A sulfuramide compound and its preparation method and application

Abstract

The present invention provides a sulfur-containing amide compound, a preparation method, and an application thereof. The amide compound has a structure represented by Formula I. The sulfur-containing amide compound of the present invention can exhibit high insecticidal activity and good rapid-acting properties at low doses. Furthermore, due to its good effect at low doses, the dosage of the drug can be reduced, which is more environmentally friendly and has broad application prospects.

Description

Technical Field

[0001] The present invention belongs to the field of pesticides, and in particular relates to a sulfuramide compound and a preparation method and application thereof. Background Art

[0002] In agricultural and horticultural crop production, pests and other pests remain a significant threat. Due to the development of pest resistance to existing pesticides and the environmental impact of existing pesticides, there is a growing demand for new pesticides with improved activity, lower dosage requirements, and improved environmental friendliness.

[0003] The insecticidal activity of amide compounds has been reported. For example, CN101203484A discloses compound KC2 (i.e., compound 1-425 in CN101203484A) and its insecticidal activity. CN101367748A discloses compound KC3 (i.e., compound 203 in CN101367748A) and compound KC4 (i.e., compound 207 in CN101367748A) and their insecticidal activity. CN109497062A discloses amide compound KC1 (compound 62 in the invention) with a cyclopropylmethyl group and its insecticidal activity against pests such as diamondback moth and striped stem borer. However, the invention does not disclose the acaricidal activity of these compounds.

[0004]

[0005] In this field, there is still a need to actively develop insecticides that have high insecticidal activity at low doses, a broader insecticide spectrum, and are safe for the environment to meet the needs of agriculture and forestry. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention aims to provide a sulfur-containing amide compound and its preparation method and application, in particular to provide a compound containing alkylthio, alkylsulfinyl, and alkylsulfonyl groups and its preparation method and application. The amide compound has a good insecticidal effect at a low dose and has good acaricidal activity. The low dosage not only reduces the cost of the drug, but also is more conducive to environmental protection.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In one aspect, the present invention provides a sulfur-containing amide compound having a structure shown in Formula I below:

[0009]

[0010] In Formula I,

[0011] Q is selected from the following Q1, Q2, Q3 or Q4:

[0012]

[0013] Z1, Z2, Z3, Z4, and Z5 are each independently selected from hydrogen, a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group, a C3-C8 cycloalkyl group, a C1-C6 haloalkyl group, a C3-C8 halocycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylsulfinyl group, a C1-C6 haloalkylsulfinyl group, a C1-C6 alkylsulfonyl group, or a C1-C6 haloalkylsulfonyl group;

[0014] R1 is selected from C3-C8 cycloalkylalkyl;

[0015] R2 is selected from hydrogen, fluorine or methoxy;

[0016] R3 is selected from C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C1-C4 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl or C3-C8 halocycloalkyl;

[0017] Y1 is selected from hydrogen, a halogen atom, a C1-C4 alkyl group or a C1-C4 haloalkyl group;

[0018] X are the same or different and are selected from hydrogen, a halogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkoxy group or a cyano group;

[0019] W1 and W2 are independently an oxygen atom or a sulfur atom;

[0020] m represents an integer from 0 to 4;

[0021] n represents an integer from 0 to 2.

[0022] The sulfur-containing amide compound having the structure represented by Formula I of the present invention can achieve good insecticidal activity at a low dose and has a rapid onset of action. It can exert insecticidal activity one day after application and can achieve very high insecticidal activity within three days, and has good rapid effect. In addition, due to the good effect at a low dose, the harm to plants and humans caused by excessive drug concentration is reduced, and less drug residue is generated during application, which is more environmentally friendly.

[0023] In the present invention, as a preferred technical solution, in Formula I, Z1, Z2, Z3, Z4, and Z5 are independently selected from hydrogen, a halogen atom, a cyano group, a nitro group, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a tert-butoxy group, a trifluoromethyl group, Methyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; R1 is selected from cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl; R3 is selected from C1-C4 alkyl, C3-C8 cycloalkyl, C1-C4 haloalkyl or C3-C8 halocycloalkyl; Y1 is selected from a halogen atom; X is the same or different and is selected from hydrogen, a halogen atom or cyano.

[0024] As a further preferred technical solution of the present invention, the sulfuramide-containing compound is any one of the compounds having the general formula I shown in Tables 1 to 4 below.

[0025] Table 1

[0026]

[0027]

[0028]

[0029]

[0030]

[0031] Table 2

[0032]

[0033]

[0034]

[0035]

[0036] Table 3

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045] Table 4

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052] It should be noted that "H" represents a hydrogen atom, "O" represents an oxygen atom, "S" represents a sulfur atom, "F" represents a fluorine atom, "Cl" represents a chlorine atom, "Br" represents a bromine atom, "I" represents an iodine atom, "Me" represents a methyl group, "Et" represents an ethyl group, "MeO" represents a methoxy group, "n-Pr" represents a n-propyl group, "i-Pr" represents an isopropyl group, "t-Bu" represents a tert-butyl group, and "CH2CF3" represents a 2,2,2-trifluoroethyl group.

[0053] In the present invention, as a more preferred technical solution, in Formula I, Z1, Z2, Z3, Z4, and Z5 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylsulfonyl, or trifluoromethylsulfonyl; R1 is selected from cyclopropylmethyl or cyclobutylmethyl; R2 is selected from fluorine; R3 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or 2,2,2-trifluoroethyl; Y1 is selected from chlorine, bromine, or iodine; X is the same or different and is selected from hydrogen, fluorine, chlorine, bromine, or iodine; W1 and W2 are selected from oxygen.

[0054] In the present invention, as a particularly preferred technical solution, the sulfuramide compound is any one selected from the following compounds:

[0055]

[0056]

[0057] The compound numbers correspond to the compound numbers in Table 1.

[0058] The alkyl group herein refers to a linear or branched alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and n-hexyl. A haloalkyl group refers to a group in which the hydrogen atoms on the alkyl group are replaced by one or more halogen atoms. An alkoxy group refers to a group in which an oxygen atom is attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy. A haloalkoxy group refers to a group in which the hydrogen atoms on the alkoxy group are replaced by one or more halogen atoms. Halogen is F, Cl, Br, or I.

[0059] As used herein, the term "C1-C6 alkyl" refers to a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and the like. The term "C1-C6 alkoxy" refers to a straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms, including but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy, and the like. "C1-C6 haloalkyl" refers to a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, including but not limited to trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoroisopropyl, and the like. "C1-C6 haloalkoxy" refers to a straight or branched alkoxy group having 1 to 6 carbon atoms substituted with a halogen atom, including but not limited to trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, etc. The term "C3-C8 cycloalkyl" used in the present invention refers to a cyclic alkyl group having 3 to 8 carbon atoms, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. The term "C3-C8 halocycloalkyl" used in the present invention refers to a cyclic alkyl group having 3 to 8 carbon atoms substituted with a halogen on the ring, including but not limited to 1-chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl, etc.

[0060] In the present invention, C1-C6, C3-C8, etc. before the specific group represents the number of carbon atoms contained in the group. For example, C1-C6 represents a group with 1, 2, 3, 4, 5 or 6 carbon atoms, C3-C8 represents a group with 3, 4, 5, 6, 7 or 8 carbon atoms, and so on.

[0061] The compounds of formula I of the present invention can be prepared by the following methods. Unless otherwise specified, the groups in the reaction formulas have the same definitions as above.

[0062] Preparation method 1:

[0063] The structure of the compound of general formula I of the present invention is as follows, and it can be prepared by the following method:

[0064]

[0065] Wherein, LG is selected from fluorine, chlorine, bromine, C1-C 12 Alkoxy, C1-C 12 Alkyloxyacyloxy or C1-C 12 Hal is selected from fluorine, chlorine, bromine or iodine; L is selected from chlorine, bromine, iodine, C1-C6 alkyl sulfonate.

[0066] 1-(i): The compound of formula III reacts with the compound of formula IV to obtain the compound of formula V.

[0067] In the present invention, the molar ratio of the compound of formula III to the compound of formula IV in step 1-(i) is 0.5-2:1, and the reaction is carried out in the presence of an alkaline substance such as an organic base and / or an inorganic base. Preferably, the organic base is any one or a combination of at least two of triethylamine, N,N-diisopropylethylamine, pyridine, sodium methoxide, or sodium ethoxide. Preferably, the inorganic base is any one or a combination of at least two of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or sodium hydride. The reaction temperature is greater than or equal to room temperature and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.

[0068] 1-(ii): The compound of formula V reacts with the compound of formula VI to obtain the compound of formula VII.

[0069] In the present invention, the molar ratio of the compound of formula V to the compound of formula VI in step 1-(ii) is 0.5-2:1, and the reaction is carried out in the presence of an alkaline substance such as an organic base and / or an inorganic base. Preferably, the organic base is any one or a combination of at least two of triethylamine, N,N-diisopropylethylamine, pyridine, sodium methoxide, or sodium ethoxide. Preferably, the inorganic base is any one or a combination of at least two of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or sodium hydride. The reaction temperature is greater than or equal to -10°C and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.

[0070] 1-(iii): The compound of formula VII is hydrolyzed to obtain the compound of formula VIII.

[0071] Step 1-(iii) Hydrolyze the compound of Formula VII in the presence of an alkaline substance to produce a compound of Formula VIII. Preferably, the alkaline substance is lithium hydroxide, sodium hydroxide, or potassium hydroxide. Preferably, the amount of the alkaline substance used is 1-5 times the molar amount of the compound of Formula VII.

[0072] 1-(iv): The compound of formula VIII is subjected to substitution reaction to obtain the compound of formula II.

[0073] In this step, the compound of formula VIII is reacted with a compound containing an LG group, such as thionyl chloride, oxalyl chloride or triphosgene, using a known method to prepare a compound represented by formula II.

[0074] 1-(v): The compound of formula II reacts with the compound of formula IX to obtain the compound of formula I

[0075] In the present invention, the molar ratio of the compound of formula II to the compound of formula IX is 0.5-2:1, and the reaction is carried out in the presence of an alkaline substance, which is an organic base and / or an inorganic base. Preferably, the organic base is any one or a combination of at least two of triethylamine, diisopropylethylamine, pyridine, piperidine, 4-N,N-dimethylaminopyridine, an alkali metal alcoholate, or lithium amide. Preferably, the alkali metal alcoholate is sodium methoxide and / or sodium ethoxide. Preferably, the lithium amide is lithium diisopropylamide. Preferably, the inorganic base is any one or a combination of at least two of an alkali metal hydroxide, carbonate, or phosphate. Preferably, the alkali metal hydroxide is any one or a combination of at least two of lithium hydroxide, sodium hydroxide, or potassium hydroxide. Preferably, the carbonate is any one or a combination of at least two of sodium bicarbonate, sodium carbonate, or potassium carbonate. Preferably, the phosphate is dipotassium hydrogen phosphate and / or trisodium phosphate.

[0076] The solvent for the reaction in step 1-(v) is any one or a combination of at least two of a halogenated hydrocarbon, an aromatic hydrocarbon, a linear or cyclic ether, an ester, a ketone, a nitrile, or an aprotic polar inert solvent. The reaction temperature is greater than or equal to -70°C and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.

[0077] Preparation method 2:

[0078] The compound of formula I of the present invention can be prepared by another method as follows:

[0079]

[0080] 2-(i): Substitution reaction of the compound of formula X to obtain the compound of formula XI

[0081] That is, in this step, the compound of formula X is reacted with thionyl chloride, oxalyl chloride, triphosgene, etc. using a known method to prepare a compound represented by formula XI containing an LG group.

[0082] 2-(ii): The compound of formula XI reacts with the compound of formula IX to obtain the compound of formula XII.

[0083] The compound represented by the general formula XI is reacted with the compound represented by the general formula IX under the same conditions as described in 1-(v) to produce the compound represented by the general formula XII.

[0084] 2-(iii): Compound XII is subjected to reduction reaction to obtain compound XIII

[0085] Aromatic carboxylic acid amide derivatives having a nitro group represented by general formula XII can be reduced to aromatic carboxylic acid amide derivatives having an amino group represented by general formula XIII. Examples of the reduction reaction include methods utilizing hydrogenation and methods utilizing metal compounds (e.g., stannous chloride) or metals (e.g., zinc powder, iron powder, etc.).

[0086] The hydrogenation reaction can be carried out in a suitable solvent in the presence of a catalyst, under normal pressure or under pressure, in a hydrogen atmosphere. The catalyst used in the hydrogenation reaction may be a palladium catalyst such as palladium-carbon, a cobalt catalyst, a ruthenium catalyst, a platinum catalyst, or the like. The solvent may be an alcohol such as methanol or ethanol; an aromatic hydrocarbon such as benzene or toluene; a linear or cyclic ether such as diethyl ether or tetrahydrofuran; or an ester such as ethyl acetate. Preferably, the hydrogenation reaction is carried out under a pressure of 0.1-10 MPa, at a temperature of -20°C or higher and less than the boiling point of the reaction solvent, and for a reaction time of 0.5-48 hours.

[0087] The method using a metal compound or metal is carried out in any one of methanol, ethanol, or ethyl acetate, or a mixed solvent of at least two of them. Preferably, the metal compound is stannous chloride, and the metal is any one of zinc powder or iron powder, or a combination of at least two of them. Preferably, the reaction temperature of the method using a metal compound or metal is greater than or equal to -10°C and less than or equal to the boiling point of the reaction solvent. Preferably, the reaction time of the method using a metal compound or metal is 0.5-48 hours.

[0088] 2-(iv): The compound of formula XIII reacts with the compound of formula IV to obtain the compound of formula XIV.

[0089] The compound represented by the general formula XIII is reacted with the compound represented by the general formula IV under the same conditions as described in step 1-(i) to produce the compound represented by the general formula XII.

[0090] 2-(v): The compound of formula XIV reacts with the compound of formula VI to obtain the compound of formula I.

[0091] The compound represented by the general formula XIV is reacted with the compound represented by the general formula VI under the same conditions as described in step 1-(ii) to produce the compound represented by the general formula XII.

[0092] Preparation method 3:

[0093] The compound of general formula I of the present invention can be prepared as follows:

[0094]

[0095] 3-(i): Substitution reaction of the compound of formula X to obtain the compound of formula XI

[0096] The compound represented by the general formula X is reacted with the compound represented by the general formula XI under the same conditions as described in 2-(i) to prepare the compound represented by the general formula XI.

[0097] 3-(ii): The compound of formula XI reacts with the compound of formula IX to obtain the compound of formula XII.

[0098] The compound represented by the general formula XI is reacted with the compound represented by the general formula IX under the same conditions as described in 1-(v) to prepare the compound represented by the general formula XII.

[0099] 3-(iii): Compound XII is subjected to reduction reaction to obtain compound XIII

[0100] The compound represented by the general formula XII is reacted under the same conditions as described in 2-(iii) to prepare the compound represented by the general formula XIII.

[0101] 3-(iv): The compound of formula XIII reacts with the compound of formula XV to obtain the compound of formula XIV.

[0102] In the present invention, the molar ratio of the compound of formula XIII to the compound of formula XV is 0.5-2: 1. Step 3-(iv) The reaction is carried out in the presence of an acidic substance and a reducing agent.

[0103] The acidic substance is an organic acid and / or an inorganic acid, and the reducing agent is a borohydride. Preferably, the organic acid is any one of formic acid, acetic acid, trifluoroacetic acid, or methanesulfonic acid, or a combination of at least two thereof. Preferably, the inorganic acid is any one of hydrochloric acid, phosphoric acid, or sulfuric acid, or a combination of at least two thereof. The reducing agent is sodium borohydride, sodium cyanoborohydride, or sodium triacetoxyborohydride.

[0104] The reaction solvent is selected from any one of dichloromethane, toluene, ethyl acetate, acetone, tetrahydrofuran, dioxane, and N,N-dimethylformamide, or a combination of at least two thereof. The reaction temperature is greater than or equal to room temperature and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.

[0105] 3-(v): The compound of formula XIV reacts with the compound of formula VI to obtain the compound of formula I.

[0106] The compound represented by the general formula XIV is reacted with the compound represented by the general formula VI under the same conditions as described in step 1-(ii) to produce the compound represented by the general formula I.

[0107] Preparation method 4:

[0108] The compound of formula I of the present invention can be prepared by another method as follows:

[0109] The compounds of the present invention wherein n=1 or 2 are prepared by oxidizing the compounds of the present invention wherein n=0.

[0110]

[0111] 4-(i): Oxidation reaction of the compound of formula I-1 to obtain the compound of formula I-2.

[0112] In the present invention, the reaction in step 4-(i) is carried out by an oxidizing agent in the presence of a solvent such as an aliphatic halogenated hydrocarbon, alcohol, acetic acid, water, or a mixture thereof. Preferably, the oxidizing agent is sodium periodate, hydrogen peroxide, or m-chloroperbenzoic acid. Preferably, the molar ratio of the oxidizing agent to the compound of formula I-1 is 1.0-2:0. Preferably, the temperature of the reaction in step 4-(i) is -20°C to 80°C. Preferably, the reaction time in step 4-(i) is in the range of 0.5-24 hours.

[0113] 4-(ii): Oxidation reaction of the compound of formula I-2 to obtain the compound of formula I-3.

[0114] The compound represented by the general formula I-2 is reacted under the same conditions as described in 4-(i) to prepare the compound represented by the general formula I-3.

[0115] 4-(iii): Oxidation reaction of the compound of formula I-1 to obtain the compound of formula I-3.

[0116] The compound represented by formula I-1 is reacted under similar conditions as described in 4-(i) to prepare the compound represented by formula I-3, except that the molar ratio of the oxidant to the compound of formula I-1 is 2.0-4:0.

[0117] On the other hand, the present invention also provides an intermediate for preparing the above-mentioned sulfuramide-containing compound, which has a structure shown in Formula XIV:

[0118]

[0119] wherein X, W2, Y1, R1, R2, R3, m and n have the same defined ranges as those in the compound of formula I and are not further described herein.

[0120] The preparation method of the intermediate compound of formula XIV in the present invention has been mentioned above when describing the preparation method of formula I, and will not be repeated here.

[0121] In the present invention, representative compounds of the intermediate compounds of Formula XIV of the compounds of the present invention are shown in Table 5, but the intermediate compounds of the present invention are not limited to the compounds shown in Table 5.

[0122] Table 5

[0123]

[0124]

[0125] In another aspect, the present invention provides tautomers, enantiomers, diastereomers or salts thereof of the above-mentioned sulfuramide-containing compounds.

[0126] In the present invention, the tautomers, enantiomers, diastereomers or salts thereof of the sulfur-containing amide compounds can also exert the same effects as the amide compounds, and have good insecticidal effects and fast-acting properties at low doses.

[0127] In another aspect, the present invention provides the use of the above-mentioned sulfuramide-containing compounds for controlling insect pests and nematodes in the fields of agriculture, forestry and horticulture.

[0128] The sulfuramide compounds of the present invention are suitable for preventing and controlling various agricultural, forestry and horticultural pests, sanitary pests and nematodes that harm rice, corn, wheat, potatoes, fruit trees, vegetables, other crops and flowers.

[0129] In the present invention, the pests include Lepidoptera, Coleoptera, Hemiptera, Thysanoptera, Diptera, Orthoptera, Homoptera, Isoptera, Hymenoptera, spider mites and nematodes, mosquitoes, flies, ants and the like.

[0130] Preferably, the pests include but are not limited to: cotton bollworm, diamondback moth, beet armyworm, Spodoptera litura, cabbage worm, striped stem borer, yellow stem borer, stem borer, fall armyworm, rice leaf roller, rice thrips, western flower thrips, melon thrips, onion thrips, ginger thrips, mango thrips, peach aphid, cotton aphid, alfalfa aphid, apple yellow aphid, wheat aphid, flea beetle, stink bug, gray planthopper, brown planthopper, white-backed planthopper, termite, mosquito and fly, cinnabar spider mite, citrus red spider.

[0131] The compounds of the present invention have a wide range of applications, and the plants or ranges to which they are applied mainly include the following categories: fruits and vegetables, including cucumbers, loofahs, watermelons, melons, pumpkins, hanging melons, spinach, celery, cabbage, cabbage, gourds, peppers, eggplants, tomatoes, onions, ginger, garlic, leeks, lettuce, kidney beans, cowpeas, broad beans, radishes, carrots, potatoes, and yams; cereals, including wheat, barley, corn, rice, and sorghum; fruit trees, including apples, pears, bananas, citrus fruits, grapes, litchis, and mangoes; flowers, including peonies, roses, and anthuriums; oil crops, including peanuts, soybeans, rapeseed, sunflowers, and sesame seeds; sugar crops, including beets and sugarcane; other crops, such as strawberries, potatoes, sweet potatoes, tobacco, and tea; gardening, forestry, household hygiene, and public health areas, etc.; the plants or ranges listed above have no limiting effect on the scope of application of the amide compounds of the present invention.

[0132] On the other hand, the present invention provides an insecticide composition, which comprises an active ingredient and an agrochemically acceptable carrier, wherein the active ingredient is the sulfuramide compound as described above.

[0133] The composition of the present invention can be applied in the form of a formulation, wherein the compound of formula I as the active ingredient is dissolved or dispersed in a carrier or formulated into a formulation so as to be more easily dispersed when used as an insecticide.

[0134] In the present invention, the insecticide composition can be prepared into formulations such as wettable powder, suspension, aqueous emulsion or emulsifiable concentrate.

[0135] The insecticide composition of the present invention can be used in agriculture, forestry, health and other fields.

[0136] Preferably, in the insecticide composition, the weight percentage of the active ingredient is 1-99%, for example, 1%, 10%, 20%, 35%, 55%, 75%, 95% or 99%.

[0137] Preferably, the pesticidally acceptable carrier comprises a surfactant.

[0138] In the present invention, the surfactant is an ionic surfactant or a nonionic surfactant.

[0139] The surfactant includes an emulsifier, a dispersant or a wetting agent. The emulsifier can be polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty ammonia and commercially available emulsifiers (Nongru 2201B, Nongru 0203B, Nongru 100#, Nongru 500#, Nongru 600#, Nongru 600-2#, Nongru 1601, Nongru 2201, Nongru NP-10, Nongru NP-15, Nongru 507#, Nongru OX-635, Nongru OX-622, Nongru OX-653, Nongru OX-667, Ningru 36#, etc.). Dispersants include sodium lignin sulfonate, pull open powder, calcium lignin sulfonate, methyl naphthalene sulfonic acid formaldehyde condensate, etc. Wetting agents include sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, etc.

[0140] Preferably, the pesticidally acceptable carrier includes a solid carrier and / or a liquid carrier.

[0141] Preferably, the solid carrier includes natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, kaolin, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate and hexamethylenediamine. Liquid carriers include water and organic solvents. When water is used as a solvent or diluent, organic solvents can also be used as adjuvants or antifreeze additives. Suitable organic solvents include aromatic hydrocarbons such as xylene and toluene; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, dichloromethane; aliphatic hydrocarbons such as petroleum distillates, cyclohexane, light mineral oil; alcohols such as isopropyl alcohol, butanol, ethylene glycol, glycerol and cyclohexanol; and their ethers and esters; and ketones such as acetone, cyclohexanone, dimethylformamide and N-methylpyrrolidone.

[0142] During the preparation of the insecticide composition, the active ingredient can be mixed with a liquid carrier and / or a solid carrier, and a surfactant (such as an emulsifier, dispersant, stabilizer, wetting agent) can be added at the same time. Other auxiliary agents (such as adhesives, defoaming agents, oxidants, etc.) can also be added.

[0143] In another aspect, the present invention provides a method for controlling pests, comprising applying an effective dose of the above-mentioned sulfuramide compound or insecticide composition to the pests to be controlled or the medium in which they grow.

[0144] Preferably, the effective dose is 7.5-1000 g per hectare, such as 7.5 g, 50 g, 100 g, 180 g, 250 g, 350 g, 450 g, 600 g, 800 g or 1000 g per hectare, preferably 15-600 g per hectare.

[0145] The compositions of the present invention can be applied to pests or their growth medium in the form of a formulation. The compound of formula I, as the active ingredient, is dissolved or dispersed in a carrier or formulated into a formulation for easier dispersion when used as an insecticide. For example, these chemical formulations can be formulated into various liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, aqueous emulsions, dusts, wettable powders, soluble powders, granules, water-dispersible granules, or capsules.

[0146] For certain applications, such as in agriculture, one or more other insecticides, fungicides, herbicides, plant growth regulators or fertilizers may be added to the insecticidal composition of the present invention to produce additional advantages and effects.

[0147] Compared with the prior art, the present invention has the following beneficial effects:

[0148] The sulfuramide compounds of the present invention have significant effects on preventing and controlling agricultural and forestry pests and diseases, nematodes, and pests in the field of health. They can achieve good insecticidal effects at low doses and have a rapid onset of action. They can exert insecticidal activity one day after application and can achieve very high insecticidal activity within three days. They have good rapid effectiveness and can be used at low doses, thereby reducing damage to plants and humans caused by excessive drug concentrations. They also produce less drug residue during application, which is more environmentally friendly. In addition, the preparation method is simple and efficient, easy to produce on a large scale, and has broad application prospects. DETAILED DESCRIPTION

[0149] The technical solution of the present invention is further illustrated below by means of specific embodiments. Those skilled in the art should understand that the embodiments are merely helpful for understanding the present invention and should not be construed as limiting the present invention. Unless otherwise specified in the examples and the present invention: When the compounds were subjected to H NMR spectroscopy testing, the corresponding samples were dissolved in deuterated solvents and H spectral data were obtained using a 400 MHz NMR instrument. The chemical shift units are ppm (i.e., δ: ppm); the eluent used for column chromatography purification was prepared according to the volume ratio of petroleum ether (abbreviated as PE): ethyl acetate (abbreviated as EA) as shown.

[0150] Synthesis Example

[0151] Synthesis Example 1

[0152] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (Compound No. 187):

[0153] (1) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-2-fluoro-3-nitrobenzamide

[0154]

[0155] To the reaction flask, 2-fluoro-3-nitrobenzoic acid (1.43 g, 7.73 mmol), toluene (20 mL), and thionyl chloride (1.84 g, 15.46 mmol) were added in sequence. The mixture was stirred at reflux for 2 h and concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. The above-mentioned acid chloride was added to 2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-methylthioaniline (2.47 g, 6.45 mmol), potassium iodide (0.43 g, 2.58 mmol) and acetonitrile (30 mL). The temperature was raised to 110°C and the reaction mixture was reacted for 3 hours. The reaction solution was cooled to room temperature, 200 mL of ethyl acetate and 100 mL of water were added, and the mixture was extracted and separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA=10:1) to obtain the target product (3.09 g, yield 87%).

[0156] 1 H NMR (CDCl3): 8.48-8.43 (m, 1H), 8.29-8.23 (m, 1H), 8.03 (d, J = 11.6Hz, 1H), 7.69 (s, 1H), 7.50 (t, J = 8.0Hz, 1H), 7.41 (s, 1H), 2.49 (s, 3H).

[0157] (2) Synthesis of 3-amino-N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-2-fluorobenzamide

[0158]

[0159] N-[2-Bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-2-fluoro-3-nitrobenzamide (3.04 g, 5.51 mmol) was dissolved in THF (50 mL). Acetic acid (1.78 mL), water (1.3 mL), and iron powder (1.23 g, 22.04 mmol) were added sequentially. The mixture was heated to 80°C and refluxed for 4 h. TLC was used to monitor the reaction until completion. The reaction solution was filtered through celite, the filtrate was spin-dried, water (50 mL) was added, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain 2.44 g of a yellow-brown solid, with a yield of 85%.

[0160] 1H NMR(CDCl3):8.11(d,J=14.0Hz,1H),7.68(s,1H),7.53-7.47(m,1H),7.4 0(s,1H),7.11-7.06(m,1H),7.03-6.97(m,1H),3.76(s,2H),2.47(s,3H).

[0161] (3) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-(cyclopropylmethylamino)-2-fluorobenzamide

[0162]

[0163] 3-Amino-N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-2-fluorobenzamide (2.50 g, 4.80 mmol) was dissolved in dichloroethane (30 mL). Cyclopropanecarboxaldehyde (0.34 g, 4.80 mmol) and acetic acid (0.29 g, 4.80 mmol) were added sequentially. The mixture was stirred at room temperature for 30 min, and sodium triacetoxyborohydride (1.02 g, 4.80 mmol) was added. The reaction was monitored by TLC until completion. The reaction solution was adjusted to pH 8 with saturated aqueous sodium bicarbonate solution and extracted with dichloromethane (50 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 30:1) to obtain a yellow solid (1.21 g, 44% yield).

[0164] 1 H NMR(CDCl3): 8.10(d,J=14.0Hz,1H),7.67(s,1H),7.43-7.37(m,2H),7.13(t,J=8.0Hz,1H),6.91-6.85(m,1H ), 4.26 (s, 1H), 3.04 (d, J = 6.8Hz, 2H), 2.47 (s, 3H), 1.19-1.11 (m, 1H), 0.64-0.59 (m, 2H), 0.32-0.27 (m, 2H).

[0165] (4) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-[N-(cyclopropylmethyl)benzamido]-2-fluorobenzamide

[0166]

[0167] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-3-(cyclopropylmethylamino)-2-fluorobenzamide (0.50 g, 0.86 mmol) in toluene (5 mL) were added DIPEA (223 mg, 1.73 mmol) and benzoyl chloride (133 mg, 0.95 mmol) in sequence, and the mixture was allowed to react at 130°C for 4 hours. The reaction solution was cooled to room temperature, extracted with water (10 mL) and ethyl acetate (50 mL). The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 10:1) to obtain the desired product (0.50 g, 84% yield).

[0168] Compound 187 1 HNMR(CDCl3): 8.02(s,1H),7.89(d,J=11.6Hz,1H),7.66(s,1H),7.52-7.46(m,1H),7.36(d,J=14.8Hz,3H), 7.28-7.18(m,4H),3.93-3.71(m,2H),2.46(s,3H),1.18-1.07(m,1H),0.55-0.44(m,2H),0.26-0.10(m,2H).

[0169] Synthesis Example 2

[0170] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-methanesulfinylphenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (Compound No. 190):

[0171]

[0172] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (0.43 g, 0.63 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (98 mg, 0.56 mmol). The reaction mixture was allowed to react at -10-0°C for 1 h. The reaction mixture was then stirred at 25°C for 2 h and monitored by TLC. The reaction mixture was quenched with water, adjusted to pH 8 by adding anhydrous K₂CO₃, and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain the desired product (0.30 g, 68% yield).

[0173] Compound 190 1HNMR(CDCl3): 8.43(s,1H),8.24(s,1H),7.99(s,1H),7.98-7.92(m,1H),7.56(t,J=6.4Hz,1H),7.39-7.26(m ,4H),7.22(s,2H),3.93-3.66(m,2H),2.89(s,3H),1.16-1.05(m,1H),0.52-0.45(m,2H),0.25-0.09(m,2H).

[0174] Synthesis Example 3

[0175] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-methanesulfonylphenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (Compound No. 191):

[0176]

[0177] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (0.25 g, 0.36 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (250 mg, 1.08 mmol). The mixture was heated to 80°C and refluxed for 2 hours, monitored by TLC. The reaction mixture was quenched with water, the pH was adjusted to 8 with anhydrous K₂CO₃, and then extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 3:1) to obtain the desired product (0.17 g, 64% yield).

[0178] Compound 191 1 H NMR(CDCl3): 8.90(s,1H),8.27(d,J=1.8Hz,1H),8.18(d,J=1.6Hz,1H),7.98(s,1H),7.54(t,J=7.2Hz,1H),7.40–7.3 2(m,2H),7.30-7.20(m,4H),3.93-3.70(m,2H),2.99(s,3H),1.16-1.06(m,1H),0.51-0.47(m,2H),0.24-0.08(m,2H).

[0179] Synthesis Example 4

[0180] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-4-fluorobenzamide (Compound No. 434):

[0181] (1) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-4-fluoro-3-nitrobenzamide

[0182]

[0183] To the reaction flask, 4-fluoro-3-nitrobenzoic acid (2.30 g, 12.43 mmol), toluene (20 mL), and thionyl chloride (2.95 g, 24.86 mmol) were added sequentially. The reaction mixture was stirred at reflux for 2 h and concentrated under reduced pressure to obtain 4-fluoro-3-nitrobenzoyl chloride. The above acid chloride was added to 2-bromo-4-(perfluoroisopropyl)-6-methylthioaniline (3.70 g, 9.58 mmol), potassium iodide (0.76 g, 4.60 mmol), and acetonitrile (50 mL). The reaction mixture was heated to 110°C for 3 h. After cooling to room temperature, 200 mL of ethyl acetate and 100 mL of water were added, and the mixture was extracted and separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 10:1) to obtain the desired product (4.85 g, 91% yield).

[0184] (2) Synthesis of 3-amino-N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-4-fluorobenzamide

[0185]

[0186] N-[2-Bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-4-fluoro-3-nitrobenzamide (5.57 g, 10.09 mmol) was dissolved in THF (100 mL). Acetic acid (3.26 mL), water (1.01 mL), and iron powder (2.26 g, 40.30 mmol) were added sequentially. The mixture was heated to 80°C and refluxed for 4 h. TLC was used to monitor the reaction until completion. The reaction solution was filtered through celite, the filtrate was dried, water (100 mL) was added, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain 4.41 g of a white solid, with a yield of 83%.

[0187] (3) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-(cyclopropylmethylamino)-4-fluorobenzamide

[0188]

[0189] 3-Amino-N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-4-fluorobenzamide (3.25 g, 6.22 mmol) was dissolved in dichloroethane (30 mL). Cyclopropylcarboxaldehyde (0.43 g, 6.22 mmol) and acetic acid (0.37 g, 6.22 mmol) were added sequentially. The mixture was stirred at room temperature for 30 min, and sodium triacetoxyborohydride (1.31 g, 6.22 mmol) was added. The reaction was monitored by TLC until completion. The reaction solution was adjusted to pH 8 with saturated aqueous sodium bicarbonate solution and extracted with dichloromethane (100 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 30:1) to obtain a white solid (2.4 g, 67% yield).

[0190] (4) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-4-fluorobenzamide

[0191]

[0192] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-3-(cyclopropylmethylamino)-4-fluorobenzamide (0.50 g, 0.86 mmol) in toluene (5 mL) were added DIPEA (448 mg, 3.40 mmol) and 2-fluoro-4-cyanobenzoyl chloride (238 mg, 1.30 mmol) in sequence. The mixture was allowed to react at 130°C for 4 hours. The reaction solution was cooled to room temperature, extracted with water (10 mL) and ethyl acetate (50 mL). The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain the desired product (0.43 g, 68% yield).

[0193] Compound 434 1 H NMR(CDCl3): 7.90–7.79(m,2H),7.68(s,1H),7.52(t,J=7.2Hz,1H),7.43–7.34(m,3H),7.17–7.07 (m,2H),3.92–3.72(m,2H),2.49(s,3H),1.11–1.02(m,1H),0.56–0.41(m,2H),0.26–0.14(m,2H).

[0194] Synthesis Example 5

[0195] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-methanesulfinylphenyl]-3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-4-fluorobenzamide (Compound No. 436):

[0196]

[0197] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-4-fluorobenzamide (0.43 g, 0.59 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (124 mg, 0.53 mmol). The reaction mixture was allowed to react at -10-0°C for 1 h. The reaction mixture was then stirred at 25°C for 2 h and monitored by TLC. The reaction mixture was quenched with water, the pH was adjusted to 8 with anhydrous K₂CO₃, and the organic phase was extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain the desired product (0.31 g, 70% yield).

[0198] Compound 436 1 H NMR(CDCl3): 9.25(s,1H),8.04–7.97(m,3H),7.91(s,1H),7.56-7.49(m,1H),7.38-7.34(m,1H),7.16- 7.05(m,2H),3.85-3.76(m,2H),2.91(s,3H),1.08–1.03(m,1H),0.54–0.47(m,2H),0.23-0.13(m,2H).

[0199] Synthesis Example 6

[0200] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-methanesulfonylphenyl]-3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-4-fluorobenzamide (Compound No. 437):

[0201]

[0202] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-4-fluorobenzamide (0.18 g, 0.24 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (170 mg, 0.74 mmol). The mixture was heated to 80°C and refluxed for 2 hours, monitored by TLC. The reaction mixture was quenched with water, the pH was adjusted to 8 with anhydrous K₂CO₃, and then extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 3:1) to obtain the desired product (0.15 g, 79% yield).

[0203] Compound 437 1 HNMR(CDCl3): 8.81(s,1H),8.26(s,1H),8.21(s,1H),8.09-8.06(m,1H),7.99(d,J=8.0Hz,1H),7.96–7.88(m,2H),7.60–7.53(m,2 H),7.44–7.37(m,2H),7.19-7.12(m,2H),3.94-3.69(m,2H),3.03(s,3H),1.10-1.03(m,1H),0.54-0.42(m,2H),0.24–0.16(m,2H).

[0204] Synthesis Example 7

[0205] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-ethylthiophenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (Compound No. 196):

[0206] (1) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-ethylthiophenyl]-2-fluoro-3-nitrobenzamide

[0207]

[0208] 2-Fluoro-3-nitrobenzoic acid (1.82 g, 9.85 mmol), toluene (20 mL), and thionyl chloride (2.34 g, 19.70 mmol) were added to the reaction flask in sequence. The mixture was stirred at reflux for 2 h and concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. The above acid chloride was added to 2-bromo-4-(perfluoroisopropyl)-6-ethylthioaniline (3.04 g, 7.60 mmol), potassium iodide (0.61 g, 3.65 mmol), and acetonitrile (50 mL). The reaction mixture was heated to 110°C for 3 h. After cooling to room temperature, 200 mL of ethyl acetate and 100 mL of water were added for extraction and separation. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 10:1) to obtain the desired product (4.1 g, 95% yield).

[0209] (2) Synthesis of 3-amino-N-[2-bromo-4-(perfluoroisopropyl)-6-ethylthiophenyl]-2-fluorobenzamide

[0210]

[0211] N-[2-Bromo-4-(perfluoroisopropyl)-6-ethylthiophenyl]-2-fluoro-3-nitrobenzamide (4.30 g, 7.50 mmol) was dissolved in THF (100 mL). Acetic acid (2.46 mL), water (0.76 mL), and iron powder (1.70 g, 30.30 mmol) were added sequentially. The mixture was heated to 80°C and refluxed for 4 h. TLC was used to monitor the reaction until completion. The reaction solution was filtered through celite, the filtrate was spin-dried, water (100 mL) was added, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain 3.7 g of a yellow-brown liquid, with a yield of 92%.

[0212] (3) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-(ethylthio)phenyl]-3-(cyclopropylmethylamino)-2-fluorobenzamide

[0213]

[0214] 3-Amino-N-[2-bromo-4-(perfluoroisopropyl)-6-ethylthiophenyl]-2-fluorobenzamide (4.07 g, 7.59 mmol) was dissolved in dichloroethane (30 mL). Cyclopropylcarboxaldehyde (0.53 g, 7.59 mmol) and acetic acid (0.45 g, 7.59 mmol) were added sequentially. The mixture was stirred at room temperature for 30 min, and sodium triacetoxyborohydride (1.60 g, 7.59 mmol) was added. The reaction was monitored by TLC until completion. The reaction solution was adjusted to pH 8 with saturated aqueous sodium bicarbonate solution and extracted with dichloromethane (50 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 30:1) to obtain a yellow-brown liquid (2.5 g, 55% yield).

[0215] (4) Synthesis of N-[2-bromo-4-(perfluoroisopropyl)-6-(ethylthio)phenyl]-3-[N-(cyclopropylmethyl)benzamido]-2-fluorobenzamide

[0216]

[0217] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-ethylthiophenyl]-3-(cyclopropylmethylamino)-2-fluorobenzamide (0.49 g, 0.83 mmol) in toluene (5 mL) were added DIPEA (214 mg, 1.66 mmol) and benzoyl chloride (128 mg, 0.91 mmol) in sequence, and the mixture was allowed to react at 130°C for 4 hours. The reaction solution was cooled to room temperature, extracted with water (10 mL) and ethyl acetate (50 mL). The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain the desired product (0.50 g, 88% yield).

[0218] Compound 196 1 H NMR(CDCl3): 8.02(s,1H),7.94(d,J=12.8Hz,1H),7.67(s,1H),7.53-7.44(m,2H),7.39-7.30(m,2H),7.27-7.13(m,4H), 3.92-3.68(m,2H),2.92(q,J=7.2Hz,2H),1.31(t,J=7.2Hz,3H),1.17-1.03(m,1H),0.54-0.43(m,2H),0.27–0.08(m,2H).

[0219] Synthesis Example 8

[0220] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-ethylsulfinylphenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (Compound No. 197):

[0221]

[0222] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-(ethylthio)phenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (0.37 g, 0.53 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (110 mg, 0.47 mmol). The reaction mixture was allowed to react at -10-0°C for 1 h. The reaction mixture was then stirred at 25°C for 2 h and monitored by TLC. The reaction mixture was quenched with water, the pH was adjusted to 8 with anhydrous K₂CO₃, and the mixture was extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain the desired product (0.32 g, 85% yield).

[0223] Compound 197 1 H NMR(CDCl3): 8.35(s,1H),8.12(s,1H),8.00(s,1H),7.97-7.90(m,1H),7.55(t,J=6.4Hz,1H),7.40–7.28(m,4H),7.24-7.10(m,2H), 3.93–3.68(m,2H),3.20–3.05(m,1H),2.80–2.69(m,1H),1.27–1.23(m,3H),1.17–1.04(m,1H),0.51-0.45(m,2H),0.23-0.05(m,2H).

[0224] Synthesis Example 9

[0225] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-ethylsulfonylphenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (Compound No. 198):

[0226]

[0227] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-(ethylthio)phenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide (0.21 g, 0.29 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (204 mg, 0.88 mmol). The mixture was heated to 80°C and refluxed for 2 hours, monitored by TLC. The reaction mixture was quenched with water, the pH was adjusted to 8 with anhydrous K₂CO₃, and then extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 3:1) to obtain the desired product (0.13 g, 60% yield).

[0228] Compound 198 1 HNMR(CDCl3): 9.03(s,1H),8.21(s,1H),8.18(s,1H),8.00-7.92(m,1H),7.55-7.48(m,1H),7.38-7.31(m,2H),7.28-7.19(m ,4H),3.91-3.71(m,2H),3.09-2.97(m,2H),1.18(t,J=7.2Hz,3H),1.14-1.06(m,1H),0.51-0.45(m,2H),0.21-0.07(m,2H).

[0229] Synthesis Example 10

[0230] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-[N-(cyclopropylmethyl)-nicotinamido]-4-fluorobenzamide (Compound No. 444):

[0231]

[0232] To a solution of N-[2-bromo-4-(perfluoroisopropyl)-6-(methylthio)phenyl]-3-(cyclopropylmethylamino)-4-fluorobenzamide (0.50 g, 0.87 mmol) in toluene (5 mL) were added N,N-diisopropylethylamine (0.22 g, 1.73 mmol) and nicotinoyl chloride (0.14 g, 0.92 mmol) in sequence. The mixture was allowed to react at 130°C for 3 hours, monitored by TLC until completion. The reaction solution was cooled to room temperature, extracted with water (10 mL) and ethyl acetate (50 mL). The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 3:1) to obtain the desired product (332 mg, 56.02% yield).

[0233] Synthesis Example 11

[0234] Preparation of N-[2-bromo-4-(perfluoroisopropyl)-6-methylthiophenyl]-3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-2-fluorobenzamide (Compound No. 278):

[0235]

[0236] To the reaction flask, 3-[N-(cyclopropylmethyl)-2-fluoro-4-cyanobenzamido]-2-fluorobenzoic acid (1.10 g, 3.09 mmol), toluene (11 mL), and thionyl chloride (1.10 g, 12.36 mmol) were added in sequence. The reaction was stirred at 120°C for 2 h. The toluene was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (3 mL) for later use.

[0237] 2-Bromo-4-perfluoroisopropyl-6-methylthioaniline (1.19 g, 3.09 mmol), DIPEA (0.80 g, 6.17 mmol), and DMAP (76 mg, 620 μmol) were added sequentially to a reaction flask. The acyl chloride solution prepared in the previous step was slowly added at room temperature. The system was allowed to react at 110°C for 2-3 hours. TLC was used to monitor the reaction until completion. Water (40 mL) was added to the reaction solution to quench the reaction. The mixture was extracted with ethyl acetate (60 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 4:1) to obtain the desired product as a yellow liquid (0.50 g, 33.25% yield).

[0238] Compound 278 1 HNMR(CDCl3): 8.07(t,J=7.2Hz,1H),7.81(d,J=13.6Hz,1H),7.68(s,1H),7.54(q,J=9.2,8.0Hz,2H),7.37(dd,J=8.0,1.3Hz,2H),7.26(s ,2H),7.16(dd,J=8.8,1.2Hz,1H),3.83(d,J=7.2Hz,2H),2.50(s,3H),1.09(dt,J=12.0,6.1Hz,1H),0.58–0.49(m,2H),0.32–0.15(m,2H).

[0239] Some of the compounds in Tables 6 and 7 were prepared by methods similar to those in Synthesis Examples 1-11. The following Tables 6 and 7 provide the NMR data of some of the compounds synthesized with reference to Synthesis Examples 1-11.

[0240] Table 6

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] Table 7

[0247]

[0248]

[0249]

[0250] Other compounds of general formula I of the present invention can be synthesized by referring to the above method.

[0251] Preparation Example 1

[0252] In this example, the preparation was prepared using Compound 2 of the present invention as a representative compound, as follows:

[0253] 30 parts by weight of the compound 2 of the present invention, 15 parts by weight of polyoxyethylene styrylphenyl ether, 10 parts by weight of phosphorous acid, and 45 parts by weight of xylene were uniformly mixed to obtain an emulsifiable concentrate with a concentration of 30% of the compound 2 of the present invention.

[0254] Preparation Example 2

[0255] In this example, the preparation was prepared using compound 187 of the present invention as a representative compound, as follows:

[0256] 20 parts by weight of the present compound 187, 2 parts by weight of sodium lauryl sulfate, 2 parts by weight of dialkyl sulfosuccinate, 1 part by weight of sodium salt of β-naphthalenesulfonic acid formaldehyde condensate, and 75 parts by weight of diatomaceous earth were uniformly stirred to obtain a 20% wettable powder of the present compound 187.

[0257] Preparation Example 3

[0258] In this example, the compound 350 of the present invention was used as a representative compound to prepare a formulation, as follows:

[0259] 30 parts by weight of the compound 350 of the present invention, 10 parts by weight of ethylene glycol, 6 parts by weight of nonylphenol polyethylene glycol ether, 10 parts by weight of sodium lignin sulfonate, 10 parts by weight of carboxymethyl cellulose, 1 part by weight of a silicone oil aqueous solution, and water to make up to 100 parts by weight to obtain a 30% suspension of the compound 350 of the present invention.

[0260] Biological Activity Test Example

[0261] The compounds of the present invention obtained above were tested against various pests. Unless otherwise specified in the Examples and the present invention, sample preparation was performed by weighing 10 mg of the original sample to be tested and dissolving it in 1 mL of DMF to prepare a 10,000 ppm stock solution. This stock solution was then diluted with 0.05% Tween-80 water to the desired concentration for activity testing. The mortality rate was the pest mortality rate at the test concentration of the compound, calculated as: mortality (%) = number of dead insects / total number of insects * 100.

[0262] Insecticidal activity of the compound of test example 1 against armyworms

[0263] Activity testing was performed using the corn seedling soaking and feeding method. Cut the aerial portion of fresh corn seedlings grown indoors, approximately 10 cm in diameter, and set aside. Dip the seedlings in the solution for 10 seconds. After drying in a cool, shady place, cut them into 3-5 cm leaf segments and place them in petri dishes, with three segments per dish. Seed 10 third-instar armyworm larvae per dish, repeating three times. Place the animals in a lighted incubator at 25°C, with a light intensity of 14 hours L:10 hours D, and incubate. Count the number of dead insects 1, 2, and 3 days after application, and calculate mortality.

[0264] At a concentration of 1 ppm, compounds 190, 191, 278, 287, 292, 360, and 381 of the present invention caused a mortality rate of ≥80% against armyworms three days after application. At a concentration of 1 ppm, control compounds KC2, KC3, and KC4 caused a mortality rate of 0% against armyworms three days after application. The compounds of the present invention were significantly more active than the control compounds.

[0265] Insecticidal activity of the compound of test example 2 against Plutella xylostella

[0266] Activity testing was performed using a leaf disc feeding method. Leaf discs were immersed in the drug solution for 10 seconds, allowed to dry, and then placed in Petri dishes, four discs per dish, with filter paper placed inside to retain moisture. Ten diamondback moths were seeded per dish, with three replicates. The dish was incubated in a lighted incubator at 25°C, with a light intensity of 14 hours L:10 hours D. The number of dead diamondback moths was counted 1, 2, and 3 days after application, and mortality was calculated.

[0267] At a concentration of 1 ppm, compounds 187, 190, 191, 222, 228, 229, 278, 287, 236, 239, 240, 286, 401, and 464 of the present invention caused a mortality rate of ≥90% against the diamondback moth three days after application. At a concentration of 1 ppm, control compounds KC2, KC3, and KC4 caused a mortality rate of 0% against the diamondback moth three days after application. The compounds of the present invention were significantly more active than the control compounds.

[0268] Indoor biological activity of the compound of test example 3 against Tetranychus cinnabarinus

[0269] Cut a single broad bean leaf with stem and insert it into a penicillin bottle filled with 20 mL of water. Seed approximately 20 adult Tetranychus cinnabarinus mites per leaf. After 24 hours, check the adult mite population and select leaves with at least 15 mites for testing. Immerse the leaf with adult mites in the solution for 10 seconds, remove and air dry, and incubate in an observation room at 20-26°C, 14 hours light: 10 hours dark, and 40-60% humidity. Count the number of dead and living mites three days after treatment to calculate mortality.

[0270] When the concentration of compounds 63, 260, 263, 266, 416, 417, 421 and 422 of the present invention is 100 ppm, the mortality rate of Tetranychus cinnabarinus is ≥80% 3 days after administration.

[0271] When the concentration of the compounds 260, 263, 417 and 421 of the present invention is 10 ppm, the mortality rate of Tetranychus cinnabarinus is ≥80% 3 days after the application.

[0272] According to the above method, compounds 260, 263, 417, and 421 were selected and tested in parallel with KC1, KC2, KC3, and KC4 for their insecticidal activity against Tetranychus cinnabarinus. The test results are shown in Table 8.

[0273] Table 8 Comparison of the insecticidal activity of compound 260 and the reference compound against Tetranychus cinnabarinus

[0274]

[0275] As can be seen from Table 8, compared with existing compounds, the compounds of the present invention not only have greatly improved insecticidal activity, but also have the advantage of still being able to exert good insecticidal effects even after a significant reduction in dosage.

[0276] Indoor biological activity of the compound of test example 4 against brown planthopper

[0277] Immerse the entire rice seedling in the solution for 10 seconds, remove, and air dry on absorbent paper until no visible water is visible. Place a piece of filter paper flat on the bottom of a plastic cup and moisten with 1 mL of water (suck out any excess water). Inoculate 15 to 30 brown planthopper nymphs into the cup. Place the dried rice seedlings into the cup, root-side down, touching the filter paper. Cover the cup with plastic wrap, puncture holes for ventilation, and incubate in an observation room at 20 to 26°C, 14 hours light:10 hours dark, and 40 to 60% humidity. Count dead insects 3 days after application and calculate mortality.

[0278] When the concentration of the compounds 196, 202, 269, 295, 305, 308, 309, 337, 338, 339, 392, 393, 401, 409, 423, 426, 438, 445, 447, 448, 464, 472, 474 and 476 of the present invention is 400 ppm, the mortality rate against brown planthopper ≥ 80% 3 days after application.

[0279] When the concentration of the compounds 305, 309, 337, 447, 448, 464 and 476 of the present invention is 100 ppm, the mortality rate of the brown planthopper ≥80% 3 days after the application.

[0280] According to the above method, compounds 305, 309, 337, 447, 448, 464, and 476 were selected and tested in parallel with KC1, KC2, KC3, and KC4 for their insecticidal activity against brown planthoppers. The test results are shown in Table 9.

[0281] Table 9 Comparison of the insecticidal activity of compound 305 of the present invention and the reference compound against brown planthopper

[0282]

[0283]

[0284] As can be seen from Table 9, compared with existing compounds, the compounds of the present invention not only have greatly improved insecticidal activity, but also have the advantage of still being able to exert good insecticidal effects even after a significant reduction in dosage.

[0285] The present invention uses the above-described examples to illustrate the sulfuramide compounds, their preparation methods, and applications. However, the present invention is not limited to these examples, and it does not necessarily rely on these examples for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent substitutions for raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A sulfuramide compound, characterized in that: The sulfuramide compound is any one selected from the following compounds:

2. A salt of any one of the sulfuramide compounds according to claim 1.

3. Use of any one of the sulfuramide compounds according to claim 1 or the salt of the sulfuramide compound according to claim 2 in controlling plant pests.

4. An insecticide composition, characterized in that The insecticide composition comprises an active component and an agrochemically acceptable carrier, wherein the active component is any one of the sulfuramide compounds according to claim 1 or the salt of the sulfuramide compound according to claim 2.

5. The insecticide composition according to claim 4, characterized in that The weight percentage of the active ingredient in the insecticide composition is 1-99%.

6. A method for controlling pests, characterized in that: The method comprises applying an effective dose of any one of the sulfuramide compounds according to claim 1 or the salt of the sulfuramide compound according to claim 2 or the insecticide composition according to claim 4 or 5 to the harmful organisms to be controlled or the medium in which they grow.

7. The method for controlling pests according to claim 6, characterized in that: The effective dose is 7.5-1000g per hectare.

8. The method for controlling pests according to claim 6, characterized in that: The effective dose is 15-600 g per hectare.

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