CN112225710A

CN112225710A - Sulfone-containing heterocyclic derivatives, and preparation method and application thereof

Info

Publication number: CN112225710A
Application number: CN202011097431.6A
Authority: CN
Inventors: 徐汉虹; 赵伟靖; 赵晨; 田永清; 江薰垣; 姚光凯; 李兆栋
Original assignee: South China Agricultural University
Current assignee: South China Agricultural University
Priority date: 2020-10-14
Filing date: 2020-10-14
Publication date: 2021-01-15

Abstract

The invention relates to a sulfone-containing heterocyclic derivative and a preparation method and application thereof. The general formula of the structure is shown as (I). The compound has excellent insecticidal and acaricidal activity and certain bactericidal activity, is safe to crops, and can be widely used for preventing and treating pests, mites and certain diseases.

Description

Sulfone-containing heterocyclic derivatives, and preparation method and application thereof

Technical Field

The invention relates to a sulfone-containing heterocyclic derivative and a preparation method and application thereof.

Background

The heterocyclic new pesticide represented by the nitrogen-containing heterocycle has high insecticidal activity, wide insecticidal spectrum, low toxicity to mammals and proper field stability, and the heterocyclic compound becomes an important hotspot field for creating new pesticides. In recent years, among newly developed pesticides, Flupyrimin, flupyradifurone, cycloxaprid, sulfoxaflor, flonicamid, spirotetramat, cyflumetofen, cyenopyrafen, cyantraniliprole and the like belong to nitrogen-containing heterocyclic compounds (see patents US2013150414, CN103960242, CN103254125, CN102892290, DE102006015467, WO2010069266, WO2007095229, EP 35 580374, WO 9805638, WO 2002014263, JP 2003201280 and WO 2004067528).

However, due to the serious resistance problem and cross resistance caused by the frequent use of the excessive single pesticide, the pesticide has higher toxicity to the environment while killing pests, so that the pesticide effect is reduced, the use of the pesticide is limited, and the development of agriculture and forestry is restricted. Therefore, how to develop a new, more efficient and environment-friendly pesticide and solve the resistance problem becomes a technical problem which needs to be solved urgently in the field. Aiming at the problem, the subject group makes a great deal of research and development work for developing more efficient and environment-friendly new pesticides, and provides a plurality of new compounds with better biological activity so as to relieve the resistance problem of the existing pesticides.

Disclosure of Invention

The invention provides a brand-new sulfone-containing heterocyclic derivative and a preparation method and application thereof, and the compound has excellent insecticidal, acaricidal and bactericidal biological activities.

The technical scheme of the invention is as follows:

the invention provides a sulfone-containing heterocyclic derivative, which is shown as a general formula I:

in the formula:

R¹and R²Each independently hydrogen, halogen, -NO₂、-CN、-COR⁶、-CO₂R⁶、 -CONR⁶R⁷、-S(O)R⁶、-S(O)₂R⁶、-NR⁶R⁷、-NR⁶COR⁷、-NR ⁶CONR⁷ R ⁸、 -NR⁶CO₂ R⁷、-NR⁶S(O)₂R⁷Alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, or heteroaryl; wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl is unsubstituted or substituted by one or more substituents R⁸Substitution;

R⁶、R⁷and R⁸Each independently is hydrogen, alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl, or heteroaryl; wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl is unsubstituted or substituted by one or more substituents R⁹Substitution;

R⁹is halogen, C1-C6 alkyl, C2-C6 alkenyl, substituted or unsubstituted cycloalkyl, cycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclyl, -CN, -NH₂、-OR’、-NR’R”、-COR’、-CO₂R’、-CONR’R”、-NR’COR”、-NR’CONR”、 -NR’CO₂R”、-S(O)₂R 'or-NR' S (O)₂R ' wherein R ' and R ' are independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl;

Z₁、Z₂each independently is C, N, O or S, Z₃Independently O or S, with the proviso that:

when m is equal to 1, the compound is,

Z₁、Z₂may be C at the same time, N, O, S at the same time, and contains Z₁And Z₂Is an aromatic ring, Z₃Independently is O or S;

when m is equal to 2, the compound is,

Z₁、Z₂can be C or N at the same time, is not O, S at the same time, and contains Z₁And Z₂Is an aromatic ring, Z₃Independently is O or S;

n＝0,1,2

R³represents containing Z₁And Z₂Substituents on the ring, R³May be one or more, each R³Independently of one another hydrogen, halogen, CF₃or-NO₂1-6 carbon alkyl, 1-6 carbon halogen alkyl, 1-6 carbon alkoxy, 1-6 carbon halogen alkoxy, 1-6 carbon alkylthio, 1-6 carbon halogen alkylthio, 1-6 carbon alkoxy oxygen, 2-6 carbon alkenyl, 2-6 carbon alkynyl, 3-6 carbon alkoxy, 3-6 carbon alkynoxy, naphthyl, benzyl, 1-6 carbon alkoxy alkyl, 3-8 carbon cycloalkyl, containing one or more than one nitrogen, oxygen, sulfur atoms five-membered heterocyclic ring and six-membered heterocyclic ring and substituted by one or more than one of the following groups: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon halogenated alkoxy, 1-4 carbon alkyl oxygen, 1-4 carbon halogenated alkyl, 1-4 carbon halogenated alkoxy, 1-4 alkoxy alkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulfinyl, 1-4 carbon alkyl sulfonyl nitro, cyano, amino, hydroxyl, carboxyl, trifluoromethyl, trifluoromethoxy, 1-4 carbon alkyl carboxyl, 1-4 carbon alkoxy carboxyl or imino;

R⁴、R⁵represents hydrogen, halogen, CF₃or-NO₂1-6 carbon alkyl, 1-6 carbon halogenated alkyl, 1-6 carbon cyanogen alkyl, 1-6 carbon alkoxy, 1-6 carbon halogenated alkoxy, 1-6 carbon alkylthio, 1-6 carbon halogenated alkylthio, 1-6 carbon alkyl oxygen base, 2-6 carbon alkyl alkenyl, 2-6 carbon alkyl alkynyl, 3-6 carbon alkenyl, 3-6 carbon alkynoxy, naphthyl, benzyl, 1-6 carbon alkyl oxygen alkyl, 3-8 carbon cycloalkyl, containing one or more than one nitrogen, oxygen, sulfur atoms five-membered heterocyclic ring and six-membered heterocyclic ring and substituted by one or more than one of the following groups: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon halogenated alkoxy, 1-4 carbon alkyl oxygen radical, 1-4 carbon halogenated alkyl, 1-4 carbon halogenated alkoxy, 1-4 alkoxy alkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulfinyl, 1-4 carbon alkyl sulfonyl nitro, cyano, amino, hydroxyl, carboxyl, trifluoromethylA group, a trifluoromethoxy group, a 1-4 carbon alkylcarboxyl group, a 1-4 carbon alkoxycarboxyl group or an imino group.

The invention relates to the sulfone-containing heterocyclic derivative, or an optical isomer, a cis-trans isomer or an agriculturally and pharmaceutically acceptable salt of the sulfone-containing heterocyclic derivative,

when Z is₃Is S, R⁴、R⁵When the heterocyclic derivative is H, the general formula of the heterocyclic derivative containing sulfone is shown as a formula (a)

Wherein R is¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, halogen, -NO₂、-CN、-COR⁶、-CO₂R⁶、-CONR⁶R⁷、-S(O)R⁶、-S(O)₂R⁶、-NR⁶R⁷、 -NR⁶COR⁷、-NR⁶CONR⁷ R⁸、-NR⁶CO₂ R⁷、-NR⁶S(O)₂R⁷Alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, or heteroaryl; wherein the alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl radical is unsubstituted or substituted by one or more substituents R⁸Substitution;

R³represents a five-membered heterocyclic ring and a six-membered heterocyclic ring containing one or more nitrogen, oxygen, sulfur atoms and substituted by one or more of the following groups: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon halogenated alkoxy, 1-4 carbon alkyl oxygen, 1-4 carbon halogenated alkyl, 1-4 carbon halogenated alkoxy, 1-4 alkoxy alkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulfinyl, 1-4 carbon alkyl sulfonyl nitro, cyano, amino, hydroxyl, carboxyl, 1-4 carbon alkyl carboxyl, 1-4 carbon alkoxy carboxyl or imino;

m is 1 or 2; z₁、Z₂Each independently C, N, O or S, with the proviso that:

when m is equal to 1, the compound is,

Z₁、Z₂can be C or N at the same time, is not O, S at the same time, and contains Z₁And Z₂The ring (b) is an aromatic ring;

when m is equal to 2, the compound is,

Z₁、Z₂can be C, N or O at the same time, is not O, S at the same time, and contains Z₁And Z₂The ring (b) is an aromatic ring;

or when Z is₁、Z₃Is S, Z₂Is N, R⁴、R⁵When the heterocyclic derivative is H, the general formula of the heterocyclic derivative containing the sulfone is shown as a formula (b)

Wherein n is 0 or 1, m is 1 or 2; r¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃； R²Represents hydrogen, halogen, -NO₂、-CN、-COR⁶、-CO₂R⁶、-CONR⁶R⁷、-S(O)R⁶、-S(O)₂R⁶；

or when Z is₁Is S, Z₃Is O, Z₂Is N, R⁴、R⁵When the heterocyclic derivative is H, the general formula of the heterocyclic derivative containing sulfone is shown as a formula (c)

Wherein n is 0 or 1, m is 1 or 2; r¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃； R²Represents hydrogen, halogen, alkyl, -NO₂；R³Represents halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon halogenated alkoxy, 1-4 carbon halogenated alkyl, amino, hydroxyl and carboxyl;

or when Z is₃Is S, Z₂Is N, Z₁Is C, R⁴、R⁵When the heterocyclic derivative is H, the general formula of the heterocyclic derivative containing sulfone is shown as a formula (d)

Wherein R is¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, alkyl, heteroalkyl; r³Is a monosubstitution in the 4-or 6-position in the 2-position or 3-position on the pyridine ring, R³Is halogen, alkyl, heteroalkyl;

or when Z is₁、Z₃Is S, Z₂When N is 1 and m is 1, the general formula of the heterocyclic derivative containing sulfone is formula (e)

Wherein R is¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, halogen, alkyl, heteroalkyl, 1-4 carbon haloalkoxy, 1-4 carbon alkyloxy; r³Represents halogen, -NO₂、-CN、 -CF₃、-OCF₃；R⁴、R⁵Represents halogen, 1-4 carbon alkyl, 1-4 carbon haloalkyl, 1-4 carbon haloalkoxy, 1-4 carbon alkylsulfonylnitro and cyano;

or when Z is₁、Z₂Is C, Z₃Is S, R⁴、R⁵When n is 1 and m is 2, the sulfone is containedHeterocyclic derivatives of the general formula (f)

Wherein R is¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCCF₃；R²Represents hydrogen, alkyl, heteroalkyl; r³Is the 2, 6-position 3, 5-position or 3, 4-position or 4, 5-position disubstituted on the benzene ring, or the 2, 3, 4, 5, 6-position monosubstituted, R³Represents halogen, -NO₂、-CN、-CF₃、-OCF₃Alkyl, heteroalkyl.

Preferably, R⁴、R⁵Each independently is H, halogen, alkyl; r³Represents halogen, -CF₃An alkyl group.

Preferably, when the sulfone-containing heterocyclic derivative is represented by formula (a) or formula (b), R¹Represents halogen, R²Represents hydrogen, R³Represents a five-membered heterocyclic ring and a six-membered heterocyclic ring containing one or more nitrogen, oxygen, sulfur atoms and substituted by one or more of the following groups: halogen, 1-4 carbon alkyl and 1-4 carbon alkoxy, n is 0 or 1, and m is 1 or 2.

Preferably, when the sulfone-containing heterocyclic derivative is represented by the formula (c), R¹Represents hydrogen or halogen, R²Represents hydrogen or alkyl, R³Represents halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, n is 0 or 1, and m is 1 or 2.

Preferably, when the sulfone-containing heterocyclic derivative is represented by formula (d), R¹Represents halogen, R²Represents hydrogen or alkyl, R³Is halogen or alkyl.

Preferably, when the sulfone-containing heterocyclic derivative is represented by formula (e), R¹Represents hydrogen or halogen, R²Represents hydrogen, halogen or alkyl, R³Represents hydrogen, halogen, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms.

Preferably, when the sulfone-containing heterocyclic derivative is represented by formula (f), R¹Represents halogen, R²Represents hydrogenOr alkyl, R³Is disubstituted at 2, 6 or 3, 5 positions on a benzene ring, or monosubstituted at 3, 4, 6 positions, R³Represents halogen, -NO₂、-CF₃、-OCF₃An alkyl group.

The general formula of the present invention is further illustrated by some of the compounds listed in Table 1, but is not intended to limit the present invention.

The preparation method of the sulfone-containing heterocyclic derivative comprises the following steps:

s1, 1mol of 2-methylimidazole and 2.5mol of Na₂CO₃Dissolving the mixture in 100mL of acetonitrile, vacuumizing a reaction system, introducing sulfonyl fluoride gas, and reacting at room temperature for 18-24h under the participation of the sulfonyl fluoride gas; after the reaction, extracting the reaction solution with DCM, washing the combined organic phases with a large amount of saturated saline solution, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure at the temperature lower than 20 ℃, and drying in vacuum; dissolving the obtained colorless transparent oily liquid in dichloromethane at the temperature of 0 ℃ by using nitrogen as protective gas, dropwise adding methyl trifluoromethanesulfonate into the mixed solution at the speed of 4.5mL/min, reacting for 10min, moving to room temperature, and continuing to react for 2-4 h; after the reaction is finished, concentrating the mixed solution under reduced pressure to obtain brown thick liquid, washing with methyl tert-butyl ether, and drying in vacuum to obtain white solid, namely an intermediate I;

s2, dissolving 1mol of 2-chloro-5-aminomethyl thiazole in acetonitrile, adding 1mol of an intermediate I at the temperature of 0 ℃, moving the mixed solution to room temperature for reaction for 2 hours, washing the reaction solution with saturated saline solution after the reaction is finished, extracting an organic phase with ethyl acetate, combining the organic phases, washing with a large amount of saturated saline solution, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, drying in vacuum, and purifying with a silica gel chromatographic column to obtain a yellow oily liquid, thereby obtaining an intermediate II;

s3, dissolving 1mmol of the intermediate II and 1mmol of 2-chloro-5-aminomethyl thiazole in 30mL of acetonitrile, adding 0.15mL of triethylamine and 30mg of 4-dimethylaminopyridine, and heating and refluxing the mixed solution at 80 ℃ for 4-5h until the reaction is complete; after the reaction is finished, concentrating the reaction solution under reduced pressure, adding 20mL of saturated saline solution, extracting for 3 times by using 20mL of ethyl acetate, washing an organic phase by using saturated saline solution, drying by using anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and purifying by using a silica gel chromatographic column to obtain a solid, namely the sulfone-containing heterocyclic derivative;

or dissolving 1mmol of the intermediate II and 1mmol of 4-isopropyl aniline in 30mL of acetonitrile, adding 0.15mL of triethylamine, and heating and refluxing the mixed solution at 80 ℃ for 4-5h until the reaction is complete; after the reaction is finished, concentrating the reaction solution under reduced pressure, adding 20mL of saturated saline solution, extracting for 3 times by using 20mL of ethyl acetate, washing an organic phase by using saturated saline solution, drying by using anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and purifying by using a silica gel chromatographic column to obtain a solid, namely the sulfone-containing heterocyclic derivative.

The application of the sulfone-containing heterocyclic derivative, or the optical isomer, cis-trans isomer or agriculturally and pharmaceutically acceptable salt of the sulfone-containing heterocyclic derivative in preparing pesticides for killing or preventing agricultural and forestry pests, sanitary pests and pests harmful to animal health.

According to the application of the pesticide, the pesticide is directly applied to pests or places in contact with the pests.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a novel structure of sulfone-containing heterocyclic derivatives. The sulfone-containing heterocyclic derivative and the optical isomer, cis-trans isomer or salt acceptable in agriculture and forestry have high killing activity on agricultural and forestry pests, sanitary pests and the like. The structures of some compounds in the compounds shown in the general formula (I) are shown in Table 1.

Partial compound structure in the compounds shown in table 1 and general formula (I)

The NMR data of the compounds shown in Table 1 are shown in Table 2.

TABLE 2 NMR hydrogen spectrum data of Compounds (1) - (27)

Detailed Description

Through long-term and intensive research, the inventor designs, synthesizes and screens a novel sulfone-containing heterocyclic compound based on the problems of increasingly serious resistance, harmfulness to the environment and the like of the existing heterocyclic pesticide, and the compound has remarkably improved insecticidal activity and an expanded insecticidal spectrum. The present invention will be further explained with reference to specific examples, which are not intended to limit the present invention in any way. Unless otherwise indicated, the reagents and methods referred to in the examples are those commonly used in the art.

EXAMPLE 1 preparation of Compound (1)

1mol of 2-methylimidazole (commercially available) and 2.5mol of Na₂CO₃Dissolving the mixture in 100mL of acetonitrile, vacuumizing the reaction system, introducing sulfonyl fluoride gas, and reacting at room temperature for 18-24h in the presence of the sulfonyl fluoride gas. After the reaction was complete, the reaction was extracted with DCM and the combined organic phases were washed with copious amounts of saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure below 20 ℃ and dried in vacuo. Dissolving the obtained colorless transparent oily liquid in dichloromethane at 0 ℃ by using nitrogen as protective gas, dropwise adding methyl trifluoromethanesulfonate into the mixed solution at the speed of 4.5mL/min, reacting for 10min, moving to room temperature, and continuously reflecting for 2-4 h. After the reaction is finished, the mixed solution is decompressed and concentrated to obtain brown thick liquid, and the brown thick liquid is washed by methyl tert-butyl ether and dried in vacuum to obtain white solidThe intermediate I is obtained. Yield: 93 percent.¹H NMR(600MHz, DMSO-d₆)δ7.50(dd,J＝25.6,2.0Hz,2H),3.71(s,3H),2.53(s,3H)。

Dissolving 1mol of 2-chloro-5-aminomethyl thiazole in acetonitrile, adding 1mol of intermediate I at the temperature of 0 ℃, moving the mixed solution to room temperature for reaction for 2 hours, washing the reaction solution with saturated saline solution after the reaction is finished, extracting an organic phase with ethyl acetate, combining the organic phases, washing with a large amount of saturated saline solution, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, drying in vacuum, and purifying with a silica gel chromatographic column to obtain a yellow oily liquid, namely the intermediate II. Yield: 95 percent.¹H NMR(600MHz,Chloroform-d)δ7.45(d,J＝0.9Hz,1H),6.92(d,J＝6.2 Hz,1H),4.58(dt,J＝6.0,1.3Hz,2H)。

1mmol of the intermediate II and 1mmol of 2-chloro-5-aminomethylthiazole are dissolved in 30mL of acetonitrile, 0.15mL of triethylamine and 30mg of 4-dimethylaminopyridine are added, and the mixture is heated and refluxed at 80 ℃ for 4-5h until the reaction is completed. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and then saturated brine (20 mL. times.3) was added, followed by extraction with ethyl acetate (20 mL. times.3 times), and the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by a silica gel column to obtain a solid, i.e., compound (1). Yield: 51 percent.¹H NMR (600MHz,DMSO-d₆)δ7.84(t,J＝6.1Hz,2H),7.56(s,2H),4.22(d,J＝6.0Hz, 4H)。

EXAMPLE 2 preparation of Compound (22)

Dissolving 1mmol of the intermediate II and 1mmol of 4-isopropyl aniline in 30mL of acetonitrile, adding 0.15mL of triethylamine, and heating and refluxing the mixed solution at 80 ℃ for 4-5h until the reaction is complete. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and then saturated brine (20 mL. times.3) was added, followed by extraction with ethyl acetate (20 mL. times.3 times), and the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain a solid, i.e., compound (22). Yield: 98 percent.¹H NMR(600MHz,DMSO-d₆)δ9.68(s,1H), 8.09(t,J＝6.1Hz,1H),7.46(d,J＝1.0Hz,1H),7.14(d,J＝2.0Hz,1H),7.13(d,J＝ 2.0Hz,1H),7.04(d,J＝2.1Hz,1H),7.02(d,J＝1.8Hz,1H),4.23(d,J＝1.1Hz, 1H),4.22(d,J＝1.0Hz,1H),2.86–2.80(m,1H),1.18(s,3H),1.17(s,3H)。

EXAMPLE 3 evaluation of the biological Activity of some Compounds on Plutella xylostella

The insect tested was Plutella xylostella (Plutella xylostella), a lepidopteran pest with a chewing mouthpart, a common vegetable pest. The 2 nd larva of diamondback moth is taken as a test object and is tested by a dipping method.

The operation process is as follows: accurately weighing each sample, adding 200 microliters of dimethyl sulfoxide to prepare 10g/L mother solution respectively, and diluting the mother solution into a series of gradient concentrations by using an aqueous solution containing 0.5 thousandth of tween-80 during experiment. Preparing cleaned cabbage leaves into leaf disks by using a puncher with the diameter of 1.0 cm, soaking the leaf disks into the liquid medicine, taking out after 5 seconds, naturally drying, and transferring into a clean vessel. Inoculating about 35 larvae of diamondback moth of 2 th instar, and feeding at 28 deg.C. Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.5 part per thousand of Tween-80. After 24 hours of treatment, the dead number of the diamondback moth is counted, and according to the formula: the mortality (%) was calculated as the ratio of control number of live insects to number of treated live insects/control number of live insects × 100%, and LC was determined by the Kouyan method₅₀The results are shown in Table 3.

EXAMPLE 4 insecticidal Activity of some of the Compounds on 2 nd Larvae of beet armyworm

Spodoptera exigua belonging to Lepidoptera pests, having chewing mouthparts, is a common vegetable pest. The 2 nd instar larvae of the asparagus caterpillars are taken as a test object and tested by a leaf soaking feeding method.

The operation process is as follows: accurately weighing each sample, adding 200 microliters of dimethyl sulfoxide to prepare 10g/L mother solution respectively, and diluting the mother solution into a series of gradient concentrations by using an aqueous solution containing 0.5 thousandth of tween-80 during experiment. Preparing cleaned cabbage leaves into leaf disks by using a puncher with the diameter of 1.0 cm, soaking the leaf disks into the liquid medicine, taking out after 5 seconds, naturally drying, and transferring into a clean vessel. About 35 larvae of spodoptera exigua 2 instar are inoculated into the vessel and raised at a constant temperature of 28 ℃. Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.5 part per thousand of Tween-80. After 24 hours of treatment, the number of dead beet armyworm is counted, and according to the formula: mortality (%) (control alive)The mortality (%) is calculated by multiplying the number of insects by the number of treated live insects/the number of control live insects by 100%, and LC is calculated by the Kouyan method₅₀The results are shown in Table 3.

EXAMPLE 5 insecticidal Activity of some Compounds against adult aphids

The aphid belongs to the same-wing suborder pests, has a piercing-sucking mouthpart and is a common vegetable pest. The aphid of radish (Lipophis erysimi) is used as a test object and is tested by adopting a dipping method.

The operation process is as follows: accurately weighing each sample, adding 200 microliters of dimethyl sulfoxide to prepare 10g/L mother solution respectively, and diluting the mother solution into a series of gradient concentrations by using an aqueous solution containing 0.5 thousandth of tween-80 during experiment. After the wingless adult aphids are stably absorbed on the radish aphids, the radish aphids and the wingless adult aphids are soaked into the liquid medicine together, taken out after 5 seconds, naturally dried, moved into a clean vessel, and fed at the constant temperature of 23 ℃. Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.5 part per thousand of Tween-80. After 24 hours of treatment, the number of dead aphids was counted and the mortality (%) was calculated according to the formula: the mortality rate (%) - (number of control live insects-number of treated live insects)/number of control live insects × 100%, and LC was determined by the Kouyama method₅₀The results are shown in Table 3.

EXAMPLE 6 evaluation of the biological Activity of some of the Compounds on Tetranychus cinnabarinus

The method for measuring the biological activity of tetranychus cinnabarinus comprises the following steps: tetranychus cinnabarinus (Tetranychus cinnabarinus) is a sensitive strain inoculated on a bean seedling in a greenhouse for feeding. The test method was a slide dipping method. The double-sided adhesive tape is cut into 2cm long, the double-sided adhesive tape is attached to one end of a glass slide, healthy female adult mites are selected, the backs of the healthy female adult mites are stuck, and 30 heads of the mites are stuck. Preparing a test compound into a mother solution by using dimethyl sulfoxide, and then adding 0.5 thousandth of tween-80 aqueous solution to dilute the mother solution to prepare a solution with the required concentration. And soaking the glass slide in the liquid medicine, slightly shaking for 10s, taking out, sucking excess liquid medicine by using filter paper, and then putting the glass slide into a culture dish filled with wet sponge. The culture dish is placed in an insect rearing room with the temperature of 25 ℃ and the humidity of 75 percent for rearing. Each treatment was repeated 3 times, and the control was treated with an aqueous solution containing an equal amount of dimethyl sulfoxide and one thousandth of 0.5 tween-80. Observing the experimental result under the binoculars after 48h, counting the death rate and calculating LC of the death rate₅₀. The results are shown in Table 3.

EXAMPLE 7 evaluation of the biological Activity of some of the Compounds on Aedes albopictus

The method for measuring the biological activity of Aedes albopictus comprises the following steps: the insect Aedes albopictus (Aedes albopictus) to be tested is a sensitive strain artificially fed indoors. Preparing a mother solution with a certain concentration by using acetone, adding an aqueous solution containing 0.1% tween-80 to prepare a liquid medicine with a required concentration, adding 50mL of the prepared liquid medicine into a 100mL beaker, adding 20 larvae of Aedes albopictus of 4 th age into the beaker, and treating a control by using an aqueous solution containing the same amount of acetone and 0.1% tween-80. Repeating each treatment for 3 times, examining results 24h after treatment, counting mortality and calculating LC₅₀. The results of the biological activity assay of the test compounds against aedes albopictus are shown in table 3.

TABLE 3 24-hour lethal middle concentration LC of test compound against diamond back moth, beet armyworm, radish aphid, tetranychus cinnabarinus, and termite₅₀Values (μ g/mL, mean. + -. standard error)

EXAMPLE 85% preparation of emulsifiable concentrate of Compound (1) and field control of Plutella xylostella

1. The compound (1) is prepared into missible oil, and the components and the weight percentage of each component are as follows:

the effective component (compound (1)) is 5%

Emulsifier (farm milk 0204): 9 percent of

Cosolvent (cyclohexanone): 12 percent of

Stabilizer (benzenesulfonate): 8 percent of

66 percent of solvent (ethanol)

The preparation process of the missible oil comprises the following steps: dissolving the compound (1) in ethanol, adding other auxiliary agents such as an emulsifier and the like according to the weight percentage of the components, mixing and dissolving under stirring, and then filtering to prepare a homogeneous transparent liquid, namely a 5% compound (1) missible oil product.

2. The field test of the diamondback moth is carried out by using the prepared 5% compound (1) emulsifiable solution, the tested crop is the cabbage heart, the plot with better growth vigor and more insects is selected, the pesticide application mode is that the cabbage heart is diluted by clear water, the cabbage heart is prepared into liquid medicine and then is sprayed, 3 test concentrations are set, each concentration is repeated for 3 times (3 cells), and each cell is 25 square meters. The investigation method adopts a diagonal sampling method, 5 points are fixed in each cell, completely unfolded leaves of 5 plants are checked at each point, the total leaf number and the leaf number of the belt worms are recorded before the pesticide application, the total leaf number and the leaf number of the belt worms are investigated again on days 1, 3, 5 and 10 after the pesticide application, and the insect leaf rate and the prevention and treatment effect are calculated. Control area was applied with clear water.

The formula for calculating the insect leaf rate is as follows:

the prevention and treatment effect calculation formula is as follows:

3. results

The field control effect of the 5% compound (1) missible oil on the plutella xylostella is shown in table 4.

Table 4.5% of the compound (1) emulsifiable concentrate has field control effect (spraying) on plutella xylostella.

EXAMPLE 913% preparation of emulsifiable concentrate of Compound (1) and Effect on field control of Plutella xylostella

the effective component (compound (1)) is 13%

Emulsifier (farm milk 2201): 14 percent of

Stabilizer (methylsulfonate): 11 percent of

Co-solvent (methanol): 14 percent of

Solvent (ethanol) 48%

The preparation process of the missible oil comprises the following steps: dissolving the compound (1) in ethanol, adding other auxiliary agents such as a stabilizer, an emulsifier and the like according to the proportion, uniformly mixing, mixing and dissolving under stirring, and then filtering to prepare a homogeneous transparent liquid, namely a 13% compound (1) missible oil product.

2. The field test of diamondback moth using the 13% emulsifiable concentrate of the compound (1) prepared above was carried out using the same experimental design and calculation formula as in example 8 except that the dilution factor was 25000,50000,100000 times, respectively.

3. Results

The field control effect of the 13 percent compound (1) missible oil on the plutella xylostella is shown in table 5.

Table 5.13% Compound (1) emulsifiable concentrate for the control of diamondback moth in the field (spray)

EXAMPLE 105 formulation of Compound (1) suspending agent and Effect on Tetranychus cinnabarinus control in the field

1. The compound (1) is prepared into a suspending agent, and the components and the weight percentage of each component are as follows

Active ingredient (compound (1)):5 percent of

Dispersant (sodium lignosulfonate): 3 percent of

Wetting agent (sodium lauryl sulfate): 1 percent of

Antifoam agent (polyoxyethylene glyceryl ether): 5 percent of

Antifreeze (ethylene glycol): 8 percent of

Thickener (xanthan gum): 5 percent of

Mildew preventive (sodium benzoate): 0.1 percent of

pH adjuster (tween 20): 0.5 percent

Crystallization inhibitor (polyethylene glycol): 3 percent of

Organic solvent (liquid paraffin) such as mineral: 10 percent of

Deionized water: 59.4 percent

The preparation process of the suspending agent comprises the following steps: adding weighed raw medicine, a dispersing agent, a thickening agent and water into a grinding cylinder, uniformly stirring, pre-dispersing for 30min under high-speed stirring (the rotating speed is 18000 r/min), and stopping pre-dispersing. Adding a sanding medium, starting a motor and beginning sanding. And (3) stopping sanding after 2h, filtering, removing glass beads, and adding other auxiliary agents for blending to obtain the 5% compound (1) suspending agent. The process needs to be kept in a condensed state all the time.

2. The 5 percent compound (1) suspending agent prepared above is used for carrying out field test on the tetranychus cinnabarinus adults, the test crop is cowpea, and plots with better growth vigor and more insects are selected for carrying out the field test. Before spraying, investigating the base number of tetranychus cinnabarinus in the morning, fixing 5 points in each cell according to a diagonal sampling method, fixing 5 leaves in each point, investigating 25 leaves in each cell, and inspecting the number of live mites on the leaves by using a magnifier. The application method comprises preparing medicinal liquid with clear water, spraying, setting 3 test concentrations, repeating for 3 times (3 cells), and each cell has 25 square meters. The number of live mites on each leaf was investigated on days 1, 3, 5 and 10 after application, and the decline rate and the control effect were calculated. Control area was applied with clear water.

3. Results

The control effect of 5% of the compound (1) suspending agent on tetranychus cinnabarinus adults by spray application is shown in table 6.

Control effect (spray) of compound (1) suspending agent with content shown in table 65% on tetranychus cinnabarinus adults

Example 1110% formulation of Compound (1) suspending agent and Effect on Tetranychus cinnabarinus control in the field

Active ingredient (compound (1)): 10 percent of

Dispersant (sodium lignosulfonate): 3 percent of

Wetting agent (sodium lauryl sulfate): 1 percent of

Antifoam agent (polyoxyethylene glyceryl ether): 5 percent of

Antifreeze (propylene glycol): 8 percent of

Thickener (polyethylene glycol): 5 percent of

Mildew preventive (sodium benzoate): 0.1 percent of

pH adjuster (tween 20): 0.5 percent

Crystallization inhibitor (polyethylene glycol): 3 percent of

Organic solvent (liquid paraffin) such as mineral: 10 percent of

Deionized water: 54.4 percent

The preparation process of the suspending agent comprises the following steps: uniformly mixing a compound (1), an auxiliary agent and a filler, adding water to prepare slurry with 35% of solid content, adding the slurry into a grinding cylinder, uniformly stirring in a homogenizer, shearing at a high speed (the rotating speed is 18000 r/min) for 30min, adding a grinding medium, grinding in a grinding dispersion machine (the process needs to be kept in a condensation state all the time), stopping grinding when the particle size is below 5 mu m, filtering to remove pickaxe beads, discharging, drying and granulating in a spray dryer, setting the hot air inlet temperature to be 150 ℃, setting the tail gas outlet temperature to be 65 ℃, setting the water content of a product to be 1%, wherein the preparation produced by spray drying is almost hollow spherical particles, and screening to obtain a 10% compound (1) suspending agent with the particle size of 50-100 mu m.

2. The field test of adult tetranychus cinnabarinus was carried out using the 10% compound (1) suspending agent prepared above, and the experimental design and calculation formula were the same as those of example 10, except that the dilution times were 35000, 40000, and 50000 times, respectively.

3. Results

The control effect of the 10% compound (1) suspending agent on tetranychus cinnabarinus adults is shown in table 7.

Table 710% Compound (1) suspending agent control Effect (spray) on Tetranychus cinnabarinus adults

Example preparation of 125% Compound (1) aqueous emulsion and Effect of controlling Lipaphis erysimi in field

The compound (1) is prepared into 5 percent aqueous emulsion, and the components and the weight percentage of each component are as follows:

1. active ingredient (compound (1)):5 percent of the total weight of the mixture,

solvent (acetonitrile): 2 percent of the total weight of the mixture,

2 percent of emulsifier (JX-0401),

coemulsifier (alkyl polyglycol ether): 8 percent of the total weight of the mixture,

1 percent of antifreeze agent (1, 2-propylene glycol),

antimicrobial agent (benzoic acid): 1 percent of

Density modifier (calcium chloride): 0.5 percent of the total weight of the mixture,

pH adjuster (phosphoric acid): 0.1 percent of the total weight of the mixture,

antifoam (octadecyl trimethyl ammonium chloride): 0.1 percent of the total weight of the mixture,

water (deionized water): 80.3 percent.

The compound (1), acetonitrile, JX-0401 and alkyl polyglycol ether are added together to dissolve into homogeneous oil phase. Water, 1, 2-propanediol, benzoic acid, etc. are mixed together to form a homogeneous aqueous phase. Under the stirring of high speed (the rotating speed is 18000 r/min), the water phase is added into the oil phase to form well dispersed aqueous emulsion, namely well dispersed 5 percent compound (1) aqueous emulsion.

2. The field test is carried out on the turnip aphids by using the prepared 5% compound (1) aqueous emulsion, the test crop is broad beans, plots with good growth vigor and more insects are selected for carrying out the test, the pesticide application mode is that the plots are diluted by clear water and then sprayed, 3 test concentrations are set, each concentration is repeated for 3 times (3 cells), and each cell is 20 square meters. Fixing 10 leaves in each cell, recording aphid base number on each leaf before application, investigating insect quantity on days 1, 3, 5 and 10 after application, calculating mortality and evaluating the control effect. Control area was applied with clear water.

3. Results

The control effect of the 5% compound (1) water emulsion on the aphis erysimi by spraying is shown in table 8.

Table 85% prevention and control effect (spraying) of compound (1) water emulsion on aphids of radish

Example 1310% preparation of an aqueous emulsion of Compound (1) and Effect on controlling Aphis erysimi in the field

The compound (1) is prepared into an aqueous emulsion, and the components and the weight percentage of each component are as follows:

1. active ingredient (compound (1)): 10 percent of the total weight of the mixture,

solvent (acetonitrile): 8 percent of the total weight of the mixture,

9 percent of emulsifier (ethoxylated alkyl ether),

co-emulsifier (butanol): 5 percent of the total weight of the mixture,

2 percent of antifreeze (glycerin),

density modifier (calcium chloride): 1.5 percent of the total weight of the mixture,

pH adjuster (phosphoric acid): 0.1 percent of the total weight of the mixture,

0.1 percent of defoaming agent (X-10C type defoaming agent),

water (deionized water): and (4) 64.3%.

Mixing the effective components, solvent, emulsifier and co-emulsifier to obtain uniform oil phase, mixing the rest components to obtain uniform water phase, and adding the water phase into the oil phase under high speed (18000 rpm) stirring to obtain well dispersed 10% compound (1) water emulsion.

2. The field test of the aphid radish with the 10% compound (1) aqueous emulsion prepared above was carried out, and the experimental design and the calculation formula were the same as those in example 12, except that the dilution times were 40000, 45000, and 50000, respectively.

3. Results

The control effects of the 10% compound (1) aqueous emulsion on aphid radish by spray application are respectively shown in table 9.

Table 910% prevention and control Effect (spray) of Compound (1) emulsion in water on Aphis citricola

EXAMPLE 145 preparation of emulsifiable concentrate of Compound (2) and Effect of controlling Plutella xylostella in the field

1. The compound (2) is prepared into missible oil, and the components and the weight percentage of each component are as follows:

the effective component (compound (2)) is 5%

Emulsifier (farm milk 530): 12 percent of

Cosolvent (cyclohexanone): 10 percent of

Stabilizer (benzenesulfonate): 10 percent of

Solvent (ethanol) 63%

The preparation process of the missible oil comprises the following steps: dissolving the compound (2) in ethanol, adding other auxiliary agents such as an emulsifier and the like according to the weight percentage of the components, mixing and dissolving under stirring, and then filtering to prepare a homogeneous transparent liquid, namely a 5% compound (2) missible oil product.

2. The field test of the diamondback moth is carried out by using the prepared 5% compound (2) emulsifiable solution, the tested crop is the cabbage heart, the plot with better growth vigor and more insects is selected, the pesticide application mode is that the cabbage heart is diluted by clear water, the cabbage heart is prepared into liquid medicine and then is sprayed, 3 test concentrations are set, each concentration is repeated for 3 times (3 cells), and each cell is 25 square meters. The investigation method adopts a diagonal sampling method, 5 points are fixed in each cell, completely unfolded leaves of 5 plants are checked at each point, the total leaf number and the leaf number of the belt worms are recorded before the pesticide application, the total leaf number and the leaf number of the belt worms are investigated again on days 1, 3, 5 and 10 after the pesticide application, and the insect leaf rate and the prevention and treatment effect are calculated. Control area was applied with clear water.

The formula for calculating the insect leaf rate is as follows:

the prevention and treatment effect calculation formula is as follows:

3. results

The field control effect of 5% of compound (2) missible oil on diamond back moth is shown in table 10.

Table 10.5% of the compound (2) emulsifiable concentrate has field control effect (spraying) on plutella xylostella.

EXAMPLE 1513% preparation of emulsifiable concentrate of Compound (2) and Effect on field control of Plutella xylostella

the effective component (compound (2)): 13%

Emulsifier (farm milk 2201): 12 percent of

Stabilizer (methylsulfonate): 11 percent of

Co-solvent (methanol): 15 percent of

Solvent (ethanol) 49%

The preparation process of the missible oil comprises the following steps: dissolving the compound (2) in ethanol, adding other auxiliary agents such as a stabilizer, an emulsifier and the like according to the proportion, uniformly mixing, mixing and dissolving under stirring, and then filtering to prepare a homogeneous transparent liquid, namely a 13% compound (2) missible oil product.

2. A field test was conducted on plutella xylostella using the 13% compound (2) emulsifiable concentrate prepared above, and the experimental design and calculation formula were the same as those of example 14, except that the dilution factor was 2500,5000,10000 times, respectively.

3. Results

The field control effect of the 13 percent compound (2) missible oil on the plutella xylostella is shown in table 11.

Table 11.13% Compound (2) emulsifiable concentrate for Plutella xylostella control in the field (spray)

EXAMPLE 165% preparation of Compound (2) suspending agent and Effect on Tetranychus cinnabarinus control in the field

1. The compound (2) is prepared into a suspending agent, and the components and the weight percentage of each component are as follows

Active ingredient (compound (2)):5 percent of

Dispersant (sodium lignosulfonate): 4 percent of

Wetting agent (sodium lauryl sulfate): 2 percent of

Antifoam agent (polyoxyethylene glyceryl ether): 6 percent of

Antifreeze (ethylene glycol): 8 percent of

Thickener (xanthan gum): 4 percent of

Mildew preventive (sodium benzoate): 0.1 percent of

pH adjuster (tween 20): 0.5 percent

Crystallization inhibitor (polyethylene glycol): 3 percent of

Organic solvent (liquid paraffin) such as mineral: 10 percent of

Deionized water: 57.4 percent

The preparation process of the suspending agent comprises the following steps: adding weighed raw medicine, a dispersing agent, a thickening agent and water into a grinding cylinder, uniformly stirring, pre-dispersing for 30min under high-speed stirring (the rotating speed is 18000 r/min), and stopping pre-dispersing. Adding a sanding medium, starting a motor and beginning sanding. And (3) stopping sanding after 2h, filtering, removing glass beads, and adding other auxiliary agents for blending to obtain the 5% compound (2) suspending agent. The process needs to be kept in a condensed state all the time.

2. The 5 percent compound (2) suspending agent prepared above is used for carrying out field test on the tetranychus cinnabarinus adults, the test crop is cowpea, and plots with better growth vigor and more insects are selected for carrying out the field test. Before spraying, investigating the base number of tetranychus cinnabarinus in the morning, fixing 5 points in each cell according to a diagonal sampling method, fixing 5 leaves in each point, investigating 25 leaves in each cell, and inspecting the number of live mites on the leaves by using a magnifier. The application method comprises preparing medicinal liquid with clear water, spraying, setting 3 test concentrations, repeating for 3 times (3 cells), and each cell has 25 square meters. The number of live mites on each leaf was investigated on days 1, 3, 5 and 10 after application, and the decline rate and the control effect were calculated. Control area was applied with clear water.

3. Results

The control effect of 5% of the compound (2) suspending agent on tetranychus cinnabarinus adults by spray application is shown in table 12.

Control effect (spray) of compound (2) suspending agent with content shown in table 125 on tetranychus cinnabarinus adults

Example 1710% preparation of Compound (2) suspending agent and Effect on Tetranychus cinnabarinus control in the field

Active ingredient (compound (2)): 10 percent of

Dispersant (sodium lignosulfonate): 3 percent of

Wetting agent (sodium lauryl sulfate): 2 percent of

Antifoam agent (polyoxyethylene glyceryl ether): 4 percent of

Antifreeze (propylene glycol): 9 percent of

Thickener (polyethylene glycol): 4 percent of

Mildew preventive (sodium benzoate): 0.1 percent of

pH adjuster (tween 20): 0.5 percent

Crystallization inhibitor (polyethylene glycol): 3 percent of

Organic solvent (liquid paraffin) such as mineral: 10 percent of

Deionized water: 54.4 percent

The preparation process of the suspending agent comprises the following steps: uniformly mixing the compound (2), an auxiliary agent and a filler, adding water to prepare slurry with 35% of solid content, adding the slurry into a grinding cylinder, uniformly stirring in a homogenizer, shearing at a high speed (the rotating speed is 18000 r/min) for 30min, adding a grinding medium, grinding in a grinding dispersion machine (the process needs to be kept in a condensation state all the time), stopping grinding when the particle size is below 5 mu m, filtering to remove pickaxe beads, discharging, drying and granulating in a spray dryer, setting the hot air inlet temperature to be 150 ℃, setting the tail gas outlet temperature to be 65 ℃, keeping the water content of a product to be 1%, producing a preparation by spray drying to be approximately hollow spherical particles, and screening to obtain the 10% compound (2) suspending agent, wherein the particle size is 50-100 mu m.

2. The field test of the tetranychus cinnabarinus adults was carried out by using the 10% compound (2) suspending agent prepared above, the experimental design and the calculation formula were the same as those of example 16, and the dilution times were 1500, 3000 and 6000 times, respectively.

3. Results

The control effect of the 10% compound (2) suspending agent on tetranychus cinnabarinus adults is shown in table 13.

TABLE 1310% Compound (2) suspending agent control Effect (spray) on Tetranychus cinnabarinus adults

Example 185% formulation of Compound (2) aqueous emulsion and Effect on controlling Lipaphis erysimi in the field

Preparing the compound (2) into a 5% aqueous emulsion, wherein the components and the weight percentage of each component are as follows:

1. active ingredient (compound (2)):5 percent of the total weight of the mixture,

solvent (acetonitrile): 2.5 percent of the total weight of the mixture,

2.3 percent of emulsifier (JX-0401),

coemulsifier (alkyl polyglycol ether): 7 percent of the total weight of the mixture,

1.2 percent of antifreeze agent (1, 2-propylene glycol),

antimicrobial agent (benzoic acid): 1 percent of

pH adjuster (phosphoric acid): 0.1 percent of the total weight of the mixture,

water (deionized water): 80.3 percent.

The compound (2), acetonitrile, JX-0401 and alkyl polyglycol ether are added together to dissolve into homogeneous oil phase. Water, 1, 2-propanediol, benzoic acid, etc. are mixed together to form a homogeneous aqueous phase. Under the stirring of high speed (the rotating speed is 18000 r/min), the water phase is added into the oil phase to form well dispersed aqueous emulsion, namely well dispersed 5 percent compound (2) aqueous emulsion.

2. The field test is carried out on the turnip aphids by using the prepared 5% compound (2) aqueous emulsion, the test crop is broad beans, plots with good growth vigor and more insects are selected for carrying out the test, the pesticide application mode is that the plots are diluted by clear water and then sprayed, 3 test concentrations are set, each concentration is repeated for 3 times (3 cells), and each cell is 20 square meters. Fixing 10 leaves in each cell, recording aphid base number on each leaf before application, investigating insect quantity on days 1, 3, 5 and 10 after application, calculating mortality and evaluating the control effect. Control area was applied with clear water.

3. Results

The control effect of the 5% compound (2) water emulsion on the aphis erysimi by spraying is shown in table 14.

Control effect (spray) of compound (2) emulsion in water on aphids of radish in table 145%

Example 1910% preparation of Compound (2) emulsion in water and Effect on controlling Lipaphis erysimi in the field

Preparing the compound (2) into an aqueous emulsion, wherein the components and the weight percentage of each component are as follows:

1. active ingredient (compound (2)): 10 percent of the total weight of the mixture,

solvent (acetonitrile): 7 percent of the total weight of the mixture,

emulsifier (ethoxylated alkyl ether) 8.5%,

co-emulsifier (butanol): 5.5 percent of the total weight of the mixture,

2 percent of antifreeze (glycerin),

density modifier (calcium chloride): 1.6 percent of the total weight of the mixture,

pH adjuster (phosphoric acid): 0.1 percent of the total weight of the mixture,

0.2 percent of defoaming agent (X-10C type defoaming agent),

water (deionized water): 65.1 percent.

Mixing the effective components, solvent, emulsifier and co-emulsifier to obtain uniform oil phase, mixing the rest components to obtain uniform water phase, and adding the water phase into the oil phase under high speed (18000 rpm) stirring to obtain well dispersed 10% compound (2) water emulsion.

2. The field test of the aphid radish with the 10% compound (2) aqueous emulsion prepared above was performed, and the experimental design and the calculation formula were the same as those in example 18, except that the dilution times were 3000, 6000, and 12000 times, respectively.

3. Results

The control effects of the 10% compound (2) aqueous emulsion on aphid radish by spray application are respectively shown in table 15.

Control Effect (spray) of Compound (2) emulsion in water on Aphis citricola (Table 1510%) on Aphis citricola

EXAMPLE 205 preparation of emulsifiable concentrate of Compound (8) and Effect on field control of Plutella xylostella

1. The compound (8) is prepared into missible oil, and the components and the weight percentage of each component are as follows:

the effective component (compound (8)) is 5%

Emulsifier (farm milk 600): 13 percent of

Cosolvent (cyclohexanone): 9 percent of

Stabilizer (benzenesulfonate): 11 percent of

Solvent (ethanol) 62%

The preparation process of the missible oil comprises the following steps: dissolving the compound (8) in ethanol, adding other auxiliary agents such as an emulsifier and the like according to the weight percentage of the components, mixing and dissolving under stirring, and then filtering to prepare a homogeneous transparent liquid, namely a 5% compound (8) missible oil product.

2. The field test of the plutella xylostella is carried out by using the prepared 5% compound (8) emulsifiable solution, the tested crop is the cabbage heart, the plot with better growth vigor and more insects is selected, the pesticide application mode is that the cabbage heart is diluted by clear water, liquid medicine is prepared and sprayed, 3 test concentrations are set, each concentration is repeated for 3 times (3 cells), and each cell is 25 square meters. The investigation method adopts a diagonal sampling method, 5 points are fixed in each cell, completely unfolded leaves of 5 plants are checked at each point, the total leaf number and the leaf number of the belt worms are recorded before the pesticide application, the total leaf number and the leaf number of the belt worms are investigated again on days 1, 3, 5 and 10 after the pesticide application, and the insect leaf rate and the prevention and treatment effect are calculated. Control area was applied with clear water.

The formula for calculating the insect leaf rate is as follows:

the prevention and treatment effect calculation formula is as follows:

3. results

The field control effect of 5% of compound (8) missible oil on plutella xylostella is shown in Table 16.

Table 16.5% compound (8) emulsifiable concentrate field control effect (spray) on plutella xylostella.

EXAMPLE 2113 preparation of emulsifiable concentrate of Compound (8) and Effect on field control of Plutella xylostella

the effective component (compound (8)): 13%

Emulsifier (farm milk 2201): 11 percent of

Stabilizer (methylsulfonate): 9 percent of

Co-solvent (methanol): 17 percent of

50 percent of solvent (ethanol)

The preparation process of the missible oil comprises the following steps: dissolving the compound (8) in ethanol, adding other auxiliary agents such as a stabilizer, an emulsifier and the like according to the proportion, uniformly mixing, mixing and dissolving under stirring, and then filtering to prepare a homogeneous transparent liquid, namely a 13% compound (8) missible oil product.

2. A field test was conducted on plutella xylostella using the 13% compound (8) emulsifiable concentrate prepared above, and the experimental design and calculation formula were the same as in example 20 except that the dilution factor was 8000,16000,32000 times, respectively.

3. Results

The field control effect of the 13 percent compound (8) missible oil on the plutella xylostella is shown in Table 17.

Table 17.13% Compound (8) emulsifiable concentrate for Plutella xylostella control in the field (spray)

EXAMPLE 225 preparation of Compound (8) suspending agent and Effect on Tetranychus cinnabarinus control in the field

1. The compound (8) is prepared into a suspending agent, and the components and the weight percentage of each component are as follows

Active ingredient (compound (8)):5 percent of

Dispersant (sodium lignosulfonate): 6 percent of

Wetting agent (sodium lauryl sulfate): 2 percent of

Antifoam agent (polyoxyethylene glyceryl ether): 4 percent of

Antifreeze (ethylene glycol): 7 percent of

Thickener (xanthan gum): 5 percent of

Mildew preventive (sodium benzoate): 0.1 percent of

pH adjuster (tween 20): 0.5 percent

Crystallization inhibitor (polyethylene glycol): 3 percent of

Organic solvent (liquid paraffin) such as mineral: 9 percent of

Deionized water: 58.4 percent

The preparation process of the suspending agent comprises the following steps: adding weighed raw medicine, a dispersing agent, a thickening agent and water into a grinding cylinder, uniformly stirring, pre-dispersing for 30min under high-speed stirring (the rotating speed is 18000 r/min), and stopping pre-dispersing. Adding a sanding medium, starting a motor and beginning sanding. And stopping grinding after 2h, filtering, removing glass beads, and adding other auxiliary agents for blending to obtain the 5% compound (8) suspending agent. The process needs to be kept in a condensed state all the time.

2. The 5 percent compound (8) suspending agent prepared above is used for carrying out field test on the tetranychus cinnabarinus adults, the test crop is cowpea, and plots with better growth vigor and more insects are selected for carrying out the field test. Before spraying, investigating the base number of tetranychus cinnabarinus in the morning, fixing 5 points in each cell according to a diagonal sampling method, fixing 5 leaves in each point, investigating 25 leaves in each cell, and inspecting the number of live mites on the leaves by using a magnifier. The application method comprises preparing medicinal liquid with clear water, spraying, setting 3 test concentrations, repeating for 3 times (3 cells), and each cell has 25 square meters. The number of live mites on each leaf was investigated on days 1, 3, 5 and 10 after application, and the decline rate and the control effect were calculated. Control area was applied with clear water.

3. Results

The control effect of 5% of the compound (8) suspension on tetranychus cinnabarinus adults by spray application is shown in table 18.

Control effect (spray) of compound (8) suspending agent with content shown in table 185 on tetranychus cinnabarinus adults

EXAMPLE 2310% formulation of Compound (8) suspending agent and efficacy in controlling Tetranychus cinnabarinus in the field

Active ingredient (compound (8)): 10 percent of

Dispersant (sodium lignosulfonate): 4 percent of

Wetting agent (sodium lauryl sulfate): 3 percent of

Antifoam agent (polyoxyethylene glyceryl ether): 5 percent of

Antifreeze (propylene glycol): 8 percent of

Thickener (polyethylene glycol): 4 percent of

Mildew preventive (sodium benzoate): 0.1 percent of

pH adjuster (tween 20): 0.5 percent

Crystallization inhibitor (polyethylene glycol): 2 percent of

Organic solvent (liquid paraffin) such as mineral: 11 percent of

Deionized water: 52.4 percent

The preparation process of the suspending agent comprises the following steps: uniformly mixing a compound (8), an auxiliary agent and a filler, adding water to prepare slurry with 35% of solid content, adding the slurry into a grinding cylinder, uniformly stirring in a homogenizer, shearing at a high speed (the rotating speed is 18000 r/min) for 30min, adding a grinding medium, grinding in a grinding dispersion machine (the process needs to be kept in a condensation state all the time), stopping grinding when the particle size is below 5 mu m, filtering to remove pickaxe beads, discharging, drying and granulating in a spray dryer, setting the hot air inlet temperature to be 150 ℃, setting the tail gas outlet temperature to be 65 ℃, keeping the water content of a product to be 1%, producing a preparation by spray drying to be approximately hollow spherical particles, and screening to obtain a 10% compound (8) suspending agent, wherein the particle size is 50-100 mu m.

2. The field test of adult tetranychus cinnabarinus was carried out using the 10% compound (8) suspension prepared above, and the experimental design and calculation formula were the same as in example 22, except that the dilution times were 8000,16000, and 32000 times, respectively.

3. Results

The control effect of the 10% compound (8) suspending agent on tetranychus cinnabarinus adults is shown in table 19.

Control effect (spray) of compound (8) suspending agent in 1910% of table on tetranychus cinnabarinus adults

Example 245% formulation of Compound (8) aqueous emulsion and Effect on controlling Aphis fabae in the field

The compound (8) is prepared into 5 percent aqueous emulsion, and the components and the weight percentage of each component are as follows:

1. active ingredient (compound (8)):5 percent of the total weight of the mixture,

solvent (acetonitrile): 3.5 percent of the total weight of the mixture,

2.3 percent of emulsifier (JX-0401),

1.2 percent of antifreeze agent (1, 2-propylene glycol),

antimicrobial agent (benzoic acid): 2 percent of

pH adjuster (phosphoric acid): 0.1 percent of the total weight of the mixture,

water (deionized water): 77.3 percent.

The compound (8), acetonitrile, JX-0401 and alkyl polyglycol ether are added together to dissolve into homogeneous oil phase. Water, 1, 2-propanediol, benzoic acid, etc. are mixed together to form a homogeneous aqueous phase. Under the stirring of high speed (the rotating speed is 18000 r/min), the water phase is added into the oil phase to form well dispersed aqueous emulsion, namely well dispersed 5 percent compound (8) aqueous emulsion.

2. The field test is carried out on the turnip aphids by using the prepared 5% compound (8) water emulsion, the test crop is broad beans, plots with good growth vigor and more insects are selected for carrying out the test, the pesticide application mode is that the plots are diluted by clear water and then sprayed, 3 test concentrations are set, each concentration is repeated for 3 times (3 cells), and each cell is 20 square meters. Fixing 10 leaves in each cell, recording aphid base number on each leaf before application, investigating insect quantity on days 1, 3, 5 and 10 after application, calculating mortality and evaluating the control effect. Control area was applied with clear water.

3. Results

The control effect of the 5% compound (8) water emulsion on the aphis erysimi by spraying is shown in table 20.

Table 205% control Effect (spray) of Compound (8) emulsion in water on Aphis erysimi

Example 2510% preparation of Compound (8) emulsion in Water and Effect on controlling Aphis Raphani in the field

Preparing the compound (8) into an aqueous emulsion, wherein the components and the weight percentage of each component are as follows:

1. active ingredient (compound (8)): 10 percent of the total weight of the mixture,

solvent (acetonitrile): 6 percent of the total weight of the mixture,

emulsifier (ethoxylated alkyl ether) 8.5%,

co-emulsifier (butanol): 6 percent of the total weight of the mixture,

2.5 percent of antifreezing agent (glycerin),

pH adjuster (phosphoric acid): 0.1 percent of the total weight of the mixture,

0.2 percent of defoaming agent (X-10C type defoaming agent),

water (deionized water): 65.1 percent.

Mixing the effective components, solvent, emulsifier and co-emulsifier to obtain uniform oil phase, mixing the rest components to obtain uniform water phase, and adding the water phase into the oil phase under high speed (18000 rpm) stirring to obtain well dispersed 10% compound (8) water emulsion.

2. The field test of the aphid radish was carried out using the 10% aqueous compound (8) emulsion prepared above, and the experimental design and the calculation formula were the same as those in example 24, except that the dilution times were 8000,16000, and 32000 times, respectively.

3. Results

The control effects of the 10% compound (8) aqueous emulsion on aphid radish by spray application are respectively shown in Table 21.

TABLE 2110% control of aphid in radish (spray) with Compound (8) in water

EXAMPLE 26 evaluation of the safety of a portion of the Compounds on Cruciferae crops

LC for preventing and controlling diamondback moth₉₅The dose is the lowest dose, and 4 concentration gradients of 100mg/L, 200mg/L, 400mg/L and 800mg/L are set. Preparing mother liquor with a certain concentration from test compound (1), compound (2) and chlorfenapyr with acetone respectively, and adding aqueous solution containing 0.1% Tween-80 to obtain the above 4 medicinal liquids. The tested cabbage heart varieties are stone leaf rape heart and willow leaf rape heart. Before experiment, seedlings were cultivated in flowerpots containing medium (perlite: peat: soil: 2: 1: 2, m: m: m), 20 seedlings per pot were cultivated in a phytotron. During the experiment, plants with consistent size and good growth vigor are selected and placed uniformly after treatmentCulturing in a greenhouse. The prepared pesticide is used for spraying pesticide liquid to 3-4 leaf well-growing flowering plants in the order from low concentration to high concentration, the whole seedling is taken as the standard, the seedlings are moved into a greenhouse for culture after being sprayed for 4 hours, and the growth management conditions of each treatment are consistent. Repeat for 4 times per dose, 1 plant per repeat. The plants were investigated for phytotoxicity after 21 days by treatment with an aqueous solution containing equal amounts of acetone and 0.1% tween-80 as a blank Control (CK). The test compounds (1) and (2) are safe to crucifer flowering cabbage and do not cause phytotoxicity within 21 days of application. The results of the safety evaluation experiments on cruciferous plants with the test compounds are shown in Table 22.

TABLE 22 evaluation of the safety of part of the compounds on cabbage plants

A is a compound (1); b is a compound (2); c is chlorfenapyr

Note: phytotoxicity investigation grading standard:

0: the plant grows normally

+: the degree of phytotoxicity (discoloration, necrosis, deformity, wilting, etc.) is slight, but does not affect the growth of plants, so the plant is safer to the plants;

++: the degree of phytotoxicity (discoloration, necrosis, deformity, wilting, etc.) is certain, the influence on the growth of plants is small, and the phytotoxicity to plants is slight

+++: the degree of phytotoxicity (discoloration, necrosis, deformity, wilting, etc.) is large, the influence on the growth of plants is obvious, and the phytotoxicity to plants is caused

++++: the degree of phytotoxicity (discoloration, necrosis, deformity, wilting, etc.) is great, which is very harmful to the growth of plants and plants.

Claims

1. A sulfone-containing heterocyclic derivative, characterized in that the sulfone-containing heterocyclic derivative comprises a structure shown in the following general formula (I):

in the formula:

R¹and R²Each independently hydrogen, halogen, -NO₂、-CN、-COR⁶、-CO₂R⁶、-CONR⁶R⁷、-S(O)R⁶、-S(O)₂R⁶、-NR⁶R⁷、-NR⁶COR⁷、-NR⁶CONR⁷R⁸、-NR⁶CO₂R⁷、-NR6S(O)₂R⁷Alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, or heteroaryl; wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl is unsubstituted or substituted by one or more substituents R⁸Substitution;

R⁹is halogen, C1-C6 alkyl, C2-C6 alkenyl, substituted or unsubstituted cycloalkyl, cycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclyl, -CN, -NH₂、-OR’、-NR’R”、-COR’、-CO₂R’、-CONR’R”、-NR’COR”、-NR’CONR”、-NR’CO₂R”、-S(O)₂R 'or-NR' S (O)₂R ' wherein R ' and R ' are independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl;

when m is equal to 1, the compound is,

when m is equal to 2, the compound is,

n＝0，1，2

R⁴、R⁵represents hydrogen, halogen, CF₃or-NO₂1-6 carbon alkyl, 1-6 carbon halogen alkyl, 1-6 carbon cyanogen alkyl, 1-6 carbon alkoxy, 1-6 carbon halogen alkoxy, 1-6 carbon alkylthio, 1-6 carbon halogen alkylthio, 1-6 carbon alkyl oxygen base, 2-6 carbon alkyl alkenyl, 2-6 carbon alkyl alkynyl, 3-6 carbon alkenyl, 3-6 carbon alkynoxy, naphthyl, benzyl, 1-6 carbon alkyl oxygen alkyl, 3-8 carbon cycloalkyl, containing one or more than one nitrogen, oxygen, sulfur atoms five-membered heterocyclic ring and six-membered heterocyclic ring and its by one or more than oneThe following groups are substituted: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon halogenated alkoxy, 1-4 carbon alkyl oxygen, 1-4 carbon halogenated alkyl, 1-4 carbon halogenated alkoxy, 1-4 alkoxy alkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulfinyl, 1-4 carbon alkyl sulfonyl nitro, cyano, amino, hydroxyl, carboxyl, trifluoromethyl, trifluoromethoxy, 1-4 carbon alkyl carboxyl, 1-4 carbon alkoxy carboxyl or imino.

2. The sulfone-containing heterocyclic derivative or an optical isomer, a cis-trans isomer or an agriculturally-pharmaceutically acceptable salt of the sulfone-containing heterocyclic derivative according to claim 1,

Wherein R is¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, halogen, -NO₂、-CN、-COR⁶、-CO₂R⁶、-CONR⁶R⁷、-S(O)R⁶、-S(O)₂R⁶、-NR⁶R⁷、-NR⁶COR⁷、-NR⁶CONR⁷R⁸、-NR⁶CO₂R⁷、-NR⁶S(O)₂R⁷Alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, or heteroaryl; wherein the alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl radical is unsubstituted or substituted by one or more substituents R⁸Substitution;

R³represents a five-membered heterocyclic ring and a six-membered heterocyclic ring containing one or more nitrogen, oxygen, sulfur atoms and substituted by one or more of the following groups: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon halogenated alkoxy, 1-4 carbon halogenated alkylHaloalkoxy, 1-4 alkoxyalkyl, 1-4 carboalkylthio, 1-4 carboalkylsulfinyl, 1-4 carboalkylsulfonylnitro, cyano, amino, hydroxy, carboxy, 1-4 carboalkylcarboxy, 1-4 carboalkoxycarboxy or imino;

m is 1 or 2; z₁、Z₂Each independently C, N, O or S, with the proviso that:

when m is equal to 1, the compound is,

when m is equal to 2, the compound is,

Wherein n is 0 or 1, m is 1 or 2; r¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, halogen, -NO₂、-CN、-COR⁶、-CO₂R⁶、-CONR⁶R⁷、-S(O)R⁶、-S(O)₂R⁶；

Wherein n is 0 or 1, m is 1 or 2; r¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, halogen, alkyl, -NO₂；R³Represents halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon halogenated alkoxy, 1-4 carbon halogenated alkyl, amino, hydroxyl and carboxyl;

Wherein R is¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, halogen, alkyl, heteroalkyl, 1-4-carbon haloalkoxy, 1-4-carbonAn alkoxyalkoxy group; r³Represents halogen, -NO₂、-CN、-CF₃、-OCF₃；R⁴、R⁵Represents halogen, 1-4 carbon alkyl, 1-4 carbon haloalkyl, 1-4 carbon haloalkoxy, 1-4 carbon alkylsulfonylnitro and cyano;

or when Z is₁、Z₂Is C, Z₃Is S, R⁴、R⁵When n is 1 and m is 2, the general formula of the heterocyclic derivative containing sulfone is shown as formula (f)

Wherein R is¹Represents hydrogen, halogen, -NO₂、-CN、-CF₃、-OCF₃；R²Represents hydrogen, alkyl, heteroalkyl; r³Is a 2, 6, 3, 5 or 3, 4 or 4, 5 double substitution on the benzene ring, or a 2, 3, 4, 5, 6 single substitution, R3 represents halogen, -NO₂、-CN、-CF₃、-OCF₃Alkyl, heteroalkyl.

3. The sulfone-containing heterocyclic derivative of claim 2, or an optical isomer, cis-trans isomer or an agriculturally-pharmaceutically acceptable salt of said sulfone-containing heterocyclic derivative, wherein R is⁴、R⁵Each independently is H, halogen, alkyl; r³Represents halogen, -CF₃An alkyl group.

4. The sulfone-containing heterocyclic derivative of claim 2, or an optical isomer, a cis-trans isomer or an agriculturally-pharmaceutically acceptable salt of said sulfone-containing heterocyclic derivative, wherein when said sulfone-containing heterocyclic derivative is represented by formula (a) or formula (b), R is¹Represents halogen, R²Represents hydrogen, R³Represents a five-membered heterocyclic ring and a six-membered heterocyclic ring containing one or more nitrogen, oxygen, sulfur atoms and substituted by one or more of the following groups: halogen, 1-4 carbon alkyl and 1-4 carbon alkoxy, n is 0 or 1, and m is 1 or 2.

5. The sulfone-containing heterocyclic derivative of claim 2, or an optical isomer, a cis-trans isomer or an agriculturally-pharmaceutically acceptable salt of said sulfone-containing heterocyclic derivative, wherein when said sulfone-containing heterocyclic derivative is represented by formula (c), R is¹Represents hydrogen or halogen, R²Represents hydrogen or alkyl, R³Represents halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, n is 0 or 1, and m is 1 or 2.

6. The sulfone-containing heterocyclic derivative of claim 2, or an optical isomer, a cis-trans isomer or an agriculturally-pharmaceutically acceptable salt of said sulfone-containing heterocyclic derivative, wherein when said sulfone-containing heterocyclic derivative is represented by formula (d), R is¹Represents halogen, R²Represents hydrogen or alkyl, R³Is halogen or alkyl.

7. The sulfone-containing heterocyclic derivative of claim 2, or an optical isomer, a cis-trans isomer or an agriculturally-pharmaceutically acceptable salt of said sulfone-containing heterocyclic derivative, wherein when said sulfone-containing heterocyclic derivative is represented by formula (e), R is¹Represents hydrogen or halogen, R²Represents hydrogen, halogen or alkyl, R³Represents hydrogen, halogen, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms.

8. The sulfone-containing heterocyclic derivative of claim 2, or an optical isomer, a cis-trans isomer or an agriculturally pharmaceutically acceptable salt of said sulfone-containing heterocyclic derivative, wherein when said sulfone-containing heterocyclic derivative is represented by formula (f), R is¹Represents halogen, R²Represents hydrogen or alkyl, R³Is disubstituted at 2, 6 or 3, 5 positions on a benzene ring, or monosubstituted at 3, 4, 6 positions, R³Represents halogen, -NO₂、-CF₃、-OCF₃An alkyl group.

9. A process for the preparation of a sulfone-containing heterocyclic derivative according to claim 1, characterized in that it comprises the steps of:

10. Use of the sulfone-containing heterocyclic derivative of claim 1, or an optical isomer, a cis-trans isomer or an agriculturally pharmaceutically acceptable salt of said sulfone-containing heterocyclic derivative, for the preparation of a pesticide for the killing or prevention of agroforestry pests, hygiene pests and pests that are harmful to the health of animals.