Bis-benzyl aryl sulfide and preparation method and application thereof

Abstract

The invention relates to the technical field of pesticides, and particularly discloses dibenzyl aryl sulfide as well as a synthesis method and application thereof. The bisbenzyl aryl sulfide is a compound with a structure shown as a formula I or an agriculturally acceptable salt thereof. The dibenzyl aryl sulfide and the agriculturally acceptable salt thereof provided by the invention show an excellent effect on various pests, especially on spider mites represented by tetranychus cinnabarinus, tetranychus urticae, tetranychus shennieri, panonychus citri and the like, and can be used for preventing and treating various pest mites. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and particularly relates to a bis-benzyl aryl sulfide, a preparation method and application thereof, an agricultural composition, and a method for controlling invertebrate pests. Background Art

[0002] JP201142611A discloses that the following general formula compounds have acaricidal activity:

[0003]

[0004] wherein, A is oxygen or sulfur, and R 5 is a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted amino group, a nitrogen-containing heterocycle, etc.

[0005] WO2018015852 (CN109803956A) discloses compounds with the following general formula, which have acaricidal activity.

[0006]

[0007] wherein R 4 represents hydrogen, formyl, C 1-6 alkyl group, etc.; R 5 , R 6 are the same or different and each represents hydrogen, halogen or C 1-6 alkyl group, etc.; R 7 , R 8 , R 9 , R 10 , R 11 are the same or different and each represents hydrogen, halogen, etc.; X represents oxygen or sulfur.

[0008] CN111825585A discloses compounds with the following general formula, which have acaricidal activity.

[0009]

[0010] However, the above compounds still have low killing activity when controlling harmful pests, especially mites. In particular, their acaricidal activity is often unsatisfactory at low application rates, and the control effect on resistant spider mites is even worse. Therefore, there is still an urgent need in agricultural production for new drugs with high efficiency, low toxicity, and excellent killing effects on resistant mites. Summary of the Invention

[0011] In view of the deficiencies of the prior art, the object of the present invention is to overcome the technical problem that existing compounds have low killing activity in the control of invertebrate pests (especially mites) in the prior art, and to provide an aryl sulfide, a preparation method and application thereof, an agricultural composition, and a method for controlling invertebrate pests.

[0012] The technical solution of the present invention is as follows:

[0013] In the first aspect of the present invention, a dibenzyl aryl sulfide is provided, and the dibenzyl aryl sulfide is a compound represented by the formula I or an agriculturally acceptable salt thereof,

[0014]

[0015] wherein,

[0016] n is 0 or 1;

[0017] X and Y are each independently a halogen, a cyano group, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;

[0018] R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 or R 11 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro group, amino group, hydroxymethyl, carboxyl group, hydroxyl group, mercapto group, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkoxycarbonyl, C 1 -C 10 haloalkoxycarbonyl, C 1 -C 10 alkylsulfonyloxy, C 1 -C 10 alkylsulfonyl, C 1-C 10 haloalkylsulfonyl, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 2 -C 10 alkenyloxycarbonyl, C 2 -C 10 alkynyloxycarbonyl, C 1 -C 10 alkylcarbonyl, aminocarbonyl, C 2 -C 10 cyanoalkoxycarbonyl, C 1 -C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C 1 -C 10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl, C 1 -C 10 alkylsulfinyl or C 1 -C 10 haloalkylsulfinyl;

[0019] R 6 is C 1 -C 6 haloalkyl, C 2 -C 6 alkynyl, C 2 -C 6 alkenyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 epoxyalkyl.

[0020] In some embodiments, the compound of formula I, wherein,

[0021] n is 0 or 1;

[0022] X is fluorine, chlorine or methyl; Y is chlorine or methyl;

[0023] R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 or R 11 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxy, mercapto, C1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 1 -C 6 alkylsulfonyloxy, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 2 -C 6 alkenyloxycarbonyl, C 2 -C 6 alkynyloxycarbonyl, C 1 -C 6 alkylcarbonyl, aminocarbonyl, C 2 -C 6 cyanoalkoxycarbonyl, C 1 -C 6 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C 1 -C 6 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl, C 1 -C 6 alkylsulfinyl or C 1 -C 6 haloalkylsulfinyl;

[0024] R 6 is C 1 -C 4 haloalkyl, C 2 -C 4 alkynyl, C 2 -C 4 alkenyl, C 1 -C 4 alkyl, C 3 -C 4 cycloalkyl or C 3 -C 6 epoxyalkyl.

[0025] In some exemplary embodiments, the compound of Formula I, wherein,

[0026] n is 0 or 1;

[0027] X is fluorine; Y is chlorine or methyl;

[0028] R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 or R 11 are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkoxycarbonyl.

[0029] R 6 is C 1 -C 4 haloalkyl or C 1 -C 4 alkyl;

[0030] In some exemplary embodiments, the compound of Formula I, wherein,

[0031] n is 0 or 1;

[0032] X is fluorine; Y is chlorine or methyl;

[0033] R 4 、R 5 、R 10 、R 11 are each independently selected from H;

[0034] R 1 、R 2 、R 3 、R 7 、R 8 or R 9 are each independently hydrogen, F, Cl, Br, CN, CF 3 、OCF 3 、OMe、CO 2 Me、NO 2 or CO 2 Et;

[0035] R6 Selected from CH 2 CF 3 .

[0036] In some exemplary embodiments, the compound of Formula I, wherein,

[0037] n is 0 or 1;

[0038] X is fluorine; Y is chlorine or methyl;

[0039] R 7 or R 11 Selected from CO 2 Me or H;

[0040] R 2 or R 4 Selected from CO 2 Me, H or Cl;

[0041] R 1 or R 5 Selected from NO 2 、CO 2 Me or H

[0042] R 8 、R 9 or R 10 Selected from H;

[0043] R 3 Selected from CO 2 Me or H;

[0044] R 6 Selected from CH 2 CF 3 .

[0045] In some embodiments, the compound of Formula I or an agriculturally acceptable salt thereof has the structure shown in Formula II:

[0046] Wherein,

[0047] n is 0 or 1;

[0048] X, Y are each independently halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;

[0049] R 6 is C 1 -C6 Halogenated alkyl, C 2 -C 6 alkynyl, C 2 -C 6 alkenyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 epoxyalkyl;

[0050] R 12 or R 13 is C 1 -C 10 alkyl, C 1 -C 10 halogenated alkyl.

[0051] In some exemplary embodiments, the dibenzyl aryl sulfide has the structure shown in Table 1, however, the compounds included in the derivatives of the present invention are by no means limited to these compounds only. Additionally, the compound numbers shown in Table 1 refer to the descriptions in the following (Table 1).

[0052] In Table 1: The groups corresponding to the following expressions (such as Me, Et, tBu, CF 3 、Ac) are as described below:

[0053] Me: Methyl

[0054] Et: Ethyl

[0055] tBu: tert-Butyl

[0056] CF 3 : Trifluoromethyl

[0057] Ac: Acetyl

[0058] Table 1:

[0059] X is selected from F, R 6 is selected from CH 2 CF 3 ,R 4 、R 5 、R 10 、R 11 are each independently selected from H;

[0060]

[0061]

[0062]

[0063]

[0064] The present invention provides the following compounds, their agriculturally acceptable salts, or their isomers

[0065]

[0066] In the present invention, in the dibenzyl aryl sulfides and their derivatives, there are cases of E-type and Z-type geometric isomers according to the types of substituents. The compounds of the present invention include these E-type, Z-type, or mixtures containing E-type and Z-type in any ratio. In addition, among the compounds included in the present invention, there are cases of optical isomers caused by having one or more asymmetric carbon atoms and asymmetric sulfur atoms. The compounds of the present invention include all optical isomers, racemates, or diastereomers.

[0067] In the present invention, the so-called agriculturally acceptable salts, in the compounds of the present invention represented by Formula I, when hydroxyl, carboxyl, or amino, etc. are present in their structures, refer to the salts formed by them with metal or organic bases or the salts formed by them with inorganic acids or organic acids, such as potassium salts, sodium salts, magnesium salts, or calcium salts, etc. As organic bases, for example, triethylamine or diisopropylamine, etc., as inorganic acids, for example, hydrochloric acid, sulfuric acid, hydrobromic acid, etc., as organic acids, for example, formic acid, acetic acid, methanesulfonic acid, fumaric acid, maleic acid, etc.

[0068] The second aspect of the present invention provides a method for preparing dibenzyl aryl sulfides, the method comprising:

[0069] Contacting the compound represented by Formula III with the compound represented by Formula IV to obtain the compound represented by Formula I,

[0070]

[0071] wherein, in Formula III and Formula VI, the definitions of n, X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 or R 11 are the same as those defined for the compound of General Formula I; Q is halogen, mesylate, benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, or substituted anhydride.

[0072] The present invention has no particular limitation on the halogen, mesylate, benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, or substituted anhydride, as long as it can provide a group for the compound represented by Formula I That's all.

[0073] In some embodiments, the conditions for the contact include: the temperature is -20°C to 210°C, preferably -10°C to 150°C; the time is 1 - 50 h, preferably 3 - 25 h;

[0074] and / or, the molar ratio of the compound shown in Formula I to the compound shown in Formula III is 1:(1 - 5), preferably 1:(2 - 3);

[0075] and / or, the contact is carried out in the presence of a solvent. Preferably, relative to 1 g of the compound shown in Formula I, the amount of the solvent used is 5 - 30 mL, preferably 10 - 20 mL; wherein, the solvent is selected from at least one of N,N - dimethylformamide, dichloromethane, acetonitrile, acetone, tetrahydrofuran, N - methylpyrrolidone, water, methanol, ethanol, dimethyl sulfoxide, toluene, 1,2 - dichloroethane, chloroform, xylene, and ethyl acetate;

[0076] and / or, the contact is carried out in the presence of a base. Preferably, relative to 1 mol of the compound shown in Formula I, the amount of the base used is 1 - 5 mol, preferably 2 - 3 mol; wherein, the base is selected from at least one of triethylamine, diisopropylethylamine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine, and 1,8 - diazabicycloundec - 7 - ene.

[0077] In the present invention, preferably, there is no particular limitation on the post - treatment of the contact, as long as it can meet the requirements of the present invention. For example, it can be carried out in the following manner: adding an extraction solvent and water to the reaction solution after contact, performing extraction and liquid separation to obtain an organic phase, and discarding the aqueous phase; the organic phase is dried and then separated by column chromatography to obtain a purified product (the compound shown in Formula I). Among them, there is no particular limitation on the extraction solvent, for example, it can be selected from dichloromethane and / or ethyl acetate.

[0078] The third aspect of the present invention provides an application of the dibenzyl aryl sulfide described in the first aspect of the present invention in controlling invertebrate pests.

[0079] According to some embodiments of the present invention, the invertebrate pests can be mite pests and / or nematodes.

[0080] In the present invention, preferably, the dibenzyl aryl sulfide can be used to protect important crops, livestock, etc. in agriculture and horticulture from being damaged by or less damaged by mite pests.

[0081] In the present invention, in order to obtain ideal effects, in some applications, the dosage of the dibenzyl aryl sulfide varies due to various factors, such as the compounds used, the pre-protected crops, the type of pests, the degree of infestation, the application method, the application environment, the application dosage form, and other factors.

[0082] The fourth aspect of the present invention provides an agricultural composition, which comprises at least one dibenzyl aryl sulfide described in the first aspect of the present invention and at least one liquid carrier or solid carrier.

[0083] Among them, there is 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 dibenzyl aryl sulfide can be 0.5 - 35 mg / L.

[0084] In the present invention, the liquid carrier can be water, various aromatic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, etc., such as one or several of toluene, xylene, acetone, cyclohexanone, xylene, benzene, cyclohexane, isopropanol, ethylene glycol, sorbitol, methanol, ethanol, butanol, dimethylformamide, N-methylpyrrolidone, decalin, machine oil, petroleum ether, cyclohexanone, methyl oleate, methylated soybean oil, etc.; the solid carrier can include natural or synthetic clays and silicates, and the solid carriers suitable for powders can include naturally formed rock powders, chalk, quartz, clay, montmorillonite, silica white, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, pottery clay, and synthetically ground minerals (such as microdispersed silica or alumina). Suitable particulate carriers can include crushed and classified natural rocks such as calcite, marble, pumice, sepiolite, and dolomite, and synthetic particles made from powders of organic and inorganic substances.

[0085] In the present invention, preferably, the composition can be applied in the form of a formulation. Among them, the compound shown in Formula I is dissolved or dispersed in the carrier as an active ingredient, or formulated into a formulation so as to be more easily dispersed when used for acaricidal purposes. For example: the composition can be made into wettable powders, water-dispersible granules, suspensions, emulsifiable concentrates, aqueous solutions or emulsifiable oils, etc. In the composition, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant can also be added. Among them, the surfactant can include dodecylbenzenesulfonate, fatty alcohol sulfate, Tween, agricultural emulsifier, sorbitan polyoxyethylene ether, fatty alcohol polyoxyethylene ether, lignosulfonate, alkyl naphthalene sulfonate, etc.

[0086] In the present invention, preferably, for certain applications, such as in agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers, etc. can be added to the agricultural composition of the present invention, whereby additional advantages and effects can be produced.

[0087] The fifth aspect of the present invention provides a method for controlling invertebrate pests, which comprises directly or indirectly applying an insecticidally effective amount of the bis(benzyl)phenyl sulfide described in the first aspect of the present invention to the invertebrate pests to be controlled and / or the medium on which they grow.

[0088] Among them, there is no particular limitation on the direct or indirect method, as long as the purpose of controlling invertebrate pests can be achieved. For example, the direct method may include directly contacting the invertebrate pests with a substance containing the bis(benzyl)phenyl sulfide component (including the invertebrate pests directly consuming the substance containing the bis(benzyl)phenyl sulfide component, the body surface of the invertebrate pests directly contacting the substance containing the bis(benzyl)phenyl sulfide component, etc.); the indirect method may include treating the places where the invertebrate pests appear (their habitats or breeding grounds or the plants or soil on which the invertebrate pests grow) with the substance containing the bis(benzyl)phenyl sulfide component or treating their food chain with the substance containing the bis(benzyl)phenyl sulfide component.

[0089] In the present invention, preferably, the invertebrate pests are pests of the family Tetranychidae and / or nematodes.

[0090] According to a preferred embodiment of the present invention, the method comprises treating the plants on which the invertebrate pests grow with an insecticidally effective amount of the bis(benzyl)phenyl sulfide described in the first aspect of the present invention.

[0091] In the present invention, the invertebrate pests are pests of the family Tetranychidae and / or nematodes.

[0092] In the present invention, the plants are plants of the phylum Gymnospermae and / or Angiospermae, preferably at least one of plants of the family Rutaceae, Solanaceae, Brassicaceae, and Rosaceae.

[0093] In the present invention, there is no particular limitation on the insecticidally effective amount. For example, it may refer to a dose of applying 8 grams to 3 kilograms of the bis(benzyl)phenyl sulfide per hectare, which can provide sufficient control. Preferably, the insecticidally effective amount can be 8 grams to 1000 grams per hectare, and the preferred effective amount is 15 grams to 300 grams per hectare.

[0094] It should be clear that within the scope defined by the claims of the present invention, various transformations and modifications can be made.

[0095] Compared with the prior art, the present invention has at least the following advantages:

[0096] (1) The bis(benzyl)phenyl sulfide provided by the present invention shows excellent effects on various pests, especially on tetranychid mites represented by Tetranychus urticae Koch, Tetranychus kanzawai Kishida, Panonychus citri McGregor, etc.

[0097] (2) The dibenzyl aryl sulfide provided by the present invention has good characteristics in the application of protecting important crops, livestock, etc. in the agricultural and horticultural industries from the damage of harmful mites. Detailed implementation manners

[0098] The following examples can enable those skilled in the art of this specialty to more comprehensively understand the present invention, but do not limit the present invention to the scope of the described examples.

[0099] In order to enable the personnel in the technical field to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the scope of protection of the present invention.

[0100] In the following examples, without special instructions, various raw materials used are obtained commercially or prepared according to the prior art. For example, the compound can be prepared according to the method disclosed in CN111825585A.

[0101] Example 1

[0102] Synthesis of methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)(3-(methoxycarbonyl)benzyl)amino)methyl)benzoate (Compound 98)

[0103]

[0104] Methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (0.816 g, 2 mmol) was added to 3 ml of DMF, and methyl 3-bromomethylbenzoate (0.92 g, 4 mmol) and potassium carbonate (0.55 g, 4 mmol) were successively added. After the system was heated to 50 °C and reacted for 10 h, the system was extracted with water twice, and the organic phase was washed, dried, and rotary evaporated to dryness, and then purified by column chromatography to obtain 0.52 g of a white solid.

[0105] 11H NMR (400 MHz, Chloroform-d) δ 7.95–7.83 (m, 3H), 7.52–7.41 (m, 3H), 7.41–7.28 (m, 2H), 7.12 (d, J=12.1 Hz, 1H), 7.03 (d, J=8.8 Hz, 1H), 4.73 (s, 2H), 4.41 (s, 2H), 3.90 (s, 3H), 3.84 (s, 3H), 3.21 (q, J=9.6 Hz, 2H).

[0106] MS: [M+Na] + : 578.38 / 580.31。

[0107] Example 2

[0108] Synthesis of methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)(3-chlorobenzyl)amino)methyl)benzoate (Compound 91)

[0109]

[0110] Methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (0.816 g, 2 mmol) was added to 3 ml of DMF. 3-Chlorobenzyl bromide (0.82 g, 4 mmol) and potassium carbonate (0.55 g, 4 mmol) were successively added. After the reaction system was heated to 50 °C for 10 h, the system was extracted with water twice, and the organic phase was washed, dried and evaporated to dryness, and purified by column chromatography to obtain 0.35 g of white solid

[0111] 1 1H NMR (400 MHz, Chloroform-d) δ 7.90–7.84 (m, 1H), 7.46 (dd, J=6.3, 1.5 Hz, 2H), 7.32 (dtd, J=6.5, 4.8, 4.1, 2.2 Hz, 2H), 7.25–7.20 (m, 3H), 7.11 (d, J=2.6 Hz, 1H), 7.05 (d, J=8.9 Hz, 1H), 4.74 (s, 2H), 4.35 (s, 2H), 3.85 (s, 3H), 3.22 (q, J=9.6 Hz, 2H).

[0112] MS: [M+H] + : 532.29 / 534.28。

[0113] Example 3

[0114] Synthesis of Methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)(4-(methoxycarbonyl)benzyl)amino)methyl)benzoate (Compound 108)

[0115]

[0116] Methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (0.816 g, 2 mmol) was added to 3 ml of DMF. Methyl 4-bromomethylbenzoate (0.92 g, 4 mmol) and potassium carbonate (0.55 g, 4 mmol) were successively added. After the reaction system was heated to 50 °C for 10 h, the system was extracted with water twice, washed with water, dried, and the organic phase was evaporated to dryness. It was purified by column chromatography to obtain 0.28 g of a white solid.

[0117] 1 H NMR (400 MHz, Chloroform-d) δ 8.00–7.93 (m, 2H), 7.87 (dd, J = 7.5, 1.2 Hz, 1H), 7.51–7.41 (m, 2H), 7.36–7.27 (m, 3H), 7.12 (d, J = 12.1 Hz, 1H), 7.02 (d, J = 8.9 Hz, 1H), 4.74 (s, 2H), 4.42 (s, 2H), 3.90 (s, 3H), 3.84 (s, 3H), 3.20 (q, J = 9.6 Hz, 2H).

[0118] MS: [M+H] + : 556.25 / 558.02.

[0119] Example 4

[0120] Synthesis of Methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)(2-nitrobenzyl)amino)methyl)benzoate (Compound 88)

[0121]

[0122] Methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (0.816 g, 2 mmol) was added to 3 ml of DMF. 2-Bromomethylnitrobenzene (0.86 g, 4 mmol) and potassium carbonate (0.55 g, 4 mmol) were successively added. After the reaction system was heated to 50 °C for 10 h, the system was extracted with water twice, washed with water, dried, and the organic phase was evaporated to dryness. It was purified by column chromatography to obtain 0.29 g of a white solid

[0123] 11H NMR (400 MHz, Chloroform-d) δ 8.05 (d, J = 8.1 Hz, 1H), 7.97 (dd, J = 7.8, 1.3 Hz, 1H), 7.61 (dd, J = 14.1, 6.8 Hz, 2H), 7.49 (d, J = 7.4 Hz, 1H), 7.43 (t, J = 7.2 Hz, 2H), 7.35 (t, J = 7.5 Hz, 1H), 7.09 (d, J = 12.5 Hz, 1H), 6.96 (s, 1H), 4.88 (s, 4H), 3.85 (s, 3H), 3.24 (s, 2H).

[0124] MS: [M+H] + : 543.33 / 545.30。

[0125] Example 5

[0126] Synthesis of dimethyl 2,2'-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)azetidinyl)bis(methylene))dibenzoate (Compound 29)

[0127]

[0128] Methyl 2-(((4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (0.816 g, 2 mmol) was added to 3 ml of DMF. Methyl 2-bromomethylbenzoate (0.92 g, 4 mmol) and potassium carbonate (0.55 g, 4 mmol) were successively added. After the system was heated to 50 °C and reacted for 10 h, the system was extracted with water twice, washed with water, dried, and the organic phase was rotary evaporated to dryness, and purified by column chromatography to obtain 0.62 g of a white solid.

[0129] 1 1H NMR (400 MHz, Chloroform-d) δ 7.99–7.92 (m, 2H), 7.54–7.44 (m, 4H), 7.36–7.28 (m, 2H), 7.06 (d, J = 12.6 Hz, 1H), 6.91 (d, J = 9.1 Hz, 1H), 4.89 (s, 4H), 3.84 (s, 6H), 3.20 (q, J = 9.7 Hz, 2H).

[0130] MS: [M+H] + : 556.45 / 558.42。

[0131] Application Example 1

[0132] Tetranychus cinnabarinus activity test:

[0133] Dissolve the test compound in acetone and dilute it to the required concentration with an aqueous solution of 0.1 wt% Tween 80, with the acetone content not exceeding 5 wt%.

[0134] Remove one true leaf from the kidney bean seedlings that have grown to two true leaves, investigate the base number after inoculating with Tetranychus cinnabarinus, and perform whole-plant spraying treatment with a hand-held sprayer. Each treatment is repeated 3 times (the application rate of the preparation is about 0.5 g). After treatment, observe in a constant-temperature observation room, and investigate the number of live mites 72 hours later to calculate the mortality rate. The experiment is repeated 3 times, and the number of Tetranychus cinnabarinus inoculated each time is 35 - 100.

[0135] Mortality rate % = (number of inoculated insects - number of live insects after treatment) ÷ number of inoculated insects × 100%.

[0136] In this test, Compound 88, Compound 91, Compound 98, and Compound 108 showed a mortality rate of over 90% against Tetranychus cinnabarinus at 500 ppm (500 mg / L) respectively.

[0137] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A compound of formula I or an agriculturally acceptable salt thereof, or an isomer thereof, wherein, n is 0 or 1; X and Y are each independently a halogen, a cyano group, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy; R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 or R 11 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxy, mercapto, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkoxycarbonyl, C1-C10 haloalkoxycarbonyl, C1-C10 alkylsulfonyloxy, C1-C10 alkylsulfonyl, C1-C10 haloalkylsulfonyl, C1-C10 alkylthio, C1-C10 haloalkylthio, C2-C10 alkenyloxycarbonyl, C2-C10 alkynyloxycarbonyl, C1-C10 alkylcarbonyl, aminocarbonyl, C2-C10 cyanoalkoxycarbonyl, C1-C10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C1-C10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl, C1-C10 alkylsulfinyl or C1-C10 haloalkylsulfinyl; R 6 is C 1 -C 6 haloalkyl, C 2 -C 6 alkynyl, C 2 -C 6 alkenyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 epoxyalkyl.

2. The compound of formula II or an agriculturally acceptable salt thereof according to claim 1, characterized in that, n is 0 or 1; X is fluorine, chlorine or methyl; Y is chlorine or methyl; R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 or R 11 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxy, mercapto, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 1 -C 6 alkylsulfonyloxy, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 2 -C 6 alkenyloxycarbonyl, C 2 -C 6 alkynyloxycarbonyl, C 1 -C 6 alkylcarbonyl, aminocarbonyl, C 2 -C 6 cyanoalkoxycarbonyl, C 1 -C 6 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C 1 -C 6 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl, C 1 -C 6 alkylsulfinyl or C 1 -C 6 haloalkylsulfinyl; R 6 is C 1 -C 4 haloalkyl, C 2 -C 4 alkynyl, C 2 -C 4 alkenyl, C 1 -C 4 alkyl, C 3 -C 4 cycloalkyl or C 3 -C 6 epoxyalkyl; Preferably, n is 0 or 1; X is fluorine; Y is chlorine or methyl; R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 or R 11 each independently is hydrogen, fluorine, chlorine, bromine, cyano, nitro, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkoxycarbonyl. R 6 is C 1 -C 4 haloalkyl or C 1 -C 4 alkyl.

3. The compound of formula I or an agriculturally acceptable salt thereof according to claim 1, characterized in that, n is 0 or 1; X is fluorine; Y is chlorine or methyl; R 4 、R 5 、R 10 、R 11 Each independently selected from H; R 1 、R 2 、R 3 、R 7 、R 8 or R 9 each independently is hydrogen, F, Cl, Br, CN, CF 3 、OCF 3 、OMe, CO 2 Me, NO 2 or CO 2 Et; R 6 selected from CH 2 CF 3 ; Preferably, n is 0 or 1; X is fluorine; Y is chlorine or methyl; R 7 or R 11 selected from CO 2 Me or H; R 2 or R 4 selected from CO 2 Me, H or Cl; R 1 or R 5 selected from NO 2 , CO 2 Me or H; R 8 、R 9 or R 10 selected from H; R 3 selected from CO 2 Me or H; R 6 Selected from CH 2 CF 3 。 4. The following compound or an agriculturally acceptable salt thereof, 5. A method for preparing the compound of formula I according to claim 1, characterized in that, the method comprises: contacting the compound of formula III with the compound of formula IV to obtain the compound of formula I, Among them, in Formula III and Formula IV, n, X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 or R 11 are all defined in the same way as those in Claim 1; Q is halogen, mesylate group, benzenesulfonate group, p-toluenesulfonate group, trifluoromethanesulfonate group or substituted acid anhydride.

6. The method according to claim 5, wherein, the conditions of the contact include: the temperature is -20°C to 210°C, preferably -10°C to 150°C; the time is 1 - 50 h, preferably 3 - 25 h; and / or, the molar ratio of the compound of formula I to the compound of formula III is 1:(1 - 5), preferably 1:(2 - 3); and / or, the contact is carried out in the presence of a solvent, preferably, relative to 1 g of the compound of formula I, the amount of the solvent used is 5 - 30 mL, preferably 10 - 20 mL; wherein, the solvent is selected from at least one of N,N-dimethylformamide, dichloromethane, acetonitrile, acetone, tetrahydrofuran, N-methylpyrrolidone, water, methanol, ethanol, dimethyl sulfoxide, toluene, 1,2-dichloroethane, chloroform, xylene and ethyl acetate; and / or, the contact is carried out in the presence of a base, preferably, relative to 1 mol of the compound of formula I, the amount of the base used is 1 - 5 mol, preferably 2 - 3 mol; wherein, the base is selected from at least one of triethylamine, diisopropylethylamine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine and 1,8-diazabicyclo[5.4.0]undec-7-ene.

7. Use of the aryl sulfide according to any one of claims 1 - 4 in controlling invertebrate pests, preferably, the invertebrate pests are pests of the family Tetranychidae and / or nematodes.

8. An agricultural composition, characterized in that, the composition comprises at least one aryl sulfide according to any one of claims 1 - 4 and at least one liquid carrier or solid carrier.

9. A method for controlling invertebrate pests, characterized in that, the method comprises directly or indirectly applying an insecticidally effective amount of the aryl sulfide according to any one of claims 1 - 4 to the invertebrate pests to be controlled and / or the medium on which they grow.

10. The method according to claim 9, wherein, the method comprises treating the plants on which invertebrate pests grow with an insecticidally effective amount of the aryl sulfide according to any one of claims 1 - 4; and / or, the invertebrate pest is a pest of the family Tetranychidae and / or a nematode; and / or, the plant is a plant of the division Gymnospermae and / or the division Angiospermae, preferably at least one of a plant of the family Rutaceae, a plant of the family Solanaceae, a plant of the family Brassicaceae, and a plant of the family Rosaceae.

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