A benzopentaheterocyclic compound and application thereof

Abstract

The present application belongs to the field of insecticides, and particularly relates to a benzopentaheterocyclic compound and application thereof. The structure is shown in general formula I, wherein definitions of the substituents are shown in the description. The compound of general formula I has excellent insecticidal activity and can be used for preventing and treating various pests.

Description

Technical Field

[0001] This invention belongs to the field of insecticides, specifically relating to a benzo[a] 5-membered heterocyclic compound and its applications. Background Technology

[0002] In crop production in agriculture and horticulture, pest damage remains significant and pests have developed resistance to existing pesticides, necessitating continuous research and development of new pesticides and their combinations.

[0003] CN108484517B discloses a benzoxazole compound, but no specific insecticidal activity data has been published.

[0004]

[0005] WO2012086848 discloses a fused heterocyclic compound, some of which show a certain mortality rate against peach aphid, cotton aphid, brown planthopper and diamondback moth.

[0006]

[0007] In order to discover novel insecticides, the inventors, through dedicated research, discovered the benzo[a]₅ heterocyclic compound of this invention, as shown in general formula I, which has a novel structure and excellent insecticidal activity. The benzo[a]₅ heterocyclic compound and its insecticidal activity shown in this invention have not been reported before. Summary of the Invention

[0008] The purpose of this invention is to provide a benzo[5]-heterocyclic compound and its application as an insecticide.

[0009] To achieve the above objectives, the technical solution of the present invention is as follows:

[0010] A benzo[a]heterocyclic compound: The structure of a benzo[a]five-membered heterocyclic compound is shown in general formula I:

[0011]

[0012] In the formula:

[0013] Q 1 Selected from nitro, amino, C1-C6 alkylamino or

[0014] R is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, or cyanomethylene;

[0015] Q 2 Selected from

[0016] X 1Selected from hydrogen, halogen, nitro, cyano, CONH2, CHO, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamino, C1-C6 dialkylamino, C1-C6 alkoxycarbonyl, C1-C6 alkylcarbonyl, C1-C6 haloalkylcarbonyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylaminocarbonyl or C1-C6 alkylaminosulfonyl;

[0017] m is selected from 0, 1, 2, 3, 4 or 5;

[0018] X 2 and X 3 They may be selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio or C1-C6 haloalkylthio, respectively, whether the same or different.

[0019] Y is selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio or C1-C6 haloalkylthio.

[0020] Z is selected from O or S.

[0021] Preferably, in the general formula I:

[0022] Q 1 Selected from C1-C4 alkylamino or

[0023] R is selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, or cyanomethylene;

[0024] Q 2 Selected from

[0025] X 1Hydrogen, halogen, nitro, cyano, CONH2, CHO, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylamino, C1-C4 dialkylamino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, C1-C4 haloalkylcarbonyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C1-C4 alkylaminocarbonyl or C1-C4 alkylaminosulfonyl;

[0026] m is selected from 0, 1, 2, 3, 4 or 5;

[0027] X 2 and X 3 They may be selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio, respectively, whether the same or different;

[0028] Y is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio;

[0029] Z is selected from O or S.

[0030] Further preferably, in the general formula I:

[0031] Q 1 Selected from

[0032] R is selected from hydrogen, C1-C4 alkyl, or cyanomethylene;

[0033] Q 2 Selected from

[0034] X 1 Selected from hydrogen, halogen, nitro, cyano, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio;

[0035] m is selected from 0, 1, 2, or 3;

[0036] X 2 and X 3 They can be selected from hydrogen or halogens, either the same or different;

[0037] Y is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy or C1-C4 haloalkylthio;

[0038] Z is selected from O or S.

[0039] Further preferred, in the general formula I:

[0040] Q 1 Selected from

[0041] R is selected from hydrogen or C1-C4 alkyl;

[0042] Q 2 Selected from

[0043] X 1 Selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, difluoromethoxy, trifluoromethoxy, or trifluoromethylthio;

[0044] m is selected from 0, 1, or 2;

[0045] X 2 and X 3 They can be selected from F respectively, whether they are the same or different;

[0046] Y is selected from hydrogen, halogen, C1-C4 alkyl, or C1-C4 haloalkoxy;

[0047] Z is selected from O or S.

[0048] Further preferred, in the general formula I:

[0049] Q 1 Selected from

[0050] R is selected from hydrogen, methyl, ethyl, n-propyl, or methylcyclopropyl;

[0051] Q 2 Selected from

[0052] m is selected from 0, 1, or 2;

[0053] X 1 Selected from hydrogen, fluorine, chlorine, bromine, cyano, trifluoromethyl, or trifluoromethoxy;

[0054] X 2 and X 3 They can be selected from fluorine, either the same or different;

[0055] Y is selected from hydrogen, halogen, methyl, or difluoromethoxy;

[0056] Z is selected from O or S.

[0057] The compound of general formula I of the present invention can be prepared by the following method, wherein, unless otherwise specified, the definitions of each group in the formula are the same as above.

[0058]

[0059] The specific synthesis method is as follows: 2-fluoro-3-nitrobenzoic acid is reacted with an acyl chloride reagent (such as oxaloyl chloride and thionyl chloride) to prepare 2-fluoro-3-nitrobenzoyl chloride; 2-fluoro-3-nitrobenzoyl chloride is reacted with substituted aniline V to prepare compound of general formula XI; compound of general formula XI is dehydrated with a dehydrating reagent (such as p-toluenesulfonic acid) to prepare compound of general formula X; compound of general formula X is nitro-reduced to prepare compound of general formula IX; compound of general formula IX is alkylated to prepare compound of general formula VI; compound of general formula VI is condensed with acyl chloride V-1 to prepare benzo[a]heterocyclic compound, i.e. compound of general formula I.

[0060] The sources of the raw materials and intermediates involved in the above preparation method are as follows:

[0061] Intermediate V can be prepared according to method US8853440B2.

[0062] Acyl halide reagents, other common raw materials and reagents are usually commercially available, or they can be prepared in-house using conventional methods.

[0063] In the definitions of general formula compounds given above, the terms used in the compilation generally represent the following substituents:

[0064] Halogens: refer to fluorine, chlorine, bromine or iodine.

[0065] Alkyl: Straight-chain, branched, or cyclic alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, or cyclopropyl.

[0066] Halogenated alkyl groups: straight-chain, branched, or cyclic alkyl groups in which hydrogen atoms may be partially or completely replaced by halogens, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, or heptafluoroisopropyl.

[0067] Alkenyl groups: straight-chain, branched, or cyclic alkenyl groups, such as vinyl, 1-propenyl, 2-propenyl, and various butenyl, pentenyl, and hexenyl isomers; alkenyl groups also include polyenes such as 1,2-propadienyl and 2,4-hexadienyl.

[0068] Haloalkenyl: An alkenyl group in which at least one or more hydrogen atoms can be replaced by halogen atoms.

[0069] Alkynyl groups include straight-chain or branched alkynes, such as ethynyl, 1-propynyl and various butynyl, penynyl and hexynyl isomers; alkynyl groups also include groups composed of multiple triple bonds, such as 2,5-hexadiynyl.

[0070] Halogenated alkynyl group: an alkynyl group in which at least one or more hydrogen atoms can be replaced by a halogen atom.

[0071] Alkoxy groups: straight-chain, branched, or cyclic alkoxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropyloxy, or n-butoxy.

[0072] Halogenated alkoxy groups: straight-chain, branched, or cyclic alkoxy groups in which the hydrogen atoms can be partially or completely replaced by halogens, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, heptafluoroisopropyl, etc.

[0073] Alkylthio groups: straight-chain, branched, or cyclic alkyl groups, which are attached to the structure via sulfur atoms, such as methylthio and ethylthio.

[0074] Alkenyl thioyl: Straight-chain, branched or cyclic alkyl groups, attached to the structure by sulfur atoms, such as 1-propenyl-3-thioyl, 2-butenyl-4-thioyl, etc.

[0075] Alkynethyl group: a straight-chain, branched or cyclic alkyl group that is attached to the structure by a sulfur atom bond, such as 1-propynyl-3-thio, 2-butynyl-4-thio, etc.

[0076] Halogenated alkylthio groups: straight-chain, branched, or cyclic alkylthio groups, in which hydrogen atoms can be partially or completely replaced by halogens, such as difluoromethylthio and trifluoroethylthio.

[0077] Alkylamino: Straight-chain, branched or cyclic alkyl groups, linked to the structure by nitrogen bonds, such as methylamino, ethylamino, n-propylamino, isopropylamino or isomeric butylamine.

[0078] Dialkylamino: Two identical or different straight-chain, branched or cyclic alkyl groups are linked together in a structure by a nitrogen atom bond, such as dimethylamino, methylethylamino, cyclopropylamino, etc.

[0079] Alkoxycarbonyl: alkyl-O-CO-, for example CH3OCO-.

[0080] Alkyl carbonyl: alkyl-CO-, for example CH3CO-

[0081] Alkyl sulfonyl: alkyl-S(O)2-, for example, methyl sulfonyl.

[0082] Alkyl sulfinyl group: alkyl-S(O)-, such as methyl sulfinyl group.

[0083] Alkylaminocarbonyl: alkyl-NH-CO-, for example CH3NHCO-.

[0084] Alkylaminosulfonyl: alkyl-NH-S(O)2-, for example CH3NH-S(O)2-.

[0085] In the compounds of this invention, due to X 2 and X 3 Unlike other compounds, those of Formula I are chiral compounds. In this case, the compound can exist as a single chiral isomer or a mixture of two chiral isomers. The compound of Formula I to be protected by this invention is not limited to the above-mentioned isomer structure.

[0086] The specific compounds listed in Tables 1 and 2 are used to illustrate the present invention, but do not limit the present invention.

[0087] Table 1

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] Table 2

[0107]

[0108]

[0109]

[0110]

[0111] Some compounds 1 The ¹H NMR (600MHz, CDCl₃, ppm) and physicochemical properties are as follows:

[0112]

[0113]

[0114]

[0115]

[0116] In organic molecules, due to differences in the electronegativity, size, or spatial configuration of substituents, the overall molecule's transport properties or binding to receptors can vary greatly in organisms such as insects and plants, resulting in significant differences in biological activity. Furthermore, the molecule's transport properties and suitability for binding to receptors are unpredictable and require a great deal of creative work to determine.

[0117] The novel benzo[a]-5-membered heterocyclic compound (compound of general formula I) of this invention exhibits excellent insecticidal activity and can control the following pests: Lepidoptera pests, such as armyworms, beet armyworms, and diamondback moths; Homoptera pests, such as peach aphids, leafhoppers, and planthoppers; Hemiptera pests, such as corn stink bugs, tomato mirid bugs, and rice ailanthus; Thysanoptera pests, such as cotton thrips, alfalfa thrips, soybean thrips, and western flower thrips; Coleoptera pests, such as potato beetles and click beetles; Diptera pests, such as flies and mosquitoes; and Hymenoptera pests, such as bees and ants. Therefore, this invention also includes the use of the compound of general formula I for pest control in agriculture, forestry, and sanitation.

[0118] The technical solution of the present invention also includes a method for controlling pests: applying the insecticidal compound of the present invention to the pests or their growth medium. A generally suitable effective amount is 10 to 1000 grams per hectare, preferably 20 to 500 grams per hectare.

[0119] It should be clearly stated that various modifications and alterations can be made within the scope defined by the claims of this invention.

[0120] Advantages of this invention:

[0121] The compound of this invention has a novel structure, insecticidal activity, and a wide range of applications. Detailed Implementation

[0122] The following specific embodiments are used to further illustrate the present invention, but the present invention is by no means limited to these examples.

[0123] Synthesis Examples

[0124] Example 1: Preparation of compound I-41

[0125] 1) Preparation of N-(2-hydroxy-4-heptafluoroisopropyl-6-bromophenyl)-2-fluoro-3-nitrobenzamide

[0126]

[0127] 2-Fluoro-3-nitrobenzoic acid (8.23 g, 44.00 mmol), thionyl chloride (34.08 g), and DMF (0.35 g) were added to a reaction flask. The mixture was heated to 80 °C and reacted for 8 hours. The thionyl chloride was then distilled off under reduced pressure to obtain an acyl chloride. Tetrahydrofuran (50 mL) was added to the acyl chloride, followed by slow dropwise addition of 2-hydroxy-6-bromo-4-heptafluoroisopropylaniline (14.25 g, 40.00 mmol) in tetrahydrofuran (80 mL) at 0-5 °C. After the addition was complete, the reaction was continued at this temperature for another 6 hours. The reaction solution was heated to room temperature, and the insoluble matter was removed by filtration. The organic solvent was then distilled off under reduced pressure after filtration. The residue was purified by column chromatography to obtain the title compound, a white solid, 17.26 g, with a yield of 82.5% (based on 2-hydroxy-6-bromo-4-heptafluoroisopropylaniline).

[0128] 1 H NMR (600MHz, CDCl3, ppm): 9.15 (d, 1H), 8.55-8.52 (m, 1H), 8.34-8.31 (m, 1H), 7.58-7.55 (m, 1H), 7.49 (s, 1H), 7.36 (s, 1H).

[0129] 2) Preparation of 2-(2-fluoro-3-nitrophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole

[0130]

[0131] N-(2-hydroxy-4-heptafluoroisopropyl-6-bromophenyl)-2-fluoro-3-nitrobenzamide (2.62 g, 5.00 mmol), p-toluenesulfonic acid (0.18 g, 1.00 mmol), and xylene (15 mL) were added to a reaction flask, and the mixture was heated to 140 °C and reacted for 8 hours. The reaction solution was cooled to room temperature, and the organic solvent was evaporated under reduced pressure. The residue was purified by column chromatography to give the title compound as a white solid, 2.01 g, with a yield of 79.6% (based on N-(2-hydroxy-4-heptafluoroisopropyl-6-bromophenyl)-2-fluoro-3-nitrobenzamide).

[0132] 1 H NMR (600MHz, CDCl3, ppm): 8.66-8.63(m,1H),8.29-8.26(m,1H),7.92(s,1H),7.86(s,1H),7.54-7.51(m,1H).

[0133] 3) Preparation of 2-(2-fluoro-3-aminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole

[0134]

[0135] Add 2-(2-fluoro-3-nitrophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole (1.52 g, 3.00 mmol), dioxane (10 mL), and stannous chloride dihydrate (2.73 g, 12.00 mmol) to the reaction flask, and slowly add 36% concentrated hydrochloric acid (3 mL). Heat to 65°C and maintain the reaction temperature, monitoring the reaction by TLC until complete. Cool the reaction system to room temperature, pour the reaction solution into ice water (15 mL), add ethyl acetate (30 mL), and slowly add 5% sodium hydroxide aqueous solution to neutralize to pH 8-9. Filter the precipitate through diatomaceous earth, wash the filter cake with ethyl acetate (10 mL), and separate the filtrate into layers. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the organic solvent was removed by vacuum distillation. The residue was purified by column chromatography to obtain the title compound, a yellow solid of 1.26 g, with a yield of 88.4% (based on 2-(2-fluoro-3-nitrophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole).

[0136] 1 H NMR (60MHz, CDCl3, ppm): 7.86 (s, 1H), 7.80 (s, 1H), 7.63-7.61 (m, 1H), 7.12-7.09 (m, 1H), 7.03-7.00 (t, 1H), 3.97 (brs, 2H).

[0137] 4) Preparation of 2-(2-fluoro-3-methylaminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole

[0138]

[0139] Add 98% concentrated sulfuric acid (6 mL) and 2-(2-fluoro-3-aminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole (0.95 g, 2.00 mmol) to the reaction flask and stir thoroughly to dissolve. Slowly add 37-40% formaldehyde aqueous solution (5 mL) at 30-35 °C. After the addition is complete, raise the temperature to 40 °C and continue the reaction. Monitor the reaction by TLC until it is complete. Cool the reaction system to room temperature and slowly pour the reaction solution into ice water (20 mL). Stir thoroughly to precipitate a solid. Filter the solution and purify the filter cake by column chromatography to obtain the title compound, 0.85 g of white solid, with a yield of 86.9% (based on 2-(2-fluoro-3-aminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole).

[0140] 1 H NMR (600MHz, CDCl3, ppm): 7.86 (s, 1H), 7.80 (s, 1H), 7.54-7.51 (m, 1H), 7.20-7.17 (m, 1H), 6.91-6.88 (m, 1H), 4.28 (brs, 1H), 2.96 (s, 3H).

[0141] 5) Preparation of 2-(2-fluoro-3-(N-methyl-benzamido)phenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole

[0142]

[0143] Toluene (10 mL), benzoyl chloride (0.16 g, 1.11 mmol), and 2-(2-fluoro-3-methylaminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole (0.49 g, 1.00 mmol) were added to a reaction flask. The mixture was heated to 110 °C and the reaction was monitored by TLC until complete. The reaction system was cooled to room temperature, and the organic solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain the target product, 0.48 g of white solid, with a yield of 81% (based on 2-(2-fluoro-3-methylaminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole).

[0144] 1 H NMR (600MHz, CDCl3, ppm): 8.17-8.14(m,1H),7.88(s,1H),7.83(s,1H),7.37-7.34(m,2H),7.28-7.25(m,2H),7.21-7.18(m,3H),3.50(s,3H).

[0145] Example 2: Preparation of compound I-103

[0146] 1) Preparation of 2-(2-fluoro-3-n-propylaminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole

[0147]

[0148] 2-(2-fluoro-3-aminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole (0.95 g, 2.00 mmol) was dissolved in methanol (10 mL). Propanal (0.18 g, 3.00 mmol), glacial acetic acid (0.36 g, 6.00 mmol), and sodium cyanoborohydride (0.20 g, 3.00 mmol) were added sequentially at room temperature. The mixture was heated to 40 °C and the reaction was monitored by TLC until complete. The reaction system was cooled to room temperature, and saturated sodium bicarbonate solution (20 mL) was added. The mixture was extracted with dichloromethane (40 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain the target product: 0.78 g of white solid, yield 75.4% (based on 2-(2-fluoro-3-aminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole).

[0149] 1 H NMR (600MHz, CDCl3, ppm):7.86(s,1H),7.80(s,1H),7.51-7.48(m,1H),7.17-7.14(m ,1H),6.91-6.88(m,1H),4.17(brs,1H),3.18(t,2H),1.73-1.70(m,2H),1.04(t,3H).

[0150] 2) Preparation of 2-(2-fluoro-3-(N-n-propyl-(4-fluorobenzamido)phenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole

[0151]

[0152] Toluene (10 mL), 4-fluorobenzoyl chloride (0.18 g, 1.11 mmol), and 2-(2-fluoro-3-n-propylaminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole (0.52 g, 1.00 mmol) were added to the reaction flask. The mixture was heated to 110 °C and the reaction was monitored by TLC until complete. The reaction system was cooled to room temperature, and the organic solvent was removed under reduced pressure. The residue was purified by column chromatography to give the title compound as a white solid, 0.50 g, with a yield of 78.2% (based on 2-(2-fluoro-3-n-propylaminophenyl)-4-bromo-6-heptafluoroisopropylbenzoxazole).

[0153] 1H NMR(600MHz, CDCl3,ppm):8.20-8.17(m,1H),7.87(s,1H),7.82(s,1H),7.37-7.34(m,3 H),7.27-7.24(m,1H),6.88-6.85(m,2H),3.86(br,2H),1.69-1.66(m,2H),0.97(m,3H).

[0154] Other compounds represented by general formula I can also be prepared in accordance with the methods described above.

[0155] Bioactivity assay

[0156] Example 3 Insecticidal Activity Determination

[0157] Based on the solubility of the compound to be tested, dissolve it in acetone or dimethyl sulfoxide, and then prepare 50 mL of the test solution of the required concentration with 0.1% Tween 80 solution. The content of acetone or dimethyl sulfoxide in the total solution shall not exceed 10%.

[0158] Example 3.1 Determination of activity against armyworms

[0159] Select fresh corn leaves from the middle section, cut them into 3 cm segments, and immerse them in the prepared solution for 10 seconds. After air-drying, place them in a 9 cm diameter petri dish lined with filter paper. Inoculate healthy, uniform 3rd instar insects into each treatment, with 14 insects per treatment. The experiment was repeated 4 times, with a water treatment as a blank control. After treatment, the insects were placed indoors at 24℃, 60%-70% relative humidity, and natural light. After 72 hours, the number of surviving insects was counted, and the mortality rate was calculated.

[0160] Among some of the compounds tested, compounds I-1, I-33, 1-41, I-42, I-49, I-91, I-99, I-100, I-103, I-105, I-118, I-1 63. I-165, I-169, I-219, I-225, I-235, I-275, I-283, I-325, I-333, I-339, I-341, I-375 I-391, I-392, I-397, I-399, I-410, I-455, I-461, I-511, I-527, I-568, I-607, I-640, I-747, II-9, II-19, II-21, II-33, II-45, II-57, and II-69 showed good control efficacy against armyworms at a concentration of 600 mg / L, with a mortality rate of 100%.

[0161] Example 3.2 Determination of activity against diamondback moth

[0162] Select cabbage leaves grown at room temperature, remove the surface wax layer, and punch holes to create circular leaf discs with a diameter of 2 cm. Immerse the leaf discs in the prepared solution for 10 seconds, air dry, and then place them in a 9 cm diameter petri dish containing filter paper. Inoculate healthy, uniform second-instar insects into each treatment, with 10 insects per treatment. The experiment is repeated 4 times, with a water treatment as a blank control. After treatment, incubate the leaves indoors at 24℃, 60%-70% relative humidity, and natural light. After 72 hours, count the number of surviving insects and calculate the mortality rate.

[0163] Among some of the compounds tested, compounds I-1, I-33, I-42, I-43, I-45, I-83, I-100, I-101, I-103, I-118, I- 163, I-219, I-225, I-275, I-279, I-283, I-325, I-333, I-337, I-341, I-351, I-367 I-391, I-392, I-393, I-395, I-397, I-410, I-461, I-551, I-567, I-568, I-640, I-741, I-743, I-745, II-7, II-19, II-21, and II-33 showed good control efficacy against diamondback moth at a concentration of 600 mg / L, with a mortality rate of 100%.

[0164] Other compounds of general formula I obtained through the preparation process described above in this invention also possess the corresponding properties described above, achieving unexpected effects.

Claims

1. A benzo[5]-heterocyclic compound, characterized in that: The structures of benzo[5]-membered heterocyclic compounds are shown in general formula I: I； In the formula: Q 1 Selected from ; R is selected from hydrogen, C1-C6 alkyl, or cyanomethylene; Q 2 Selected from , ; X 1 Selected from hydrogen, halogen, nitro, cyano, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, and C1-C6 haloalkylthio; m is selected from 0, 1, 2, 3, 4 or 5; X 2 and X 3 They can be selected from hydrogen or halogens, either the same or different; Y is selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy or C1-C6 haloalkylthio; Z is selected from O or S.

2. The benzo[a]five-membered heterocyclic compound according to claim 1, characterized in that: In the general formula I: Q 1 Selected from ; R is selected from hydrogen, C1-C4 alkyl, or cyanomethylene; Q 2 Selected from , ; X 1 Selected from hydrogen, halogen, nitro, cyano, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, and C1-C4 haloalkylthio; m is selected from 0, 1, 2, 3, 4 or 5; X 2 and X 3 They can be selected from hydrogen or halogens, either the same or different; Y is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, and C1-C4 haloalkylthio. Z is selected from O or S.

3. The benzo[a]five-membered heterocyclic compound according to claim 2, characterized in that: In the general formula I: Q 1 Selected from ; R is selected from hydrogen, C1-C4 alkyl, or cyanomethylene; Q 2 Selected from , ; X 1 Selected from hydrogen, halogen, nitro, cyano, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, or C1-C4 haloalkylthio; m is selected from 0, 1, 2, or 3; X 2 and X 3 They can be selected from hydrogen or halogens, either the same or different; Y is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy or C1-C4 haloalkylthio; Z is selected from O or S.

4. The benzo[a]five-membered heterocyclic compound according to claim 3, characterized in that: In the general formula I: Q 1 Selected from ; R is selected from hydrogen or C1-C4 alkyl; Q 2 Selected from , ; X 1 Selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, difluoromethoxy, trifluoromethoxy, or trifluoromethylthio; m is selected from 0, 1, or 2; X 2 and X 3 They can be selected from F respectively, whether they are the same or different; Y is selected from hydrogen, halogen, C1-C4 alkyl, or C1-C4 haloalkoxy; Z is selected from O or S.

5. The benzo[a]five-membered heterocyclic compound according to claim 4, characterized in that: In the general formula I: Q 1 Selected from ; R is selected from hydrogen, methyl, ethyl, n-propyl, or methylcyclopropyl; Q 2 Selected from , ; m is selected from 0, 1, or 2; X 1 Selected from hydrogen, fluorine, chlorine, bromine, cyano, trifluoromethyl, or trifluoromethoxy; X 2 and X 3 They can be selected from fluorine, either the same or different; Y is selected from hydrogen, halogen, methyl, or difluoromethoxy; Z is selected from O or S.

6. An application of a benzo[a]five-membered heterocyclic compound according to any one of claims 1-5, characterized in that: The compound represented by general formula I is used as an insecticide in agriculture and forestry.

7. A method for controlling pests, characterized in that: The compound of claim 1 is applied to the pest that needs to be controlled, or to the medium in which it grows, at an effective dose of 10 to 1000 grams per hectare.

Images