6.31–6.21(m,1H),3.93(s,3H),3.09–2.94(m,2H),2.85–2.72(m,2H),2.38(s,3H),2.15–1.89(m,2H). 13 C NMR(101MHz,Chloroform-d)δ166.7,141.8,141.1,141.0,138.5,132.7,130.3,129 .9,129.8,129.2,128.8,128.6,126.6,126.3,125.4,58.7,52.4,28.8,24.6,21.7.

[0056] Example 10: Preparation of compound 2-((1E,3Z)-4-chloro-4-(4-nitrophenyl)buta-1,3-dien-1-yl)-2-(4-propylphenyl)-1,3-dithiane:

[0057] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(4-nitrophenyl)vinyl)-1,3-dithiane (0.1 mmol), trimethyl((4-propylphenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0058] The structure and NMR data of the product 2-((1E,3Z)-4-chloro-4-(4-nitrophenyl)buta-1,3-dien-1-yl)-2-(4-propylphenyl)-1,3-dithiane obtained in Example 10 are as follows:

[0059]

[0060] 1 H NMR(400MHz,Chloroform-d)δ8.23(d,J=9.0Hz,2H),7.81(d,J=9.0Hz,2H),7.66(d,J=8.2Hz,2H),7.19(d,J=8.1Hz,2H),7.10–6.93(m,2H),6 .34(d,J=14.6Hz,1H),3.04–2.93(m,2H),2.84–2.73(m,2H),2.65–2.5 3(m,2H),2.15–1.92(m,2H),1.73–1.59(m,2H),0.94(t,J=7.3Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ147.6,143.5,143.0,142.6,138.1,131.2,129.2,128.8,128.2,128.1,127.0,123.8,58.5,37.7,28.8,24.5,24.4,13.9.

[0061] Example 11: Preparation of the compound 2-(4-butylphenyl)-2-((1E,3Z)-4-chloro-4-(4-(trifluoromethyl)phenyl)buta-1,3-dien-1-yl)-1,3-dithiane:

[0062] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(4-(trifluoromethyl)phenyl)vinyl)-1,3-dithiane (0.1 mmol), ((4-butylphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0063] The structure and NMR data of the product 2-(4-butylphenyl)-2-((1E,3Z)-4-chloro-4-(4-(trifluoromethyl)phenyl)buta-1,3-dien-1-yl)-1,3-dithiane obtained in Example 11 are as follows:

[0064]

[0065] 1 H NMR(600MHz,Chloroform-d)δ7.76(d,J=8.2Hz,2H),7.67(d,J=8.4Hz,2H),7.6 3(d,J=8.3Hz,2H),7.19(d,J=8.4Hz,2H),7.02–6.95(m,2H),6.33–6.22(m,1H) ,3.03–2.96(m,2H),2.81–2.76(m,2H),2.63–2.58(m,2H),2.12–2.05(m,1H),2 .01–1.93(m,1H),1.63–1.56(m,2H),1.38–1.33(m,2H),0.92(t,J=7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ143.2,141.3,141.1,138.3,132.1,130.7(q,J=32.6Hz),129.5,128.8,12 8.2,126.7,126.6,125.57(q,J=3.8Hz),124.1(d,J=272.3Hz),58.6,35.4,33.6,28.8,24.6,22.5,14.1.

[0066] Example 12: Preparation of compound (3aR,4S,6S,7aR)-2-(4-((1Z,3E)-1-chloro-4-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)phenyl)-5,5,7a-trimethylhexahydro-4,6-methanobenzo[d][1,3,2]dioxaborole:

[0067] In a 25 ml round-bottom flask, (3aR,4S,6S,7aR)-2-(4-((Z)-1-chloro-2-(1,3-dithian-2-yl)vinyl)phenyl)-5,5,7a-trimethy lhexahydro-4,6-methanobenzo[d][1,3,2]dioxaborole (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0068] The structure and NMR data of the product (3aR,4S,6S,7aR)-2-(4-((1Z,3E)-1-chloro-4-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)phenyl)-5,5,7a-trimethylhexahydro-4,6-methanobenzo[d][1,3,2]dioxaborole obtained in Example 12 are as follows:

[0069]

[0070] 1 H NMR(600MHz,Chloroform-d)δ7.82(d,J=8.3Hz,2H),7.67(d,J=8.4Hz,2H),7.07(s,2H),6.96( s,2H),6.20(d,J=14.1Hz,1H),4.46(dd,J=8.8,1.9Hz,1H),3.88(s,6H),3.86(s,3H),3.03–2.9 6(m,2H),2.84–2.77(m,2H),2.46–2.39(m,1H),2.27–2.21(m,1H),2.16(t,J=5.5Hz,1H),2.10– 2.04(m,1H),2.01–1.93(m,3H),1.49(s,3H),1.32(s,3H),1.20(d,J=10.9Hz,1H),0.89(s,3H). 13CNMR(151MHz,Chloroform-d)δ153.2,139.9,139.6,137.9,136.8,135.0,134.2,130.1,125.7,125 .1,105.9,86.6,78.5,60.9,59.1,56.4,51.5,39.7,38.3,35.7,28.9,28.8,27.2,26.6,24.5,24.2.

[0071] Example 13: Preparation of compound 2-((1E,3Z)-4-chloro-4-(4-(trifluoromethoxy)phenyl)buta-1,3-dien-1-yl)-2-(4-methoxyphenyl)-1,3-dithiane:

[0072] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(4-(trifluoromethoxy)phenyl)vinyl)-1,3-dithiane (0.1 mmol), ((4-methoxyphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0073] The structure and NMR data of the product 2-((1E,3Z)-4-chloro-4-(4-(trifluoromethoxy)phenyl)buta-1,3-dien-1-yl)-2-(4-methoxyphenyl)-1,3-dithiane obtained in Example 13 are as follows:

[0074]

[0075] 1 H NMR(400MHz,Chloroform-d)δ7.75–7.64(m,4H),7.21(d,J=8.5Hz,2H),7.01–6.83(m,4H),6 .22(d,J=14.7Hz,1H),3.81(s,3H),3.04–2.91(m,2H),2.83–2.71(m,2H),2.12–1.87(m,2H).13 C NMR(101MHz,Chloroform-d)δ159.5,149.6,140.5,136.4,133.1,132.3,129.8,1 29.7,128.0,125.5,120.9,120.6(d,J=257.9Hz),114.0,58.3,55.5,28.9,24.6.

[0076] Example 14: Preparation of compound 2-((1E,3Z)-4-chloro-4-phenylbuta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane:

[0077] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-phenylvinyl)-1,3-dithiane (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of dichloromethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0078] The structure and NMR data of the product 2-((1E,3Z)-4-chloro-4-phenylbuta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithi ane obtained in Example 14 are as follows:

[0079]

[0080] 1 H NMR(600MHz,Chloroform-d)δ7.66(d,J=7.2Hz,2H),7.40–7.32(m,3H),7.08(s,2H),6.99(dd,J=15.0,10.3Hz,1H),6.91(d,J=10.4H z,1H),6.18(d,J=15.1Hz,1H),3.88(s,6H),3.86(s,3H),3.02–2.95(m,2H),2.83–2.77(m,2H),2.11–2.04(m,1H),2.03–1.95(m,1H).13 C NMR (101MHz, Chloroform-d) δ153.1,139.1,137.8,137.5,136.8,134.2,130.2,129.0,128.6,126.4,124.4,105.8,60.9,59.1,56.3,28.9,24.5.

[0081] Example 15: Preparation of compound 2-((1E,3Z)-4-chloro-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane:

[0082] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(4-methoxyphenyl)vinyl)-1,3-dithiane (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of dichloromethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0083] The structure and NMR data of the product 2-((1E,3Z)-4-chloro-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane obtained in Example 15 are as follows:

[0084]

[0085] 1H NMR(600MHz,Chloroform-d)δ7.60(d,J=8.9Hz,2H),7.08(s,2H),6.96(dd,J=15.2,10.3Hz,1H),6.90(d,J=8.9Hz,2H),6.80(dd,J=10.3,0.8Hz,1H ),6.12(dd,J=15.1,0.8Hz,1H),3.88(s,6H),3.86(s,3H),3.84(s,3H),3. 03–2.95(m,2H),2.83–2.76(m,2H),2.11–2.04(m,1H),2.03–1.96(m,1H). 13 C NMR (151MHz, Chloroform-d) δ160.4,153.2,138.1,136.9,134.1,130.4,130.2,127.9,122.7,114.0,105.9,61.0,59.3,56.4,55.5,29.0,24.6.

[0086] Example 16: Preparation of the compound 2-(4-butylphenyl)-2-((1E,3Z)-4-chloro-4-(3,4-dimethoxyphenyl)buta-1,3-dien-1-yl)-1,3-dithiane:

[0087] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(3,4-dimethoxyphenyl)vinyl)-1,3-dithiane (0.1 mmol), ((4-butylphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of dichloromethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0088] The structure and NMR data of the product 2-(4-butylphenyl)-2-((1E,3Z)-4-chloro-4-(3,4-dimethoxyphenyl)buta-1,3-dien-1-yl)-1,3-dithiane obtained in Example 16 are as follows:

[0089]

[0090] 1 H NMR(400MHz,Chloroform-d)δ7.67(d,J=8.3Hz,2H),7.24–7.20(m,1H),7.19 –7.13(m,3H),6.96(dd,J=15.1,10.4Hz,1H),6.86–6.76(m,2H),6.15(d,J=15 .1Hz,1H),3.91(s,3H),3.89(s,3H),3.04–2.95(m,2H),2.80–2.72(m,2H),2. 63–2.56(m,2H),1.65–1.54(m,2H),1.40–1.28(m,2H),0.91(t,J=7.3Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ150.0,148.9,143.1,138.9,138.6,133.7,130.7,130.2,1 28.7,128.2,123.3,119.5,111.0,109.7,58.7,56.1,35.3,33.6,28.9,24.7,22.5,14.1.

[0091] Example 17: Preparation of the compound 2-(4-butylphenyl)-2-((1E,3Z)-4-chloro-4-(3,4,5-trimethoxyphenyl)buta-1,3-dien-1-yl)-1,3-dithiane:

[0092] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(3,4,5-trimethoxyphenyl)vinyl)-1,3-dithiane (0.1 mmol), ((4-butylphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of dichloromethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0093] The structure and NMR data of the product 2-(4-butylphenyl)-2-((1E,3Z)-4-chloro-4-(3,4,5-trimethoxyphenyl)buta-1,3-dien-1-yl)-1,3-dithiane obtained in Example 17 are as follows:

[0094]

[0095] 1 H NMR(400MHz,Chloroform-d)δ7.68(d,J=8.4Hz,2H),7.18(d,J=8.2Hz,2H),6.97(d d,J=15.1,10.3Hz,1H),6.87(s,2H),6.83(d,J=10.4Hz,1H),6.20(d,J=15.1Hz,1H ),3.90(s,6H),3.87(s,3H),3.06–2.93(m,2H),2.84–2.71(m,2H),2.63–2.58(m,3 H),2.13–1.89(m,2H),1.65–1.56(m,2H),1.41–1.29(m,2H),0.92(t,J=7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ153.1,143.1,139.6,139.1,138.5,133.7,133.4,1 29.9,128.7,128.2,124.4,61.1,58.7,56.4,35.3,33.5,28.8,24.7,22.5,14.1.

[0096] Example 18: Preparation of compound 2-((1E,3Z)-4-chloro-4-(naphthalen-2-yl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxypheny l)-1,3-dithiane:

[0097] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(naphthalen-2-yl)vinyl)-1,3-dithiane (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of chloroform were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0098] The structure and NMR data of the product 2-((1E,3Z)-4-chloro-4-(naphthalen-2-yl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxypheny l)-1,3-dithiane obtained in Example 18 are as follows:

[0099]

[0100] 1 H NMR(600MHz,Chloroform-d)δ8.17(s,1H),7.90–7.87(m,1H),7.85–7.82(m,2H),7.75(dd,J=8.7,2.0Hz,1H),7.53–7.49(m,2H),7.09 (s,2H),7.09–7.05(m,2H),6.23(d,J=14.4Hz,1H),3.90(s,6H),3.87(s,3H),3.05–2.98(m,2H),2.85–2.80(m,2H),2.13–1.96(m,2H). 13 C NMR(151MHz,Chloroform-d)δ153.2,139.3,137.8,136.8,134.6,134.2,133.4,133.2,130.2, 128.6,128.2,127.7,126.9,126.8,126.4,124.8,123.5,105.8,60.9,59.2,56.4,28.9,24.5.

[0101] Example 19: Preparation of compound 2-((1E,3Z)-4-chloro-4-(2-fluorophenyl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane:

[0102] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(2-fluorophenyl)vinyl)-1,3-dithiane (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of chloroform were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0103] The structure and NMR data of the product 2-((1E,3Z)-4-chloro-4-(2-fluorophenyl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane obtained in Example 19 are as follows:

[0104]

[0105] 1 H NMR(600MHz,Chloroform-d)δ7.63(td,J=7.9,1.8Hz,1H),7.33–7.28(m,1H),7.18( td,J=7.6,1.2Hz,1H),7.10(ddd,J=11.4,8.2,1.2Hz,1H),7.07(s,2H),6.98(dd,J=1 5.0,10.4Hz,1H),6.92(d,J=10.4Hz,1H),6.18(d,J=14.8Hz,1H),3.89(s,6H),3.87 (s,3H),3.04–2.96(m,2H),2.84–2.77(m,2H),2.13–2.05(m,1H),2.03–1.95(m,1H). 13C NMR(101MHz,Chloroform-d)δ27.4(d,J=3.7Hz),153.1,139.8,137.8,136.7,130.4(d,J=1.9Hz),130.3(d,J=8.5Hz),129.9,129.5(d ,J=9.1Hz),127.4(d,J=3.7Hz),126.0(d,J=11.1Hz),124.29(d,J=3.7Hz),116.2(d,J=22.8Hz),105.8,60.9,59.0,56.3,28.9,24.5.

[0106] Example 20: Preparation of compound 2-((1E,3Z)-4-chloro-4-(thiophen-2-yl)buta-1,3-dien-1-yl)-2-(4-methoxyphenyl)-1,3-di thiane:

[0107] In a 25 ml round-bottom flask, (Z)-2-(2-chloro-2-(thiophen-2-yl)vinyl)-1,3-dithiane (0.1 mmol), ((4-methoxyphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of chloroform were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0108] The structure and NMR data of the product 2-((1E,3Z)-4-chloro-4-(thiophen-2-yl)buta-1,3-dien-1-yl)-2-(4-methoxyphenyl)-1,3-di thiane obtained in Example 20 are as follows:

[0109]

[0110] 1H NMR(400MHz,Chloroform-d)δ7.69(d,J=8.8Hz,2H),7.33(d,J=3.6Hz,1H),7.26(d,J=4.4Hz,1H),7.01(dd,J=5.1,3.7Hz,1H),6. 98–6.82(m,4H),6.17(d,J=14.2Hz,1H),3.81(s,3H),3.02–2.93(m,2H),2.81–2.71(m,2H),2.12–2.02(m,1H),2.00–1.90(m,1H). 13 C NMR (101MHz, Chloroform-d) δ159.5,142.1,139.5,133.3,129.7,129.5,127.8,127.2,126.5,126.3,123.2,114.0,58.4,55.5,28.9,24.7.

[0111] Example 21: Preparation of compound (E)-4-chloro-5-(2-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)vinyl)-3,6-dihydro-2H-pyran:

[0112] In a 25 ml round-bottom flask, 4-chloro-5-(1,3-dithian-2-yl)-3,6-dihydro-2H-pyran (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of chloroform were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0113] The structure and NMR data of the product (E)-4-chloro-5-(2-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)vinyl)-3,6-dihydro-2H-pyran obtained in Example 21 are as follows:

[0114]

[0115] 1H NMR(600MHz,Chloroform-d)δ7.04(s,2H),6.88(d,J=16.2Hz,1H),5.75(d,J=16.3Hz,1H),4.39(t,J=2.2Hz,2H),3.87(s,6H ),3.87(s,2H),3.86(s,3H),2.96–2.90(m,2H),2.81–2.76(m,2H),2.59–2.55(m,2H),2.08–2.02(m,1H),2.01–1.94(m,1H). 13 C NMR (151MHz, Chloroform-d) δ153.2,137.9,136.6,132.1,129.5,128.2,127.9,106.0,66.6,65.0,61.0,59.3,56.4,34.1,28.9,24.5.

[0116] Example 22: Preparation of the compound ethyl(2Z,4E)-2-chloro-5-(2-(4-propylphenyl)-1,3-dithian-2-yl)penta-2,4-dienoate:

[0117] In a 25 ml round-bottom flask, ethyl(Z)-2-chloro-3-(1,3-dithian-2-yl)acrylate (0.1 mmol), trimethyl((4-propylphenyl)ethynyl)silane (0.2 mmol) and 6 ml of chloroform were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0118] The structure and NMR data of the product ethyl(2Z,4E)-2-chloro-5-(2-(4-propylphenyl)-1,3-dithian-2-yl)penta-2,4-dienoate obtained in Example 22 are as follows:

[0119]

[0120] 1H NMR(600MHz,Chloroform-d)δ7.65–7.56(m,3H),7.20–7.13(m,2H),6.93(dd,J=15.1,11.0Hz,1H),6.46(d,J=15.2Hz,1H),4.31(q,J=7.1Hz,2H),3.00–2. 90(m,2H),2.79–2.72(m,2H),2.58(t,J=7.5Hz,2H),2.11–2.03(m,1H),1.99– 1.90(m,1H),1.67–1.59(m,2H),1.35(t,J=7.1Hz,3H),0.93(t,J=7.2Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ162.9,146.2,143.2,137.8,136.4,128.8,128.0,123.9,62.4,58.1,37.7,28.8,24.4,14.3,13.9.

[0121] Example 23: Preparation of the compound methyl4-((1Z,3E)-1-chloro-4-(2-(3,4,5-trimethoxyphenyl)-1,3-dithiolan-2-yl)buta-1,3-dien-1-yl)benzoate:

[0122] In a 25 ml round-bottom flask, methyl(Z)-4-(1-chloro-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of chloroform were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0123] The structure and NMR data of the product methyl4-((1Z,3E)-1-chloro-4-(2-(3,4,5-trimethoxyphenyl)-1,3-dithiolan-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 23 are as follows:

[0124]

[0125] 1 H NMR(600MHz,Chloroform-d)δ8.02(d,J=8.5Hz,2H),7.71(d,J=8.5Hz,2H),6.99(d,J=10.4Hz,1H),6.94(s,2H),6.89(dd, J=14.6,10.4Hz,1H),6.41(d,J=14.6Hz,1H),3.92(s,3H),3.88(s,6H),3.86(s,3H),3.51–3.45(m,2H),3.43–3.37(m,2H). 13 C NMR(151MHz,Chloroform-d)δ166.6,152.9,141.9,141.7,137.8,136.5,132 .4,130.2,129.8,126.5,126.2,125.6,105.5,74.0,60.9,56.4,52.3,40.0.

[0126] Example 24: Preparation of the compound methyl4-((1Z,3E)-1-bromo-4-(2-(4-methoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0127] In a 25 ml round-bottom flask, methyl(Z)-4-(1-bromo-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), ((4-methoxyphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and then ferric chloride hexahydrate and boron trifluoride etherate were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0128] The structure and NMR data of the product methyl4-((1Z,3E)-1-bromo-4-(2-(4-methoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 24 are as follows:

[0129]

[0130] 1 H NMR(400MHz,Chloroform-d)δ8.01(dd,J=8.4,1.8Hz,2H),7.75–7.57(m,4H),7.10(d,J=10.1Hz,1H),7.01–6.82( m,3H),6.30(d,J=15.1Hz,1H),3.93(s,3H),3.81(s,3H),3.08–2.91(m,2H),2.83–2.71(m,2H),2.17–1.87(m,2H). 13 CNMR(101MHz,Chloroform-d)δ166.6,159.5,143.5,141.7,133.0,132.2,13 0.3,130.0,129.8,129.7,127.5,125.4,114.0,58.3,55.5,52.4,28.9,24.6.

[0131] Example 25: Preparation of the compound methyl4-((1Z,3E)-1-bromo-4-(2-(4-butylphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0132] In a 25 ml round-bottom flask, methyl(Z)-4-(1-bromo-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), methyl(Z)-4-(1-bromo-2-(1,3-dithian-2-yl)vinyl)benzoate (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferric chloride hexahydrate and boron trifluoride etherate were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0133] The structure and NMR data of the product methyl4-((1Z,3E)-1-bromo-4-(2-(4-butylphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 25 are as follows:

[0134]

[0135] 1 H NMR(400MHz,Chloroform-d)δ8.01(d,J=8.4Hz,2H),7.77–7.54(m,4H),7.18(d,J =7.5Hz,2H),7.10(d,J=10.1Hz,1H),6.96(dd,J=15.0,10.1Hz,1H),6.30(d,J=15. 0Hz,1H),3.92(s,3H),3.07–2.89(m,2H),2.84–2.68(m,2H),2.61(t,J=7.7Hz,2H ),2.15–1.86(m,2H),1.66–1.49(m,2H),1.43–1.28(m,2H),0.92(t,J=7.3Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ166.6,143.5,143.2,141.7,138.2,132.2,130.3,130. 0,129.8,128.8,128.2,127.5,125.4,58.5,52.3,35.3,33.5,28.8,24.6,22.5,14.1.

[0136] Example 26: Preparation of the compound methyl4-((1Z,3E)-1-bromo-4-(2-(p-tolyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0137] In a 25 ml round-bottom flask, methyl(Z)-4-(1-bromo-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), trimethyl(p-tolylethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and then ferric chloride hexahydrate and boron trifluoride etherate were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and it was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0138] The structure and NMR data of the product methyl4-((1Z,3E)-1-bromo-4-(2-(4-butylphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 26 are as follows:

[0139]

[0140] 1H NMR(400MHz,Chloroform-d)δ8.02(d,J=8.7Hz,2H),7.67(dd,J=15.2,8.3Hz,4H),7.18(d,J=8.0Hz,2H),7.09(d,J=10.1Hz,1H),6.96 (dd,J=15.0,10.2Hz,1H),6.30(d,J=15.0Hz,1H),3.93(s,3H),3.08–2.93(m,2H),2.84–2.73(m,2H),2.35(s,3H),2.14–1.91(m,2H). 13 C NMR(101MHz,Chloroform-d)δ166.6,143.5,141.6,138.2,138.1,132.2,130 .3,130.0,129.8,129.5,128.3,127.6,125.4,58.5,52.4,28.8,24.6,21.2.

[0141] Example 27: Preparation of the compound methyl4-((1Z,3E)-1-bromo-4-(2-(4-fluorophenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0142] In a 25 ml round-bottom flask, methyl(Z)-4-(1-bromo-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), ((4-fluorophenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and anhydrous ferric chloride and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0143] The structure and NMR data of the product methyl4-((1Z,3E)-1-bromo-4-(2-(4-fluorophenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 27 are as follows:

[0144]

[0145] 1 H NMR(400MHz,Chloroform-d)δ8.02(dd,J=8.3,1.4Hz,2H),7.83–7.72(m,2H),7.69(dd,J=8.3,1.3Hz,2H),7.13–6.99(m,3H), 6.91(dd,J=15.1,10.1Hz,1H),6.29(d,J=15.1Hz,1H),3.93(s,3H),3.08–2.90(m,2H),2.85–2.70(m,2H),2.16–1.87(m,2H). 13 CNMR(101MHz,Chloroform-d)δ166.6,162.5(d,J=248.1Hz),143.4,141.1,136.9(d,J=3.1Hz),132.6 ,130.5(d,J=8.3Hz),129.8,129.7,129.6,127.6,125.9,115.6(d,J=21.6Hz),58.2,52.4,28.8,24.5.

[0146] Example 28: Preparation of the compound methyl4-((1Z,3E)-1-bromo-4-(2-(4-(methoxycarbonyl)phenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0147] In a 25 ml round-bottom flask, methyl(Z)-4-(1-bromo-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), methyl4-((trimethylsilyl)ethynyl)benzoate (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and anhydrous ferric chloride and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0148] The structure and NMR data of the product methyl4-((1Z,3E)-1-bromo-4-(2-(4-(methoxycarbonyl)phenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 28 are as follows:

[0149]

[0150] 1 H NMR(400MHz,Chloroform-d)δ8.03(dd,J=13.8,8.4Hz,4H),7.89(d,J=8.3Hz,2H),7.68(d,J=8.6Hz,2H),7.07(d,J=10.1Hz,1H ),6.88(dd,J=15.2,10.1Hz,1H),6.29(d,J=15.1Hz,1H),3.93(s,6H),3.03–2.93(m,2H),2.83–2.72(m,2H),2.15–1.92(m,2H). 13 C NMR(101MHz,Chloroform-d)δ166.8,166.6,146.1,143.4,140.6,132.7,130 .4,130.0,129.8,129.7,128.8,127.6,126.2,58.7,52.3,29.8,28.6,24.4.

[0151] Example 29: Preparation of the compound methyl4-((1Z,3E)-1-bromo-4-(2-(m-tolyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate:

[0152] In a 25 ml round-bottom flask, methyl(Z)-4-(1-bromo-2-(1,3-dithian-2-yl)vinyl)benzoate (0.1 mmol), trimethyl(m-tolylethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and anhydrous ferric bromide and boron trifluoride ether were added, and then stirred at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum. The product was obtained by column chromatography.

[0153] The structure and NMR data of the product methyl4-((1Z,3E)-1-bromo-4-(2-(m-tolyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)benzoate obtained in Example 29 are as follows:

[0154]

[0155] 1 H NMR(400MHz,Chloroform-d)δ8.07–7.97(m,2H),7.69(d,J=8.3Hz,2H),7.61–7.52(m,2H),7.29–7.23(m,1H),7.15–7.05(m,2H),6.98 (dd,J=15.0,10.1Hz,1H),6.30(d,J=15.0Hz,1H),3.92(s,3H),3.09–2.94(m,2H),2.86–2.70(m,2H),2.38(s,3H),2.17–1.87(m,2H). 13 C NMR(101MHz,Chloroform-d)δ166.6,143.5,141.5,141.0,138.5,132.2,130.3,130 .0,129.8,129.2,128.8,128.6,127.5,125.5,125.4,58.6,52.3,28.8,24.6,21.7.

[0156] Example 30: Preparation of compound 2-((1E,3Z)-4-bromo-4-(4-nitrophenyl)buta-1,3-dien-1-yl)-2-(4-butylphenyl)-1,3-dithiane:

[0157] In a 25 ml round-bottom flask, (Z)-2-(2-bromo-2-(4-nitrophenyl)vinyl)-1,3-dithiane (0.1 mmol), ((4-butylphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and anhydrous ferric bromide and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0158] The structure and NMR data of the product 2-((1E,3Z)-4-bromo-4-(4-nitrophenyl)buta-1,3-dien-1-yl)-2-(4-butylphenyl)-1,3-dithiane obtained in Example 30 are as follows:

[0159]

[0160] 1 H NMR(600MHz,Chloroform-d)δ8.21(d,J=8.9Hz,2H),7.78(d,J=8.9Hz,2H),7.66(d,J=8.4 Hz,2H),7.19(d,J=8.3Hz,2H),7.15(dd,J=10.2,0.8Hz,1H),6.95(dd,J=15.1,10.1Hz,1H) ,6.37(d,J=15.1Hz,1H),3.03–2.96(m,2H),2.82–2.75(m,2H),2.63–2.57(m,3H),2.13–2. 05(m,1H),2.03–1.94(m,1H),1.62–1.57(m,2H),1.37–1.32(m,2H),0.92(t,J=7.4Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ147.62,145.25,143.27,143.01,137.96,131.77,131.58,1 28.80,128.25,128.12,123.77,123.63,58.44,35.32,33.52,28.76,24.54,22.44,14.06.

[0161] Example 31: Preparation of compound 2-((1E,3Z)-4-bromo-4-phenylbuta-1,3-dien-1-yl)-2-(4-methoxyphenyl)-1,3-dithiane:

[0162] In a 25 ml round-bottom flask, (Z)-2-(2-bromo-2-phenylvinyl)-1,3-dithiane (0.1 mmol), ((4-methoxyphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and anhydrous ferric bromide and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0163] The structure and NMR data of the product 2-((1E,3Z)-4-bromo-4-phenylbuta-1,3-dien-1-yl)-2-(4-methoxyphenyl)-1,3-dithiane obtained in Example 31 are as follows:

[0164]

[0165] 1 H NMR(400MHz,Chloroform-d)δ7.70(s,2H),7.63–7.58(m,2H),7.38–7.27(m,3H),7.01–6.85(m,4 H),6.22(d,J=13.9Hz,1H),3.79(s,3H),3.04–2.93(m,2H),2.80–2.70(m,2H),2.11–1.86(m,2H). 13 C NMR (101MHz, Chloroform-d) δ159.4,140.2,139.4,133.2,132.5,129.7,128.9,128.5,128.2,127.6,126.9,113.9,58.3,55.4,28.8,24.6.

[0166] Example 32: Preparation of compound 2-((1E,3Z)-4-bromo-4-phenylbuta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane:

[0167] In a 25 ml round-bottom flask, (Z)-2-(2-bromo-2-phenylvinyl)-1,3-dithiane (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0168] The structure and NMR data of the product 2-((1E,3Z)-4-bromo-4-phenylbuta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane obtained in Example 32 are as follows:

[0169]

[0170] 1 H NMR(400MHz,Chloroform-d)δ7.62(d,J=7.7Hz,2H),7.39–7.29(m,3H),7.02–6.89(m,2H),6.21(d, J=14.0Hz,1H),3.89(s,6H),3.86(s,3H),3.05–2.94(m,2H),2.86–2.76(m,2H),2.13–1.92(m,2H). 13 C NMR (101MHz, Chloroform-d) δ153.2,139.7,139.3,137.9,136.7,132.7,129.1,128.5,128.0,127.6,127.3,105.9,60.9,59.1,56.4,28.9,24.5.

[0171] Example 33: Preparation of the compound 2-(4-butylphenyl)-2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-1,3-dithiane:

[0172] In a 25 ml round-bottom flask, (E)-2-(4-methoxystyryl)-1,3-dithiane (0.1 mmol), ((4-butylphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0173] The structure and NMR data of the product 2-(4-butylphenyl)-2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-1,3-dithiane obtained in Example 33 are as follows:

[0174]

[0175] 1 H NMR(400MHz,Chloroform-d)δ7.69(d,J=8.4Hz,2H),7.33(d,J=8.8Hz,2H),7.16(d,J=8.4Hz,2 H),6.85(d,J=8.8Hz,2H),6.78(dd,J=15.6,10.5Hz,1H),6.54(d,J=15.6Hz,1H),6.47(dd,J=15 .1,10.5Hz,1H),6.02(d,J=15.1Hz,1H),3.80(s,3H),3.01–2.88(m,2H),2.79–2.70(m,2H),2.6 5–2.57(m,2H),2.09–1.90(m,2H),1.65–1.55(m,2H),1.39–1.32(m,2H),0.93(t,J=7.3Hz,3H). 13 CNMR(101MHz,Chloroform-d)δ159.5,142.8,138.9,135.6,134.7,133.2,130.1,1 28.6,128.5,127.8,126.0,114.3,58.9,55.4,35.4,33.6,28.9,24.8,22.5,14.1.

[0176] Example 34: Preparation of compound 2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(m-tolyl)-1,3-dithiane:

[0177] In a 25 ml round-bottom flask, (E)-2-(4-methoxystyryl)-1,3-dithiane (0.1 mmol), trimethyl(m-tolylethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0178] The structure and NMR data of the product 2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(m-tolyl)-1,3-dithiane obtained in Example 34 are as follows:

[0179]

[0180] 1 H NMR(600MHz,Chloroform-d)δ7.62(s,1H),7.60(d,J=7.9Hz,1H),7.35(d,J=8.6Hz,2H),7. 28–7.23(m,2H),7.10(d,J=7.5Hz,1H),6.86(d,J=8.7Hz,2H),6.80(dd,J=15.5,10.6Hz,1H) ,6.56(d,J=15.6Hz,1H),6.47(dd,J=15.1,10.7Hz,1H),6.01(d,J=15.1Hz,1H),3.81(s,3H ),2.99–2.92(m,2H),2.79–2.72(m,2H),2.38(s,3H),2.09–2.01(m,1H),1.99–1.92(m,1H). 13C NMR(101MHz,Chloroform-d)δ159.6,141.6,138.3,135.5,134.7,133.2,130.0, 129.2,128.8,128.5,127.8,125.9,125.7,114.3,59.0,55.4,28.9,24.8,21.7.

[0181] Example 35: Preparation of compound 2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(3-nitrophenyl)-1,3-dithiane:

[0182] In a 25 ml round-bottom flask, (E)-2-(4-methoxystyryl)-1,3-dithiane (0.1 mmol), trimethyl((3-nitrophenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0183] The structure and NMR data of the product 2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(3-nitrophenyl)-1,3-dithiane obtained in Example 35 are as follows:

[0184]

[0185] 1H NMR (600MHz, Chloroform-d) δ8.73 (s, 1H), 8.20 (d, J = 8.0 Hz, 1H), 8.17 (dd, J = 8.1, 2. 2Hz,1H),7.56(t,J=8.0Hz,1H),7.34(d,J=8.8Hz,2H),6.86(d,J=8.7Hz,2H),6.76(dd ,J=15.6,10.5Hz,1H),6.55(d,J=15.6Hz,1H),6.38(dd,J=15.1,10.5Hz,1H),6.00(d, J=15.1Hz,1H),3.81(s,3H),2.99–2.89(m,2H),2.78–2.69(m,2H),2.09–1.94(m,2H). 13 C NMR(151MHz,Chloroform-d)δ159.7,148.6,144.4,135.7,135.2,134.4,133 .8,129.7,129.6,128.0,125.3,124.2,123.0,114.3,58.4,55.4,28.7,24.3.

[0186] Example 36: Preparation of compound 2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane:

[0187] In a 25 ml round-bottom flask, (E)-2-(4-methoxystyryl)-1,3-dithiane (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0188] The structure and NMR data of the product 2-((1E,3E)-4-(4-methoxyphenyl)buta-1,3-dien-1-yl)-2-(3,4,5-trimethoxyphenyl)-1,3-dithiane obtained in Example 36 are as follows:

[0189]

[0190] 1 H NMR(600MHz,Chloroform-d)δ7.35(d,J=8.6Hz,2H),7.10(s,2H),6.86(d,J=8.8Hz,2H),6.78(dd,J=15.5,10.6Hz,1H),6.56(d,J=15.6Hz,1H),6.4 5(dd,J=15.1,10.6Hz,1H),5.99(d,J=15.1Hz,1H),3.87(s,6H),3.87(s,3 H),3.81(s,3H),2.95–2.90(m,2H),2.82–2.75(m,2H),2.07–1.93(m,2H). 13 C NMR (151MHz, Chloroform-d) δ159.6,153.1,137.6,137.2,135.1,134.8,133.5,129.9,127.8,125.7,114.3,106.1,60.9,59.4,56.3,55.4,28.9,24.6.

[0191] Example 37: Preparation of compound 2-((1E,3E)-4-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)furan:

[0192] In a 25 ml round-bottom flask, (E)-2-(2-(1,3-dithian-2-yl)vinyl)furan (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0193] The structure and NMR data of the product 2-((1E,3E)-4-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)furan obtained in Example 37 are as follows:

[0194]

[0195] 1 H NMR(600MHz,Chloroform-d)δ7.38(d,J=1.9Hz,1H),7.08(s,2H),6.82(dd,J=15.5,10.9Hz,1H),6.48–6.37(m,3H),6.29(d ,J=3.3Hz,1H),6.04(d,J=15.1Hz,1H),3.87(s,6H),3.86(s,3H),2.95–2.89(m,2H),2.80–2.74(m,2H),2.06–1.94(m,2H). 13 C NMR (151MHz, Chloroform-d) δ153.1,153.0,142.5,137.6,137.0,136.3,134.2,126.2,121.3,111.8,109.1,106.0,60.9,59.3,56.3,28.9,24.5.

[0196] Example 38: Preparation of compound 2-((1E,3E)-4-(2-(thiophen-2-yl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)furan:

[0197] In a 25 ml round-bottom flask, (E)-2-(2-(1,3-dithian-2-yl)vinyl)furan (0.1 mmol), trimethyl(thiophen-2-ylethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride etherate were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0198] The structure and NMR data of the product 2-((1E,3E)-4-(2-(thiophen-2-yl)-1,3-dithian-2-yl)buta-1,3-dien-1-yl)furan obtained in Example 38 are as follows:

[0199]

[0200] 1H NMR(600MHz,Chloroform-d)δ7.36(d,J=1.8Hz,1H),7.33(dd,J=5.2,1.3Hz,1H),7.27 –7.25(m,2H),7.01(dd,J=5.2,3.6Hz,1H),6.72(dd,J=15.5,10.8Hz,1H),6.37(dd,J=3 .3,1.8Hz,1H),6.33(d,J=15.5Hz,1H),6.26(d,J=3.3Hz,1H),6.22(dd,J=14.9,10.8Hz ,1H),6.08(d,J=14.9Hz,1H),2.96–2.90(m,2H),2.86–2.80(m,2H),2.04–1.94(m,2H). 13 C NMR (101MHz, Chloroform-d) δ153.0,148.1,142.6,136.3,133.5,128.4,127.3,127.2,126.2,121.9,111.8,109.2,55.3,29.0,24.3.

[0201] Example 39: Preparation of the compound ethyl(2E,4E)-5-(2-(4-butylphenyl)-1,3-dithian-2-yl)penta-2,4-dienoate:

[0202] In a 25 ml round-bottom flask, ethyl(E)-3-(1,3-dithian-2-yl)acrylate (0.1 mmol), ((4-butylphenyl)ethynyl)trimethylsilane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0203] The structure and NMR data of the product ethyl(2E,4E)-5-(2-(4-butylphenyl)-1,3-dithian-2-yl)penta-2,4-dienoate obtained in Example 39 are as follows:

[0204]

[0205] 1H NMR (600MHz, Chloroform-d) δ7.60 (d, J = 8.3Hz, 2H), 7.44 (dd, J = 15.4, 11.1Hz, 1H), 7.17 (d, J = 8. 1Hz,2H),6.53(dd,J=15.1,11.1Hz,1H),6.36(d,J=15.1Hz,1H),5.96(d,J=15.4Hz,1H),4.22(q, J=7.1Hz,2H),2.94–2.88(m,2H),2.78–2.71(m,2H),2.62–2.56(m,2H),2.10–2.02(m,1H),1.99– 1.90(m,1H),1.61–1.55(m,2H),1.38–1.32(m,2H),1.30(t,J=7.1Hz,3H),0.92(t,J=7.4Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ166.9,144.5,143.2,143.2,137.9,131.4,128.7,128.1,122.5,60.5,58.1,35.3,33.5,28.8,24.5,22.5,14.4,14.0.

[0206] Example 40: Preparation of the compound ethyl(2E,4E)-5-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)penta-2,4-dienoate:

[0207] In a 25 ml round-bottom flask, ethyl(E)-3-(1,3-dithian-2-yl)acrylate (0.1 mmol), trimethyl((3,4,5-trimethoxyphenyl)ethynyl)silane (0.2 mmol) and 6 ml of 1,2-dichloroethane were added in sequence, and ferrous chloride tetrahydrate and boron trifluoride ether were added, followed by stirring at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, water was added to the reaction system to quench the reaction, and the mixture was extracted three times with dichloromethane (15 ml). The organic phases were combined, washed three times with saturated brine (15 ml), dried over anhydrous sodium sulfate, filtered, and the volatiles were removed under vacuum, and the product was obtained by column chromatography.

[0208] The structure and NMR data of the product ethyl(2E,4E)-5-(2-(3,4,5-trimethoxyphenyl)-1,3-dithian-2-yl)penta-2,4-dienoate obtained in Example 40 are as follows:

[0209]

[0210] 1 H NMR(600MHz,Chloroform-d)δ7.43(dd,J=15.4,11.0Hz,1H),7.01(s,2H),6.50(dd,J=15.1,11.1Hz,1H),6.33(d,J=15.1Hz,1H),5.98(d,J=15.4Hz,1H),4.22(q,J=7.1Hz,2H),3.87(s,6H),3.86(s,3H),2.94–2.87(m,2H),2.81–2.74(m,2H),2.09–1.92(m,2H),1.30(t,J=7.1 Hz,3H). 13 C NMR(151 MHz,Chloroform-d)δ166.8,153.2,144.0,142.9,137.9,136.2,131.5,122.9,105.7,60.9,60.6,58.6,56.3,28.8,24.3,14.4.

Claims

1. A method for preparing a 1,3-dithiane substituted diene derivative, characterized in that: Under the action of Lewis acid, vinyl-1,3-dithiane derivative (I) and alkyne compound (II) react in a suitable organic solvent at room temperature to obtain 1,3-dithiane substituted diene derivative (III), and the reaction equation is as follows: X in the vinyl-1,3-dithiane derivative (I) is hydrogen, chlorine, or bromine; the structure of the 1,3-dithiane substituted diene derivative (III) is: The organic solvent is one of dichloromethane, chloroform and 1,2-dichloroethane; the Lewis acid is one of ferrous chloride tetrahydrate, ferric chloride hexahydrate, anhydrous ferric chloride and anhydrous ferric bromide.

2. The method for preparing a 1,3-dithiane substituted diene derivative according to claim 1, characterized in that: The molar ratio of Lewis acid, vinyl-1,3-dithiane derivative (I) and alkyne compound (II) is 0.5-1.5:1.0:2.0.

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