Preparation method and application of pyrazole compound containing fluorophenyl oxydipyridine unit

Abstract

The invention relates to a preparation method and application of a pyrazole compound containing a fluorophenyl oxygen dipyridine unit. The fluorine-containing phenyl oxypyridine methyl amine is obtained through condensation of fluorine-containing phenyl oxypyridine methyl amine and substituted pyrazole formic acid. The pyrazole compound containing the fluorophenyl oxygen bipyridine unit 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 invention relates to the field of chemical pesticides, and in particular to a preparation method and application of pyrazole compounds containing fluorinated phenyloxy bipyridine units. Background Art

[0002] In recent years, pesticides have played an important role in pest control. However, with the continuous use of traditional pesticides, some pests have developed resistance to traditional pesticides, and even cross-resistance. Therefore, it is necessary for pesticide researchers to research and develop novel, high-efficiency, and low-toxic pesticides.

[0003] The pyrazole ring is a key member of the nitrogen heterocyclic unit, and pyrazole-containing compounds play an important role in the field of plant protection. In addition, the pyridine group is also an important nitrogen heterocyclic fragment, and pyridine-containing compounds often show significant insecticidal effects.

[0004] Therefore, in order to further explore compounds with good insecticidal activity from pyrazole compounds, a fluorinated phenyloxybipyridine unit is introduced into the molecular structure of the pyrazole compound. The present invention discloses a class of pyrazole compounds containing a fluorinated phenyloxybipyridine unit with agricultural insecticidal application value. Summary of the invention

[0005] The purpose of the present invention is to provide a pyrazole compound containing a fluorinated phenyloxy bipyridine unit which has a good insecticidal effect on pests such as armyworms, so as to meet the demand for efficient insecticides in crop protection.

[0006] Another object of the present invention is to provide a method for preparing the above compound.

[0007] Another object of the present invention is to provide the use of the above compounds in preparing insecticides.

[0008] In order to solve the above technical problems, the first aspect of the present invention provides a pyrazole compound containing a fluorinated phenyloxy bipyridine unit, having the following structure:

[0009]

[0010]

[0011] The second aspect of the present invention provides a method for preparing the pyrazole compound containing the fluorinated phenyloxy bipyridine unit, which is characterized by comprising the following reaction steps:

[0012]

[0013]

[0014] Among them, the synthesis of the fluorinated phenyloxypyridylamine intermediate and the substituted pyrazole carboxylic acid intermediate are both prepared by conventional methods.

[0015] The compounds of the present invention show good insecticidal activity against pests such as armyworms, and thus the compounds of the present invention can be used to prepare insecticides to protect agricultural and horticultural plants.

[0016] When the compounds of the present invention are used as pesticides in the fields of agriculture, horticulture, etc., they can be used alone or in the form of insecticide compositions, such as using the compounds as active ingredients and adding pesticide adjuvants commonly used in the art to process them into aqueous emulsions, suspensions, water-dispersible granules, emulsifiable concentrates, 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 compound of the present invention is used as an active ingredient in an insecticide, the content in the insecticide is selected within the range of 0.1% to 99.5%, and the appropriate active ingredient content can be determined according to the formulation form and the application method. Usually, the active ingredient is contained in an aqueous emulsion at 5% to 50% (weight percentage, the same below), preferably 10% to 40%; the active ingredient is contained in a suspension at 5% to 50%, preferably 5% to 40%.

[0019] For the use of the pesticide of the present invention, commonly used application methods can be selected, such as stem and leaf spraying, water surface application, soil treatment and seed treatment, etc. For example, when stem and leaf spraying is adopted, the usable concentration range of the compound as the active ingredient is 1 to 1000 μg / mL of aqueous emulsion, suspension, water dispersible granule, emulsifiable concentrate.

[0020] The pyrazole compound containing fluorinated phenyloxy bipyridine units disclosed in the present invention has a good control effect on pests such as armyworms, and can therefore be used to prepare insecticides used in agriculture, horticulture and other fields. DETAILED DESCRIPTION

[0021] The above scheme is further described below in conjunction with specific examples. These examples are used to illustrate the present invention but are not limited to the scope of the present invention. The implementation conditions used in the examples can be further adjusted according to the conditions of the specific manufacturer, and the unspecified implementation conditions are usually the conditions in conventional experiments.

[0022] Embodiment 1:

[0023]

[0024] Dissolve 2mmol of intermediate IIIa and 2mmol of benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) in 30mL of N,N-dimethylacetamide (DMA), stir at room temperature for 15min, add 6mmol of N,N-diisopropylethylamine (DIPEA) and 2.2mmol of intermediate IIa, and continue stirring at room temperature for 10 hours. Stop the reaction, add 30mL of water to the reaction solution, precipitate solid, and purify the crude product by silica gel column chromatography to obtain the target compound Ia; 1 H NMR (400MHz, DMSO-d6): δ9.32(t,J=6.0Hz,1H),8.50~8.52(m,1H),8.19~8.21(m,1H),8.0 4(s,1H),7.72~7.74(m,1H),7.62~7.65(m,1H),7.02~7.26(m,6H),4.32(d,J=5.6Hz,2H).

[0025] Embodiment 2:

[0026]

[0027] 2mmol of intermediate IIIa, 2mmol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), and 2mmol of 1-hydroxybenzotriazole (HOBt) were dissolved in 35mL of DMSO, stirred at room temperature for 20min, and then 2.1mmol of intermediate IIb was added thereto. After addition, stirring was continued at room temperature for 8 hours. The reaction was stopped, and 25mL of water was added to the reaction solution to precipitate a solid. The crude product was separated by silica gel column chromatography to obtain the target compound Ib; 1 H NMR (400MHz, DMSO-d6): δ9.36 (t, J=6.0Hz, 1H), 8.54~8.56 (m, 1H), 8.23~8.26 (m, 1H), 8.0 5(s,1H),7.79~7.82(m,1H),7.67~7.70(m,1H),7.16~7.49(m,5H),4.37(d,J=5.6Hz,2H).

[0028] Embodiment 3:

[0029]

[0030] 3mmol of intermediate IIIb and 3mmol of benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) were dissolved in 35mL of DMF, and 6mmol of triethylamine was added thereto under stirring at room temperature. After stirring at room temperature for 15min, 3mmol of intermediate IIb was added thereto. After the addition, stirring was continued at room temperature for 7 hours. The reaction was stopped, 35mL of water was added to the reaction solution, and a solid was precipitated. The crude product was separated by silica gel column chromatography to obtain the target compound Ic; 1 H NMR (400MHz, DMSO-d6): δ9.36 (t, J=5.6Hz, 1H), 8.42~8.44 (m, 1H), 8.23~8.25 (m, 1H), 8.0 0(s,1H),7.74~7.77(m,1H),7.62~7.65(m,1H),7.12~7.48(m,4H),4.36(d,J=5.6Hz,2H).

[0031] Embodiment 4:

[0032] Insecticidal activity test of compounds against armyworms

[0033] The leaf dip method proposed by the International Resistance Action Committee (IRAC) was used: the test object was armyworms, that is, appropriate amounts of corn leaves were fully soaked in the prepared solution, dried naturally in the shade, placed in a culture dish lined with filter paper, and inoculated with 3rd instar larvae of armyworms, placed in a 25℃ observation room for culture, and the results were investigated after 48 hours. The insect body was touched with a brush, and no reaction was considered dead. The test concentration was 500μg / mL.

[0034] It can be seen from Table 1 that the target substances Ⅰa, Ⅰb and Ⅰc all showed good insecticidal effects on the armyworm. When the test concentration was 500 μg / mL, the insecticidal activities of the target substances Ⅰa, Ⅰb and Ⅰc on the armyworm were 100%, 100% and 100%, respectively.

[0035] Table 1. Preliminary insecticidal activity data of Ia~Ic

[0036]

[0037] The above test results show that the new pyrazole compounds obtained by introducing the fluorinated phenyloxy bipyridine unit into the molecular structure of pyrazole compounds have good insecticidal effects.

[0038] The above shows and describes 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 to the above examples. The above examples and descriptions are only for explaining the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A pyrazole compound (I) containing a fluorinated phenyloxybipyridine unit, characterized in that The structure is:

2. The method for preparing the pyrazole compound (I) containing fluorinated phenyloxy bipyridine unit according to claim 1, characterized in that Here’s how:

3. Use of the pyrazole compound (I) containing a fluorinated phenyloxybipyridine unit as claimed in claim 1 in the preparation of insecticides, characterized in that: The compound is used alone; or the compound (I) 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 emulsifiable concentrate.

4. Use of the pyrazole compound (I) containing a fluorinated phenyloxybipyridine unit as claimed in claim 3 in the preparation of insecticides, characterized in that: When compound (I) is used as an active ingredient of an insecticide, the content of compound (I) in the insecticide is selected within the range of 0.1% to 99.5%.

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