一种[1,2,4]三唑[4,3-a]吡啶类含硫化合物在制备杀虫剂中的应用

本发明属于农业用杀虫剂领域，具体来说涉及一种[1,2,4]三唑[4,3-a]吡啶类含硫化合物在制备杀虫剂中的应用。

技术领域
本发明属于农业用杀虫剂领域，具体来说涉及一种[1,2,4]三唑[4,3-a]吡啶类含硫化合物在制备杀虫剂中的应用。
背景技术
[1,2,4]三唑[4,3-a]吡啶类衍生物具有多种生物，如除草（Pest Manag. Sci. 2015，71，292-301）、杀菌活性（Chin. J. Struct. Chem. 2016，35，457-464； Chin. J. Struct. Chem.， 2016，35，651-655； Chem. Biol. Drug Des. 84 (2014) 342-347）、抗惊厥(Arzneimittelforsch. 2012，62， 372-377)等，是新药物的研发的热点领域。此外，含硫化合物也是近年来备受关注的一类活性物质，其中硫醚、砜类化合物在农用杀菌剂的报道较多（J. Heterocyclic Chem. 2016，53，865-875；Bioorg. & Med. Chem. 2007，15,3981–3989；Chin. J. Struct. Chem. 2016，35，457-464；Chin. J. Struct. Chem.，2016，35，651-655），其中，一些含硫醚的化合物被报道具有较好的杀虫活性（Aust. J. Chem. 2014，67，1491-1503；Pestic. Sc. 48 (1996) 31-35；Chem. Pap. 68 (2014) 969-975；Chinese Chemical Letters, 2013，24，673-676）。近期，一些含硫醚的[1,2,4]三唑[4,3-a]吡啶类化合物被报道具有良好的抗油菜菌核病菌、立枯丝核菌、尖孢镰刀菌、雪腐镰刀菌、烟曲霉菌和白色念珠菌等活性（Chem. Biol. Drug Des.，2014，84，342-347）。硫醚的[1,2,4]三唑[4,3-a]吡啶类化合物在杀菌剂的应用方面有所涉及（Chem. Biol. Drug Des.，2014，84，342-347），但迄今为止，还没有任何报道将[1,2,4]三唑[4,3-a]吡啶类含硫化合物作为杀虫剂的应用。
发明内容
本发明的目的在于提供的一种[1,2,4]三唑[4,3-a]吡啶类含硫化合物在制备抗植物病毒剂中的应用。一种[1,2,4]三唑[4,3-a]吡啶类含硫化合物在制备防治包括烟草、水稻、蔬菜、玉米、蚕豆等作物上的蚜虫、褐飞虱、棉铃虫、小菜蛾、甜菜夜蛾、烟蚜夜蛾等害虫中的应用。尤其是在防治小菜蛾、棉铃虫、甜菜夜蛾中的应用。本发明的[1,2,4]三唑[4,3-a]吡啶类含硫化合物在制备杀虫剂中的应用，化合物结构如通式I所示：                      式中：n选0、2；R选自-CH₃、乙基、3,4,4-三氟-3-烯-1-丁基、卤代苄基、甲基取代苄基、甲氧基取代苄基、卤代甲氧基取代苄基、卤代甲氧基取代1,3,4-噁二唑-2-基甲基、卤代吡啶-2-基甲基、三氟乙氧基取代吡啶-2-基甲基。进一步地，当n=0时，通式I所代表的化合物如下：                      当n=2时，通式I所代表的化合物如下：                              本发明的通式 I 化合物可按照以下合成路线所示的方法进行制备，其中，各个中间体1、2、3及目标化合物4可参照专利 CN 105017247报道的方法进行制备;目标化合物5参照文献Pestic. Biophy. Biochem. 2011, 101, 6-15；Molecules. 2010, 15(2), 766-779；Bioorg. & Med. Chem. 15, 3981–3989等报道的方法进行制备：                      反应式中，化合物的取代基与上述相同。所合成得到的目标化合物核磁数据如下：化合物4a: 收率： 94.8%; 黄色固体; m.p. 114.6-116.6 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.73 (dt, ³J = 8.6 Hz, ⁴J = 4.3 Hz, 1H), 7.33 (d, ³J = 1.8 Hz, 1H), 7.29 (dd, ³J = 7.2, ³J = 0.7 Hz, 1H), 7.00 – 6.93 (m, 2H, Ph-H), 6.72 (t, ³J = 7.0 Hz, 1H, P-H), 4.38 (s, 2H, -CH₂-). ¹³C NMR (125 MHz, Chloroform-D) δ 149.19, 141.95, 134.76, 134.71, 133.18, 131.72, 129.73, 127.38, 126.53, 122.75, 121.39, 113.92, 37.07. Anal. Calc. for C₁₃H₈Cl₃N₃S: C 45.30%, H 2.34%, N 12.19%. Found: C 45.32%, H 2.36%, N 12.17%.化合物4b: 收率： 84.7%; 淡黄色固体; m.p. 88,6-90.1 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.67 (d, ³J= 6.9 Hz, 1H, Ar-H), 7.26 (d, ³J= 9.4 Hz, 1H, Ar-H), 7.09 (dd, ³J= 8.5 Hz, ³J= 5.3 Hz, 2H, Ar-H), 6.87 – 6.79 (m, 2H, Ph-H), 6.68 (t,³J= 7.0 Hz, 1H, Ar-H), 4.27 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 162.42 (d, ¹J_C-F = 247.6 Hz), 149.06, 142.24, 132.62, 130.56 (d, ²J_C-F =21.6 Hz), 126.47, 122.62, 121.46, 115.75 (d, ²J_C-F 21.6 Hz), 113.77, 39.39; Anal. Calc. for C₁₃H₉ClFN₃S: C 53.15%, H 3.09%, N 14.30%. Found: C 53.17%, H 3.19%, N 14.33%.化合物4c: 收率：98.5%; 黄色固体; m.p. 76.4-78.3 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.67 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.25 (d, ³J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.02 (d, ³J = 8.6 Hz, 1H, Ph-H), 6.67 (d, ³J = 8.6 Hz, 1H, Ph-H), 6.64 (t, ³J = 7.0 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 4.26 (s, 2H, -CH₂-), 3.71 (s, 3H, -CH₃). ¹³C NMR (126 MHz, Chloroform-D) δ 159.38, 154.10, 149.01, 143.47, 130.06, 128.66, 126.37, 123.14, 122.48, 121.69, 115.12, 114.18, 113.56, 55.39, 39.98; Anal. Calc. for C₁₄H₁₂ClN₃OS: C 54.99%, H 3.96%, N 13.74%. Found: C 54.86%, H 3.97%, N 13.84%.化合物4d: 收率： 27.3%; 黄色固体; m.p. 108.4-109.1°C; ¹H NMR (500 MHz, Chloroform-D) δ 8.26 (d, ³J = 2.5 Hz, 1H), 7.77 (d,³J = 6.9 Hz, 1H), 7.53 (dd, ³J = 8.2, ⁴J = 2.5 Hz, 1H), 7.30 (d,³J = 7.2 Hz, 1H), 7.13 (d, ³J = 8.2 Hz, 1H), 6.77 (t, ³J = 7.0 Hz, 1H), 4.35 (s, 2H,- CH₂-). ¹³C NMR (126 MHz, Chloroform-D) δ 151.03, 149.81, 149.20, 141.61, 139.29, 131.80, 126.58, 124.26, 122.90, 121.21, 114.21, 35.63; Anal. Calc. for C₁₂H₈Cl₂N₄S: C 46.32%, H 2.59%, N 18.00%. Found: C 46.37%, H 2.63%, N 18.05%.化合物4e: 收率： 76.8%; Brown solid; m.p. 67.9-68.8 °C; ¹H NMR (500 MHz, Chloroform-D) δ 8.27 (d, ³J = 7.1 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.38 (d, ³J = 7.2 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 6.78 (t, ³J = 7.1 Hz, 1H [1,2,4]triazolo [4,3-a]pyridine-H), 4.06 (s, 3H, -CH₃); ¹³C NMR (126 MHz, Chloroform-D) δ149.06, 144.30, 126.19, 122.81, 121.54, 113.82, 16.61; Anal. Calc. for C₇H₆ClN₃S: C 42.11%, H 3.03%, N 21.05%. Found: C 42.16%, H 3.13%, N 21.15%.化合物4f: 收率：76.8%; 黄色固体; m.p. 96.7-97.8 °C; ¹H NMR (500 MHz, Chloroform-D) δ 8.04 (d, ³J = 6.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.32 (d, ³J = 7.8 Hz, 1H, Ar-H), 6.85 (t, ³J = 7.0 Hz, 1H, Ar-H), 3.16 (q, ³J= 7.3 Hz, 2H, -CH₂-), 1.34 (t, ³J = 7.2 Hz, 3H, -CH₃); ¹³C NMR (126 MHz, Chloroform-D) δ 145.78, 136.39, 126.32, 122.80, 121.73, 113.90, 29.33, 15.38; Anal. Calc. for C₈H₈ClN₃S: C 44.97%, H 3.77%, N 19.66%. Found: C 44.02%, H 3.79%, N 19.68%.化合物4g: 收率： 99.3%; Brown solid; m.p. 79.8-81.1 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.51 (d, J = 6.9 Hz, 1H, Ar-H), 7.25 (d, ³J = 6.3 Hz, 1H, Ar-H), 7.11 – 7.04 (m, 2H, Ar-H), 6.85 (t,³J = 7.2 Hz, 1H, Ar-H), 6.76 (d, ³J = 7.5 Hz, 1H, Ar-H), 6.58 (t, ³J = 7.0 Hz, 1H, Ar-H), 4.28 (s, 2H, -CH₂-), 2.39 (s, 3H, -CH₃). ¹³C NMR (125 MHz, Chloroform-D) δ 149.05, 142.47, 136.53, 134.58, 130.80, 129.60, 128.37, 126.44, 126.33, 122.43, 121.49, 113.59, 38.58, 19.18; Anal. Calc. for C₁₄H₁₂ClN₃S: C 58.03%, H 4.17%, N 14.50%. Found: C 58.13%, H 4.13%, N 14.52%.化合物4h: 收率： 79.5%; 灰色固体; m.p. 90.2-91.3 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.62 (dd, ³J = 6.9 Hz, ⁴J =0.7 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.27 (d, ⁴J = 0.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.15 (d, 2H, Ph-H), 6.99 (d, J = 8.1 Hz, 2H, Ph-H), 6.64 (t, ³J = 7.1 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.28 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 149.12, 148.82, 141.94, 135.76, 130.30, 126.48, 122.65, 121.42, 121.31, 119.35, 113.80, 77.38, 77.13, 76.87, 39.40; Anal. Calc. for C₁₄H₁₂ClN₃S: 46.74%, H 2.52%, N 11.68%. Found: C 46.72%, H 2.53%, N 11.78%.化合物4i: 收率： 58.9%; 白色固体; m.p. 101.1-102.2 °C; ¹H NMR (500 MHz, Chloroform-D) δ7.63 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.41 (d, ³J = 7.9 Hz, 2H, Ph-H), 7.27 (d, ³J = 7.7 Hz, 2H, Ph-H), 7.25 (d, ³J= 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.66 (t, ³J = 7.1 Hz, 1H), 4.35 (s, 2H, -CH₂-). ¹³C NMR (126 MHz, Chloroform-D) δ 149.12, 148.82, 141.94, 135.76, 130.30, 126.48 (q, ¹J_C-F= 129.1 Hz), 123.45, 122.65, 121.42, 121.31, 119.35, 117.31, 113.80, 77.38, 77.13, 76.87, 39.40, 0.09; Anal. Calc. for C₁₄H₉ClF₃N₃S: 48.92%, H 2.64%, N 12.22%. Found: C 48.82%, H 2.56%, N 12.08%.化合物4j: 收率： 89.2%; 褐色; m.p. 109.7-110.8 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.73 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.60 (d, ³J = 7.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.33 – 7.20 (m, 3H, Ph-H), 7.10 (d, ³J = 7.5 Hz, 1H), 6.70 (dd, ³J = 9.0, ³J = 5.0 Hz, 1H, Ph-H), 4.46 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 149.20, 142.14, 135.08, 132.20, 131.72, 128.67 (q, ¹J_C-F= 129.4 Hz), 127.95, 127.56, 126.61, 125.38, 123.20, 122.67, 121.47, 113.97, 77.40, 77.15, 76.89, 36.59; Anal. Calc. for C₁₄H₉ClF₃N₃S: 48.92%, H 2.64%, N 12.22%. Found: C 48.85%, H 2.57%, N 12.18%.化合物4k: 收率： 90.5%; 白色固体; m.p. 100.0-101.7 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.80 (dd, ³J =6.9 Hz, ⁴J = 0.6 Hz, 1H), 7.30 (dd,³J = 7.2 Hz, ⁴J = 0.7 Hz, 1H), 7.02 (td, ³J =8.6, ³J = 6.3 Hz, 1H), 6.77 – 6.70 (m, 2H, Ph-H), 6.62 (dd, J = 7.1, 1.6 Hz, 1H), 4.30 (s, 2H); ¹³C NMR (126 MHz, Chloroform-D) δ 162.86 (d, ¹J_C-F= 257.1 Hz), 160.59 (d, ¹J_C-F= 213.4 Hz), 152.33, 149.19, 142.04, 131.75 (d, ²J_C-F= 9.7 Hz), 126.54, 122.78, 121.40, 120.00, 111.54 (d, ²J_C-F= 21.2 Hz), 104.25 (t, ²J_C-F = 25.3 Hz), 32.64; Anal. Calc. for C₁₃H₈ClF₂N₃S: 50.09 %, H 2.59%, N 13.48%. Found: 50.19 %, H 2.61%, N 13.50%.化合物4l: 收率： 84.6%; 黄色固体; m.p. 89.7-90.5 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.82 (dd,³J = 6.9, 0.8 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.33 – 7.29 (m, 1H, Ar-H), 6.93 (td, ³J = 8.9 Hz, ⁴J = 4.5 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.86 (m, 2H, Ar-H), 6.75 (t,³J = 7.0 Hz, 1H, ArH), 4.30 (s, 2H, -CH₂-). ¹³C NMR (126 MHz, Chloroform-D) δ 158.39 (d, ¹J_C-F = 241.9 Hz), 156.70 (d, ¹J_C-F = 244.9 Hz), 149.25, 141.89, 126.55, 122.85, 121.40, 117.39, 116.83 (d, ²J_C-F = 8.6 Hz), 116.64 (d, ²J_C-F = 8.5 Hz), 116.48 (d, ²J_C-F = 8.5 Hz), 116.29 (d, ²J_C-F = 8.4 Hz), 114.00, 32.75; Anal. Calc. for C₁₃H₈ClF₂N₃S: 50.09 %, H 2.59%, N 13.48%. Found: 50.19 %, H 2.61%, N 13.50%.化合物4m: 收率： 88.1%; Brown solid; m.p. 145.2-146.2 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.95 (dd, ³J = 6.9, ⁴J = 0.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.33 (dd, ³J = 7.2, ⁴J =0.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.21 (dd, ³J = 7.2, ⁴J =4.5,1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.77 (m, 3H, PH-H), 4.25 (s, 2H); ¹³C NMR (126 MHz, Chloroform-D) δ 161.03 (d, ¹J_C-F = 250.5 Hz), 160.97 (d, ¹J_C-F = 250.4 Hz), 149.34, 141.58, 130.09, 130.01, 129.93, 126.67, 122.92, 121.58, 114.04, 113.31, 113.16 (t, J = 19.0 Hz), 111.54 (d, ²J_C-F = 20.4 Hz), 111.51 (d, ²J_C-F = 20.3 Hz), 26.85; Anal. Calc. for C₁₃H₈ClF₂N₃S: 50.09 %, H 2.59%, N 13.48%. Found: 50.12 %, H 2.63%, N 13.51%.化合物4n: 收率： 95.7%; White solid; m.p. 112.7-113.5 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.78 (dd, ³J = 6.85 Hz, ⁴J = 1.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.31 (dd, ³J = 6.8 Hz, ⁴J = 0.85 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.15 (dd, ³J = 9.3 Hz, ⁴J = 1.8 Hz, 1H, Ar-H), 7.02 (dd, ³J = 8.3 Hz, ⁴J = 1.8 Hz, 1H, Ar-H), 6.92 (t, J = 8.1 Hz, 1H, Ar-H), 6.75 (t, J = 7.1 Hz, 1H, Ar-H), 4.27 (s, 2H, -CH₂); ¹³C NMR (126 MHz, Chloroform-D) δ 160.44 (d, ¹J_C-F= 253.0 Hz), 149.20, 141.90, 131.96, 131.93, 127.70, 126.59, 123.34 (d, ²J_C-F = 14.7 Hz), 122.47 (d, ²J_C-F = 9.6 Hz), 122.43, 121.40, 119.47, 119.28, 114.03, 32.64; Anal. Calc. for C₁₃H₈BrClFN₃S: 41.90 %, H 2.16%, N 11.28%, Found: 41.95%, H 2.23%, N 11.25%.化合物4o: 收率： 99.1%; 黄色固体; m.p. 121.1-122.3 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.74 (dd, ³J = 6.9, ⁴J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.29 (dd, ³J = 7.2, ⁴J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.07 (dd, ³J = 8.4, ⁴J = 2.6 Hz, 1H, Ph-H), 7.00 (dd, J = 8.6, 6.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.73 – 6.67 (m, 2H, Ph-H), 4.38 (s, 2H, -CH₂); ¹³C NMR (126 MHz, Chloroform-D) δ 162.22 (d, ¹J_C-F= 251.4 Hz), 149.17, 142.03, 134.81, 132.05, 131.98, 130.56, 126.53, 122.71, 121.40, 117.34 (d, ²J_C-F= 25.0 Hz), 114.34 (d, ²J_C-F= 20.9 Hz), 113.89, 37.05; Anal. Calc. for C₁₃H₈Cl₂FN₃S: 47.58 %, H 2.46%, N 12.80%, Found: 47.54 %, H 2.33%, N 12.88%.化合物4p: 收率： 82.8%; 黄色固体; m.p. 105.4-107.3 °C; ¹H NMR (500 MHz, CHLOROFORM-D) δ 7.79 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.29 (d, ³J =7.1 Hz, 1H, Ar-H), 7.23 – 7.18 (m, 1H, Ar-H), 6.90 (dd, ³J = 10.3 Hz, ⁴J = 3.8 Hz, 1H), 6.80 (t, ³J = 7.8 Hz, 1H, Ar-H), 6.74 (t, ³J = 7.0 Hz, 1H, Ar-H), 4.33 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 156.19 (d, ¹J_C-F= 250.6 Hz), 149.19, 141.82, 130.55, 129.21, 126.58, 125.80 (d, ²J_C-F= 14.5 Hz), 124.74, 124.71,122.72, 121.40, 113.95, 33.21; Anal. Calc. for C₁₃H₈Cl₂FN₃S: 47.58 %, H 2.46%, N 12.80%, Found: 47.49%, H 2.53%, N 12.85%.化合物4q: 收率： 88.23%; Drab solid; m.p. 168.7-169.3 °C; ¹H NMR (500 MHz, CHLOROFORM-D) δ 7.75 (d, ³J = 6.9 Hz, 1H, ArH), 7.45 (dd, ³J = 8.8, ³J = 5.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.29 (d, ³J = 7.2 Hz, 1H, Ar-H), 6.86 (dd, ³J =8.7 Hz, ⁴J = 2.9 Hz, 1H, ArH), 6.80 (td,³J = 8.4 Hz, ⁴J = 3.0 Hz, 1H, ArH), 6.72 (t,³J =7.0 Hz, 1H, ArH), 4.39 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 161.71 (d, ¹J_C-F= 248.8 Hz), 149.26, 141.85, 138.22, 126.53, 122.80, 121.42, 118.48, 118.03 (d, J = 23.5 Hz), 116.89 (d, J = 22.5 Hz), 113.92, 39.99; Anal. Calc. for C₁₃H₈BrClFN₃S: 41.90 %, H 2.16%, N 11.28%, Found: 41.93 %, H 2.17%, N 11.31%.化合物4r: 收率： 99.6%; White solid; m.p. 168.1-168.6 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.74 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.74 (d, ³J = 6.9 Hz, 1H, Ar-H), 7.30 – 7.23 (m, 3H, Ar-H), 7.01 (dd, ³J = 8.5, ³J =5.9 Hz, 1H, Ar-H), 6.73 (dd,³J = 11.2, ³J = 4.8 Hz, 2H, Ar-H), 4.40 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 161.99 (d, ¹J_C-F = 252.4 Hz), 149.18, 141.98, 132.25, 131.98, 131.91, 126.5, 124.53, 122.70, 121.44, 120.52 (d, ²J_C-F = 24.9 Hz), 114.88 (d, ²J_C-F = 20.8 Hz), 113.88, 39.65; Anal. Calc. for C₁₃H₈Cl₂FN₃S: 41.90 %, H 2.16%, N 11.28%, Found: 41.93 %, H 2.17%, N 11.31%; Anal. Calc. for C₁₃H₈BrClFN₃S: 41.90 %, H 2.16%, N 11.28%, Found: 41.95 %, H 2.14%, N 11.33%.化合物4s: 收率： 53.1%; 黄色固体; m.p. 90.0-91.1 °C; ¹H NMR (500 MHz, Chloroform-D) δ 8.08 (d,³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.41 (d, ³J = 7.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.93 (t, ³J = 7.1 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.55 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 165.30, 155.95 (q, ¹J_C-F = 44.8 Hz), 149.62, 139.74, 127.13, 123.18, 121.57, 117.00, 114.82, 28.82. Anal. Calc. for C₁₀H₅ClF₃N₅OS: 35.78%, H 1.50%, N 20.86%, Found: 35.85%, H 1.52%, N 20.87%.化合物4t: 收率： 57.1%; Gray solid; m.p. 110.0-112.0 °C; ¹H NMR (500 MHz, Chloroform-D) δ 8.18 (d, ³J = 5.6 Hz, 1H, pyridine-H), 7.95 (d, ³J = 6.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.31 (d, ³J = 7.1 Hz, 1H, pyridine-H), 6.78 (t, ³J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.60 (d, ³J = 5.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.51 (s, 2H, -CH₂-), 4.37 (q,³J = 7.8 Hz, 2H, -CH₂-CF₃), 2.21 (s, 3H); ¹³C NMR (126 MHz, Chloroform-D) δ 161.70, 155.54, 149.14, 148.12, 142.54, 126.40, 122.74, 121.89, 121.48, 113.75, 105.70, 65.43 (q, ¹J_C-F = 36.7 Hz), 39.13, 10.68; Anal. Calc. for C₁₅H₁₂ClF₃N₄OS: C 46.34%, H 3.11%, N 14.41%, Found: 46.41%, H 3.16%, N 14.48%.化合物4u: 收率： 76.8%; White solid; m.p. 92.1-93.2 °C; ¹H NMR (500 MHz, Chloroform-D) δ 7.76 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.48 – 7.42 (m, 1H, Ar-H), 7.31 – 7.26 (m, 2H, Ph-H), 7.09 (t, ³J = 8.9 Hz, 1H, Ph-H), 6.73 (t, ³J = 7.0 Hz, 1H), 4.34 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 162.41 (d, ¹J_C-F = 254.4 Hz), 128.21, 127.32, 125.31 (d, ²J_C-F = 15.9 Hz), 124.35, 122.91, 122.19, 121.19, 116.42 (d, ²J_C-F = 22.8 Hz), 114.13, 32.83; Anal. Calc. for C₁₄H₈BrClF₄N₃S: C 46.48%, H 2.23%, N 11.62%, Found: C 46.53%, H 2.27%, N 11.64%.化合物4v: 收率： 76.8% ; 黄色固体; m.p. 46.8-47.5 °C; ¹H NMR (500 MHz, Chloroform-D) δ 8.28 (d, ³J = 7.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.40 (d, ³J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.80 (t, ³J = 7.1 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.67 (t, ³J = 7.2 Hz, 2H, -CH₂-), 3.03 – 2.95 (m, 2H, -CH₂CF=CF₂); ¹³C NMR (126 MHz, Chloroform-D) δ 153.76 (ddd, ¹J _C-F = 287.8, ¹J _C-F =274.6, ²J _C-F = 45.7 Hz), 149.17, 142.21, 127.60 (ddd, ¹J _C-F = 234.9 Hz, J = 53.3 Hz, ²J _C-F = 16.9 Hz) , 126.43, 122.92, 121.47, 114.12, 30.22, 26.62 (d, ²J_C-F= 21.6 Hz); Anal. Calc. for C₁₀H₇ClF₃N₃S: C 40.90%, H 2.40%, N 14.31%, Found: C 40.87%, H 2.43%, N 14.34%.化合物5a: 收率：61.8%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.74 (dt, ³J = 8.6 Hz, ⁴J = 4.3 Hz, 1H), 7.36 (d, ³J = 1.8 Hz, 1H), 7.27 (dd, ³J = 7.2, ³J = 0.7 Hz, 1H), 7.00 – 6.94 (m, 2H, Ph-H), 6.71 (t, ³J = 7.0 Hz, 1H, P-H), 4.59 (s, 2H, -CH₂-). ¹³C NMR (125 MHz, Chloroform-D) δ 149.2, 141.8, 134.76, 134.73, 133.2, 131.8, 129.8, 127.5, 126.6, 122.7, 121.4, 114.2, 37.17.化合物5b: 收率： 47.2%; 淡黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.69 (d, ³J= 6.9 Hz, 1H, Ar-H), 7.29 (d, ³J= 9.4 Hz, 1H, Ar-H), 7.19 (dd, ³J= 8.5 Hz, ³J= 5.3 Hz, 2H, Ar-H), 6.76 – 6.89 (m, 2H, Ph-H), 6.87 (t,³J= 7.0 Hz, 1H, Ar-H), 4.89 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 162.46 (d, ¹J_C-F = 247.6 Hz), 149.66, 142.66, 132.7, 130.7 (d, ²J_C-F =21.6 Hz), 126.8, 122.7, 121.7, 115.7 (d, ²J_C-F 21.6 Hz), 113.8, 39.5.化合物5c: 收率：63.5%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.69 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.28(d, ³J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.04 (d, ³J = 8.6 Hz, 1H, Ph-H), 6.66 (d, ³J = 8.6 Hz, 1H, Ph-H), 6.67 (t, ³J = 7.0 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 4.57 (s, 2H, -CH₂-), 3.73 (s, 3H, -CH₃). ¹³C NMR (126 MHz, Chloroform-D) δ 159.4, 154.3, 1493, 143.5, 130.4, 128.7, 126.6, 123.3 1226, 121.7, 115.4, 114.3, 113.6, 55.4, 39.4.化合物5d: 收率： 47.3%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 8.31 (d, ³J = 2.5 Hz, 1H), 7.79 (d,³J = 6.9 Hz, 1H), 7.54 (dd, ³J = 8.2, ⁴J = 2.5 Hz, 1H), 7.33 (d,³J = 7.2 Hz, 1H), 7.16 (d, ³J = 8.2 Hz, 1H), 6.79 (t, ³J = 7.0 Hz, 1H), 4.57 (s, 2H,- CH₂-). ¹³C NMR (126 MHz, Chloroform-D) δ 151.1, 149.8, 149.5, 141.7, 139.3, 131.8, 126.58, 124.5, 122.92, 121.3, 114.3, 35.5; Anal. Calc. for C₁₂H₈Cl₂N₄S: C 46.32%, H 2.59%, N 18.00%. Found: C 46.37%, H 2.63%, N 18.05%.化合物5e: 收率： 67.8%; 褐色固体; ¹H NMR (500 MHz, Chloroform-D) δ 8.29 (d, ³J = 7.1 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.37 (d, ³J = 7.2 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 6.79 (t, ³J = 7.1 Hz, 1H [1,2,4]triazolo [4,3-a]pyridine-H), 4.46 (s, 3H, -CH₃); ¹³C NMR (126 MHz, Chloroform-D) δ 149.06, 144.33, 126.18, 122.84, 121.59, 113.88, 17.66.化合物5f: 收率：72.8%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 8.24 (d, ³J = 6.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.32 (d, ³J = 7.8 Hz, 1H, Ar-H), 6.95 (t, ³J = 7.0 Hz, 1H, Ar-H), 3.36 (q, ³J = 7.3 Hz, 2H, -CH₂-), 1.54 (t, ³J = 7.2 Hz, 3H, -CH₃); ¹³C NMR (126 MHz, Chloroform-D) δ 145.79, 136.38, 126.32, 122.81, 121.73, 113.91, 29.32, 15.39.化合物5g: 收率： 34.3%;褐色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.54 (d, J = 6.9 Hz, 1H, Ar-H), 7.27 (d, ³J = 6.3 Hz, 1H, Ar-H), 7.10 – 7.08 (m, 2H, Ar-H), 6.88 (t,³J = 7.2 Hz, 1H, Ar-H), 6.77 (d, ³J = 7.5 Hz, 1H, Ar-H), 6.59 (t, ³J = 7.0 Hz, 1H, Ar-H), 4.48 (s, 2H, -CH₂-), 2.38 (s, 3H, -CH₃). ¹³C NMR (125 MHz, Chloroform-D) δ 149.07, 142.49, 136.57, 134.59, 130.84, 129.63, 128.34, 126.43, 126.32, 122.42, 121.48, 113.57, 38.52, 19.19.化合物5h: 收率： 79.5%; 灰色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.68 (dd, ³J = 6.85 Hz, ⁴J =0.75 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.28 (d, ⁴J = 0.85 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.14 (d, 2H, Ph-H), 6.87 (d, J = 8.0 Hz, 2H, Ph-H), 6.66 (t, ³J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.48 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 149.17, 148.82, 141.99, 135.78, 130.32, 126.49, 122.63, 121.41, 121.32, 119.34, 113.82, 77.35, 77.12, 76.83, 39.43.化合物5i: 收率：34.6%; 白色固体;; ¹H NMR (500 MHz, Chloroform-D) δ7.63 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.41 (d, ³J = 7.9 Hz, 2H, Ph-H), 7.27 (d, ³J = 7.7 Hz, 2H, Ph-H), 7.25 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.66 (t, ³J = 7.1 Hz, 1H), 4.35 (s, 2H, -CH₂-). ¹³C NMR (126 MHz, Chloroform-D) δ 149.12, 148.82, 141.94, 135.76, 130.30, 126.48 (q, ¹J_C-F= 129.1 Hz), 123.45, 122.65, 121.42, 121.31, 119.35, 117.31, 113.80, 77.38, 77.13, 76.87, 39.40, 0.09; Anal. Calc. for C₁₄H₉ClF₃N₃S: 48.92%, H 2.64%, N 12.22%. Found: C 48.82%, H 2.56%, N 12.08%.化合物5j: 收率：67.8 %; 褐色; ¹H NMR (500 MHz, Chloroform-D) δ 7.74 (d, ³J = 6.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.62 (d, ³J = 7.5 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.32 – 7.21 (m, 3H, Ph-H), 7.10 (d, ³J = 7.0 Hz, 1H), 6.72 (dd, ³J = 9.5, ³J = 5.5 Hz, 1H, Ph-H), 4.66 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 149.20, 142.14, 135.08, 132.22, 131.71, 128.64 (q, ¹J_C-F= 129.4 Hz), 127.92, 127.52, 126.63, 125.33, 123.25, 122.69, 121.45, 113.94, 77.42, 79.95, 79.89, 36.62.化合物5k: 收率： 56.5%; 白色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.82 (dd, ³J =6.8 Hz, ⁴J = 0.7 Hz, 1H), 7.32 (dd,³J = 7.1 Hz, ⁴J = 0.8 Hz, 1H), 7.12 (td, ³J =8.5, ³J = 6.0 Hz, 1H), 6.77 – 6.71 (m, 2H, Ph-H), 6.60 (dd, J = 7.2, 1.6 Hz, 1H), 4.33 (s, 2H); ¹³C NMR (126 MHz, Chloroform-D) δ 162.84 (d, ¹J_C-F= 257.1 Hz), 160.53 (d, ¹J_C-F= 213.4 Hz), 152.31, 149.12, 142.14, 131.72 (d, ²J_C-F= 9.7 Hz), 126.52, 122.72, 121.42, 120.02, 111.52 (d, ²J_C-F= 21.2 Hz), 104.23 (t, ²J_C-F = 25.3 Hz), 32.64.化合物5l: 收率：78.6%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.85 (dd,³J = 6.8, 0.8 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.33 – 7.28 (m, 1H, Ar-H), 6.95 (td, ³J = 8.5 Hz, ⁴J = 4.5 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.84 (m, 2H, Ar-H), 6.70 (t,³J = 7.0 Hz, 1H, ArH), 4.33 (s, 2H, -CH₂-). ¹³C NMR (126 MHz, Chloroform-D) δ 158.42 (d, ¹J_C-F = 241.9 Hz), 156.72 (d, ¹J_C-F = 244.9 Hz), 149.23, 141.87, 126.53, 122.89, 121.42, 117.34, 116.85 (d, ²J_C-F = 8.6 Hz), 116.66 (d, ²J_C-F = 8.5 Hz), 116.47 (d, ²J_C-F = 8.5 Hz), 116.25 (d, ²J_C-F = 8.4 Hz), 114.03, 32.71.化合物5m: 收率： 56.1%;褐色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.98 (dd, ³J = 6.85, ⁴J = 0.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.33 (dd, ³J = 7.15, ⁴J =0.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.24 (dd, ³J = 7.0, ⁴J =4.3,1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.72 (m, 3H, PH-H), 4.55 (s, 2H); ¹³C NMR (126 MHz, Chloroform-D) δ 161.03 (d, ¹J_C-F = 250.5 Hz), 160.97 (d, ¹J_C-F = 250.4 Hz), 149.34, 141.58, 130.09, 130.01, 129.93, 126.67, 122.92, 121.58, 114.04, 113.31, 113.16 (t, J = 19.0 Hz), 111.54 (d, ²J_C-F = 20.4 Hz), 111.51 (d, ²J_C-F = 20.3 Hz), 26.85; Anal. Calc. for C₁₃H₈ClF₂N₃S: 50.09 %, H 2.59%, N 13.48%. Found: 50.12 %, H 2.63%, N 13.51%.化合物5n: 收率：62.7%; 白色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.83 (dd, ³J = 6.9 Hz, ⁴J = 1.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.35 (dd, ³J = 6.8 Hz, ⁴J = 0.85 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.19 (dd, ³J = 9.3 Hz, ⁴J = 1.8 Hz, 1H, Ar-H), 7.22 (dd, ³J = 8.3 Hz, ⁴J = 1.8 Hz, 1H, Ar-H), 6.97 (t, J = 8.1 Hz, 1H, Ar-H), 6.85 (t, J = 7.1 Hz, 1H, Ar-H), 4.37 (s, 2H, -CH₂); ¹³C NMR (126 MHz, Chloroform-D) δ 160.46 (d, ¹J_C-F= 253.0 Hz), 149.25, 141.91, 131.97, 131.92, 127.76, 126.58, 123.34 (d, ²J_C-F = 14.7 Hz), 122.46 (d, ²J_C-F = 9.6 Hz), 122.42, 121.43, 119.46, 119.21, 114.01, 32.62.化合物5o: 收率：43.1%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.76 (dd, ³J = 6.85, ⁴J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.26 (dd, ³J = 7.2, ⁴J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.17 (dd, ³J = 8.4, ⁴J = 2.6 Hz, 1H, Ph-H), 7.04 (dd, J = 8.6, 6.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.73 – 6.62 (m, 2H, Ph-H), 4.69 (s, 2H, -CH₂); ¹³C NMR (126 MHz, Chloroform-D) δ 162.21 (d, ¹J_C-F= 251.4 Hz), 149.13, 142.13, 134.11, 132.15, 131.93, 130.54, 126.54, 122.73, 121.42, 117.33 (d, ²J_C-F= 25.0 Hz), 114.14 (d, ²J_C-F= 20.9 Hz), 113.85, 37.15.化合物5p: 收率： 61.4%; 黄色固体; ¹H NMR (500 MHz, CHLOROFORM-D) δ 7.82 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.34 (d, ³J =7.1 Hz, 1H, Ar-H), 7.24 – 7.19 (m, 1H, Ar-H), 6.93 (dd, ³J = 9.3 Hz, ⁴J = 3.8 Hz, 1H), 6.82 (t, ³J = 7.5 Hz, 1H, Ar-H), 6.78 (t, ³J = 7.0 Hz, 1H, Ar-H), 4.54 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 156.16 (d, ¹J_C-F= 250.6 Hz), 149.34, 141.80, 130.15, 129.24, 126.52, 125.81 (d, ²J_C-F= 14.5 Hz), 124.77, 124.72,122.76, 121.43, 113.85, 33.24.化合物5q:收率： 65.3%; 灰色固体; ¹H NMR (500 MHz, CHLOROFORM-D) δ 7.78 (d, ³J = 6.85 Hz, 1H, ArH), 7.43 (dd, ³J = 8.5, ³J = 5.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.25 (d, ³J = 7.2 Hz, 1H, Ar-H), 6.87 (dd, ³J =8.5 Hz, ⁴J = 2.9 Hz, 1H, ArH), 6.85 (td,³J = 8.0 Hz, ⁴J = 3.0 Hz, 1H, ArH), 6.70 (t,³J =7.0 Hz, 1H, ArH), 4.55 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 161.73 (d, ¹J_C-F= 248.8 Hz), 149.24, 141.85, 138.24, 126.56, 122.82, 121.41, 118.47, 118.13 (d, J = 23.5 Hz), 116.86 (d, J = 22.5 Hz), 113.91, 40.91;化合物5r: 收率：63.4%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.78 (d, ³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.75 (d, ³J = 6.9 Hz, 1H, Ar-H), 7.30 – 7.21 (m, 3H, Ar-H), 7.21 (dd, ³J = 8.5, ³J =5.9 Hz, 1H, Ar-H), 6.72 (dd,³J = 11.2, ³J = 4.8 Hz, 2H, Ar-H), 4.51 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 161.90 (d, ¹J_C-F = 252.4 Hz), 149.15, 143.32, 132.25, 131.78, 131.92, 126.54, 124.45, 122.71, 121.43, 120.54 (d, ²J_C-F = 24.9 Hz), 114.82 (d, ²J_C-F = 20.8 Hz), 113.81, 40.65.化合物5s: 收率：53.1%; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 8.18 (d,³J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.44 (d, ³J = 7.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.92 (t, ³J = 7.1 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.72 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 165.31, 155.94 (q, ¹J_C-F = 44.8 Hz), 149.65, 139.74, 127.12, 123.19, 121.54, 117.01, 114.82, 29.89.化合物5t: 收率： 53.7%; 白色固体; ¹H NMR (500 MHz, Chloroform-D) δ 8.21 (d, ³J = 5.5 Hz, 1H, pyridine-H), 7.89 (d, ³J = 6.5 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.34 (d, ³J = 7.1 Hz, 1H, pyridine-H), 6.77 (t, ³J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.65 (d, ³J = 5.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.73 (s, 2H, -CH₂-), 4.35 (q,³J = 7.8 Hz, 2H, -CH₂-CF₃), 2.22 (s, 3H); ¹³C NMR (126 MHz, Chloroform-D) δ 161.71, 155.52, 149.15, 148.11, 142.53, 126.43, 122.73, 121.83, 121.43, 113.73, 105.73, 65.46 (q, ¹J_C-F = 36.7 Hz), 40.13, 10.45.化合物5u: 收率：62.6%; 白色固体; ¹H NMR (500 MHz, Chloroform-D) δ 7.75 (d, ³J = 6.85 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.43 – 7.38 (m, 1H, Ar-H), 7.32 – 7.24 (m, 2H, Ph-H), 7.05 (t, ³J = 8.5 Hz, 1H, Ph-H), 6.71 (t, ³J = 7.05Hz, 1H), 4.64 (s, 2H, -CH₂-); ¹³C NMR (126 MHz, Chloroform-D) δ 162.42 (d, ¹J_C-F = 254.4 Hz), 128.23, 127.32, 125.33 (d, ²J_C-F = 15.9 Hz), 124.32, 122.93, 122.15, 121.15, 116.41 (d, ²J_C-F = 22.8 Hz), 114.11, 35.82.化合物5v: 收率： 54.3% ; 黄色固体; ¹H NMR (500 MHz, Chloroform-D) δ 8.18 (d, ³J = 7.15 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.37 (d, ³J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.82 (t, ³J = 7.1 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.68 (t, ³J = 7.2 Hz, 2H, -CH₂-), 3.13 – 2.94 (m, 2H, -CH₂CF=CF₂); ¹³C NMR (126 MHz, Chloroform-D) δ 153.72 (ddd, ¹J _C-F = 287.8, ¹J _C-F =274.6, ²J _C-F = 45.7 Hz), 149.27, 142.23, 127.61 (ddd, ¹J _C-F =234.9 Hz, J = 53.3 Hz, ²J _C-F = 16.9 Hz), 126.44, 122.92, 121.45, 114.22, 35.22, 26.79 (d, ²J_C-F= 21.6 Hz).本发明的化合物制备的杀虫剂，主要用于防治蚜虫、褐飞虱、小菜蛾、棉铃虫、甜菜夜蛾等农作物害虫。
具体实施方式
以杀小菜蛾、棉铃虫、及甜菜夜蛾的活性为例，但并不限定本发明化合物防治其它害虫的应用。实施例1：对小菜蛾的杀虫活性采用国际抗性行动委员会(IRAC)提出的浸叶法(J. Agric. Food Chem., 2007,55(23): 9614–9619.)。用配制好的待测药液。用直头眼科镊子浸渍甘蓝叶片，时间3-5秒，甩掉余液。每次1片，每个样品共3片。按样品标记顺序依次放在处理纸上。待药液干后，放入具有标记的10 cm长的直型管内，接入2龄小菜蛾幼虫30头，用纱布盖好管口。将试验处理置于标准处理室内，96 h检查结果以拨针轻触虫体，不动者为死亡。计算死亡率(实验做3次重复，取平均值)。以商品药毒死蜱为对照药剂。计算死亡率和校正死亡率:          (1)式中：P₁—死亡率; K—死亡虫数; N—处理总虫数。           (2)式中：P₂—校正死亡率；P_t—处理死亡率; P₀ —空白对照死亡率。若对照死亡率＜5%，无需校正；对照死亡率在5-20%之间，应按公式(2)进行校正；对照死亡率＞20%，试验需重做。部分化合物的活性结果如表1.表1 部分化合物对小菜蛾的杀虫活性                              实施例2：对棉铃虫的杀虫活性测试采用饲料混药法，从配置好的溶液中移取3 mL加入到27 g的刚配置好的饲料中，得到稀释十倍的所需浓度。药剂混匀后均匀地倒入干净的24孔板中，晾凉后接入24头棉铃虫，观察3-4天后检查结果。计算死亡率和校正死亡率:          (1)式中：P₁—死亡率; K—死亡虫数; N—处理总虫数。          (2)式中：P₂—校正死亡率；P_t—处理死亡率; P₀ —空白对照死亡率。若对照死亡率＜5%，无需校正；对照死亡率在5-20%之间，应按公式(2)进行校正；对照死亡率＞20%，试验需重做。部分化合物的活性结果如表2.表2 部分化合物对棉铃虫的杀虫活性                              实施例3：对甜菜夜蛾的杀虫活性采用的浸叶法(J. Agric. Food Chem., 2007,55(23): 9614–9619.)。用配制好的待测药液，将甘蓝叶片浸渍3-5秒，甩掉余液。按样品标记顺序依次放在处理纸上。待药液干后，放入具有标记的60 cm长的培养皿内，接入3龄甜菜夜蛾幼虫30头，盖好盖子。将试验处理置于标准处理室内，96 h检查结果以拨针轻触虫体，不动者为死亡。计算死亡率(实验做3次重复，取平均值) 。计算死亡率和校正死亡率:           (1)式中：P₁—死亡率; K—死亡虫数; N—处理总虫数。           (2)式中：P₂—校正死亡率；P_t—处理死亡率; P₀ —空白对照死亡率。若对照死亡率＜5%，无需校正；对照死亡率在5-20%之间，应按公式(2)进行校正；对照死亡率＞20%，试验需重做。部分化合物的活性结果如表3.表3 部分化合物对甜菜夜蛾的杀虫活性                              实施例4：对小菜蛾的IC₅₀测定采用与实施例1相同的测试方法，在浓度上设置上采用二倍稀释法，对部分化合物的IC₅₀值进行测试（以毒死蜱为对照药剂），计算其毒力方程及IC₅₀值。所得结果表4所示。表4 部分化合物对小菜蛾的IC₅₀值                              实施例5：对棉铃虫的IC₅₀测定采用与实施例2相同的测试方法，在浓度上设置上采用二倍稀释法，对部分化合物的IC₅₀值进行测试（以毒死蜱为对照药剂），计算其毒力方程及IC₅₀值。所得结果表5所示。表5 部分化合物对棉铃虫的IC₅₀值                      以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，任何未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。