Substituted benzimidazole compounds and / or salts thereof, and methods of making and using the same, and insecticidal and miticidal agents

Abstract

A substituted benzimidazole compound and / or its salt, a method for their preparation, applications, and insecticides / acaricides are disclosed. The substituted benzimidazole compound has the structure shown in formula (I). The substituted benzimidazole compound provided by this invention exhibits good acaricidal effects when used at low concentrations.

Description

A substituted benzimidazole compound and / or its salt, preparation method and application thereof, and insecticide and acaricide

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application 202311762666.6 filed on December 20, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the technical field of pesticides, and in particular to a substituted benzimidazole compound and / or its salt, a preparation method and application thereof, and an insecticide and acaricide. Background Art

[0004] In crop production in agriculture and horticulture, losses caused by pests and other factors continue to be significant. Furthermore, pests resistant to existing pesticides are emerging. From the perspectives of impact on environmental organisms and labor conservation, there is a desire to develop insecticides and acaricides for agricultural and horticultural use that have novel properties, minimal impact on natural enemies and beneficial insects, and possess penetrating and translocation activities.

[0005] WO2022179501A1 discloses the following compounds:

[0006] However, due to the high resistance development speed of pests and mites and the national requirement to reduce pesticide use, it is still necessary to develop new compounds with higher activity so that they can produce excellent killing effects on pests and mites at lower concentrations. Summary of the Invention

[0007] The present invention aims to overcome the defect that existing aromatic heterocyclic compounds can only exhibit insecticidal and acaricidal activity when used at high concentrations, which makes it difficult to meet the demand for controlling field pest mites. The present invention provides a new substituted benzimidazole compound and / or its salt, which can be used as an active ingredient in an insecticide and acaricide and can have a high control effect when used at a low concentration (not higher than 100 ppm).

[0008] In order to achieve the above object, the first aspect of the present invention provides a substituted benzimidazole compound and / or its salt, characterized in that the substituted benzimidazole compound has a structure shown in formula (I):

[0009] wherein R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, or substituted or unsubstituted phenyl, wherein the substituted substituents are each independently selected from halogen, C1-C3 alkyl, halo-C1-C3 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C3 alkoxy, halo-C1-C3 alkoxy, C3-C6 cycloalkyloxy, or halo-C3-C6 cycloalkoxy;

[0010] Y 1 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl;

[0011] Y 2 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl;

[0012] T 1 is selected from substituted or unsubstituted C2-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, wherein the substituted substituents are each independently selected from CN or halogen;

[0013] T 2 is selected from H, halogen, CN, NO2, methyl or trifluoromethyl;

[0014] T 3 Selected from H, halogen, CN, NO2, formyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C1-C6 alkylthio, substituted or unsubstituted C1-C6 alkylsulfinyl, substituted or unsubstituted C1-C6 alkylsulfonyl, substituted or unsubstituted C1-C6 alkylcarbonyl, substituted or unsubstituted C1-C6 alkoxycarbonyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C1-C6 alkylcarbonyloxy, wherein the substituted substituents are each independently selected from CN or halogen.

[0015] In some embodiments, in formula (I), R is selected from C1-C6 alkyl or halogenated C1-C6 alkyl;

[0016] Y 1is selected from halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl;

[0017] Y 2 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl;

[0018] T 1 Selected from ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopropyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl;

[0019] T 2 is selected from H, halogen, CN, NO2, methyl or trifluoromethyl;

[0020] T 3 Selected from H, halogen, CN, NO2, formyl, CH3, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopropyl, CF3, CHF2, 2,2,2-trifluoroethyl, heptafluoroisopropyl, OCH3, tert-butoxy, OCHF2, OCF3, 2,2,2-trifluoroethoxy, heptafluoroisopropoxy, SCH3, SCH2CH3, SCHF2, SCF3, 2,2,2-trifluoroethylthio, heptafluoroisopropylthio, trifluoromethanesulfinyl, trifluoromethanesulfonyl, trifluoroethanesulfinyl or trifluoroethanesulfonyl.

[0021] In some embodiments, in formula (I), R is selected from methyl, ethyl, chloroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or trifluoromethyl;

[0022] Y 1 is selected from halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl;

[0023] Y 2 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl;

[0024] T 1Selected from ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopropyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl;

[0025] T 2 is selected from H, halogen, CN, NO2, methyl or trifluoromethyl;

[0026] T 3 Selected from H, halogen, CN, NO2, formyl, CH3, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopropyl, CF3, CHF2, 2,2,2-trifluoroethyl, heptafluoroisopropyl, OCH3, tert-butoxy, OCHF2, OCF3, 2,2,2-trifluoroethoxy, heptafluoroisopropoxy, SCH3, SCH2CH3, SCHF2, SCF3, 2,2,2-trifluoroethylthio, heptafluoroisopropylthio, trifluoromethanesulfinyl, trifluoromethanesulfonyl, trifluoroethanesulfinyl or trifluoroethanesulfonyl.

[0027] In some typical embodiments, in formula (I), R is selected from ethyl;

[0028] Y 1 selected from halogen;

[0029] Y 2 Selected from H;

[0030] T 1 Selected from ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl;

[0031] T 2 Selected from H;

[0032] T 3 Selected from CH3, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

[0033] Among the compounds included in the substituted benzimidazole compounds of the present invention, there may be E-type and Z-type geometric isomers depending on the type of substituents, and the present invention includes these E-types, Z-types, or mixtures containing E-types and Z-types in any proportion. In addition, among the compounds included in the present invention, there may be optical isomers caused by having one or more asymmetric carbon atoms and asymmetric sulfur atoms, and the present invention includes all optical isomers, racemates, or diastereomers.

[0034] In some embodiments, the compound of formula I is selected from at least one of the compounds shown in Table 1.

[0035] Table 1

[0036] In a second aspect, the present invention provides the following compounds and / or salts thereof:

[0037] In a third aspect, the present invention provides a method for preparing a substituted benzimidazole compound and / or a salt thereof, the method comprising:

[0038] (1) in a first solvent, in the presence of a first alkaline substance and a condensing agent, subjecting compound V and compound IV to a condensation reaction to obtain compound III;

[0039] (2) in a second solvent, subjecting the compound III to a cyclization reaction with an acidic substance to obtain a compound II;

[0040] (3) in a third solvent, in the presence of a second alkaline substance, subjecting the compound II to a sulfonylation reaction with a sulfonyl-containing compound to obtain compound I;

[0041] Wherein, the compound V has a structure represented by formula (V), the compound IV has a structure represented by formula (IV), the compound III has a structure represented by formula (III), the compound II has a structure represented by formula (II), the compound I has a structure represented by formula (I), and the sulfonyl-containing compound has a structure represented by formula (VI);

[0042] In formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI), R, Y 1 、Y 2 、T 1 、T 2 、T 3The definitions of are the same as those in the first aspect, and L is selected from halogen.

[0043] In some embodiments, in step (1), the conditions of the condensation reaction include: a temperature of -10°C to 150°C, and a reaction time of 0.5-48h;

[0044] and / or, the molar ratio of the compound V to the compound IV is 0.5-2:1;

[0045] And / or, the condensing agent is selected from at least one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide or its hydrochloride, carbonyldiimidazole, 1,3-dicyclohexylcarbodiimide, diethyl cyanophosphate, chlorocarbonate compounds, and 2-chloro-1-methylpyridinium iodide;

[0046] and / or, the molar ratio of the condensing agent to the compound IV is 1-2:1;

[0047] and / or, the first alkaline substance is at least one selected from pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene;

[0048] And / or, the molar ratio of the first alkaline substance to the compound IV is 0.1-10:1.

[0049] In some embodiments, in step (2), the conditions of the cyclization reaction include: a temperature of -10°C to 300°C, and a reaction time of 0.5-48h;

[0050] and / or, the acidic substance is selected from at least one of p-toluenesulfonic acid or its hydrate, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, trichloroacetic acid, benzoic acid, and phosphoric acid;

[0051] And / or, the molar ratio of the acidic substance to the compound IV is 0.01-10:1.

[0052] In some embodiments, in step (3), the conditions of the sulfonylation reaction include: temperature of -10°C to 100°C, reaction time of 0.5-48h;

[0053] and / or, the molar ratio of the sulfonyl-containing compound to the compound II is 0.8-10:1;

[0054] and / or, the second alkaline substance is at least one selected from pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene;

[0055] And / or, the molar ratio of the second alkaline substance to the compound II is 1-10:1.

[0056] In a fourth aspect, the present invention provides a method for preparing a substituted benzimidazole compound and / or a salt thereof, characterized in that the method comprises:

[0057] (a) condensing compound X and compound VI in the presence of a fourth solvent and a third basic substance to obtain compound IX;

[0058] (b) subjecting compound IX to a reduction reaction with a reducing substance in the presence of a fifth solvent to obtain compound VIII;

[0059] (c) condensing compound VIII and compound XI in the presence of a sixth solvent to obtain compound VII;

[0060] (d) in the presence of a seventh solvent, subjecting Compound VII to an addition ring-closure reaction to obtain Compound I;

[0061] Wherein, the compound I has the structure shown in formula (I), the compound VII has the structure shown in formula (VII), the compound VIII has the structure shown in formula (VIII), the compound IX has the structure shown in formula (IX), the compound X has the structure shown in formula (X), the compound XI has the structure shown in formula (XI), and the compound VI has the structure shown in formula (VI);

[0062] In Formula (I), Formula (VI), Formula (VII), Formula (VIII), Formula (IX), Formula (X) and Formula (XI), R, Y 1 、Y 2 、T 1 、T 2 、T 3 The definitions of are the same as those in the first aspect, and L is selected from halogen.

[0063] In some embodiments, the third basic substance is selected from at least one of pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene;

[0064] and / or, the molar ratio of the compound X to the compound VI is 0.5-2:1;

[0065] And / or, in step (a), the condensation reaction conditions include: temperature of -20°C to 150°C, and reaction time of 0.1-48h.

[0066] In some embodiments, the reducing substance is selected from at least one of hydrogen, metal, sulfide, borane and its complexes, and hydrosulfite;

[0067] And / or, in step (b), the reduction reaction conditions include: temperature of -10°C to 200°C, and reaction time of 0.5-72h.

[0068] In some embodiments, the molar ratio of the compound VIII to the compound XI is 0.5-2:1;

[0069] and / or, the reaction in step (c) may be carried out in the presence of a first catalyst;

[0070] and / or, the first catalyst is selected from at least one of glacial acetic acid, propionic acid, amino acid and Lewis acid;

[0071] And / or, in step (c), the condensation reaction conditions include: temperature of -20°C to 150°C, and reaction time of 0.1-48h.

[0072] In some embodiments, the reaction described in step (d) can be carried out in the presence of a second catalyst;

[0073] and / or, the second catalyst is selected from iodide, bromide, glacial acetic acid, propionic acid, amino acid, Lewis acid;

[0074] and / or, the fourth to seventh solvents are each independently selected from at least one of methanol, ethanol, isopropanol, propanol, butanol, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, ethyl acetate, toluene, xylene, acetonitrile, tetrahydrofuran, acetone, N,N-dimethylformamide, N-methylpyrrolidone, dioxane, and water;

[0075] And / or, in step (d), the condensation reaction conditions include: temperature of -20°C to 150°C, and reaction time of 0.1-48h.

[0076] In a fifth aspect, the present invention provides a use of the aforementioned compound or its isomers in controlling invertebrate pests in agriculture, forestry, animal husbandry or health fields, wherein the invertebrate pests are acarid pests, insects and / or nematodes.

[0077] In some embodiments, the method for controlling invertebrate pests comprises applying an insecticidally effective amount of at least one of the aforementioned compounds or compounds prepared by the aforementioned preparation methods directly or indirectly to the invertebrate pests to be controlled and / or the medium in which they grow.

[0078] In some typical embodiments, the method comprises treating a plant where an invertebrate pest grows with an insecticidally effective amount of at least one substituted benzimidazole compound or a salt thereof.

[0079] In a sixth aspect, the present invention provides an agricultural composition comprising at least one of the aforementioned compounds or the compound obtained by the aforementioned preparation method and at least one liquid carrier or solid carrier.

[0080] The present invention has no particular limitation on the liquid carrier or solid carrier, as long as it can meet the requirements of the present invention. In the composition, the concentration of the substituted benzimidazole compound or its salt provided by the present invention is 0.5-35 mg / L. Preferably, the concentration of the substituted benzimidazole compound or its salt is 1-30 mg / L, and more preferably, the concentration of the substituted benzimidazole compound or its salt is 10-25 mg / L.

[0081] In the present invention, liquid carrier can be water, various aromatic hydrocarbons, aliphatic hydrocarbons, ketones, ethers etc., such as toluene, xylene, acetone, cyclohexanone, xylene, benzene, cyclohexane, isopropyl alcohol, ethylene glycol, sorbitol, methanol, ethanol, butanol, dimethylformamide, N-methylpyrrolidone, decalin, motor oil, petroleum ether, cyclohexanone, methyl oleate, methylated soybean oil etc. one or more; Solid carrier can include natural or synthetic clay and silicate, solid carrier suitable for powder can include naturally formed rock powder, chalk, quartz, clay, montmorillonite, white carbon black, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, clay and synthetic ground mineral matter (such as micro-dispersed silicic acid or aluminum oxide). Suitable particle carrier can include crushed and graded natural rock such as calcite, marble, pumice, sepiolite and dolomite and synthetic particles made of organic and inorganic powder.

[0082] In the present invention, the composition can be applied in the form of a preparation. The substituted benzimidazole compound or its salt provided by the present invention is dissolved or dispersed in a carrier as an active ingredient, or is configured into a preparation so that it is easier to disperse when used for insecticide or acaricide. For example, the composition can be prepared into a wettable powder, a water-dispersible granule, a suspension, an emulsion in water, an aqueous solution or an emulsifiable concentrate. At least one liquid or solid carrier is added to the composition, and when necessary, an appropriate surfactant can also be added. The surfactant can include dodecylbenzene sulfonate, fatty alcohol sulfate, Tween, agricultural milk, sorbitol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, lignin sulfonate, alkylnaphthalene sulfonate, etc.

[0083] In the present invention, for certain applications, such as in agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers may be added to the agricultural composition of the present invention, thereby producing additional advantages and effects.

[0084] In the present invention, the substituted benzimidazole compounds or their salts also include derivatives thereof, but the compounds included in the derivatives of the present invention are by no means limited to these compounds.

[0085] In the present invention, the compound can be used to protect important crops, livestock and the like in agriculture and horticulture from or from being harmed by harmful mites.

[0086] In the present invention, in order to obtain the desired effect, in some applications, the dosage of the compound varies depending on various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, the application method, the application environment, the application formulation, and the like.

[0087] The present invention has no particular limitation on direct or indirect methods, as long as the purpose of controlling invertebrate pests can be achieved. For example, a direct method may include directly contacting a substance containing the components of the substituted benzimidazole compound or its salt with an invertebrate pest (including invertebrate pests directly consuming a substance containing the components of the substituted benzimidazole compound or its salt, direct contact between the body surface of an invertebrate pest and a substance containing the components of the substituted benzimidazole compound or its salt, etc.); an indirect method may include treating a place where invertebrate pests are present (their habitat or breeding ground or plants or soil where invertebrate pests grow) with a substance containing the components of the substituted benzimidazole compound or its salt, or treating its food chain with a substance containing the components of the substituted benzimidazole compound or its salt.

[0088] In the present invention, the invertebrate pests are acarid pests, insects and / or nematodes.

[0089] In the present invention, the plant is a plant of the phylum Gymnosperms and / or Angiosperms, preferably at least one of the family Rutaceae, Solanaceae, Cruciferae and Rosaceae.

[0090] The present invention does not particularly limit the insecticidally effective amount. For example, a dosage of 5 grams to 3 kilograms of the substituted benzimidazole compound or its salt per hectare can provide sufficient control. Preferably, the insecticidally effective amount can be 8 grams to 1000 grams per hectare, and more preferably, the insecticidally effective amount can be 10 grams to 300 grams per hectare.

[0091] Compared with the prior art, the present invention has at least the following advantages:

[0092] The substituted benzimidazole compounds or salts thereof provided by the present invention are used as active ingredients as insecticides and acaricides. When used at low concentrations, they can have excellent control effects. At the same time, the compounds provided by the present invention have good safety. In the acute toxicity test in rats, the compounds of the present invention did not show obvious toxicity at a dose of 1000 mg / kg.

[0093] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0094] The following examples may enable those skilled in the art to more fully understand the present invention, but the present invention is not limited to the scope of the examples.

[0095] In some embodiments of the present invention, preferably, the present invention has no particular limitation on the preparation method of the insecticide and acaricide, and those skilled in the art may refer to the methods in existing literature and standards in the field or adopt existing methods in the field to prepare the agent to obtain the desired composition and dosage form.

[0096] The present invention will be described in detail below through examples.

[0097] In the following examples, unless otherwise specified, all raw materials used are commercially available.

[0098] In the following examples, unless otherwise specified, room temperature refers to 25±2°C.

[0099] Example 1 Preparation of Compound 326

[0100] The specific preparation process is as follows:

[0101] (1) Sodium hydride (139 g, 3.48 mol, 60% content) was added to tetrahydrofuran (1 L) under nitrogen protection and cooled to 0°C in an ice bath. X-2 (200 g, 1.16 mol) was added to the reaction solution and stirred for 3 hours. Ethylsulfonyl chloride (163 g, 1.27 mol) was added dropwise with bubbles generated. The addition was completed within 1 hour. After stirring for half an hour, the reaction solution was slowly poured into ice water and ethyl acetate (1 L) was added for extraction. The organic phase was dried and purified by column chromatography to obtain 188 g of a white solid.

[0102] 1 H NMR (500MHz, CDCl3) δ9.75 (s, 1H), 8.15 (d, J = 9.0Hz, 1H), 7.87 (d, J = 2.1Hz, 1H), 7.10 (dd, J = 9.0, 2.1Hz, 1H), 3.22 (q, J = 7.4Hz, 2H), 1.36 (t, J = 7.4Hz, 3H).

[0103] (2) IX-2 (268 g, 1.0 mol) was added to ethanol, and then iron powder (168 g, 3 mol) was added. The temperature was raised to above 60°C, and a saturated aqueous ammonium chloride solution was added dropwise. The reaction solution was heated under reflux until the solution turned reddish brown and translated for 2 hours. After the reaction was complete, the solid was filtered out by padding with diatomaceous earth. The filter cake was washed with ethyl acetate, and the filtrate was extracted with water and EA. After separation, the organic phase was evaporated to dryness and purified by column chromatography to obtain 85 g of solid.

[0104] 1 H NMR (500MHz, CDCl3) δ7.06 (d, J=2.4Hz, 1H), 7.00 (dd, J=8.6, 2.4Hz, 1H), 6.66 (d,J=8.6Hz,1H),3.90-3.37(m,2H),3.11(q,J=7.4Hz,2H),1.42-1.31(m,3H).

[0105] (3) VIII-2 (2.76 g, 12.7 mmol) was added to ethanol (10 mL), and then intermediate XI-1 (2.7 g, 11.5 mol) was added. The mixture was heated under reflux for 48 hours. The reaction solution was concentrated to dryness under reduced pressure, and tetrahydrofuran (10 mL) and NIS (4.27 g, 19 mmol) were added. The reaction was continued at room temperature for 6 hours. Sodium thiosulfate aqueous solution (50 mL) and ethyl acetate (50 mL) were added to the reaction solution. After extraction and separation, the organic phase was rotary evaporated to dryness and purified by column chromatography to obtain 1.58 g of a white solid. MS: [M+H] + :433.36 / 435.33.

[0106] 1H NMR(400MHz,Chloroform-d)δ8.07(d,J=2.0Hz,1H),7.76(d,J=8.6Hz,1H),7.60(t,J=1.8Hz,1H),7.56( d,J=1.8Hz,2H),7.42(dd,J=8.6,2.0Hz,1H),3.10(q,J=7.4Hz,2H),1.37(s,18H),1.09(t,J=7.4Hz,3H).

[0107] The preparation methods of representative compounds of the present invention are listed above. The preparation of other compounds can refer to the method of Example 1, simply replacing the raw materials with simple commercially available ones. The mass spectrum and hydrogen spectrum data of some compounds of the present invention are shown in Table 2.

[0108] Table 2

[0109] Biological activity test

[0110] This test example tests the acaricidal activity of the compound prepared above, specifically the acaricidal activity against Tetranychus cinnabarinus. The specific test process is as follows:

[0111] (1) The test compound was dissolved in acetone and diluted with a 0.1 wt % Tween 80 aqueous solution to the desired concentration (see Test Examples 1-A to 1-B below), with the acetone content not exceeding 5 wt %, to prepare a pharmaceutical agent;

[0112] (2) Remove one true leaf from the bean seedlings that have grown to two true leaves, inoculate with Tetranychus cinnabarinus (the number of Tetranychus cinnabarinus mites inoculated per bean seedling is 25-100), and investigate the base number of inoculated mites 24 hours later. Use a handheld sprayer to spray the agent prepared in step (1) on the entire plant of three bean seedlings (the spray volume for each plant is 0.5 mL). After treatment, place them in a constant temperature observation room (25°C) for observation. After 72 hours, investigate the number of live mites and calculate the mortality rate:

[0113] Lethality rate (%) = (number of inoculated mites - number of live mites after spraying) / number of inoculated mites × 100%.

[0114] Test Example 1-A

[0115] The agent was diluted to a concentration of 100 mg / L of the test compound, and then tested according to the above process. In this test, compounds 31, 76, 86, 102, and 326 showed a mortality rate greater than 90% against adult Tetranychus cinnabarinus mites.

[0116] The agent was diluted to a concentration of 25 mg / L of the test compound, and then tested according to the above process. In this test, compounds 86, 102, and 326 showed a mortality rate greater than 100% against adult Tetranychus cinnabarinus mites.

[0117] The compounds were diluted to a concentration of 6.25 mg / L and then tested according to the above procedure.

[0118] In this test, compounds 86, 102, and 326 showed greater than 90% mortality against adult Tetranychus cinnabarinus mites.

[0119] Test Example 1-B

[0120] According to the above test method, compounds 326, CK1, CK2, CK3 and CK4 were selected for parallel tests on killing mites (Tetranychus cinnabarinus). The test results are shown in Table 3 below:

[0121] Table 3

[0122] In Table 3, the structures of CK1, CK2, CK3, and CK4 are as follows:

[0123] CK1, CK2, CK3 and CK4 are compounds in WO2022179501A1, and were prepared by a method similar to Example 1 in WO2022179501A1, except that the types and / or amounts of the raw materials were different, and the rest were the same as Example 1 in WO2022179501A1.

[0124] CK1: 1 H NMR(400MHz, CDCl3)δ8.02-7.95(m,1H),7.90-7.81(m,2H),7.59(s,1H),7.5 7(s,1H),7.52-7.44(m,2H),3.48-2.99(m,2H),1.50-0.67(m,3H).MS:[M+H] + :451.24.

[0125] CK2: 1 H NMR (500MHz, CDCl3) δ8.05-7.98(m,1H),7.89-7.81(m,1H),7.63(t,J=1.5Hz,1H),7.43-7.34(m,2H) ,7.04(t,J=1.6Hz,1H),7.00(t,J=1.5Hz,1H),3.26(q,J=8.0Hz,2H),1.29(t,J=8.0Hz,3H).MS:[M+H] + :405.14.

[0126] CK3: 1 H NMR (400MHz, CDCl3) δ8.04(s,1H),7.86(d,J=8.4Hz,1H),7.78(d,J=10.7Hz,1H),7.72(t,J=8.1Hz,1H),7.63 (d,J=13.9Hz,1H),7.32(d,J=8.2Hz,1H),3.29-3.03(m,2H),2.72-2.46(m,3H),1.20-0.83(m,3H).MS:[M+H] + :436.00.

[0127] CK4: 1 H NMR (400MHz, CDCl) δ8.24 (s, 2H), 8.16 (d, J = 10.7Hz.1H), 8.07 (s, 1H), 7.95 (d, J = 13.5Hz, 1H), 3.20 (q, J = 7.4Hz, 2H), 1.23-0.82 (m, 3H).

[0128] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A substituted benzimidazole compound and / or its salt, characterized in that: The substituted benzimidazole compound has a structure shown in formula (I): Wherein, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted phenyl, wherein the substituted substituents are each independently selected from halogen, C1-C3 alkyl, halo-C1-C3 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C3 alkoxy, halo-C1-C3 alkoxy, C3-C6 cycloalkyloxy or halo-C3-C6 cycloalkyloxy; Y 1 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; Y 2 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; T 1 is selected from substituted or unsubstituted C2-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, wherein the substituted substituents are each independently selected from CN or halogen; T 2 is selected from H, halogen, CN, NO2, methyl or trifluoromethyl; T 3 Selected from H, halogen, CN, NO2, formyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C1-C6 alkylthio, substituted or unsubstituted C1-C6 alkylsulfinyl, substituted or unsubstituted C1-C6 alkylsulfonyl, substituted or unsubstituted C1-C6 alkylcarbonyl, substituted or unsubstituted C1-C6 alkoxycarbonyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C1-C6 alkylcarbonyloxy, wherein the substituted substituents are each independently selected from CN or halogen.

2. The compound and / or its salt according to claim 1, characterized in that R is selected from C1-C6 alkyl or halogenated C1-C6 alkyl; Y 1 is selected from halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; Y 2 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; T 1 Selected from ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, cyclopropyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl; T 2 is selected from H, halogen, CN, NO2, methyl or trifluoromethyl; T 3 is selected from H, halogen, CN, NO2, formyl, CH3, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopropyl, CF3, CHF2, 2,2,2-trifluoroethyl, heptafluoroisopropyl, OCH3, tert-butoxy, OCHF2, OCF3, 2,2,2-trifluoroethoxy, heptafluoroisopropoxy, SCH3, SCH2CH3, SCHF2, SCF3, 2,2,2-trifluoroethylthio, heptafluoroisopropylthio, trifluoromethanesulfinyl, trifluoromethanesulfonyl, trifluoroethanesulfinyl or trifluoroethanesulfonyl.

3. The compound and / or its salt according to claim 1, characterized in that R is selected from methyl, ethyl, chloroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or trifluoromethyl; Y 1 is selected from halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; Y 2 is selected from H, halogen, CN, NO2, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; T 1 Selected from ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, cyclopropyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl; T 2 is selected from H, halogen, CN, NO2, methyl or trifluoromethyl; T 3 is selected from H, halogen, CN, NO2, formyl, CH3, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopropyl, CF3, CHF2, 2,2,2-trifluoroethyl, heptafluoroisopropyl, OCH3, tert-butoxy, OCHF2, OCF3, 2,2,2-trifluoroethoxy, heptafluoroisopropoxy, SCH3, SCH2CH3, SCHF2, SCF3, 2,2,2-trifluoroethylthio, heptafluoroisopropylthio, trifluoromethanesulfinyl, trifluoromethanesulfonyl, trifluoroethanesulfinyl or trifluoroethanesulfonyl.

4. The compound and / or salt thereof according to claim 1, characterized in that R is selected from ethyl; Y 1 is selected from halogen; Y 2 Selected from H; T 1 Selected from ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl; T 2 Selected from H; T 3 Selected from CH3, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

5. A method for preparing a substituted benzimidazole compound and / or its salt, characterized in that: The method includes: (1) in a first solvent, in the presence of a first alkaline substance and a condensing agent, subjecting compound V and compound IV to a condensation reaction to obtain compound III; (2) in a second solvent, subjecting the compound III to a cyclization reaction with an acidic substance to obtain a compound II; (3) in a third solvent, in the presence of a second alkaline substance, subjecting the compound II to a sulfonylation reaction with a sulfonyl group-containing compound to obtain a compound I; Wherein, the compound V has a structure shown in formula (V), the compound IV has a structure shown in formula (IV), the compound III has a structure shown in formula (III), the compound II has a structure shown in formula (II), the compound I has a structure shown in formula (I), and the sulfonyl-containing compound has a structure shown in formula (VI); In formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI), R, Y 1 , Y 2 、T 1 、T 2 、T 3 The definition is the same as that in any one of claims 1 to 4, and L is selected from halogen.

6. The method according to claim 5, wherein: In step (1), the conditions of the condensation reaction include: temperature of -10°C to 150°C, reaction time of 0.5-48h; and / or, the molar ratio of the compound V to the compound IV is 0.5-2:1; And / or, the condensing agent is selected from at least one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide or its hydrochloride, carbonyldiimidazole, 1,3-dicyclohexylcarbodiimide, diethyl cyanophosphate, chlorocarbonate compounds, and 2-chloro-1-methylpyridinium iodide; and / or, the molar ratio of the condensing agent to the compound IV is 1-2:1; and / or, the first alkaline substance is at least one selected from pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene; And / or, the molar ratio of the first alkaline substance to the compound IV is 0.1-10:

1.

7. The method according to claim 5 or 6, wherein: In step (2), the conditions of the cyclization reaction include: temperature of -10°C to 300°C, reaction time of 0.5-48h; And / or, the acidic substance is selected from at least one of p-toluenesulfonic acid or its hydrate, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, trichloroacetic acid, benzoic acid, and phosphoric acid; And / or, the molar ratio of the acidic substance to the compound IV is 0.01-10:

1.

8. The method according to any one of claims 5 to 7, wherein: In step (3), the conditions of the sulfonylation reaction include: temperature of -10°C to 100°C, reaction time of 0.5-48h; and / or, the molar ratio of the sulfonyl-containing compound to the compound II is 0.8-10:1; and / or, the second alkaline substance is at least one selected from pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene; And / or, the molar ratio of the second alkaline substance to the compound II is 1-10:

1.

9. A method for preparing a substituted benzimidazole compound and / or its salt, characterized in that: The method includes: (a) in the presence of a fourth solvent and a third alkaline substance, subjecting compound X and compound VI to a condensation reaction to obtain compound IX; (b) in the presence of a fifth solvent, subjecting compound IX and a reducing substance to a reduction reaction to obtain compound VIII; (c) in the presence of a sixth solvent, subjecting compound VIII and compound XI to a condensation reaction to obtain compound VII; (d) in the presence of a seventh solvent, subjecting compound VII to an addition ring-closure reaction to obtain compound I; Wherein, the compound I has a structure shown in formula (I), the compound VII has a structure shown in formula (VII), the compound VIII has a structure shown in formula (VIII), the compound IX has a structure shown in formula (IX), the compound X has a structure shown in formula (X), the compound XI has a structure shown in formula (XI), and the compound VI has a structure shown in formula (VI); In Formula (I), Formula (VI), Formula (VII), Formula (VIII), Formula (IX), Formula (X) and Formula (XI), R, Y 1 , Y 2 , T 1 , T 2 , T 3 The definition is the same as that in any one of claims 1 to 4, and L is selected from halogen.

10. The method according to claim 9, wherein: The third alkaline substance is selected from at least one of pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide and 1,8-diazabicyclo[5.4.0]undec-7-ene; and / or, the molar ratio of the compound X to the compound VI is 0.5-2:1; And / or, in step (a), the conditions of the condensation reaction include: temperature of -20°C to 150°C, and reaction time of 0.1-48h.

11. The method according to claim 9 or 10, wherein: The reducing substance is selected from at least one of hydrogen, metal, sulfide, borane and its complex and hydrosulfite; And / or, in step (b), the conditions of the reduction reaction include: temperature of -10°C to 200°C, and reaction time of 0.5-72h.

12. The method according to any one of claims 9 to 11, wherein: The molar ratio of the compound VIII to the compound XI is 0.5-2:1; and / or, the reaction in step (c) may be carried out in the presence of a first catalyst; and / or, the first catalyst is selected from at least one of glacial acetic acid, propionic acid, amino acid and Lewis acid; And / or, in step (c), the conditions of the condensation reaction include: temperature of -20°C to 150°C, and reaction time of 0.1-48h.

13. The method according to any one of claims 9 to 12, wherein: The reaction described in step (d) may be carried out in the presence of a second catalyst; and / or, the second catalyst is selected from iodide, bromide, glacial acetic acid, propionic acid, amino acid, Lewis acid; and / or, the fourth to seventh solvents are each independently selected from at least one of methanol, ethanol, isopropanol, propanol, butanol, dichloromethane, chloroform, carbon tetrachloride, ethylene dichloride, ethyl acetate, toluene, xylene, acetonitrile, tetrahydrofuran, acetone, N,N-dimethylformamide, N-methylpyrrolidone, dioxane and water; And / or, in step (d), the conditions of the condensation reaction include: temperature of -20°C to 150°C, and reaction time of 0.1-48h.

14. Use of the substituted benzimidazole compound and / or its salt according to any one of claims 1 to 4 in the preparation of insecticides and acaricides.

15. An insecticide and acaricide, characterized in that: The insecticide and acaricide contains an active ingredient, wherein the active ingredient is selected from at least one of the aromatic ring compounds and / or salts thereof according to any one of claims 1 to 4; Preferably, based on the total weight of the insecticide and acaricide, the content of the active ingredient is 1-99% by weight, more preferably 5-60% by weight.

16. Use of the insecticide and acaricide according to claim 15 for killing insects and / or acaricides in agriculture, forestry and gardening.

Images