TW200306154A - Novel oxime O-ether compound, production process, and agricultural or horticultural bactericide - Google Patents

Abstract

This invention relates to a novel oxime O-ether compound represented by the following formula [I]; a process for producing the compound, a novel intermediate thereof; and an agricultural or horticultural bactericide containing the compound as an active ingredient.

Description

200306154 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a novel oxime o-ether compound, a method for producing the same, and an agricultural fungicide using the compound as an active ingredient. [Prior art] In the cultivation of agricultural and horticultural materials, many control agents are used for crop diseases. However, due to insufficient control effectiveness, the use of pathogen-resistant pathogens has limited their use or caused plant diseases. Hazards and pollution, or strong toxicity to humans, animals and fish, are difficult to be called as control medicines that must be satisfying. Therefore, there is a strong demand for the appearance of such medicaments which have few disadvantages and are safe to use. Compounds related to the compounds of the present invention include compounds having insecticidal and acaricidal activity, for example, in EP4754, EP24888, and W093 / 21 157. In Japanese Patent Application Laid-Open No. 9-3047, it is described that an I-O-ether compound containing a compound other than the following structural formula can be used as a fungicide. 〇CH3

h3c Furthermore, in wo 0 1/3 4 5 68, the oxime O-ether compound having a pyridyl group having a fluorine atom at the 4th position which can be used as a fungicide is shown in Table 1 ', but it is not described Their manufacturing examples, biological test examples. (2) (2) 200306154 [Disclosure of the invention] The present invention is to provide a novel oxime for agricultural and horticultural fungicides that can be advantageously synthesized industrially and can be used effectively, and has less phytotoxicity. O-ether compounds are used for this purpose. The present inventors have found that in the following formula [I], the oxime ether compound substituted with a fluorine atom at the 4th position of the pyridine moiety is a more well-known compound and has a particularly excellent control effect on agricultural and horticultural diseases, and has completed the present invention. That is, the present invention is an oxime o-ether compound represented by formula [I] or a salt thereof.

(In the formula, R1 represents a Cw alkyl group, a C2 to 6 alkenyl group, a C2 to 6 alkynyl group, a C3 to 6¾ group group, a Ci to 6 group oxygen group, a Cl to 6 group thio group, an amine group, a mono or mono-Cl group 6 amines, Cl ～ 6 ore oxy, Cl ～ 6 oxy Cl ～ 6 oxo, Cl ～ 6 oxy Ci ～ 6 alkoxy, nitro, cyano, hydroxyl or halogen atom An integer from 0 to 3, when m is 2 or more, R1 may be the same or different. R2, R3 are the same or different and represent a hydrogen atom, Cl ~ 6 alkyl. R is a table of Cl ~ 6, and C3 ~ 6 ring courtyard, C2 ~ 6 alkyl, C2 ~ 6 alkynyl, Ci ~ 6 courtyard_base, C; i ~ 6 courtyard oxygen Cl ~ 6 courtyard, Cl ~ 6 courtyard oxygen Cl ~ 6 courtyard oxygen, C2 ~ 6 alkenyloxy, c2 ~ 6 alkynyloxy, Ci ~ 6 alkoxyl, C6 oxocarbonyloxy, mono- or diCl ~ 6 alkylaminomethyloxy, Ci ~ 6 alkylsulfonyloxy Group, Ch haloalkanesulfonyloxy group, Ci ~ 6 haloalkyl group, Cl ~ 6 alkylthio group, amine group (3) (3) 200306154, Zirconium or mono Cm alkylamino group, (^ alkylcarbonylamino group, Hydroxy or halogen atom, η is an integer representing 0 to 5, when ^ is 2 or more, R4 may be the same or different, and two R4 are used to form an alkylene chain containing a hetero atom and form 5 to 7 members condensation Ring, its manufacturing method, novel manufacturing intermediates, and agricultural fungicides containing one or two or more kinds of shoE 0-ether compounds or salts thereof as active ingredients. [Embodiment] Weiming's implementation form is In the present invention, R1 is methyl, ethyl, propyl, isopropyl, butyl, second butyl, isobutyl, third butyl, pentyl and its isomers, hexyl and its isomers C1-6, C2-6 alkenyl groups such as vinyl, propenyl, isopropenyl, etc. C2-6 alkenyl groups such as ethenyl, allyl, cyclopropyl, cyclopentyl, 1-methyl C3 ~ 6 cycloalkyl, which may also have a substituent, such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, Ci-6 alkoxy groups such as second butoxy, isobutoxy, and third butoxy groups, methyl-6, methylthio, ethylthio, isopropylthio, butylthio, etc. alkyl-6 groups, amino groups , Methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylisopropylamino, etc. mono- or di-Cb6 alkylamino groups, ethoxyl , Propionyloxy, Ci-6-methoxy, such as pentyloxy, -8-(4) (4) 200306154 Ci-6, methoxymethyl, methoxyethyl, ethoxyfluorenyl, propoxymethyl, butoxymethyl ', etc. Ci-6 Ci radical, Ci ~ 6alkoxyalkoxy, nitro, cyano, methoxymethoxy, ethoxyethoxy, ethoxymethoxy, propoxyfluorenyl, butoxymethoxy, etc. , Hydroxy, or halogen atom of fluorine, chlorine, bromine, iodine, etc. When π is an integer from 0 to 3, and m is 2 or more, R1 can be the same or different. · R2, R3 are the same or different C of hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, second butyl, isobutyl, third butyl, pentyl and its isomers, hexyl and its isomers, etc. 1. .6 courtyards. R4 is C representing methyl, ethyl, propyl, isopropyl, butyl, second butyl, isobutyl, third butyl, pentyl and its isomers, hexyl and its isomers, etc. ^ C4 ~ 6 cycloalkyl, alkyl, cyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, etc., vinyl, propenyl, isopropenyl, etc. C2 ~ 6 alkenyl, ethynyl, propynyl, etc. c2 ~ 6 alkynyl, fluorenyl, ethoxy, propoxy, isopropoxy, butoxy, second butoxy, isobutyl (^ ~ 6 alkoxy, methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, butoxymethyl, etc.) Cl ~ 6 oxygen ~ 6 yuan, Cb6 alkoxy Ci, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, propoxymethoxy-9- (5) (5) 200306154, butoxymethoxy, etc. ~ 6 alkoxy, 'C 2 alkenyloxy such as vinyloxy, propyleneoxy, isopropenyloxy, C2 ~ 6 alkynyloxy such as ethynyloxy, propynyloxy, ethoxyl, propionyl Ch6 alkylcarbonyloxy groups such as methoxy, pivaloyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxy Etc. Ci ~ 6 alkoxycarbonyloxy, _ methylamine formyloxy, dimethylamine formyloxy, ethylamine formyloxy, third butylaminoformyloxy, etc. Di Ciw alkylaminomethaneoxy, methanesulfonyloxy, ethanesulfonyloxy, etc. Ci-6 alkylsulfonyloxy, chloromethanesulfonyloxy, fluoromethanesulfonyloxy, trifluoromethanesulfonyl Cb6 haloalkanesulfonyloxy, such as methoxy, chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, Ci ~ 6 haloalkyl groups such as tribromomethyl, trichloroethyl, trifluoroethyl, pentafluoroethyl, etc. Ci alkylthio groups such as methylthio, ethylthio, isopropylthio, and amines Groups, methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylisopropylamino, etc., mono or di Ci ~ 6 alkylamino groups, ethyl Ci alkylcarbonylamino groups such as fluorenylamino, propylamino, and pentamidine, -10- (6) 200306154 hydroxyl atom or halogen atom of fluorine, chlorine, bromine, iodine, etc., ni is an integer of 0 ~ 3 When 111 is 2 or more, R1 can be interrelated or different, and two R4 can be methyldioxy The alkylene group containing hetero atom of the chain and form a condensed ring of 5-7.

Among the compounds of the present invention, compounds in which R1 is a Cl-6 alkyl group or a halogen atom, and R4 is a CN6 alkyl group, a CN6 alkoxy group, or a halogen atom are preferable, and a compound in which R1 is substituted at the 6th position is particularly preferable. The compound of the present invention can be produced by the following processes.

(In the formula, 'R, R, R3, R4, m, and η represent the same meanings as above.' The compound represented by formula [I] is a compound represented by formula [11] and formula [III]. The compound or its salt is obtained in a solvent-free, preferably solvent, and stirred at a reaction temperature of 0 to 15 ° C for 10 minutes to 24 hours. Examples of usable solvents include alcohols such as ethanol, methanol, ethers such as diethyl ether, tetrahydrofuran, and dioxane, cellosolvents such as methyl cellosolve, ethyl cellosolve, and benzene, toluene, and the like. Aromatic hydrocarbons, acetic acid, water, N, N-monomethylformamide, monomethylimine, etc. These solvents can be used singly or in the form of one or more mixed solvents with various mixing ratios of -11-(7) 200306154. Although this reaction is not necessarily in the presence of a catalyst ', the reaction can be significantly promoted if an acid or a base is added. Examples of the acid include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as p-toluenesulfonic acid, and examples of the base include sodium acetate. The compound represented by the formula [π] as a starting material of the compound of the present invention can be

(In the formula, R1 and m have the same meanings as above.)

It can be obtained by making the compound represented by formula [IV] or its salt in a solvent-free, preferably a solvent, in the presence of a suitable oxidant, and stirring at a reaction temperature of 0 to 150 t for 10 minutes to 24 hours. Solvents that can be used include two

Ethers such as diethyl ether, tetrahydrofuran, and dioxane; esters such as methyl acetate and ethyl acetate; aromatic hydrocarbons such as benzene and toluene; 'water acetic acid; N, N-dimethylformamide; Methyl Yashuo et al. These solvents may be used singly or in a mixture of two or more kinds of various mixing ratios. Examples of usable oxidizing agents include metal oxides such as dioxide and halogen oxides such as sodium hypochlorite and the like. Oxyamines represented by the formula [III] can be manufactured as follows.

NH0〇- [HI] 〇 (R) n -12-(8) 200306154 (wherein 'R2, R3, R4 and n have the same meanings as above. L is a halogen atom representing chlorine, bromine, iodine, etc. (Leaving groups such as methylsulfonyloxy, p-toluenesulfonyloxy and the like) By reacting the compound represented by the formula (V) in the presence of a base such as triethylamine, with N-hydroxyphthalimide, By converting to a compound represented by the formula [VI], and then acting with hydrazine, benzyloxyamines represented by the formula [III] can be produced. Among the compounds represented by the formula [V], the compounds represented by the formula [V-1] wherein R2 and r3 are hydrogen atoms and L is a halogen atom can be produced by the following treatment.

(rV Η tv-1] (R4) n. Halogenating agent Η [VII] (where R4 and η have the same meanings as above, and L1 is a halogen atom representing chlorine, bromine, iodine, etc.)

That is, the compound represented by the formula [VII] is irradiated with N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), and N-iodosuccinimide through light irradiation. The reaction of halogenated succinimine imine (NIS) and the like can synthesize a compound represented by the formula {V-1]. Furthermore, a compound having a halomethyl group represented by the formula [V-1] can also be synthesized by the following treatment. (R4) m P reducing agent (R) n

Halogenating agent Η or sulfonium halide 〇Η —— (r4) 『'0- Η [IX] Η Η [Vl] -13- 200306154 〇) (where R4, n, and L have the same meanings as above) W In order to represent a halogen atom, a hydroxyl group, a hydrogen atom, or a lower alkoxy group such as chlorine), that is, by appropriately reducing the compound represented by the formula [VII] with LiAlH4, NaBH4, and the like, the reaction can be obtained as After the compound shown, then use a halogenating agent such as thionyl chloride to replace the hydroxyl group with a halogen atom, or react with a sulfonyl halide such as sulfanylsulfonyl chloride to convert it to oxysulfanyl group, then

A compound represented by the formula [V-1] can be produced. Among the compounds represented by the formula [V], compounds represented by the formula [V-2] wherein R2 and / or R3 are (^ -6 alkyl, C3-6 cycloalkyl, or haloalkyl can be synthesized by the following method.

[X] R3-Mg-L2 [XI] [XU] Halogenating agent

[V-2] (in the formula, 112, ^ 4, 11 and 1 ^ represent the same meaning as above; L2 is a leaving group representing a halogen atom such as chlorine, bromine, iodine, etc.) The ketones or aldehydes represented by the formula [X] are reacted with the Grignard reagent shown by the formula [XI] to obtain alcohols represented by the formula [XI], and a halogenating agent such as thionyl chloride is used. The compound represented by the formula [V-2] can be produced by converting a hydroxyl group into a halogen atom, or a sulfonium halide such as formazan sulfonium chloride, and converting it into an oxysulfonyl group. The salt of the compound represented by the formula [1] can be obtained by reacting the compound represented by the formula [I] with an inorganic or organic acid in a suitable solvent. After the completion of the reaction, the object can be obtained by performing a normal post-treatment. The oxime moiety of the compound of the present invention is present in isomers, and these isomers are included in the scope of the present invention. The structure of the compound of the present invention is determined by NMR, mass spectrometry, and the like. Best Mode for Carrying Out the Invention The present invention will be described more specifically with reference to examples. Example 1 _ Production of 4- (6-6-methyl-2-methylsulfonyl) residue 0-[(2'6-Dimethoxybenzyl (methyl) oxime (Compound No. 72) i) Production of 2,6-dimethoxybenzyloxyamine

8.9 g (52.97 mmol) of 2,6-dimethoxybenzyl alcohol and 5.88 g (52.97 mmol) of pyridine were dissolved in 100 ml of benzene 'and 6.9 3 was added to this solution at room temperature. G (5 8.2 6 mmol) of thionyl chloride. After stirring at room temperature for 1.5 hours, the organic layer of the reaction solution was treated with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude product of 2'6-dimethoxybenzyl chloride. -15- (11) 200306154 On the other hand, 8.63 g (52.97 mmol) of N-hydroxyphthaliminoimide was dissolved in 90 ml of N, N-dimethylformamide. In this solution, at room temperature, the entire amount of the crude 2,6-dimethoxybenzyl chloride previously prepared and 5.88 g (58.26 mmol) of triethylamine were sequentially added. The temperature was raised to 70 ° C, and after stirring for 5 hours, it was cooled to room temperature, 100 ml of water was added, and the precipitate was filtered to obtain 12.80 g.

12.80 g (40.89 mmol) of n_ (2,6-dimethoxybenzyloxy) phthalimide was dissolved in 60 ml of methanol. To this solution was added 2.45 g (49.06 mmol) of hydrazine-hydrate at room temperature. After stirring at the same temperature for 6 hours, it was concentrated under reduced pressure. When water and ethyl acetate were sequentially added, insoluble matters were precipitated, so they were filtered off and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 6.0 1 g of the target substance. ii) Production of 4-fluoro-6-methyl-2pyridinecarboxyaldehyde 0-[(2,6-dimethoxyphenyl) methyl] oxime

0.12 g (0.86 mmol) of 4-fluoro-6-methyl-2-D-pyridinecarboxaldehyde was dissolved in 3 ml of acetic acid, and 0.17 g (0.94 mmol) was added at room temperature. Ear) 2,6-dimethoxybenzyloxyamine and stirred for 1 hour. An aqueous sodium carbonate solution was added to the reaction mixture for neutralization. It was extracted with ethyl acetate, and the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. -16- (12) (12) 200306154 This material is concentrated under reduced pressure, and the obtained crude product is purified by silica gel column chromatography (eluent; Kojima: ethyl acetate = 7: 3 (v / V), 0.17 g of the target substance was obtained. Melting point 1 0 1 ~ 1 0 5 t Example 2 Fluoro-6-methyl-2-D is more specific than B fixed residues 〇- [(2-methoxy-6- Production of methylphenyl) methyl] oxime (Compound No. 6 2) i) Production of 2-methoxy-6-methylbenzyloxyamine

1.37 g (9.01 mmol) of 2-methoxymethylbenzyl alcohol and 0.85 g (10.81 mmol) of pyridine were dissolved in 18 ml of benzene, and 1.28 was added to this solution at room temperature. G (10.8 1 mmol) of thionyl chloride. After stirring at room temperature for 1.5 hours, the reaction solution was treated with water, and the organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude product of 2-methoxy-6-methylbenzyl chloride. On the other hand, 1.46 g (9.01 mmol) of N-hydroxyphthalocyanine (13) 200306154 imine was dissolved in 18 ml of N, N-dimethylformamide. In this solution, at room temperature, the previously prepared crude product of 2-methoxy-6-methylbenzyl chloride, whole amidine and ^ 00 g (9.91 mmol) of triethylamine were sequentially added. The temperature was raised to 70 ° C until 'stirred for 5 hours, and then cooled to room temperature' and 20 ml of water was added. The Shen Dianwu was filtered to obtain 2.1 g. 2.10 g (7.07 mmol) of N- (2-fluorenyl-6-methylbenzyloxy) phthalimide was dissolved in 20 ml of methanol. To this solution was added 0.46 g (9.19 mmol) of hydrazone-hydrate at room temperature. After stirring at the same temperature for 6 hours, it was concentrated under reduced pressure. If water and ethyl acetate are sequentially added, a soluble substance is precipitated, so it is filtered off and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain the target product 1. 1 8 g. ii) Manufacture of 4-fluoro-6-methyl-2-pyridinylcarboxaldehyde 0-[(2-methoxy-6-phenyl) methyl] oxime

0.25 g (1.79 mmol) of 4-fluoro-6-methyl-2-pyridinecarboxylate was dissolved in 3 ml of acetic acid, and 0.20 g (20 mmol) was added at room temperature. ) Of 2-methoxy-6-methylbenzyloxyamine 'and stirred for 1 hour. An aqueous sodium carbonate solution was added to the reaction mixture for neutralization. It was extracted with ethyl acetate, and the organic layer was washed with saturated brine 'and dried over anhydrous magnesium sulfate. This material was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column layer-18- (14) (14) 200306154 (eluent, hexane: ethyl acetate = 7: 3 (V / V)), To obtain the target substance 0.17 g.

Melting points 4 4 to 4 6 ° C include the above examples, and representative examples of the compounds of the present invention are shown in Table 1.

-19- (15) 200306154 Table 1 F r1 r2

R3 Compound Number (R1) m (; ΐ) R2 R3 r1 r2 r3 r4 r5

Physical constant Lmp; " CJ 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1 -9 1-10 1-11 1-12 1 -13 1-14 1 -15 1-16 1-17 1-18 1-19 1-20 1-21 1-22 1-23 1-24 1-25 1-26 1-27 1-28 1-29 1-30 1-31 1-32 1-33 1-34 1-35 1-36 Η 3-CH3 5-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6 -CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6_CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6- CH3 6-C2H5 6-C3H7 6-CH (CH3) 2 6-cycloPr 3-OCH3 5-OCH,

H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

〇ch3 och3 0CH3 ch3 HH OCH3 HH CH2〇CH3 och2〇ch3 OCH2CH = CH2 och2c = ch OCOCH3 OCOOCH3 OCONHCH3 〇cOn (ch3) 2 〇so2ch3 0 s〇2〇f 3 cf3 sch3 nhCHCH3NH (NH3) OH FHH 3 3 3 3 3 3 I Η Η Η Η Η H ccccccc 000000

H H H H CH3 H H OCH3 H H H H H H H H H H H H H H H H H H F H H H H H H

H H H H H CH3 H H OCH3 H H H H H H H H H H H H H H H H H F H H H H H H

H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

H H H H

H H H H H H H H H H H H H H

H H H H H H H H H H H H

-20- (16) 200306154 Compound (R1) m (Note) R2 R3 rl r2 r3 r4 r5 Physical constant No. L_ 广 Cj

1-37 6-〇CH3 HH 1-38 6-OCH2CH3 HH 1-39 6-〇CH (CH3) 2 HH 1-40 6-SCH3 HH 1-41 6-NH2 HH 1-42 6-NHCH3 HH 1- 43 6-N (CH3) 2 HH 1-44 6-0CH20CH3 HH 1-45 6-〇C〇CH3 HH 1-46 6-CF3 HH 1-47 6-〇HHH 1-48 3-FHH 1-49 5 -FHH 1-50 6-FHH 1-51 3-CI HH 1-52 5-Cl HH 1-53 6-Cl HH 1-54 6-Br HH 1-55 6-1 HH 1-56 HHH 1-57 3-CH3 HH 1-58 5-〇H3 HH 1-59 6-CH3 HH 1-60 6-CH3 HH 1-61 6-CH3 HH 1-62 6-CH3 HH 1-63 6 ~ CH3 HH 1-64 6-CH3 HH 1-65 6-CH3 HH 1-66 6-CH3 HH 1-67 6-CH3 HH 1-68 6-CH3 HH 1-69 6-CH3 HH 1-70 6-CH3 HH 1-71 6 -CH3 HH 1-72 6-CH3 HH 1-73 6-CH3 HH 1 -74 6-CH3 HH 1-75 6-CH3 HH 1-76 6-CH3 HH 1-77 6-CH3 HH 1-78 6- CH3 HH 1 -79 6-CH3 HH OCH3 0ch3 0ch3 0ch3 0ch3 0ch3 0ch3 0ch3 0ch3 0ch3 0ch3 0ch3 och3 0ch3 0ch3 0ch3 0ch3 OchHHHHHH3 cccccccccccccccccccccc

3 3 3 Η Η HHHHHHHHHHHHHHHHHHHHH HHHHHHHHHHHHHHHHHHHHH HHHHHHHHHHHHHHHHHHHHH HHHHHHHHHHHHHHHHH 〇ch3 〇ch3 HHH HHH 〇ch3 ch3 HHHH ch3 HHHH ch3 HHHH ch3 · HHH CH2CH5 HHH C3H7 HHH CH (CH3) 2 HHH cycloPr HHHC three CH HHH ch = ch2 〇ch3 〇ch3 HHHH HHHH OCH, 丨 HHHH OCH3 HHH ch2〇ch3 HHH och2och3 HHH 〇CH2CH diCH: HHH och2cech HHH OCOCH3 HHH OCOOCH3 HHH OCONHCH, 101-105 44-46 -21-(17) 200306154 Compound No. (R1) 3 (Note) rl r2 r3 r4 r5 1-80 6-CH3 Η Η OCH3 HHH OCON (CH3); 1-81 6-CH3 Η Η OCH3 HHH 〇s〇2ch3 1-82 6-CH3 Η Η OCH3 HHH OSO2CF3 1-83 6- CH3 Η Η OCH3 HHH cf3 1-84 6-CH3 Η Η OCH3 HHH nh2 1-85 6-CH3 Η Η OCH3 HHH NHCH3 1-86 6-CH3 Η Η OCH3 HHHN (CH3) 2 1-87 6-CH3 Η Η Η OCH3 HHH NHCOCH3 1-88 6-CH3 Η Η OCH3 HHH sch3 1-89 6-CH3 Η Η OCH3 OH HHH 1-90 6-CH3 Η Η OCH3 H OH HH 1-91 6-CH3 Η Η OCH3 HH OH H 1-92 6-CH3 Η Η OCH3 HHH OH 1-93 6-CH3 Η Η OCH3 FHHH 1-94 6-CH3 Η Η OCH3 HFHH 1- 95 6-CH3 Η Η OCH3 HHFH 1-96 6-CH3 Η Η OCH3 HHHF 1-97 6-CH3 Η Η OCH3 HHH Cl 1-98 6-CH3 Η Η OCH3 HHH Br 1-99 6-CH3 Η Η OCH3 HHHI 1-100 6-CH3 Η Η 〇C2H5 HHH ch3 1-101 6-CH3 Η Η 〇c2h5 HHHF 1-102 6-CH3 Η ch2〇ch3 HHH ch3 1-103 6-CH3 Η ch2〇gh3 HHHF 1- 104 6-CH3 Η 〇 〇ch2〇ch3 HHH ch3 1-105 6-CH3 Η Η 〇〇h2〇ch3 HHHF 1-106 6-CH3 Η Η OCOCH3 HHH ch3 1-107 6-CH3 Η Η OCOCH3 HHHF 1 -108 6-CH3 Η CH OCH2CH = CH2 HHH ch3 1-109 6-CH3 Η Η 〇ch2ch two ch2 HHHF 1-110 6-CH3 Η Η och2c = ch HHH ch3 1-111 6-CH3 Η Η och2c = ch HHHF 1- 112 6-CH3 Η Η OCOCH3 HHH ch3 1-113 6-CH3 Η Η OCOCH3 HHHF 1-114 6-CH3 Η OCOOCH3 HHH ch3 1-115 6-CH3 Η OC OCOOCH3 HHHF 1-116 6-CH3 Η Η OCONHCH3 HH ch3 1-117 6-CH3 Η Η OCONHCH3 HHHF 1-118 6-C H3 Η CON OCON (CH3) 2 HHH ch3 1-119 6-CH3 Η 〇 〇c〇n (ch3) 2 HHHF 1-120 6-CH3 Η Η 〇s〇2ch3 HHH ch3 1-121 6-CH3 Η oso oso2ch3 HHHF 1-122 6-CH3 Η Η OS02CF3 HHH ch3

Physical constant Lmp Guang CJ 53-55 -22- (18) 200306154 Compound (R1) m (Note) R3 r1 r2 r3 r4 r5 Physical constant No. Lmp; uCj

1 -123 6-CH3 HH 〇S〇2CF3 HHH 1-124 6-CH3 HH cf3 HHH 1-125 6-CH3 HH cf3 HHH 1-126 6-CH3 HH sch3 HHH 1-127 6-CH3 HH sch3 HHH 1- 128 6-CH3 HH nh2 HHH 1-129 6-CH3 HH nh2 HHH 1-130 6-CH3 HH NHCH3 HHH 1-131 6-CH3 HH NHCH3 HHH 1-132 6-CH3 HHN (CH3) 2 HHH 1-133 6 -CH3 HH n (ch3) 2 HH Ή 1-134 6-CH3 HH NHCOCH3 HHH 1-135 6-CH3 HH NHCOCH3 HHH 1-136 6-CH3 HH OH HHH 1-137 6-CH3 HH OH HHH 1-138 6 -CH3 HH OCH3 H OCH3 H 1-139 6-CH3 HH OCH3 OCH3 HH 1-140 6-CH3 HH OCH3 ch3 HH 1-141 6-CH3 HH OCH3 H ch3 H 1-142 6-CH3 HH OCH3 FHH 1-143 6-CH3 HH OCH3 HFH 1-144 6-CH3 HH OCH3 FHH 1-145 6-CH3 HH OCH3 HFH 1-146 6-CH3 HH OCH3 HHF 1-147 6-CH3 HH OCH3 OCH3 HH 1-148 6-CH3 HH OCH3 H OCH3 H 1-149 6-CH3 HH OCH3 HH 〇CH: 1-150 6-CH3 HH 〇ch2ch2〇 ~ H OCH; 1-151 6-CH3 HH och3 ch3 HH 1-152 6-CH3 HH OCH3 H ch3 H 1-153 6-CH3 HH OCH3 HH ch3 1-154 6-CH3 HH OCH3 FHH 1-155 6-CH3 HH OCH3 HF H 1-156 6-CH3 HH OCH3 HHF 1-157 6-CH3 HH OCH3 ch3 HH 1-158 6-CH3 HH OCH3 H ch3 H 1-159 6-CH3 HH OCH3 HH ch3 1-160 6-CH3 HH OCH3 OCH3 HH 1-161 6-CH3 HH 0CH3 H OCH3 H 1-162 6-CH3 HH OCH3 HH OCH; 1-163 6-CH3 ch3 H 0CH3 HHH 1-164 6-CH3 ch3 H OCH3 HHH 1-165 6-CH3 c2h5 H OCH3 HHH

F CHFCHFCHFCHFCHFCHFCHFgochggocl-ocl-CHCHCHCHCHCH3CH3CH3CH3CH3

3 3 3 3 3 3 92 Η Η Η Η H 92-94

F F F F F 3 3 F F F F H c c 〇〇 95-97 ND (21.3) 1.5486 -23- (19) 200306154

Compound (R1) m (Note) R2 R3 r1 r2 r3 r4 r5 Physical constant number Lmp; uCJ 1-166 1-167 1-168 1-169 1-171 1-172 1-173 1-174 1- 175 1-176 1-177 1-178 1-179 1-180 1-181 1-182 1-183 1-184 1-185 1-186 1-187 1-188 1-189 1-190 1-191 1 -192 1-193 1-194 1-195 1-196 1-197 1-198 1-199 1-200 1-201 1-202 1-203 1-204 1-205 1-206 1-207 1-208 33333333331 HHHHHHHHHHHH ccccccccccc IIIIIIIIIII 66666666666 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-CH3 6-C2H5 6-C2H5 6-C2H5 6-C2H5 6-C2H5 6-C2H5 6-C2H5 6- 6-C3H7 6-CH (CH3) 2 6-cycloPr 3-OCH3 5- 〇CH3 6- OCH3 6-OCH3 6-OCH3 6-OCH3 6-OCH3 6-OCH3 6-OCH3 6-OCH3 6-〇CH3 6- 〇C2H5 6-〇C2H5 6-〇C2H5

7 33333333333333 3 3 3HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH C3CCCCCCCCCCCCCCCC OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 〇CH3 〇CH3 〇CH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 HHHHHHHFHHHHHHHHFHHHHHHHHFHHHHHHHHHHHHHFHHH HHHHH ^ HHHHHHHH ^ HHHHHHHH ^ hHHHHHHHHHHHH ^ HHHHH hhhhfhfhhhhhhfhfhhhhhhfhfhhhhhhhhhhhfhfhhhh OCH3 NHCH3 SCH3 F OCH3 OCH3 FF CH3 OCH3 NHCH3 SCH3 F OCH3 OCH3 FF CH3 60-62 〇CH3 ND (20.5) 1.5520 NHCH3 S〇H3 F ND (20.6) 1.5451 OCH3 OCH3 FF OCH3 OCH3 OCH3 OCH3 OCH3 CH3 OCH3 NHCH3 sch3 F OCH3 OCH3 FF CH3 OCH3 NHCH3 24- (20) 200306154 Compound (R1) m (Note) R2 R3 r1 r2 r3 r4 r5 Physical constant number Lmp; uCj

Bu 209 6-〇C2H5 HH 1-210 6-〇C2H5 HH 1-211 6-〇C2H5 HH 1-212 6-〇C2H5 HH 1-213 6-〇C2H5 HH 1-214 6-〇C2H5 HH 1-215 6-〇CH (CH3) 2 HH 1-216 6-SCH3 HH 1-217 6-NH2 HH 1-218 6-NHCH3 HH 1-219 6-N (CH3) 2 HH BU 220 6-〇CH2〇CH3 HH 1-221 6-OCOCH3 HH 1-222 6-CN HH 1-223 6-〇HHH 1-224 3-FHH 1-225 5_F HH 1-226 6-FHH 1-227 6-FHH 1-228 6-FHH 1-229 6-FHH 1-230 6-FHH 1-231 6-FHH 1-232 6-FHH 1-233 6-FHH 1-234 6-FHH 1-235 3-CI HH 1-236 5-CI HH 1-237 6-Cl HH 238 6-CI HH 1-239 6-Cl HH 1-240 6-CI HH 1-241 6-CI HH 1-242 6-CI HH 1-243 6-CI HH 1- 244 6-CI HH 1-245 6-CI HH 1-246 6-Br HH 1-247 6-1 HH 1-248 3,5- (CH3) 2 HH 1-249 3,6- (CH3) 2 HH 1-250 5r6- (CH3) 2 HH 1-251 3 - F-6-CH3 HH HHHHHFHHHHHHHHHHHHHHHHHHHFHHHHHHHHHHFHHHHHH 3 3 3 hhhchhhhhhhhhhhhhhhhhhhhchhhhhhhhhhhchhhhhhhhh HHFHFHHHHHHHHHHHHHHHHHFHFHHHHHHHHFHFHHHHHHH 33333333333333333333333 HHHHHHHHHHHHHHHHHHHHHHH ccccccccccccccccccccccc 〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 00 00 00 00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 0 3 0 0 3 3333 3333 3333333 J 3 HHHHHHHHHHHHHHHHHHHHH cccccccccccccccccccccc sch3 F OCH3 OCH3 FF OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 CH3 OCH3 NHCH3 SCH3 F OCH3 OCH3 FF OCH3 OCH3 CH3 OCH3 NHCH3 sch3 F OCH3 OCH3 FF OCH3 OCH3 OCH3 OCH3 OCH3 OCH3 OCHq 91-154 06-25 ) m wins) R2 R3 rl r2 r3 r4 r5 Physical constant number fmp; ° C 1-252 3-F each CH3 Η 〇 〇CH3 Η Η och3 1-253 5-F-6-CH3 Η Η OCH3 Η Η Η 0CH3 (Note) In the table, (R 1) m = Η represents r η = 0 1 represents the following structure

Example 3 Production of 4-Cyano-6-methyl-2-pyridinecarboxaldehyde

Add 2.03 g (14.39 mmol) of 4-fluoro-6-methyl-2-D to pyridine

Methanol was dissolved in 60 ml of benzene. To this solution, 11.0 g of active manganese dioxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised to the reflux temperature, followed by stirring overnight. After the reaction mixture was cooled to room temperature, insoluble matter was filtered off. The obtained filtrate was concentrated under reduced pressure to obtain 1.30 g of the target product. The above examples are included. Representative examples of the compounds of the present invention are shown in Table 2. -26- (22) 200306154 Table 2

(RDm ^ fN Η

Compound number R1 physical properties Compound number R1 physical properties 2-1-2-15 6-NH2 2-2 3-CH3 2-16 6-NHCH3 2-3 5-CH3 2-17 6-N (CH3) 2 2- 4 6-CH3 * 1 2-18 6-OCH2OCH3 2-5 6-C2H5 * 2 2-19 6-OCOCH3 2-6 6-C3H7 2-20 6-OH 2-7 6-CH (CH3) 2 2- 21 3-F 2-8 6-cycloPr 2-22 5-F 2-9 3-OCH3 2-23 6-F 2-10 5-OCH3 2-24 3-C1 2-11 6-OCH3 2-25 5 -C1 2-12 6-OCH2CH3 2-26 6-C1 * 3 2-13 6-OCH (CH3) 2 2-27 6-Br 2-14 6-SCH3 2-28 6-1: 1 to * 3 1H-NMR (CDC13, TMS, 5 ppm) data '1: 2.58 (s, 3H), 7.10 (dd, 1H), 7.49 (dd, 1H), 10.01 (d, 1H) * 2: 1.36 (t , 3Η), 2.92 (q, 2Η), 7.10 (dd, 1H

-27- (23) 200306154), 7.48 (dd, 1H), 10.02 (d, 1H) ○ * 3: 7.33 (dd, 1H), 7.63 (dd, 1H), 9.98 (d1H). Embodiment of the Invention (Fungicide for Agriculture and Horticulture)

The compound represented by formula [1] of the present invention or a salt thereof belongs to a wide range of filamentous fungi, such as Oomycetes, Ascomycetes, Deuteromycetes, and Basidiomycetes. The bacteria have excellent bactericidal power. The composition containing the compound of the present invention as an active ingredient can be used to control various diseases that occur when cultivating agricultural and horticultural crops including flowers, grasses, and pastures through seed treatment, stem and leaf spreading, soil application, or water surface application. For example, it can be used to control beet brown spot disease (Cercosporabeticola) and peanut brown spot disease (Mycosphaerella arachidis)

Mycosphaerella berkeleyi Cucumber powdery mildew (Sphaerotheca fuliginea) Mycosphaerella melonis Sclerotinia sclerotiorum Botrytis cinerea Black star disease (Cladosporium cucumerinum) Tomato gray cine Cladosporium ful vum Botrytis cinerea -28- (24) (24) 200306154 Corynespora melongenae Erysiphe cichoracearum Botrytis cinerea Botrytis cinerea Sohaerotheca aphanis) Onion gray rot (Botrytisa 11 ii) Botrytis cinerea Sclerotinia sclerotiorum Botrytiscinerea _ Podosphaera leucotricha Black star disease (V enturia inaequ s) Mongolia disease (M ο ni 1 iniama 1 i) Phyllactinia kakicola Gloeosporium kaki Cercosporakaki peach and cherry gray star disease (Monilinia fructicola) grape gray mold (Botrytiscinerea) _ Uncinula necator Late rot (G lomerella cingulata) pear black star disease (Venturianashicola) red star disease (Gymnosporangium asiaticum) black spot disease (Alternaria kikuchiana) tea wheel spot disease (Pestalotiatheae) anthracnose (Colletotrichum theae-sinensis) phase orange flower disease (Elsinoe-29) 25) 200306154 Penicillium italicum Penicillium digitatum Botrytis cinerea Barley powdery mildew (Erysiphe gramini s f. Sp. Hordei) Bare smut (Usti 1 ag ο nuda) of wheat Red mold (G ibbere 11 azeae) Red rust (Puccinia recondita)

Cochliobolussativus Pseudocercospore 11 a herpotrichoides Leptosphaeria nodorum Erysiphe graminis f. Sp. Tritici Red snow rot Micronectriella nivalis Pyriculariaoryza Disease (Rhizoctonia solani), Seedling Disease (Gibberellafujikuroi)

Cochliobolus niyabeanus, Sclerotinia sclerotiorum, Erysiphe cichoracearum, Botrytis cinerea, Sclerotinia borealis, Erysiphe graminis ) Cercospora kikuchii, Phytophthora infestans, Puc eu doper ο η ospora cubensis -30- (26) (26) 200306154 Plasmoparaviticola and so on. In addition, in recent years, various pathogenic bacteria have developed resistance to benzimidazole-based fungicides and dicarboxyfluorenimide-based fungicides, and the effectiveness of these agents has been insufficient, and it is expected that the agents are also effective against resistant bacteria. The compounds of the present invention are not only sensitive to the pathogenic bacteria of these agents, but also agents having excellent bactericidal effects against resistant bacteria. Furthermore, the compound of the present invention is also a dicarboxyfluorenimide-based bactericide (for example, Vinclozolin), Pythium (P r 〇cymid ο ne), and Ibuprofen (I pr 〇di ο ne). Botrytiscinerea showing resistance is also effective as sensitive bacteria. In addition, the compound of the present invention can also be used as an antifouling agent to prevent aquatic organisms from adhering to water contacts in ship bottoms, fish nets, and the like. Contains one or two or more compounds of the present invention as an effective ingredient. When the obtained compound of the present invention is actually used, it can be used in pure form without adding other ingredients, and for the purpose of using it as a pesticide, it can be used as a general pesticide. It can also be used in the form of hydration agent, granule, powder, emulsion, water solvent, suspending agent, flow agent, etc. Additives and carriers that can be added to pesticide preparations, and the purpose of solid agent 'Soy flour, wheat flour, and other plant-based powders, diatomaceous earth, apatite, red mercury oxide, talc, bentonite' Organic and inorganic compounds of powder, benzoic acid soda, urea, mirabilite, etc. For the purpose of liquid dosage forms, kerosene, xylene and petroleum fractions such as -31-(27) (27) 200306154 agent naphtha, Cyclohexane, cyclohexanone, dimethylamidoxamine, dimethylasco, alcohols, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. are used as solvents here. In order to show a uniform and stable form in some preparations, a surfactant may be added as needed. Examples of the surfactant include polyphenylene oxide alkyl polyether, polyether ethylene alkyl ether, polyoxyethylene Non-ionic surfactants such as ethylene higher fatty acid esters, sorbitan higher fatty acid esters with added polyoxyethylene, tristyrenyl phenyl ether with added polyoxyethylene, and polyoxyethylene alkane Sulfate of Alkyl Phenyl Ether, Alkylbenzene Sulfonate, Sulfate of Higher Alcohol, Alkyl Naphthalene Sulfonate, Polycarboxylate, Lignin Sulfonate, Formaldehyde Condensate of Alkyl Naphthalene Sulfonate , Isobutene-co-butadiene anhydride copolymer, etc. The amount of the ingredient is generally 0.01 to 90% by weight, and more preferably 0.05 to 85% by weight relative to the entire composition (formulation). The bactericide composition of the present invention formulated as such is treated as it is or with water It is diluted and applied to plants, seeds, water or soil hydration agents, emulsions, and flowable agents. It is diluted with water to the specified concentration to make suspensions or emulsions, and powders and granules are sprayed as they are to The method for plants is for use. The amount of application varies depending on weather conditions, formulation form, application period, application method, application site, target disease prevention, target crops, etc., usually the amount of active ingredient compound is 1 to 1 per hectare. 000 grams, preferably 10 to 100 grams. When hydrating agents, emulsions, flow agents, suspending agents, liquids, etc. are diluted with water and (28) 200306154 is applied, its application concentration is 1 to 1000 ppm, preferably 1 〇 ~ 250PPm Although the compound of the present invention can be said to be sufficiently effective even if it is alone, it can also be used in combination with one or two or more kinds of various fungicides, insecticides, acaricides or synergists. Representative examples of fungicides, insecticides, acaricides, and plant growth regulators which can be used in combination with the compounds of the present invention are shown below.

Bactericide: Copper agent; basic copper chloride, basic copper sulfate, etc. Sulfur agents; thiuram, zinc (Zineb), maneb (Maneb), mancozeb (Diram), zinc (Propineb), zinc (Polycarbamate) and so on. Polyhalide sulphur-based agent; Captan, Folpet, Dichlorofluridine and so on.

Organochlorine agents; Chlorothalonil, Fusaride, etc. Organophosphorus agents; IBP, EDDP, Trichlorfon, Pyrazopos, Triethylphosphonic acid, etc. Benzimid CI is Thiophanate-methyl, Benomyl, Carbendazine, Thiabendazole, and the like. Mono-Carboxyimidine; Iprodione, Procymidone, Vincizolm, Fluoromid, etc. 0-33- (29) 200306154 Amines; Oxy car bo xin, Mepro ni 1, Flutolanil, Tecloftalam, Triclamide, Pencycuron ) And other fluorenyl anilines; metalaxyl, Oxadiryl, Furalaxyl, and the like.

Methoxypropionate esters; phenoxyl deficiency methyl, Azoxystrobin, Metominostrobing 0 aniline pyrrolidine; An d o p u r i n e, me p a n i p y r i m, Pyrinethanil, Diprodinil and so on. SBI Qi | J; Triazimephon, Triazimenol, Bitertanol, Myclobutanil, hexaconazole, Propiconazole, Fluoride

Triflumizole), Prochloraz, Pefurazoate, Fenarimol, Pyrifenox, Triforine, Flusilazol, B Etaconazole, Diclobutrazol, Fluotrimazol, Flutriafen, Penconazole, Diniconazole, Antifungal Oral (Imazalil), tridemorph (Tridemorph), fenpropimorph (Finpropimorph), Buthiobate (Buthiobate), epoxy fluorenol (

Epoxyconazole), Metconazole, etc. Antibiotics; polyoxins, blasticidin S, kasugamycin, mycotoxins, streptomycin sulfate, and the like. -34- (30) 200306154 Others: Propamocarb Hydrochloride, Kin tosen, Hydroxyl DZ, Methasulfocarb, Anilazine, Isoprothiolane, Probenazole, Kino methionate, Dithianon, Dinoterb, Diclomezin, Felmson, Fluadinam, Pyroquilon, Tricyclic Tricy clazole), oxaquinol, dithianon, biguanine

(Iminoctadine), acetate, Cymoxanil, Pyrroinitrin, Methansulfocarb, Diethofencarb, Binapacryl, Lecithin, Bicarbonate Sodium hydrogen, Fenaminosulf, Dodine, Dimethomorph, Phenazin Oxide, Calpropamide, Flusulfamide, Fludioxonil, Famoxadon et al.

Insecticides and acaricides: Organophosphorus and urethane insecticides;

Phenthion, Phenitrothion, Diazinon, Chlorpyrifos, ESP, Vamidothion, Phenthoate, Dimethoate, Formothion, Malathion (Malathion), Trichlofon, Thiometon, Phosmet, Dichlorvos, Acephate, EPBP, methyl parathion Methyl-Parathion), Asia-35- (31) 200306154

Oxydemeton-methyl, Ethion, Salithion, Cyanophos, Isoxathion, pyridaphenthion, Phosalone ), Methidathion, Sulprofos, Chlorfenvinphos, Tetrachlorvinphos, Dimethylvinphos, Propaphos, Isosalophosphate Isofenphos), Ethyl Thiometon, Prefenophos, Pyraclofos, Monocrotophos, Azinphos-methyl, Aldicarb ), Methomyl, Thiodicarb, Carbofuran, Carbosulfan, B enfuracarb, Furathiocarb, Paracetamol (Propoxur), BPMC, MTMC, MIPC, Carbary 1

, Pirimicarb, Ethiofencarb, Fenoxycarb, etc. Synthetic pyrethroid insecticides; Permethrin, Cypermethrin, Deltamethrin, Fenvalerate, Fenpropathrin, Pyrethrum (Pyrethrin), Allethrin, Tetramethrin, Resmethrin, Dimethrin, Proparthrin, Phenethrin ( Phenothrin), Prothrin, Fluvalinate, Cyhalothrin (-36- (32) 200306154

Cyfluthrin), Cyhalothrin, Flucythrinate, Etofenprox, Cycloprothrin, Tralomethrin, Silafluofen ), Brofenprox, Acrinathrin and other insecticides of the benzamidine series;

Diflubenzuron, Chlorfluazuron, Hexaflumuron, Triflumuron, Tetraberzuron, Flufenoxuron, Fluey cloxuron , Profezine, Py riproxy fen, Methoprene, Benziepin, Diafenthiuron, Acetarniprid,

Imidacloprid, Nitenpyram, Fipronil, Cartap, Thiocyclam, Bensultap, Sulfate, Rotenone (Rotenone), acetaldehyde (Metaldehyde), mechanical oil, BT and insect pathogenic viruses and other microbial pesticides. Nematicides; Fenamiphos, Fosthiazate, etc. ° Acaricides; Chlorobenzilate, Phenisobromorate, Dicofol, Bisonitrile (Dicofol) Amitraz), BPPS, Benzomate, Hexythiazox, Fenbutatin Oxide, Polynacritin, Kinomethionate, -37- (33) 200306154 CPCBS, Triclosan, Averm (Abamectin), Milbemectin, Clofentezine, Cyhexatin, Pyridaben, Fenpyroximate, Tebufenpyrad, Pyramid Ether (Pyrimidifen), fenthiocarb (Fenothiocarb), Dianochlor and so on. Plant growth regulators: gibberellins (for example, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA, etc. The best form for implementing the invention (agricultural and horticultural fungicides): Next 'shown There are several examples of the composition of the present invention, but the additives and addition ratios are not necessarily limited to these examples, and can be changed in a wide range. Parts in the formulation examples are parts by weight. Example 4 Hydrating agent Compound of the present invention 40 parts of clay 48 parts of dioctyl sulfosuccinate sodium salt 4 parts of sodium lignosulfonate

When the above is uniformly mixed and finely pulverized, a hydrating agent with an active ingredient of 40% can be obtained. Example 5 Emulsion-38- (34) 200306154 Compound 1 () of the invention

Sorbat e 200 53 f knife cyclohexanone 26 $ calcium dodecylbenzenesulfonate 1 part polyoxyethylene alkyl allyl ether 10 parts If the above mixture is dissolved and dissolved, an emulsion of 10% of the active ingredient can be obtained. Example 6 Powder 10 parts of the compound of the present invention 90 parts of clay If the above-mentioned ingredients are uniformly mixed and finely pulverized, a powder with 10% of the active ingredient can be obtained. Example 7 Granules Compounds of the present invention Clay Bentonite Dioctyl sulfosuccinate sodium salt Potassium phosphate

After 20 parts 1 part was added with water and well kneaded, granulated and dried. Example 8 Suspending agent 10 parts of the compound of the present invention -39- (35) 200306154 Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts glycerol 10 Parts of Gutton gum 0.2 parts of water 7 3. 8 parts If the above is mixed and wet pulverized to a particle size of 3 microns or less, a suspension agent of 10% of the active ingredient is obtained. Example 9 Granular Hydrating Agent Compound of the present invention 40 parts clay 36 6 parts potassium chloride 10 parts sodium alkylbenzenesulfonic acid sodium salt 1 part sodium ligninsulfonic acid salt 8 parts formaldehyde condensate of sodium alkylbenzenesulfonic acid salt 5 parts , Then

After the above was uniformly mixed and finely pulverized, an appropriate amount of water was added and kneaded to make a clay. If it is granulated into a clay and then dried, a granular hydrating agent with an effective content of 40% can be obtained. Industrial Applicability: Next, test examples in which the compound of the present invention can be used as various plant disease control agents are shown. The control effect is the phytopathogenesis at the time of macroscopic observation and investigation. -40- (36) (36) 200306154 state, that is, the degree of growth of diseased spots and strains appearing in leaves, stems, etc. by macroscopic observation, and compared with the untreated group To find the control effect. The comparative compound was Compound A represented by the following structural formula described in WO 00/07744 (Compound No. 262 in Table 1).

Test Example 1 Lentil gray mold control test The flowers of lentils (variety "Longhua lentils") cultivated in a nursery tank were cut and immersed in a medicinal solution in which the emulsion of the compound of the present invention was adjusted to a concentration of 200 ppm as an active ingredient. After impregnation, it was naturally dried at room temperature, and sprayed with Botrytis cinerea. The inoculated flowers were placed on untreated lentils and repeated in a bright and dark high-humidity constant temperature greenhouse (20 ° C) every 12 hours for 7 days. The diameter of the lesion on the leaf was compared with that of the non-treated group, and the control of tritium was determined. As a result, the following compounds showed 100% thallium control. The compound numbers correspond to the compound numbers in Tables 1 to 3. In addition, the compound A used in the comparison also showed 100% thallium control. 1-62, 1-72, 1-96, 1-150, 1-238, 1-241, 1-306 ° Test Example 2 Lentil gray mold residual effect test Lentils grown in pots (variety "Longhua lentils") The first leaf of the herbicide was sprayed to adjust the emulsion of Compounds 62, 1-72 or Comparative Compound A of the present invention to a concentration of 200 ppm as an active ingredient. After air-drying, place the lentils basin in a -41-(37) ^ (37) ^ 200306154 glass greenhouse. After 7 days, the first leaf was cut out, and a lentil flower inoculated with Bouytis cinerea was placed on the leaf. After holding in a high-humidity constant temperature room (20 ° C) for 5 days, the diameter of the lesions formed on the leaves was compared with that of the untreated group, and the control of radon was determined. As a result, the compounds 1-62 and 1-72 of the present invention showed 100% thallium control, and comparative compound A was 3 6%. From these results, it is understood that the compound of the present invention is a compound which is more excellent in practical activity than the known compound. ·

-42-

Claims (1)

(1) 200306154 Scope of patent application, oxime O-ether compound represented by formula [I] or its salt [I] _. Alkenyl, c2 ~ 6 alkynyl , C3 ~ 6 cycloalkyl, Ci ~ 6 alkoxy, Cm alkylthio, amine, mono or dialkylamino, Ci ~ 6 alkoxy, Ci ~ 6 alkoxy, Ci ~ 6 alkyl, Ci ～ 6 courtyard oxygen Ci ～ 6 courtyard oxygen, nitro, truncated, meridian, or halogen atom 5 m is an integer representing 0 ~ 3, when m is 2 or more, R1 can be the same or different, R2 and R3 are The same or different means a hydrogen atom, Ci ~ 6 alkyl, R4 represents Cm alkyl, C3 ~ 6 cycloalkyl, C2 ~ 6 alkenyl, C2 ~ 6 alkynyl, Ci ~ 6 alkoxy, Ci ~ 6 alkoxy Ci ~ 6 alkyl, Ci ~ 6 alkoxy Ci ~ 6 alkoxy group, C2 ~ 6 alkenyloxy group, C2 ~ 6 alkynyloxy group, d ~ 6 alkoxy group, Ch alkoxycarbonyloxy group, mono- or di-C ^ 6 alkylamine formyloxy group, Ci- Alkylsulfonyloxy, Cl ~ 6 halogenated ore oxygen, Cl ~ 6_yuan, Cl ~ 6, sulfur, amine, mono- or di-C ^ 6 alkylamino, Ci ~ 6 alkylcarbonylamino , Hydroxy or halogen atom, η is an integer representing 0 ~ 5, when η is 2 or more, R4 may be the same or different, and two R4 may form an alkylene chain containing a hetero atom and form 5 to 7 members (Condensed ring). 2. —Method for producing oxime O-ether compound represented by formula [I] F -43- (2) 200306154 is characterized in that the compound represented by formula [II] is: (R4) n [Ml] (wherein R1 and m represent the meaning of the application) and react with the compound represented by formula [III] (R) m • (R4) r (where 1 ^ 2, 1 ^, 1 ^, and 11 have the same meaning as the term). 3. —A kind of combination not like the general formula [II] (In the formula, R1 and m represent the same fluorine atom as described above and m is the same, and R1 is a hydroxyl group. 4. An agricultural and horticultural fungicide having the characteristics The first item in the U range is the same. [I] The meaning of the first item or its salt in the patent application range, except that R1 is the case). It contains one or two or more of the oxime O-ether compound or its salt represented by the formula [I] with the same meaning as described above -44- (3) 200306154) as an effective ingredient. -45- 200306154 Lu, (1), the designated representative of the case is: None (2), the component representative symbols of this representative map are simply explained: 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: