Preparation method and use of pyrazole compounds containing fluorinated phenyloxy bipyridine units

Abstract

The present invention relates to a preparation method and use of a pyrazole compound containing a fluorinated phenyloxybipyridine unit. The compound is obtained by condensing a fluorinated phenyloxypyridylamine with a substituted pyrazole carboxylic acid. The pyrazole compound containing a fluorinated phenyloxybipyridine unit has excellent insecticidal activity against harmful insects and can be used to prepare insecticides for use in agriculture, horticulture, and other fields.

Description

Technical Field

[0001] The present 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 a vital role in pest control. However, with the continued use of traditional pesticides, some pests have developed resistance to them, and even cross-resistance. Therefore, pesticide researchers are required to research and develop novel, highly effective, and low-toxic pesticides.

[0003] The pyrazole ring is a key member of the nitrogen heterocyclic ring, and compounds containing pyrazolyl groups play an important role in plant protection. Furthermore, the pyridine group is also an important nitrogen heterocyclic fragment, and compounds containing pyridyl groups often exhibit significant insecticidal effects.

[0004] Therefore, in order to further explore compounds with better 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 present invention aims to provide a pyrazole compound containing a fluorinated phenyloxybipyridine unit which has a good insecticidal effect on pests such as armyworms, so as to meet the demand for high-efficiency 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 compound 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 phenyloxybipyridine unit, having the following structure:

[0009]

[0010]

[0011] A second aspect of the present invention provides a method for preparing the pyrazole compound containing a fluorinated phenyloxybipyridine unit, characterized by comprising the following reaction steps:

[0012]

[0013]

[0014] The synthesis of the fluorinated phenyloxy picolylamine intermediate and the substituted pyrazolecarboxylic acid intermediate are both prepared by conventional methods.

[0015] The compounds of the present invention exhibit 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 field 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, its content in the insecticide is selected within the range of 0.1% to 99.5%, and the appropriate active ingredient content can be determined based on the formulation form and application method. Typically, an aqueous emulsion contains 5% to 50% (weight percentage, the same below) of the active ingredient, preferably 10% to 40%; a suspension concentrate contains 5% to 50% of the active ingredient, preferably 5% to 40%.

[0019] For the use of the insecticide of the present invention, commonly used application methods can be selected, such as foliar spraying, surface application, soil treatment, seed treatment, etc. For example, when foliar spraying is adopted, the active ingredient compound can be used in an aqueous emulsion, suspension, water-dispersible granules, or emulsifiable concentrate at a concentration ranging from 1 to 1000 μg / mL.

[0020] The pyrazole compound containing a fluorinated phenyloxy bipyridine unit 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, gardening and other fields. DETAILED DESCRIPTION

[0021] The above scheme is further described below with reference to specific examples. These examples are intended to illustrate the present invention and are not intended to limit 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. The implementation conditions not specified are generally those used in routine experiments.

[0022] Example 1:

[0023]

[0024] 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 at room temperature for 15 minutes. Then, add 6 mmol of N,N-diisopropylethylamine (DIPEA) and 2.2 mmol of intermediate IIa. Stir at room temperature for 10 hours. Stop the reaction, add 30 mL of water, and a solid will precipitate. The crude product is purified 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] Example 2:

[0026]

[0027] Dissolve 2 mmol of intermediate IIIa, 2 mmol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), and 2 mmol of 1-hydroxybenzotriazole (HOBt) in 35 mL of DMSO. After stirring at room temperature for 20 minutes, add 2.1 mmol of intermediate IIb. Continue stirring at room temperature for 8 hours. Stop the reaction, add 25 mL of water, and a solid will precipitate. The crude product is then 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] Example 3:

[0029]

[0030] Dissolve 3 mmol of intermediate IIIb and 3 mmol of benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) in 35 mL of DMF. Add 6 mmol of triethylamine while stirring at room temperature. After stirring at room temperature for 15 minutes, add 3 mmol of intermediate IIb. Continue stirring at room temperature for 7 hours. Stop the reaction, add 35 mL of water to the reaction mixture, and a solid will precipitate. The crude product is 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] Example 4:

[0032] Insecticidal activity test of compounds against armyworms

[0033] The International Resistance Action Committee (IRAC) leaf dip method was used. The test subjects were armyworms. Appropriate amounts of corn leaves were thoroughly soaked in the prepared solution, allowed to air dry, and then placed in a Petri dish lined with filter paper. Third-instar larvae of the armyworm were then inoculated and incubated in a 25°C observation room. Results were observed after 48 hours. Insects were considered dead if no reaction was detected by prodding with a brush. The test concentration was 500 μg / mL.

[0034] As can be seen from Table 1, target compounds Ⅰa, Ⅰb and Ⅰc all showed good insecticidal effects on the armyworm. At the test concentration of 500 μg / mL, the insecticidal activities of target compounds 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 fluorinated phenyloxy bipyridine units into the molecular structure of pyrazole compounds have good insecticidal effects.

[0038] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above examples. The above examples and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications are possible without departing from the spirit and scope of the present invention. Such changes and modifications are intended to fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended 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 units according to claim 1, wherein 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 can be used alone or in the form of an insecticide composition in which 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, a suspension, a water-dispersible granule or an 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, its content in the insecticide is selected within the range of 0.1% to 99.5%.

Images