A method for preparing unsaturated carbonyl compounds by carbonyl-alkyne metathesis reaction

Abstract

Invention Title: A Method for Preparing Unsaturated Carbonyl Compounds via Carbonyl-Alkyne Metathesis Reaction. This invention belongs to the field of organic chemistry and provides a method for preparing unsaturated carbonyl compounds via a carbonyl-alkyne metathesis reaction. Specifically, using carbonyl compounds and alkynylthiane compounds as raw materials, a carbonyl-alkyne metathesis reaction occurs under the promotion of a base to obtain a class of unsaturated carbonyl compounds. The method provided by this invention uses inexpensive and readily available bases as promoters, avoiding the use of precious metal catalysts. Furthermore, the reaction exhibits high stereoselectivity, mild conditions, simple operation, and broad substrate applicability. It does not require anhydrous or oxygen-free operation, thus possessing strong practicality and promising prospects for industrial application. The method provided by this invention can be used for the synthesis and post-modification of natural products, drug molecules, and functional material molecules.

Description

Technical Field

[0001] This invention belongs to the field of organic chemistry, specifically relating to a method for preparing unsaturated carbonyl compounds by a carbonyl-alkyne metathesis reaction. Background Technology

[0002] Carbonyl-alkyne metathesis (CAM) is a highly stereoselective and atom-economical tool for constructing carbon-carbon double bonds. This reaction has been widely used in organic synthesis for the efficient construction of various α,β-unsaturated carbonyl compounds (Curr. Green Chem. 2020, 7, 5-39; ACS Catal. 2023, 13, 2696-2701). Typically, this reaction is catalyzed by Lewis or Brønsted acids. However, using these acidic catalysts can cause problems, such as requiring harsh conditions, using transition metal catalysts, poor functional group tolerance of the substrate, and unwanted side reactions. In 2014, Professor Akira Aso's group successfully achieved the metathesis reaction of carbon-carbon and carbon-oxygen double bonds in allenoates and aldehydes, a method that can prepare unsaturated carbonyl compounds with high stereoselectivity (Angew. Chem. Int. Ed. 2014, 53, 3214-3217). Therefore, it is of great value to develop a non-precious metal-catalyzed, mild, and efficient carbonyl-alkyne metathesis reaction to prepare unsaturated carbonyl compounds. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing unsaturated carbonyl compounds via a carbonyl-alkyne metathesis reaction. This method involves sequentially adding a carbonyl compound, an alkynylthiane compound, a suitable solvent, and a base to a reactor, and reacting at a suitable temperature to obtain a class of unsaturated carbonyl compounds. This method does not require noble metal catalysis, does not require anhydrous or oxygen-free operation, has mild conditions, broad substrate applicability, high stereoselectivity, and high yield.

[0004] This invention employs the following technical solution: At room temperature, a carbonyl compound and an alkynylthiane compound are dissolved in an organic solvent. After adding an alkali, the mixture is stirred and reacted at a specific temperature for a period of time. Once the reaction is complete, the mixture is separated and purified to obtain an unsaturated carbonyl compound. The chemical reaction equation for this technical solution is as follows:

[0005]

[0006] R in carbonyl compound (I) 1 and R 2It is hydrogen, tert-butyl, substituted phenyl (substituents are selected from hydrogen, methoxy, methylthio, trifluoromethoxy, fluorine, chlorine, bromine, trifluoromethyl, diphenylamino, diphenylphosphino), naphthyl, pyrene, pyrazolyl, thiophene, indolyl, furanyl, benzodihydrofuranyl, carbazole, and Dianhong derivatives;

[0007] R in the alkyne compound (II) 3 It is a substituted phenyl group (the substituent is selected from hydrogen, methoxy, trifluoromethoxy, carbazolyl).

[0008] In the above technical solution, the alkali is one of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, sodium ethoxide, potassium methoxide, potassium hydroxide, triethylamine, 1,8-diazobisspirocyclic[5.4.0]undec-7-ene, potassium phosphate, and cesium carbonate.

[0009] In the above technical solution, the organic solvent is one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, acetonitrile, and 1,4-dioxane.

[0010] In the above technical solution, the molar ratio of the alkali, carbonyl compound, and alkynylthiane compound is (0.5-2.5):(1.0-2.5):1.

[0011] In the above technical solution, the specific reaction steps include: adding a carbonyl compound, an alkynylthiane compound, a suitable solvent, and a base sequentially to a reaction flask; stirring the reaction at 20℃~60℃ for 5~30 minutes; monitoring the reaction using thin-layer chromatography; quenching the reaction with 10 mL of water after the raw materials are completely consumed; extracting the reaction three times with ethyl acetate; combining all organic phases and washing three more times with saturated brine; drying; filtering; concentrating the filtrate under reduced pressure; and purifying the product by silica gel column chromatography with petroleum ether / ethyl acetate. Detailed Implementation

[0012] The following examples are intended to provide a more comprehensive understanding of the present invention by those skilled in the art, but do not limit the invention in any way. All raw materials used in this invention are known compounds, which can be commercially available or synthesized using methods known in the art.

[0013] Example 1: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-phenylprop-2-en-1-one:

[0014] In a 25 mL round-bottom flask, anisaldehyde (27 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-phenylprop-2-en-1-one, with a yield of 79%.

[0015] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-phenylprop-2-en-1-one obtained in Example 1 are as follows:

[0016]

[0017] 1 H NMR(400MHz,Chloroform-d)δ7.73(s,1H),7.47–7.35(m,3H),7.31–7.23(m,3H),7.00–6.91(m,2H),6.67(d,J=8 .9Hz,2H),4.41(s,1H),3.74(s,3H),3.48–3.35(m,2H),2.59–2.48(m,2H),2.21–2.08(m,1H),2.07–1.88(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.4,160.7,139.8,137.0,136.0,133.0,130.1,129.5,128.3,127.4,113.9,55.3,41.3,25.8,25.3.

[0018] Example 2: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(4-(methylthio)phenyl)-2-phenylprop-2-en-1-one:

[0019] In a 25 mL round-bottom flask, 30 mg (0.2 mmol) of 4-(methylthio)benzaldehyde, 44 mg (0.2 mmol) of 2-(phenylethynyl)-1,3-dithiane, and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with petroleum ether / ethyl acetate to obtain (E)-1-(1,3-Dithian-2-yl)-3-(4-(methylthio)phenyl)-2-phenylprop-2-en-1-one, in 74% yield.

[0020] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(4-(methylthio)phenyl)-2-phenylprop-2-en-1-one obtained in Example 2 are as follows:

[0021]

[0022] 1 H NMR(400MHz,Chloroform-d)δ7.44–7.37(m,3H),7.27–7.24(m,2H),6.98(d,J=8.8Hz,2H),6.91(d,J=8.6Hz ,2H),4.41(s,1H),3.47–3.35(m,2H),2.57–2.49(m,2H),2.40(s,3H),2.21–2.10(m,1H),2.04–1.88(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.2,141.3,139.4,137.5,136.7,131.4,131.1,129.9,129.5,128.4,125.4,41.3,25.7,25.3,15.0.

[0023] Example 3: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one:

[0024] In a 25 mL round-bottom flask, 4-(trifluoromethoxy)benzaldehyde (38 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one, with a yield of 69%.

[0025] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one obtained in Example 3 are as follows:

[0026]

[0027] 1 H NMR(400MHz,Chloroform-d)δ7.70(s,1H),7.46–7.39(m,3H),7.27–7.23(m,2H),7.06–7.01(m,2H),7.0 1–6.96(m,2H),4.40(s,1H),3.46–3.34(m,2H),2.59–2.50(m,2H),2.20–2.09(m,1H),2.03–1.90(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.0,149.6,139.2,137.8,136.0,133.3,132.5,129.8,129.6,128.7,120.5,120.4(q,J=258.1Hz),41.4,25.7,25.2.

[0028] Example 4: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(4-fluorophenyl)-2-phenylprop-2-en-1-one:

[0029] In a 25 mL round-bottom flask, 25 mg of 4-fluorobenzaldehyde (0.2 mmol), 44 mg of 2-(phenylethynyl)-1,3-dithiane (0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(4-fluorophenyl)-2-phenylprop-2-en-1-one, with a yield of 75%.

[0030] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(4-fluorophenyl)-2-phenylprop-2-en-1-one obtained in Example 4 are as follows:

[0031]

[0032] 1 H NMR(400MHz,Chloroform-d)δ7.70(s,1H),7.47–7.37(m,3H),7.28–7.22(m,2H),7.05–6.96(m,2H),6.83( t,J=8.5Hz,2H),4.40(s,1H),3.49–3.25(m,2H),2.62–2.49(m,2H),2.23–2.10(m,1H),2.06–1.88(m,1H). 13 C NMR(101MHz,Chloroform-d)δ193.2,163.2(d,J=251.9Hz),138.5,138.2,136.3,133.0(d, J=8.5Hz),131.0(d,J=3.8Hz),129.9,129.6,128.6,115.6(d,J=21.3Hz),41.4,25.7,25.3.

[0033] Example 5: Preparation of compound (E)-3-(4-Chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0034] In a 25 mL round-bottom flask, 28 mg of 4-chlorobenzaldehyde (0.2 mmol), 44 mg of 2-(phenylethynyl)-1,3-dithiane (0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(4-Chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 76%.

[0035] The structure and NMR data of the product (E)-3-(4-Chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 5 are as follows:

[0036]

[0037] 1 H NMR(400MHz,Chloroform-d)δ7.67(s,1H),7.45–7.37(m,3H),7.26–7.22(m,2H),7.12(d,J=8.4Hz,2H),6.9 3(d,J=8.4Hz,2H),4.39(s,1H),3.47–3.33(m,2H),2.61–2.47(m,2H),2.23–2.11(m,1H),2.05–1.89(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.0,139.0,138.2,136.1,135.4,133.2,132.2,129.8,129.6,128.7,128.6,41.3,25.7,25.2.

[0038] Example 6: Preparation of compound (E)-3-(4-Bromophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0039] In a 25 mL round-bottom flask, 4-bromobenzaldehyde (37 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(4-Bromophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 71%.

[0040] The structure and NMR data of the product (E)-3-(4-Bromophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 6 are as follows:

[0041]

[0042] 1 H NMR(400MHz,Chloroform-d)δ7.64(s,1H),7.43–7.36(m,3H),7.27–7.20(m,4H),6.84(d,J=8.4H z,2H),4.37(s,1H),3.43–3.31(m,2H),2.59–2.47(m,2H),2.18–2.07(m,1H),2.01–1.86(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.0,139.1,138.3,136.1,133.6,132.4,131.6,129.8,129.6,128.6,123.9,41.3,25.6,25.2.

[0043] Example 7: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one:

[0044] In a 25 mL round-bottom flask, 35 mg of 4-trifluoromethylbenzaldehyde (0.2 mmol), 44 mg of 2-(phenylethynyl)-1,3-dithiane (0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one, with a yield of 65%.

[0045] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one obtained in Example 7 are as follows:

[0046]

[0047] 1 H NMR(600MHz,Chloroform-d)δ7.72(s,1H),7.46–7.37(m,5H),7.26–7.22(m,2H),7.11(d,J=8.2H z,2H),4.40(s,1H),3.43–3.32(m,2H),2.60–2.52(m,2H),2.20–2.13(m,1H),2.03–1.92(m,1H). 13 C NMR (101MHz, Chloroform-d) δ192.9,140.8,138.2,137.5,135.8,130.9,130.7 (q, J=32. 4Hz), 129.8, 129.6, 128.8, 125.2 (q, J = 3.8Hz), 121.2 (d, J = 272.3Hz), 41.4, 25.6, 25.2.

[0048] Example 8: Preparation of compound (E)-3-(3-Chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0049] In a 25 mL round-bottom flask, 28 mg of 3-chlorobenzaldehyde (0.2 mmol), 44 mg of 2-(phenylethynyl)-1,3-dithiane (0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(3-Chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 74%.

[0050] The structure and NMR data of the product (E)-3-(3-Chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 8 are as follows:

[0051]

[0052] 1 H NMR(400MHz,Chloroform-d)δ7.64(s,1H),7.46–7.39(m,3H),7.26–7.22(m,2H),7.19–7.15(m,1H),7.07(t,J=7.9Hz,1H),6.97( t,J=1.9Hz,1H),6.88(d,J=8.0Hz,1H),4.40(s,1H),3.44–3.34(m,2H),2.61–2.51(m,2H),2.20–2.12(m,1H),2.04–1.90(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.0,139.9,137.9,136.6,135.9,134.3,130.8,129.8,129.6,129.3,129.0,128.7,41.5,25.7,25.3.

[0053] Example 9: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(2-methoxyphenyl)-2-phenylprop-2-en-1-one:

[0054] In a 25 mL round-bottom flask, 27 mg of 3-methoxybenzaldehyde (0.2 mmol), 44 mg of 2-(phenylethynyl)-1,3-dithiane (0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(2-methoxyphenyl)-2-phenylprop-2-en-1-one, with a yield of 70%.

[0055] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(2-methoxyphenyl)-2-phenylprop-2-en-1-one obtained in Example 9 are as follows:

[0056]

[0057] 1 H NMR(400MHz,Chloroform-d)δ8.07(s,1H),7.38–7.29(m,3H),7.25–7.21(m,2H),7.20–7.14(m,1H),6.83(d,J=8.5Hz,1H),6.64(dd,J=7.8 ,1.7Hz,1H),6.54(t,J=7.6Hz,1H),4.56(s,1H),3.85(s,3H),3.50–3.32(m,2H),2.62–2.47(m,2H),2.21–2.08(m,1H),2.05–1.90(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.9,158.8,138.3,136.7,134.4,130.8,130.6,130.1,129.1,128.1,123.8,120.0,110.7,55.7,41.3,25.7,25.3.

[0058] Example 10: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(2,4,6-trimethoxyphenyl)prop-2-en-1-one:

[0059] In a 25 mL round-bottom flask, 2,4,6-trimethoxybenzaldehyde (38 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(2,4,6-trimethoxyphenyl)prop-2-en-1-one, with a yield of 62%.

[0060] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(2,4,6-trimethoxyphenyl)prop-2-en-1-one obtained in Example 10 are as follows:

[0061]

[0062] 1 H NMR(400MHz,Chloroform-d)δ7.62(s,1H),7.25–7.16(m,3H),7.15–7.08(m,2H),5.94(s,2H),4.7 3(s,1H),3.77(s,3H),3.52–3.39(m,8H),2.63–2.54(m,2H),2.19–2.11(m,1H),2.07–1.94(m,1H). 13 C NMR (101MHz, Chloroform-d) δ194.9,162.6,159.1,139.7,138.6,133.3,129.3,127.8,127.1,106.7,90.4,55.2,41.9,26.1,25.5.

[0063] Example 11: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one:

[0064] In a 25 mL round-bottom flask, 3,4,5-trimethoxybenzaldehyde (38 mg, 0.2 mmol), anisaldehyde (27 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-phenyl-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one, with a yield of 73%.

[0065] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-phenylprop-2-en-1-one obtained in Example 11 are as follows:

[0066]

[0067] 1 H NMR(400MHz,Chloroform-d)δ7.67(s,1H),7.49–7.42(m,2H),7.40–7.35(m,1H),7.34–7.30(m,2H),6.29(s,2H),4 .43(s,1H),3.80(s,3H),3.53(s,6H),3.46–3.32(m,2H),2.60–2.49(m,2H),2.21–2.11(m,1H),2.04–1.91(m,1H). 13 C NMR (101MHz, Chloroform-d) δ192.9,152.8,139.8,139.4,137.4,136.9,130.2,129.9,129.6,128.4,108.6,61.0,55.8,41.4,25.8,25.3.

[0068] Example 12: Preparation of compound (E)-3-(4-(Diphenylamino)phenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0069] In a 25 mL round-bottom flask, 4-diphenylaminobenzaldehyde (55 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(4-(Diphenylamino)phenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 76%.

[0070] The structure and NMR data of the product (E)-3-(4-(Diphenylamino)phenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 12 are as follows:

[0071]

[0072] 1 H NMR(400MHz,Chloroform-d)δ7.70(s,1H),7.44–7.38(m,2H),7.37–7.33(m,1H),7.30–7.26(m,3H),7.25–7.21(m,3H),7.08–7.03(m,6H) ),6.84(d,J=8.9Hz,2H),6.74(d,J=8.6Hz,2H),4.40(s,1H),3.48–3.37(m,2H),2.59–2.47(m,2H),2.21–2.08(m,1H),2.04–1.87(m,1H). 13 C NMR(101MHz,Chloroform-d)δ193.3,149.3,146.9,139.9,137.3,135.4,132. 6,130.1,129.6,129.5,128.3,125.7,125.3,124.2,120.8,41.3,25.8,25.4.

[0073] Example 13: Preparation of compound (E)-3-(2-(Diphenylphosphaneyl)phenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0074] In a 25 mL round-bottom flask, 2-(diphenylphosphine)benzaldehyde (58 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(2-(Diphenylphosphaneyl)phenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 61%.

[0075] The structure and NMR data of the product (E)-3-(2-(Diphenylphosphaneyl)phenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 13 are as follows:

[0076]

[0077] 1 H NMR(400MHz,Chloroform-d)δ8.20(d,J=4.0Hz,1H),7.38–7.30(m,10H),7.22–7.16(m,3H),7.08(t,J=7.5Hz,1H),6.95(t,J=7.5Hz,1H),6.90(dd,J=7. 8,4.1Hz,1H),6.86–6.81(m,2H),6.76(dd,J=7.9,4.2Hz,1H),4.40(s,1H), 3.33–3.20(m,2H),2.52–2.43(m,2H),2.15–2.04(m,1H),2.00–1.87(m,1H). 13 C NMR(101MHz,Chloroform-d)δ193.7,140.1(d,J=2.5Hz),139.7(d,J=22.7Hz),139.2(d,J=14.2Hz),137.9(d,J=23.7Hz),135.8( d,J=9.6Hz),134.6,134.4,132.6,130.4(d,J=3.9Hz),130.1,129.2,128.8,128.8,128.6,128.0(d,J=18.3Hz),42.1,25.8,25.3.

[0078] Example 14 Preparation of compound (E)-3-(5-Chloro-1,3-dimethyl-1H-pyrazol-4-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0079] In a 25 mL round-bottom flask, 32 mg (0.2 mmol) of 5-chloro-1,3-dimethyl-1H-pyrazol-4-carboxaldehyde, 44 mg (0.2 mmol) of 2-(phenylethynyl)-1,3-dithiane (0.2 mmol) and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(5-Chloro-1,3-dimethyl-1H-pyrazol-4-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 77%.

[0080] The structure and NMR data of the product (E)-3-(5-Chloro-1,3-dimethyl-1H-pyrazol-4-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 14 are as follows:

[0081]

[0082] 1 H NMR(400MHz,Chloroform-d)δ7.39(s,1H),7.35–7.28(m,3H),7.24–7.19(m,2H),4.54(s,1H),3.7 1(s,3H),3.47–3.34(m,2H),2.62–2.52(m,2H),2.20–2.10(m,1H),2.06–1.92(m,1H),1.52(s,3H). 13 C NMR (101MHz, Chloroform-d) δ194.3,147.8,139.1,136.6,130.5,129.5,129.0,128.9,128.2,112.7,41.9,36.3,25.9,25.3,13.6.

[0083] Example 15: Preparation of compound (E)-3-(6-Bromobenzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0084] In a 25 mL round-bottom flask, 6-bromopiperaldehyde (46 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(6-Bromobenzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 60%.

[0085] The structure and NMR data of the product (E)-3-(6-Bromobenzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 15 are as follows:

[0086]

[0087] 1 H NMR(400MHz,Chloroform-d)δ7.83(s,1H),7.41–7.32(m,3H),7.20(dd,J=7.3,2.0Hz,2H),7.02(s,1H),6.14( s,1H),5.86(s,2H),4.51(s,1H),3.45–3.35(m,2H),2.61–2.52(m,2H),2.20–2.10(m,1H),2.07–1.92(m,1H). 13 C NMR (101MHz, Chloroform-d) δ193.6,149.1,146.9,139.2,138.1,135.5,130.1,129.2,128.5,128.3,118.6,113.0,110.4,102.0,41.9,25.8,25.3.

[0088] Example 16: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one:

[0089] In a 25 mL round-bottom flask, 2-thiophenecarboxaldehyde (22 mg, 0.2 mmol), 2-((6-methoxynaphthalen-2-yl)ethynyl)-1,3-dithiane (60 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the reaction was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one, with a yield of 71%.

[0090] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one obtained in Example 16 are as follows:

[0091]

[0092] 1 H NMR(400MHz,Chloroform-d)δ8.11(s,1H),7.87(d,J=8.4Hz,1H),7.78–7.72(m,2H),7.34(dd,J=8.4,1.8Hz,1H),7.19(d,J=8.3Hz,3H),7.1 6(d,J=5.0Hz,1H),6.93–6.88(m,1H),4.38(s,1H),3.96(s,3H),3.47– 3.37(m,2H),2.58–2.48(m,2H),2.20–2.10(m,1H),2.02–1.87(m,1H). 13C NMR(101MHz,Chloroform-d)δ192.4,158.5,139.3,135.2,134.8,134.5,133.8,131.6, 130.7,129.9,129.9,129.6,128.5,128.3,126.9,119.4,105.9,55.5,41.6,25.8,25.3.

[0093] Example 17: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(1-methyl-1H-indol-3-yl)prop-2-en-1-one:

[0094] In a 25 mL round-bottom flask, 1-methylindol-3-carboxaldehyde (32 mg, 0.2 mmol), 2-((6-methoxynaphthalen-2-yl)ethynyl)-1,3-dithiaane (60 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the reaction was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(1-methyl-1H-indol-3-yl)prop-2-en-1-one, with a yield of 81%.

[0095] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(1-methyl-1H-indol-3-yl)prop-2-en-1-one obtained in Example 17 are as follows:

[0096]

[0097] 1H NMR(400MHz,Chloroform-d)δ8.35(s,1H),7.88–7.83(m,2H),7.77–7.71(m,2H),7.40(dd,J=8.3,1.7Hz,1H),7.24–7.16(m,5H), 5.98(s,1H),4.48(s,1H),3.96(s,3H),3.53–3.44(m,2H),3.42(s,3H),2.61–2.49(m,2H),2.20–2.09(m,1H),2.02–1.89(m,1H). 13 C NMR(101MHz,Chloroform-d)δ192.9,158.2,136.4,134.3,133.7,132.9,132.1,131.7,129.8,129.7,129 .0,128.8,128.6,128.4,123.0,121.2,119.2,118.8,111.4,109.7,105.9,55.5,41.8,33.4,26.1,25.5.

[0098] Example 18: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one:

[0099] In a 25 mL round-bottom flask, anisaldehyde (27 mg, 0.2 mmol), 2-((6-methoxynaphthalen-2-yl)ethynyl)-1,3-dithiaane (60 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one, with a yield of 76%.

[0100] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-2-(6-methoxynaphthalen-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one obtained in Example 18 are as follows:

[0101]

[0102] 1 H NMR(400MHz,Chloroform-d)δ7.82–7.76(m,2H),7.73–7.68(m,2H),7.32(dd,J=8.4,1.6Hz,1H),7.20–7.15(m,2H),6.99(d,J=8.9Hz,2H), 6.62(d,J=8.9Hz,2H),4.43(s,1H),3.95(s,3H),3.71(s,3H),3.47–3.35(m,2H),2.58–2.49(m,2H),2.18–2.09(m,1H),2.02–1.88(m,1H). 13 C NMR(101MHz,Chloroform-d)δ193.8,160.7,158.3,139.9,136.0,134.3,133.1,132.0,129 .8,129.4,128.9,128.5,128.1,127.5,119.4,114.0,105.9,55.5,55.3,41.5,25.8,25.3.

[0103] Example 19: Preparation of compound (E)-3-(5-(4-Bromophenyl)furan-2-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0104] In a 25 mL round-bottom flask, 5-(4-bromophenyl)furfural (50 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(5-(4-Bromophenyl)furan-2-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 65%.

[0105] The structure and NMR data of the product (E)-3-(5-(4-Bromophenyl)furan-2-yl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 19 are as follows:

[0106]

[0107] 1 H NMR(400MHz,Chloroform-d)δ7.66(s,1H),7.50–7.45(m,3H),7.42–7.38(m,2H),7.36–7.31(m,2H),7.13–7.08(m,2H),6.56(d ,J=3.6Hz,1H),6.19(d,J=3.6Hz,1H),4.40(s,1H),3.48–3.36(m,2H),2.59–2.49(m,2H),2.20–2.11(m,1H),2.03–1.91(m,1H). 13 CNMR(101MHz,Chloroform-d)δ192.1,155.2,151.1,137.2,134.8,132.0,129 .6,129.3,128.7,128.2,126.7,125.8,122.4,119.3,108.2,41.4,25.8,25.3.

[0108] Example 20: Preparation of compound (E)-3-(2,3-Dihydrobenzofuran-5-yl)-1-(1,3-dithian-2-yl)-2-(3-methoxyphenyl)prop-2-en-1-one:

[0109] In a 25 mL round-bottom flask, 2,3-dihydrobenzofuran-5-carboxaldehyde (30 mg, 0.2 mmol), 2-((3-methoxyphenyl)ethynyl)-1,3-dithiane (50 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the reaction was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-3-(2,3-Dihydrobenzofuran-5-yl)-1-(1,3-dithian-2-yl)-2-(3-methoxyphenyl)prop-2-en-1-one, with a yield of 63%.

[0110] The structure and NMR data of the product (E)-3-(2,3-Dihydrobenzofuran-5-yl)-1-(1,3-dithian-2-yl)-2-(3-methoxyphenyl)prop-2-en-1-one obtained in Example 20 are as follows:

[0111]

[0112] 1 H NMR(600MHz,Chloroform-d)δ7.72(s,1H),7.37–7.32(m,1H),6.96–6.91(m,1H),6.89(dd,J=8.5,2.0Hz,1H),6.88–6.82(m,3H),6.58(d,J=8.4Hz,1H ),4.54(t,J=8.7Hz,2H),4.38(s,1H),3.80(s,3H),3.47–3.40(m,2H),3.05 (t,J=8.7Hz,2H),2.57–2.51(m,2H),2.19–2.13(m,1H),2.01–1.92(m,1H). 13 C NMR(151MHz,Chloroform-d)δ193.3,161.7,160.5,140.4,138.5,135.0,132.8,130 .7,128.0,127.5,127.4,122.3,115.0,114.2,109.5,71.9,55.5,29.3,25.7,25.3.

[0113] Example 21: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(naphthalen-2-yl)-2-phenylprop-2-en-1-one:

[0114] In a 25 mL round-bottom flask, 31 mg of 2-naphthaldehyde (0.2 mmol), 44 mg of 2-(phenylethynyl)-1,3-dithiane (0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(naphthalen-2-yl)-2-phenylprop-2-en-1-one, with a yield of 69%.

[0115] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(naphthalen-2-yl)-2-phenylprop-2-en-1-one obtained in Example 21 are as follows:

[0116]

[0117] 1 H NMR(400MHz,Chloroform-d)δ7.91(s,2H),7.93–7.78(m,4H),7.62–7.53(m,2H),7.55–7.44(m,3H),7.46–7.32(m,5 H),7.33(s,2H),4.11(s,1H),3.37–3.24(m,2H),2.49(dt,J=13.8,2.6Hz,2H),2.15–2.04(m,1H),1.97–1.80(m,1H). 13 CNMR(101MHz,Chloroform-d)δ193.4,139.9,138.6,136.6,133.5,133.0,132.4,132 .3,130.2,129.4,128.7,128.5,127.8,127.6,127.3,127.1,126.4,41.4,25.7,25.3.

[0118] Example 22: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(9-ethyl-9H-carbazol-3-yl)-2-phenylprop-2-en-1-one:

[0119] In a 25 mL round-bottom flask, N-ethylcarbazole-3-carbaldehyde (45 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(9-ethyl-9H-carbazol-3-yl)-2-phenylprop-2-en-1-one, with a yield of 73%.

[0120] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(9-ethyl-9H-carbazol-3-yl)-2-phenylprop-2-en-1-one from Example 22 are as follows:

[0121]

[0122] 1 H NMR(400MHz,Chloroform-d)δ8.01(s,1H),7.75(d,J=7.8Hz,1H),7.68(s,1H) ,7.52–7.45(m,3H),7.43(d,J=7.5Hz,1H),7.39–7.33(m,3H),7.22–7.15(m,3 H),4.52(s,1H),4.28(q,J=7.2Hz,2H),3.47(ddd,J=13.8,11.2,2.6Hz,2H),2 .62–2.52(m,2H),2.22–2.13(m,1H),2.06–1.92(m,1H),1.38(t,J=7.2Hz,3H). 13C NMR(101MHz,Chloroform-d)δ193.5,141.7,140.7,140.5,137.7,135.2,130.3,129.8,129.7,128.2,126.3,125. 6,124.1,123.1,120.5,119.7,108.9,108.3,77.5,77.2,76.8,41.5,37.8,25.9,25.5,13.9.ESI-MS(TOF):[M+H] + calcd.for C 27 H 26 NOS2 + 444.1450, found 444.1450.

[0123] Example 23: Preparation of compound (E)-1,1-Bis(ethylthio)-4-(4-methoxyphenyl)-3-phenylbut-3-en-2-one:

[0124] In a 25 mL round-bottom flask, anisaldehyde (27 mg, 0.2 mmol), (3-phenylprop-2-yne-1,1-diyl)bis(ethylsulfane) (47 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1,1-Bis(ethylthio)-4-(4-methoxyphenyl)-3-phenylbut-3-en-2-one, with a yield of 73%.

[0125] The structure and NMR data of the product (E)-1,1-Bis(ethylthio)-4-(4-methoxyphenyl)-3-phenylbut-3-en-2-one obtained in Example 23 are as follows:

[0126]

[0127] 1H NMR(600MHz,Chloroform-d)δ7.74(s,1H),7.47–7.38(m,3H),7.35–7.29(m,2H),6.97(d,J=8.9Hz,2H),6. 67(d,J=8.9Hz,2H),4.69(s,1H),3.75(s,3H),2.66–2.58(m,2H),2.56–2.48(m,2H),1.17(t,J=7.5Hz,6H). 13 C NMR (151MHz, Chloroform-d) δ192.1,160.7,140.0,137.0,135.9,133.1,130.2,129.4,128.3,127.3,113.9,55.3,54.1,24.0,14.2.

[0128] Example 24: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-4,4-dimethyl-2-phenylpent-2-en-1-one:

[0129] In a 25 mL round-bottom flask, trimethylacetaldehyde (34 mg, 0.4 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of N,N-dimethylformamide were added sequentially. Potassium tert-butoxide (45 mg, 0.4 mmol) was then added. The mixture was stirred at 60 °C for 5 minutes, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-4,4-dimethyl-2-phenylpent-2-en-1-one, with a yield of 53%.

[0130] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-4,4-dimethyl-2-phenylpent-2-en-1-one obtained in Example 24 are as follows:

[0131]

[0132] 1H NMR(400MHz,Chloroform-d)δ7.38–7.30(m,3H),7.25–7.17(m,2H),6.97(s,1H),4.27(s,1H) ),3.41–3.28(m,2H),2.54–2.45(m,2H),2.17–2.07(m,1H),1.99–1.85(m,1H),0.92(s,9H). 13 C NMR(101MHz,Chloroform-d)δ193.8,153.0,137.2,136.5,130.6,128.2,127.9,40.9,34.6,30.5,25.6,25.3.ESI-MS(TOF):[M+Na] + calcd.for C 17 H 22 OS2Na + 329.1004, found 329.1017.

[0133] Example 25: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-2-(3-methoxyphenyl)-4,4-dimethylpent-2-en-1-one:

[0134] In a 25 mL round-bottom flask, trimethylacetaldehyde (34 mg, 0.4 mmol), 2-((3-methoxyphenyl)ethynyl)-1,3-dithiane (50 mg, 0.2 mmol), and 4 mL of N,N-dimethylformamide were added sequentially. Potassium tert-butoxide (45 mg, 0.4 mmol) was then added. The mixture was stirred at 60 °C for 5 minutes, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-2-(3-methoxyphenyl)-4,4-dimethylpent-2-en-1-one, with a yield of 57%.

[0135] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-2-(3-methoxyphenyl)-4,4-dimethylpent-2-en-1-one obtained in Example 25 are as follows:

[0136]

[0137] 1H NMR(400MHz,Chloroform-d)δ7.24(d,J=7.9Hz,1H),6.88–6.82(m,2H),6.80(t,J=2.1Hz,1H),5.91(s,1H),4.37(s,1H ),3.81(s,3H),3.22(ddd,J=14.1,9.3,3.5Hz,2H),2.57(ddd,J=13.9,6.5,3.4Hz,2H),2.10–1.94(m,2H),1.21(s,9H). 13 C NMR (101MHz, Chloroform-d) δ198.8,159.8,148.7,140.8,137.8,129.8,120.0,113.7,112.9,77.5,77.2,76.8,55.5,47.6,34.7,30.3,27.1,25.2.

[0138] Example 26: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one:

[0139] In a 25 mL round-bottom flask, anisaldehyde (27 mg, 0.2 mmol), 2-((4-(trifluoromethoxy)phenyl)ethynyl)-1,3-dithiane (60 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one, with a yield of 69%.

[0140] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one obtained in Example 26 are as follows:

[0141]

[0142] 1 H NMR(400MHz,Chloroform-d)δ7.72(s,1H),7.34–7.26(m,4H),6.94(d,J=9.0Hz,2H),6.74–6.65(m,2H) ,4.48(s,1H),3.76(s,3H),3.47–3.32(m,2H),2.62–2.50(m,2H),2.19–2.10(m,1H),2.06–1.92(m,1H). 13 C NMR(101MHz,Chloroform-d)δ192.9,161.0,149.2,140.7,135.5,134.7,132. 9,131.8,126.9,121.7,120.6(q,J=257.7Hz),114.1,55.4,41.6,25.9,25.3.

[0143] Example 27: Preparation of compound (E)-2-(3,4-Dimethoxyphenyl)-1-(1,3-dithian-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one:

[0144] In a 25 mL round-bottom flask, anisaldehyde (27 mg, 0.2 mmol), 2-((3,4-dimethoxyphenyl))ethynyl)-1,3-dithiane (56 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-2-(3,4-Dimethoxyphenyl)-1-(1,3-dithian-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one, with a yield of 75%.

[0145] The structure and NMR data of the product (E)-2-(3,4-Dimethoxyphenyl)-1-(1,3-dithian-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one obtained in Example 27 are as follows:

[0146]

[0147] 1H NMR(400MHz,Chloroform-d)δ7.70(s,1H),7.03(d,J=9.0Hz,2H),6.92(d,J=8.7Hz,1H),6.84–6.78(m,2H),6.70(d,J=9.0Hz,2H) ,4.42(s,1H),3.93(s,3H),3.82(s,3H),3.76(s,3H),3.48–3.37(m,2H),2.60–2.48(m,2H),2.20–2.10(m,1H),2.04–1.90(m,1H). 13 C NMR(101MHz,Chloroform-d)δ193.9,160.8,149.8,149.0,139.8,135.7,133.0 ,129.3,127.5,122.3,114.0,113.0,112.1,56.1,56.0,55.4,41.1,25.8,25.4.

[0148] Example 28: Preparation of compound (E)-2-(Benzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one:

[0149] In a 25 mL round-bottom flask, anisaldehyde (27 mg, 0.2 mmol), 5-((1,3-dithian-2-yl))ethynyl)benzo[d][1,3]dioxol-1-one (53 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-2-(Benzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one, with a yield of 70%.

[0150] The structure and NMR data of the product (E)-2-(Benzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-3-(4-methoxyphenyl)prop-2-en-1-one obtained in Example 28 are as follows:

[0151]

[0152] 1 H NMR(400MHz,Chloroform-d)δ7.68(s,1H),7.05(d,J=9.0Hz,2H),6.86(d,J=7.8Hz,1H),6.75–6.69(m,4H),6.0 2(s,2H),4.47(s,1H),3.77(s,3H),3.46–3.37(m,2H),2.59–2.50(m,2H),2.20–2.10(m,1H),2.05–1.90(m,1H). 13 C NMR(101MHz,Chloroform-d)δ193.6,160.8,148.6,147.7,140.0,135.5,133 .0,130.3,127.4,123.5,114.0,110.4,109.4,101.4,55.4,41.1,25.8,25.3.

[0153] Example 29: Preparation of compound (E)-2-(3,4-Dimethoxyphenyl)-1-(1,3-dithian-2-yl)-3-(pyren-1-yl)prop-2-en-1-one:

[0154] In a 25 mL round-bottom flask, 1-pyrenecarboxaldehyde (46 mg, 0.2 mmol), 2-((3,4-dimethoxyphenyl))ethynyl)-1,3-dithiane (56 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-2-(3,4-Dimethoxyphenyl)-1-(1,3-dithian-2-yl)-3-(pyren-1-yl)prop-2-en-1-one, with a yield of 43%.

[0155] The structure and NMR data of the product (E)-2-(3,4-Dimethoxyphenyl)-1-(1,3-dithian-2-yl)-3-(pyren-1-yl)prop-2-en-1-one obtained in Example 29 are as follows:

[0156]

[0157] 1 H NMR(400MHz,Chloroform-d)δ8.62(s,1H),8.42(d,J=9.2Hz,1H),8.22–8.14(m,3H ),8.06(d,J=8.8Hz,1H),8.02(t,J=7.7Hz,1H),7.95(d,J=8.8Hz,1H),7.83(d,J=8. 2Hz,1H),7.54(d,J=8.2Hz,1H),6.78–6.73(m,3H),4.65(s,1H),3.84(s,3H),3.60( s,3H),3.58–3.48(m,2H),2.72–2.60(m,2H),2.27–2.19(m,1H),2.12–2.02(m,1H). 13 C NMR(101MHz,Chloroform-d)δ194.9,149.3,149.1,140.6,137.1,131.7,131.4,131.0,130.5,129.7,128.4,128 .4,127.8,127.5,126.3,126.0,125.8,124.8,124.5,123.6,123.2,113.6,111.7,56.0,55.9,42.0,26.0,25.4.

[0158] Example 30: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-(9-phenyl-9H-carbazol-3-yl)prop-2-en-1-one:

[0159] In a 25 mL round-bottom flask, anisaldehyde (27 mg, 0.2 mmol), 3-((1,3-dithiazyl-2-yl))ethynyl)-9-phenyl-9H-carbazole (77 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the reaction was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-(9-phenyl-9H-carbazol-3-yl)prop-2-en-1-one, with a yield of 63%.

[0160] The structure and NMR data of the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-(9-phenyl-9H-carbazol-3-yl)prop-2-en-1-one obtained in Example 30 are as follows:

[0161]

[0162] 1 H NMR(400MHz,Chloroform-d)δ8.09(d,J=7.8Hz,1H),8.05(d,J=1.7Hz,1H),7.81(s,1H),7.66–7.59(m,4H),7.52–7.40(m,4H),7.32–7.26(m,2H),7 .02(d,J=8.8Hz,2H),6.63(d,J=9.0Hz,2H),4.49(s,1H),3.70(s,3H),3. 50–3.37(m,2H),2.59–2.48(m,2H),2.19–2.07(m,1H),2.02–1.88(m,1H). 13 C NMR(101MHz,Chloroform-d)δ194.3,160.6,141.4,140.7,139.7,137.6,136.6,133.1,130.1,128.3,127 .9,127.8,127.2,126.5,124.4,123.3,121.8,120.8,120.4,114.0,111.0,110.1,55.3,41.4,25.8,25.4.

[0163] Example 31: Preparation of compound 1-(1,3-Dithian-2-yl)-3,3-bis(4-fluorophenyl)-2-phenylprop-2-en-1-one:

[0164] In a 25 mL round-bottom flask, 4,4'-difluorobenzophenone (44 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product 1-(1,3-Dithian-2-yl)-3,3-bis(4-fluorophenyl)-2-phenylprop-2-en-1-one, with a yield of 71%.

[0165] The structure and NMR data of the product 1-(1,3-Dithian-2-yl)-3,3-bis(4-fluorophenyl)-2-phenylprop-2-en-1-one obtained in Example 31 are as follows:

[0166]

[0167] 1 H NMR(600MHz,Chloroform-d)δ7.32–7.27(m,2H),7.24–7.15(m,5H),7.11–7.06(m,2H),6.94–6.90(m,2H),6.83–6.7 7(m,2H),3.86(s,1H),3.23(ddd,J=14.4,12.3,2.6Hz,2H),2.52–2.43(m,2H),2.11–2.04(m,1H),1.95–1.86(m,1H). 13 C NMR(101MHz,Chloroform-d)δ197.8,162.39(d,J=249.2Hz),163.35(d,J=250.5Hz),146.3,140.5,139.4,137.4(d,J=3.3Hz),137.0(d,J =3.4Hz), 133.13 (d, J = 8.2Hz), 132.13 (d, J = 8.4Hz), 130.9, 128.6, 127.7, 116.29 (d, J = 21.6Hz), 115.08 (d, J = 21.6Hz), 44.5, 25.5, 24.8.

[0168] Example 32: Preparation of compound 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one:

[0169] In a 25 mL round-bottom flask, 4,4'-dichlorobenzophenone (50 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one, with a yield of 77%.

[0170] The structure and NMR data of the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 32 are as follows:

[0171]

[0172] 1 H NMR(400MHz,Chloroform-d)δ7.40–7.33(m,2H),7.26–7.23(m,2H),7.23–7.17(m,5H),7.11–7.05(m,2H),6 .90–6.84(m,2H),3.88(s,1H),3.28–3.14(m,2H),2.54–2.43(m,2H),2.13–2.03(m,1H),1.99–1.84(m,1H). 13 C NMR(101MHz,Chloroform-d)δ197.4,146.0,141.0,139.7,139.3,138.9,135. 5,134.2,132.6,131.4,130.8,129.4,128.7,128.3,127.9,44.5,25.5,24.8.

[0173] Example 33: Preparation of compound (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-phenylprop-2-en-1-one:

[0174] In a 25 mL round-bottom flask, 4,4'-dibromobenzophenone (68 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (E)-1-(1,3-Dithian-2-yl)-3-(4-methoxyphenyl)-2-phenylprop-2-en-1-one, with a yield of 70%.

[0175] The structure and NMR data of the product 3,3-Bis(4-bromophenyl)-1-(1,3-dithian-2-yl)-2-phenylprop-2-en-1-one obtained in Example 33 are as follows:

[0176]

[0177] 1 H NMR(600MHz,Chloroform-d)δ7.53–7.49(m,2H),7.24–7.17(m,9H),6.82–6.77(m,2H),3 .87(s,1H),3.26–3.17(m,2H),2.52–2.44(m,2H),2.11–2.05(m,1H),1.96–1.86(m,1H). 13 C NMR(151MHz,Chloroform-d)δ197.3,146.0,141.0,140.0,139.7,138.8,132. 8,132.3,131.7,131.2,130.8,128.7,127.9,123.8,122.6,44.4,25.5,24.7.

[0178] Example 34: Preparation of compound 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(4-methoxyphenyl)prop-2-en-1-one:

[0179] In a 25 mL round-bottom flask, 4,4'-dichlorobenzophenone (50 mg, 0.2 mmol), 2-((4-methoxyphenyl)ethynyl)-1,3-dithiane (50 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(4-methoxyphenyl)prop-2-en-1-one, with a yield of 76%.

[0180] The structure and NMR data of the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(4-methoxyphenyl)prop-2-en-1-one obtained in Example 34 are as follows:

[0181]

[0182] 1 H NMR(400MHz,Chloroform-d)δ7.37–7.29(m,2H),7.25–7.19(m,2H),7.13–7.04(m,4H),6.92–6.84(m,2H),6.77–6 .68(m,2H),3.89(s,1H),3.75(s,3H),3.30–3.16(m,2H),2.53–2.40(m,2H),2.13–2.00(m,1H),1.97–1.82(m,1H). 13 CNMR(101MHz,Chloroform-d)δ197.8,159.1,145.1,140.6,139.8,139.6,135.3, 134.0,132.5,132.1,131.4,131.2,129.3,128.3,114.1,55.2,44.4,25.5,24.7.

[0183] Example 35: Preparation of compound 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one:

[0184] In a 25 mL round-bottom flask, 4,4'-dichlorobenzophenone (50 mg, 0.2 mmol), 2-((4-(trifluoromethoxy)phenyl)ethynyl)-1,3-dithiane (60 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the reaction was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(4-(trifluoromethoxy)phenyl)prop-2-en-1-on, with a yield of 72%.

[0185] The structure and NMR data of the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one obtained in Example 35 are as follows:

[0186]

[0187] 1 H NMR(400MHz,Chloroform-d)δ7.38(d,J=8.4Hz,2H),7.26–7.20(m,4H),7.11(d,J=8.3Hz,2H),7.05(d,J=8.2Hz, 2H),6.90–6.82(m,2H),3.81(s,1H),3.27–3.15(m,2H),2.54–2.44(m,2H),2.14–2.04(m,1H),1.96–1.83(m,1H). 13 CNMR(101MHz,Chloroform-d)δ197.2,148.7,146.5,139.7,139.2,138.8,137.7,136.0,1 34.7,132.5,132.4,131.6,129.6,128.5,120.8,120.5(q,J=257.6Hz),44.6,25.5,24.6.

[0188] Example 36: Preparation of compound 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(3,4,5-trimethoxyphenyl)prop-2-en-1-one:

[0189] In a 25 mL round-bottom flask, 4,4'-dichlorobenzophenone (50 mg, 0.2 mmol), 2-((3,4,5-trimethoxyphenyl)ethynyl)-1,3-dithiane (62 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the reaction was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(3,4,5-trimethoxyphenyl)prop-2-en-1-one, with a yield of 74%.

[0190] The structure and NMR data of the product 3,3-Bis(4-chlorophenyl)-1-(1,3-dithian-2-yl)-2-(3,4,5-trimethoxyphenyl)prop-2-en-1-one obtained in Example 36 are as follows:

[0191]

[0192] 1 H NMR(400MHz,Chloroform-d)δ7.36(d,J=8.3Hz,2H),7.25(s,2H),7.13(d,J=8.6Hz,2H),6.91(d,J=8.5Hz,2H),6.44(s, 2H),3.89(s,1H),3.82(s,3H),3.61(s,6H),3.37–3.19(m,2H),2.57–2.42(m,2H),2.16–2.05(m,1H),2.00–1.86(m,1H). 13 C NMR(101MHz,Chloroform-d)δ197.6,153.2,145.4,140.8,139.6,139.4,137.8,135 .5,134.3,133.8,132.2,131.4,129.3,128.3,108.2,61.0,56.0,44.1,25.4,24.6.

[0193] Example 37: Preparation of compound 2-(Benzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-3,3-bis(3-fluorophenyl)prop-2-en-1-one:

[0194] In a 25 mL round-bottom flask, 3,3'-difluorobenzophenone (44 mg, 0.2 mmol), 5-((1,3-dithian-2-yl))ethynyl)benzo[d][1,3]dioxol-1-one (53 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 10 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product 2-(Benzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-3,3-bis(3-fluorophenyl)prop-2-en-1-one, with a yield of 69%.

[0195] The structure and NMR data of the product 2-(Benzo[d][1,3]dioxol-5-yl)-1-(1,3-dithian-2-yl)-3,3-bis(3-fluorophenyl)prop-2-en-1-one obtained in Example 37 are as follows:

[0196]

[0197] 1 H NMR(400MHz,Chloroform-d)δ7.36(td,J=8.1,5.9Hz,1H),7.15–7.04(m,3H),7.03–6.97(m,1H),6.91–6.83(m,1H),6.78(d,J=7.6Hz,1H),6.75(d ,J=1.8Hz,1H),6.72–6.66(m,2H),6.63(d,J=8.0Hz,1H),5.90(s,2H),3. 31–3.14(m,2H),2.56–2.40(m,2H),2.14–2.01(m,1H),1.98–1.81(m,1H). 13C NMR(101MHz,Chloroform-d)δ197.1,162.9(d,J=248.6Hz),162.4(d,J=246.4Hz),147.8,14 7.3,145.1,143.1(d,J=7.4Hz),142.9(d,J=7.6Hz),141.2,132.4,130.7(d,J=8.4Hz),129.6 (d,J=8.4Hz),126.8(d,J=3.2Hz),126.0(d,J=2.9Hz),125.0,117.8(d,J=22.1Hz),116.(d,J =21.9Hz),116.4(d,J=21.1Hz),115.2(d,J=21.2Hz),110.7,108.5,101.2,44.3,25.4,24.7.

[0198] Example 38: Preparation of compound 1,1-Bis(ethylthio)-3,4,4-triphenylbut-3-en-2-one:

[0199] In a 25 mL round-bottom flask, benzophenone (36 mg, 0.2 mmol), (3-phenylprop-2-yne-1,1-diyl)bis(ethylsulfane) (47 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was then added. The mixture was stirred at 20 °C for 10 min, and the reaction was quenched with 10 mL of water. The mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product 1,1-Bis(ethylthio)-3,4,4-triphenylbut-3-en-2-one, with a yield of 65%.

[0200] The structure and NMR data of the product 1,1-Bis(ethylthio)-3,4,4-triphenylbut-3-en-2-one obtained in Example 38 are as follows:

[0201]

[0202] 1H NMR(600MHz,Chloroform-d)δ7.42–7.36(m,3H),7.32–7.25(m,4H),7.20–7.07(m,6H),7. 01–6.94(m,2H),4.21(s,1H),2.55–2.41(m,2H),2.37–2.23(m,2H),1.05(t,J=7.5Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ195.9,148.4,141.5,141.3,140.4,139.6,131. 2,131.1,130.4,129.1,129.0,128.2,127.9,127.9,127.4,58.7,24.0,13.8.

[0203] Example 40: Preparation of compound (Z)-3-(2-(1,3-Dithian-2-yl)-2-oxo-1-phenylethylidene)-1-methylindolin-2-one:

[0204] In a 25 mL round-bottom flask, N-methylindoline-2,3-dione (32 mg, 0.2 mmol), 2-(phenylethynyl)-1,3-dithiane (44 mg, 0.2 mmol), and 4 mL of dimethyl sulfoxide were added sequentially. Potassium tert-butoxide (17 mg, 0.24 mmol) was added, and the mixture was stirred at 20 °C for 30 min. The reaction was then quenched with 10 mL of water, and the mixture was extracted three times with ethyl acetate. All organic phases were combined and washed three times with saturated brine. The mixture was dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate to give the product (Z)-3-(2-(1,3-Dithian-2-yl)-2-oxo-1-phenylethylidene)-1-methylindolin-2-one, with a yield of 39%.

[0205] The structure and NMR data of the product (Z)-3-(2-(1,3-Dithian-2-yl)-2-oxo-1-phenylethylidene)-1-methylindolin-2-one obtained in Example 40 are as follows:

[0206]

[0207] 1H NMR(400MHz,Chloroform-d)δ7.69–7.60(m,2H),7.49–7.42(m,3H),7.26–7.18(m,1H),6.78(d,J=7.8Hz,1H),6.75–6.68(m,1H),6.60(dd,J=7.8,1.2Hz,1H),5.01(s,1H),3.23(s,3H),2.99–2.85(m,2H),2.50–2.38(m,2H),2.03–1.88(m,2H). 13 C NMR(101MHz,Chloroform-d)δ196.3,166.8,149.9,144.6,135.4,130.5,129.4,128.8,128.3,126.6,123.8,122.2,120.9,108.4,77.5,77.2,76.8,48.3,26.1,26.0,24.9.

Claims

1. A method for the preparation of unsaturated carbonyl compounds by carbonyl-alkyne metathesis, characterized in that: In the presence of a base, a carbonyl compound I and an alkynylthiacyclic compound II are reacted in an organic solvent to obtain an unsaturated carbonyl compound III, and the chemical reaction equation is as follows: R 1 and R 2 are hydrogen, tert-butyl, substituted phenyl, naphthyl, pyrenyl, pyrazolyl, thienyl, indolyl, furanyl, benzodihydrofuranyl, carbazolyl, the substituents of the substituted phenyl being hydrogen, methoxy, methylthio, trifluoromethoxy, fluorine, chlorine, bromine, trifluoromethyl, diphenylamino, diphenylphosphino; R in the alkynylthiacyclic compound II 3 is a substituted phenyl, the substituents of which are hydrogen, methoxy, trifluoromethoxy, carbazolyl; The base is potassium tert-butoxide; the organic solvent is dimethyl sulfoxide, N,N-dimethylformamide.

2. A method of preparing unsaturated carbonyl compounds by carbonyl- alkyne metathesis reaction according to claim 1, characterized in that: The molar ratio of the base, the carbonyl compound I and the alkynylthiacyclic compound II is (0.5-2.5):(1.0-2.5):

1.

3. A method of preparing unsaturated carbonyl compounds by carbonyl- alkyne metathesis reaction according to claim 1, characterized in that: The reaction temperature is 20-60 DEG C.

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