Preparation and application of pyrazole derivative containing triazole benzyl arylether structure

Abstract

The invention relates to preparation and application of a pyrazole derivative containing a triazole benzyl arylether structure. The pyrazole oxime derivative is obtained by condensation of triazole benzyl oxyaryl methyl chloride and pyrazole oxime. The pyrazole derivative containing the triazole benzyl aryl ether structure has a good insecticidal effect on harmful insects, and can be used for preparing insecticides in the fields of agriculture, horticulture and the like.

Description

Technical Field

[0001] The present invention relates to the field of chemical pesticides, and specifically to the preparation and use of pyrazole derivatives containing a triazole benzyl aryl ether structure. Background Art

[0002] The effective prevention and control of pests is one of the hot fields in pesticide scientific research. The use of insecticides has effectively controlled most pests. In recent years, some pests have developed certain resistance to traditional insecticides. Therefore, it is necessary for pesticide researchers to develop novel-structured, highly efficient and low-toxic insecticides.

[0003] The pyrazole ring is an important nitrogen-containing heterocycle, and its pyrazole derivatives often exhibit excellent insecticidal activity. Among them, the typical compound is fenpyroximate, which has a wide application in the field of plant protection.

[0004]

[0005] In addition, the triazole ring is also an important member of nitrogen-containing heterocycles. Substituted triazole compounds often show good biological activity and also play an important role in agricultural production.

[0006] Therefore, in order to continue to explore compounds with good insecticidal activity from pyrazole derivatives and organically connect the substituted triazole structural unit with the pyrazole skeleton, the present invention discloses a class of pyrazole derivatives containing a triazole benzyl aryl ether structure with agricultural insecticidal application value. Summary of the Invention

[0007] The object of the present invention is to provide pyrazole derivatives containing a triazole benzyl aryl ether structure that have good insecticidal effects against a variety of pests and are highly efficient, so as to meet the demand for highly efficient insecticides in crop protection.

[0008] Another object of the present invention is to provide a preparation method of the above compounds.

[0009] Another object of the present invention is to provide the use of the above compounds in the preparation of insecticides.

[0010] To solve the above technical problems, the first aspect of the present invention provides pyrazole derivatives containing a triazole benzyl aryl ether structure, which have the following structure:

[0011]

[0012] The second aspect of the present invention provides a preparation method of the above pyrazole derivatives containing a triazole benzyl aryl ether structure, which is characterized by including the following steps:

[0013]

[0014] Among them, the synthesis of the triazole benzyl-oxy arylmethyl chloride intermediate and the pyrazole oxime intermediate are both prepared by conventional synthesis methods.

[0015] The compounds of the present invention show good insecticidal effects against pests such as Mythimna separata and Plutella xylostella, so 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 compounds of the present invention as active ingredients, together with commonly used pesticide adjuvants in the art, they are processed into aqueous emulsion, 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, nonionic surfactants and amphoteric surfactants; other adjuvants such as wetting agents, thickeners, etc.

[0018] When the compounds of the present invention are used as active ingredients in insecticides, their 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 aqueous emulsion 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 insecticides of the present invention, commonly used application methods can be selected, such as foliar spraying, soil treatment and seed treatment, etc. For example, when foliar spraying is adopted, the applicable concentration range of the compound as the active ingredient is 1 to 1000 μg / mL of aqueous emulsion, suspension concentrate, water dispersible granules, emulsifiable concentrate, and the preferred concentration is 1 to 500 μg / mL.

[0020] The pyrazole derivatives containing triazole benzyl aryl ether structure disclosed in the present invention have good control effects on harmful insects, so they can be used to prepare insecticides for the fields of agriculture, horticulture, etc. Detailed implementation mode

[0021] The above solutions are 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] Add 2.2 mmol of intermediate Ⅲa, 2 mmol of intermediate Ⅱa and 30 mL of acetonitrile to a reaction flask. Add 4 mmol of cesium carbonate under stirring, and then heat the reaction solution to reflux for 9 hours. Stop the reaction, remove the solvent under reduced pressure, and separate the obtained crude product by column chromatography to obtain the target product Ia; 1 H NMR(400MHz,CDCl 3 ):δ8.00(s,1H),7.84(s,1H),7.74~7.77(m,3H),7.57(d,J=8.40Hz,2H),7.22(d,J=8.80Hz,2H),6.91~7.00(m,4H,Ar-H),6.82~6.85(m,2H),5.12(s,2H,CH 2 ),4.93(s,2H),3.59(s,3H),2.35(s,3H).

[0025] Example 2:

[0026]

[0027] Add 2 mmol of intermediate Ⅲa, 2 mmol of intermediate Ⅱb and 35 mL of N,N-dimethylformamide (DMF) to a reaction flask. Add 5 mmol of cesium carbonate under stirring, and then heat the reaction solution to 85 °C and react for 12 hours. Stop the reaction, remove the solvent under reduced pressure, and separate the obtained crude product by column chromatography to obtain the target product Ib; 1 H NMR(400MHz,CDCl 3 ):δ8.00(s,1H),7.85(s,1H),7.74~7.78(m,3H),7.58(d,J=8.40Hz,2H),7.20~7.27(m,4H),6.91(d,J=8.40Hz,2H),6.81(d,J=8.80Hz,2H),5.12(s,2H),4.91(s,2H),3.59(s,3H),2.35(s,3H).

[0028] Example 3:

[0029]

[0030] Add 3 mmol of intermediate IIIb, 2 mmol of intermediate IIc and 30 mL of N,N-dimethylformamide (DMF) to a reaction flask. Add 6 mmol of potassium carbonate under stirring, then heat the reaction solution to 85 °C and react for 13 hours. Stop the reaction, remove the solvent under reduced pressure, and separate the obtained crude product by column chromatography to obtain the target product Ic; 1 H NMR(CDCl 3 , 400 MHz): δ 8.00 (s, 1H), 7.84 (s, 1H), 7.78 (s, 1H), 7.73 (d, J = 8.40 Hz, 2H), 7.59 (d, J = 8.40 Hz, 2H), 6.81~6.93 (m, 7H), 5.20 (s, 2H), 4.94 (s, 2H), 3.88 (s, 3H), 3.76 (s, 3H), 3.59 (s, 3H), 2.38 (s, 3H).

[0031] Example 4:

[0032]

[0033] Add 3 mmol of intermediate IIIc, 4 mmol of intermediate IId and 35 mL of 1,4-dioxane to a reaction flask. Add 8 mmol of cesium carbonate under stirring, then heat the reaction solution to 85 °C and react for 10 hours. Stop the reaction, remove the solvent under reduced pressure, and separate the obtained crude product by column chromatography to obtain the target product Id; 1 H NMR(CDCl 3 , 400 MHz): δ 8.00 (s, 1H), 7.84 (s, 1H), 7.79 (s, 1H), 7.65~7.73 (m, 4H), 7.07 (d, J = 7.60 Hz, 1H), 6.80 (d, J = 7.60 Hz, 1H), 6.59 (s, 2H), 6.30 (s, 1H), 5.05 (s, 2H), 4.96 (s, 2H), 3.83 (s, 6H), 3.59 (s, 3H), 2.42 (s, 3H), 2.31 (s, 3H), 2.21 (s, 3H).

[0034] Example 5:

[0035]

[0036] Add 4 mmol of intermediate IIIc, 3 mmol of intermediate IIe and 30 mL of DMSO to a reaction flask. Add 6 mmol of triethylamine under stirring, then heat the reaction solution to 65 °C and react for 15 hours. Stop the reaction, remove the solvent under reduced pressure, and separate the obtained crude product by column chromatography to obtain the target product Ie; 1 H NMR(CDCl 3, 400 MHz): δ 8.00 (s, 1H), 7.83 (d, J = 6.00 Hz, 2H), 7.65 - 7.73 (m, 4H), 7.14 - 7.25 (m, 2H), 7.06 (s, 1H), 6.81 - 6.83 (m, 1H), 6.57 (s, 2H), 5.06 (s, 2H), 4.93 (s, 2H), 3.83 (s, 6H), 3.61 (s, 3H), 2.39 (s, 3H).

[0037] Example 6:

[0038] Screening of the insecticidal activities of the samples against Mythimna separata and Plutella xylostella

[0039] The leaf-dipping method proposed by the Insecticide Resistance Action Committee (IRAC) was adopted: the test objects were Mythimna separata and Plutella xylostella. An appropriate amount of corn leaves or radish leaves were fully soaked in the prepared liquid medicine and then air-dried naturally, placed in a petri dish lined with filter paper, inoculated with Mythimna separata or Plutella xylostella larvae, and cultured in an observation room at 25°C. The results were investigated after 2 days. When the body of the insect was touched with a writing brush and there was no reaction, 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] The insecticidal activity test data (Table 1) showed that at the test concentration of 500 μg / mL, the insecticidal effects of compounds Ia - Ie against Mythimna separata were 50%, 80%, 100%, 100% and 100% respectively; at 100 μg / mL, the insecticidal activities of compounds Ic - Ie against Mythimna separata were 100%, 60% and 90% respectively; at the test concentration of 500 μg / mL, the killing effects of compounds Ia - Ie against Plutella xylostella were 100%, 100%, 80%, 100% and 100% respectively, and at 100 μg / mL, the insecticidal activities of compounds Ia and Ib against Plutella xylostella were 90% and 50% respectively.

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

[0042]

[0043] The above experimental results indicated that by connecting the substituted triazole structural unit with the pyrazole skeleton, the new compounds obtained showed good insecticidal effects.

[0044] The basic principles, main features and advantages of the present invention have been shown and described above. 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 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 triazole benzyl aryl ether structure, characterized in that The structure is:

2. The method for preparing the pyrazole derivative (I) containing a triazole benzyl aryl ether structure as claimed in claim 1, characterized in that Here’s how:

3. Use of the pyrazole derivative (I) containing a triazole benzyl aryl ether structure as claimed in claim 1 in the preparation of insecticides.

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