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WO2011046082A1 - Dérivé d'éther d'oxime ou son sel, et germicide agricole/horticole - Google Patents

Dérivé d'éther d'oxime ou son sel, et germicide agricole/horticole Download PDF

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WO2011046082A1
WO2011046082A1 PCT/JP2010/067751 JP2010067751W WO2011046082A1 WO 2011046082 A1 WO2011046082 A1 WO 2011046082A1 JP 2010067751 W JP2010067751 W JP 2010067751W WO 2011046082 A1 WO2011046082 A1 WO 2011046082A1
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Inventor
裕紀 古川
加恵 天野
頼人 ▲桑▼原
一彌 清水
元亮 佐藤
陽子 大沢
照幸 飯濱
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
    • C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/83—Oxygen atoms

Definitions

  • the present invention relates to an oxime ether derivative or a salt thereof, and an agricultural and horticultural fungicide. More specifically, the present invention relates to a novel oxime ether derivative or a salt thereof, and an agricultural and horticultural fungicide containing as an active ingredient at least one selected from the oxime ether derivative or a salt thereof.
  • the present application claims priority based on Japanese Patent Application No. 2009-236427 filed in Japan on October 13, 2009, the contents of which are incorporated herein by reference.
  • Patent Document 1 discloses an oxyamine derivative represented by the formula (III) having a chemical structure similar to that of the compound of the present invention, and an agricultural and horticultural fungicide containing it as an active ingredient. ing.
  • R 1a represents a hydrogen atom, a C1-6 alkyl group, a C1-6 alkylcarbonyl group, or a C1-6 alkylsulfonyl group.
  • R 2a represents a C1-6 alkyl group or a C1-6 alkoxy group.
  • R 3a represents a halogen atom, a C1-6 alkyl group, or a C1-6 alkoxy group.
  • a a represents a C1-6 alkylene group which may be branched or a bond.
  • Q a represents a phenyl group which may be substituted with G, a group represented by the formula (IV), or a group represented by the formula (V).
  • m ′ represents 0 or an integer of 1 to 4.
  • R 4a represents a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, or SiR 5a R 6a R 7a .
  • R 5a , R 6a and R 7a each independently represents a C1-6 alkyl group.
  • R 8a represents a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, or a phenyl group which may be substituted with G.
  • Y a is substituted with a hydrogen atom, a C1-6 alkyl group, a C3-6 cycloalkyl group, a C3-6 cycloalkyl-C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, or G. And may represent a phenyl C1-6 alkyl group.
  • G represents a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group, and these G may be the same or different and may be substituted by 2 to 5 .
  • Patent Document 1 describes embodiments of several tens of compounds among oxyamine derivatives represented by the formula (III). Among them, when Q a is the formula (V), in Table 3 of Patent Document 1, Y a is a methyl group, an isopropyl group, a 2-chloro-benzyl group, a 3-chlorobenzyl group, a 4-chlorobenzyl group, Or compounds that are benzyl groups are specifically described.
  • the oxyamine derivative described in Patent Document 1 can be advantageously synthesized industrially, has a certain effect, and can be safely used as an agricultural and horticultural fungicide.
  • the demand level for safety such as reduction of phytotoxicity to plants and reduction or detoxification of human and livestock fish is increasing year by year, and the emergence of new resistant bacteria
  • the oxyamine derivatives described in Patent Document 1 Cannot fully meet the demand for agricultural and horticultural fungicides.
  • the present invention is a novel oxime ether derivative and a salt thereof, and at least selected from the oxime ether derivative and a salt thereof, which can be an active ingredient of an agricultural and horticultural fungicide that is reliable and can be used safely.
  • An object of the present invention is to provide an agricultural and horticultural fungicide containing one kind as an active ingredient.
  • the present invention includes the following aspects. ⁇ 1> An oxime ether derivative represented by the formula (I) or the formula (II) or a salt thereof.
  • R 1 is a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
  • R 2 represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, It represents a substituted or substituted C1-8 acyl group, an unsubstituted or substituted C1-8 alkylsulfonyl group, or an unsubstituted or substituted C6-10 arylsulfonyl group.
  • X represents a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • n represents the number of X and is an integer from 0 to 4. When n is 2 or more, Xs may be the same or different. When n is 2 or more, Xs may be combined to form a ring.
  • Y represents an oxygen atom or a sulfur atom.
  • Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR 7 .
  • R 7 represents a hydrogen atom or an unsubstituted or substituted C1-8 alkyl group.
  • R 3 represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
  • R 4 and R 5 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or an unsubstituted group. Alternatively, it represents a C1-8 alkoxy group having a substituent.
  • R 4 and R 5 may be combined to form a ring.
  • m represents the number of repeating units in parentheses and is an integer of 0-2. When m is 2, R 4 and / or R 5 may be the same or different from each other.
  • R 6 represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • A represents an oxygen atom, a sulfur atom, or a group represented by CR 8 R 9 .
  • R 8 and R 9 each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • p represents the number of repetitions of A and is an integer of 1 to 3. When p is 2 or more, A's may be the same or different.
  • B represents an oxygen atom, a sulfur atom, or a group represented by CR 10 R 11 .
  • R 10 and R 11 each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • R 4 ′ and R 5 ′ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or A substituted or substituted C1-8 alkoxy group is represented.
  • R 4 ′ and R 5 ′ may be combined to form a ring.
  • m ′ represents the number of repeating units in parentheses, and is an integer of 0 to 2. When m ′ is 2, R 4 ′ and / or R 5 ′ may be the same or different from each other.
  • a ′ represents an oxygen atom, a sulfur atom, or a group represented by CR 8 'R 9 '.
  • R 8 ′ and R 9 ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • p ′ represents the number of repetitions of A ′ and is an integer of 1 to 3.
  • a ′ may be the same as or different from each other.
  • B ′ represents an oxygen atom, a sulfur atom, or a group represented by CR 10 'R 11 '.
  • R 10 ′ and R 11 ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • q ′ represents the number of repetitions of B ′ and is an integer from 0 to 1. However, the sum of p ′ and q ′ is 2 or 3.
  • Q ′ represents an unsubstituted or substituted C6-10 arylene group or an unsubstituted or substituted divalent heteroaryl group.
  • Q in formula (I) and Q ′ in formula (II) are each independently an unsubstituted or substituted phenylene group, an unsubstituted or substituted pyridinylene group, an unsubstituted Alternatively, a substituted pyrazinylene group, an unsubstituted or substituted pyrimidinylene group, an unsubstituted or substituted pyridazinylene group, an unsubstituted or substituted pyrrolinylene group, an unsubstituted or substituted imidazolinylene
  • An agricultural and horticultural fungicide containing as an active ingredient at least one selected from the oxime ether derivatives or salts thereof according to ⁇ 1> or ⁇ 2>.
  • the oxime ether derivatives and salts thereof of the present invention are novel compounds useful as active ingredients of agricultural and horticultural fungicides that can be advantageously produced industrially, have a certain effect, and can be used safely.
  • the agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.
  • the oxime ether derivative according to the present invention is a compound represented by formula (I) or formula (II).
  • R 1 , R 2 , R 7 , X, Y, and Z, and m and n are as follows.
  • R 3 to R 6 , R 8 to R 11 , Q, A and B, and p and q are as follows.
  • R 4 ′ to R 5 ′, R 8 ′ to R 11 ′, Q ′, A ′ and B ′, and p ′ and q ′ are as follows.
  • “Substituent” is a group having a structure different from that of a mother nucleus substituted with a group serving as a mother nucleus.
  • the number of substituents may be one, or two or more. Two or more substituents may be the same or different.
  • a C1-6 alkyl group having a substituent is a group in which the parent nucleus is a C1-6 alkyl group, and any one of these hydrogen atoms is replaced with a group having a different structure (“substituent"). is there.
  • the term “C1-6” indicates that the group serving as the mother nucleus has 1 to 6 carbon atoms. This number of carbons does not include the number of carbons present in the substituent.
  • a butyl group having an ethoxy group as a substituent is classified as a C4 alkyl group.
  • the “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention.
  • a group that can be a “substituent” Halogeno groups such as fluorine, chlorine, bromine and iodine; C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
  • C1-6 haloalkyl groups such as chloromethyl group, chloroethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group;
  • a C2-6 haloalkenyl group such as a 2-chloro-1-propenyl group and a 2-fluoro-1-butenyl group;
  • a C2-6 haloalkynyl group such as 4,4-dichloro-1-butynyl group, 4-fluoro-1-pentynyl group, 5-bromo-2-pentynyl group;
  • C1-6 haloalkoxy groups such as 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group;
  • a C2-6 haloalkenyloxy group such as a 2-chloropropenyloxy group and a 3-bromobutenyloxy group
  • a mercapto group such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group; C2-6 alkenylthio groups such as vinylthio group and allylthio group; A C2-6 alkynylthio group such as an ethynylthio group or a propargylthio group; A C6-10 arylthio group such as a phenylthio group or a naphthylthio group; A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group; A C2-6 alkenylsulfonyl group
  • X represents a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • n represents the number of X and is an integer from 0 to 4. When n is 2 or more, Xs may be the same or different. When n is 2 or more, Xs may be combined to form a ring.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the C1-8 alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group and the like. Of these, C1-6 alkyl groups are preferred.
  • C1-8 alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, i-heptyloxy group, t-heptyloxy group, n-octyloxy group, i-octyloxy group, t-octyloxy group, 2-ethylhexyloxy group, etc. It is done. Of these, C1-6 alkoxy groups are preferred.
  • the C1-8 alkyl group and / or the C1-8 alkoxy group may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group that can be substituted with a C1-8 alkyl group and / or a C1-8 alkoxy group in X is a halogen atom. That is, a C1-8 haloalkyl group and / or a C1-8 haloalkoxy group.
  • C1-8 haloalkyl groups include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, 2,2,2 -A trifluoroethyl group, a 2,2,2-trichloroethyl group, a pentafluoroethyl group and the like can be mentioned.
  • C1-8 haloalkoxy groups include chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoroethoxy group And pentafluoroethoxy group.
  • Y represents an oxygen atom or a sulfur atom.
  • Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR 7 .
  • R 7 represents a hydrogen atom or an unsubstituted or substituted C1-8 alkyl group.
  • Examples of the C1-8 alkyl group for R 7 are the same as those listed above.
  • the C1-8 alkyl group may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group that can be substituted with the C1-8 alkyl group in R 7 is a halogen atom. That is, a C1-8 haloalkyl group.
  • R 1 is a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, or It represents an unsubstituted or substituted C3-8 cycloalkyl group. Examples of the C1-8 alkyl group for R 1 are the same as those listed above.
  • C2-8 alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2 -Propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group Group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, heptenyl group, octenyl group and the like. Of these, C2-6 alkenyl groups are preferred.
  • C2-8 alkynyl groups include ethynyl, 1-propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl Group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl Examples include -2-butynyl group, heptynyl group, octynyl group and the like. Of these, C2-6 alkynyl groups are preferred.
  • the C3-8 cycloalkyl group is a monocyclic or polycyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bicyclo [3.2.1] octyl group. Groups and the like.
  • the C1-8 alkyl group, C2-8 alkenyl group, C2-8 alkynyl group, and / or C3-8 cycloalkyl group in R 1 may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group that can be substituted with a C1-8 alkyl group, a C2-8 alkenyl group, or a C2-8 alkynyl group in R 1 is a halogen atom. That is, a C1-8 haloalkyl group, a C1-8 haloalkenyl group, or a C2-8 haloalkynyl group.
  • a preferred group which can be substituted with a C3-8 cycloalkyl group in R 1 is a halogen atom or a C1-6 alkyl group.
  • Examples of the C1-8 haloalkyl group for R 1 include the same as those listed above.
  • the C2-8 haloalkenyl group includes a 3-chloro-2-propenyl group, a 4-chloro-2-butenyl group, a 4,4-dichloro-3-butenyl group, a 4,4-difluoro-3-butenyl group, 3, And 3-dichloro-2-propenyl group.
  • C2-8 haloalkynyl groups include 3-chloro-1-propynyl group, 3-chloro-1-butynyl group, 3-bromo-1-butynyl group, 3-bromo-2-propynyl group, 3-iodo-2 -Propynyl group and the like.
  • R 2 represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, It represents a substituted or substituted C1-8 acyl group, an unsubstituted or substituted C1-8 alkylsulfonyl group, or an unsubstituted or substituted C6-10 arylsulfonyl group. Examples of the C1-8 alkyl group, C2-8 alkenyl group, and C2-8 alkynyl group in R 2 are the same as those listed above.
  • An acyl group means a group in which a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or the like is bonded to a carbonyl group.
  • Examples of the C1-8 acyl group include formyl group; acetyl group, propionyl group, butyroyl group, pivaloyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group and other alkylcarbonyl groups; acryloyl group, methacryloyl group, allyl Examples include alkenylcarbonyl groups such as carbonyl group and cinnamoyl group; ethynylcarbonyl group, propynylcarbonyl group; arylcarbonyl groups such as benzoyl group; heteroarylcarbonyl groups such as 2-pyridylcarbonyl group and thienylcarbonyl group. Of these, C1-7 acyl groups are preferred.
  • Examples of the C1-8 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, and an i-propylsulfonyl group. Of these, C1-6 alkylsulfonyl groups are preferred.
  • Examples of the C6-10 arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.
  • the C1-8 alkyl group, C1-8 acyl group, C1-8 alkylsulfonyl group, or C6-10 arylsulfonyl group in R 2 may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group which can be substituted with a C1-8 alkyl group in R 2 is a C1-6 alkoxy group or a C1-6 acyloxy group. That is, a C1-6 alkoxy C1-8 alkyl group or a C1-6 acyloxy C1-8 alkyl group.
  • C1-6 alkoxy C1-8 alkyl group includes methoxymethyl group, ethoxymethyl group, i-propoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, Examples include 1-methoxy-n-propyl group, 2-methoxy-n-propyl group, 3-methoxy-n-propyl group and the like.
  • Examples of the C1-6 acyl C1-8 alkyl group include an acetyloxymethyl group, a propionyloxymethyl group, and pivaloyloxymethyl.
  • a preferred group that can be substituted with a C1-8 acyl group, a C1-8 alkylsulfonyl group, or a C6-10 arylsulfonyl group in R 2 is a C1-6 alkyl group or a halogen atom.
  • Examples of the C1-8 acyl group having a substituent include a trifluoroacetyl group, a trichloroacetyl group, a 4-methylbenzoyl group, and a 2-chlorobenzoyl group.
  • Examples of the C6-10 arylsulfonyl group having a substituent include a 4-methylphenylsulfonyl group, a 2-chlorophenylsulfonyl group, and a 2,4-dimethylphenylsulfonyl group.
  • R 3 represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
  • Examples of the C1-8 alkyl group, the C2-8 alkenyl group, the C2-8 alkynyl group, and the C3-8 cycloalkyl group in R 3 are the same as those listed above.
  • the C1-8 alkyl group, C2-8 alkenyl group, C2-8 alkynyl group, or C3-8 cycloalkyl group in R 3 may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group that can be substituted with a C1-8 alkyl group, a C2-8 alkenyl group, or a C2-8 alkynyl group in R 3 is a halogen atom. That is, a C1-8 haloalkyl group, a C1-8 haloalkenyl group, or a C2-8 haloalkynyl group.
  • a preferred substituent which can be substituted with a C3-8 cycloalkyl group in R 3 is a halogen atom or a C1-6 alkyl group.
  • R 4 and R 5 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or an unsubstituted group. Alternatively, it represents a C1-8 alkoxy group having a substituent. R 4 and R 5 may be combined to form a ring. m represents the number of repeating units in parentheses and is an integer of 0-2. When m is 2, R 4 and / or R 5 may be the same as or different from each other. As the halogen atom, C1-8 alkyl group, C3-8 cycloalkyl group, and C1-8 alkoxy group for R 4 or R 5 , the same as those listed above can be mentioned.
  • the C1-8 alkyl group, C1-8 alkoxy group, and / or C3-8 cycloalkyl group in R 4 or R 5 may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R 4 or R 5 is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
  • a preferred group that can be substituted with a C3-8 cycloalkyl group in R 4 or R 5 is a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a nitro group, or a cyano group.
  • examples of the ring include C3-10 cycloalkane rings such as a cyclopropane ring, a cyclopentane ring, and a cyclohexane ring.
  • R 4 ′ and R 5 ′ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or A substituted or substituted C1-8 alkoxy group is represented.
  • R 4 ′ and R 5 ′ may be combined to form a ring.
  • m ′ represents the number of repeating units in parentheses, and is an integer of 0 to 2. When m ′ is 2, R 4 ′ and / or R 5 ′ may be the same as or different from each other.
  • the halogen atom, C1-8 alkyl group, C3-8 cycloalkyl group, and C1-8 alkoxy group for R 4 ′ or R 5 ′ the same groups as those listed above can be mentioned.
  • the C1-8 alkyl group, C1-8 alkoxy group, and / or C3-8 cycloalkyl group in R 4 ′ or R 5 ′ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R 4 ′ or R 5 ′ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
  • a preferred group that can be substituted with a C3-8 cycloalkyl group in R 4 ′ or R 5 ′ is a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a nitro group, or a cyano group.
  • examples of the ring include C3-10 cycloalkane rings such as cyclopropane ring, cyclopentane ring, and cyclohexane ring.
  • R 6 represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R 6 include the same as those listed above.
  • the C1-8 alkyl group or C1-8 alkoxy group in R 6 may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R 6 is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
  • A represents an oxygen atom, a sulfur atom, or a group represented by CR 8 R 9 .
  • R 8 and R 9 each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • p represents the number of repetitions of A and is an integer of 1 to 3. When p is 2 or more, A's may be the same or different. Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R 8 and R 9 include the same as those listed above.
  • the C1-8 alkyl group or C1-8 alkoxy group in R 8 and R 9 may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group that can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R 8 and R 9 is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
  • a ′ represents an oxygen atom, a sulfur atom, or a group represented by CR 8 'R 9 '.
  • R 8 ′ and R 9 ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • p ′ represents the number of repetitions of A ′ and is an integer of 1 to 3. When p ′ is 2 or more, A ′ may be the same as or different from each other.
  • Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R 8 ′ and R 9 ′ include the same as those listed above.
  • the C1-8 alkyl group or C1-8 alkoxy group in R 8 ′ and R 9 ′ may have one or more substituents.
  • substituents When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R 8 ′ and R 9 ′ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
  • [B, R 10, R 11 , B ', R 10', R 11 '] B represents an oxygen atom, a sulfur atom, or a group represented by CR 10 R 11 .
  • R 10 and R 11 each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • q represents the number of repetitions of B and is an integer from 0 to 1. However, the sum of p and q is 2 or 3.
  • Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R 10 and R 11 include the same as those listed above.
  • the C1-8 alkyl group or C1-8 alkoxy group in R 10 and R 11 may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • Preferred groups at R 10 and R 11, may be replaced by C1 ⁇ 8 alkyl or C1 ⁇ 8 alkoxy group, is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
  • B ′ represents an oxygen atom, a sulfur atom, or a group represented by CR 10 ′ R 11 ′ .
  • R 10 ′ and R 11 ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
  • q ′ represents the number of repetitions of B and is an integer from 0 to 1. However, the sum of p ′ and q ′ is 2 or 3.
  • Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R 10 ′ and R 11 ′ include the same ones listed above.
  • the C1-8 alkyl group or C1-8 alkoxy group in R 10 ′ and R 11 ′ may have one or more substituents.
  • substituents When it has two or more substituents, the substituents may be the same as or different from each other.
  • a preferred group that can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R 10 ′ and R 11 ′ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
  • [Q, Q '] Q and Q ′ each represents an unsubstituted or substituted C6-10 arylene group or an unsubstituted or substituted divalent heteroaryl group.
  • Examples of the C6-10 arylene group include a phenylene group, a biphenylene group, a naphthylene group, and an anthracenylene group.
  • divalent heteroaryl group examples include pyridinylene group, pyrazinylene group, pyrimidinylene group, pyridazinylene group, pyrrolinylene group, imidazolinylene group, pyrazolinylene group, quinolinylene group, isoquinolinylene group, indolinylene group, isoindolinylene group, 2,2′-bipyridinylene group.
  • heteroarylene groups such as an oxazolidinylene group, an oxazolinylene group, and an oxazepinylene group.
  • ring moiety (formula (VI)) formed by B, Q, A and R 6 in formula (I) include those represented by formula (VI-1) to formula (VI-27): Groups.
  • the C6-10 arylene group or divalent heteroaryl group may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
  • Preferred groups that can be substituted with a C6-10 arylene group or a divalent heteroaryl group are halogen atoms, C1-6 alkyl groups, C1-6 haloalkyl groups, C1-6 alkoxy groups, C1-6 haloalkoxy groups, C2 A -6 alkynyl group or a cyano group;
  • the oxime ether derivative represented by the formula (I) according to the present invention includes, for example, an oxyamine compound represented by the formula (3) (hereinafter sometimes referred to as a compound (3)) and a formula. It can be produced by reacting the compound represented by (4) (hereinafter sometimes referred to as compound (4)).
  • the amount of compound (4) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (3).
  • this reaction can be performed in the absence of a catalyst, it is preferably performed in the presence of an acid catalyst or a base catalyst, more preferably in the presence of an acid catalyst.
  • the acid catalyst to be used include trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid and the like.
  • the base catalyst include pyridine, triethylamine, potassium hydroxide and the like.
  • the amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (3).
  • a dehydrating agent such as anhydrous sodium sulfate or molecular sieve may be added to the reaction system.
  • This reaction can be carried out in a suitable solvent.
  • the solvent to be used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent
  • Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane
  • Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • Nitrile solvents such as acetonitrile and benzonitrile
  • alcohol solvents such as methanol, ethanol and n-propanol
  • mixed solvents composed of two or more of
  • the reaction temperature is a temperature ranging from room temperature to the boiling point of the solvent used.
  • the reaction time is usually several minutes to several tens of hours.
  • Compound (3) can be produced by a conventionally known method for producing an oxyamine compound.
  • the compound represented by the formula (1) is reacted with carbon tetrabromide and triphenylphosphine to obtain the compound represented by the formula (2).
  • a base By reacting Nt-butoxycarbonylhydroxylamine, an oxyamine compound represented by formula (9) (hereinafter sometimes referred to as compound (9)) is obtained, and an acid is allowed to act on this compound.
  • an oxyamine compound represented by the formula (3) can be obtained.
  • reaction In the case of reacting the compound (3) and the compound (4), after mixing the compound (4) and the compound (9), an acid such as trifluoroacetic acid is added, and the compound is reacted in the reaction system.
  • the reaction may be carried out by generating (3).
  • Compound (4) is, for example, a compound represented by formula (6) in the presence of a base in a fluoride compound represented by formula (5) (hereinafter sometimes referred to as compound (5)).
  • a compound represented by the formula (7) (hereinafter sometimes referred to as the compound (7)) is obtained by reacting with the compound (6). (7) is reacted with an amide compound represented by formula (8) (hereinafter sometimes referred to as compound (8)) in the presence of a base to obtain the desired compound (4). be able to.
  • the amount of the compound (6) to be used is generally 0.8 to 5 mol, preferably 1 to 3 mol, per 1 mol of the compound (5).
  • Examples of the base used in the reaction for obtaining the compound (7) include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide.
  • Metal alkoxides such as potassium ethoxide and potassium t-butoxide; metal hydrides such as sodium hydride, potassium hydride and calcium hydride; triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0]
  • organic bases such as undec-7-ene (DBU) and 1,4-diazabicyclo [2.2.2] octane.
  • the amount of the base to be used is generally 1 to 20 mol per 1 mol of compound (5).
  • This reaction can be carried out in a suitable organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • n-pentane n- Aliphatic hydrocarbon solvents such as hexane and n-heptane
  • amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone
  • nitrile solvents such as acetonitrile and benzonitrile
  • the amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (5).
  • the reaction to obtain compound (7) proceeds smoothly at a temperature ranging from 0 ° C. to the boiling point of the solvent used.
  • the compound (8) used in the reaction for obtaining the compound (4) include N, N-dimethylacetamide, N, N-dimethylpropionamide and the like.
  • the amount of compound (8) to be used is generally 0.8 to 5 mol, preferably 1 to 3 mol, per 1 mol of compound (7).
  • Examples of the base used in the reaction for obtaining the compound (4) include organic lithium compounds such as n-butyllithium, s-butyllithium, t-butyllithium and lithium diisopropylamide; alkali metals such as metallic sodium and metallic potassium; sodium hydride , Metal hydrides such as potassium hydride and calcium hydride;
  • the amount of the base to be used is generally 1 to 20 mol per 1 mol of compound (7).
  • This reaction can be carried out in a suitable organic solvent.
  • the solvent to be used is not particularly limited as long as it is inert to the reaction.
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; and the like.
  • the reaction for obtaining the compound (4) proceeds smoothly at a temperature ranging from ⁇ 100 ° C. to the boiling point of the solvent used.
  • the compound (4-a) in which R 1 is a t-butyl group, R 2 is a hydrogen atom and Y and Z are oxygen atoms is a halogenoformate compound (4- Compound (4-b) converted to intermediate compound (4-b) by reacting with d) and then reacted with an acid to convert R 1 (t-butyl group) to other substituent R 1 ′ c) can be obtained.
  • the base used for the reaction of the compound (4-a) with the halogenoformate compound (4-d) includes metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide.
  • Metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide; metal hydrides such as sodium hydride, potassium hydride, calcium hydride; triethylamine, diisopropylethylamine, pyridine,
  • organic bases such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,4-diazabicyclo [2.2.2] octane.
  • the amount of the base to be used is generally 1 to 20 mol per 1 mol of compound (4-a).
  • the reaction of the compound (4-a) and the halogenoformate compound (4-d) is performed in a suitable organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane
  • sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran
  • Aromatic hydrocarbon solvents such as toluene, benzene and xylene
  • aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane
  • Amide solvents such as N-methylpyrrolidone
  • the reaction between the compound (4-a) and the halogenoformate compound (4-d) proceeds smoothly at a temperature ranging from ⁇ 20 ° C. to the boiling point of the solvent used. Although the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.
  • Acids used for the reaction for obtaining the compound (4-c) from the intermediate compound (4-b) include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid and the like. Can be mentioned.
  • the amount of the acid to be used is generally 1 to 20 mol per 1 mol of compound (4-b).
  • the reaction for obtaining the compound (4-c) from the intermediate compound (4-b) is carried out in a suitable organic solvent.
  • the organic solvent to be used is not particularly limited as long as it is inert to the reaction, and examples thereof include those listed as solvents that can be used for the reaction with the halogenoformate compound.
  • the reaction for obtaining the compound (4-c) from the intermediate compound (4-b) proceeds smoothly at a temperature ranging from ⁇ 20 ° C. to the boiling point of the solvent used. Although the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.
  • the compound (4-e) in which Y and Z are oxygen atoms is a compound in which the substituent R 1 is converted to another substituent R 1 ′′ by a known transesterification method. It can be guided to (4-f).
  • the oxime ether derivative represented by the formula (I) according to the present invention can also be produced by the method as shown in Example 1. Specifically, N-hydroxyphthalimide or the like is reacted with the compound represented by the formula (1) to obtain an isoindoledione derivative, which is reacted in the presence of methyl hydrazine or the like, and then the reaction product And compound (4) can also be produced.
  • the oxime ether derivative represented by the formula (II) according to the present invention includes, for example, an oxyamine compound represented by the formula (10) (hereinafter sometimes referred to as the compound (10)) and the formula (11). It can be produced by reacting a compound represented (hereinafter sometimes referred to as compound (11)).
  • the amount of compound (10) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (11).
  • This reaction can be performed by the same method as the above-described reaction between the compound (3) and the compound (4).
  • Compound (11) can be obtained, for example, by subjecting compound (4) to hydride reduction, and obtaining the resulting alcohol compound in the same manner as in the production of compound (3) from compound (1) exemplified above. it can.
  • Sodium borohydride and its analogs can be used for hydride reduction.
  • the desired product can be isolated by purifying by a conventional post-treatment operation and, if desired, known and conventional purification means such as distillation, recrystallization and column chromatography.
  • known and conventional purification means such as distillation, recrystallization and column chromatography.
  • the structure of the target product can be identified and confirmed by known analytical means such as IR spectrum, NMR spectrum, mass spectrum, and elemental analysis.
  • the salt of the oxime ether derivative according to the present invention is a salt of the compound represented by formula (I) or formula (II).
  • the salt is not particularly limited as long as it is an agro-horticulturally acceptable salt. Examples thereof include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid. These salts can be produced by a conventionally known method using an acid corresponding to the oxime ether derivative represented by the formula (I) or the formula (II).
  • the oxime ether derivative or a salt thereof according to the present invention includes each stereoisomer based on a carbon-nitrogen double bond and an asymmetric carbon atom, and a mixture thereof. Moreover, when a solvate and a crystal polymorph exist, they are also included.
  • the agricultural and horticultural fungicide of the present invention (hereinafter sometimes referred to as "the present bactericidal agent") is an oxime ether represented by the formula (I) or the formula (II) of the present invention. It contains at least one selected from a derivative or a salt thereof as an active ingredient.
  • the fungicide of the present invention is excellent against a wide variety of fungi, for example, bacteria belonging to algae (Oomycetes), Ascomycetes, Deuteromycetes, and Basidiomycetes. Has sterilizing power.
  • the fungicide of the present invention can be used by seed treatment, foliage spraying, soil application or water surface application for the control of various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf and grass.
  • Sugar beet brown spot (Cercospora beticola), black root (Aphanomyces cochlloides), root rot (Thanatephorus cucumeris), leaf rot (Thanatephorus cucumeris), etc.
  • Cucumber powdery mildew (Sphaerotheca fuliginea), downy mildew (Pseudoperonospora cubensis), vine blight (Mycosphaerella melonis), vine split disease (Fusarium oxysporum), mycotic disease (Sclerotinia sclerotiorum), gray mold disease (Botrytiscine , Anthracnose (Colletotrichum orbiculare), black spot (Cladosporium cucumerinum), brown spot (Corynespora cassicola), seedling blight (Pythium debaryanam, Rhizoctonia solani Kuhn), spot bacterial disease (Pseudomonas syringae pv.
  • Gray mold disease (Botrytis cinerea), leaf mold disease (Cladosporium fulvum), plague (Phytophthora infestans), etc.
  • Strawberries gray mold (Botrytis cinerea), powdery mildew (Sohaerotheca humuli), anthracnose (Colletotrichum acutatum, fragletotrichum, epilepsy) (Phytophthora cactorum)
  • Onions gray rot (Botrytis allii), gray mold (Botrytis cinerea), vitiligo leaf (Botrytis squamosa), downy mildew (Peronospora destructor)
  • Cabbage root-knot disease (Plasmodiophora brassicae), soft rot disease (Erwinia carotovora), downy mildew (Peronospora parasitica), etc.
  • Kidney mycorrhizal disease (Sclerotinia sclerotiorum), gray mold disease (Botrytis cinerea), etc.
  • Apples powdery mildew (Podosphaera leucotricha), black spot disease (Venturia inaequalis), monilinia disease (Monilinia mali), black spot disease (Mycosphaerella pomi), rot disease (Valsa mali), spotted leaf disease (Alternaria mali), red star disease (Gymnosporang) yamadae), ring rot (Botryosphaeria berengeriana), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), soot spot (Zygophiala jamaicensis), soot spot (Gloeodes pomigena), etc.
  • Peach (Phyllactinia kakicola), anthracnose (Gloeosporium kaki), keratodeciduous leaf disease (Cercospora kaki), etc. Peaches: Monilinia fructicola, black scab (Cladosporium carpophilum), homopsis rot (Phomopsis sp.), Etc.
  • Asperum disease (Monilinia fructicola) Grapes: Gray mold disease (Botrytis cinerea), powdery mildew (Uncinula necator), late rot (Glomerella cingulata, Colletotrichum acutatum), sticky (Plasmopara viticola), black scab (Elsinoe ampelina), brown spot (Pseudocercospora vitis), black rot (Guignardia bidwellii), etc.
  • Citrus scab (Elsinoe fawcetti), blue mold Disease (Penicillium italicum), green mold disease (Penicillium digitatum), gray mold disease (Botrytis cinerea), sunspot disease (Diaporthe citri), scab disease (Xanthomonas campestris pv.Citri), etc.
  • Rice Rice blast (Pyricularia oryzae), blight (Rhizoctonia solani), idiot seedlings Diseases (Gibberella fujikuroi), sesame leaf blight (Cochliobolus niyabeanus), seedling blight (Pythium graminicolum), white leaf blight (Xanthomonas oryzae), seedling blight (Burkholderia plantarii), brown streak (Acidovorax avenae), Bacterial blight disease (B urkholderia glumae) Tobacco: Sclerotinia sclerotiorum, powdery mildew (Erysiphe cichoracearum), etc.
  • Tulip Gray mold, Botrytis cinerea, etc.
  • Bentgrass Snow rot, Scylotinia borealis, Pythium aphanidermatum etc.
  • Orchard Grass Powdery mildew (Erysiphe graminis), etc.
  • Soybean Purpura (Cercospora kikuchii), downy mildew (Peronospora Manshurica), stem blight (Phytophthora sojae), etc.
  • Potato Can be used to control Phytophthora infestans, etc. .
  • the bactericidal agent of the present invention has an excellent bactericidal effect against bacteria that have become resistant to conventional bactericides such as benzimidazole bactericides and dicarboximide fungicides.
  • gray mold fungus (Botrytis cinerea), sugar beet fungus (Cercospora beticola), apple black rot (Venturia inaequalis), pear black star
  • dicarboximide fungicides for example, vinclozolin, procymidone, iprodione
  • the diseases to which the fungicide of the present invention is more preferably applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple scab, cucumber gray mold, peanut brown.
  • the fungicide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.
  • the fungicide of the present invention is used in a form that can be taken by general agricultural chemicals, that is, in the form of agrochemical preparations such as wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, and wettable granules. May be.
  • Additives and carriers used for solid preparations include vegetable powders such as soybean flour and wheat flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay, benzoic acid Examples include organic and inorganic compounds such as soda, urea, and sodium sulfate.
  • Solvents used in liquid formulations include kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, Water etc. are mentioned.
  • a surfactant can be added as necessary in order to take a uniform and stable form.
  • the surfactant that can be added is not particularly limited.
  • alkylphenyl ether added with polyoxyethylene alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, polyoxyethylene Sorbitan higher fatty acid ester added with polyoxyethylene, nonionic surfactant such as tristyryl phenyl ether added with polyoxyethylene, sulfate ester salt of alkylphenyl ether added with polyoxyethylene, alkylbenzene sulfonate, sulfuric acid of higher alcohol
  • Examples include ester salts, alkyl naphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkyl naphthalene sulfonates, and isobutylene-maleic anhydride copolymers.
  • the wettable powder, emulsion, flowable powder, aqueous solvent, and granular wettable powder thus obtained are diluted with water to a predetermined concentration and sprayed to plants as a solution, suspension or emulsion. Used in. Powders and granules are used as they are sprayed on plants.
  • the amount of the active ingredient in the fungicide of the present invention is usually preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight, based on the whole preparation.
  • the application amount of the fungicide of the present invention varies depending on weather conditions, formulation form, application magnetism, application method, application place, disease to be controlled, target crop, etc., but usually 1 to 1,000 g of active ingredient compound per hectare, 10 to 100 g is preferred.
  • the applied concentration is 1 to 1000 ppm, preferably 10 to 250 ppm.
  • fungicides in addition to the compounds of the present invention, other fungicides, insecticides / acaricides and the like can be mixed with the fungicides of the present invention.
  • Typical examples of other fungicides, insecticides / acaricides, nematicides, acaricides, and plant growth regulators that can be used in combination are shown below.
  • Fungicide Benzimidazoles such as benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate methyl; Dicarboximides such as clozolinate, iprodione, procymidone, vinclozolin; Imazaril, oxpoconazole, pefazoate, prochloraz, triflumizole, triphorin, pyrifenox, fenarimol, nuarimol, azaconazole, viteltanol, bromconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, full Quinconazole, flusilazole, flutriazole, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, penconazole, propiconazole, prothioconazole, cimeconazole,
  • AP fungicides such as cyprodinil, mepanipyrim, pyrimethanil; N-phenyl carbamates such as dietofencarb; azoxystrobin, picoxystrobin, pyraclostrobin, cresoxime-methyl, trifloxystrobin, dimoxystrobin, metminostrobin, orizastrobin, famoxadone, floxastrobin QoI-bactericides (Qo inhibitors) such as phenamidon, metminophen, pyribencarb; PP fungicides (phenylpyrrole) such as fenpiconyl, fludioxonil; Quinoline series such as quinoxyphene; AH fungicides (aromatic hydrocarbons) such as biphenyl, chloroneb, dichlorane, kintozen, technazen, tortofos-methyl; MBI-R such as fusalide, pyrokilone
  • Phosphoric acid esters such as phosphorous acid, tolcrofosmethyl, fosetyl; Phthalamic acid such as teclophthalam; Benzotriazines such as triazoxide; Benzenesulfonamides such as fursulfamide; Pyridazinones such as dichromedin; CAA fungicides (carboxylic amides) such as dimethomorph, flumorph, bench avaricarb, iprovaricarb, mandipropamide; Tetracyclines such as oxytetracycline; Thiocarbamates such as metasulfocarb; Etridiazole, polyoxin, oxolinic acid, hydroxyisoxazole, octinoline, sylthiophane, diflumetrim, acibenzoral S methyl, probenazole, thiazinyl, ethaboxam, cyflufenamide, proquinazide, metolaphen
  • Insecticides and acaricides Organophosphorus and carbamate insecticides: Fenthion, Fenitrothion, Diazinon, Chlorpyrifos, ESP, Bamidthione, Fentoate, Dimethoate, Formothion, Marathon, Trichlorfone, Thiomethone, Phosmet, Dichlorvos, Acephate, EPBP, Methyl parathion, Oxydimethone methyl, Ethion, Salicione, Cyanophos, Fenthion, Salon Methidathione, Sulprophos, Chlorfenvinphos, Tetrachlorvinphos, Dimethylvinphos, Propafos, Isophenphos, Ethylthiomethone, Profenofos, Piracrofos, Monocrotophos, Adinfosmethyl, Aldicarb, Mesomil, Thiodicarb, Carbofuran, Carbosulfan, Benhracarb, Furatiocarb Propoxy
  • Pyrethroid insecticides Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotorin, tralomethrin , Silafluophene, brofenprox, aclinasrin and so on.
  • Benzoylurea and other insecticides Diflubenzuron, Chlorfluazuron, Hexaflumuron, Triflumuron, Tetrabenzuron, Flufenoxuron, Flucycloxuron, Buprofezin, Pyriproxyfen, Metoprene, Benzoepine, Diafenthiuron, Acetamiprid, Imidacloprid, Nitenpyram, Fipronil, Cartap , Thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.
  • Nematicides Phenamifos, phostiazates, etc.
  • Acaricide Chlorbenzilate, phenisobromolate, dicophore, amitraz, BPPS, benzomate, hexithazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, thiomidibene Dienochlor etc.
  • Plant growth regulator Abscisic acid, indole butyric acid, uniconazole, etiquelozate, etephone, cloxiphonac, chlormecote, chlorella extract, calcium peroxide, cyanamide, dichlorprop, gibberellin, daminozide, decyl alcohol, trinexapac ethyl, mepicoat chloride, pack Lobutrazole, paraffin, wax, piperonyl butoxide, pyraflufenethyl, flurprimidol, prohydrojasmon, prohexadione calcium salt, benzylaminopurine, pendimethalin, forchlorphenuron, potassium hydrazide maleate, 1- Naphtylacetamide, 4-CPA, MCPB, choline, oxyquinoline sulfate, ethiclozate, butorualine, 1-methylcyclopropene, abiglycine hydrochloride.
  • Example 1 [Production of 5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-ol] 5-Bromo-1-tetralone (2.00 g) is dissolved in N, N-dimethylformamide (18 ml), then diisopropylamine (15 ml), copper iodide (0.10 g), and dichlorobistriphenylphosphine palladium (0.19 g). And stirred at 80 ° C. for 8 hours under a propyne atmosphere. Ethyl acetate and aqueous ammonium chloride were added thereto, and the mixture was filtered through celite to separate the organic layer.
  • bactericidal agent of the present invention will be shown, but the additives and addition ratios are not limited to these examples, and can be varied in a wide range.
  • the part in a formulation Example shows a weight part.
  • Formulation Example 1 Wetting agent Compound of the present invention 40 parts Clay 48 parts Dioctyl sulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts The above is uniformly mixed and finely pulverized, and a 40% active ingredient wettable powder Get.
  • Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above is mixed and dissolved to obtain an emulsion containing 10% active ingredient.
  • Formulation Example 3 Powder 10 parts of the present compound 90 parts of clay The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.
  • Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part The above is pulverized and mixed well, water is added and kneaded and granulated and dried. As a result, granules containing 5% active ingredient are obtained.
  • Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts Mix the above and wet until the particle size is 3 microns or less Grind to obtain a suspension of 10% active ingredient.
  • Formulation Example 6 Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Ligninsulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt 5 parts After finely pulverizing, add an appropriate amount of water and knead to make clay. The clay-like product is granulated and then dried to obtain a wettable powder with 40% active ingredient.
  • Test examples of the fungicide of the present invention obtained as described above are shown below.
  • (Test Example 1) Apple black spot disease control test The emulsion of Production Example 2 was sprayed at a concentration of 100 ppm active ingredient on apple seedlings (variety “Kokumitsu”, 3-4 leaf stage) cultivated in an unglazed pot. After naturally drying at room temperature, conidia spores of Venturia inaequalis were inoculated and kept in a room at 20 ° C. and high humidity for 2 weeks, repeating light and darkness every 12 hours. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
  • Test Example 2 Wheat powdery mildew control test The wet seedling of Formulation Example 1 was sprayed at a concentration of 100 ppm to wheat seedlings (variety “Chihoku”, 1.0-1.2 leaf stage) cultivated in an unglazed pot. After air-drying the leaves, conidia of wheat powdery mildew (Erysiphe graminis f.sp.tritici) were shaken off and inoculated and kept in a greenhouse at 22-25 ° C. for 7 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
  • Test Example 3 Wheat Red Rust Control Test Wheat powder of Formulation Example 1 was sprayed at a concentration of 100 ppm to wheat seedlings (variety “Noribayashi No. 61”, 1.0-1.2 leaves) grown in an unglazed pot. After the leaves were air-dried, they were inoculated with summer spores of wheat rust (Puccinia recondita) and kept in a greenhouse at 22-25 ° C. for 10 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
  • the oxime ether derivative and the salt thereof according to the present invention are novel compounds useful as active ingredients of agricultural and horticultural fungicides that can be produced industrially advantageously, have reliable effects, and can be used safely.
  • the agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.

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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un dérivé d'éther d'oxime représenté par la formule (I), ou son sel. (1) (Dans ladite formule, X représente un atome d'halogène, un groupe alkyle, ou analogue ; Y représente un atome d'oxygène ou analogue ; Z représente un atome d'oxygène ou analogue ; R1 représente un groupe alkyle ou analogue ; R2 représente un atome d'hydrogène ou analogue ; R3 représente un groupe alkyle ou analogue ; R4 ou R5 représente un atome d'hydrogène ou analogue ; m représente un nombre entier compris entre 0 et 2 ; A ou B représente un atome d'oxygène, CH2, ou analogue ; et Q représente un groupe arylène ou un groupe hétéroaryle.)
PCT/JP2010/067751 2009-10-13 2010-10-08 Dérivé d'éther d'oxime ou son sel, et germicide agricole/horticole Ceased WO2011046082A1 (fr)

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JP2009236427A JP2013006771A (ja) 2009-10-13 2009-10-13 オキシムエーテル誘導体またはその塩、並びに農園芸用殺菌剤

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022058580A1 (fr) * 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Composés microbiocides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004168683A (ja) * 2002-11-19 2004-06-17 Nippon Soda Co Ltd オキシアミン誘導体、製造中間体及び農園芸用殺菌剤
WO2008124092A2 (fr) * 2007-04-03 2008-10-16 E. I. Du Pont De Nemours And Company Fongicides contenant du benzène substitué
WO2009075112A1 (fr) * 2007-12-11 2009-06-18 Nippon Soda Co., Ltd. Derive d'ether d'oxime et bactericide a usage agricole et horticole
WO2010018676A1 (fr) * 2008-08-11 2010-02-18 日本曹達株式会社 Dérivé d’éther d’oxime et bactéricide pour un usage agricole et horticole

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004168683A (ja) * 2002-11-19 2004-06-17 Nippon Soda Co Ltd オキシアミン誘導体、製造中間体及び農園芸用殺菌剤
WO2008124092A2 (fr) * 2007-04-03 2008-10-16 E. I. Du Pont De Nemours And Company Fongicides contenant du benzène substitué
WO2009075112A1 (fr) * 2007-12-11 2009-06-18 Nippon Soda Co., Ltd. Derive d'ether d'oxime et bactericide a usage agricole et horticole
WO2010018676A1 (fr) * 2008-08-11 2010-02-18 日本曹達株式会社 Dérivé d’éther d’oxime et bactéricide pour un usage agricole et horticole

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022058580A1 (fr) * 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Composés microbiocides

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