Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
  • C07D213/53—Nitrogen atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

• the present invention relates to a novel oxime ether compound and a fungicide for agricultural horticultural use containing the compound as an active ingredient.
• EP 475 In connection with the compounds of the present invention, EP 475, EP 2,488,884, WO 93/211 157, etc., certain oxime ether compounds, insecticide, It is described as having acaricidal activity.
• Japanese Patent Application Laid-Open No. 9-30747 describes that an oximeter compound containing a compound represented by the following formula is effective as an agricultural and horticultural fungicide.
• WO 01/34568 describes that an oxime ether compound containing a compound represented by the following formula is useful as an agricultural and horticultural fungicide.
• An object of the present invention is to provide a novel oxime ether compound which can be synthesized industrially advantageously, has a certain effect, and is an excellent agricultural and horticultural fungicide with little phytotoxicity.
• the present inventors have found that in the following general formula [I], the oxime ether compound in which the substituent R 2 at the 4-position of the pyridine moiety is a haloalkyl group has a particularly excellent control effect on agricultural and horticultural crop diseases. And completed the present invention.
• R i is, C 1 - 6 alkyl group, C 3 - 8 cycloalkyl group, C ie alkoxy groups, C 1 - 6 alkylthio group, amino group, mono C ⁇ 1-6 alkylamino group, di CL ⁇ ⁇ S alkylamino group, C 1 ⁇ 6 Ashiruokishi groups, C alkoxy C i ⁇ s alkyl group, C 1 ⁇ 6 alkoxide aryloxycarbonyl groups, C 2 ⁇ 6 alkenyl group, tri C 1 ⁇ 6 alkyl silicate b alkoxy C 1 1-6 ⁇ alkyl group, human Dorokishi C 1 ⁇ 6 alkyl group, arsenate Dorokishi group, Shiano group, a formyl group or a halogen atom.
• n represents an integer of 0 to 3, and when m is 2 or more, R 1 may be the same or different.
• R 2 represents a C i- 6 haloalkyl group.
• R 3 and R 4 are the same or different and represent a hydrogen atom or a C alkyl group.
• R 5, R 6, R 7 , R 8 and R 9 are the same or different and are each a hydrogen atom; ; ⁇ 6 alkyl le groups, C 3 ⁇ 8 cycloalkyl groups, C 2 ⁇ 6 alkenyl groups, C 2 ⁇ 6 alkynyl groups, C i ⁇ s alkoxy groups, C alkoxy C alkyl groups, C alkoxy C i ⁇ s alkoxy group, C 2 ⁇ 6 Arukeniruokishi group, C 2 ⁇ 6 Arukiniruokishi group, C i ⁇ e Ashiruoki shea group, C, ⁇ 6 alkylcarbonyl O alkoxy group, mono-C i to 6 alkyl force Rubamoiruokishi group di C 1 - 6 alkyl force Rubamoiruokishi group, C i to 6 alkylsulfonyl O carboxymethyl group, C ⁇ 1-6 haloalkylsulfonyl O carboxy
• R 5 , R 6 , R 7 , R 8, and R 9 form an alkylene chain containing a heteroatom, and are reduced to 5 to 7 members.
• a ring may be formed.
• the present invention provides an oxime ester compound represented by the formula:
• the R 5 is, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 alkoxy C iota 6 alkoxy group, C 2 ⁇ 6 Arukeniruokishi group, C 2 ⁇ 6 Arukiniruokishi group, C i ⁇ ⁇ s Ashiruokishi group, C iota ⁇ 6 alkylcarbonyl O alkoxy group, mono-C 1 ⁇ 6 alkyl carba mode Iruokishi group, di-C alkyl force Rubamoiruokishi group, C 1 ⁇ 6 alkylsulfonyl Okishi groups and C i ⁇ 6 haloalkylsulfonyl O carboxymethyl It is preferably one group selected from the group consisting of groups.
• R 9 is, C i S alkyl group, C 3 ⁇ 8 cycloalkyl group, C 2 ⁇ 6 alkenyl Le group, C 2 ⁇ 6 alkynyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 alkoxy C i 1-6 alkyl groups, C 6 alkoxy C i ⁇ s alkoxy groups, C 2 - 6 Arukeniruokishi groups, C 2 - 6 Al Kiniruokishi groups, C 1 - 6 Ashiruokishi groups, C alkylcarbonyl O alkoxy group, mono C i 1-6 alkyl force Rubamoiruokishi group, di C i-6 alkyl force Rubamoiruokishi groups, C 1-6 alkylsulfonyl O carboxymethyl groups, C 1-6 haloalkylsulfonyl O carboxymethyl groups, C haloalkyl groups, C 1 - 6 alkylthio group, amino group,
• the present invention provides a fungicide for agricultural gongs comprising one or more of the oximetel compound represented by the general formula [I] or a salt thereof.
• a first aspect of the present invention is an oxime ether compound represented by the general formula [1].
• R 1 is a C i- 6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, n-xyl, etc. Group;
• Ci- 6 alkylthio groups such as methylthio, ethylthio, n-propylthio, isopropylthio, and n-butylthio;
• Mechiruami Bruno Echiruamino
• n- Puropiruami Roh isopropyl ⁇ Mi Bruno, mono C 1 ⁇ 6 alkylamino amino group such as n- flop Chiruamino group;
• Jimechiruami Bruno Jechiruami Bruno, di n - Puropiruami Bruno, di one n - butylamine Bruno, di C i ⁇ 6 Arukiruami amino group such as E chill isopropyl ⁇ Mi cyano group;
• Ci to 6 alkoxy Cis such as methoxymethyl, 1-methoxyhexyl, 2-methoxyhexyl, ethoxymethyl, n-propoxymethyl, and n-butoxymethyl groups; ⁇ .
• Ci- 6 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl ', isobutoxycarbonyl, t-butoxycarbonyl; ethenyl, 11 Propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-12-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, etc.
• C 2 —s alkenyl group
• a hydroxy C alkyl group such as hydroxymethyl, 1-hydroxyl, 2-hydroxyl, 1-hydroxyl 2-propyl, 2-hydroxyn-propyl, 3-hydroxyn-propyl;
• n represents an integer of 0 to 3, and when m is 2 or more, R 1 may be the same or different.
• R 2 is fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1 difluoroethyl, 2,2-difluoroethyl, 2,2,2—trufluoroethyl, penta Fluoroethyl, 2-chloroethyl, Represents a C haloalkyl group such as 22-dichloroethyl, 2-bromoethyl, and 22-dibromoethyl.
• RR 4 is the same or different and represents a hydrogen atom; or C such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, n-hexyl, etc. Represents an alkyl group.
• R 5 R 6 RR 8 and R 9 are the same or different and are each a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, C 1 ⁇ 6 alkyl group such as n-hexyl group;
• C 6 alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy;
• C alkoxy C alkyl groups such as methoxymethyl, methoxethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl groups;
• C alkoxy C- 6 alkoxy groups such as methoxy methoxy, 1-methoxy ethoxy, 2-methoxy ethoxy, ethoxy methoxy, n-propoxy methoxy, n-butoxy methoxy groups;
• C-Acyoxy groups such as acetoxy, propionyloxy, and bivaloyloxy groups; methoxycarbonyloxy, ethoxycarbonyloxy, n-propoxycarbonyloxy, isopropoxycarbonyloxy, n-butoxycarbonyloxy, t-butoxycarbonyl
• a C i _ 6 alkoxycarbonyloxy group such as an alkoxy group
• Mono-Ci- fi alkyl-functional rubamoyloxy groups such as methylcarbamoyloxy, ethylcarbamoyloxy, n-propyl carbamoyloxy, n-butyl carbamoyloxy;
• Di C 16 alkylcarbamoyloxy groups such as dimethylcarbamoyloxy and getylcarbamoyloxy;
• C i _ 6 alkylsulfonyloxy groups such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, n-butylsulfonyloxy;
• C haloalkylsulfonyloxy groups such as trifluoromethylsulfonyloxy, 2,2,2-trifluoroethylsulfonyloxy, and pentafluoroethylsulfonyloxy;
• Haloalkyl group
• C-alkylthio groups such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, and t-butylthio groups; methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec — butylamino, t — butylamino, 1-methylbutylamino, n — mono-C- 6 alkylamino group such as pentylamino group; dimethylamino, getylamino, di-n-propylamino, di-n-butylamino, ethylisopropylamino, methyl n-diamino such as propylamino group-6 alkylamino group;
• C acylamino groups such as acetylamino, propionylamino, and piperoylamino; Represents an amino group, a hydroxy group, or a halogen atom such as fluorine, chlorine, bromine, or iodine.
• an oxime ether compound having an oxygen functional group at the 2-position (R 5 ) of the benzene ring is preferred because of its excellent bactericidal activity, and the 2-position (R 5 ) is an oxygen functional group, and the 6-position Oximeter compounds having a substituent at (R 9 ) are more preferred because they have particularly good bactericidal activity.
• the compound of the present invention can be produced as follows.
• RR 2 , R 3 , R 4 , R 5 , R 6 , RR 8 , R 9 and m represent the same meaning as described above, and L represents a halogen atom such as chlorine, bromine, iodine and the like, and methanesulfonylo. Represents a leaving group such as a xy group or a para-toluenesulfonyloxy group.
• the compound represented by the formula [I] is obtained by reacting a compound represented by the formula [II] with a compound represented by the formula [111] in the presence of a deacidifying agent such as a base without a solvent, preferably in a solvent. It can be obtained by stirring at a temperature of 0 to 15 (10 minutes to 24 hours at TC.
• Solvents that can be used in this reaction include ketones such as acetone, 2-butanone and cyclohexanone; ethers such as getyl ether and tetrahydrofuran; aromatics such as benzene and toluene. Hydrocarbons; alcohols such as methanol and ethanol; acetate nitrile, N, N-dimethylformamide, dimethylsulfoxide, water and the like. Further, these solvents can be used as a mixed solvent of two or more kinds.
• Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and sodium hydride; alkali metal alkoxides such as sodium methoxide and sodium methoxide; Organic bases such as pyridine, triethylamine, 14-diazabicyclo [5,4,0] indene 7-ene (hereinafter abbreviated as DBU) can be used.
• inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and sodium hydride
• alkali metal alkoxides such as sodium methoxide and sodium methoxide
• Organic bases such as pyridine, triethylamine, 14-diazabicyclo [5,4,0] indene 7-ene (hereinafter abbreviated as DBU) can be used.
• the compound represented by the formula [ ⁇ ] as a starting material of the compound of the present invention can be produced by the following method.
• R 2 and m have the same meaning as described above.
• 2-methylpyridines represented by the formula [IV] are oxidized with an oxidizing agent such as hydrogen peroxide and m-chloroperbenzoic acid (hereinafter abbreviated as mC PBA) to obtain the formula [V Pyridine-N-oxide represented by the formula [VI] and reacting with acetic anhydride to obtain 2-acetoxymethylpyridines represented by the formula [VI].
• an oxidizing agent such as hydrogen peroxide and m-chloroperbenzoic acid (hereinafter abbreviated as mC PBA)
• mC PBA m-chloroperbenzoic acid
• the 2-pyridinecarboxyaldehydes represented by the formula [VIII] can also be produced by the following method.
• R i, R 2 and m represent the same meaning as described above, Z represents a halogen atom such as chlorine, bromine, and iodine, and R represents a hydrogen atom or a CLC 6 alkyl group.
• a pyridine having a halogen atom at the 2-position represented by the formula [IX] is reacted with an alkyllithium such as n-butyllithium to lithiate the 2-position, and then is reacted with a formylating agent such as DMF.
• a formylating agent such as DMF.
• 2-pyridinecarboxyaldehydes represented by the formula [VIII] can be obtained.
• a cyanogenating agent such as copper cyanide is allowed to act on a pyridine having a halogen substituted at the 2-position represented by the formula [IX], or a 2-position unsubstituted pyridine N represented by the formula [X] —Oxides are reacted with a cyanating agent such as trimethylsilyl cyanide (hereinafter abbreviated as TMSCN) to give the cyanopyridines represented by the formula [XI].
• TMSCN trimethylsilyl cyanide
• DIB AH diisobutylaluminum hydride
• 2-cyanopyridines represented by the formula [XI] To a 2-pyridinecarboxylic acid ester represented by the formula [XII], and by using a reducing agent such as LiAlH 4 to form a 2-hydroxymethylpyridine represented by the formula [VII]; Converted to formyl group by oxidizing agent such as manganese That way Can also produce 2-pyridinecarboxyaldehydes represented by the formula [VIII].
• DIB AH diisobutylaluminum hydride
• pyridines substituted with a halogen at the 2-position represented by the formula [IX] are reacted with carbon monoxide in alcohol in the presence of a catalyst such as a palladium complex to form an alkoxycarbonyl group at the 2-position.
• a catalyst such as a palladium complex
• the 2-hydroxycarboxylic methyl pyridines you express by the formula [VII] by a reducing agent such as LiAlH 4, wherein by a method of converting into a ho mill base with an oxidizing agent such as manganese dioxide
• the 2-pyridinecarboxy aldehydes represented by [VIII] can be produced.
• the halides are obtained by converting a heterocyclic compound having a methyl group represented by the formula [XIII] to a halogenated succinimide such as N-chlorosuccinimide, N-promosuccinimide, or N-phenylsuccinimide. It can be obtained by reacting under light irradiation.
• R 5 , R 6, RR 8, and R 9 represent the same meaning as described above, and Li represents a halogen atom such as chlorine, bromine, and iodine.
• R 3 and R 4 are hydrogen atoms
• L is a halogen atom or a sulfonyloxy group.
• R 5, R 6 , R 7 , R 8 , R 9 and L have the same meanings as described above.
• W is a halogen atom such as chlorine, a hydroxy group, a hydrogen atom or a methoxy, ethoxy group, etc. Represents a ci- 6 alkoxy group.
• a formyl group, a carboxyl group, a halocarbonyl group represented by the formula [XIV] After obtaining a benzyl alcohol by reduction, a hydroxymethyl group is converted into a halogenomethyl group using a halogenating agent such as thionyl chloride, or a sulfonyl halide such as methanesulfonyl chloride is obtained.
• a compound represented by the formula [III-2] can be produced by converting a hydroxymethyl group into a sulfonyloxymethyl group by reacting the compound with a compound represented by the formula [III-2].
• the compound represented by the formula [III] which are the starting materials of the compound of the present invention
• the compound represented by the formula [ ⁇ -3] wherein R 3 and R or R 4 are C i _ 6 alkyl groups is It can be synthesized by the following method.
• R 3, R 4, R 5, R 6 R 7, R 8, R 9, and L represent the same meaning as described above, and L 2 represents a halogen atom such as chlorine, bromine, and iodine.
• a ketone or an aldehyde represented by the formula [XV] is reacted with a Grignard reagent represented by the formula [XVI] to obtain a benzyl alcohol, which is then halogenated with a thionyl chloride or the like.
• a hydroxymethyl group is converted to a halogenomethyl group by the action of an agent, or a sulfonyl halide such as methanesulfonyl chloride is reacted to convert a hydroxymethyl group to a sulfonyloxymethyl group.
• the compound represented by the formula [III-3] can be produced.
• the compound represented by the formula [I] can be prepared by mixing a compound represented by the formula [XVII] and a compound represented by the formula [XVIII] or a salt thereof in a solvent-free state, preferably in a solvent, at a reaction temperature of 0 to 1; 50 ° C For 10 minutes to 24 hours.
• solvent used in the reaction examples include alcohols such as ethanol and methanol; ethers such as ethyl ether, tetrahydrofuran and dioxane; cellosolps such as methyl sorb and ethyl sorb; benzene and toluene. And aromatic hydrocarbons such as acetic acid, water, N, N-dimethylformamide, dimethylsulfoxide and the like. These solvents can be used alone or as a mixed solvent of two or more.
• This reaction does not necessarily require the presence of a catalyst, but the addition of an acid or base may significantly accelerate the reaction.
• an inorganic acid such as sulfuric acid or hydrochloric acid, an organic acid such as p-toluenesulfonic acid, and sodium acetate or the like as a base can be used.
• the benzyloxyamines represented by the formula [XVIII] can be produced as follows.
• R 3, R 4, R 5, R 6, R 7, R 8 and R 9 have the same meanings as described above.
• a compound represented by the formula [III] is added to a base such as triethylamine.
• a base such as triethylamine.
• N-hydroxyphthalimide the compound represented by the formula [XIX] is obtained, and then hydrazine is allowed to act on the compound, whereby the benzene represented by the formula [XVIII] is obtained.
• Xiamins can be produced.
• the compound represented by the formula [1-2] wherein R 2 is a CH 2 F group can be produced as follows.
• RR2, R3, R4 , R5, R6, R7, R8, R9 and m represent the same meaning as described above.
• PG represents a protecting group such as t-butyldimethylsilyl group or the like. Represents.
• Oxidation with an oxidizing agent such as manganese gives 2-pyridinecarboxyaldehydes of the formula [XXIII].
• 2-pyridinecarboxyaldehydes and 0-benzyloxyamide represented by the formula [XVIII] are added.
• the compound represented by the formula [XXIV] is obtained by condensing the compound with a compound and deprotecting the protecting group.
• the compound represented by the formula [1-2] can be obtained by fluorination with a fluorinating agent such as getylaminosulfur trifluoride (hereinafter abbreviated as DAST).
• the compound represented by the formula [1-3] wherein R 2 is a CHF 2 group can be produced as follows.
• a pyridine having a hydroxymethyl group at the 4-position represented by the formula [XXV] is oxidized with an oxidizing agent to convert the hydroxymethyl group into a formyl group, and then is converted to a fluorinating agent such as DAST.
• a fluorinating agent such as DAST.
• the compound represented by [1-3] can be obtained.
• various derivatives can be synthesized by further chemically modifying the obtained product.
• the chemical modification described here includes the deprotection of functional groups recognized as protecting groups in the field of organic synthesis such as t-butyldimethylsilyl group, and the conversion of primary or secondary hydroxyl groups to carbonyl groups by manganese dioxide or the like.
• Functional group conversion such as wittig reaction utilizing the carbonyl group, functional group conversion such as derivation of ester group by hydrolysis reaction of cyano group, halogen atom
• the desired product can be obtained by performing ordinary post-treatment.
• the structure of the compound of the present invention can be determined by measurement of various spectra such as NMR spectrum, IR spectrum, and mass spectrum, elemental analysis and the like.
• the compounds of the present invention are useful in a wide variety of filamentous fungi, such as oomycetes (Oomycetes), ascomycetes (Ascomyce t_e_s), incomplete fungi (Deuteromycetes), and basidiomycetes (Basidiomycetes). It has excellent bactericidal activity against the bacterium to which it belongs. In particular, it has an excellent bactericidal activity against gray mold as compared to the known compounds.
• the composition containing the compound of the present invention as an active ingredient is used for controlling various diseases that occur in the cultivation of agricultural and horticultural crops including flowers, turf and pasture, by seed treatment, foliage application, soil application or water application. be able to.
• Rakkasei brown spot (Myc 0 s P a e r e 1 1 a a r a c h i d i s)
• Vine blight My Cos Pha e re e 11 i am e 10 n i S
• Sclerotia S c 1 e ro t i i n i a s c 1 e ro t i o r u m
• Gray mold B 0 t r y t i i c i n e r e a
• Leaf mold (C 1 ados Por i u m f u 1 V u m) Eggplant Gray mold (B o t r y t i s c i n e ⁇ e a)
• Apple powdery mildew (Pod os p ae a la l e u c o t r i c a) Scab (V e n t u r i a i n a e g u a 1 i s)
• Bentgrass Snow rot Bacterial rot Bacterial rot (Sc1erotinborreals) Orchardgrass Powdery mildew (Erysiphipegraminis_) Soybean purpura (Cercosp_orkiikkucchii)
• Potatoes' Tomato Blight (Phytophthhorainfinfestans) Kibebe disease (PseU-d—o_p_erono sjorr_acubenssies) Grapevine disease (Plasmaipara)
• It can be used for pest control.
• the compounds of the present invention have an excellent bactericidal effect not only on pathogenic bacteria sensitive to such drugs but also on resistant bacteria.
• Botrytiscinerea and ercosporabetico 1 a which are resistant to existing drugs such as thiophane-methyl, benomyl, and carbendazim, and the brown spot of sugar beet, Venturia _i_naequa 1 i_ss ) And pear scab (Y_enturianashico 1a), like the susceptible bacteria, the compound of the present invention has an excellent bactericidal effect.
• Botrytiscinerea is resistant to dicarboximide fungicides (eg, vinclozolin, procymidone, iprodione, etc.).
• dicarboximide fungicides eg, vinclozolin, procymidone, iprodione, etc.
• the compounds of the present invention also have an excellent bactericidal effect against susceptible bacteria.
• the compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to aquatic organisms such as ship bottoms and fish nets.
• compositions fungicide for agricultural and horticultural use
• the composition fungicide for agricultural and horticultural use
• the compound of the present invention as an active ingredient
• sugar beet scab wheat powdery mildew
• rice blast apple scab
• apple bean scab Gray mold and brown spot of laccasei.
• composition containing the compound of the present invention as an active ingredient contains one or more of the compounds of the present invention as an active ingredient.
• the compound of the present invention can be used in a pure form without adding other components. It can be used in the form of powders, emulsions, aqueous solvents, suspensions, flowables and the like.
• Additives and carriers that can be added to the pesticide formulation include, for solid formulations, plant powders such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, and pyrophyllite.
• Organic and inorganic compounds such as mineral fine powders such as clay, clay, sodium benzoate, urea, and sodium sulfate are used.
• petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methyl Isobutyl ketone, mineral oil, vegetable oil, water, etc. can be used as the solvent.
• a surfactant can be added as required.
• the surfactant that can be added include, for example, alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, and polyoxyethylene to be added.
• Sorbitan higher fatty acid esters such as tristyryl ether added with polyoxyethylene, sulfates of alkylphenyl ether added with polyoxyethylene, alkylbenzene sulfonates, sulfuric acid of higher alcohols
• non-ionic surfactants such as tristyryl ether added with polyoxyethylene, sulfates of alkylphenyl ether added with polyoxyethylene, alkylbenzene sulfonates, sulfuric acid of higher alcohols
• examples thereof include an ester salt, an alkyl naphthalene sulfonate, a polycarboxylate, a lignin sulfonate, a formaldehyde condensate of an alkyl naphthalene sulfonate, and a copolymer of isobutylene-maleic anhydride.
• the amount of the active ingredient of the agricultural and horticultural fungicide of the present invention is usually based on the total amount of the composition (formulation). Te, preferably 0. 0 1-9 0 weight 0/0, more preferably 0 5-8 5% by weight 0.1.
• the obtained wettable powder, emulsion, floor pull and the like are diluted with water to a predetermined concentration, and used as a suspension or an emulsion.
• the formulated fungicide composition of the present invention is applied as it is or diluted with water or the like to plants, seeds, water surface or soil.
• the amount of application varies depending on the weather conditions, formulation, application time, application method, application site, target disease, target crop, etc., but usually 1 to 100 hectares of active ingredient compound. g, preferably 10 to 100 g.
• the application concentration is 1 to 100 ppm, preferably 10 to 250 ppm. In the case of powders, powders and the like, they can be applied as is without dilution.
• the compound of the present invention is effective alone, but it can also be used in combination with one or more of various fungicides, insecticides, acaricides or synergists.
• various fungicides, insecticides, acaricides, nematicides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.
• Copper agent Basic copper chloride, basic copper sulfate, etc.
• Sulfur agent Sulfur agent; thiuram, zinep, maneb, mancozeb, ziram, provevineb, polycarbamate, etc.
• Polyhaloalkylthio agents captan, phorpet, dichlorofluanid and the like.
• Organic chlorine agent chlorothalonil, fusaride, etc.
• Organic phosphorus agents IBP, EDDPP, triclofosmethyl, pyrazophos, Josetyl and the like.
• Benzimidazole agents thiophanate methyl, benomyl, carbendazim, thiabendazole and the like.
• Dicarboxymid agents iprodione, procymidone, vinclozolin, fluorimide and the like.
• Carboxamide agents oxycarboxin, mepronil, flutranil, techopen phthalam, trichloramide, pencyclone and the like.
• Asylalanine agent metalaxyl, oxazixil, furalaxyl and the like.
• Methoxycrylates kresoxime methyl, azoxystrobin, methinostrobin and the like.
• Anilinopyrimidine agents andpurine, mepanipyrim, pyrimethanil, dibrodinyl and the like.
• SBI agent triazimefone, triadimenol, bitertanol, microbutanil, hexaconazole, propiconazole, triflumizol, prochloraz, difrazoate, fenarimol, pyriphenox, trifolin, flusilazol, etaconazo , Diclobudrazol, fluorotriazole, flutriafen, penconazole, diniconazole, imazalil, tridemorph, fenpropimorph, petiobeto, epoxyconazole, metconazole, etc.
• Antibiotics polyoxin, blasticidin S, kasugamycin, validamycin, dihydrostrephtomycin sulfate and the like.
• Nematicides phenamiphos, phosthiazetate, etc.
• Chlorbenzylate phenisopromolate, dicophor, amitraz, BPPS, benzomate, hexthiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezine, cihexatin, pyridabene, pyridavene Tepfenvirad, pyrimidifene, fenochiocalp, dienochlor, etc.
• Plant growth regulator Plant growth regulator
• Example 1 Preparation of 6-methyl-14-trifluoromethyl-12-pyridinepyridinecarboxyaldehyde 0— (2,6-dimethoxybenzyl) oxime (Compound No. 5666) i) Production of 6-methyl-4-trifluoromethyl-2-ethylpyridinecarboxylate
• TBDMS t-butyldimethylsilyl group
• the whole amount of the crude product was added to 10 ml of acetic anhydride and refluxed at 70 ° C. for 2 hours. After the reaction mixture was concentrated under reduced pressure, the resulting residue was dissolved in 30 ml of methanol, 0.6 g (10.7 mmol) of potassium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. Stirred. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain 2.5 g of a crude product.
• the crude product obtained by concentrating the filtrate under reduced pressure was dissolved in 50 ml of acetic acid, and 2.05 g (11.2 mimol) of 2,6-dimethoxybenzyloxyamine was added. And stirred at room temperature for 1 hour.
• the reaction mixture was poured into ice water, neutralized with sodium hydrogen carbonate, and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and filtered.
• the crude ester product was dissolved in 60 ml of methanol, 50 ml of water and 15.0 g of potassium hydroxide were added to the solution, and the mixture was stirred at room temperature for 4 hours.
• the reaction mixture obtained by concentrating the reaction solution under reduced pressure was diluted with water and extracted with ethyl acetate.
• the total amount of the obtained crude 6- (tert-butyldimethylsilyloxy) methyl-4-trifluoromethyl-2-pyridinepyridinecarboxyaldehyde was dissolved in 10 ml of acetic acid, and 1.15 g (6.28) was added to the solution. 2,6-Dimethoxybenzyloxyamine) was added at the same temperature, and the mixture was stirred for 1.5 hours. After the reaction mixture was concentrated under reduced pressure, it was neutralized by adding an aqueous solution of sodium hydrogen carbonate. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate.
• 6-Hydroxymethyl-4 4-Trifluoromethyl-2-pyridinecarboxyal Dissolve 0.96 g (2.59 millimoles) of O- (2,6-dimethoxybenzyl) oxoxide in 10 mL of benzene, and add 1.2 g of activated manganese dioxide. The mixture was heated under reflux for 8 hours.
• the total amount of the obtained 6- (tert-butyldimethylsilyloxy) methyl-1-cyano-4-trifluoromethylpyridine was dissolved in 20 ml of THF, and the solution was cooled to 0 and cooled to 0% with tetramethylammonium fluoride (lmol / lmol).
• L, THF solution 3.5 ml (3.5 mmol) was added, and the mixture was stirred at 0 ° C for 1 hour, then returned to room temperature and stirred for 3 hours.
• the reaction mixture was poured into ice water, extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate.
• Table 1 shows typical examples of the compounds of the present invention including the above Examples.
• the above is pulverized and mixed well, water is added and kneaded well, and the mixture is granulated and dried to obtain granules having an active ingredient of 5%.
• the above ingredients are mixed and wet-pulverized to a particle size of 3 microns or less to obtain a 10% active ingredient suspension.
• Example 17 wettable powder for granules
• Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents.
• the control effect was determined by visually observing the diseased state of the test plant at the time of the survey, that is, the degree of the growth of the fungal spots appearing on the leaves, stems, etc., and comparing it with the untreated one to determine the control effect.
• Test example 1 Green bean blight control test

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Pyridine Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=19044349

Family Applications (1)

Country Status (2)

Cited By (1)

Citations (2)

• 2002
  • 2002-07-09 JP JP2003512204A patent/JPWO2003006432A1/ja not_active Withdrawn
  • 2002-07-09 WO PCT/JP2002/006947 patent/WO2003006432A1/ja active Application Filing

Patent Citations (2)

Also Published As

Similar Documents

Legal Events