Biphenyl trifluoroethyl sulfide compound and its application

Abstract

The present invention provides a compound having excellent control effect on plant diseases and insect pests, and specifically relates to a biphenyl trifluoroethyl sulfide compound shown in formula I and its application. The compound of formula I has excellent acaricidal and fungicidal activity and can be used to control various harmful mites and pathogens. #imgabs0#

Description

Technical Field

[0001] The invention belongs to the field of agricultural acaricides and fungicides, and specifically relates to a biphenyl trifluoroethyl sulfide compound and application thereof. Background Art

[0002] Biphenyl sulfide derivatives have good acaricidal activity. Patent WO9955668 records that 3-arylphenyl sulfide derivatives have insecticidal and acaricidal activity, among which the compound of formula II (listed compound I-575) has a lethal activity against two-spotted spider mites greater than 90% at a concentration of 500ppm; Patent WO2017067500 discloses a compound of formula III (listed compound 1) as an acaricide. Other related patent documents include WO2007034755, JP2009023910A, WO2012176856, WO2013027660, WO2022012483 and CN114957062A.

[0003]

[0004] In the prior art, the compound represented by formula I of the present invention and its acaricidal and fungicidal activities have not been disclosed. At the same time, the compound of the present invention has a more excellent control effect on plant diseases and insect pests. Summary of the invention

[0005] The present invention studies compounds with excellent control effects on plant diseases and insect pests. As a result, it is found that the biphenyl trifluoroethyl sulfide compound shown in the following formula I has excellent acaricidal and fungicidal activities and can be used in the control of harmful mites and pathogens in the fields of agriculture, forestry and health.

[0006] The technical solution of the present invention is as follows:

[0007] A biphenyl trifluoroethyl sulfide compound, represented by formula I:

[0008]

[0009] The compound of formula I is used as a miticide in the fields of agriculture, forestry and sanitation.

[0010] The compound of formula I is used as a fungicide in the fields of agriculture, forestry and sanitation.

[0011] A miticide composition comprises the compound of formula I and an agriculturally acceptable carrier; the compound of formula I is used as an active component, and the weight percentage of the active component in the composition is 0.1-99%.

[0012] A bactericidal composition comprises the compound of formula I and an agriculturally acceptable carrier; the compound of formula I is used as an active component, and the weight percentage of the active component in the composition is 0.1-99%.

[0013] The compound of formula I of the present invention has excellent pest control effect and can be applied to the control of mite and fungal pests in the fields of agriculture, forestry and health.

[0014] The examples of pests and diseases mentioned below are only used to illustrate the present invention, but they are by no means limiting the present invention.

[0015] Order Acarina (Mites): Acarina, such as citrus rust gall mite and apple rust mite; Tenuiphora, such as Polyphagous tarsonemus; Tenuipalpis, such as purple-red short-palpis mite; Tetranychus, such as Verniciflua, Kanzawa spider mite, Pacific spider mite, cotton spider mite and two-spotted spider mite, apple spider mite, citrus spider mite, etc.

[0016] The compound represented by formula I of the present invention also exhibits excellent control effect on various harmful mites when used at low concentrations, and has acaricidal activity at each stage of the life cycle of harmful mites. For those harmful mites that have developed resistance to traditional acaricides, the compound represented by formula I of the present invention also exhibits excellent control activity. At the same time, the compound represented by formula I has low toxicity to many beneficial insects and mites, mammals, fish, and birds, and has no phytotoxicity.

[0017] Plant diseases: Oomycete diseases, such as downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew, beet downy mildew, sugarcane downy mildew, tobacco downy mildew, pea downy mildew, loofah downy mildew, wax gourd downy mildew, melon downy mildew, cabbage downy mildew, spinach downy mildew, radish downy mildew, grape downy mildew, onion downy mildew), white rust (rape white rust, cabbage white rust), damping-off (rape damping-off , tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton seedling damping-off), cotton rot (pepper cotton rot, loofah cotton rot, wax gourd cotton rot), blight (broad bean blight, cucumber blight, pumpkin blight, wax gourd blight, watermelon blight, melon blight, pepper blight, leek blight, garlic blight, cotton blight), late blight (potato late blight, tomato late blight), etc.;Deuteromycin diseases, such as wilt (sweet potato wilt, cotton wilt, sesame wilt, castor wilt, tomato wilt, kidney bean wilt, cucumber wilt, loofah wilt, pumpkin wilt, wax gourd wilt, watermelon wilt, melon wilt, pepper wilt, broad bean wilt, rapeseed wilt, soybean wilt), root rot (pepper root rot, eggplant root rot, kidney bean root rot, cucumber root rot, bitter melon root rot, cotton black root rot, broad bean root rot), damping-off (cotton seedling damping-off, sesame damping-off, pepper damping-off, cucumber damping-off, cabbage damping-off), anthracnose (sorghum anthracnose, cotton anthracnose, hemp anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, mulberry anthracnose Disease, pepper anthracnose, eggplant anthracnose, bean anthracnose, cucumber anthracnose, bitter gourd anthracnose, zucchini anthracnose, wax gourd anthracnose, watermelon anthracnose, melon anthracnose, litchi anthracnose), Verticillium wilt (cotton wilt, sunflower wilt, tomato wilt, pepper wilt, eggplant wilt), black spot (zucchini black spot, wax gourd black spot, melon black spot), gray mold (cotton boll gray mold, hemp gray mold, tomato gray mold, pepper gray mold, kidney bean gray mold, celery gray mold, spinach gray mold, kiwifruit gray mold), brown spot (cotton brown spot, jute brown spot, beet brown spot, peanut brown spot, pepper brown spot, wax gourd brown spot, soybean brown spot, sunflower brown spot, pea brown spot Black spot (false black spot of flax, black spot of rape, black spot of sesame, black spot of sunflower, black spot of castor, black spot of tomato, black spot of pepper, black spot of eggplant, black spot of kidney bean, black spot of cucumber, black spot of celery, black rot of carrot, black spot of carrot, black spot of apple, black spot of peanut), spot blight (spot blight of tomato, spot blight of pepper, spot blight of celery), early blight (early blight of tomato, early blight of pepper, early blight of eggplant, early blight of potato, early blight of celery), ring rot (soybean ring rot, sesame ring rot, kidney bean ring rot), leaf blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, melon leaf blight), stem base rot (stem base rot of tomato, vegetable Bean stem base rot), and others (corn round spot, jute waist break disease, rice blast, chestnut black sheath disease, sugarcane eye spot disease, cotton boll Aspergillus disease, peanut crown rot, soybean stem blight, soybean black spot disease, melon large spot disease, peanut web spot disease, tea red leaf spot disease, pepper white star disease, wax gourd leaf spot disease, celery black rot, spinach heart rot, jute leaf mold, jute spot disease, jute stem spot disease, soybean purple spot disease, sesame leaf spot disease, castor gray spot disease, tea brown leaf spot disease, eggplant brown round star disease, kidney bean red spot disease, bitter melon white spot disease, watermelon spot disease, jute blight rot, sunflower root and stem rot disease, kidney bean charcoal rot, soybean target spot disease, eggplant coryneform leaf spot disease, cucumber target spot disease, tomato leaf mold disease, eggplant leaf mold disease, broad bean red spot disease, etc.);Basidiomycete diseases, such as rust (wheat stripe rust, wheat stem rust, wheat leaf rust, flower rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust), smut (corn silk smut, corn powdery mildew, sorghum silk smut, sorghum loose smut, sorghum hard smut, sorghum column powdery mildew, chestnut kernel smut, sugarcane smut, bean rust) and others (such as wheat sheath blight, rice sheath blight, etc.); Ascomycete diseases, such as powdery mildew (wheat powdery mildew, rape powdery mildew, sesame powdery mildew, Powdery mildew of sunflower, beet, eggplant, pea, loofah, pumpkin, zucchini, wax gourd, melon, grape, broad bean), sclerotinia (flax, rape, soybean, peanut, tobacco, pepper, eggplant, bean, pea, cucumber, bitter melon, wax gourd, watermelon, celery), scab (apple scab, pear scab), etc. ;

[0018] Due to their positive properties, the compounds according to the invention can be advantageously used for protecting important agricultural and horticultural crops, domestic and breeding animals, and environments frequented by humans from harmful mites or pathogens.

[0019] To obtain the desired effect, the amount of compound used will vary depending on factors such as the crop to be applied, the type of pest, the degree of infestation, climatic conditions, the method of application, and the formulation employed.

[0020] The compounds of formula I can be formulated in a variety of ways according to the usual biological and / or chemical physical parameters. Suitable formulation options include: wettable powders (WP), wettable liquids (SL), soluble powders (SP), dispersible liquids (DC), aqueous solutions (AS), microemulsions (ME), emulsifiable concentrates (EC), aqueous emulsions (EW), sprayable solutions, suspensions (SC), dispersible oil suspensions (OD), dusts (DP), microcapsule suspensions (CS), water-dispersible granules (WG), water-soluble granules (SG), large granules (GG), granules for broadcasting and soil application (GR), aerosols (AE), ultra-low volume agents (ULV) and wax products. Necessary formulation adjuvants, such as inert substances, surfactants, solvents and other additives.

[0021] For practical use in agriculture, it is often advantageous to use a composition containing a compound of formula I of the present invention.

[0022] Therefore, another technical solution of the present invention also includes an acaricidal or fungicidal composition, characterized in that: the composition contains a compound of formula I and an agriculturally acceptable carrier; the compound of formula I is used as an active ingredient, and the weight percentage of the active ingredient in the composition is 0.1-99%.

[0023] The composition of the present invention can be applied in the form of a preparation. The compound shown in Formula I is dissolved or dispersed in a carrier as an active ingredient or formulated into a preparation so that it is easier to disperse when used as a bactericidal agent. For example, these chemical preparations can be made into wettable powders, oil suspensions, water suspensions, aqueous emulsions, aqueous solutions or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant can be added.

[0024] Useful solid diluents or carriers may be silicon dioxide, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicate, attapulgite, sepiolite and the like.

[0025] In addition to water, available liquid diluents are aromatic organic solvents (mixtures of xylene or alkylbenzenes, chlorobenzene, etc.), paraffin (petroleum fractions), alcohols (methanol, propanol, butanol, octanol, glycerol), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides (N,N-dimethylformamide, N-methylpyrrolidone, etc.).

[0026] Usable surfactants are sodium, calcium, triethylamine or triethanolamine salts of alkyl sulfonates, alkyl aryl sulfonates, polyoxyethylene alkylphenols, polyoxyethylene esters of sorbitol, lignin sulfonates and the like.

[0027] The composition may also contain special additives for specific purposes, for example, binders such as gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone and the like.

[0028] The concentration of the active ingredient in the above composition can vary within a wide range depending on the active ingredient, its intended use, environmental conditions and the type of formulation employed. Typically, the concentration of the active ingredient ranges from 1-90%, preferably 5-50%.

[0029] For certain applications, such as in agriculture, one or more other fungicides, insecticides, acaricides, herbicides, plant growth regulators or fertilizers may be added to the acaricide or fungicidal composition of the present invention, thereby producing additional advantages and effects.

[0030] It should be understood that various changes and modifications can be made within the scope of the present invention as defined by the claims. DETAILED DESCRIPTION

[0031] The following specific examples are used to further illustrate the present invention, but the present invention is by no means limited to these examples (unless otherwise noted, all raw materials used are commercially available).

[0032] Synthesis Example

[0033] Example 1: Preparation of the compound represented by formula I

[0034] At room temperature, 15.4 g (0.1 mol) of 2-fluoro-4-methylbenzeneboronic acid, 30.3 g (0.1 mol) of 2-fluoro-4-methyl-5-trifluoroethylthiobromobenzene (see the synthesis of compound VIIa-1 in patent WO2014202505), 0.58 g of tetrakistriphenylphosphine palladium and 20.7 g (0.15 mol) of potassium carbonate were placed in a 1000 ml three-necked flask, ethylene glycol dimethyl ether (200 ml) and water (200 ml) were added, and the mixture was stirred and refluxed under nitrogen protection for 4 hours. After the reaction was completed, the mixture was cooled and ethyl acetate was added, and the organic layer was extracted and separated, and then washed with water and saturated brine in turn, dried over anhydrous magnesium sulfate, filtered, and desolventized under reduced pressure. The residue was purified by column chromatography to obtain 26.7 g of a white solid. 1 H NMR (600MHz, CDCl3) δ (ppm): 7.56 (d, 1H), 7.23 (t, 1H), 7.05 (d, 1H), 7.02 (d, 1H), 6.98 (d, 1H), 3.33 (q, 2H), 2.52 (s, 3H), 2.40 (s, 3H).

[0035] Biological Activity Assay Example

[0036] Example 2: Activity determination of killing adult Tetranychus cinnabarinus mites

[0037] According to the solubility of the compound to be tested, dissolve it with acetone or dimethyl sulfoxide, and then prepare 50 ml of the test solution of the required concentration with 0.1% Tween 80 solution. The content of acetone or dimethyl sulfoxide in the solution shall not exceed 10%, and then set aside. Take two true leaf bean seedlings, inoculate adult mites of Tetranychus cinnabarinus and investigate the base number, then use a handheld sprayer to spray the whole plant, with 3 replicates for each treatment, and place it in a standard observation room after treatment. After 72 hours, investigate the number of surviving adult mites and calculate the mortality rate.

[0038] When the concentration of the compound of the present invention is 600 mg / L, the lethality rate of the adult mites of Tetranychus cinnabarinus is 100%; at a lower concentration of 100 mg / L, the control effect on the adult mites of Tetranychus cinnabarinus is still very good, with a mortality rate of 100%.

[0039] According to the above method, the compound of the present invention and the following comparative compounds KC1 (compound Ⅰ-636 listed in WO9955668), KC2 (compound 5 listed in CN114957062A) and KC3 (synthesized by referring to the method of Example 1 of the present invention) were tested in parallel for acaricidal activity. The specific compound structures are as follows:

[0040]

[0041] The test results of parallel tests on the activity of killing adult mites of Tetranychus cinnabarinus are shown in the following table:

[0042]

[0043] Example 3: In vivo protective activity assay against cucumber powdery mildew

[0044] Using the in vivo pot test method, the compound sample to be tested is dissolved with a small amount of solvent (the type of solvent is such as acetone, methanol, DMF, etc., and is selected according to its solubility for the sample, and the volume ratio of the solvent amount to the spray liquid amount is equal to or less than 0.05), and diluted with water containing 0.1% Tween 80 to prepare a test solution with a concentration of 400 mg / L. On a crop sprayer, the test solution is sprayed on the disease host plant (the host plant is a standard potted seedling cultivated in a greenhouse), and the disease is inoculated 24 hours later. According to the characteristics of the disease, the diseased plants that need to be cultivated with temperature control and moisture retention are inoculated and placed in an artificial climate chamber for cultivation. After the disease infection is completed, they are moved to the greenhouse for cultivation. The diseased plants that do not need moisture retention cultivation are directly inoculated and cultivated in the greenhouse. After the control is fully diseased (usually one week), the disease prevention effect of the compound is evaluated.

[0045] The compound of the present invention has a 100% protective effect on cucumber powdery mildew.

[0046] According to the above method, the in vivo protective activity of the compound of formula II and the compound of formula III described in the background art against cucumber powdery mildew was tested, and the result showed that the protective effect was 0%.

[0047] In summary, the compound of formula I of the present invention has outstanding effects on sterilization and acaricide. It can be seen that the positions of different substituents and different selections will directly affect the effect characteristics, which needs to be further studied.

Claims

1. An application of a biphenyl trifluoroethyl sulfide compound, characterized in that: The application is the application of biphenyl trifluoroethyl sulfide compound in preventing and controlling cucumber powdery mildew; The biphenyl trifluoroethyl sulfide compound is a compound as shown in Formula I: 。 2. The use of the biphenyl trifluoroethyl sulfide compound according to claim 1, characterized in that: The concentration of the biphenyl trifluoroethyl sulfide compound is 400 mg / L.

3. An application of a composition containing a biphenyl trifluoroethyl sulfide compound, characterized in that: The application is the application of the composition containing biphenyl trifluoroethyl sulfide compound in preventing and controlling cucumber powdery mildew; The composition containing biphenyl trifluoroethyl sulfide compound contains the biphenyl trifluoroethyl sulfide compound and an agriculturally acceptable carrier; the biphenyl trifluoroethyl sulfide compound is used as an active component, and the weight percentage of the active component in the composition containing biphenyl trifluoroethyl sulfide compound is 0.1-99%; the biphenyl trifluoroethyl sulfide compound is a compound as shown in Formula I: 。

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