Preparation method and application of pyrazole compound containing aromatic mercapto biphenyl triazole unit

Abstract

The invention relates to a preparation method and application of a pyrazole compound containing an aromatic sulfydryl biphenyl triazole unit. The pyrazole oxime compound is obtained by reacting substituted pyrazole oxime with an aromatic sulfydryl biphenyl triazole compound. The pyrazole compound containing the aromatic sulfydryl biphenyl triazole unit shows a good insecticidal effect on harmful insects, and can be used for preparing insecticides in the fields of agriculture, gardening and the like.

Description

Technical Field

[0001] The present invention relates to the field of chemical pesticides, and specifically relates to a preparation method and use of a pyrazole compound containing an arylmercaptobiphenyltriazole unit. Background Art

[0002] In recent years, pesticides have played a very important role in pest control. However, with the frequent use of pesticides, some pests have developed certain resistance to traditional pesticides. Therefore, pesticide developers need to continuously develop new and highly effective pesticides.

[0003] The substituted pyrazole ring is an active fragment of common drug molecules and pesticide molecules, and pyrazole compounds have functions such as insecticidal, bacteriostatic, and herbicidal effects in the field of pesticides.

[0004] Therefore, in order to further search for new compounds with good insecticidal effects from pyrazole compounds, and reasonably connect the arylmercaptobiphenyltriazole unit with the substituted pyrazole ring, the present invention discloses a class of pyrazole compounds containing an arylmercaptobiphenyltriazole unit with agricultural insecticidal application value. Summary of the Invention

[0005] The purpose of the present invention is to provide a pyrazole compound containing an arylmercaptobiphenyltriazole unit that exhibits good insecticidal effects against pests such as aphids and diamondback moths and is highly efficient, so as to meet the demand for highly effective insecticides in crop protection.

[0006] Another purpose of the present invention is to provide a preparation method of the above compound.

[0007] Another purpose of the present invention is to provide the use of the above compound in the preparation of insecticides.

[0008] To solve the above technical problems, the first aspect of the present invention provides a pyrazole compound containing an arylmercaptobiphenyltriazole unit, which has the following structure:

[0009]

[0010]

[0011] The second aspect of the present invention provides a preparation method of the above pyrazole compound containing an arylmercaptobiphenyltriazole unit, which includes the following reaction steps:

[0012]

[0013]

[0014] The intermediates substituted pyrazole oxime and arylmercaptobiphenyltriazole compound are both prepared by conventional synthesis methods.

[0015] The compounds of the present invention have excellent insecticidal effects on pests such as aphids and diamondback moths. Therefore, the compounds of the present invention can be used to prepare insecticides to protect plants in agriculture, horticulture, etc. Of course, the pests 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, they can be processed into emulsion in water, suspension concentrate, water dispersible granules, and emulsifiable concentrate.

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

[0020] The pyrazole compounds containing an arylthiol biphenyl triazole unit disclosed in the present invention show good insecticidal activity against pests such as aphids and diamondback moths, and thus can be used to prepare insecticides for the fields of agriculture, horticulture, etc. Detailed implementation mode

[0021] The above scheme will be further described below in conjunction with specific examples. It should be understood that these examples are for illustrating the present invention and not for limiting the scope of the present invention. The implementation conditions adopted in the examples 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] 4 mmol of intermediate Ⅲa, 10 mmol of potassium carbonate and 30 mL of acetonitrile were added to a reaction flask. After stirring for a while, 5 mmol of intermediate Ⅱa was added, and then the mixture was heated under reflux for 10 hours. The reaction was stopped, and the crude product obtained after removing the solvent under reduced pressure was separated by column chromatography to obtain the target compound Ia; 1 H NMR(400MHz,CDCl 3 )δ7.96(s,1H),7.82(s,1H),7.78(s,1H),7.63(d,J=8.40Hz,2H),7.41(d,J=8.40Hz,2H),7.16~7.28(m,4H),6.96(t,J=8.60Hz,2H),6.80~6.84(m,2H),4.93(s,2H),4.13(s,2H),3.59(s,3H),2.33(s,3H).

[0025] Example 2:

[0026]

[0027] 5 mmol of intermediate Ⅲb, 12 mmol of cesium carbonate and 35 mL of acetonitrile were added to a reaction flask. After stirring for a while, 6 mmol of intermediate Ⅱa was added, and then the mixture was heated under reflux for 12 hours. The reaction was stopped, and the crude product obtained after removing the solvent under reduced pressure was separated by column chromatography to obtain the target compound Ib; 1 H NMR(400MHz,CDCl 3 )δ7.96(s,1H),7.82(s,1H),7.78(s,1H),7.63(d,J=8.40Hz,2H),7.37~7.43(m,4H),7.14~7.28(m,4H),6.75(d,J=8.80Hz,2H),4.92(s,2H),4.14(s,2H),3.58(s,3H),2.33(s,3H).

[0028] Example 3:

[0029]

[0030] 5 mmol of intermediate Ⅲc, 20 mmol of 4-dimethylaminopyridine (DMAP) and 30 mL of acetone were added to a reaction flask. After stirring for a while, 4 mmol of intermediate Ⅱa was added, and then the mixture was heated under reflux for 9 hours. The reaction was stopped, and the crude product obtained after removing the solvent under reduced pressure was separated by column chromatography to obtain the target compound Ic; 1 H NMR(400MHz,CDCl 3)δ 7.97 (s, 1H), 7.82 (s, 1H), 7.80 (s, 1H), 7.63 (d, J = 8.40 Hz, 2H), 7.41 (d, J = 8.40 Hz, 2H), 6.74~7.29 (m, 8H, Ar-H), 4.92 (s, 2H), 4.13 (s, 2H), 3.59 (s, 3H), 2.34 (s, 3H).

[0031] Example 4:

[0032]

[0033] 5 mmol of intermediate Ⅲd, 30 mmol of N,N-diisopropylethylamine (DIPEA), and 35 mL of N,N-dimethylformamide (DMF) were added to a reaction flask. After stirring for a while, 5.5 mmol of intermediate Ⅱa was added. Then the temperature was raised to 80 °C and stirred for 16 hours. The reaction was stopped, and the solvent was removed under reduced pressure. The crude product obtained was separated by column chromatography to obtain the target compound Id; 1 H NMR (400 MHz, CDCl 3 )δ 7.97 (s, 1H), 7.82 (s, 1H), 7.76 (s, 1H), 7.63 (d, J = 8.40 Hz, 2H), 7.40 (d, J = 8.40 Hz, 2H), 7.18~7.28 (m, 4H), 6.65~7.09 (m, 4H), 4.94 (s, 2H), 4.13 (s, 2H), 3.88 (s, 3H), 3.62 (s, 3H), 2.34 (s, 3H).

[0034] Example 5:

[0035] Determination of the insecticidal activity of the compound against aphids

[0036] By the spraying method proposed by the Insecticide Resistance Action Committee (IRAC): Select aphids as the test object. Spray the broad bean leaves with aphids under a Potter spray tower, and then place the aphids in an observation room at 25 °C for cultivation. After 2 days, investigate the test results. Touch the insect body with a writing brush, and those with no response are regarded as dead insects. The test concentration is 500 μg / mL (the liquid medicine of other concentrations can be diluted from the 500 μg / mL liquid medicine).

[0037] Example 6:

[0038] Determination of the insecticidal activity of the compound against Plutella xylostella

[0039] Leaf-dipping method proposed by the Insecticide Resistance Action Committee (IRAC): Select Plutella xylostella as the test object. Dip an appropriate amount of corn leaves in the prepared liquid medicine, air-dry them naturally, then place them in a petri dish lined with filter paper, inoculate Plutella xylostella larvae, and culture them in an observation room at 25°C. After 2 days, investigate the test results. Touch the insect body with a writing brush, and those with no response are regarded as dead insects. The test concentration is 500 μg / mL.

[0040] As can be seen from Table 1, when the test concentration is 500 μg / mL, the mortality rates of compounds Ia - Id against aphids are all 100%. When the concentration is 100 μg / mL, the mortality rates of compounds Ia, Ic, and Id against aphids are 40%, 50%, and 100% respectively. In addition, the mortality rates of compounds Ia - Id against Plutella xylostella at 500 μg / mL are 70%, 100%, 100%, and 50% respectively.

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

[0042]

[0043] The above test results show that by connecting the arylthiol - biphenyltriazole unit with a substituted pyrazole ring, the obtained new compounds exhibit good insecticidal effects.

[0044] 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 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, the present invention will have various changes and improvements, and these changes and improvements all 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 an aromatic mercaptobiphenyl triazole unit, characterized in that The structure is:

2. The method for preparing the pyrazole compound I containing an aromatic mercapto biphenyl triazole unit as claimed in claim 1, characterized in that Here’s how:

3. Use of the pyrazole compound containing an aromatic mercaptobiphenyl triazole unit as claimed in claim 1 in the preparation of insecticides.

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