A pyrazole derivative containing a trifluoromethylpyridine biphenoxy structure, a preparation method thereof, and uses thereof

Abstract

The present invention relates to a pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure, a preparation method thereof and uses thereof. It is obtained by reacting a substituted pyrazole acyl chloride with a trifluoromethylpyridineoxy arylmethylamine. The pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure exhibits good insecticidal effects on harmful insects, and this compound can be used to prepare insecticides in the fields of agriculture, horticulture, etc.

Description

Technical Field

[0001] The present invention relates to the field of chemical pesticides, and particularly relates to a pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure, a preparation method thereof, and a use thereof. Background Art

[0002] In recent years, the prevention and control of pests has been one of the important research contents in the field of plant protection. However, with the large-scale use of traditional insecticides, some pests have developed certain resistance to traditional insecticides. This requires a large number of pesticide researchers to continuously develop new high-efficiency and low-toxic insecticides.

[0003] As an important class of nitrogen-containing heterocycles, pyrazole derivatives exhibit good insecticidal effects. Among them, a typical compound is fenpyroximate, which has a wide application in the field of plant protection. In addition, the trifluoromethylpyridine ring is also an important member of nitrogen-containing heterocycles, and trifluoromethylpyridine compounds also have good insecticidal activities and play an important role in the field of agricultural production.

[0004] Therefore, in order to continue to explore compounds with good insecticidal activities from pyrazole derivatives and organically connect the trifluoromethylpyridine structure with the pyrazole skeleton, the present invention discloses a pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure with agricultural insecticidal application value. Summary of the Invention

[0005] The object of the present invention is to provide a pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure that shows good insecticidal effects against pests and is highly efficient, so as to meet the requirements of crop protection for high-efficiency and low-toxic insecticides.

[0006] Another object of the present invention is to provide the use of the above compound in the preparation of insecticides.

[0007] Another object of the present invention is to provide a preparation method of the above compound.

[0008] To solve the above technical problems, the first aspect of the present invention provides a pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure, which has the following structure:

[0009]

[0010]

[0011] The second aspect of the present invention provides a preparation method of the above pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure, which includes the following reaction steps:

[0012]

[0013]

[0014] Among them, the intermediate pyrazole acyl chloride and trifluoromethylpyridyloxy arylmethylamine are both synthesized by conventional preparation methods.

[0015] The compound has excellent control effects on harmful insects, so the compound of the present invention can be used to prepare insecticides, thereby protecting plants in agriculture, horticulture, etc. The insects include Lepidoptera pests such as Mythimna separata. Of course, the harmful organisms that can be controlled by the compound of the present invention are not limited to the scope exemplified above.

[0016] When the compound of the present invention is used as an insecticide in the fields of agriculture, horticulture, etc., it can be used alone or in the form of an insecticidal composition. For example, with the compound as the active ingredient, it is processed into an emulsion in water, a suspension concentrate, a water dispersible granule, an emulsifiable concentrate, etc. by adding commonly used pesticide adjuvants in the art.

[0017] Commonly used pesticide adjuvants include: liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; common surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; other adjuvants such as wetting agents, thickeners, etc.

[0018] When the compound of the present invention is used as the active ingredient in an insecticide, its content in the insecticide is selected within the range of 0.1% to 99.5%, and the appropriate content of the active ingredient can be determined according to the formulation form and application method. Usually, the emulsion in water contains 5% to 50% (weight percentage, the same below) of the active ingredient, and preferably its content is 10% to 40%; the suspension concentrate contains 5% to 50% of the active ingredient, and preferably its content is 5% to 40%.

[0019] For the use of the insecticide of the present invention, common application methods can be selected, such as foliar spraying, surface application on water, soil treatment and seed treatment, etc. For example, when foliar spraying is adopted, the available concentration range of the compound represented by general formula I as the active ingredient is 1 to 1000 μg / mL for the emulsion in water, suspension concentrate, water dispersible granule, emulsifiable concentrate, and preferably its concentration is 1 to 500 μg / mL.

[0020] A pyrazole derivative containing a trifluoromethylpyridine biaryloxy structure disclosed by the present invention shows good insecticidal effects on pests, so it can be used to prepare insecticides for the fields of agriculture, horticulture, etc. Detailed implementation mode

[0021] The above solution will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are used to illustrate the present invention and are not intended to limit the scope of the present invention. The implementation conditions adopted in the embodiments can be further adjusted according to the conditions of specific manufacturers, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0022] Example 1:

[0023]

[0024] Dissolve 5 mmol of intermediate IIIa in 35 mL of dichloromethane, add 22 mmol of triethylamine, and dropwise add 6 mmol of intermediate IIa thereto under ice bath conditions. After dropping, continue to react for 8 hours under ice bath conditions. Stop the reaction, remove the solvent under reduced pressure, and the obtained crude product is separated by column chromatography to obtain the target product Ia; 1 H NMR(400MHz,DMSO-d 6 )δ:9.37(t,J=6.00Hz,1H,NH),8.51~8.55(m,2H,Py-H),8.19~8.24(m,2H,Py-H),7.62~7.65(m,1H,Py-H),7.33(d,J=8.80Hz,2H,Ar-H),7.28(s,1H,Pyrazole-H),7.23(d,J=8.40Hz,1H,Py-H),7.16(d,J=8.40Hz,2H,Ar-H),4.39(d,J=6.00Hz,2H,CH 2 ).HRMS calcd for C 22 H 14 BrClF 3 N 5 O 2 Na[M+Na] + 573.9869,found 573.9865.

[0025] Example 2:

[0026]

[0027] Dissolve 6 mmol of intermediate IIIb in 35 mL of dichloromethane, add 30 mmol of pyridine, and dropwise add 5 mmol of intermediate IIa thereto under ice bath conditions. After dropping, continue to react for 6 hours under ice bath conditions. Stop the reaction, remove the solvent under reduced pressure, and the obtained crude product is separated by column chromatography to obtain the target product Ib; 1 H NMR(400MHz,DMSO-d 6) δ: 9.37 (t, J=6.00 Hz, 1H, NH), 8.51~8.52 (m, 2H, Py-H), 8.17~8.22 (m, 2H, Py-H), 7.63~7.66 (m, 1H, Py-H), 7.30 (s, 1H, Pyrazole-H), 7.13~7.22 (m, 2H, Py-H and Ar-H), 7.06 (s, 1H, Ar-H), 6.89 (d, J=8.00 Hz, 1H, Ar-H), 4.39 (d, J=5.60 Hz, 2H, CH 2 ), 3.66 (s, 3H, OCH 3 ). HRMS calcd for C 23 H 16 BrClF 3 N 5 O 3 Na[M + Na] + 603.9975, found 603.9977.

[0028] Example 3:

[0029]

[0030] Dissolve 6 mmol of intermediate Ⅲc in 35 mL of acetonitrile, add 20 mmol of triethylamine, and dropwise add 6 mmol of intermediate Ⅱa thereto at room temperature. After dropping, continue the reaction at room temperature for 10 hours. Stop the reaction, remove the solvent under reduced pressure, and the obtained crude product is separated by column chromatography to obtain the target product Ic; 1 1H NMR (400 MHz, DMSO-d 6 ) δ: 9.38 (t, J=6.00 Hz, 1H, NH), 8.56 (d, J=2.00 Hz, 1H, Py-H), 8.52~8.53 (m, 1H, Py-H), 8.49 (s, 1H, Py-H), 8.19~8.22 (m, 1H, Py-H), 7.62~7.66 (m, 1H, Py-H), 7.34 (d, J=8.80 Hz, 2H, Ar-H), 7.29 (s, 1H, Pyrazole-H), 7.21 (d, J=8.40 Hz, 2H, Ar-H), 4.40 (d, J=6.00 Hz, 2H, CH 2 ). HRMS calcd for C 22 H 13 BrCl 2 F 3 N 5 O 2 Na[M + Na] +607.9479, found 607.9473.

[0031] Example 4:

[0032]

[0033] Dissolve 6 mmol of intermediate Ⅲd in 35 mL of chloroform, add 18 mmol of pyridine, and dropwise add 8 mmol of intermediate Ⅱa thereto at room temperature. After dropping, continue the reaction at room temperature for 12 hours. Stop the reaction, remove the solvent under reduced pressure, and the obtained crude product is separated by column chromatography to obtain the target product Id; 1 H NMR(400MHz, DMSO-d 6 )δ: 9.39(t, J=6.00Hz, 1H, NH), 8.51~8.53(m, 2H, Py-H), 8.46(s, 1H, Py-H), 8.19~8.22(m, 1H, Py-H), 7.62~7.66(m, 1H, Py-H), 7.31(s, 1H, Pyrazole-H), 7.19(d, J=8.40Hz, 1H, Ar-H), 7.08(s, 1H, Ar-H), 6.91(d, J=8.00Hz, 1H, Ar-H), 4.40(d, J=6.00Hz, 2H, CH 2 ), 3.68(s, 3H, OCH 3 ). HRMS calcd for C 23 H 15 BrCl 2 F 3 N 5 O 3 Na[M+Na] + 637.9585, found 637.9579.

[0034] Example 5:

[0035]

[0036] Dissolve 7 mmol of intermediate Ⅲd in 50 mL of chloroform, add 30 mmol of 4-dimethylaminopyridine (DMAP), and dropwise add 9 mmol of intermediate Ⅱb thereto at room temperature. After dropping, continue the reaction at room temperature for 15 hours. Stop the reaction, remove the solvent under reduced pressure, and the obtained crude product is separated by column chromatography to obtain the target product Ie; 1 H NMR(400MHz, DMSO-d 6) δ: 9.44 (t, J = 6.00 Hz, 1H, NH), 8.64 (d, J = 2.00 Hz, 1H, Py - H), 8.57 (d, J = 2.00 Hz, 1H, Py - H), 8.54 (d, J = 2.00 Hz, 1H, Py - H), 8.47 (s, 1H, Py - H), 7.34 (s, 1H, Pyrazole - H), 7.20 (d, J = 8.40 Hz, 1H, Ar - H), 7.08 (s, 1H, Ar - H), 6.91 (d, J = 8.40 Hz, 1H, Ar - H), 4.41 (d, J = 5.60 Hz, 2H, CH 2 ), 3.68 (s, 3H, OCH 3 ). HRMS calcd for C 23 H 14 BrCl 3 F 3 N 5 O 3 Na[M + Na] + 671.9195, found 671.9194.

[0037] Example 6:

[0038] Insecticidal activity test of the compound against Mythimna separata

[0039] The leaf - dipping method proposed by the Insecticide Resistance Action Committee (IRAC) was adopted: The test object was Mythimna separata. That is, an appropriate amount of corn leaves were fully soaked in the prepared liquid medicine and then naturally dried, and then placed in a petri dish. 10 middle - instar larvae of Mythimna separata were inoculated per dish and cultured in an observation room at 25 °C. The results were investigated 48 hours later. When touching the insect body with a writing brush, no response was regarded as a dead insect. The test concentration was 500 μg / mL (other concentration liquid medicines were obtained by diluting the 500 μg / mL liquid medicine).

[0040] As can be seen from Table 1, the target compounds Ⅰa - Ⅰe all showed good insecticidal effects against Mythimna separata. At the test concentration of 500 μg / mL, the killing rates of the target compounds Ⅰa - Ⅰe against Mythimna separata were all 100%; when the test concentration was 100 μg / mL, the killing rates of the target compounds Ⅰa - Ⅰe against Mythimna separata were 90%, 70%, 100%, 70% and 80% respectively; in addition, the target compounds Ia, Ib, Ic and Ie still showed insecticidal activity when the test concentration was reduced to 20 μg / mL, and their control effects were 50%, 30%, 60% and 50% respectively.

[0041] Table 1. Preliminary insecticidal activity data of Ia - Ie

[0042]

[0043] The above experimental results indicate that by reasonably connecting the trifluoromethylpyridine structure with the pyrazole unit, the resulting new compound exhibits good insecticidal activity.

[0044] The above has shown and described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above examples. The above examples and the descriptions in the specification only illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, various changes and improvements will occur to the present invention, and these changes and improvements all fall within the scope of the present invention claimed. The scope of the present invention claimed is defined by the appended claims and their equivalents.

Claims

1. A pyrazole derivative I containing a trifluoromethylpyridine biaryloxy structure, characterized in that The structure is:

2. The method for preparing a pyrazole derivative I containing a trifluoromethylpyridine biaryloxy structure according to claim 1, characterized in that Here’s how:

3. Use of a pyrazole derivative I containing a trifluoromethylpyridine biaryloxy structure as claimed in claim 1 in the preparation of an insecticide, characterized in that: The compound is used alone; or the derivative I in claim 1 is used as an active ingredient, and is added with pesticide adjuvants commonly used in the art to be processed into an aqueous emulsion, suspension, water-dispersible granule, or an emulsifiable concentrate.

4. Use of a pyrazole derivative I containing a trifluoromethylpyridine biaryloxy structure as claimed in claim 3 in the preparation of an insecticide, characterized in that: When the derivative I described in claim 1 is used as an active ingredient of an insecticide, its content in the insecticide is selected within the range of 0.1% to 99.5%.

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