Crystal form of para-substituted diphenyl sulfide compound as well as preparation method and application of crystal form

Abstract

The invention relates to the field of compound crystal forms, in particular to a crystal form of a para-substituted diphenyl sulfide compound as well as a preparation method and application of the crystal form, and the crystal form is prepared by taking the para-substituted diphenyl sulfide compound as a raw material. The crystal form provided by the invention is a dominant crystal form of the para-substituted diphenyl sulfide compound, so that the stability of the compound is further improved, and the compound is convenient to transport and store; meanwhile, the compound has excellent solubility and dissolution rate, and the bioavailability of the compound is obviously improved. The crystal form disclosed by the invention has the advantages of convenience in preparation, low cost, convenience in large-scale production, high melting point, high water solubility value and high bioavailability, and is suitable for being applied to the production process of pesticide preparations.

Description

Technical Field

[0001] The invention belongs to the field of compound crystal forms, and specifically relates to a crystal form of a para-substituted biphenyl sulfide compound, and also relates to a preparation method and use of the crystal form. Background Art

[0002] Trifluoroethyl sulfide (sulfoxide) compounds are a new class of compounds with good acaricidal activity. In 2020, Japan's Kumamoto Chemical developed the first commercial trifluoroethyl sulfide compound, flupentiofenox, which has a good preventive effect on two-spotted spider mites, and has since triggered a wave of research and development in this field. It is known that the active compounds recorded in the above-mentioned literature still have low killing activity when controlling harmful animals, especially mites, but their acaricidal activity at low concentrations is often unsatisfactory, and the control effect on spider mites that have acquired drug resistance is even worse. Therefore, there is still a lack of new drugs with high efficiency, low toxicity, and excellent killing effect on resistant mites in agricultural production. In view of the insufficient killing activity of the agents for controlling mites in the prior art, the applicant focused on the prospects of this type of compound, and through a lot of creative work, developed a series of this new type of compound, and obtained a new type of para-substituted diphenyl sulfide compound with insecticidal or acaricidal activity (see patent CN202210783893.6), which shows excellent control effects on various harmful organisms, especially on spider mites represented by cinnabarinus spider mite, two-spotted spider mite, Kanzawa spider mite, citrus mites, etc., among which the more representative compounds have the structure shown in Formula I:

[0003]

[0004] Although this compound has many advantages as a new type of insecticide, it still faces some challenges in practical application due to some of its physical and chemical properties. The compound has poor water solubility, which has caused considerable trouble for its practical application; and its amorphous melting point is lower than 40°C. Therefore, how to simply and effectively improve its physical and chemical properties is an extremely critical factor for the further development and application of this compound. The currently commonly used methods to change its properties usually require changing its structure or adding additives, which are not only costly, but also have uncertain effects. Therefore, there is an urgent need for an efficient and simple method to improve the melting point, solubility and other properties of this compound. Summary of the invention

[0005] The object of the present invention is to overcome the inconvenience caused by the lower water solubility and lower melting point of the compound shown in Formula I in the prior art, the original medicine, the preparation and storage process of the pesticide preparation. The commonly used method for changing its properties at present usually requires changing its structure, adding adjuvants, etc., which is not only costly, but also affects the performance of its practical application due to the change of its structure in some ways. The technical solution of the present invention further improves the stability of the compound, which is convenient for transportation and storage; at the same time, it has excellent solubility and dissolution rate, and significantly improves the bioavailability of the compound. The technical solution of the present invention has the advantages of convenient preparation and low cost, is convenient for large-scale production, has the advantages of high melting point, high water solubility value, and high bioavailability, and is suitable for application in the production process of pesticide preparations.

[0006] In order to achieve the above technical objectives, the present invention provides the following technical solution: a crystalline form I of a para-substituted biphenyl sulfide compound, wherein the para-substituted biphenyl sulfide compound has a structure as shown in Formula I:

[0007]

[0008] At least 3 of the following diffraction peaks given in 2θ values ​​are present in the spectrum:

[0009] 9.613°±0.2, 10.357°±0.2, 13.120°±0.2, 15.358°±0.2, 16.178°±0.2, 16.981°±0.2, 17.518°±0.2, 19.239°±0.2, 19.761°±0.2, 20.477°±0.2, 22.500°±0.2, 23.357°±0.2, 24.181°±0.2, 24.774°±0.2, 26.435°±0.2, 27.422°±0.2, 29.022°±0.2, and 35.940°±0.2.

[0010] Furthermore, at least 4 of the following diffraction peaks given in 2θ values ​​are shown in the spectrum:

[0011] 9.613°±0.2, 10.357°±0.2, 13.120°±0.2, 15.358°±0.2, 16.178°±0.2, 16.981°±0.2, 17.518°±0.2, 19.239°±0.2, 19.761°±0.2, 20.477°±0.2, 22.500°±0.2, 23.357°±0.2, 24.181°±0.2, 24.774°±0.2, 26.435°±0.2, 27.422°±0.2, 29.022°±0.2, and 35.940°±0.2.

[0012] Furthermore, at least 5 of the following diffraction peaks given in 2θ values ​​are shown in the spectrum:

[0013] 9.613°±0.2, 10.357°±0.2, 13.120°±0.2, 15.358°±0.2, 16.178°±0.2, 16.981°±0.2, 17.518°±0.2, 19.239°±0.2, 19.761°±0.2, 20.477°±0.2, 22.500°±0.2, 23.357°±0.2, 24.181°±0.2, 24.774°±0.2, 26.435°±0.2, 27.422°±0.2, 29.022°±0.2, and 35.940°±0.2.

[0014] The present invention also discloses a method for preparing the crystal form I, comprising adding a polar protic solvent to a para-substituted biphenyl sulfide compound raw material drug of formula I, stirring the raw material under heating or non-heating conditions and then filtering the raw material, allowing the filtrate to stand to precipitate a solid phase, and collecting the solid phase to obtain the biphenyl sulfide compound crystal form I;

[0015] Further, the polar protic solvent is one or more of methanol, ethanol or propanol, the heating or non-heating condition is heating to 30-50° C., the stirring time is 2-6 hours, and the filtrate is left standing for 3-6 days;

[0016] Furthermore, the solid-liquid ratio of the raw material to the polar protic solvent is (0.333-0.335) g: (5-6) mL.

[0017] A crystalline form II of a para-substituted biphenyl sulfide compound, wherein the para-substituted biphenyl sulfide compound has a structure as shown in Formula I:

[0018]

[0019] At least 3 of the following diffraction peaks given in 2θ values ​​are present in the spectrum:

[0020] 5.442°±0.2、9.198°±0.2、10.975°±0.2、11.282°±0.2、13.085°±0.2、15.063°±0.2、16.680°±0.2、17.561°±0.2、19.182°±0.2、19.726°±0.2、20.814° ±0.2, 22.696°±0.2, 23.292°±0.2, 24.201°±0.2, 24.859°±0.2, 26.356°±0.2, 27.740°±0.2, 29.019°±0.2, 32.367°±0.2, 34.841°±0.2, and 35.918°±0.2.

[0021] Furthermore, at least 5 of the following diffraction peaks given in 2θ values ​​are shown in the spectrum:

[0022] 5.442°±0.2、9.198°±0.2、10.975°±0.2、11.282°±0.2、13.085°±0.2、15.063°±0.2、16.680°±0.2、17.561°±0.2、19.182°±0.2、19.726°±0.2、20.814° ±0.2, 22.696°±0.2, 23.292°±0.2, 24.201°±0.2, 24.859°±0.2, 26.356°±0.2, 27.740°±0.2, 29.019°±0.2, 32.367°±0.2, 34.841°±0.2, and 35.918°±0.2.

[0023] The present invention also discloses a method for preparing the crystal form II as described above, comprising adding a polar aprotic solvent to a para-substituted biphenyl sulfide compound raw material drug represented by formula I, stirring under heating or without heating and then filtering, allowing the filtrate to stand to precipitate a solid phase, and collecting the solid phase to obtain the crystal form II of the biphenyl sulfide compound;

[0024] Further, the polar aprotic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, and N,N-dimethylformamide, the heating or non-heating condition is heating to 30-50° C., the stirring time is 2-6 hours, and the filtrate is allowed to stand for 3-6 days;

[0025] Furthermore, the solid-liquid ratio of the raw material to the polar protic solvent is (0.333-0.335) g: (5-6) mL.

[0026] The invention also discloses an agricultural formulation, comprising an effective amount of crystals having the crystal form of the para-substituted biphenyl sulfide compound as described above.

[0027] Furthermore, it also includes agriculturally acceptable formulation carriers or formulation adjuvants.

[0028] The present invention also discloses a method for controlling pests and / or mites, comprising applying an insecticidal or acaricidal effective amount of crystals of the para-substituted biphenyl sulfide compound or the agricultural formulation to the pests and / or mites and / or their habitats.

[0029] The present invention also discloses the use of the crystal of the para-substituted biphenyl sulfide compound or the agricultural formulation in controlling pests and / or mites.

[0030] Due to the adoption of the above technology, the present invention has the following significant advantages compared with the prior art:

[0031] 1) The crystal form of the present invention is the dominant crystal form of the compound of formula I, which further improves the stability and melting point of the compound, raising the melting point from 42°C to above 49°C, making it easy to transport and store; at the same time, it has excellent solubility and dissolution rate, significantly improving the bioavailability of the compound, and is suitable for use in the production process of pesticide formulations, solving the inconvenience caused by the low water solubility and low melting point of acetamiprid in the prior art during the preparation and storage of pesticide formulations;

[0032] 2) The preparation method of the crystal form I and the crystal form II of the present invention is a solvent volatilization method and a cooling method. The crystals are subjected to relevant characterizations such as PXRD and melting point determination and dissolution rate tests. The prepared crystals have better purity and crystallinity, can remain stable for a long time without deterioration, have a simple preparation process, low cost, and are suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The PXRD spectrum of the para-substituted biphenyl sulfide compound crystalline form I of the present invention;

[0034] Figure 2 This is the PXRD spectrum of the para-substituted biphenyl sulfide compound crystal form II. DETAILED DESCRIPTION

[0035] In order to make the technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments.

[0036] Example 1

[0037] This embodiment is a method for preparing a para-substituted biphenyl sulfide compound crystal form I, which is implemented according to the following steps:

[0038] 0.334 g of the raw material of the compound shown in formula I was placed in a round-bottom flask, 5 mL of methanol was added to the raw material powder, heated and stirred in a 30°C water bath for 3 hours, and then filtered. The filtrate was allowed to stand for 4 days to evaporate the solvent, and the solid phase was collected to obtain the para-substituted biphenyl sulfide compound crystal form I, a white crystalline powder, with a yield of 88.4%. The measurement was performed using a D8 X-ray diffractometer from the German BRUKER company, and the test conditions were a Cu-Kα target tube voltage of 40 kV, a tube current of 10 mA, and a scanning speed of 2° / min. The PXRD diffraction pattern of the product can be found in Figure 1 .

[0039] The PXRD characteristic diffraction peaks of this embodiment appear at 9.613°, 10.357°, 13.120°, 15.358°, 16.178°, 16.981°, 17.518°, 19.239°, 19.761°, 20.477°, 22.500°, 23.357°, 24.181°, 24.774°, 26.435°, 27.422°, 29.022°, and 35.940°.

[0040] Example 2

[0041] This embodiment is a method for preparing a para-substituted biphenyl sulfide compound crystal form I, which is implemented according to the following steps:

[0042] 3.340 g of the raw material of the compound shown in formula I was placed in a round-bottom flask, 30 mL of methanol was added to the raw material powder, heated and stirred in a 50°C water bath for 3 hours, and then filtered. The filtrate was allowed to stand for 3 days to evaporate the solvent, and the solid phase was collected to obtain a para-substituted biphenyl sulfide compound crystal form I, a white crystalline powder. The measurement was performed using a D8 X-ray diffractometer from the German BRUKER company, and the test conditions were a Cu-Kα target tube voltage of 40 kV, a tube current of 10 mA, and a scanning speed of 2° / min. The PXRD diffraction pattern of the product was the same as that of Example 1.

[0043] Example 3

[0044] This embodiment is a method for preparing a para-substituted biphenyl sulfide compound crystal form II, which is implemented according to the following steps:

[0045] 0.334 g of the raw material of the compound shown in formula I was placed in a round-bottom flask, 5 mL of tetrahydrofuran was added to the raw material powder, heated and stirred in a 30°C water bath for 3 hours, and then filtered. The filtrate was allowed to stand for 4 days to evaporate the solvent, and the solid phase was collected to obtain the para-substituted biphenyl sulfide compound crystal form II, a white crystalline powder, with a yield of 87.2%. The measurement was performed using a D8 X-ray diffractometer from the German BRUKER company, and the test conditions were a Cu-Kα target tube voltage of 40 kV, a tube current of 10 mA, and a scanning speed of 2° / min. The PXRD diffraction pattern of the product can be found in Figure 2 .

[0046] The PXRD characteristic diffraction peaks of this embodiment appear at 5.442°, 9.198°, 10.975°, 11.282°, 13.085°, 15.063°, 16.680°±0.2, 17.561°, 19.182°, 19.726°, 20.814°, 22.696°, 23.292°, 24.201°, 24.859°, 26.356°, 27.740°, 29.019°, 32.367°, 34.841°, and 35.918°.

[0047] Example 4

[0048] This embodiment is a method for preparing a para-substituted biphenyl sulfide compound crystal form II, which is implemented according to the following steps:

[0049] 3.340 g of the raw material of the compound shown in formula I was placed in a round-bottom flask, 30 mL of tetrahydrofuran was added to the raw material powder, heated and stirred in a 50°C water bath for 3 h, and then filtered while hot, the filtrate was allowed to stand for 3 days to evaporate the solvent, and the solid phase was collected to obtain a para-substituted biphenyl sulfide compound crystal form II, a white crystalline powder. The measurement was performed using a D8 X-ray diffractometer from German BRUKER Company, and the test conditions were a Cu-Kα target tube voltage of 40 kV, a tube current of 10 mA, and a scanning speed of 2 ° / min. The PXRD diffraction pattern of the product was the same as that of Example 3.

[0050] Example 5

[0051] This embodiment is a method for preparing an amorphous form of a para-substituted biphenyl sulfide compound, which is implemented according to the following steps:

[0052] The compound raw material drug as shown in formula I was prepared according to the method described in patent CN202210783893.6, which was a white solid. The measurement was performed using a D8 X-ray diffractometer from the German BRUKER company. The test conditions were a Cu-Kα target tube voltage of 40 kV, a tube current of 10 mA, and a scanning speed of 2 ° / min. The PXRD diffraction pattern of the product was diffuse, indicating that the product was amorphous.

[0053] Example 6

[0054] The melting range of the crystals prepared in Example 1 was measured by using a Shanghai Jiahang WRS-1C melting point apparatus to be 50.3-51.2°C, the melting range of the crystals prepared in Example 3 was 49.7-50.6°C, and the melting range of the solid prepared in Example 5 was 42.5-43.6°C. Compared with the amorphous form of the compound of formula I prepared in Example 5, the melting points of form I and form II were increased by about 8°C and 7°C, respectively, which greatly promoted the stability of the solid-state compound of formula I.

[0055] Example 7

[0056] Preparation stability and biological activity test of solid para-substituted diphenyl sulfide compounds:

[0057] 1) Preparation of suspension containing crystalline form I of formula I:

[0058] Preparation formula: 20% of the crystalline form I of the compound of formula (I), 1% of fatty alcohol polyoxyethylene ether, 3% of phenethylphenol polyether phosphate salt, 1% of polycarboxylic acid sodium salt, 3% of alkylaryl polyoxyethylene polyoxypropylene, 1% of magnesium aluminum silicate, 0.25% of xanthan gum, 0.1% of methylisothiazolinone, 5% of ethylene glycol, 0.4% of organosilicon defoamer, and deionized water to make up the balance;

[0059] Preparation method: According to the formula ratio, the active ingredients, surfactants and other functional additives are placed in the reactor in turn, mixed evenly, and then subjected to high-speed shearing, wet sand grinding, and finally homogenized filtration to obtain the suspension product. The product is tested in accordance with the "GB / T19136-2021 Pesticide Thermal Storage Stability Determination Method" (extending the thermal storage time to 100 days), and the product test results show that the degradation rate of the active ingredient is less than 5%.

[0060] 2) Preparation of suspension containing the crystalline form II of the compound of formula I:

[0061] Preparation formula: 20% crystal form II of the compound of formula (I), 1% fatty alcohol polyoxyethylene ether, 3% phenethylphenol polyether phosphate salt, 1% polycarboxylic acid sodium salt, 3% alkylaryl polyoxyethylene polyoxypropylene, 1% magnesium aluminum silicate, 0.25% xanthan gum, 0.1% methylisothiazolinone, 5% ethylene glycol, 0.4% organosilicon defoamer, and deionized water to make up the balance;

[0062] Preparation method: According to the formula ratio, the active ingredients, surfactants and other functional additives are placed in the reactor in turn, mixed evenly, and then subjected to high-speed shearing, wet sand grinding, and finally homogenized filtration to obtain the suspension product. The product is tested in accordance with the "GB / T19136-2021 Pesticide Thermal Storage Stability Determination Method" (extending the thermal storage time to 100 days), and the product test results show that the degradation rate of the active ingredient is less than 5%.

[0063] 3) Preparation of a suspension containing an amorphous form of the compound of formula I:

[0064] Preparation formula: 20% amorphous form of the compound of formula (I) (prepared according to the method of Example 5), 1% fatty alcohol polyoxyethylene ether, 3% phenethylphenol polyether phosphate salt, 1% polycarboxylic acid sodium salt, 3% alkylaryl polyoxyethylene polyoxypropylene, 1% magnesium aluminum silicate, 0.25% xanthan gum, 0.1% methylisothiazolinone, 5% ethylene glycol, 0.4% organosilicon defoamer, and deionized water to make up the balance;

[0065] Preparation method: According to the formula ratio, the active ingredients, surfactants and other functional additives are placed in the reactor in turn, mixed evenly, and then subjected to high-speed shearing, wet sand grinding, and finally homogenized filtration to obtain the suspension product. The product is tested in accordance with the "GB / T19136-2021 Pesticide Thermal Storage Stability Determination Method" (extending the thermal storage time to 100 days), and the product test results show that the degradation rate of the active ingredient is greater than 5%.

[0066] 4) Biological activity test:

[0067] Pea seedlings at the two-leaf stage were inoculated with cinnabarinus spider mites and the base number was investigated. A suspension containing crystalline form I, crystalline form II, and amorphous form of the compound of formula I (the formulation and preparation method are as described above) was diluted with water to an appropriate concentration and then sprayed on the whole plant using a spray tower. Each treatment was repeated 3 times. After treatment, the seedlings were placed in an artificial incubator. After 48 hours, the number of surviving mites was investigated and the mortality rate was calculated (retained to an integer).

[0068] Group Active ingredient concentration (ppm) Fatality rate (%) Example 1 0.5 95 Example 3 0.5 90 Example 5 0.5 80

[0069] The above embodiments are only preferred technical solutions of the present invention and should not be regarded as limitations of the present invention. The protection scope of the present invention should be the technical solutions recorded in the claims, including equivalent replacement solutions of the technical features in the technical solutions recorded in the claims, that is, equivalent replacement improvements within this scope are also within the protection scope of the present invention.

Claims

1. A crystalline form I of a para-substituted biphenyl sulfide compound, It is characterized in that The para-substituted biphenyl sulfide compound has a structure as shown in Formula I: At least 3 of the following diffraction peaks given in 2θ values ​​are present in the spectrum: 9.613°±0.2, 10.357°±0.2, 13.120°±0.2, 15.358°±0.2, 16.178°±0.2, 16.981°±0.2, 17.518°±0.2, 19.239°±0.2, 19.761°±0.2, 20.477°±0.2, 22.500°±0.2, 23.357°±0.2, 24.181°±0.2, 24.774°±0.2, 26.435°±0.2, 27.422°±0.2, 29.022°±0.2, and 35.940°±0.

2.

2. The crystalline form I according to claim 1, It is characterized in that At least 4 of the following diffraction peaks given in 2θ values ​​are present in the spectrum: 9.613°±0.2, 10.357°±0.2, 13.120°±0.2, 15.358°±0.2, 16.178°±0.2, 16.981°±0.2, 17.518°±0.2, 19.239°±0.2, 19.761°±0.2, 20.477°±0.2, 22.500°±0.2, 23.357°±0.2, 24.181°±0.2, 24.774°±0.2, 26.435°±0.2, 27.422°±0.2, 29.022°±0.2, and 35.940°±0.

2.

3. The crystalline form I according to claim 1, It is characterized in that At least 5 of the following diffraction peaks given in 2θ values ​​are present in the spectrum: 9.613°±0.2, 10.357°±0.2, 13.120°±0.2, 15.358°±0.2, 16.178°±0.2, 16.981°±0.2, 17.518°±0.2, 19.239°±0.2, 19.761°±0.2, 20.477°±0.2, 22.500°±0.2, 23.357°±0.2, 24.181°±0.2, 24.774°±0.2, 26.435°±0.2, 27.422°±0.2, 29.022°±0.2, and 35.940°±0.

2.

4. The method for preparing the crystalline form I according to any one of claims 1 to 3, It is characterized in that Adding a polar protic solvent to the para-substituted biphenyl sulfide compound raw material represented by formula I, stirring under heating or without heating and then filtering, allowing the filtrate to stand to precipitate a solid phase, and collecting the solid phase to obtain a biphenyl sulfide compound crystal form I; Preferably, the polar protic solvent is one or more of methanol, ethanol or propanol, the heating or non-heating condition is heating to 30-50° C., the stirring time is 2-6 hours, and the filtrate is allowed to stand for 3-6 days; Preferably, the solid-to-liquid ratio of the raw material to the polar protic solvent is (0.333-0.335) g: (5-6) mL.

5. A crystalline form II of a para-substituted biphenyl sulfide compound, It is characterized in that The para-substituted biphenyl sulfide compound has a structure as shown in Formula I: At least 3 of the following diffraction peaks given in 2θ values ​​are present in the spectrum: 5.442°±0.2、9.198°±0.2、10.975°±0.2、11.282°±0.2、13.085°±0.2、15.063°±0.2、16.680°±0.2、17.561°±0.2、19.182°±0.2、19.726°±0.2、20.814° ±0.2, 22.696°±0.2, 23.292°±0.2, 24.201°±0.2, 24.859°±0.2, 26.356°±0.2, 27.740°±0.2, 29.019°±0.2, 32.367°±0.2, 34.841°±0.2, and 35.918°±0.

2.

6. The crystalline form II according to claim 1, It is characterized in that At least 5 of the following diffraction peaks given in 2θ values ​​are present in the spectrum: 5.442°±0.2、9.198°±0.2、10.975°±0.2、11.282°±0.2、13.085°±0.2、15.063°±0.2、16.680°±0.2、17.561°±0.2、19.182°±0.2、19.726°±0.2、20.814° ±0.2, 22.696°±0.2, 23.292°±0.2, 24.201°±0.2, 24.859°±0.2, 26.356°±0.2, 27.740°±0.2, 29.019°±0.2, 32.367°±0.2, 34.841°±0.2, and 35.918°±0.

2.

7. The method for preparing the crystal form II according to any one of claims 5 to 6, It is characterized in that Adding a polar aprotic solvent to the para-substituted biphenyl sulfide compound drug substance represented by formula I, stirring with or without heating and then filtering, allowing the filtrate to stand to precipitate a solid phase, and collecting the solid phase to obtain biphenyl sulfide compound crystal form II; Preferably, the polar aprotic solvent is one or more of acetone, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, and N,N-dimethylformamide, the heating or non-heating condition is heating to 30-50° C., the stirring time is 2-6 hours, and the filtrate is allowed to stand for 3-6 days; Preferably, the solid-to-liquid ratio of the raw material to the polar protic solvent is (0.333-0.335) g: (7-8) mL.

8. An agricultural preparation, It is characterized in that The invention comprises an effective amount of crystals having the crystalline form of the para-substituted biphenyl sulfide compound according to any one of claims 1 to 7; preferably, it also comprises an agriculturally acceptable formulation carrier or formulation adjuvant.

9. A method for controlling pests and / or mites, It is characterized in that The method comprises applying an insecticidal or acaricidal effective amount of the crystal of the para-substituted biphenyl sulfide compound according to any one of claims 1 to 7 or the agricultural formulation according to claim 8 to pests and / or mites and / or their habitats.

10. Use of a crystal having a crystalline form of a para-substituted diphenyl sulfide compound according to any one of claims 1 to 7 or an agricultural formulation according to claim 8 in controlling pests and / or mites.

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