Preparation and Use of Pyrazole Compounds Containing 3,5-Dichloropyridyloxyarylmethyl

Abstract

The present invention relates to the preparation and use of pyrazole compounds containing 3,5-dichloropyridyloxyarylmethyl. It is obtained by the condensation of 3,5-dichloropyridyloxyarylmethylamine with substituted pyrazole acids. The pyrazole compounds containing 3,5-dichloropyridyloxyarylmethyl exhibit good insecticidal effects against harmful insects, and these compounds 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 to the preparation and use of pyrazole compounds containing 3,5-dichloropyridyloxyarylmethyl. Background Art

[0002] The effective control of pests is one of the core areas of pesticide scientific research. The use of pesticides has effectively controlled most pests, but some pests have developed resistance to traditional pesticides in recent years. Therefore, pesticide chemists urgently need to develop new and highly efficient pesticides.

[0003] As a common active fragment of pesticide molecules, pyridine ring-containing compounds have good insecticidal effects in the field of pesticides. Pyrazole compounds are also an important member of the nitrogen-containing heterocyclic family, and substituted pyrazole compounds show excellent insecticidal activity and play an important role in the field of agricultural production.

[0004] In order to further search for and discover new compounds with good insecticidal effects from pyrazole compounds, the 3,5-dichloropyridyloxyarylmethyl unit is reasonably combined with the substituted pyrazole fragment. The present invention discloses a class of pyrazole compounds containing 3,5-dichloropyridyloxyarylmethyl with agricultural insecticidal application value. Summary of the Invention

[0005] The object of the present invention is to provide pyrazole compounds containing 3,5-dichloropyridyloxyarylmethyl that show good insecticidal effects against pests such as armyworms and mites, and are highly efficient and environmentally friendly, so as to meet the demand for highly efficient insecticides in crop protection.

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

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

[0008] To solve the above technical problems, the first aspect of the present invention provides pyrazole compounds containing 3,5-dichloropyridyloxyarylmethyl, and their structures are as follows:

[0009]

[0010]

[0011] The second aspect of the present invention provides a preparation method of the above pyrazole compounds containing 3,5-dichloropyridyloxyarylmethyl, which includes the following steps:

[0012]

[0013]

[0014] Among them, the 3,5-dichloropyridyloxy aromatic methylamine intermediate and the substituted pyrazole acid intermediate are both prepared by conventional methods.

[0015] The compounds of the present invention exhibit good insecticidal effects against pests such as armyworms and mites. Therefore, the compounds of the present invention can be used to prepare insecticides, thereby protecting plants in agriculture, horticulture, etc. Of course, the pests that can be controlled by the compounds of the present invention are not limited to the scope exemplified above.

[0016] When the compounds of the present invention are used as insecticides in the fields of agriculture, horticulture, etc., they can be used alone or in the form of insecticidal compositions. For example, taking the compound as the active ingredient and adding the commonly used pesticide adjuvants in the art to process into emulsion in water, suspension concentrate, water dispersible granules, emulsifiable concentrate, etc.

[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; commonly used surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, non-ionic surfactants and amphoteric surfactants; other adjuvants such as wetting agents, thickeners, etc.

[0018] When the compounds of the present invention are used as the active ingredient in insecticides, the content in the insecticides 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 the content is 10% to 40%; the suspension concentrate contains 5% to 50% of the active ingredient, and preferably the content is 5% to 40%.

[0019] For the use of the insecticides of the present invention, commonly used 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 of emulsion in water, suspension concentrate, water dispersible granules, emulsifiable concentrate, and preferably the concentration is 1 to 500 μg / mL.

[0020] The pyrazole compounds containing 3,5-dichloropyridyloxy aromatic methyl groups disclosed in the present invention exhibit good insecticidal effects against pests such as armyworms and mites. Therefore, they 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 for illustrating the present invention and not for limiting 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 1 mmol of intermediate IIIa and 1 mmol of benzotriazol-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) in 10 mL of N,N-dimethylformamide (DMF), stir at room temperature for 10 min, then add 1 mmol of triethylamine and 1 mmol of intermediate IIa thereto. After adding, continue to stir at room temperature for 7 hours. Add 20 mL of water to the reaction solution, and a solid precipitates. The obtained crude product is purified by silica gel column chromatography to obtain the target product Ia; 1 H NMR (400 MHz, DMSO-d 6 ) δ: 9.38 (t, J = 6.00 Hz, 1H, NH), 8.51 (d, J = 4.80 Hz, 1H, Py-H), 8.34 (d, J = 2.40 Hz, 1H, Py-H), 8.25~8.27 (m, 1H, Py-H), 8.15 (d, J = 2.40 Hz, 1H, Py-H), 7.63~7.66 (m, 1H, Py-H), 7.32 (d, J = 8.80 Hz, 2H, Ar-H), 7.16 (d, J = 8.80 Hz, 2H, Ar-H), 4.41 (d, J = 6.00 Hz, 2H, CH 2 ). HRMS calcd for C 21 H 12 BrCl 4 N 5 O 2 Na[M+Na] + 607.8826, found 607.8832.

[0025] Example 2:

[0026]

[0027] Dissolve 1 mmol of intermediate Ⅲb and 1 mmol of benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) in 20 mL of DMSO, stir for 10 min at room temperature, then add 3 mmol of N,N-diisopropylethylamine (DIPEA) and 1 mmol of intermediate Ⅱa thereto. After addition, continue stirring at room temperature for 9 h. Add 25 mL of water to the reaction solution, and a solid precipitates. The obtained crude product is purified by silica gel column chromatography to obtain the target compound Ib; 1 H NMR(400MHz,DMSO-d 6 )δ:9.36(t,J=6.00Hz,1H,NH),8.52(d,J=4.80Hz,1H,Py-H),8.33(d,J=2.40Hz,1H,Py-H),8.19~8.21(m,1H,Py-H),8.14(d,J=2.40Hz,1H,Py-H),7.62~7.65(m,1H,Py-H),7.31(d,J=8.40Hz,2H,Ar-H),7.28(s,1H,Pyrazole-H),7.14(d,J=8.80Hz,2H,Ar-H),4.38(d,J=6.00Hz,2H,CH 2 ).HRMScalcd for C 21 H 13 BrCl 3 N 5 O 2 Na[M+Na] + 573.9216;found 573.9216.

[0028] Example 3:

[0029]

[0030] Dissolve 2 mmol of intermediate Ⅲa and 2 mmol of benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) in 30 mL of N,N-dimethylacetamide (DMA), stir for 15 min at room temperature, then add 6 mmol of triethylamine and 2 mmol of intermediate Ⅱb thereto. After addition, heat to 50 °C and react for 10 h. Add 30 mL of water to the reaction solution, and a solid precipitates. The obtained crude product is purified by silica gel column chromatography to obtain the target compound Ic; 1 H NMR(400MHz,DMSO-d 6) δ: 9.38 (t, J = 6.00 Hz, 1H, NH), 8.49 (d, J = 4.80 Hz, 1H, Py-H), 8.29 (d, J = 2.02 Hz, 1H, Py-H), 8.25 - 8.27 (m, 1H, Py-H), 8.09 (d, J = 2.02 Hz, 1H, Py-H), 7.63 - 7.66 (m, 1H, Py-H), 7.16 (d, J = 8.02 Hz, 1H, Ar-H), 7.07 (s, 1H, Ar-H), 6.88 - 6.90 (m, 1H, Ar-H), 4.42 (d, J = 6.00 Hz, 2H, CH 2 ), 3.66 (s, 3H, OCH 3 ). HRMS calcd for C 22 H 14 BrCl 4 N 5 O 3 Na[M + Na] + 637.8932, found 637.8931.

[0031] Example 4:

[0032]

[0033] Dissolve 3 mmol of intermediate IIIb and 3 mmol of benzotriazol - N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) in 50 mL of N,N-dimethylformamide (DMF), stir at room temperature for 20 min, then add 8 mmol of 4-dimethylaminopyridine (DMAP) and 3 mmol of intermediate IIb thereto. After addition, react at room temperature for 6 hours. Add 35 mL of water to the reaction solution, and a solid precipitates. The crude product obtained is purified by silica gel column chromatography to obtain the target compound Id; 1 1H NMR (400 MHz, DMSO-d 6 ) δ: 9.35 (t, J = 6.00 Hz, 1H, NH), 8.51 (d, J = 4.80 Hz, 1H, Py-H), 8.29 (d, J = 2.40 Hz, 1H, Py-H), 8.19 - 8.22 (m, 1H, Py-H), 8.08 (d, J = 2.00 Hz, 1H, Py-H), 7.62 - 7.65 (m, 1H, Py-H), 7.29 (s, 1H, Pyrazole-H), 6.86 - 7.15 (m, 3H, Ar-H), 4.37 (d, J = 5.60 Hz, 2H, CH 2 ), 3.65 (s, 3H, OCH 3 ). HRMS calcd for C 22 H15 BrCl 3 N 5 O 3 Na[M+Na] + 603.9322, found 603.9321.

[0034] Example 5:

[0035] Screening of the insecticidal activity of the sample against Mythimna separata

[0036] The leaf-dipping method proposed by the Insecticide Resistance Action Committee (IRAC) was adopted: the test target was Mythimna separata. An appropriate amount of corn leaves were fully soaked in the prepared liquid medicine and then naturally air-dried, placed in a petri dish lined with filter paper, and 10 mid-3rd instar larvae of Mythimna separata were inoculated per dish. They were placed in an observation room at 25°C for cultivation, and the results were investigated after 2 days. When the body of the insect was touched with a writing brush and there was no response, it was regarded as a dead insect. The test concentration was 500 μg / mL (the liquid medicines of other concentrations were diluted from the 500 μg / mL liquid medicine).

[0037] Example 6:

[0038] Screening of the insecticidal activity of the sample against mites

[0039] The spraying method proposed by the Insecticide Resistance Action Committee (IRAC) was adopted: the test target was Tetranychus cinnabarinus. The broad bean leaves with Tetranychus cinnabarinus were sprayed under a Potter spray tower, and after the treatment, Tetranychus cinnabarinus was placed in an observation room at 25°C for cultivation, and the results were investigated after 2 days. When the body of the insect was touched with a writing brush and there was no response, it was regarded as a dead insect. The test concentration was 500 μg / mL (the liquid medicines of other concentrations were diluted from the 500 μg / mL liquid medicine).

[0040] Table 1. Preliminary insecticidal activity data of Ia - Id

[0041]

[0042] “-”: indicates not determined

[0043] It can be seen from Table 1 that when the test concentration was 500 μg / mL, the control effects of compounds Ia - Id against Mythimna separata were all 100%; when the concentration dropped to 100 μg / mL, the control effects of compounds Ia, Ib and Id against Mythimna separata were 60%, 80% and 50% respectively; in addition, the control effects of compounds Ia and Ib against Tetranychus cinnabarinus were 50% and 30% respectively when the concentration was 500 μg / mL. The above experimental data show that the prepared novel pyrazole compounds have good insecticidal activity.

[0044] The foregoing 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. What is described in the above examples and the specification only illustrates 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 all these changes and improvements fall within the scope of the present invention claimed. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. A pyrazole compound (I) containing 3,5-dichloropyridyloxyarylmethyl, characterized in that The structure is:

2. The method for preparing the pyrazole compound (I) containing 3,5-dichloropyridyloxyarylmethyl as claimed in claim 1, characterized in that Here’s how:

3. Use of the pyrazole compound (I) containing 3,5-dichloropyridyloxyarylmethyl as claimed in claim 1 in the preparation of an insecticide.

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