Preparation and application of dichloropropenyl phenyl ethers containing the trifluoromethylphenylbioxadiazole structure

Abstract

This invention relates to the preparation and application of a dichloropropenyl phenyl ether (I) containing a trifluoromethylphenylbioxadiazole structure. It is obtained by reacting a trifluoromethylphenylbioxadiazole thiol intermediate (II) with a dichloropropenyloxyphenoxy bromide (III). The dichloropropenyl phenyl ether containing the trifluoromethylphenylbioxadiazole structure exhibits excellent control effects against harmful insects.

Description

Technical Field

[0001] This invention relates to the field of chemical pesticides, specifically to the preparation and application of dichloropropenyl phenyl ether containing a trifluoromethylphenyl bioxadiazole structure. Background Technology

[0002] As the scale and duration of use of traditional insecticides increase, many pests have gradually developed resistance to them. Therefore, it is necessary to research and develop new, highly effective insecticides.

[0003] Oxadiazoles are an important class of compounds with wide applications in industrial production. Dichloropropenylphenyl ether is also an important class of compounds, playing a vital role in agricultural production. Furthermore, the trifluoromethylphenyl unit is also an important structural skeleton, playing an indispensable role in industrial production.

[0004] Therefore, by organically linking the trifluoromethylphenyl and oxadiazole units with the dichloropropenylphenyl ether skeleton, it is hoped that compounds exhibiting good biological activity can be obtained. Summary of the Invention

[0005] The purpose of this invention is to provide a dichloropropenyl phenyl ether containing a trifluoromethylphenyl bioxadiazole structure that exhibits good control effects against armyworms and other pests, in order to meet the demand for highly effective insecticides in crop protection.

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

[0007] Another object of the present invention is to provide the use of the above-mentioned compound in the preparation of an insecticide for killing armyworms.

[0008] To solve the above-mentioned technical problems, a first aspect of the present invention provides a dichloropropenyl phenyl ether containing a trifluoromethylphenyl bioxadiazole structure, having the following structure:

[0009]

[0010]

[0011] This invention provides a method for preparing the above-mentioned dichloropropenyl phenyl ether containing a trifluoromethylphenyl bioxadiazole structure, characterized by comprising the following reaction steps:

[0012]

[0013] The compounds of this invention exhibit good control effects against armyworms and other pests. Therefore, the compounds of this invention can be used to prepare insecticides to protect agricultural and horticultural plants.

[0014] When the compounds of the present invention represented by general formula I are used as insecticides in agriculture, horticulture and other fields, they can be used alone or in the form of insecticidal compositions, such as using formula I as the active ingredient and adding common adjuvants to process them into emulsions, suspensions, water-dispersible granules, emulsifiable concentrates, etc.

[0015] Commonly used additives 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 surface agents such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; and other additives such as wetting agents and thickeners.

[0016] When the compounds of the present invention, represented by general formula I, are used as active ingredients in insecticides, their content in the insecticide is selected in the range of 0.1% to 99.5%, and the appropriate content of the active ingredient can be determined according to the formulation and method of application. Typically, the active ingredient is contained in aqueous emulsions at 5% to 50% (by weight), preferably 10% to 40%; and in suspensions at 5% to 50%, preferably 5% to 40%.

[0017] For the use of the insecticide of the present invention, common application methods can be selected, such as foliar spraying, water surface application, etc. For example, when using foliar spraying, the active ingredient, represented by general formula I, can be an emulsion, suspension, water-dispersible granule, or emulsifiable concentrate with a concentration range of 1 to 500 μg / mL.

[0018] The dichloropropenyl phenyl ether containing a trifluoromethylphenyl bioxadiazole structure disclosed in this invention exhibits good control effects against armyworms and other pests. Therefore, it can be used to prepare armyworm-killing drugs, thereby protecting agricultural and horticultural plants. Detailed Implementation

[0019] The above-described solution will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. The implementation conditions used in the embodiments may be further adjusted according to the conditions of specific manufacturers, and the implementation conditions not specified are generally those in routine experiments.

[0020] Example 1:

[0021]

[0022] 9 mmol of intermediate IIa was dissolved in 60 mL of acetone, and 35 mmol of potassium carbonate was added, followed by 11 mmol of intermediate III. After the addition was complete, the reaction mixture was refluxed for 9 hours. The reaction was stopped, and the solvent was removed. The crude product was then subjected to column chromatography to obtain compound Ia.1 H NMR (400MHz, CDCl3): δ8.02~8.04(m, 1H, Ar-H), 7.85~7.87(m, 1H, Ar-H), 7.68~7.71( m, 2H, Ar-H), 6.85 (s, 2H, Ar-H), 6.12 (t, J=6.00Hz, 1H, CH), 4.58 (d, J=6.40Hz, 2H, CHC H2 O), 4.13 (t, J=6.00Hz, 2H, OCH2), 3.63 (t, J=7.20Hz, 2H, SCH2), 2.34~2.41 (m, 2H, CH2).

[0023] Example 2:

[0024]

[0025] 10 mmol of intermediate IIb was dissolved in 60 mL of acetonitrile, and 30 mmol of sodium acetate was added. Then, 13 mmol of intermediate III was added. After the addition, the reaction solution was refluxed for 13 hours. The reaction was stopped, and the solvent was removed. The crude product was then subjected to column chromatography to obtain compound Ib. 1 H NMR (400MHz, CDCl3): δ7.28 (s, 1H, Ar-H), 7.25 (s, 1H, Ar-H), 6.95 (d, J=8.80Hz, 2 H, Ar-H), 6.85 (s, 2H, Ar-H), 6.12 (t, J=6.00Hz, 1H, CH), 4.58 (d, J=6.00Hz, 2H, CHC H22 O), 4.09 (t, J=5.60Hz, 2H, OCH2), 3.59 (t, J=7.20Hz, 2H, SCH2), 2.31~2.37 (m, 2H, CH2).

[0026] Example 3:

[0027]

[0028] 7 mmol of intermediate IIc was dissolved in 50 mL of tetrahydrofuran, and 28 mmol of 4-dimethylaminopyridine was added. Then, 9 mmol of intermediate III was added at room temperature. After the addition, the reaction mixture was allowed to continue reacting at room temperature for 18 hours. The reaction was stopped, and the solvent was removed. The crude product was then subjected to column chromatography to obtain compound Ic. 1H NMR (400MHz, CDCl3): δ8.14 (d, J=8.00Hz, 2H, Ar-H), 7.77 (d, J=8.40Hz, 2H, Ar-H), 6.86 (s, 2H, Ar-H), 6.11 (t, J=6.00Hz, 1H, CH), 4.59 (d, J=6.40Hz, 2H, CHC H2 O), 4.13 (t, J=5.60Hz, 2H, OCH2), 3.66 (t, J=7.20Hz, 2H, SCH2), 2.37N2.43 (m, 2H, CH2).

[0029] Example 4:

[0030] Screening of compounds for their bioactivity against armyworms

[0031] The bioactivity of the compound against armyworms was tested using the leaf immersion method. A suitable amount of corn leaves were thoroughly soaked in a pre-prepared solution and allowed to air dry naturally. The leaves were then placed in petri dishes lined with filter paper, and 10 mid-third instar armyworm larvae per dish were introduced. The dishes were then incubated in an observation room at 25°C, and the results were observed after 2 days.

[0032] The insecticidal activity data of compounds Ia-Ic are listed in Table 1. As can be seen from Table 1, targets Ia, Ib, and Ic all exhibited good control effects against armyworms. At test doses of 500 μg / mL and 100 μg / mL, the insecticidal efficacy of targets Ia, Ib, and Ic against armyworms was 100%. When the test dose was reduced to 20 μg / mL, targets Ia, Ib, and Ic still showed good control efficacy against armyworms, with insecticidal efficacies of 100%, 100%, and 100%, respectively.

[0033] Table 1. Bioactivity data of compounds Ia-Ic

[0034]

[0035] 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 to the above examples; the examples and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A dichloropropenyl phenyl ether I containing a trifluoromethylphenyl bioxadiazole structure, characterized in that... The structure is as follows:

2. The method for preparing dichloropropenyl phenyl ether I containing a trifluoromethylphenyl bioxadiazole structure as described in claim 1, characterized in that... The method is as follows:

3. The use of dichloropropenyl phenyl ether I containing the trifluoromethylphenyl bioxadiazole structure as described in claim 1 in the preparation of an insecticide for killing armyworms.

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