Benzyloxy-substituted bipyridyl ketone compounds and their applications

Abstract

The present invention relates to benzyloxy-substituted bipyridyl ketone compounds and their applications. Specifically, the present invention provides a compound of formula (I) or a pesticidally acceptable salt thereof, wherein R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, cyano, hydroxy, etc.; X is halogen; Y is alkyl or haloalkyl; Z is alkoxy or haloalkoxy. The compounds of the present invention have excellent fungicidal activity against cucumber powdery mildew and cucumber gray mold pathogens.

Description

Technical Field

[0001] The present invention relates to benzyloxy-substituted bipyridylmethanone compounds and their applications, which can be used for controlling cucumber powdery mildew and cucumber gray mold; the present invention also relates to the preparation and compositions of such compounds. Background Art

[0002] Worldwide, one of the serious problems faced by agricultural production is crop diseases caused by phytopathogenic fungi. Phytopathogenic fungi often rapidly infect many crops, resulting in reduced food production and the production of mycotoxins harmful to animal and human health. Continuously researching and developing new compounds with excellent bactericidal effects, reducing the dosage, improving the efficacy, prolonging the residual period, expanding the bactericidal spectrum, and avoiding phytotoxicity to crops, etc., are of great significance in ensuring agricultural production.

[0003] The prior art CN1440389A discloses a class of benzoylpyridine derivatives or their salts, which have preventive and therapeutic effects on powdery mildew of barley, vegetables, fruits, and flowering plants, but do not disclose the compounds of the present invention. Summary of the Invention

[0004] The purpose of the present invention is to provide a new benzyloxy-substituted bipyridylmethanone compound with excellent bactericidal effects.

[0005] On the one hand, the present invention provides a compound represented by formula (I) or a pesticidally acceptable salt thereof:

[0006]

[0007] Wherein:

[0008] R 1 、R 2 、R 3 、R 4 and R 5 are each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, cycloalkyl or cycloalkyloxy;

[0009] X is halogen;

[0010] Y is alkyl or haloalkyl;

[0011] Z is alkoxy or haloalkoxy.

[0012] As used herein, "alkyl" refers to a saturated straight-chain or branched-chain monovalent hydrocarbon group containing 1 to 20 carbon atoms; in one embodiment, the alkyl group contains 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-10 carbon atoms; in one embodiment, the alkyl group contains 1-8 carbon atoms; in another embodiment, the alkyl group contains 1-6 carbon atoms; in yet another embodiment, the alkyl group contains 1-4 carbon atoms; still in one embodiment, the alkyl group contains 1-3 carbon atoms.

[0013] As used herein, "alkenyl" refers to a straight-chain or branched-chain monovalent hydrocarbon group containing 2-12 carbon atoms, having at least one unsaturated site, i.e., having a carbon-carbon sp 2 double bond, wherein the alkenyl may optionally be substituted by one or more substituents described herein, including "cis" and "tans" configurations, or "E" and "Z" configurations. In one embodiment, the alkenyl contains 2-10 carbon atoms; in one embodiment, the alkenyl contains 2-8 carbon atoms; in another embodiment, the alkenyl contains 2-6 carbon atoms; in yet another embodiment, the alkenyl contains 2-4 carbon atoms.

[0014] As used herein, "alkynyl" refers to a straight-chain or branched-chain monovalent hydrocarbon group containing 2-12 carbon atoms, having at least one carbon-carbon sp triple bond, wherein the alkynyl may optionally be substituted by one or more substituents described herein. In one embodiment, the alkynyl contains 2-10 carbon atoms; in one embodiment, the alkynyl contains 2-8 carbon atoms; in another embodiment, the alkynyl contains 2-6 carbon atoms; in yet another embodiment, the alkynyl contains 2-4 carbon atoms.

[0015] As used herein, "haloalkyl" refers to an alkyl group substituted by one or more halogen atoms.

[0016] As used herein, "haloalkenyl" refers to an alkenyl group substituted by one or more halogen atoms.

[0017] As used herein, "haloalkynyl" refers to an alkynyl group substituted by one or more halogen atoms.

[0018] As used herein, "alkoxy" refers to an alkyl group connected to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. In one embodiment, the alkoxy contains 1-12 carbon atoms; in one embodiment, the alkoxy contains 1-10 carbon atoms; in one embodiment, the alkoxy contains 1-8 carbon atoms; in one embodiment, the alkoxy contains 1-6 carbon atoms; in another embodiment, the alkoxy contains 1-4 carbon atoms; in yet another embodiment, the alkoxy contains 1-3 carbon atoms.

[0019] As used herein, "haloalkoxy" means an alkoxy group substituted by one or more halogen atoms.

[0020] As used herein, "alkenyloxy" means an alkenyl group linked to the remainder of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as defined herein.

[0021] As used herein, "haloalkenyloxy" means an alkenyloxy group substituted by one or more halogen atoms.

[0022] As used herein, "alkynyloxy" means an alkynyl group linked to the remainder of the molecule through an oxygen atom, wherein the alkynyl group has the meaning as defined herein.

[0023] As used herein, "haloalkynyloxy" means an alkynyloxy group substituted by one or more halogen atoms.

[0024] As used herein, "cycloalkyl" means a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic system containing 3 - 15 carbon atoms. In one embodiment, the cycloalkyl contains 3 - 12 carbon atoms; in one embodiment, the cycloalkyl contains 3 - 10 carbon atoms; in another embodiment, the cycloalkyl contains 3 - 8 carbon atoms; in yet another embodiment, the cycloalkyl contains 3 - 6 carbon atoms. The cycloalkyl group is optionally substituted by one or more substituents described herein. Such examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0025] As used herein, "cycloalkyloxy" means a cycloalkyl group linked to the remainder of the molecule through an oxygen atom, wherein the cycloalkyl group has the meaning as defined herein.

[0026] As used herein, "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0027] As used herein, "room temperature" means a temperature in the range of about 15°C - 35°C or about 20°C - 30°C or about 23°C - 28°C or about 25°C.

[0028] As used herein, "overnight" means a time period of about 4 - 20 h or about 6 - 15 h or about 8 - 12 h or about 8 h or about 9 h or about 10 h or about 12 h.

[0029] In the context of the present invention, all numbers disclosed herein are approximate values, whether or not the words "about" or "approximate" are used. The numerical value of each number may vary by 1%, 2%, 3%, 4% or 5%, etc.

[0030] According to some embodiments of the present invention, R 1 , R 2 , R3 , R 4 and R 5 are each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 2-6 alkenyloxy, halo C 2-6 alkenyloxy, C 2-6 alkynyloxy, halo C 2-6 alkynyloxy, C 3-8 cycloalkyl or C 3-8 cycloalkyloxy.

[0031] According to further embodiments of the present invention, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxy, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 2-4 alkenyloxy, halo C 2-4 alkenyloxy, C 2-4 alkynyloxy, halo C 2-4 alkynyloxy, C 3-6 cycloalkyl or C 3-6 cycloalkyloxy.

[0032] According to further embodiments of the present invention, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropoxy, cyclobutoxy, cyclopentyloxy or cyclohexyloxy.

[0033] According to further embodiments of the present invention, R 1 is hydrogen, fluorine or methyl; R2 is fluorine, chlorine or bromine; R 3 is hydrogen or methoxy; R 4 is hydrogen, fluorine, chlorine or trifluoromethyl; R 5 is hydrogen, fluorine or methoxy.

[0034] According to some embodiments of the present invention, X is a halogen; Y is C 1-6 alkyl or halo C 1-6 alkyl; Z is C 1-6 alkoxy or halo C 1-6 alkoxy.

[0035] According to some other embodiments of the present invention, X is a halogen; Y is C 1-4 alkyl or halo C 1-4 alkyl; Z is C 1-4 alkoxy or halo C 1-4 alkoxy.

[0036] According to some other embodiments of the present invention, X is chlorine or bromine; Y is methyl; Z is methoxy.

[0037] Preferably, the compound of formula (I) according to the present invention is selected from the following compounds or their agrochemically acceptable salts:

[0038] Or

[0039] Compared with the compounds disclosed in the prior art CN1440389A, the compounds of the present invention replace the benzene ring with a pyridine ring and further introduce an optionally substituted benzyloxy group as a substituent of the pyridine ring, resulting in a novel structure of benzyloxy-substituted dipyridylmethanone compounds.

[0040] The prior art CN1440389A mainly targets powdery mildew of barley, vegetables, fruits and flowering plants. In addition to being effective against powdery mildew, the compounds of the present invention also have good control effects against gray mold, showing a more obvious broad-spectrum advantage.

[0041] Studies have shown that the compounds of the present invention have more excellent bactericidal effects. For example, using the bactericidal activity test method described in the present invention, at a concentration of 500 ppm, the control effect of the disclosed compound No. 27 in the prior art CN1440389A (the structural formula is as follows, and the specific synthesis is referred to Synthesis Example 6) against gray mold of cucumber is below 65%, while the control effect of the compounds of the present invention is above 80%.

[0042]

[0043] On the other hand, the present invention provides a pesticidal composition comprising at least one compound described in the present invention or a pesticidally acceptable salt thereof, further optionally comprising a pesticidally acceptable adjuvant; the adjuvant includes, but is not limited to, solvents, liquid diluents, solid diluents, emulsifiers, dispersants, defoamers, thickeners, binders, penetrants, preservatives, antifreeze agents, fillers, etc.

[0044] When the compound described in the present invention contains an acid moiety, the pesticidally acceptable salts include, but are not limited to, inorganic acid salts and organic acid salts, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid or toluenesulfonic acid, etc.; when the compound described in the present invention contains a basic moiety, the pesticidally acceptable salts include, but are not limited to, potassium salts, sodium salts, magnesium salts or ammonium salts, etc.

[0045] According to some embodiments of the present invention, the pesticidal composition is a bactericidal composition.

[0046] Preferably, the content of the active ingredient in the bactericidal composition is 1-99.9% by weight; more preferably 5-95% by weight.

[0047] On another aspect, the present invention provides the use of the compound of the present invention or a composition comprising the compound described in the present invention in agriculture.

[0048] On another aspect, the present invention provides the use of the compound of the present invention or a composition comprising the compound described in the present invention as a bactericide.

[0049] Preferably, the present invention provides the use of the compound of the present invention or a composition comprising the compound described in the present invention in controlling cucumber powdery mildew.

[0050] Preferably, the present invention provides the use of the compound of the present invention or a composition comprising the compound described in the present invention in controlling cucumber gray mold.

[0051] The compound described in the present invention can also be formulated into conventional formulations for actual use. Examples of formulations include solutions, wettable powders, emulsions, emulsifiable concentrates, suspensions, powders, water-dispersible granules, tablets, granules, microcapsules, etc. These formulations can be prepared by conventional methods in the art. For example, the active compound can be mixed with a pesticidally acceptable adjuvant, and the pesticidally acceptable adjuvant includes, but is not limited to, solvents, liquid diluents, solid diluents, emulsifiers, dispersants, defoamers, thickeners, binders, penetrants, preservatives, antifreeze agents, fillers, etc.

[0052] When in use, if necessary, commercially available formulations are diluted in a conventional manner. For example, when they are wettable powders, concentrated emulsions, suspensions, and granules suspended in water, water is used for dilution. Powders, granules for soil application, or solutions for broadcasting and spraying generally do not require further dilution with inert substances before use. Depending on changes in external conditions such as temperature, humidity, and the nature of the fungicides used, etc., the application rates of the active compounds are also different.

[0053] The compounds according to the invention can be used for controlling the following diseases: Oomycete diseases such as downy mildew, white rust, damping-off, Pythium rot, Phytophthora blight, late blight, etc.; Deuteromycete diseases such as Fusarium wilt, root rot, Rhizoctonia rot, anthracnose, Verticillium wilt, scab, gray mold, brown spot, black spot, Septoria leaf spot, early blight, ring spot, leaf blight, basal stem rot, and others; Basidiomycete diseases such as rust, smut, and others; Ascomycete diseases such as powdery mildew, sclerotinia, scab, etc.

[0054] The compounds according to the invention can be used for the following crops: Cereals (wheat, barley, rye, oats, rice, maize, sorghum, and related species); Sugar beet (sugar beet and fodder beet); Pome fruits, stone fruits, and soft fruits (apple, pear, plum, peach, almond, cherry, strawberry, raspberry, and blackberry); Leguminous plants (lentil, fava bean, pea, soybean); Oil crops (rape, mustard, olive, sunflower, coconut, castor oil plant, cocoa bean, peanut, or soybean); Cucurbitaceous plants (pumpkin, cucumber, melon); Fiber plants (cotton, flax, jute); Citrus fruits (orange, lemon, grapefruit, tangerine); Vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, red pepper); Lauraceous plants (avocado, Cinnamomum, camphor) or plants such as tobacco, nut, coffee, eggplant, sugar cane, tea, pepper, grapevine, hop, banana, and natural rubber plants, together with turf, ornamental, and forest plants such as flowers, shrubs, broad-leaved trees or evergreen trees such as conifers, and plant propagation materials.

[0055] The compounds according to the invention may also be mixed with other active substances such as insecticides, acaricides, herbicides, and fungicides, and can also be mixed with safeners, fertilizers, and / or plant growth regulators, thereby producing additional advantages and effects.

[0056] The compounds of the present invention are preferably used in combination with fungicides, which include but are not limited to, benzimidazoles: benomyl, carbendazim, fenfuram, thiabendazole, thiophanate-methyl, etc.; dicarboximides: ethirimol, iprodione, procymidone, vinclozolin, etc.; DMI-fungicides: imazalil, imidazole, blastricidin S, prochloraz, triflumizole, tridemorph, fenarimol, chlorobenzilate, fluobenzilate, difenoconazole, diniconazole, epoxiconazole, cyproconazole, hexaconazole, imibenconazole, tebuconazole, metconazole, flusilazole, difenoconazole, triadimefon, triadimenol, bitertanol, etaconazole, furconazole-cis, etc.; phenylamides: benalaxyl, ofurace, metalaxyl, metalaxyl-M, furathiocarb, etc.; amines: dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine, etc.; phosphorothioates: EDDP, isoprothiolane, pyrazophos, etc.; dithiolanes: isoprothiolane, etc.; carboxamides: carboxin, boscalid, oxycarboxin, fenfuram, flutolanil, furametpyr, fenfuram, oxycarboxin, pyraclostrobin, thifluzamide, etc.; hydroxy-(2-amino)pyrimidines: ethirimol, dimethirimol, ethirimol, etc.; AP fungicides (anilinopyrimidines): cyprodinil, mepanipyrim, pyrimethanil, etc.; N-phenylcarbamates: diethofencarb, etc.; QoI-fungicides (Qo inhibitors): azoxystrobin, picoxystrobin, pyraclostrobin, kresoxim-methyl, trifloxystrobin, enestroburin, metominostrobin, orysastrobin, famoxadone, fluoxastrobin, fenamidone, metominostrobin, etc.; PP fungicides (phenylpyrroles): fenpiclonil, fludioxonil, etc.; quinolines: quinoxyfen, etc.; AH fungicides (aromatic hydrocarbons): biphenyl, chloroneb, chlorothalonil, quintozene, tecnazene, tolclofos-methyl, etc.; MBI-R: tecnazene, pyroquilon, tricyclazole, etc.; MBI-D: carpropamid, diclocymet, cymoxanil, etc.; SBI agents: fenhexamid, pyributicarb, terbinafine, etc.; phenylureas: dimefuron, etc.; QiI-fungicides (Qi inhibitors): cyazofamid, etc.; benzamides: zoxamide, etc.; enolpyranosides: blasticidin S, validamycin, etc.; hexopyranosides: kasugamycin, etc.; glucopyranosides: streptomycin, jinggangmycin, etc.; cyanoacetamides: cymoxanil, etc.; carbamates: milbemectin, propamocarb, thiocarb, zineb, etc.; deconjugators: binapacryl, dinocap, fenoxanil, fluazinam, etc.; organotin compounds: triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide, etc.; phosphates: phosphorous acid, tolclofos-methyl, phosphorous acid, etc.; phthalimides: blasticidin S, etc.; benzotriazines: imazalil, etc.; benzenesulfonamides: sulfafamide, etc.; pyridazinones: pyridazinone, etc.; fungicides (carboxamides): dimethomorph, flumorph, benthiavalicarb, mancozeb, mandipropamid, etc.; tetracyclines: oxytetracycline, etc.; thiocarbamates: thiocarb, etc.;Other compounds: edifenphos, polyoxin, oxolinic acid, hydroxyisoxazole, octhilinone, silthiofam, diflufenican, S-methyl benzenesulfonothioate, probenzazole, tiadinil, thiazoleamine, cyflufenamid, propoxyquinoline, metrafenone, fluopicolide, copper hydroxide, organic copper, sulfur, ferric dimethyldithiocarbamate, mancozeb, maneb, metiram, propineb, thiram, zineb, zinc dimethyldithiocarbamate, captan, captafol, dichlofluanid, anilazine, dodine, guanidine salts, guazatine acetate, guazatine dodecylbenzenesulfonate, anilide, dithianon, chloropicrin, dazomet, metam-sodium, dimethomorph, silthiofam, agrobacterium, isoxaben, etc.; Detailed implementation mode

[0057] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, various raw materials used are commercially available or can be prepared by conventional methods in the art. The following examples are not all of the present invention, and other examples obtained by those of ordinary skill in the art without creative efforts belong to the protection scope of the present invention.

[0058] Example 1 (5-chloro-2-methoxy-4-methylpyridin-3-yl)(6-((3-chloro-5-(trifluoromethyl)benzyl)oxy)pyridin-2-yl)methanone

[0059]

[0060] (a) 2-(6-Hydroxypyridin-2-yl)acetonitrile (134 mg, 1 mmol), 1-(bromomethyl)-3-chloro-5-(trifluoromethyl)benzene (273.5 mg, 1 mmol), and silver carbonate (27.6 mg, 1 mmol) were added to toluene (30 mL). The mixture was stirred at 60 °C overnight, cooled and filtered, and then concentrated under reduced pressure; column chromatography separation (eluent: petroleum ether / ethyl acetate (v / v) = 20 / 1) gave 2-(6-((3-chloro-5-(trifluoromethyl)benzyl)oxy)pyridin-2-yl)acetonitrile as a yellow solid (13 mg).

[0061] (b) To a solution of 2-(6-((3-chloro-5-(trifluoromethyl)benzyl)oxy)pyridin-2-yl)acetonitrile (65.34 mg, 0.2 mmol) in anhydrous DMF (5 mL) under nitrogen protection, potassium tert-butoxide (246.8 mg, 2.2 mmol) was added. After stirring for 30 minutes, 3-bromo-5-chloro-2-methoxy-4-methylpyridine (47.3 mg, 0.2 mmol) was added, and the reaction was carried out overnight at room temperature. The reaction was quenched at low temperature, extracted with ethyl acetate (10 mL), dried over anhydrous magnesium sulfate, and 2-(5-chloro-2-methoxy-4-methylpyridin-3-yl)-2-(6-((3-chloro-5-(trifluoromethyl)benzyl)oxy)pyridin-2-yl)acetonitrile was obtained as a yellow solid (21 mg).

[0062] (c) 2-(5-Chloro-2-methoxy-4-methylpyridin-3-yl)-2-(6-((3-chloro-5-(trifluoromethyl)benzyl)oxy)pyridin-2-yl)acetonitrile (1447 mg, 3 mmol) and dimethyl sulfoxide (30 mL) were added to a flask, and then an aqueous solution of potassium carbonate (1.00 g, 7.2 mmol) in water (2 mL) was added. The mixture was stirred overnight at room temperature, added to ice water (100 mL), extracted with ether (30 mL), the organic phase was washed with water (20 mL), dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. After column chromatography separation (eluent: dichloromethane / hexane (v / v) = 20 / 1), a light yellow solid (471 mg) was obtained.

[0063] MS-ESI: m / z 471.1 [M+H] + ;

[0064] 1 1H NMR (500 MHz, CDCl3) δ 8.11 (t, J = 15.0 Hz, 1H), 7.87 (s, 1H), 7.62 (t, J = 3.0 Hz, 1H), 7.46 (t, J = 2.9 Hz, 1H), 7.35 (dd, J = 15.0, 3.1 Hz, 1H), 7.13 (t, J = 3.0 Hz, 1H), 7.09 (dd, J = 15.0, 3.1 Hz, 1H), 5.21 (s, 2H), 4.17 (s, 3H), 2.43 (s, 3H).

[0065] Example 2 (5-Chloro-2-methoxy-4-methylpyridin-3-yl)(6-((3,5-dichlorobenzyl)oxy)pyridin-2-yl)methanone

[0066]

[0067] Referring to the preparation method of Reference Example 1, the difference is only that 1-(bromomethyl)-3-chloro-5-(trifluoromethyl)benzene is replaced by 1-(bromomethyl)-3,5-dichlorobenzene to obtain 2-(6-((3,5-dichlorobenzyl)oxy)pyridin-2-yl)acetonitrile, and further the compound of Example 2 is a yellow solid.

[0068] MS-ESI: m / z 437.1 [M+H] + ;

[0069] 1 1H NMR (500 MHz, CDCl3) δ 8.06 (t, J = 15.0 Hz, 1H), 7.75 (s, 1H), 7.56 (t, J = 3.0 Hz, 1H), 7.34 (d, J = 3.0 Hz, 2H), 7.28 (dd, J = 15.0, 3.1 Hz, 1H), 7.04 (dd, J = 15.0, 3.1 Hz, 1H), 5.20 (s, 2H), 4.18 (s, 3H), 2.45 (s, 3H).

[0070] Example 3 (6-((3-bromo-6-methoxy-2-methylbenzyl)oxy)pyridin-2-yl)(5-chloro-2-methoxy-4-methylpyridin-3-yl)methanone

[0071]

[0072] Referring to the preparation method of Reference Example 1, the difference is only that 1-(bromomethyl)-3-chloro-5-(trifluoromethyl)benzene is replaced by 1-bromo-3-(bromomethyl)-4-methoxy-2-methylbenzene to obtain 2-(6-((3-bromo-6-methoxy-2-methylbenzyl)oxy)pyridin-2-yl)acetonitrile, and further the compound of Example 3 is a yellow solid.

[0073] MS-ESI: m / z 491.1 [M+H] + ;

[0074] 1 1H NMR (500 MHz, CDCl3) δ 8.03 (t, J = 15.0 Hz, 1H), 7.69 (s, 1H), 7.47 (d, J = 15.0 Hz, 1H), 7.30 (dd, J = 15.0, 3.1 Hz, 1H), 7.23 (d, J = 14.8 Hz, 1H), 7.04 (dd, J = 15.0, 3.1 Hz, 1H), 5.16 (s, 2H), 4.21 (s, 3H), 3.72 (s, 3H), 2.52 (s, 3H), 2.45 (s, 3H).

[0075] Example 4 (5-chloro-2-methoxy-4-methylpyridin-3-yl)(6-((2,3,5,6-tetrafluoro-4-methoxybenzyl)oxy)pyridin-2-yl)methanone

[0076]

[0077] Referring to the preparation method of Reference Example 1, except that 1-(bromomethyl)-3-chloro-5-(trifluoromethyl)benzene was replaced with 1-(bromomethyl)-2,3,5,6-tetrafluoro-4-methoxybenzene, 2-(6-((2,3,5,6-tetrafluoro-4-methoxybenzyl)oxy)pyridin-2-yl)acetonitrile was obtained, and further the compound of Example 4 was obtained as a yellow solid.

[0078] MS-ESI: m / z 471.1 [M+H] + ;

[0079] 1 1H NMR (500 MHz, CDCl3) δ 8.05 (t, J = 15.0 Hz, 1H), 7.77 (s, 1H), 7.30 (dd, J = 15.0, 3.1 Hz, 1H), 7.04 (dd, J = 15.0, 3.1 Hz, 1H), 5.17 (s, 2H), 4.23 (s, 3H), 3.92 (s, 3H), 2.47 (s, 3H).

[0080] Fungicidal activity test

[0081] The compounds of Examples 1-4 of the present invention were dissolved in DMF to prepare 1% EC for standby. Using the in-vivo potted plant method, the fungicidal activities of the compounds of Examples 1-4 of the present invention against Sphaerotheca fuliginea and Botrytis cinerea on cucumbers at 500 ppm were evaluated.

[0082] Test method for Sphaerotheca fuliginea: Select cucumber seedlings at the true leaf stage with consistent growth. After spraying treatment, dry in the shade for 24 h. Wash and collect fresh spores on cucumber leaves covered with Sphaerotheca fuliginea, filter with double-layer gauze, and prepare a suspension with a spore concentration of about 100,000 / ml for spray inoculation. The inoculated test materials were transferred into an artificial climate chamber, with the relative humidity maintained between 60-70% and the temperature maintained at 21-23 °C. After about 10 days, the disease grading investigation was carried out according to the disease situation of the blank control, and the control effect was calculated according to the disease index.

[0083] Grading standard:

[0084] Grade 0: Disease-free;

[0085] Grade 1: The diseased area accounts for less than 5% of the entire leaf area;

[0086] Level 3: The area of the lesion accounts for 5 - 15% of the area of the whole leaf;

[0087] Level 5: The area of the lesion accounts for 15 - 25% of the area of the whole leaf;

[0088] Level 7: The area of the lesion accounts for 25 - 50% of the area of the whole leaf;

[0089] Level 9: The area of the lesion accounts for 50 - 75% of the area of the whole leaf;

[0090] Level 11: The area of the lesion accounts for more than 75% of the area of the whole leaf.

[0091] Calculation method:

[0092]

[0093] Testing method for Botrytis cinerea of cucumber: The leaf inoculation method is adopted. Select two potted cucumber seedlings with the same growth vigor at the true leaf stage. After the medicament spray dries, inoculate the inoculation cake on the leaf. After moisturizing in the dark at 24 - 26°C for 24 h, restore natural light and moisturize and culture for about 3 d. After the control is fully diseased, use a caliper to measure the diameter (mm) of the lesion at each inoculation point, and calculate the control effect.

[0094] Calculation method:

[0095] Control effect = [(control lesion diameter - treated lesion diameter) / control lesion diameter] * 100%

[0096] The test results show that the compounds of Examples 1 - 4 of the present invention have bactericidal activities against Sphaerotheca fuliginea of cucumber of 100%, 95%, 90% and 100% respectively at 500 ppm; and have bactericidal activities against Botrytis cinerea of cucumber of 85%, 80%, 80% and 90% respectively at 500 ppm. And during the use of the compounds of the present invention, no phytotoxicity was caused to the crops. The compounds of the present invention have great promotion value.

[0097] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A compound of formula (I) or a pesticidally acceptable salt thereof: Wherein: R 1 、R 2 、R 3 、R 4 and R 5 each independently represents hydrogen, halogen, C 1-6 alkyl, halo-C 1-6 alkyl, C 1-6 alkoxy, halo-C 1-6 alkoxy; X is a halogen; Y is C 1-6 alkyl or halo-C 1-6 alkyl; Z is C 1-6 alkoxy or halo C 1-6 alkoxy.

2. The compound according to claim 1, wherein: R 1 、 R 2 、 R 3 、 R 4 and R 5 each independently represents hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy.

3. The compound according to claim 2, wherein: R 1 、 R 2 、 R 3 、 R 4 and R 5 each independently is hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy.

4. The compound according to claim 3, wherein: R 1 is hydrogen, fluorine or methyl; R 2 is fluorine, chlorine or bromine; R 3 is hydrogen or methoxy; R 4 is hydrogen, fluorine, chlorine or trifluoromethyl; R 5 is hydrogen, fluorine or methoxy.

5. The compound according to claim 1, wherein: X is a halogen; Y is C 1-4 alkyl or halo C 1-4 alkyl; Z is C 1-4 alkoxy or halo C 1-4 alkoxy.

6. The compound according to claim 5, wherein: X is chlorine or bromine; Y is methyl; Z is methoxy.

7. The compound according to any one of claims 1-6, wherein the compound of formula (I) is selected from the following compounds or a pesticidally acceptable salt thereof: Or 8. A pesticidal composition comprising the compound according to any one of claims 1-7 or a pesticidally acceptable salt thereof; further optionally comprising a pesticidally acceptable adjuvant; the pesticidal composition is a bactericidal composition.

9. Use of the compound according to any one of claims 1-7 or the pesticidal composition according to claim 8 in the preparation of a bactericide; wherein, The fungicide is used for preventing and controlling Sphaerotheca fuliginea and / or Botrytis cinerea on cucumbers.

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