Fused ring compound with sulfur-containing substituent, preparation method, insecticide composition, and use

Abstract

The present invention belongs to the field of agricultural insecticides and particularly relates to a fused ring compound with a sulfur-containing substituent, a preparation method, an insecticide composition, and use. Compared with the prior art, the present invention has the beneficial effects that: the fused ring compound with a sulfur-containing substituent provided by the present invention has good prevention and treatment effect on many kinds of pests at a relatively low test concentration, providing a basis for research and development of new pesticides.

Description

Intermediate compound 3 Step D: Synthesis of Intermediate Compound 4 According to the method described in step H of Preparation Example 1, intermediate compound 4 represented by the following formula can be obtained. Intermediate Compound 4 Step E: Synthesis of Intermediate Compound 5 Intermediate Compound 4 (5 mmol) was dissolved in dried toluene (35 mL) and cesium carbonate (7.5 mmol) was then added. The mixture was degassed with argon and then tris(dibenzylideneacetone)dipalladium (0) (0.11 mmol), 2,2'-bis(diphenylphosphino)-1,l'-binaphtyle (0.2 mmol) and 2,4-Dimethoxybenzylamine (5 mmol) were added. The mixture was stirred under argon at 105°C (oil bath). The dark violet color of the mixture changed to pale yellow within 15 min. After 20 h, the reaction was cooled, and the solvent was removed under reduced pressure. The residue was purified on 50 g of silica gel, eluent 50% ethyl acetate in hexane. The intermediate compound 5 represented by the following formula can be obtained. Intermediate Compound 5 Step F: Synthesis of intermediate compound 6 Intermediate compound 5 (3.31 mmol) was dissolved in dichloromethane (20 mL) at room temperature and trifluoroacetic acid (3.31 mmol) was then added. The orange-red solution was stirred at room temperature for 5 h. The volatiles were removed under reduced pressure. The residue was alkalized with saturated solution of NaHCOs and extracted with ethyl acetate. The organic phase was separated, dried and concentrated. The residue was purified on 40 g of silica gel, eluent ethyl acetate to give intermediate compound 6 represented by the following formula. o=s=o Intermediate Compound 6 Step G: Synthesis of intermediate compound 7 Intermediate compound 6 (1 mmol) was dissolved in acetic acid glacial (10 mL) and then anhydrous sodium acetate (1 mmol) was added. Then bromine (1.2 mmol) dissolved in acetic acid (5 mL) was added dropwise at room temperature. The mixture was stirred at room temperature. After completion, The reaction mixture was washed with sodium thiosulfate solution and extracted with ethyl acetate. Finally, the organic phase was dried over Na2SO4. The residue was purified on silica gel, eluent 50% ethyl acetate in hexane to give intermediate compound 7 represented by the following formula. Intermediate Compound 7 Step H: Synthesis of Intermediate Compound 8 Intermediate compound 7 (1 mmol) was dissolved in tetrahydrofuran, then cyclopropanecarbonyl chloride (1 mmol) and triethylamine (1.5 mmol) were added. The mixture was stirred at room temperature. After the reaction was completed, purified it by column chromatography to obtain intermediate compound 8, which was a white solid represented by the following formula. Intermediate Compound 8 *H NMR (400 MHz, Chloroform-; / ) 5 9.44 (d, J = 1.6 Hz, 1H), 8.75 (d, J = 2.0 Hz, 1H), 8.30 (d, J= 2.0 Hz, 1H), 8.12 (s, 1H), 3.91 (d, J= 1.6 Hz, 3H), 3.81 (q, J = 7.5 Hz, 2H), 1.74 - 1.68 (m, 1H), 1.39 (t, J= 7.5 Hz, 3H), 1.26 - 1.22 (m, 3H), 1.06 (dt, J= 7.5, 3.5 Hz, 2H). Step I: Synthesis of intermediate compound 9 Intermediate compound 8 (1 mmol) was dissolved in tetrahydrofuran (15 mL), followed by the addition of Lawesson's reagent (1.5 mmol) and stirring under reflux. After the reaction was completed, the solvent was evaporated, and the residue was purified by column chromatography to give intermediate compound 9, represented by the following formula, as a light yellow solid with a yield of 40%. o=s=o s Intermediate Compound 9 Step J: Synthesis of target compound 1-73 Intermediate compound 9 (1 mmol) was dissolved in 1,4-dioxane (15 mL), then cesium carbonate (1.5 mmol) was added. The reaction mixture was stirred and heated at 80°Cin oil bath. After the reaction was completed, the mixture was diluted with water and extracted with ethyl acetate.. The organic phase was dried over Na2SO4. Finally, purified by column chromatography to obtain the compound 1-73 of the present invention represented by the following formula as a white solid with a yield of 80%, m.p. 216-219°C. o=s=o Compound 1-73 of the present invention *H NMR (400 MHz, CDCL) 5 8.84 (s, 1H), 8.77 (d, J= 1.9 Hz, 1H), 8.34 (d, J= 2.1 Hz, 1H), 3.86 (s, 3H), 3.75 (q, J = 7.4 Hz, 2H), 2.51 (tt, J = 8.1, 5.3 Hz, 1H), 1.46 - 1.41 (m, 4H), 1.35 (t, J= 7 A Hz, 3H).EI-MS: 468[M+H]+o Example 4: Synthesis of target compound 1-37 Intermediate compound 8 (1 mmol) was dissolved in 1,4-dioxane (15 mL), then Cui was added (1.5 mmol) and stirred under reflux in a nitrogen atmosphere. After the reaction was completed, distilled off the solvent, and the residue was purified by column chromatography to give the compound 1-37 of the present invention, represented by the following formula, as a white solid, with a yield of 40%. m.p. 224-227°C. o=s=o Compound 1-37 of the present invention *H NMR (400 MHz, CDCL) 5 8.77 (dd, J = 2.0, 0.8 Hz, 1H), 8.69 (s, 1H), 8.31 (d, J = 2.0 Hz, 1H), 3.87 (s, 3H), 3.83 (q, J= 7 A Hz, 2H), 2.35 (tt, J = 8.2, 4.9 Hz, 1H), 1.50 -1.45 (m, 2H), 1.42 - 1.39 (m, 2H), 1.36 (d, J = 7.5 Hz, 3H).EI-MS: 452[M+H]+ Example 5: Synthesis of target compound 1-109 Step A: Synthesis of intermediate compound 10 According to the method described in step I of Preparation Example 3, the substrate (1 mmol) was dissolved in tetrahydrofuran (15 mL), followed by the addition of Lawesson's reagent (1.5 mmol) and stirring under reflux. After the reaction was completed, the solvent was evaporated, and the residue was purified by column chromatography to give the intermediate compound 10 represented by the following formula, with a yield of 70%. Intermediate Compound 10 Step B: Synthesis of target compound 1-109 Intermediate compound 10 (1 mmol) was dissolved in 1,4-dioxane (15 mL), followed by the addition of cesium carbonate (1.5 mmol). The mixture was stirred and heated at 80°Cin oil bath. Upon completion of the reaction, the mixture was diluted with water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate. Finally, the residue was purified by column chromatography to give compound 1-109 of the present invention, represented by the following formula, with a yield of 85%. m.p. 207210°C. Compound 1-109 of the present invention *H NMR (400 MHz, CDCh) 5 8.99 (s, 1H), 8.79-8.73 (m, 2H), 8.30 (dd, J= 8.8, 1.9 Hz, 2H), 3.94 (s, 3H), 3.93-3.88 (m, 2H), 2.52 (tt, J= 8.0, 4.7 Hz, 1H), 1.59-1.54 (m, 2H), 1.47 (dt, J= 8.1, 3.4 Hz, 2H), 1.41-1.37 (m, 3H).EI-MS: 468[M+H]+o Similar to the example and based on the aforementioned preparation method, the following compound of formula (I) was synthesized: (I) Table 2 Comp. No. X Y R m.p. (°C) EI-MS: [M+H]+ 1-1 N-CH3 N cyclopropyl 201-204 465 1-2 N-CH3 N -CH3 241-244 463 1-3 N-CH3 N -Ph 189-191 501 1-4 N-CH3 N -2-F-Ph 1-5 N-CH3 N -2,4-F-Ph 206-209 537 1-6 N-CH3 N -CH2CH3 1-7 N-CH3 N isopropyl 206-209 467 1-8 N-CH3 N -CH2CH2CH3 205-207 467 1-9 n-ch3 N tert-butyl 196-199 463 1-10 n-ch3 N cyclobutyl 226-228 463 1-11 n-ch3 N cyclopentyl 1-12 n-ch3 N cyclohexyl 1-13 n-ch3 N -3-F-Ph 1-14 n-ch3 N -4-F-Ph 182-184 519 1-15 n-ch3 N propenyl 1-16 n-ch3 N difluoromethyl 182-184 475 1-17 n-ch3 N cyclopropanecarbonitrile 255-258 490 1-18 n-ch3 N -2-Cl-Ph 1-19 n-ch3 N -2-Br-Ph 1-20 n-ch3 N -2-CH3-Ph 1-21 n-ch3 N -2-CF3-Ph 1-22 n-ch3 N -2-OCH3-Ph 1-23 n-ch3 N -3-OCF3-Ph 1-24 n-ch3 N -3,4-OCH3-Ph 1-25 n-ch3 N ethynyl 1-26 n-ch3 N isobutyl 1-27 n-ch3 N -CH2C1 1-28 n-ch3 N trifluoromethyl 1-29 n-ch3 N ethenyl 235-237 451 1-30 n-ch3 N propynyl 1-31 n-ch3 N butenyl 1-32 n-ch3 N butynyl 1-33 n-ch3 N -2-thiophenyl 1-34 n-ch3 N -3-Py 1-35 n-ch3 N -2-Cl-Py 1-36 n-ch3 N -5-Br-Py 1-37 0 N cyclopropyl 224-227 452 1-38 0 N -CH3 1-39 0 N -Ph 1-40 0 N -2-F-Ph 1-41 0 N -2,4-F-Ph 1-42 0 N -CH2CH3 1-43 0 N isopropyl 1-44 0 N -CH2CH2CH3 1-45 0 N tert-butyl 1-46 0 N cyclobutyl 1-47 0 N Cyclopentyl 1-48 0 N cyclohexyl 1-49 0 N -3-F-Ph 1-50 0 N -4-F-Ph 1-51 0 N propenyl 1-52 0 N difluoromethyl 1-53 0 N cyclopropanecarbonitrile 1-54 0 N -2-Cl-Ph 1-55 0 N -2-Br-Ph 1-56 0 N -2-CH3-Ph 1-57 0 N -2-CF3-Ph 1-58 0 N -2-OCH3-Ph 1-59 0 N -3-OCF3-Ph 1-60 0 N -3,4-OCH3-Ph 1-61 0 N ethynyl 1-62 0 N isobutyl 1-63 0 N -CH2C1 1-64 0 N trifluoromethyl 1-65 0 N ethenyl 1-66 0 N propynyl 1-67 0 N butenyl 1-68 0 N butynyl 1-69 0 N -2-thiophenyl 1-70 0 N -3-Py 1-71 0 N -2-Cl-Py 1-72 0 N -5-Br-Py 1-73 s N cyclopropyl 216-219 468 1-74 s N -CH3 150-152 442 1-75 s N -Ph 1-76 s N -2-F-Ph 1-77 s N -2,4-F-Ph 1-78 s N -CH2CH3 1-79 s N isopropyl 1-80 s N -CH2CH2CH3 1-81 s N tert-butyl 1-82 s N cyclobutyl 1-83 s N Cyclopentyl 1-84 s N cyclohexyl 1-85 s N -3-F-Ph 1-86 s N -4-F-Ph 212-213 522 1-87 s N propenyl 1-88 s N difluoromethyl 204-205 478 1-89 s N cyclopropanecarbonitrile 1-90 s N -2-Cl-Ph 1-91 s N -2-Br-Ph 1-92 s N -2-CH3-Ph 1-93 s N -2-CF3-Ph 1-94 s N -2-OCH3-Ph 1-95 s N -3-OCF3-Ph 1-96 s N -3,4-OCH3-Ph 1-97 s N ethynyl 1-98 s N isobutyl 1-99 s N -CH2CI I-100 s N trifluoromethyl 180-182 496 1-101 s N ethenyl 1-102 s N propynyl 1-103 s N butenyl 1-104 s N butynyl 1-105 s N -2-thiophenyl 1-106 s N -3-Py 1-107 s N -2-Cl-Py 1-108 s N -5-Br-Py 1-109 N S cyclopropyl 207-210 468 1-110 N S -CH3 1-111 N s -Ph 1-112 N s -2-F-Ph 1-113 N s -2,4-F-Ph 1-114 N s -CH2CH3 1-115 N s isopropyl 1-116 N s -CH2CH2CH3 1-117 N S tert-butyl 1-118 N S cyclobutyl 1-119 N s Cyclopentyl 1-120 N s cyclohexyl 1-121 N s -3-F-Ph 1-122 N s -4-F-Ph 1-123 N s propenyl 1-124 N s difluoromethyl 1-125 N s cyclopropanecarbonitrile 1-126 N s -2-Cl-Ph 1-127 N s -2-Br-Ph 1-128 N s -4-CH3-Ph 1-129 N s -2-CF3-Ph 1-130 N s -2-OCH3-Ph 1-131 N s -3-OCF3-Ph 1-132 N s -3,4-OCH3-Ph 1-133 N s ethynyl 1-134 N s isobutyl 1-135 N s -CH2C1 1-136 N s trifluoromethyl 1-137 N s ethenyl 1-138 N s propynyl 1-139 N s butenyl 1-140 N s butynyl 1-141 N s -2-thiophenyl 1-142 N s -3-Py 1-143 N s -2-Cl-Py 1-144 N s -5-Br-Py The nuclear magnetic resonance data of the preferred compound mentioned above are shown in Table 3: Table 3 Comp. No. 'HNMR 1-1 ‘H NMR (400 MHz, CDCh) 8 8.79 - 8.74 (m, 1H), 8.65 (s, 1H), 8.31 (d, 7=2.0 Hz, 1H), 3.99 (s, 3H), 3.83 (s, 3H), 3.68 (q, J= 7.4 Hz, 2H), 2.14 (tt, J= 8.1, 4.8 Hz, 1H), 1.42 (dt, J= 4.8, 3.2 Hz, 2H), 1.35 - 1.28 (m, 5H). 1-2 ‘H NMR (400 MHz, CDCh) 8 8.79 - 8.73 (m, 2H), 8.33 (d, J= 2.0 Hz, 1H), 3.89 (s, 3H), 3.82 (s, 3H), 3.68 (q, J= 7.5 Hz, 2H), 2.79 (s, 3H), 1.33 (t, J= 7.4 Hz, 3H). 1-3 ‘H NMR (400 MHz, CDCh) 8 8.86 - 8.80 (m, 1H), 8.66 (s, 1H), 8.41 (d, J = 2.0 Hz, 1H), 7.91 - 7.82 (m, 2H), 7.68 - 7.59 (m, 3H), 4.30 (s, 3H), 3.97 (s, 3H), 3.44 (q, J= 7.4 Hz, 2H), 1.32 (t, J= 7.5 Hz, 3H). 1-5 ‘H NMR (400 MHz, CDCh) 8 8.90 (s, 1H), 8.78 (s, 1H), 8.33 (s, 1H), 7.82 (q, J = 7.8 Hz, 1H), 7.23 - 7.02 (m, 2H), 3.99 - 3.84 (m, 6H), 3.76 (q, J= 7.4 Hz, 2H), 1.36 (t, J= 7.4 Hz, 3H). 1-7 ‘H NMR (400 MHz, CDCh) 8 8.70 (s, 2H), 8.24 (d, J = 2.0 Hz, 1H), 3.84 (s, 3H), 3.77 (s, 3H), 3.62 (q, J= 7.4 Hz, 2H), 3.27 (d, J= 6.7 Hz, 1H), 1.46 (d, J= 6.8 Hz, 6H), 1.24 (d, J= 7.5 Hz, 4H). 1-8 ‘H NMR (400 MHz, CDCh) 8 8.80 - 8.72 (m, 2H), 8.32 (dd, J= 2.1, 0.7 Hz, 1H), 3.89 (s, 3H), 3.84 (s, 3H), 3.70 (q, J = 7.4 Hz, 2H), 3.00 (dd, J= 8.1, 7.2 Hz, 2H), 2.06 - 1.96 (m, 2H), 1.33 (t, J= 7.4 Hz, 4H), 1.14 (t, J = 7.4 Hz, 3H). 1-9 ‘H NMR (400 MHz, CDCh) 8 8.75 - 8.67 (m, 2H), 8.25 (d, J= 2.0 Hz, 1H), 4.01 (s, 3H), 3.77 (s, 3H), 1.56 (s, 9H). 1-10 ‘H NMR (400 MHz, CDCh) 8 8.82 - 8.72 (m, 2H), 8.31 (d, J = 2.0 Hz, 1H), 3.92 - 3.85 (m, 1H), 3.82 (d, J= 10.8 Hz, 6H), 3.69 (q, J= 7.4 Hz, 2H), 2.74 - 2.63 (m, 2H), 2.62 - 2.52 (m, 2H), 2.26 (dt, J= 11.3,8.9 Hz, 1H), 2.18 - 2.09 (m, 1H), 1.32 (t, . / = 6.8 Hz, 3H). 1-14 ‘H NMR (400 MHz, CDCh) 8 8.86 (s, 1H), 8.78 (dd, J= 1.9, 0.9 Hz, 1H), 8.33 (d, J= 1.9 Hz, 1H), 7.98 - 7.89 (m, 2H), 7.33 (t, J= 8.6 Hz, 2H), 4.05 (s, 3H), 3.87 (s, 3H), 3.75 (q, J = 7.4 Hz, 2H), 1.36 (t, J= 7.4 Hz, 3H). 1-16 ‘H NMR (400 MHz, CDCh) 8 8.90 (s, 1H), 8.70 (d, J= 1.8 Hz, 1H), 8.26 (d, . / = 2.0 Hz, 1H), 6.94 (t, J= 52.1 Hz, 1H), 4.05 (s, 3H), 3.79 (s, 3H), 3.70 (q, J= 7.4 Hz, 2H), 1.27 (t, J= 7.4 Hz, 3H). 1-17 ‘H NMR (400 MHz, CDCh) 8 8.78 (d, J = 2.0 Hz, 2H), 8.32 (d, J= 2.0 Hz, 1H), 4.20 (s, 3H), 3.85 (s, 3H), 3.74 (q, J= 7.4 Hz, 2H), 2.08 - 2.03 (m, 2H), 2.02 - 1.97 (m, 2H), 1.33 (t, J= 7.4 Hz, 3H). 1-28 ‘H NMR (400 MHz, CDCI3) 8 9.03 (s, 1H), 8.83 - 8.76 (m, 1H), 8.34 (d, J= 1.9 Hz, 1H), 4.12 (d, J= 1.2 Hz, 3H), 3.87 (s, 3H), 3.77 (q, J= 7.4 Hz, 2H), 1.35 (t, J= 7.4 Hz, 3H). 1-29 ‘H NMR (400 MHz,CDC13) 8 8.79 (s, 1H), 8.77 (dd, J= 2.0, 0.8 Hz, 1H), 8.31 (dd, J = 1.9, 0.7 Hz, 1H), 6.93 (dd, J= 17.1, 10.6 Hz, 1H), 6.82 (dd, J = 17.2, 1.6 Hz, 1H), 6.01 (dd, J = 10.6, 1.6 Hz, 1H), 3.97 (s, 3H), 3.84 (s, 3H), 3.72 (q, J= 7.4 Hz, 2H), 1.33 (t, J= 7.4 Hz, 3H). 1-37 ‘H NMR (400 MHz, CDCla) 8 8.77 (dd, J= 2.0, 0.8 Hz, 1H), 8.69 (s, 1H), 8.31 (d, J= 2.0 Hz, 1H), 3.87 (s, 3H), 3.83 (q, J = 7.4 Hz, 2H), 2.35 (tt, J = 8.2, 4.9 Hz, 1H), 1.50 - 1.45 (m, 2H), 1.42 - 1.39 (m, 2H), 1.36 (d, J = 7.5 Hz, 3H). 1-73 ‘H NMR (400 MHz, CDCla) 8 8.84 (s, 1H), 8.77 (d, J= 1.9 Hz, 1H), 8.34 (d, . / =2.1 Hz, 1H), 3.86 (s, 3H), 3.75 (q, J= 7.4 Hz, 2H), 2.51 (tt, J= 8.1, 5.3 Hz, 1H), 1.46-1.41 (m, 4H), 1.35 (t, J =7 A Hz, 3H). 1-74 ‘H NMR (400 MHz, CDCla) 8 8.96 (s, 1H), 8.78 (dd, J = 2.0, 0.8 Hz, 1H), 8.34 (dd, J = 2.0, 0.7 Hz, 1H), 3.88 (s, 3H), 3.79 (t, J = 7.4 Hz, 2H), 3.00 (s, 3H), 1.37 (t, J = 7.4 Hz, 3H). 1-86 ‘H NMR (400 MHz, CDCla) 8 9.04 (s, 1H), 8.79 (dd, J = 1.9, 0.8 Hz, 1H), 8.34 (dd, J = 2.0, 0.7 Hz, 1H), 8.23 - 8.16 (m, 2H), 7.32 - 7.27 (m, 2H), 3.92 (s, 3H), 3.88 -3.82 (m, 2H), 1.41 (t, J = 7.4 Hz, 3H). 1-88 ‘H NMR (400 MHz, CDCla) 8 9.21 (s, 1H), 8.83 - 8.78 (m, 1H), 8.35 (d, J = 2.0 Hz, 1H), 7.00 (t, J = 54.0 Hz, 1H), 3.92 (s, 3H), 3.89 (t, J = 7.4 Hz, 2H), 1.41 (t, J = 7.4 Hz, 3H). 1-100 ‘H NMR (400 MHz, CDCla) 8 9.29 (s, 1H), 8.81 (dd, J = 2.0, 0.8 Hz, 1H), 8.35 (dd, J = 2.0, 0.8 Hz, 1H), 3.95 - 3.87 (m, 6H), 1.41 (t, J = 7.4 Hz, 3H). 1-109 ‘H NMR (400 MHz, CDCla) 8 8.99 (s, 1H), 8.79-8.73 (m, 2H), 8.30 (dd, J = 8.8, 1.9 Hz, 2H), 3.94 (s, 3H), 3.93-3.88 (m, 2H), 2.52 (tt, J= 8.0, 4.7 Hz, 1H), 1.59-1.54 (m, 2H), 1.47 (dt, J= 8.1, 3.4 Hz, 2H), 1.41-1.37 (m, 3H). Biological Examples: This test case is used to illustrate the insecticidal activity inhibition (%) of compounds with the structure shown in formula (I) (dosage of lOOppm). Example 1: Activity against Myzus persicae (Green peach aphid): Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into agueous test solutions prepared from 10’000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions. The following compounds resulted in at least 90% mortality at a test rate of 100 ppm: I-l> I-2> I-3> I-5> 1-7 > I-8> I-9> I-10> I-14> I-16> I-17> I-29> I-37> I- 73 and 1-109. Example 2: Activity against Plutella xylostella'. 24-well microtiter plates with artificial diet were treated with agueous test solutions prepared from 10’000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. The following compounds gave an effect of at least 90% in at least one of the two categories (mortality or growth inhibition) at an application rate of 100 ppm: I-l> I-2> I-3> I-5> 1-7 > I-8> I-9> I-10> 1-14. 1-16. 1-17. I-29> 1-37. 1-73 and 1-109. Further, The following compounds gave an effect of 100% at an application rate of 4 ppm: 1-73 and 1-109 Example 3: Activity against Leucania separate'. Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with agueous test solutions prepared from 10’000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation. The following compounds gave an effect of at least 90% in at least one of the two categories (mortality or growth inhibition) at an application rate of 100 ppm: I-l> I-2> I-3> I-5> 1-7 > I-8> I-9> 1-10. 1-14. 1-16. 1-17. I-29> 1-37. 1-73 and 1-109. Example 4: Activity against Nilaparvata lugens'. Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with agueous test solutions prepared from 10’000 ppm DMSO stock solutions. After drying the leaf discs were infested with adult Nilaparvata lugens. The samples were checked for mortality 6 days after incubation. The following compounds resulted in at least 90% mortality at a test rate of 100 ppm: I-l> I-2> I-3> I-5> 1-7 > I-8> I-9> I-10> 1-14. I-16> I-17> I-29> I-37> 1-73> I-100 and 1-109. Further, The following compounds gave an effect of 95% at an application rate of 45 ppm: 1-73. I-100 and 1-109. Example 5: Activity against Laphygma exigua: 24-well microtiter plates with artificial diet were treated with agueous test solutions prepared from 10’000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. The following compounds gave an effect of at least 90% in at least one of the two categories (mortality or growth inhibition) at an application rate of 100 ppm: I-l> I-2> I-3> I-5> I-7> I-8> I-9> I-10> 1-14. 1-16. 1-17. I-29> 1-37. 1-73. I-74> 1-86 and 1-109. Further, The following compounds gave an effect of 100% at an application rate of 4 ppm: 1-73 and 1-109. Example 6: Activity against Aphis craccivora Koch'. Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into agueous test solutions prepared from 10’000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions. The following compounds resulted in at least 90% mortality at a test rate of 100 ppm: I-K I-2> I-3> I-5> 1-7 > I-8> I-9> I-10> 1-14» I-16> I-17> I-29> I-37> 1-73> I-74> I-86> 1-88 and 1-109. Further, The following compounds gave an effect of 100% at an application rate of 4 ppm: I-l> I-37> I-73> I-100 and 1-109. Example 7: Activity against Chilo suppressalis'. Take 5~6 rice seedlings, each 3~4 cm in height, soak them thoroughly in the prepared solution, After drying, the plates were infested with L2 larvae (10 per well). Keep them in an observation room for rearing and observation. Use 0.1% warm water as a blank control. Incubate them in an observation room at 25 to 27°C. After 96 hours, assess the samples based on mortality rates The following compounds gave an effect of 100% at an application rate of 5 ppm: 1-73 and 1-109. What has been described above are merely preferred embodiments of the present invention. It should be noted that for those skilled in the art, several variations and improvements can be made without departing from the inventive concept of the present invention, and all of these fall within the scope of protection of the present invention.

Claims

1. A fused ring compound with a sulfur-containing substituent of formula (I):wherein,X is selected from N, NR1, O or S;Y is selected from N or S; when Y is selected from N, X is selected from NR1, O or S; when Y is selected from S, X is selected from N;R1 is selected from methyl or ethyl;R is selected from cyclopropyl, isopropyl, cyclobutyl, cyclopentyl, vinyl, phenyl, cyanocyclopropyl, 4-fluorophenyl, 3-fluorophenyl, 2,4-difluorophenyl, 2-thienyl, 2-pyridyl, 2-chloropyridyl or 5-bromopyridyl.

2. The fused ring compound with a sulfur-containing substituent according to claim 1, comprising compounds of formula (I-a), (I-b), (I-c) and (I-d):tr                            tr z=^           z=^ o  [|      1                     O  fl 1 ^1101 z      z\llA '   CD                       CD ii                                                               ii o A A O A z  z          z  z 0  0 o             o Ll?                         lT tr                                tr / t / 0         Y\ / Z O  [|     1                      O  [|     1 Z   (4)                              to II                                                                       II o A -V     o A zx z ~       zx z 0  0 o               o co                                         co(I-c)(I-d)2023316544   27 Aug 2026wherein,R1 is selected from methyl;R is selected from cyclopropyl, isopropyl, cyclobutyl, cyclopentyl, vinyl, phenyl, cyanocyclopropyl, 4-fluorophenyl, 3-fluorophenyl, 2,4-difluorophenyl, 2-thienyl, 2-pyridyl, 2-chloropyridyl or 5-bromopyridyl.

3. The fused ring compound with a sulfur-containing substituent according to claim 1 or 2, wherein,R1 is selected from methyl; R is selected from cyclopropyl.

4. A method for preparing the fused ring compound with a sulfur-containing substituent of formula (I-a) according to claim 2 or 3, comprising:(1) stirring and refluxing a compound prepared by reacting a compound of formula(II) with a compound of formula (III) in acetic acid to give a compound of formula (IV);(2) contacting the compound of formula (IV) with ethanethiol under an alkaline condition to give a compound of formula (V);(3) reacting the compound of formula (V) with an oxidant to give a compound of formula (VI);(4) conducting a Buchwald coupling reaction of the compound of formula (VI) and 2,4-dimethoxybenzylamine to give a compound of formula (VII);(5) reacting the compound of formula (VII) with trifluoroacetic acid to give a compound of formula (VIII);(6) reacting the compound of formula (VIII) with a brominating reagent to give a compound of formula (IX);(7) reacting the compound of formula (IX) with acyl chloride in the presence of an acid binding agent to give a compound of formula (X);(8) reacting the compound of formula (X) with a Lawson’s reagent to give a2023316544   27 Aug 2026compound of formula (XI);(9) reacting the compound of formula (XI) in the presence of a base to give the finaltarget compound of formula (I-a);substituent of formula (I-b) according to claim 2 or 3, comprising:refluxing and stirring a compound of formula (X) in a solvent in the presence of CuI,2023316544   27 Aug 2026a base and a catalyst to give the compound of formula (I-b);6. A method for preparing the fused ring compound with a sulfur-containing substituent of formula (I-c) according to claim 2 or 3, comprising:(1) refluxing and stirring a compound of formula (II) in acetic acid to give a compound of formula (III);(2) reacting the compound of formula (III) with ethanethiol in the presence of a base to give a compound of formula (IV);(3) oxidizing the compound of formula (IV) to give a compound of formula (V);(4) contacting the compound of formula (V) with a substituted amine in a solvent to give a compound of formula (VI);(5) dissolving the compound of formula (VI) in concentrated sulfuric acid, and then adding dilute nitric acid dropwise at low temperature to give a compound of formula (VII);(6) reducing the compound of formula (VII) to give a compound of formula (VIII);(7) reacting the compound of formula (VIII) with a substituted acyl chloride to give a compound of formula (IX);(8) refluxing and stirring the compound of formula (IX) in acetic acid to give the compound of formula (I-c);2023316544   27 Aug 20267. A method for preparing the fused ring compound with a sulfur-containing substituent of formula (I-d) according to claim 2 or 3, comprising:(I-d)(1) contacting a compound of formula (V) obtained in (I-c) with ammonia solution in a solvent to give a compound of formula (X);(2) brominating the compound of formula (X) in a solvent in the presence of a base to give a compound of formula (XI);(3) reacting the compound of formula (XI) with a substituted acyl chloride to give a compound of formula (XII);(4) reacting the compound of formula (XII) with a Lawson’s reagent to give a compound of formula (XIII);2023316544   27 Aug 2026(5) conducting a cyclization reaction of the compound of formula (XIII) in the presence of a base to give the compound of formula (I-d);8. Use of a fused ring compound with a sulfur-containing substituent according to any one of claims 1 to 3 in the preparation of an insecticide.

9. The use according to claim 8, wherein the insecticide is an insecticide for controlling one or more insects belonging to the order lepidoptera and / or coleoptera.

10. The use according to claim 8, wherein a pest targeted by the insecticide is selected from one or more of nilaparvata lugens, laodelphax striatellus, bemisia tabaci, plutella xylostella, mythimna separata, myzus persicae, and tetranychus cinnabarinus.

11. An insecticide, comprising the fused ring compound with a sulfur-containing substituent according to any one of claims 1-3 and an adjuvant, wherein the concentration of the fused ring compound with a sulfur-containing substituent in the insecticide is 1600ppm.

12. A method of controlling one or more insects belonging to the order Lepidoptera and / or the order Coleoptera, comprising applying, to the one or more insects or to a substrate with which the one or more insects are in contact, an effective amount of a fused ring compound with a sulfur-containing substituent according to any one of claims 1 to 3.2023316544   27 Aug 202613. The method according to claim 12, wherein the one or more insects belong to the order Lepidoptera.

14. The method according to claim 13, wherein the one or more insects are selected from Plutella xylostella, Mythimna separata, Laphygma exigua and Chilo suppressalis.

15. The method according to any one of claims 12 to 14, wherein the fused ring compound with a sulfur-containing substituent is applied at a concentration of 1 to 600 ppm.

16. The method according to claim 15, wherein the fused ring compound with a sulfur-containing substituent is applied at a concentration of 4 to 100 ppm.