Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
  • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
  • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms
  • C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • 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
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P3/00—Fungicides
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  • 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
  • C07D213/60—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 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 ring carbon atoms
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/81—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
  • C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
  • C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
  • C07D237/28—Cinnolines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/32—One oxygen, sulfur or nitrogen atom
  • C07D239/34—One oxygen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
  • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
  • C07D253/06—1,2,4-Triazines
  • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
  • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
  • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
  • C07D471/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/04—Ortho-condensed systems
  • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
  • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered

Definitions

• the present invention relates to a hydrazide compound and an agricultural and horticultural fungicide. More specifically, the present invention relates to a hydrazide compound that has excellent fungicidal activity against pathogens that affect agricultural and horticultural plants, is safe, and can be synthesized industrially in an advantageous manner, and to an agricultural and horticultural fungicide containing the same as an active ingredient.
• This application claims priority based on Japanese Patent Application No. 2022-212728 filed in Japan on December 28, 2022, Japanese Patent Application No. 2023-069619 filed in Japan on April 20, 2023, and Japanese Patent Application No. 2023-131664 filed in Japan on August 10, 2023, the contents of which are incorporated herein by reference.
• Patent Document 1 discloses compounds represented by formula (A) and the like.
• the objective of the present invention is to provide a hydrazide compound that has excellent bactericidal activity against pathogens that affect agricultural and horticultural plants, is safe, and can be synthesized in an industrially advantageous manner, as well as an agricultural and horticultural fungicide that contains this compound as an active ingredient.
• Z represents an oxygen atom, a sulfur atom, or a group represented by the formula: NR b , an arrow with a + sign is bonded to a carbon atom with a + sign in the partial structure, and the other arrow is bonded to a nitrogen atom having R 7
• R b represents a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, a hydroxyl group, or a substituted or unsubstituted C1-6 alkoxy group
• R 6 represents a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a formyl group, a substituted or unsubstituted C1-6 alkylcarbonyl group, a substituted or unsubstituted C1-6 alkoxycarbonyl group, a
• the Z a is an oxygen atom
• Z is an oxygen atom
• R 6 is a hydrogen atom
• R 7 is a formyl group, a group represented by the formula: R c -CO-, a group represented by the formula: R c -CS-, a group represented by the formula: R c -CO-CO-, or a group represented by the formula: R c -SO 2 -;
• An agricultural and horticultural fungicide comprising, as an active ingredient, at least one selected from the group consisting of the compound and its salt according to any one of (1) to (4).
• a method for producing a compound represented by formula (I-1) comprising the step of reacting a compound represented by formula (im-1) with a compound represented by formula (im-2) in the presence of an acid scavenger.
• Z a represents an oxygen atom, a sulfur atom, or a group represented by the formula: NR a ;
• R a represents a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group;
• Z represents an oxygen atom, a sulfur atom, or a group represented by the formula: NR b ;
• R b represents a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, a hydroxyl group, or a substituted or unsubstituted C1-6 alkoxy group;
• R 4 each independently represents a hydrogen atom,
• G represents a halogeno group.
• a method for producing a compound represented by formula (I-3), comprising a step of reacting a compound represented by formula (im-5) with a compound represented by formula (im-6) in the presence of a condensation reagent when U 1 in formula (im-5) is a hydroxyl group, or in the presence of an acid scavenger when U 1 is a halogeno group.
• Q 1 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5- to 6-membered heterocyclyl group, or a substituted or unsubstituted 9- to 10-membered heterocyclyl group
• Q2 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5- to 6-membered heterocyclyl group, or a substituted or unsubstituted 9- to 10-membered heterocyclyl group
• a carbon atom forming a ring in Q2 may be bonded to a nitrogen atom having R7a instead of R7a ;
• R 4 each independently represents a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a substituted or unsubstituted C3-6 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5- to 6-membered heterocyclyl group,
• the hydrazide compound of the present invention has excellent fungicidal activity against pathogens that affect agricultural and horticultural plants, is safe, and can be synthesized industrially in an advantageous manner.
• the agricultural and horticultural fungicide of the present invention can effectively control diseases of agricultural and horticultural plants.
• C1-6 indicates that the number of carbon atoms in the core group is 1 to 6. This number of carbon atoms does not include the number of carbon atoms in the substituent.
• a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.
• the "substituents" are not particularly limited as long as they are chemically permissible and have the effect of the present invention.
• C1-6 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, or an n-hexyl group;
• C2-6 alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, and a 2-methyl-2-propenyl group;
• C2-6 alkynyl groups such as an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group
• Hydroxyl group C1-6 alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, or a t-butoxy group; C2-6 alkenyloxy groups such as a vinyloxy group, an allyloxy group, a propenyloxy group, or a butenyloxy group; C2-6 alkynyloxy groups such as ethynyloxy groups, propargyloxy groups, etc.; Phenoxy group, naphthoxy group; phenyl C1-6 alkoxy groups such as benzyloxy groups and phenethyloxy groups; 5- to 6-membered heteroaryloxy groups such as thiazolyloxy groups and pyridyloxy groups; 5-6 membered heteroaryl C1-6 alkyloxy groups such as thiazolylmethyloxy groups and pyridylmethyloxy
• Formyl group C1-6 alkylcarbonyl groups such as acetyl group and propionyl group; Formyloxy group; C1-6 alkylcarbonyloxy groups such as an acetyloxy group or a propionyloxy group; Benzoyl group; C1-6 alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, or a t-butoxycarbonyl group; C1-6 alkoxycarbonyloxy groups such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, an n-butoxycarbonyloxy group, or a t-butoxycarbonyloxy group; Carboxyl group;
• halogeno groups such as a fluoro group, a chloro group, a bromo group, or an iodo group
• C1-6 haloalkyl groups such as a chloromethyl group, a chloroethyl group, a trifluoromethyl group, a 1,2-dichloro-n-propyl group, a 1-fluoro-n-butyl group, and a perfluoro-n-pentyl group
• C2-6 haloalkenyl groups such as a 2-chloro-1-propenyl group and a 2-fluoro-1-butenyl group
• C2-6 haloalkynyl groups such as a 4,4-dichloro-1-butynyl group, a 4-fluoro-1-pentynyl group, or a 5-bromo-2-pentynyl group
• C1-6 haloalkoxy groups such as a trifluoromethoxy group, a 2-ch
• Amino group C1-6 alkyl-substituted amino groups such as methylamino group, dimethylamino group, and diethylamino group; Anilino group, naphthylamino group; phenyl C1-6 alkylamino groups such as benzylamino groups and phenethylamino groups; Formylamino group; C1-6 alkylcarbonylamino groups such as an acetylamino group, a propanoylamino group, a butyrylamino group, or an i-propylcarbonylamino group; C1-6 alkoxycarbonylamino groups such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, or an i-propoxycarbonylamino group; unsubstituted or substituted aminocarbonyl groups, such as an aminocarbonyl group, a dimethylaminocarbonyl group
• triC1-6 alkyl-substituted silyl groups such as a trimethylsilyl group, a triethylsilyl group, or a t-butyldimethylsilyl group; Triphenylsilyl group; Cyano group; nitro group.
• Examples of "3- to 6-membered saturated heterocyclyl groups” include aziridinyl groups, epoxy groups, azetidinyl groups, oxetanyl groups, pyrrolidinyl groups, tetrahydrofuranyl groups, thiazolidinyl groups, piperidyl groups, piperazinyl groups, morpholinyl groups, dioxolanyl groups, and dioxanyl groups.
• Q2 in formula (ZI) represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5- to 6-membered heterocyclyl group, or a substituted or unsubstituted 9- to 10-membered heterocyclyl group.
• Examples of the "5- to 6-membered saturated heterocyclyl group" in Q 1 or Q 2 include a pyrrolidinyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a thiazolidinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, a dioxolanyl group, a dioxanyl group, and the like, with a tetrahydropyranyl group or a piperidyl group being preferred.
• Examples of the "5-membered heteroaryl group" in Q1 or Q2 include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, and a tetrazolyl group.
• a thienyl group, a pyrazolyl group, or a thiazolyl group is preferable.
• Examples of the "9-membered heterocyclyl group" in Q1 or Q2 include an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothienyl group, an indazolyl group, a benzimidazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a benzothiazolyl group, a benzoisothiazolyl group, and a benzodioxolanyl group, of which a benzothiazolyl group and a benzodioxolanyl group are preferred.
• Examples of the "5- to 6-membered heterocyclyl group” include a pyrrolidinyl group, a tetrahydrofuranyl group, a thiazolidinyl group, a tetrahydro-2H-pyranyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, a dioxolanyl group, a dioxanyl group; a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, an oxazolinyl group, an isoxazolinyl group, a dihydropyranyl group, a pyrazolyl group, and the like, with a pyrazolyl group being preferred.
• R 1 and R 2 may together form a divalent organic group.
• the divalent organic group formed by R 1 and R 2 together is preferably a C3-6 alkylene group or a C3-4 alkenylene group, more preferably a trimethylene group or a divinylene group.
• Z a represents an oxygen atom, a sulfur atom, or a group represented by the formula: NR a .
• R c each independently represents a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C1-6 alkoxy group, a substituted or unsubstituted C3-6 cycloalkoxy group, a substituted or unsubstituted C1-6 alkylthio group, a substituted or unsubstituted amino group, a substituted or unsubstituted C3-6 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 3-6 membered heterocyclyl group, or a substituted or unsubstituted 3-6 membered heterocyclyloxy group.
• Examples of the "C3-6 cycloalkoxy group" in Rc include a cyclopropyloxy group, a cyclobutyloxy group, and a cyclopentyloxy group.
• An example of the hydrazide compound of the present invention is a compound represented by the following formula (I-A1) or a salt thereof.
• Each symbol in formula (IA1) has the same meaning as that in formula (ZI).
• R 7a represents a formyl group, a group represented by the formula: R c -CO-, a group represented by the formula: R c -CS-, a group represented by the formula: R c -CO-CO-, or a group represented by the formula: R c -SO 2 -.
• R c is the same as defined above for R 7 .
• the method for producing compound (Z-I) or a salt of compound (Z-I) is not particularly limited.
• compound (Z-I) or a salt of compound (Z-I) can be obtained by a known production method described in the Examples, etc.
• a salt of compound (Z-I) can be obtained from compound (Z-I) by a known method.
• the compound of formula (I-1) can be prepared by a process comprising the step of reacting a compound of formula (im-1) with a compound of formula (im-2), as shown in Scheme 1.
• Compounds of formula (im-2) are either commercially available or may be prepared by known methods.
• Compounds of formula (im-1) may be prepared by one or more of the methods described herein (see Preparation Method 4).
• the compound of formula (I-3) is a compound of compound (I) in which Z is an oxygen atom and R 7 is a group (R7 ab ) other than a hydrogen atom as defined in formula (ZI).
• the compound of formula (im-5) is a compound in which U 1 is a hydroxyl group or a halogeno group, and the other symbols are the same as defined in the compound of formula (I).
• the compound of formula (im-6) is a compound in which R 7ab is the same as defined in the compound of formula (I-1), and the other symbols are the same as defined in the compound of formula (ZI).
• the compound of formula (I-3) can be produced by reacting the compound of formula (im-5) in which U 1 is a hydroxyl group with an organic base in the presence of a condensation reagent such as a carbodiimide (e.g., N,N'-dicyclohexylcarbodiimide (DCC)), 1-hydroxy-7-azobenzotriazole (HOAt), O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), or propylphosphonic anhydride.
• a condensation reagent such as a carbodiimide (e.g., N,N'-dicyclohexylcarbodiimide (DCC)), 1-hydroxy-7-azobenzotriazole (HOAt), O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexa
• the compound of formula (I-3) can also be prepared by reacting the compound of formula (im-5) in which U 1 is a halogen atom with the compound of formula (im-6) in the presence of an acid scavenger by a well-known method.
• acid scavengers include common inorganic and organic bases, with alkali metal carbonates, alkaline earth metal acetates, tertiary amines or aromatic amines being preferred.
• the compound of formula (I-3) can be converted to a compound in which Z is a sulfur atom by using a thione oxidizing agent.
• Thione oxidizing agents include, but are not limited to, sulfur, hydrosulfic acid, sodium sulfide, sodium hydrosulfide, boron trisulfide, bis(diethylaluminum) sulfide, ammonium sulfide, phosphorus pentasulfide, Lawesson's reagent, and the like.
• the reaction may be carried out in the presence of an inorganic or organic base, preferably an alkali metal carbonate, an alkaline earth metal acetate, a tertiary amine or an aromatic amine.
• the compound of formula (im-1a) can be prepared by a process comprising the step of reacting a compound of formula (im-7) with a compound of formula (im-6), as shown in Scheme 3.
• the compound of formula (im-1a) is a compound of formula (im-1) in which Z is an oxygen atom.
• the compound of formula (im-7) is a compound in which G is a halogeno group, U 1 is a hydroxyl group or a halogeno group, and the other symbols are the same as defined in the compound of formula (ZI).
• the reagents and reaction conditions used in Production Method 3 can be the same as those described in Production Method 2.
• the compound of formula (im-9) is a compound in which U2 is a C1-6 alkoxy group, G is a halogeno group, and the other symbols are the same as defined in the compound of formula (ZI).
• the compound of formula (im-10) is a compound in which U2 is a C1-6 alkoxy group, and the other symbols are the same as defined in the compound of formula (ZI).
• the compound of formula (im-10) can be prepared by reacting the compound of formula (im-9) with the compound of formula (im-2) by a well-known method.
• the reaction may be carried out in the presence of an acid scavenger.
• acid scavengers include common inorganic and organic bases, with alkali metal carbonates, alkaline earth metal acetates, tertiary amines or aromatic amines being preferred.
• the compound of formula (im-6a) is a compound of formula (im-6) in which R 7ab is "a formyl group, a group represented by the formula: R c -CO-, a group represented by the formula: R c -CS-, a group represented by the formula: R c -CO-CO-, or a group represented by R c -SO 2 -" (hereinafter sometimes referred to as R 7a ) among the compounds of formula (Z-I), and R 6 is a hydrogen atom.
• R 7a is the same as defined in the compound of formula (im-6a).
• the compound of formula (im-20) is a compound in which U3 is a hydroxyl group or a halogeno group, and the other symbols are the same as defined in the compound of formula (ZI).
• the compound of formula (im-21) is a compound in which R 7a is the same as defined in the compound of formula (im-6a), and the other symbols are the same as defined in the compound of formula (ZI).
• the compound of formula (im-21) can be produced by reacting the compound of formula (im-20) in which U3 is a hydroxyl group with the compound of formula (im-19) in the presence of a dialkyl azodicarboxylate and triphenylphosphine. This is the so-called Mitsunobu reaction.
• dialkyl azodicarboxylates include, but are not limited to, diethyl azodicarboxylate, diisopropyl azodicarboxylate, and the like.
• the compound of formula (im-21) can be prepared by reacting the compound of formula (im-20) in which U3 is a halogen atom with the compound of formula (im-19) in the presence of an acid scavenger by a well-known method.
• acid scavengers include common inorganic and organic bases, with alkali metal carbonates, alkaline earth metal acetates, tertiary amines or aromatic amines being preferred.
• the compound of formula (im-6b) can be produced by reacting the compound of formula (im-22) with an aminating agent such as O-mesitylenesulfonylhydroxylamine or O-(2,4-dinitrophenyl)hydroxyamino, or by reacting the compound with sodium nitrite under acidic conditions to convert it to an N-nitrosamine, and then reacting the compound with a reducing agent.
• an aminating agent such as O-mesitylenesulfonylhydroxylamine or O-(2,4-dinitrophenyl)hydroxyamino
• reducing agents include, but are not limited to, lithium aluminum hydride and diisobutylaluminum hydride.
• the compound of formula (im-6c) is a compound of formula (im-6) in which R 6 is a group defined in formula (Z-I) other than a hydrogen atom (hereinafter, sometimes referred to as R 6a ).
• the compound of formula (im-23) is a compound in which G2 is a halogeno group, and R6a is the same as defined in formula (im-6c).
• the compound of formula (im-6c) can be produced by reacting the compound of formula (im-6a) or the compound of formula (im-6b) with the compound of formula (im-23). The reaction is preferably carried out in the presence of an inorganic base.
• Compounds of formula (im-23) are either commercially available or may be prepared by known methods.
• G is a halogeno group, and the other symbols are the same as defined in the compound of formula (I-A1).
• the compound of formula (im-A2) is a compound in which the symbols are the same as those defined in the compound of formula (ZI).
• the compound of formula (I-A1) can be prepared by reacting the compound of formula (im-A1) with the compound of formula (im-A2) by a known method.
• the reaction may be carried out in the presence of an acid scavenger.
• acid scavengers include common inorganic and organic bases, with alkali metal carbonates, alkaline earth metal acetates, tertiary amines or aromatic amines being preferred.
• Compounds of formula (im-A2) are either commercially available or may be prepared by known methods.
• Compounds of formula (im-A1) may be prepared by one or more of the methods described herein (see Preparation Method 10).
• the compound of formula (im-A5) is a compound in which U1 is a hydroxyl group or a halogeno group, and the other symbols are the same as defined in the compound of formula (ZI).
• the compound of formula (im-6a) is a compound in which R 7a is the same as defined in the compound of formula (I-A1), and the other symbols are the same as defined in the compound of formula (Z-I).
• the compound of formula (I-A1) can be produced by reacting a compound of formula (im-A5) in which U 1 is a hydroxyl group with a compound of formula (im-6a) in the presence of a condensing reagent.
• condensation reagents include, but are not limited to, halogenating reagents (e.g., phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus trichloride oxide, oxalyl chloride, or thionyl chloride), dehydrating agents (e.g., ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, or methanesulfonyl chloride), carbonyldiimidazole, and the like.
• halogenating reagents e.g., phosgene, phosphorus tribromide,
• the compound of formula (I-A1) can be prepared by reacting a compound of formula (im-A5) in which U 1 is a halogen atom with a compound of formula (im-6a) in the presence of an acid scavenger by a well-known method.
• acid scavengers include common inorganic and organic bases, with alkali metal carbonates, alkaline earth metal acetates, tertiary amines or aromatic amines being preferred.
• the compound of formula (im-A5) may be commercially available or may be prepared according to the methods described in the literature (e.g., JP-T-2022-508277 and JP-T-2022-514651). It may also be prepared by one or more of the methods described herein (see Preparation Methods 4 and 11).
• Compounds of formula (im-6a) may be commercially available or may be prepared by one or more of the methods described herein (see Preparation Method 5).
• the compound of formula (im-A5) can be prepared by a process comprising the steps of reacting a compound of formula (im-9) with a compound of formula (im-A2), and converting the compound of formula (im-A10) obtained by the reaction into the compound of formula (im-A5), as shown in Scheme 11.
• the compound of formula (im-9) may be commercially available or may be prepared by known methods.
• the compound represented by formula (I') (hereinafter sometimes referred to as compound (I')) can be produced, when Zb is a C1-6 alkylthio group, by thioamidating compound (I) using a thione oxidizing agent such as Lawesson's reagent, followed by reacting with a corresponding alkyl halide.
• Z b is a C1-6 alkoxy group, it can be produced by reacting with an oxonium salt such as trimethyloxonium tetrafluoroborate, triethyloxonium tetrafluoroborate, or the like.
• Plant diseases pathogens
• Sugar beet Brown spot disease (Cercospora beticola), black root disease (Aphanomyces cochlioides), root rot disease (Thanatephorus cucumeris), leaf rot disease (Thanatephorus cucumeris), rust disease (Uromyces betae), powdery mildew (Oidium sp.), leaf spot disease (Ramularia beticola), seedling damping-off disease (Aphanomyces cochlioides, Pythium ultimum), etc.
• Pepper Phytophthora capsici, Gray mold (Botrytis cinerea), Sclerotinia sclerotiorum, Anthracnose (Colletotrichum aenigma, Colletotrichum capsici, Colletotrichum fructicola, Colletotrichum jiangxiense), Powdery mildew (Leveillula taurica), etc.
• Green onion soft rot (Pectobacterium carotovorum), downy mildew (Peronospora destructor), leaf blight (Pleospora all II), black rot sclerotium rot (Sclerotium cepivorum), rust (Puccinia all II), white spotted leaf spot (Botrytis squamosa), white blight (Sclerotium rolfsII), pink root rot (Pyrenochaeta terrestris), etc.
• Cabbage clubroot (Plasmodiophora brassicae), soft rot (Erwinia carotovora), black rot (Xanthomonas campesrtis pv.
• Citrus scab (Elsinoe fawcett II), blue mold (Penicillium italicum), green mold (Penicillium digitatum), gray mold (Botrytis cinerea), black spot (Diaporthe citri), canker (Xanthomonas campestris pv.Citri), powdery mildew (Oidium sp.), blight (Phytophthora citrophthora), anthracnose (Colletotrichum fioriniae), etc.
• Rice blast (Pyricularia oryzae), Rhizoctonia solani, Gibberella fujikuroi, Cochliobolus miyabeanus, Pythium graminicola, Xanthomonas oryzae, Burkholderia plantar II, Acidovorax avenae, Burkholderia glumae, Cercospora oryzae, Ustilaginoidea virens, Alternaria alternata, Curvularia intermedia, Alternaria padwick II, Epicoccum purpurascens, etc.
• Chrysanthemums gray mold (Botrytis cinerea), white rust (Puccinia horiana), downy mildew (Paraperonospora minor, Peronospora danica), Pythium damping-off (Pythium aphanidermatum, Pythium dissotocum, Pythium helicoides, Pythium oedochilum, Pythium sylvaticum), damping-off (Rhizoctonia solani), Fusarium wilt (Fusarium solani), etc.
• Gerbera Gray mold (Botrytis cinerea), Powdery mildew (Podosphaera xanth II), etc.
• Soybean Purple spot (Cercospora kikuch II), Downy mildew (Peronospora manshurica), Stem rot (Phytophthora sojae), Rust (Phakopsora pachyrhizi), Sclerotinia sclerotiorum, Anthracnose (Colletotrichum truncatum), Gray mold (Botrytis cinerea), Black rot (Elsinoe glycines), Black spot (Diaporthe phaseolorum var.
• nigrescens black leg disease (Pectobacterium atrosepticum), soft rot (Pectobacterium carotovorum), gray mold (Botrytis cinerea), scab (Streptomyces spp.), sclerotinia sclerotiorum), etc.
• Yam leaf blight (Cylindrosporium dioscoreae), anthracnose (Colletotrichum gloeosporioides), blue mold (Penicillium sclerotigenum), etc.
• Sweet potato purple root rot (Helicobasidium mompa), vine split (Fusarium oxysporum), etc.
• the agricultural and horticultural fungicide of the present invention is not particularly limited by its formulation.
• it can be in the form of wettable powder, emulsifiable concentrate, powder, granule, water-soluble powder, suspension, granular wettable powder, tablet, etc.
• the preparation method is not particularly limited, and a known preparation method can be adopted according to the formulation.
• Step 3 Conversion to 3-(3-cyclopropyl-2-fluorophenoxy)-N'-(2,4-dimethylbenzyl)-6-methylpyridazine-4-carbohydrazide
• Step 1 Conversion to N-(2,4-dimethylbenzyl)-N-(1,3-dioxoisoindolin-2-yl)acetamide
• Step 3 Conversion to tert-butyl 2-bromo-5-(3-cyclopropyl-2-fluorophenoxy)isonicotinate
• Step 5 Conversion to 5-(3-cyclopropyl-2-fluorophenoxy)-2-methylisonicotinic acid
• Step 6 Conversion to N'-acetyl-5-(3-cyclopropyl-2-fluorophenoxy)-N'-(2,4-dimethylbenzyl)-2-methylisonicotinohydrazide
• Step 3 Conversion to methyl 2-(3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate
• Step 1 Conversion to N-(1,3-dioxoisoindolin-2-yl)methanesulfonamide
• Step 2 Conversion to N-(2,4-dimethylbenzyl)-N-(1,3-dioxoisoindolin-2-yl)methanesulfonamide
• Step 4 Conversion to N'-(3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazine-4-carbonyl)-N-(2,4-dimethylbenzyl)methanesulfonohydrazide
• Step 1 Conversion to methyl ((2,6-dichloropyridin-3-yl)methyl)(1,3-dioxoisoindolin-2-yl)carbamate
• Step 2 Conversion to methyl 1-((2,6-dichloropyridin-3-yl)methyl)hydrazine-1-carboxylate
• Step 3 Conversion to methyl 2-(3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazine-4-carbonyl)-1-((2,6-dichloropyridin-3-yl)methyl)hydrazine-1-carboxylate
• Step 2 Conversion to 3-(3-cyclopropyl-2-fluorophenoxy)-N'-(2,4-dimethylbenzyl)-N'-ethanethioyl-6-methylpyridazine-4-carbohydrazide
• Step 2 Conversion to methyl 2-(3-(3-chloro-2-fluorophenoxy)-6-methylpyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate
• Step 1 Conversion to methyl 2-(3-chloro-6,7-dihydro-5H-cyclopenta[c]pyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate
• Step 2 Conversion to methyl 2-(3-(3-bromo-2-fluorophenoxy)-6,7-dihydro-5H-cyclopenta[c]pyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate
• Step 1 Conversion to 6-chloro-3-((3-(trifluoromethyl)phenyl)amino)pyridazine-4-carboxylic acid
• Step 2 Conversion to methyl 2-(6-chloro-3-((3-(trifluoromethyl)phenyl)amino)pyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate
• Measurements were performed at a temperature of 40°C, a flow rate of 0.6 mL/min, and 2 ⁇ L injection.
• Water containing 0.1% formic acid was used as the mobile phase (A), and acetonitrile was used as the mobile phase (B).
• the concentration of the mobile phase (B) was maintained at 30% by mass for 0.15 minutes, then the concentration of the mobile phase (B) was increased at a constant rate from 30% by mass to 95% by mass over 1.35 minutes and maintained at 95% by mass for 0.5 minutes, then the concentration of the mobile phase (B) was immediately decreased to 30% by mass, and finally the concentration of the mobile phase (B) was maintained at 30% by mass for 0.50 minutes.
• LCMS (QDa) retention times were determined by the following method.
• a CORTECS UPLC C18 column Waters, 2.1 x 50 mm, 1.6 ⁇ m
• a CORTECS UPLC C18 column was attached to a system consisting of an ultra-high-speed high-resolution liquid chromatograph (ACQUITY UPLC H-Class: Waters), an HPLC/UHPLC detector (ACQUITY UPLC Photodiode Array (PDA) e ⁇ detector (Waters)), and a single quadrupole MS detector (LC/MS) (ACQUITY QDa detector (positive and negative ion electrospray mode)). Measurements were performed at a temperature of 40°C, a flow rate of 0.6 mL/min, and 2 ⁇ L injection.
• the concentration of the mobile phase (B) was maintained at 30% by mass for 0.15 minutes, then increased at a constant rate from 30% by mass to 95% by mass over 1.35 minutes and maintained at 95% by mass for 0.5 minutes, then the concentration of the mobile phase (B) was immediately decreased to 30% by mass, and finally the concentration of the mobile phase (B) was maintained at 30% by mass for 0.50 minutes.
• Step 1 Conversion to methyl 5-methoxypyridazine-4-carboxylate
• Step 4 Conversion to cyclopropyl 1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate
• Step 5 Conversion to cyclopropyl 2-(3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate (compound b-184)
• Step 1 Conversion to methyl 2-(3-(3-chloro-2-fluorophenoxy)-6-methylpyridazine-4-carbonothioyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate
• Methyl 2-(3-(3-chloro-2-fluorophenoxy)-6-methylpyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate (0.50 g) was dissolved in 1,4-dioxane (3.5 mL), Lawesson's reagent (0.43 g) was added thereto, and the mixture was stirred at 80° C. for 2 hours.
• Step 2 Conversion to methyl (Z)-2-((3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl)(methylthio)methylene-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate (compound number b-219))
• Methyl 2-(3-(3-chloro-2-fluorophenoxy)-6-methylpyridazine-4-carbonothioyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate (0.05 g) was dissolved in acetonitrile (0.34 mL). To this was added iodomethane (0.044 g) and potassium carbonate (0.028 g), and the mixture was stirred at room temperature for 2 hours.
• Methyl 2-(3-(3-chloro-2-fluorophenoxy)-6-methylpyridazine-4-carbonyl)-1-(2,4-dimethylbenzyl)hydrazine-1-carboxylate (0.10 g) was dissolved in dichloromethane (0.70 mL). Trimethyloxonium tetrafluoroborate (0.063 g) was added to the solution at 0° C. and stirred at room temperature for 3 hours.
• a drug solution containing the hydrazide compound of the present invention was then sprayed onto cucumber seedlings (variety "Jihai", cotyledon stage) grown in seedling pots, and then air-dried. Thereafter, a conidiospore suspension of Botrytis cinerea was dropwise inoculated onto the seedlings (treated area). As a control, a conidiospore suspension of Botrytis cinerea was dropwise inoculated onto cucumber seedlings that had not been sprayed with the drug solution (untreated area). These were then left to stand in a moist chamber at 20°C. Four days after inoculation, the leaves of the cucumber seedlings were visually observed, and the control value was calculated from the lesion area ratio using the following formula.
• Control value (%) 100 - ⁇ lesion area rate in treated area/lesion area rate in untreated area ⁇ x 100

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