A method for synthesizing 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compounds

Abstract

The invention discloses a method for synthesizing a 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound, wherein a sulfonylmethyl isonitrile derivative is used as a substrate, trifluoroacetic anhydride is used as a fluorine source, and copper catalysis is used to react in a solvent under alkaline conditions to synthesize a 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound. The synthetic method has the advantages of simple operation, diversified products, and one-pot efficient synthesis of products that are not easily obtained by other methods.

Description

Technical Field

[0001] The invention belongs to the technical field of organic fluorine chemical synthesis, and specifically relates to a method for synthesizing a 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound. Background Art

[0002] Oxazoles are an important class of aromatic heterocyclic compounds containing nitrogen and oxygen, which are widely present in natural products and various drug molecules. The introduction of trifluoromethyl groups into the oxazole heterocycle can change its physical and chemical properties, and it has a variety of antiviral, antifungal, antitumor and other biological activities as well as insecticidal activities. Although there are a lot of research reports on the synthesis of trifluoromethyl oxazole compounds, there are few reports on the synthesis of bis (trifluoromethyl) oxazole compounds. The present invention reports a method for preparing 4-sulfonyl-2,5-bis (trifluoromethyl) oxazole compounds under copper catalysis. Summary of the invention

[0003] The object of the present invention is to provide a method for synthesizing a 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound, which has the advantages of simple operation, diversified products, and one-pot efficient synthesis of products that are not easily obtained by other methods.

[0004] To achieve the above object, the present invention adopts the following technical solution:

[0005] A method for synthesizing a 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound comprises taking a sulfonylmethyl isonitrile derivative as a substrate and trifluoroacetic anhydride as a fluorine source, and carrying out a reaction in a solvent under alkaline conditions with copper catalysis to synthesize the 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound.

[0006] The sulfonylmethyl isonitrile derivative is any one of the following formulas 1 to 17:

[0007] .

[0008] Furthermore, the copper salt used in the copper catalysis is one of CuCl, CuI, CuBr, Cu(OTf)2, and Cu(OAc)2.

[0009] Furthermore, the base used in the alkaline condition is triethylamine.

[0010] Furthermore, the solvent is one of toluene and acetonitrile.

[0011] Furthermore, the 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound is specifically any one of the following formulas 1 to 17:

[0012] .

[0013] Furthermore, the synthesis method of the 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound is specifically to mix a sulfonylmethyl isocyanide derivative, trifluoroacetic anhydride, copper salt, triethylamine and a solvent, react at 30°C for 8-16 hours under magnetic stirring, remove the volatile solvent in the reaction mixture by rotary evaporation, and then purify it through a silica gel column to obtain the 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound.

[0014] The molar ratio of the sulfonylmethyl isocyanide derivative, trifluoroacetic anhydride, copper salt, triethylamine and solvent is (0.30-1):(1.05-3.5):(0.01-0.04):(0.60-2):(19.00-63).

[0015] The beneficial effects of the present invention are:

[0016] The present invention uses a simple and easily available sulfonylmethyl isonitrile derivative as a substrate, trifluoroacetic anhydride as a fluorine source, and copper catalyzes the reaction in a solvent under alkaline conditions to synthesize a 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound, which has good adaptability of functional groups, and has the advantages of simple operation, diversified products, and one-pot efficient synthesis of products that are not easily obtained by other methods. The 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound prepared by the present invention has good insecticidal activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The present invention provides a flow chart for synthesizing 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compounds.

[0018] Figure 2 This is a single crystal structure diagram of the 4-p-toluenesulfonyl-2,5-bis(trifluoromethyl)oxazole compound prepared in Example 2. DETAILED DESCRIPTION

[0019] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0020] Example 1

[0021] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of benzenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-benzenesulfonyl-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents (isolation yield 61%). Its characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 8.07 (d, J = 8.6 Hz, 2H), 7.78 – 7.69 (m, 1H), 7.62 (t, J = 7.9Hz, 2H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.7 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.4 (q, J = 47.0 Hz), 142.6 (q, J = 2.7 Hz), 142.0(q, J = 46.8 Hz), 137.6, 135.3, 129.8, 129.0, 116.8 (q, J = 272.0 Hz), 115.1 (q, J = 273.2 Hz).

[0022] Example 2

[0023] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of p-toluenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-p-toluenesulfonyl-2,5-bis(trifluoromethyl)oxazole (isolation yield 75%) was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents. The characterization data are as follows:1 H NMR (400 MHz, Chloroform- d ) δ 7.95 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H),2.46 (s, 3H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.7 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.3 (q, J = 46.7 Hz), 146.9, 142.9 (q, J =2.4 Hz), 141.7 (q, J = 46.6 Hz), 134.6, 130.4, 129.1, 116.8 (q, J = 271.9 Hz),115.1 (q, J = 273.0 Hz), 21.7.

[0024] Example 3

[0025] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of p-toluenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous iodide, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 ° C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and petroleum ether and dichloromethane (1:1, v / v) were used as eluents. 4-p-toluenesulfonyl-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography (isolation yield 72%), and its characterization data is shown in Example 2.

[0026] Example 4

[0027] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of p-toluenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of copper acetate, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 ° C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and petroleum ether and dichloromethane (1:1, v / v) were used as eluents. 4-p-toluenesulfonyl-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography (isolation yield 69%), and its characterization data is shown in Example 2.

[0028] Example 5

[0029] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of p-toluenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of acetonitrile solvent was added. The mixture was stirred in a closed system at 30 ° C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and petroleum ether and dichloromethane (1:1, v / v) were used as eluents. 4-p-toluenesulfonyl-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography (isolation yield 35%), and its characterization data is shown in Example 2.

[0030] Example 6

[0031] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 2-methylbenzenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(2'-toluenesulfonyl)-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents (isolation yield 48%). Its characterization data are as follows: 1 HNMR (400 MHz, Chloroform- d ) δ 8.15 (d, J = 8.0 Hz, 1H), 7.59 (t, J = 7.2 Hz, 1H),7.44 (t, J = 7.6 Hz, 1H), 7.36 (d, J= 7.6 Hz, 1H), 2.69 (s, 3H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.7 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ150.2 (q, J = 47.2 Hz), 143.0 (q, J = 2.5 Hz), 141.9 (q, J = 47.1 Hz), 139.9,135.8, 135.3, 133.1, 131.0, 127.0, 116.8 (q, J = 272.0 Hz), 115.1 (q, J = 273.2Hz), 20.5.

[0032] Example 7

[0033] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 3-toluenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(3'-toluenesulfonyl)-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents (isolation yield 62%). Its characterization data are as follows: 1 HNMR (400 MHz, Chloroform- d ) δ 7.85 (d, J = 4.7 Hz, 2H), 7.56 – 7.43 (m, 2H), 2.45 (s, 3H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.1 (s, 3F), -65.8 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.3 (q, J = 46.7 Hz), 142.7 (q, J= 2.6 Hz),141.9 (q, J = 46.5 Hz), 140.2, 137.4, 136.1, 129.6, 129.1, 126.1, 116.8 (q, J =272.1 Hz), 115.1 (q, J = 273.1 Hz), 21.2.

[0034] Example 8

[0035] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 3,5-dimethylbenzenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(3',5'-dimethylbenzenesulfonyl)-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents (isolation yield 62%). Its characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.66 (s, 2H), 7.33 (s, 1H), 2.40 (s, 6H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.8 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.3 (q, J = 47.0 Hz), 142.8 (q, J = 2.6 Hz), 141.8(q, J = 46.9 Hz), 140.0, 137.3, 137.0, 126.4, 116.8 (q, J = 271.9 Hz), 115.2 (q, J = 273.1 Hz), 21.1.

[0036] Example 9

[0037] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 4-tert-butylbenzenesulfonylmethyl isonitrile, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(4'-tert-butylbenzenesulfonyl)-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (2:3, v / v) as eluents (isolation yield 76%). Its characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.99 (d, J = 8.6 Hz, 2H), 7.63 (d, J = 8.6Hz, 2H), 1.34 (s, 9H). 19 F NMR (376 MHz, Chloroform- d ) δ -59.9 (s, 3F), -65.7 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 159.7, 150.3 (q, J = 46.9 Hz), 142.9(q, J = 2.6 Hz), 141.8 (q, J = 46.9 Hz), 134.5, 128.9, 126.8, 116.8 (q, J = 271.9Hz), 115.2 (q, J = 273.1 Hz), 35.5, 30.9.

[0038] Example 10

[0039] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 4-methoxybenzenesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(4'-methoxybenzenesulfonyl)-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:2, v / v) as eluents (isolation yield 73%). Its characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.97 (d, J = 9.0 Hz, 2H), 7.05 (d, J = 9.0Hz, 2H), 3.89 (s, 3H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.8 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 165.2, 150.3 (q, J = 46.7 Hz), 143.1(q, J = 2.6 Hz), 141.3 (q, J = 46.6 Hz), 131.4, 128.7, 116.9 (q, J = 271.8 Hz),115.2 (q, J = 273.1 Hz), 115.0, 55.8.

[0040] Embodiment 11

[0041] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of methyl 2-isocyanatomethylsulfonylformate, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and petroleum ether and dichloromethane (2:3, v / v) were used as eluents to separate methyl 2-((2',5'-bis(trifluoromethyl)oxazol-4-yl)sulfonyl)benzoate by silica gel column chromatography (isolation yield 35%). Its characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 8.37 (d, J = 7.6 Hz, 1H), 7.87 –7.74 (m, 3H), 3.87 (s, 3H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.6 (s, 3F), -65.6 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 165.9, 149.8 (q, J = 46.8 Hz),143.6 (q, J = 2.6 Hz), 140.3 (q, J = 47.1 Hz), 136.1, 135.1, 133.1, 132.0, 131.7,130.5, 116.9 (q, J = 271.7 Hz), 115.2 (q, J = 273.2 Hz), 53.2.

[0042] Example 12

[0043] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 2-isocyanatomethylsulfonylnaphthalene, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(2'-naphthalenesulfonyl)-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (2:3, v / v) as eluents (isolation yield 43%). Its characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 8.68 (s, 1H), 8.06 – 7.97 (m, 3H), 7.94 (d, J = 8.2Hz, 1H), 7.70 (dt, J = 23.0, 7.3 Hz, 2H). 19 F NMR (376 MHz, Chloroform- d ) δ -59.8(s, 3F), -65.6 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.4 (q, J = 47.1 Hz),142.7 (q, J = 2.4 Hz), 141.9 (q, J = 46.9 Hz), 136.0, 134.3, 132.1, 131.6, 130.3,130.1, 129.8, 128.1, 128.1, 122.7, 116.8 (q, J = 272.1 Hz), 115.1 (q, J = 273.2Hz).

[0044] Embodiment 13

[0045] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 4-fluorobenzenesulfonylmethyl isonitrile, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, 0.60 mmol of triethylamine, and finally 2.0 mL of toluene solvent were added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation. 4-(4'-fluorobenzenesulfonyl)-2,5-bis(trifluoromethyl)oxazole (isolation yield 87%) was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents. Its characterization data are as follows: 1 HNMR (400 MHz, Chloroform- d ) δ 8.12 (dd, J = 7.2, 4.9 Hz, 2H), 7.31 (t, J = 7.6Hz, 2H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.7 (s, 3F), -100.1(tt, J = 8.3, 5.2 Hz, 1F). 13 C NMR (101 MHz, Chloroform- d ) δ 166.8 (d, J = 259.7Hz), 150.5 (q, J = 47.1 Hz), 142.4 (q, J = 2.7 Hz), 142.0 (q, J = 46.9 Hz), 133.6(d, J = 3.2 Hz), 132.2 (d, J = 10.1 Hz), 117.2 (d, J = 22.8 Hz), 116.8 (q, J = 272.1Hz), 115.1 (q, J = 273.3 Hz).

[0046] Embodiment 14

[0047] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 3-fluorobenzenesulfonylmethyl isonitrile, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(3'-fluorobenzenesulfonyl)-2,5-bis(trifluoromethyl)oxazole (isolation yield 86%) was separated by silica gel column chromatography using petroleum ether and dichloromethane (2:3, v / v) as eluents. The characterization data are as follows: 1 HNMR (400 MHz, Chloroform- d ) δ 7.88 (d, J = 7.9 Hz, 1H), 7.75 (d, J = 7.4 Hz, 1H),7.63 (q, J = 7.4, 6.9 Hz, 1H), 7.44 (t, J = 8.3 Hz, 1H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.7 (s, 3F), -108.0 (q, J = 7.4 Hz, 1F). 13 C NMR (101 MHz, Chloroform- d ) δ 162.5 (d, J = 253.8 Hz), 150.6 (q, J = 47.2 Hz), 142.4(q, J = 46.8 Hz), 142.0 (q, J = 2.6 Hz), 139.4 (d, J = 6.9 Hz), 131.7 (d, J = 7.7Hz), 125.0 (d, J = 3.4 Hz), 122.7 (d, J = 21.3 Hz), 116.7 (q, J = 272.2 Hz), 116.3(d, J = 24.9 Hz) , 115.1 (q, J = 273.3 Hz).

[0048] Embodiment 15

[0049] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of (4-chlorobenzenesulfonyl)acetonitrile, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, 0.60 mmol of triethylamine, and finally 2.0 mL of toluene solvent were added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation. 4-(4'-chlorobenzenesulfonyl)-2,5-bis(trifluoromethyl)oxazole (isolation yield 86%) was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents. Its characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.99 (d, J = 8.6 Hz, 2H), 7.58 (d, J = 8.7 Hz, 2H). 19 FNMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.8 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.5 (q, J = 46.9 Hz), 142.4, 142.2 (q, J = 2.7 Hz), 142.1 (q, J =47.0 Hz), 136.0, 130.5, 130.1, 116.7 (q, J = 272.1 Hz), 115.1 (q, J = 273.2 Hz).

[0050] Example 16

[0051] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 4-bromobenzenesulfonylacetonitrile, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, 0.60 mmol of triethylamine, and finally 2.0 mL of toluene solvent were added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation. 4-(4'-bromobenzenesulfonyl)-2,5-bis(trifluoromethyl)oxazole (isolation yield 83%) was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.92 (d, J = 8.7 Hz, 2H), 7.76 (d, J = 9.0 Hz, 2H). 19 FNMR (376 MHz, Chloroform- d ) δ -60.0 (s, 3F), -65.7 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.5 (q, J = 47.1 Hz), 142.2 (q, J = 2.7 Hz), 142.1 (q, J = 46.9Hz), 136.5, 133.2, 131.2, 130.5, 116.7 (q, J = 272.3 Hz), 115.1 (q, J = 273.3Hz).

[0052] Embodiment 17

[0053] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of dodecylsulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-dodecylsulfonyl-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents (isolation yield 65%). Its characterization data are as follows: 1HNMR (400 MHz, Chloroform- d ) δ 3.35 (d, J = 8.2 Hz, 2H), 1.87 – 1.76 (m,2H), 1.48 – 1.39 (m,2H), 1.33 – 1.23 (m, 16H), 0.86 (t, J = 6.7 Hz, 3H). 19 F NMR (376MHz, Chloroform- d ) δ -60.1 (s, 3F), -65.7 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.5 (q, J = 47.2 Hz), 142.8 (q, J = 47.0 Hz), 141.0 (q, J = 2.5Hz), 116.7 (q, J = 272.1 Hz), 115.2 (q, J = 273.2 Hz), 54.6, 31.9, 29.5 (2C), 29.4, 29.3, 29.1, 28.8, 28.1, 22.6, 21.7, 14.0.

[0054] Embodiment 18

[0055] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of 2-phenylethylsulfonylmethyl isonitrile, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-(2'-phenylethylsulfonyl)-2,5-bis(trifluoromethyl)oxazole was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents (isolation yield 68%). Its characterization data are as follows: 1 HNMR (400 MHz, Chloroform- d ) δ 7.32 – 7.23 (m, 3H), 7.19 (d, J = 7.6 Hz, 2H),3.75 (t, J= 7.3 Hz, 2H), 3.22 (t, J = 7.7 Hz, 2H). 19 F NMR (376 MHz, Chloroform- d )δ -60.2 (s, 3F), -65.7 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.3 (q, J =47.3 Hz), 142.4 (q, J = 47.2 Hz), 140.9 (q, J = 2.5 Hz), 136.0, 128.7, 128.6,127.3, 116.5 (q, J = 272.1 Hz), 115.0 (q, J = 273.2 Hz), 55.5, 28.4.

[0056] Embodiment 19

[0057] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of phenylmethylsulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-phenylmethylsulfonyl-2,5-bis(trifluoromethyl)oxazole (isolation yield 70%) was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400MHz, Chloroform- d ) δ 7.44 – 7.35 (m,3H), 7.30 (d, J = 7.5 Hz, 2H), 4.64 (s,2H). 19 F NMR (376 MHz, Chloroform- d ) δ -60.3 (s, 3F), -65.6 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ 150.5 (q, J = 47.2 Hz), 143.6 (q,J = 47.3 Hz), 139.7(q, J = 2.7 Hz), 131.0, 129.8, 129.1, 125.3, 116.4 (q, J = 272.5 Hz), 115.2 (q, J =273.3 Hz), 61.1.

[0058] Embodiment 20

[0059] In a 5 mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 0.30 mmol of cyclohexanesulfonylmethyl isocyanide, 1.05 mmol of trifluoroacetic anhydride, 0.01 mmol of cuprous chloride, and 0.60 mmol of triethylamine were added, and finally 2.0 mL of toluene solvent was added. The mixture was stirred in a closed system at 30 °C for 16 h. After the reaction was completed, the volatile solvent in the mixture was removed by rotary evaporation, and 4-cyclohexanesulfonyl-2,5-bis(trifluoromethyl)oxazole (isolation yield 71%) was separated by silica gel column chromatography using petroleum ether and dichloromethane (1:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400MHz, Chloroform- d ) δ 3.34 – 3.23 (m, 1H), 2.09 (d, J = 12.8 Hz, 2H), 1.73 (d, J =10.6 Hz, 1H), 1.66 – 1.52 (m,2H), 1.37 – 1.19 (m, 3H). 19 F NMR (376 MHz, Chloroform- d ) δ -59.8 (s, 3F), -65.6 (s, 3F). 13 C NMR (101 MHz, Chloroform- d ) δ150.6 (q, J = 47.1 Hz), 144.0 (q, J = 46.9 Hz), 139.8 (q, J = 2.7 Hz), 116.7 (q, J =272.2 Hz), 115.2 (q, J = 273.4 Hz), 62.7, 24.8, 24.7, 24.6.

[0060] Application Example: Activity Determination of Plutella xylostella

[0061] Determination method: The compounds obtained in Examples 2, 13, 15, and 16 were dissolved in a mixed solvent of acetone / methanol (1:1, v / v), and then diluted with water containing 0.1% (wt) Tween 80 to prepare a 10 mg / L test solution for later use. The cabbage leaves were punched into leaf discs with a diameter of 2 cm using a puncher, and the pressure of the Airbrush spray treatment was 10 psi (about 0.7 kg / cm 2 ), spray each leaf disc on both sides, and the spray volume of the test liquid is 0.5 mL. After the leaf discs are dried in the shade, 10 3rd instar larvae are inoculated for each treatment, and each treatment is repeated 3 times. After treatment, they are placed in an observation room at 25°C and a relative humidity of 60-70% for cultivation. The number of surviving insects is observed after 72 hours, and the mortality rates are calculated to be 13%, 42%, 27%, and 50%, respectively. It can be seen that the 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound prepared by the present invention has good insecticidal activity.

[0062] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A method for synthesizing a 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound, characterized in that: Using sulfonylmethyl isonitrile derivatives as substrates and trifluoroacetic anhydride as a fluorine source, the reaction is carried out in a solvent under alkaline conditions and copper catalysis to synthesize 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compounds; The sulfonylmethyl isonitrile derivative is any one of the following formulas 1 to 13: ； The copper salt used in copper catalysis is one of CuCl, CuI, CuBr, Cu(OTf)2, Cu(OAc)2; The base used for alkaline conditions was triethylamine; The solvent is one of toluene and acetonitrile; The 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound is specifically any one of the following formulas 1 to 13: 。 2. The synthesis method according to claim 1, characterized in that: Specifically, a sulfonylmethyl isocyanide derivative, trifluoroacetic anhydride, copper salt, triethylamine and a solvent are mixed, reacted at 30°C for 8-16 hours under magnetic stirring, and then the volatile solvent in the reaction mixture is removed by rotary evaporation, and then purified by a silica gel column to obtain the 4-sulfonyl-2,5-bis(trifluoromethyl)oxazole compound.

3. The synthesis method according to claim 2, characterized in that: The molar ratio of the sulfonylmethyl isonitrile derivative, trifluoroacetic anhydride, copper salt and triethylamine used is (0.30-1):(1.05-3.5):(0.01-0.04):(0.60-2).

Images