A new synthetic method for a class of cyclic organic antimonyne compounds and their application in the preparation of triazoles

Abstract

The present invention aims to provide a new method for the copper-catalyzed synthesis of organic antimony acetylene compounds and their application in the preparation of triazoles. The method is characterized in that the organic antimony acetylene compounds are prepared by copper-catalyzed cross-coupling of organic antimony chloride compounds with aromatic terminal alkynes and alkyl terminal alkynes, and the organic antimony acetylene compounds are applied to copper-catalyzed three-component cross-coupling to prepare triazole compounds.

Description

[Technical field]

[0001] The invention belongs to the field of organic synthesis, and in particular relates to a new method for providing a copper-catalyzed synthesis of organic antimony acetylene compounds and applying the same to the preparation of triazoles. [Background technology]

[0002] Organoantimony compounds are important intermediates in organic synthesis and medicine. Organoantimony alkyne nitrogen heterocyclic compounds can increase the reactivity of the alkynyl part through Sb-N intramolecular coordination, thereby undergoing cross-coupling reactions with other halogenated reagents, alkenes, alkynes, acyl halides and other reagents under relatively mild conditions. The resulting products have important application value in medicine and materials science.

[0003] Since organic antimony acetylene compounds have multiple uses, there are many reports on their synthesis methods. At present, organic lithium reagents or Grignard reagents are mainly used to achieve metal exchange and obtain the target compound (Naoki K, et, al. J. Org. Chem., 2006, 691, 13, 2953–2968). This method has a high yield, but the operation is cumbersome, and strict control of anhydrous and oxygen-free conditions is required, and the substrate range is narrow and the functional group compatibility is poor. Copper exhibits good catalytic performance in the cross-coupling reaction of halogenated aromatic compounds and terminal alkynes (Simpson Quillon et, al. Org. Lett. 2018, 20, 5537-5540), but its application in the reaction of organic antimony chloride compounds and terminal alkynes has not been reported. Therefore, we have developed a new method for the synthesis of copper-catalyzed organic antimony acetylene compounds, using organic antimony chloride compounds and aromatic terminal alkynes or alkyl terminal alkynes as raw materials, respectively reacting under different conditions to obtain the corresponding organic antimony acetylene compounds, and the obtained organic antimony acetylene compounds are all new compounds. Moreover, this method does not require special equipment, has high yield, is easy to operate, has a wide range of substrates and good functional group compatibility. Subsequently, the organic antimony acetylene compound is applied to the copper-catalyzed three-component cross-coupling to prepare the triazole compound. This method does not require additional separation of the organic azide intermediate, is easy to operate, and has a wide range of substrates.

[0004] [Invention content] The purpose of the present invention is to provide a new method for the copper-catalyzed synthesis of organic antimony acetylene compounds and their application in the preparation of triazoles, characterized in that the new method is to prepare organic antimony acetylene compounds by copper-catalyzed cross-coupling of organic antimony chlorine compounds with aromatic terminal alkynes and alkyl terminal alkynes, and to apply the organic antimony acetylene compounds to copper-catalyzed three-component cross-coupling to prepare triazole compounds. Two possible reaction mechanisms for the copper-catalyzed cross-coupling of organic antimony chlorine compounds with terminal alkynes are also proposed. The mechanism is as follows: The first step is to remove hydrogen in the presence of a base to form an alkynyl anion A. Subsequently, the intermediate alkynyl anion A reacts with cuprous bromide to form an alkynyl copper intermediate B. Then, the organic antimony chlorine compound 1a coordinates with the intermediate product alkynyl copper intermediate to form a four-center transition state C, and finally the desired product organic antimony acetylene compound 3 is obtained by elimination. Another path is that the alkynyl anion A directly reacts with the organic antimony chlorine compound 1a to obtain the desired product organic antimony acetylene compound 3.

[0005] The present invention aims to provide a novel method for the copper-catalyzed synthesis of an organic antimony acetylene compound. The method for synthesizing the organic antimony acetylene compound is as follows: To a 10 mL Schlenk tube equipped with a magnetic stirring device, add an organic antimony chloride 1a (0.20 mmol), an aromatic terminal alkyne 2 (0.22 mmol, 1.1 equivalent), NaH (0.40 mmol, 2.0 equivalent, 4.8 mg) and CuBr (0.01 mmol, 5 mol%, 1.4 mg). Evacuate the flask with a pump and backfill with nitrogen three times. Then, in N 2 1.5 mL of 1,4-dioxane was added under an atmosphere. The mixture was stirred at 120°C (constant temperature oil bath) for 12 hours. After cooling to room temperature, it was quenched with water, extracted with dichloromethane (15 mL x 3), and washed with anhydrous Na 2 SO 4 The combined organic layers were dehydrated and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel to obtain organoantimony acetylene compounds (3a-3u); organoantimony chloride 1a (0.20 mmol), alkyl terminal alkyne 2 (0.22 mmol, 1.1 equivalents), Cs 2 CO 3 (0.40mmol, 2.0 equivalents, 65.0mg) and CuBr (0.01mmol, 5mol%, 1.4mg). 1.5mL of acetone was added under air atmosphere. The mixture was stirred at 80°C (constant temperature oil bath) for 12 hours. After cooling to room temperature, it was quenched with water, extracted with dichloromethane (15mL x 3), and washed with anhydrous Na 2 SO 4The combined organic layers were dried and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel to give organoantimony acetylene compounds (3v-3w).

[0006]

[0007] 2. The present invention aims to provide a novel method for synthesizing triazole compounds using copper-catalyzed organic antimony acetylene compounds, characterized in that, under a nitrogen atmosphere, a 10 ml Schlenk tube equipped with a magnetic stirring bar is sequentially charged with organic antimony acetylene compound 3 (0.2 mmol, 1.0 equivalent), halide 4 (0.3 mmol, 1.5 equivalent), cuprous iodide (CuI, 1.9 mg, 5 mol%), 4,4'-dimethoxy-2,2'-bipyridine (L 1 , 4.4 mg, 5 mol%), cesium fluoride (0.4 mmol, 2.0 equivalents). 1.5 ml of anhydrous dimethyl sulfoxide was added under a nitrogen atmosphere. The reaction mixture was stirred at 80 ° C for 12 hours (constant temperature oil bath). After the reaction was completed, it was concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel using a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to obtain the desired product.

[0008]

[0009] In summary, we have developed a new and efficient method for preparing organoantimony acetylene compounds. In the absence of ligands, we used CuBr to catalyze the cross-coupling reaction of organoantimony chloride compounds with terminal alkynes to synthesize a series of organoantimony acetylene compounds, and applied organoantimony acetylene compounds to copper-catalyzed three-component cross-coupling to prepare triazole compounds. This method has the advantages of good functional group compatibility, a wide range of substrate applicability, and simple operation.

Brief Description of the Drawings

[0010] Attached Figure 1 Shown is a new method for preparing an organic antimony acetylene compound provided by the present invention, and a summary of its synthetic substrates. [Specific implementation method]

[0011] The present invention will be further described below in conjunction with specific preparation examples:

[0012] Preparation Example 1

[0013] (Scheme for synthesizing target product 3a) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of phenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated with dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 91%. [ 1 H NMR (400MHz, Chloroform-d)δ8.33–8.26(m,2H),7.63–7.56(m,2H),7.38–7.27(m,7H),7.26–7.21(m,2H), 7.21–7.15(m,2H),7.11(d,J=8.2Hz,2H),7.00(t,J=7.3Hz,1H),4.66(d,J=15.1Hz,2H),4.35(d,J=15.1Hz,2H). 13 CNMR(101MHz, CDCl3)δ148.69,143.14,136.98,135.02,132.07,129.27,128.86,128.84,128.39, 128.17,126.36,124.40,122.59,118.19,111.74,94.13,77.48,77.16,76.84,58.15].

[0014] Preparation Example 2

[0015] (Scheme for synthesizing target product 3b) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 3-methylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated with dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 86%. [ 1H NMR(400MHz, CDCl3)δ8.29(d,J=6.5Hz,2H),7.40(d,J=10.0Hz,2H),7.35–7.27(m,4H),7.20-7.26 (m,3H),7.17(d,J=6.3Hz,2H),7.06-7.15(m,3H),6.95-7.04(m,1H),4.65(d,J=15.1Hz,2H),4.35(d,J=15.1Hz,2H),2.35(s,3H). 13 C NMR (101MHz, CDCl3) δ148.72,143.14,138.03,136.99,135.09,132.64, 129.26,129.16,129.07,128.84,128.80,128.28,126.34,124.20,122.55,118.17,111.98,93.62,77.48,77.16, 76.84,58.15,21.40].

[0016] Preparation Example 3

[0017] (Scheme for synthesizing the target product 3c) The synthesis steps of the present invention are: add 0.2mmol of the organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-ethylphenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 87%. [ 1 H NMR (400MHz, CDCl3) δ8.40–8.22(m,2H),7.51(d,J=7.8Hz,2H),7.33–7.26(m,4H),7.23(d,J=6.7 Hz,2H),7.19–7.13(m,4H),7.09(d,J=7.4Hz,2H),6.98(t,J=6.8Hz,1H),4.63(d,J=15.1Hz,2H),4.32(d, J=15.1Hz,2H),2.76–2.53(m,2H),1.23(dd,J=10.2,4.9Hz,3H). 13C NMR (101MHz, CDCl3) δ148.71,144.57,143.12,136.98,135.11,132.06,129.23,128.81,128.78,127.94,126.32,122.50,121.61,118.14,112.00, 93.12,77.48,77.16,76.84,58.11,28.97,15.57].

[0018] Preparation Example 4

[0019] (Scheme for synthesizing target product 3d) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-methoxyacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 81%. [ 1 H NMR (400MHz, CDCl3) δ8.36–8.23(m,2H),7.53(d,J=8.6Hz,2H),7.35–7.27(m,4H),7.24(d,J=6.8 Hz,2H),7.17(d,J=6.3Hz,2H),7.09(d,J=8.0Hz,2H),6.98(t,J=7.2Hz,1H),6.86(d,J=8.6Hz,2H),4.64 (d, J=15.1Hz, 2H), 4.34 (d, J=15.1Hz, 2H), 3.81 (s, 3H). 13 C NMR (101MHz, CDCl3) δ159.55,148.71, 143.13,136.96,135.12,133.51,129.24,128.81,128.77,126.33,122.48,1 18.12,116.62,113.97,111.78,92.08,77.48,77.16,76.84,58.09,55.44].

[0020] Preparation Example 5

[0021] (Scheme for synthesizing the target product 3e) The synthesis steps of the present invention are: add 0.2mmol of the organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-ethoxyacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of acetone under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated with dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 84%. [ 1 H NMR (400 MHz, CDCl3) δ8.28(d,J=6.6Hz,2H),7.51(d,J=8.2Hz,2H),7.33–7.25(m,4H),7.22(d,J=7.8Hz,2H), 7.15(d,J=6.6Hz,2H),7.08(d,J=8.0Hz,2H),6.97(t,J=7.2Hz,1H),6.84(d,J=8.2Hz,2H),4.62(d,J= 15.1Hz, 2H), 4.31 (d, J = 15.1Hz, 2H), 4.02 (q, J = 6.8Hz, 2H), 1.40 (t, J = 6.9Hz, 3H). 13 C NMR (101MHz, CDCl3) δ158.94,148.68,143.11,136.92,135.12,133.47,129.20,128.76,128.74,126.31,122.43,118.08,116.42, 114.49,111.91,91.96,77.48,77.16,76.84,63.60,58.05,14.88].

[0022] Preparation Example 6

[0023] (Scheme for synthesizing the target product 3f) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-propylbenzene, 0.4mmol of sodium hydride, 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 81%. [ 1H NMR (400MHz, CDCl3) δ8.29(d,J=6.8Hz,2H),7.50(d,J=7.8Hz,2H),7.34–7.26(m,4H),7.23(d,J=8.0 Hz,2H),7.16(t,J=7.3Hz,4H),7.09(d,J=8.1Hz,2H),6.98(s,1H),4.64(d,J=15.1Hz,2H),4.33(d,J=15.1 Hz, 2H), 2.59 (t, J = 7.5Hz, 2H), 1.64 (dd, J = 14.9, 7.4Hz, 2H), 0.94 (t, J = 7.3Hz, 3H). 13 C NMR(101MHz, CDCl3)δ148.73,143.13,143.03,137.00,135.14,131.97,129.24,128.82,128.78,128.54,126 .32,122.51,121.63,118.15,112.04,93.11,77.48,77.16,76.84,58.13,38.12,24.53,13.92].

[0024] Preparation Example 7

[0025] (Scheme for synthesizing 3g of target product) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-chlorophenylacetylene, 0.4mmol of sodium hydride, 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 80%. [ 1 H NMR(400MHz,Chloroform-d)δ8.37–8.17(m,2H),7.62-7.50(m,2H),7.37–7.28(m,4H),7.27–7.22(m, 2H),7.18(d,J=6.7Hz,2H),7.11(d,J=8.1Hz,2H),7.07–6.95(m,3H),4.66(d,J=15.1Hz,2H),4.35(d,J=15.1Hz,2H). 13CNMR(101MHz,Chloroform-d)δ163.74,161.26,148.67,143.16,136.91,134.98,133.92(d,J=8.2Hz ),129.29,128.87(d,J=1.6Hz),126.40,122.66,120.54(d,J=3.6Hz),118.23,115.60(d,J=21.9Hz), 110.57,93.87,58.18. 19 F NMR(377MHz, CDCl3)δ-111.29].

[0026] Preparation Example 8

[0027] (Scheme for synthesizing the target product of 3h) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-bromophenylacetylene, 0.4mmol of sodium hydride, 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 78%. [ 1 H NMR(400MHz, CDCl3)δ8.45–8.33(m,2H),7.66-7.57(m,1H),7.45-7.35(m,1H),7.36–7.29(m,4H), 7.28(s,1H),7.25–7.21(m,3H),7.19(d,J=6.2Hz,2H),7.12(d,J=8.1Hz,2H),7.01(t,J=7.3Hz,1H),4.67 (d,J=15.1Hz,2H),4.36(d,J=15.1Hz,2H). 13 C NMR (101MHz, CDCl3) δ148.65,143.10,137.04,134.95, 132.01,129.29,128.91,128.88,126.98,126.71,126.37,124.61,122.72,118.28,103.94,99.37,77.48,77.16,76.84,58.22].

[0028] Preparation Example 9

[0029] (Scheme for synthesizing target product 3i) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-fluorophenylacetylene, 0.4mmol of sodium hydride, 5mol% of cuprous bromide, evacuate and backfill nitrogen three times, add 1.5mL of acetone under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 80%. [1 H NMR (400 MHz, Chloroform-d) δ8.37–8.17(m,2H),7.62-7.50(m,2H),7.37–7.28(m,4H),7.27–7.22(m,2H),7.18(d, J=6.7Hz,2H),7.11(d,J=8.1Hz,2H),7.07–6.95(m,3H),4.66(d,J=15.1Hz,2H),4.35(d,J=15.1Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ163.74,161.26,148.67,143.16,136.91,134.98,133.92(d,J=8.2Hz), 129.29, 128.87 (d, J = 1.6Hz), 126.40, 122.66, 120.54 (d, J = 3.6Hz), 118.23, 115.60 (d, J = 21.9Hz), 110.57, 93.87, 58.18. 19 F NMR(377MHz, CDCl3)δ-111.29].

[0030] Preparation Example 10

[0031] (Scheme for synthesizing the target product 3j) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-ethynyl-1,1'-biphenyl, 0.4mmol of sodium hydride, 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 68%. [ 1H NMR(400MHz,Chloroform-d)δ8.31(d,J=7.7Hz,2H),7.66(d,J=7.9Hz,2H),7.64–7.54(m, 4H),7.46(t,J=7.5Hz,2H),7.39–7.28(m,6H),7.25(s,2H),7.20(d,J=7.0Hz,2H),7.12(d,J=8.1Hz,2H), 7.01(t,J=7.3Hz,1H), 4.67(d,J=15.1Hz,2H), 4.37(d,J=15.1Hz,2H). 13 C NMR (101MHz, CDCl3) δ148.73,143.16,140.90,140.66,137.01,135.09,132.50,129.28,128.98,128.88,128.85,127.68,127.18,127.09, 126.38,123.34,122.62,118.22,111.64,95.06,77.48,77.16,76.84,58.19].

[0032] Preparation Example 11

[0033] (Scheme for synthesizing target product 3k) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-ethynyl-4'-propyl-1,1'-biphenyl, 0.4mmol of sodium hydride, 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of acetone under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 77%. [ 1H NMR(400MHz,Chloroform-d)δ8.31(dd,J=5.5,3.5Hz,2H),7.72–7.60(m,2H),7.59–7.55(m,2H), 7.54–7.49(m,2H),7.31(q,J=6.5Hz,4H),7.27–7.22(m,4H),7.18(d,J=7.1Hz,2H),7.11(d,J=8.1Hz, 2H),6.99(t,J=7.4Hz,1H),4.65(d,J=15.0Hz,2H),4.35(d,J=15.1Hz,2H),2.63(t,J=7.8Hz,2H),1.68(d, J=7.5Hz,2H),0.97(td,J=7.3,1.8Hz,3H). 13 C NMR (101 MHz, CDCl 3 )δ148.73,143.15,142.37,140.87, 137.98,137.02,135.09,132.47,129.28,129.12,128.87,128.84,126.98,126.88,126.37, 122.98,122.59,118.20,111.76,94.80,77.48,77.16,76.84,58.17,37.84,24.67,14.02].

[0034] Preparation Example 12

[0035] (Scheme for synthesizing the target product 31) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 2-chlorophenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated with dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 78%. [ 1 H NMR (400 MHz, CDCl 3)δ8.31–8.18(m,2H),7.45(q,J=8.7Hz,4H),7.35-7.29(m,5.2Hz,4H),7.28–7.22 (m,2H),7.22–7.15(m,2H),7.11(d,J=8.0Hz,2H),7.01(t,J=7.3Hz,1H),4.66(d,J=15.1Hz,2H),4.35(d,J=15.1Hz,2H). 13 C NMR (101 MHz, CDCl 3 )δ148.65,143.14,136.90,134.91,133.50,131.62,129.29,128.91, 128.88,126.42,123.36,122.72,122.28,118.27,110.49,95.96,77.48,77.16,76.84,58.22].

[0036] Preparation Example 13

[0037] (Scheme for synthesizing the target product 3m) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 2-fluorophenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated with dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 79%. [ 1 H NMR(400MHz,Chloroform-d)δ8.32(d,J=6.7Hz,2H),7.56(t,J=7.2Hz,1H),7.38–7.26(m,5H),7.23(d, J=7.4Hz,2H),7.16(d,J=6.5Hz,2H),7.13–7.03(m,4H),6.98(t,J=6.8Hz,1H),4.63(d,J=15.1Hz,2H), 4.33(d,J=15.1Hz,2H). 13C NMR(101MHz,Chloroform-d)δ164.49,162.00,148.64,143.07,137.07,134.90, 133.89(d,J=1.4Hz),132.05,129.78–129.17(m),128.86(d,J=4.0Hz),126.32,123.94(d,J=3.7Hz),122.67, 118.25,115.57(d,J=21.1Hz),112.99(d,J=15.9Hz),104.28, 19 F NMR (376 MHz, CDCl 3 )δ100.70(d,J=3.6 Hz),58.20.176.2-177.6].

[0038] Preparation Example 14

[0039] (Scheme for synthesizing the target product 3n) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 3-fluorophenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of acetone under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated with dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 78%. [ 1 H NMR (400 MHz, Chloroform-d) δ8.34–8.13(m,2H),7.40–7.27(m,6H),7.22(dd,J=8.4,5.3Hz,3H),7.17(d,J=6.1 Hz, 2H), 7.09 (d, J = 8.1Hz, 2H), 7.00 (q, J = 7.7, 6.6Hz, 2H), 4.63 (d, J = 15.1Hz, 2H), 4.33 (d, J = 15.1Hz, 2H). 13C NMR(101MHz,Chloroform-d)δ162.74,160.29,147.61,142.13,135.90,133.86,128.91(d,J=8.7 Hz),128.28,127.90(d,J=2.5Hz),126.93(d,J=2.9Hz),125.71-125.70(m),121.72,117.75(d,J=22.6Hz), 117.27,114.45(d,J=21.2Hz),109.27,109.24,94.89,57.20. 19 FNMR (376MHz, CDCl 3 )δ-113.10(dd,J= 15.2,8.6Hz)].

[0040] Preparation Example 15

[0041] (Scheme for synthesizing the target product 3o) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 3,5-difluorophenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 70%. [ 1 H NMR(400MHz, CDCl3)δ8.21(d,J=6.5Hz,2H),7.36–7.28(m,4H),7.24(m,3H),7.18(d,J=6.5Hz, 2H),7.14–7.04(m,4H),7.00(t,J=7.2Hz,1H),6.77(dd,J=8.8,7.4Hz,1H),4.64(d,J=15.1Hz,2H),4.34(d,J=15.1Hz,2H). 13C NMR(101MHz,Chloroform-d)δ164.05(d,J=13.5Hz),161.58(d,J=13.2Hz),148.54, 143.12,136.84,134.71,129.31,128.96(d,J=6.1Hz),127.10(d,J=11.6Hz),126.46,122.87,118.35,115.20– 114.67(m),109.03,104.52,104.27,104.02,97.75,58.26. 19 F NMR (376MHz, Chloroform-d) δ-109.97 (t, J = 7.8Hz)].

[0042] Preparation Example 16

[0043] (Scheme for synthesizing the target product 3p) The synthesis steps of the present invention are: add 0.2mmol of the organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-nitrobenzeneacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 55%. [ 1 H NMR (400MHz, CDCl3) δ8.22 (s, 4H), 7.69 (d, J = 8.2Hz, 2H), 7.32 (s, 4H), 7.25 (s, 2H), 7.22 (s, 2H), 7.12 (d,J=6.9Hz,2H),7.03(s,1H),4.67(d,J=15.0Hz,2H),4.37(d,J=15.1Hz,2H). 13 C NMR (101MHz, CDCl3) δ148.47,146.90,143.14,136.82,134.59,132.69,131.24,129.35,129.09,128.9 6,126.54,123.74,123.00,118.42,109.52,102.38,77.48,77.16,76.84,58.31].

[0044] Preparation Example 17

[0045] (Scheme for synthesizing the target product 3q) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of methyl 4-phenylethynyl formate, 0.4mmol of sodium hydride, 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 58%. [ 1 H NMR (400MHz, CDCl3) δ8.25 (s, 2H), 8.02 (d, J = 7.2Hz, 2H), 7.63 (d, J = 6.8Hz, 2H), 7.31 (s, 4H), 7.26(s,2H),7.19(s,2H),7.12(d,J=6.2Hz,2H),7.01(s,1H),4.67(d,J=15.1Hz,1H),4.36(d,J=15.0Hz,2H),3.93(s,3H). 13 C NMR (101MHz, CDCl3) δ166.80,148.59,143.12,136.92,134.79,131.93,129.60,129.31, 129.05,128.95,128.92,126.44,122.78,118.30,110.81,98.61,77.48,77.16,76.84,58.22,52.35].

[0046] Preparation Example 18

[0047] (Scheme for synthesizing the target product 3r) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 2-phenylethynylthiophene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 90%. [ 1H NMR(400MHz,Chloroform-d)δ8.34–8.14(m,2H),7.29(dt,J=5.8,3.1Hz,5H),7.25-7.20(m,3H),7.17 (d,J=6.9Hz,2H),7.09(d,J=8.1Hz,2H),7.04-6.92(m,2H),4.63(d,J=15.1Hz,2H),4.33(d,J=15.1Hz, 2H). 13 CNMR(101MHz, CDCl3)δ148.64,143.09,137.03,134.94,132.00,129.28,128.91,128.88,126.98, 126.71,126.37,124.60,122.71,118.28,103.94,99.37,77.48,77.16,76.84,58.21].

[0048] Preparation Example 19

[0049] (Scheme for synthesizing the target product 3s) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 2-methoxyphenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 78%. [ 1 H NMR (400MHz, CDCl3) δ8.40(d,J=6.5Hz,2H),7.56(d,J=7.4Hz,1H),7.29(dd,J=5.2,3.5Hz,5H), 7.24(d,J=6.2Hz,2H),7.17(d,J=6.6Hz,2H),7.11(d,J=8.1Hz,2H),7.00(d,J=7.1Hz,1H),6.92(dd,J= 14.3,7.7Hz,2H),4.65(d,J=15.1Hz,2H),4.35(d,J=15.1Hz,2H),3.93(s,3H). 13C NMR (101MHz, CDCl3) δ160.63,148.81,143.13,137.30,135.30,133.86,129.47,129.24,128.79,128.70,126.24,122.48,120.47,118.14, 113.67,110.77,107.56,98.61,77.48,77.16,76.84,58.15,55.95].

[0050] Preparation Example 20

[0051] (Scheme for synthesizing the target product 3t) The synthesis steps of the present invention are: add 0.2mmol of the organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-pentyloxyphenylacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of 1,4-dioxane under a nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 75%. [ 1 H NMR(400MHz,Chloroform-d)δ8.29(d,J=6.6Hz,2H),7.51(d,J=8.2Hz,2H),7.37–7.25(m,5H),7.23 (d,J=7.4Hz,2H),7.17(d,J=6.7Hz,2H),7.09(d,J=8.1Hz,2H),6.98(t,J=7.4Hz,1H),6.85(d,J=8.3Hz, 2H),4.64(d,J=15.1Hz,2H),4.34(d,J=15.1Hz,2H),3.96(t,J=6.6Hz,2H),1.80(q,J=6.9Hz,2H), 1.47-1.34(m,4H),0.93(t,J=7.0Hz,3H). 13 C NMR (101MHz, CDCl3) δ159.14,148.67,143.10,136.92, 135.11,133.45,129.19,128.76,128.73,126.30,122.42,118.07,116.34,114.54,11 4.50,111.94,91.92,77.48,77.16,76.84,68.14,58.03,28.99,28.26,22.55,14.15].

[0052] Preparation Example 21

[0053] (Scheme for synthesizing target product 3u) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 1-naphthyleneacetylene, 0.4mmol of sodium hydride, and 5mol% of cuprous bromide, evacuate and backfill with nitrogen three times, add 1.5mL of acetone under nitrogen atmosphere, and react at 120°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated with dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 67%. [ 1 H NMR(400MHz, Chloroform-d)δ8.51–8.40(m,1H),7.89(dd,J=13.6,7.6Hz,2H),7.63–7.54(m,1H),7.50(t,J=7.7Hz,2H), 7.33–7.28(m,4H),7.27–7.23(m,2H),7.18(d,J=8.3Hz,2H),7.06(t,J=7.3Hz,1H),4.74(d,J=15.1Hz,1H),4.43(d,J=15.1Hz,1H). 13 C NMR (101 MHz, CDCl 3 )δ148.67,143.18,137.13,135.10,133.81,133.32, 130.79,129.30,128.88,128.57,128.35,126.84,126.45,126.41,125.4 2,122.62,122.05,118.19,109.65,99.46,77.48,77.16,76.84,58.18].

[0054] Preparation Example 22

[0055] (Scheme for synthesizing target product 3v) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of 4-bromobutyne, 0.4mmol of cesium carbonate, 5mol% of cuprous bromide, add 1.5mL of acetone under air atmosphere, and react at 80°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 65%. [ 1H NMR(400MHz,Chloroform-d)δ8.27– 8.13(m,2H),7.32(p,J=8.1,7.7Hz,5H),7.24(s,1H),7.18(d,J=7.2Hz,2H),7.10(d,J=8.1Hz,2H),7.03(t, J=7.4Hz,1H),4.63(d,J=15.1Hz,2H),4.34(d,J=15.1Hz,2H),1.55(d,J=1.7Hz,9H). 13 C NMR (101 MHz, CDCl 3 )δ152.58,148.42,142.92,137.21,134.07,129.38,129.11,129.10,126.40,123.27,118.59,102.93, 94.01,83.09,77.48,77.16,76.84,58.47,28.26].

[0056] Preparation Example 23

[0057] (Scheme for synthesizing the target product 3w) The synthesis steps of the present invention are: add 0.2mmol of organic antimony chloride compound 1a into a 10mL reaction tube, add 0.22mmol of tert-butyl propiolate, 0.4mmol of cesium carbonate, and 5mol% of cuprous bromide, add 1.5mL of acetone under air atmosphere, and react at 80°C for 12h. After the reaction is completed, water is added to quench, and the mixture is separated by dichloromethane (15mL x 3), dried, and concentrated under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure organic antimony acetylene compound with a yield of 63%. [ 1 H NMR(400MHz,Chloroform-d)δ 8.19(d,J=6.7Hz,2H),7.35–7.28(m,4H),7.24(d,J=9.8Hz,4H),7.18(d,J=6.9Hz,2H),7.09(d,J=8.2 Hz,2H),7.00(t,J=7.3Hz,1H),6.04(dd,J=17.3,11.4Hz,1H),5.82–5.72(m,1H),5.51(d,J=11.0Hz,1H), 4.64(d,J=15.1Hz,2H), 4.34(d,J=15.1Hz,2H). 13 C NMR (101 MHz, CDCl 3)δ148.69,143.11,136.94,134.94,129.27,128.84,128.83,126.83,126. 35,122.60,118.25,118.18,110.50,95.06,77.48,77.16,76.84,58.14].

[0058] Preparation Example 24

[0059] (Scheme for synthesizing the target product 5a) The synthesis steps of the present invention are: add 0.2 mmol of the organic antimony phenylacetylene compound 3a into a 10 mL reaction tube, add 0.30 mmol of benzyl bromide, 0.4 mmol of cesium fluoride, 5 mol% of cuprous iodide, 5 mol% of 4,4'-dimethoxy-2,2'-bipyridine, evacuate and backfill with nitrogen three times, add 1.5 mL of dimethyl sulfoxide under nitrogen atmosphere, and react at 80°C for 12 hours. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 85%. In a 10 mL reaction tube, add 0.2 mmol of the organoantimony phenylacetylene compound 3a, 0.30 mmol of benzyl chloride, 0.4 mmol of cesium fluoride, 0.01 mol of cuprous iodide, and 0.01 mol of 4,4'-dimethoxy-2,2'-bipyridine. Vacuum and backfill with nitrogen three times. Add 1.5 mL of dimethyl sulfoxide under nitrogen atmosphere and react at 80°C for 12 h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 75%. [ 1 H NMR (400MHz, Chloroform-d) δ7.79 (d, J=7.5Hz, 2H), 7.66 (s, 1H), 7.45–7.35 (d, J=7.6Hz, 5H), 7.31 (s, 3H), 5.57 (s, 2H)].

[0060] Preparation Example 25

[0061] (Scheme for synthesizing the target product 5b) Add 0.2mmol of the organoantimony phenylacetylene compound 3a, 0.30mmol of 4-fluorobenzyl bromide, 0.4mmol of cesium fluoride, 0.01mol of cuprous iodide, and 0.01mol of 4,4'-dimethoxy-2,2'-bipyridine into a 10mL reaction tube, evacuate and backfill with nitrogen three times, add 1.5mL of dimethyl sulfoxide under nitrogen atmosphere, and react at 80°C for 12h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 79%. [1 H NMR (400MHz, Chloroform-d) δ7.83–7.76(m,2H),7.67(d,J=4.4Hz,1H),7.44–7.23(m,5H),7.11–7.01(m, 2H),5.52(d,J=4.2Hz,2H). 13 CNMR(101MHz,CDCl3)δ164.17,161.71,148.38,130.70,130.67,130.54, 130.05,129.96,128.91,128.31,125.78,119.53,116.31,116.09,77.48,77.16,76.84,53.51. 19 F NMR(376MHz, CDCl3)δ-112.61–-112.78(m)].

[0062] Preparation Example 26

[0063] (Scheme for synthesizing the target product 5c) Add 0.2mmol of the organic antimony phenylacetylene compound 3a, 0.30mmol of 4-methoxybenzyl bromide, 0.4mmol of cesium fluoride, 0.01mol of cuprous iodide, and 0.01mol of 4,4'-dimethoxy-2,2'-bipyridine into a 10mL reaction tube, evacuate and backfill with nitrogen three times, add 1.5mL of dimethyl sulfoxide under nitrogen atmosphere, and react at 80°C for 12h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 80%. [ 1 H NMR(400MHz,Chloroform-d)δ7.82(d,J=7.3Hz,2H),7.66(s,1H),7.42(t,J=7.5Hz,2H),7.34(d,J=7.3 Hz,1H),7.29(d,J=8.5Hz,2H),6.93(d,J=8.6Hz,2H),5.52(s,2H),3.83(s,3H). 13 C NMR (101MHz, CDCl3) δ160.08,148.21,130.73,129.75,128.88,128.20,126.77,125.79,119.40,114.63,77.48,77.16,76.84,55.44,53.86].

[0064] Preparation Example 27

[0065] (Scheme for synthesizing the target product 5d) Add 0.2mmol of the organoantimony phenylacetylene compound 3a, 0.30mmol of 4-methylbenzyl bromide, 0.4mmol of cesium fluoride, 0.01mol of cuprous iodide, and 0.01mol of 4,4'-dimethoxy-2,2'-bipyridine into a 10mL reaction tube, evacuate and backfill with nitrogen three times, add 1.5mL of dimethyl sulfoxide under nitrogen atmosphere, and react at 80°C for 12h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 81%. [ 1 H NMR (400MHz, CDCl 3 )δ7.78(d,J=7.6Hz,1H),7.63(s,1H),7.37(t,J=7.4Hz,1H),7.29(t,J=7.3Hz,1H),7.17 (d,J=9.6Hz,3H),5.49(s,2H),2.34(s,3H). 13 C NMR (101 MHz, CDCl 3 )δ148.17,138.75,131.75,130.69, 129.85,128.84,128.18,128.16,125.76,119.52,77.48,77.16,76.84,54.07,21.22].

[0066] Preparation Example 28

[0067] (Scheme for synthesizing the target product 5e) Add 0.2mmol of the organoantimony phenylacetylene compound 3a into a 10mL reaction tube, add 0.30mmol of 4-(bromomethyl)-1,1'-biphenyl, 0.4mmol of cesium fluoride, 0.01mol of cuprous iodide, and 0.01mol of 4,4'-dimethoxy-2,2'-bipyridine, evacuate and backfill with nitrogen three times, add 1.5mL of dimethyl sulfoxide under nitrogen atmosphere, and react at 80°C for 12h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 77%. [ 1 H NMR (400MHz, CDCl3) δ7.81 (d, J=7.6Hz, 2H), 7.71 (s, 1H), 7.65–7.52 (m, 4H), 7.50–7.40 (m, 3H),7.41–7.35(m,4H),7.31(t,J=7.3Hz,1H),5.60(s,2H). 13C NMR (101MHz, CDCl3) δ147.40,140.92, 139.34,132.71,129.65,128.00,127.94,127.65,127.31,126.98,126.81,126.23,124.84,118.64,76.48,76.16,75.84,53.07].

[0068] Preparation Example 29

[0069] (Scheme for synthesizing the target product 5f) Add 0.2mmol of the organoantimony phenylacetylene compound 3a into a 10mL reaction tube, add 0.30mmol of 1-bromo-2-(bromomethyl)-3-fluorobenzene, 0.4mmol of cesium fluoride, 0.01mol of cuprous iodide, and 0.01mol of 4,4'-dimethoxy-2,2'-bipyridine. Vacuum and backfill with nitrogen three times. Add 1.5mL of dimethyl sulfoxide under nitrogen atmosphere and react at 80°C for 12h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 68%. [ 1 H NMR (400MHz, CDCl3) δ7.90 (d, J = 8.0Hz, 3H), 7.74-7.59 (M, 1H), 7.49 (t, J = 7.4Hz, 2H), 7.41 (t,J=7.1Hz,1H),7.03(dd,J=11.0,5.3Hz,1H),6.93(d,J=8.7Hz,1H),5.74(s,2H). 13 C NMR (101MHz, CDCl3) δ163.56,161.08,148.49,136.49,136.42,134.64,134.56,130.42,128.98,128.47,125.90,120.03,117.84, 117.61,117.39,117.30,117.26,117.15,77.48,77.16,76.84,53.70].

[0070] Preparation Example 30

[0071] (Scheme for synthesizing 5 g of the target product) Add 0.2 mmol of the organoantimony phenylacetylene compound 3a into a 10 mL reaction tube, add 0.30 mmol of 2-(bromomethyl)-1,3-difluorobenzene, 0.4 mmol of cesium fluoride, 0.01 mol of cuprous iodide, and 0.01 mol of 4,4'-dimethoxy-2,2'-bipyridine, evacuate and backfill with nitrogen three times, add 1.5 mL of dimethyl sulfoxide under a nitrogen atmosphere, and react at 80°C for 12 h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 74%. [ 1 H NMR (400MHz, Chloroform-d) δ7.70 (s, 1H), 7.38 (d, J = 6.2Hz, 3H), 7.31 (d, J = 4.7Hz, 4H), 6.73 (t, J = 8.9Hz, 1H), 5.56 (s, 2H). 13 C NMR (101MHz, CDCl3) δ164.75,164.62,162.29,162.16,146.35,146.32, 134.43,133.92,133.81,133.71,129.33,129.05,128.21,120.40,108.73,108 .65,108.54,108.46,103.62,103.37,103.12,77.48,77.16,76.84,54.45.19F NMR(376MHz,Chloroform-d)δ-109.34(q,J=7.5Hz)].

[0072] Preparation Example 31

[0073] (Scheme for synthesizing the target product in 5h) 0.2 mmol of the organoantimony phenylacetylene compound 3a, 0.30 mmol of 1-butyl bromide, 0.4 mmol of cesium fluoride, 0.01 mol of cuprous iodide, and 0.01 mol of 4,4'-dimethoxy-2,2'-bipyridine were added to a 10 mL reaction tube, and the mixture was vacuumed and backfilled with nitrogen three times. 1.5 mL of dimethyl sulfoxide was added under a nitrogen atmosphere, and the mixture was reacted at 80°C for 12 h. The mixture was concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel using a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to obtain the desired product with a yield of 82%. 0.2 mmol of the organic antimony phenylacetylene compound 3a, 0.30 mmol of 1-butyl chloride, 0.4 mmol of cesium fluoride, 0.01 mol of cuprous iodide, and 0.01 mol of 4,4'-dimethoxy-2,2'-bipyridine were added to a 10 mL reaction tube, and the mixture was vacuumed and backfilled with nitrogen three times. 1.5 mL of dimethyl sulfoxide was added under a nitrogen atmosphere, and the reaction was carried out at 80°C for 12 h. The mixture was concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel using a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to obtain the desired product with a yield of 76%. 0.2 mmol of organic antimony phenylacetylene compound 3a, 0.30 mmol of 1-butyl iodide, 0.4 mmol of cesium fluoride, 0.01 mol of cuprous iodide, and 0.01 mol of 4,4'-dimethoxy-2,2'-bipyridine were added to a 10 mL reaction tube, and the mixture was vacuumed and backfilled with nitrogen three times. 1.5 mL of dimethyl sulfoxide was added under a nitrogen atmosphere, and the mixture was reacted at 80°C for 12 h. The mixture was concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel using a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to obtain the desired product with a yield of 88%. [ 1 H NMR(400MHz,Chloroform-d)δ7.89–7.82(m,2H),7.77(s,1H),7.45(dd,J=8.3,6.7Hz,2H),7.35 (dd,J=8.4,6.2Hz,1H),4.42(t,J=7.2Hz,2H),1.96(p,J=7.4Hz,2H),1.42(h,J=7.4Hz,2H),1.00(t,J=7.4Hz,3H). 13 C NMR (101MHz, CDCl3) δ147.82,130.83,128.93,128.18,125.78,119.52,77.48,77.16,76.84,50.24,32.42,19.82,13.59].

[0074] Preparation Example 32

[0075] (Scheme for synthesizing the target product 5i) Add 0.2mmol of the organic antimony phenylacetylene compound 3c, 0.30mmol of benzyl bromide, 0.4mmol of cesium fluoride, 0.01mol of cuprous iodide, and 0.01mol of 4,4'-dimethoxy-2,2'-bipyridine into a 10mL reaction tube, evacuate and backfill with nitrogen three times, add 1.5mL of dimethyl sulfoxide under nitrogen atmosphere, and react at 80°C for 12h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 80%. [ 1 H NMR (400 MHz, Chloroform-d) δ7.74–7.67(m,2H),7.62(s,1H),7.37(d,J=7.0Hz,3H),7.29(dd,J=7.4,2.1Hz,2H), 7.23(t,J=8.0Hz,2H),5.55(s,2H),2.66(q,J=7.6Hz,2H),1.24(t,J=7.6Hz,3H). 13 C NMR (101MHz, CDCl3) δ148.46,144.52,134.92,129.25,128.86,128.41,128.16,128.11,125.84,119.30,77.48,77.16,76.84, 54.31,28.78,15.60].

[0076] Preparation Example 33

[0077] (Scheme for synthesizing the target product 5j) Add 0.2 mmol of the organic antimony phenylacetylene compound 3e, 0.30 mmol of benzyl bromide, 0.4 mmol of cesium fluoride, 0.01 mol of cuprous iodide, and 0.01 mol of 4,4'-dimethoxy-2,2'-bipyridine into a 10 mL reaction tube, evacuate and backfill with nitrogen three times, add 1.5 mL of dimethyl sulfoxide under nitrogen atmosphere, and react at 80°C for 12 h. Concentrate under reduced pressure. Use a mixed solvent system of petroleum ether (PE) and ethyl acetate (EA) to purify the crude product by flash chromatography on silica gel to obtain the desired product with a yield of 78%. [ 1 H NMR (400 MHz, Chloroform-d) δ7.74–7.66 (m, 2H), 7.56 (s, 1H), 7.38 (d, J = 7.2Hz, 3H), 7.30 (dd, J = 7.4, 2.2Hz, 2H), 6.96–6.87(m,2H),5.55(s,2H),4.05(q,J=7.0Hz,2H),1.42(t,J=7.0Hz,3H). 13C NMR (101MHz, CDCl3) δ159.16,148.33,134.95,129.28,128.88,128.19,127.15,123.30,118.77,114.93,77.48,77.16,76.84,63.65, 54.34,14.94].

[0078] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for synthesizing an organic antimony acetylene compound using copper catalyst, Features: In a 10 mL Schlenk tube equipped with a magnetic stirring device, 0.20 mmol of organoantimony chloride 1a, 0.22 mmol of aryl terminal alkyne 2, 0.40 mmol of NaH, and 0.01 mmol of CuBr were added. The flask was evacuated with a pump and backfilled with nitrogen three times. Then, the flask was heated under N 2 1.5 mL of 1,4-dioxane was added under an atmosphere of 40 °C, and the mixture was stirred at 120 °C for 12 h. After cooling to room temperature, it was quenched with water, extracted three times with 15 mL of dichloromethane, and washed with anhydrous Na 2 SO 4 The combined organic layer was dehydrated and concentrated under reduced pressure, and the crude product was purified by flash chromatography on silica gel to obtain organic antimony acetylene compounds 3a-3u; alternatively, 0.20 mmol of organic antimony chloride 1a, 0.22mmol alkyl terminal alkyne 2, 0.40mmol Cs 2 CO 3 and 0.01 mmol CuBr, 1.5 mL acetone was added under air atmosphere, the mixture was stirred at 80 °C for 12 h, cooled to room temperature, quenched with water, extracted 3 times with 15 mL dichloromethane, and then washed with anhydrous Na 2 SO 4 The combined organic layers were dehydrated and concentrated under reduced pressure, and the crude product was purified by flash chromatography on silica gel to give organoantimony acetylene compounds 3v-3w: Among them, compound 3 is specifically compound 3a-3w; 2. A method for synthesizing a triazole compound, It is characterized in that Under nitrogen atmosphere, a 10 ml Schlenk tube equipped with a magnetic stirring bar was charged with 0.2 mmol of organoantimony acetylene compound 3, 0.3 mmol of halide 4, 0.2 mmol of sodium azide, 1.9 mg of cuprous iodide, 4.4 mg of 4,4'-dimethoxy-2,2'-bipyridine, and 0.4 mmol of cesium fluoride in sequence, and 1.5 ml of anhydrous dimethyl sulfoxide was added under nitrogen atmosphere. The reaction mixture was stirred at 80°C for 12 hours. After the reaction was completed, it was concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel using a mixed solvent system of petroleum ether and ethyl acetate to obtain products 5a-5j; Among them, the chemical formula of the organic antimony acetylene compound 3 is: The chemical formula of halide 4 is: R 2 -X, X is a halogen element.

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