WO1996036615A1 - Amides cycliques fongicides - Google Patents

Amides cycliques fongicides Download PDF

Info

Publication number
WO1996036615A1
WO1996036615A1 PCT/US1995/005847 US9505847W WO9636615A1 WO 1996036615 A1 WO1996036615 A1 WO 1996036615A1 US 9505847 W US9505847 W US 9505847W WO 9636615 A1 WO9636615 A1 WO 9636615A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
optionally substituted
haloalkyl
halogen
alkoxy
Prior art date
Application number
PCT/US1995/005847
Other languages
English (en)
Inventor
Richard James Brown
King-Mo Sun
Deborah Ann Frasier
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to PCT/US1995/005847 priority Critical patent/WO1996036615A1/fr
Priority to JP8534772A priority patent/JP2771334B2/ja
Publication of WO1996036615A1 publication Critical patent/WO1996036615A1/fr
Priority to KR1019970700264A priority patent/KR970704709A/ko

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/12—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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
    • 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
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen 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
    • 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
    • C07D417/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • This invention relates to cyclic amides substituted at the ⁇ -position with various aryl groups, their agriculturally suitable salts and compositions, and methods of their use as general or selective fungicides.
  • EP-A-398,692 discloses amides of Formula i as fungicides for crop protection.
  • Compounds of Formula i are:
  • R 1 and R 2 are each hydrogen, lower alkyl, or lower cycloalkyl. All the compounds disclosed in EP-A-398,692 have an aryl moiety bonded to an acyclic alkoxyiminoacetamide group. The cyclic amides of the present invention are not disclosed therein.
  • WO 93/07116 discloses compounds of Formula ii as fungicides for crop protection.
  • Compounds of Formula ii are:
  • This invention comprises compounds of Formula I including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides:
  • A is O; S; N; NR 5 ; or CR 14 ;
  • G is C or N; provided that when G is C, A is O, S or NR 5 and the floating double bond is attached to G; and when G is N, A is N or CR 14 and the floating double bond is attached to A; W is O or S;
  • X is OR 1 ; SCO ⁇ R 1 ; or halogen;
  • R 1 is C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C 2 -C 4 alkylcarbonyl, C 2 -C alkoxy carbonyl; or benzoyl optionally substituted with R 13 ;
  • R 2 and R 5 are each independently H; C r C 6 alkyl; C C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C6 haloalkynyl; C ⁇ -Cg cycloalkyl; C2-
  • R 3 and R 4 are each independently H; halogen; cyano; nitro; C j -Cg alkyl; C C ⁇ haloalkyl; C 2 -C 6 alkenyl; C2-C6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C ⁇ -C 6 alkoxy; C r C 6 haloalkoxy; C2- alkenyloxy; or C2-Cg alkynyloxy;
  • Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to the phenyl ring and the moiety on the right side of the linkage is bonded to Z;
  • R 6 is independently H or C1-C3 alkyl;
  • R 7 is H; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; cyano; or morpholinyl; Z is CI -CI Q alkyl, C2-C1 Q .
  • each nonaromatic or aromatic ring system optionally substituted with one of R 9 , R 10 , or both R 9 and R 10 ; or R 7 and Z are taken together to form CH 2 CH 2 CH 2 , CH2CH2CH2CH2,
  • R 3 , Y, and Z are taken together with the phenyl ring to form a naphthalene ring substituted on either ring with a floating R 4 ; provided that when R 3 , Y, and
  • Z are taken together with the phenyl ring to form a napthylene ring substituted by R 4 , and A is S, W is O, X is SCH 3 and R 2 is CH 3 , then R 4 is other than H; J is -CH 2 -; -CH 2 CH 2 -; -OCH 2 -; -CH 2 O-; -SCH 2 -; -CH 2 S-; -N(R 16 )CH 2 -; or
  • R 8 is 1-6 halogen; C ⁇ -C 6 alkoxy; C ⁇ -C 6 haloalkoxy; C j -Cg alkylthio; C j -Cg haloalkylthio; C ⁇ -C 6 alkylsulfmyl; C ⁇ -C 6 alkylsulfonyl; C 3 -C 6 cycloalkyl;
  • R 8 is phenyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R 11 , R 12 , or both R 11 and R 12 ;
  • R 9 is 1-2 halogen; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C 2 -C6 alkenyl; C2 ⁇ C 6 haloalkenyl; C 2 -C6 alkynyl; C j -Cg alkylthio; C r C 6 haloalkylthio; C j
  • N(C!-C 6 alkyl) 2 ; -C(R 18 ) NOR 17 ; cyano; or nitro; or R 9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R 11 ,
  • R 12 or both R 11 and R 12 ;
  • R 10 is halogen; Cj-C 4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano; or R 9 and R 10 , when attached to adjacent atoms, are taken together as -OCH 2 O- or -OCH 2 CH 2 O-; each CH2 group optionally substituted with 1-2 halogen;
  • R 1 1 and R 12 are each independently halogen; C r C 4 alkyl; C r C haloalkyl; C r C alkoxy; C1-C4 haloalkoxy; nitro; or cyano;
  • R 13 is halogen; C ⁇ -C 3 alkyl; haloalkyl; C r C 3 alkoxy; C r C 3 haloalkoxy; nitro; or cyano;
  • R 14 is H; halogen; C 1 -C 6 alkyl; C ⁇ -C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl;
  • R 15 , R 16 , R 17 , and R 18 are each independently H; C r C 3 alkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C
  • Z is other than alkyl, haloalkyl or alkoxy
  • alkyl used either alone or in compound words such as "haloalkyl” denotes straight-chain or branched alkyl; e.g., methyl, ethyl, n-propyl, z ' -propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl denotes straight-chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also denotes polyenes such as 1,3-hexadiene.
  • Alkynyl denotes straight-chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also denote moieties comprised of multiple triple bonds; e.g., 2,4-hexadiyne.
  • Alkoxy denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkynyloxy denotes straight-chain or branched alkynyloxy moieties. Examples include HC ⁇ CCH 2 O, CH 3 C ⁇ CCH 2 O and CH 3 C ⁇ CCH 2 CH 2 O.
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl moieties.
  • nonaromatic heterocyclic ring system includes fully saturated heterocycles and partially aromatic heterocycles.
  • the total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 10.
  • Cj-Cj designates methyl through propyl
  • C2 alkoxy designates CH 3 CH2 ⁇
  • C 3 alkoxy designates, for example, CH3CH2CH2O or (CH 3 ) 2 CHO.
  • R 2 is H; C r C 6 alkyl; C r C 6 haloalkyl; or C 3 -C 6 cycloalkyl;
  • R 3 and R 4 are each independently H; halogen; cyano; nitro; C alkyl;
  • R 7 is H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; or cyano;
  • Z is CJ-CJO alkyl optionally substituted with R 8 ; or C 3 -Cg cycloalkyl or phenyl, each optionally substituted with one of R 9 , R 10 , or both R 9 and R 10 ; or Z is
  • each group optionally substituted with one R 9 , R 10 , or both R 9 and R 10 ; or
  • R 3 , Y, and Z are taken together with the phenyl ring to form a naphthalene ring substituted on either ring with a floating R 4 ; or Y and Z are taken together to form
  • R 8 is 1-6 halogen; Ci-Cg alkoxy; C j -Cg haloalkoxy; or R 8 is phenyl, phenoxy, pyridinyl, pyridinyloxy, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R 1 J , R 12 , or both R 11 and R 12 ;
  • R 9 is 1-2 halogen; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C r C 6 alkylthio; cyano; CO 2 (C r C 6 alkyl); NH(C 1 -C 6 alkyl); or N(C r C 6 alkyl) 2 ; or R 9 is C 3 -C 6 cycloalkyl, phenyl, phenoxy, pyridinyl, pyridinyloxy, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R 11 , R 12 , or both R 11 and R 12 ; and
  • R 19 is H; C ⁇ -C 6 alkyl; Cj-Cg haloalkyl; or phenyl optionally substituted with halogen, alkyl, C1-C4 haloalkyl, C r C alkoxy, C ⁇ -C 4 haloalkoxy, nitro or cyano.
  • Preferred 2 Compounds of Preferred 1 wherein:
  • Z is phenyl or Z-l to Z-21, each optionally substituted with one of R 9 , R 10 , or both R 9 and R 10 ; or Y and Z are taken together to form
  • J is -CH 2 - or -CH 2 CH 2 -; p is 0; and r is 1.
  • Preferred 3 Compounds of Preferred 2 wherein: A is O; N; NR 5 ; or CR 14 ; X is OR 1 ; R 1 is C r C 3 alkyl; R 2 is H or C r C 2 alkyl;
  • R 3 and R 4 are each H
  • R 7 is H; C r C 2 alkyl; or C r C 2 haloalkyl.
  • R 7 is H; C r C 2 alkyl; or C r C 2 haloalkyl.
  • Preferred 6 Compounds of Preferred 4 wherein: R 1 is methyl; R 2 is methyl; and Z is phenyl optionally substituted with one of R 9 , R 10 , or both R 9 and
  • Z is phenyl optionally substituted with one of R 9 , R 10 , or both R 9 and RIO.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers and geometric isomers.
  • One skilled in the art will appreciate that one stereoisomer may be more active than the others and how to separate said stereoisomers.
  • the present invention comprises mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
  • a compound of Formula I wherein R 2 is H may exist as tautomer la or lb, or both la and lb.
  • the present invention comprises all tautomeric forms of compounds of Formula I.
  • Procedures 1) to 5 describe syntheses involving construction of the amide ring after the formation of the aryl moiety.
  • Procedure 5) describes syntheses of the aryl moiety with the amide ring already in place.
  • the compounds of Formula I are prepared by treating compounds of Formula 1 with an appropriate alkyl transfer reagent in an inert solvent with or without additional acidic or basic reagents or other reagents (Scheme 1).
  • Suitable solvents are selected from the group consisting of polar aprotic solvents such as acetonitrile, dimethylformamide or dimethylsulfoxide; ethers such as tetrahydrofuran, dimethoxy ethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; and halocarbons such as dichloromethane or chloroform.
  • polar aprotic solvents such as acetonitrile, dimethylformamide or dimethylsulfoxide
  • ethers such as tetrahydrofuran, dimethoxy ethane, or diethyl ether
  • ketones such as acetone or 2-butanone
  • a protic cosolvent such as methanol.
  • compounds of Formula I can also be prepared by contacting carbonyl compounds of Formula 1 with alkyl trichloroacetimidates of Formula 3 and a Lewis acid catalyst.
  • Suitable Lewis acids include trimethylsilyl triflate and tetrafluoroboric acid.
  • the alkyl trichloroacetimidates can be prepared from the appropriate alcohol and trichloroacetonitrile as described in the literature (J. Danklmaier and H. Honig, Synth. Commun., (1990), 20, 203).
  • Compounds of Formula I can also be prepared from compounds of Formula 1 by treatment with a trialkyloxonium tetrafluoroborate (i.e., Meerwein's salt) of Formula 4 (Method 3).
  • a trialkyloxonium tetrafluoroborate i.e., Meerwein's salt
  • the use of trialkyloxonium salts as powerful alkylating agents is well known in the art (see U. Sch ⁇ llkopf, U. Groth, C. Deng, Angew. Chem., Int. Ed. Engl, (1981), 20, 798).
  • alkylating agents which can convert carbonyl compounds of Formula 1 to compounds of Formula I are dialkyl sulfates such as dimethyl sulfate, haloalkyl sulfonates such as methyl trifluoromethanesulfonate, and alky halides such as iodomethane and propargyl bromide (Method 4). These alkylations can be conducted with or without additional base.
  • Appropriate bases include alkali metal alkoxides such as potassium te/ -butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and triethylenediamine.
  • alkali metal alkoxides such as potassium te/ -butoxide
  • inorganic bases such as sodium hydride and potassium carbonate
  • tertiary amines such as triethylamine, pyridine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and triethylenediamine.
  • the nucleophiles of Formula 6 are N-substituted hydroxylamines (HO- ⁇ HR 2 ) and substituted hydrazines (H ⁇ (R 5 )- ⁇ HR 2 ). Examples of such nucleophiles are N-methylhydroxylamine and methylhydrazine.
  • the preparation of the malonate esters of Formula 5 can be prepared by methods described hereinafter.
  • T CXC1-C4 alkyl), ⁇ , 1-imidazolyl
  • Esters of Formula 5a can be prepared from copper (I)-catalyzed reaction of malonate esters of Formula 7 with substituted iodobenzenes of Formula 8 according to methods adapted from A. Osuka, T. Kobayashi and H. Suzuki, Synthesis , (1983), 67, and illustrated in Scheme 3.
  • R 20 C 1 -C 4 alkyl
  • the malonate esters of Formula 5a can be prepared by treating phenyl acetic acid esters of Formula 9 with a dialkyl carbonate or alkyl chloroformate in the presence of a suitable base such as, but not limited to, sodium metal and sodium hydride (Scheme 4).
  • a suitable base such as, but not limited to, sodium metal and sodium hydride
  • R 20 C ] -C 4 alkyl
  • Esters of Formula 9 can be prepared from acid-catalyzed alcoholysis of phenyl acetonitriles of Formula 10 or esterification of phenyl acetic acids of Formula 11 as illustrated in Scheme 5 (see Org. Synth., Coll. Vol. I, (1941), 270).
  • R 20 C l -C 4 a ⁇ ky ⁇
  • Phenyl acetic acid esters of Formula 9a can also be prepared by copper (I)-catalyzed condensation of phenyl halides of Formula 12 with compounds of Formula 13 as described in EP-A-307,103 and illustrated below in Scheme 6. 6615
  • R 20 C r C 4 alkyl
  • esters of Formula 9 can also be prepared by forming the Y 2 bridge using conventional nucleophilic substitution chemistry (Scheme 7). Displacement of an appropriate leaving group (Lg) in electrophiles of Formula 15 or 16 with a nucleophilic ester of Formula 14 affords compounds of Formula 9b.
  • a base for example sodium hydride, is used to generate the corresponding alkoxide or thioalkoxide of the compound of Formula 14.
  • R 20 C r C 4 alkyl
  • R 21 OE SH, CHR 6 OH, CHR 6 SH
  • Y 2 O, S, OCHR 6 , SCHR 6 , CH ⁇ O, CHR 6 S
  • esters of Formula 9 can also be prepared by forming the Y 3 bridge from substituted hydroxylamine 9d and carbonyl compounds 14a.
  • the hydroxylamine 9d is in turn prepared from esters 9c. This method has been described in EP-600,835 and illustrated in Scheme 8.
  • Compounds of Formula I can also be prepared by reaction of Formula 17 compounds with alkali metal alkoxides (R ⁇ 'M" 1 ") or alkali metal thioalkoxides (R ⁇ -M” 1 ") in a suitable solvent (Scheme 9).
  • the leaving group Lg 1 in the amides of Formula 17 are any group known in the art to undergo a displacement reaction of this type. Examples of suitable leaving groups include chlorine, bromine, and sulfonyl and sulfonate groups. Examples of suitable inert solvents are dimethylformamide or dimethylsulfoxide.
  • Compounds of Formula 17a can be prepared from compounds of Formula lb (compounds of Formula 1 wherein X is OH) by reaction with halogenating agents such as thionyl chloride or phosphorus oxybromide to form the corresponding ⁇ -halo-substituted derivatives (Scheme 10).
  • halogenating agents such as thionyl chloride or phosphorus oxybromide
  • compounds of Formula lb can be treated with an alkylsulfonyl halide or haloalkylsulfonyl anhydride, such as 36615
  • sulfonyl compounds of Formula 17b can be prepared by oxidation of the corresponding thio compound of Formula 18 using well-known methods for the oxidation of sulfur (see Schrenk, K. In The Chemistry ofSulphones and Sulphoxides; Patai, S. et al., Eds.; Wiley: New York, 1988). Suitable oxidizing reagents include meta-chloro-peroxybenzoic acid, hydrogen peroxide and Oxone® (KHSO5).
  • the diacyl compound of Formula 19 is treated with excess thionyl halide, for example excess thionyl chloride.
  • the product formed first is the ring-closed compound of Formula 20 which can be isolated or converted in situ to the compound of Formula 17c; see P. Molina, A. Tarraga, A. Espinosa, Synthesis, (1989), 923 for a description of this process.
  • the hydrazides of Formula 19 can be prepared as illustrated in Scheme 13.
  • Ketene dithioacetals of Formula 22a can be prepared by condensing phenyl acetic acid esters of Formula 9 with carbon disulfide in the presence of a suitable base, followed by reaction with two equivalents of an R ⁇ -halide, such as iodomethane or propargyl bromide (Scheme 15).
  • R ⁇ -halide such as iodomethane or propargyl bromide
  • the compounds of Formula 24 can be alkyl chloroformates or dialkyl carbonates. Some of these carbonylating reactions may require the addition of a base to effect reaction.
  • Appropriate bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or triethylenediamine.
  • Suitable solvents include polar aprotic solvents such as acetonitrile, dimethylformamide, or dimethylsulfoxide; ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; or halocarbons such as dichloromethane or chloroform.
  • the reaction temperature can vary between 0°C and 150°C and the reaction time can be from 1 to 72 hours depending on the choice of base, solvent, temperature, and substrates.
  • Q 1 and Q 2 are independently Cl, OCCl 3 , 0(C ⁇ -C 4 alkyl), l-iirida ⁇ Dlyl, 1,2,4-triazolyl
  • N-Amino-ureas of Formula 23 can be prepared as illustrated in Scheme 17.
  • Treatment of an aniline of Formula 25 with phosgene, thiophosgene, NN'-carbonyldiimidazole, or NN'-thiocarbonyldiimidazole produces the isocyanate or isothiocyanate of Formula 26.
  • a base can be added for reactions with phosgene or thiophosgene.
  • Subsequent treatment of the iso(thio)cyanate with an R 2 -substituted hydrazine produces the N-amino-urea of Formula 23.
  • Ureas of Formula 27 are reacted with activated 2-halocarboxylic acid derivatives such as 2-halocarboxylic acid chlorides, 2-halocarboxylic acid esters or 2-haloacyl imidazoles.
  • the initial acylation on the aniline nitrogen is followed by an intramolecular displacement of the 2-halo group to effect cyclization.
  • Base may be added to accelerate the acylation and/or the subsequent cyclization. Suitable bases include triethylamine and sodium hydride.
  • Formula lb compounds can be prepared by reaction of Formula 26 isocyanates with Formula 28a esters. As described above, base may be added to accelerate the reaction and subsequent cyclization to Formula lb compounds.
  • the ureas of Formula 27 can be prepared by either of the methods illustrated in Scheme 19.
  • an isocyanate or isothiocyanate of Formula 26 can be condensed with an amine of Formula R 2 -NH2 to form the urea.
  • the anilines and iso(thio)cyanates of Formulae 25 and 26, respectively, are commercially available or prepared by well-known methods.
  • isothiocyanates can be prepared by methods described in J. Heterocycl Chem., (1990), 6615
  • Isocyanates can be prepared as described in March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), pp 944, 1166.
  • thionating reagents such as P2 5 or Lawesson's reagent [2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4- diphosphetane-2,4-disulf ⁇ de] as illustrated in Scheme 20 (see Bull Soc Chim. Belg. , (1978), 87, 229; and Tetrahedron Lett.
  • a base for example sodium hydride
  • Benzyl halides of Formula 29 can be prepared by radical halogenation of the corresponding alkyl compound (i.e., H instead of halogen in Formula 29), or by acidic cleavage of the corresponding methylether (i.e., OMe instead of halogen in Formula 29).
  • Treatment of the benzyl halides of Formula 29 with triphenylphosphine or a trialkylphosphite produces the corresponding phosphonium salt (Formula 30) or phosphonate (Formula 31), respectively.
  • the olefins of Formula lg can be converted to the saturated compounds of Formula Hi by hydrogenation over a metal catalyst such palladium on carbon as is well-known in the art (Rylander, Catalytic Hydrogenation in Organic Synthesis; Academic: New York, 1979).
  • Formula Ii alkynes can be prepared by halogenation/dehalogenation of Formula lg olefins using procedures well-known in the art (March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), p 924). Additionally, Formula Ii alkynes can be prepared by well-known reaction of aromatic halides with alkyne derivatives in the presence of catalysts such as nickel or palladium (see J. Organomet. Chem., (1975), 93 253-257).
  • the olefin of Formula lg can also be prepared by reversing the reactivity of the reactants in the Wittig or Horner-Emmons condensation.
  • 2-alkylphenyl derivatives of Formula 31 can be converted into the corresponding dibromo-compound of Formula 33 as illustrated in Scheme 23 (see Synthesis, (1988), 330).
  • the dibromo- compound can be hydrolyzed to the carbonyl compound of Formula 34, which in turn can be condensed with a phosphorus-containing nucleophile of Formula 35 or 36 to afford the olefin of Formula lg. 6615
  • Carbamates of Formula Ik can be prepared by reacting benzyl alcohols of Formula 38 with isocyanates of Formula 39 (Scheme 25).
  • a base such as triethylamine can be added to catalyze the reaction.
  • Methyl 2-(3-methoxyphenoxy)phenylacetate (6.81 g) was dissolved in 11 mL of dimethyl carbonate and 600 mg of sodium was added. The mixture was heated at reflux for 10 h, then cooled. The reaction mixture was quenched with water, acidified with concentrated aqueous HC1 and extracted with dichloromethane. The combined organic extracts were dried (MgSO4), filtered and concentrated under reduced pressure to give an oil. The desired material was separated from unreacted starting material by flash chromatography (4: 1 hexane: ethyl acetate as eluant) to yield after concentration, 3.54 g (43%) of the title compound of Step B.
  • N-Methylhydroxylamine hydrochloride (2.79 g) was dissolved in 20 mL of methanol at reflux. The solution was cooled and treated with a solution of 3.76 g potassium hydroxide in 15 mL of methanol. The precipitated potassium chloride was removed by filtration and a solution of 3.54 g of dimethyl [2-(3-methoxyphenoxy)- phenyl]propanedioate in 25 mL of methanol was added dropwise. The mixture was stirred at room temperature overnight. The reaction mixture was concentrated under vacuum to a volume of about 30 mL and acidified with concentrated aqueous HC1, with cooling. The solvents were removed under reduced pressure and the residue was partitioned between water and dichloromethane.
  • Step A Preparation of l-(Bromomethyl>2-iodobenzene
  • Step B Preparation of l-Iodo-2-[f2-methyrphenoxy)methyl1benzene
  • Step C Preparation of Dimethyl f2-r(2-methylphenoxy)methyl1phenyllpropanedioate
  • sodium hydride (60% oil dispersion) (15.4 g) in 90 mL of l,3-dimethyl-3,4,5,6-tetrahydro-2 [lH]-pyrimidinone (DMPU)
  • DMPU l,3-dimethyl-3,4,5,6-tetrahydro-2 [lH]-pyrimidinone
  • Step D Preparation of 5-Hydroxy-4-[2-r(2-methylphenoxy ' )methyl1phenyl1-3(2H)- isoxazolone
  • N-methylhydroxylamine hydrochloride 34.7 g
  • potassium hydroxide 46.6 g
  • methanol 80 mL
  • the potassium chloride precipitate was removed by filtration and a solution of dimethyl [2-[(2-methylphenoxy)methyl]phenyl]propanedioate (44 g) in 100 mL of methanol was added to the N-methyl-hydroxylamine solution.
  • Step B Preparation of 2-Methyl-4-f 2-phenoxyphenyl)-5-thioxo- 1.2.4-triazolidin-3-one A solution of 1.54 g of l-methyl-N-(2-phenoxyphenyl)hydrazinecarboxamide in
  • Step C Preparation of 2.4-Dihvdro-2-methyl-5-f methylthio)-4-f 2-phenoxyphenylV 3H- 1.2.4 triazol-3-one
  • a solution of 900 mg of crude 2-methyl-4-(2-phenoxyphenyl)-5-thioxo- 1,2,4- triazolidin-3-one in 50 mL of tetrahydrofuran was treated with 150 mg of sodium hydride (60% oil dispersion). After 5 minutes, 0.5 mL of iodomethane was added, and the mixture was stirred at ambient temperature overnight. The solid was removed by filtration and the filtrate concentrated to an oil. The oil was partitioned between ether and IN hydrochloric acid solution.
  • Step A Preparation of 2.2-Dimethyl-N-f2-methylphenyl) hydrazine carboxamide o-Tolyl isocyanate (10.0 g) was dissolved in 75 mL toluene under N 2 . The solution was cooled to 5°C and to this was slowly added a solution in toluene of 1,1-dimethylhydrazine (5.7 mL). After addition, the ice-bath was removed and the resulting slurry allowed to stir an additional 10 minutes. The solid was filtered off rinsing successively with hexane, a small amount of 20% diethylether/hexane, then hexanes again.
  • Step B Preparation of 5-Chloro 2.4-dihydro-2-methyl-4-f2-methyrphenylV3H- 1.2.4- triazol-3-one
  • a solution of 11.1 g 2,2-dimethyl-N-(2-methylphenyl) hydrazine carboxamide dissolved in 600 mL methylene chloride under N 2 was added 17.1 g triphosgene.
  • the solution was heated at refulx overnight, cooled, then concentrated under reduced pressure.
  • the resulting residue was dissolved in ethyl acetate and washed with water, then saturated aqueous NaCl.
  • the organic phase was dried (MgSO 4 ), filtered, and concentrated under reduced pressure.
  • Step C Preparation of 2.4-Dihvdro-5-methoxy-2-methyl-4-f 2-methyl ⁇ henyl)-3H- 1.2.4- triazol-3-one
  • 8.25 g 5-chloro-2,4-dihydro-2-methyl-4-(2-methylphenyl)-3H- 1 ,2,4-triazol-3-one was dissolved in 80 mL 1 : 1 dimethoxyethane/methanol under N 2 .
  • 14.0 mL sodium methoxide (30% solution in methanol) was added and the solution was heated at reflux for 3 h. The mixture was allowed to cool, diluted with ethyl acetate, washed with water, then saturated aqueous NaCl.
  • N-bromosuccinimide (6.53 g) followed by a catalytic amount of benzoyl peroxide.
  • the solution was heated at reflux for 2 h.
  • Another 1.63 g N-bromosuccinimide and a catalytic amount of benzoyl peroxide were added and the solution was heated at reflux for an hour.
  • Step E Preparation of 2.4-Dihydro-5-methoxy-2-methyl-4-[ " 2-[Tr( , phenylmethylene - amineloxy1methyl1phenyll-3H- 1 ,2.4-triazol-3-one 0.40 g 4-[2-(bromomethyl)phenyl]-2,4-dihydro-5-methoxy-2-methyl-3H- 1 ,2,4- triazol-3-one was dissolved in approximately 5 mL N,N-dimethylformamide under ⁇ 2 and to this was added 0.20 g acetophenone oxime, followed by 0.07 g of 60% sodium hydride.
  • R 2 H X A X A X A MeO O MeS O MeO S MeS S EtO O EtS O EtO S EtS S n-PrO o n-PrS o n-PrO S n-PrS s
  • H 2 C CHCH 2 0 N
  • H 2 C CHCH 2 S N
  • H 2 C CHCH 2 0 CH
  • H 2 C CHCH 2 S HC ⁇ CCH 2 S CF 3 S (c-propyl)S
  • H 2 C CHCH 2 S N HC ⁇ CCH 2 S N CF 3 S N (c-propyl)S N
  • PhO(CH 2 ) 3 PhCH CHCH 2 PhC ⁇ CCH 2 (c-propyl)CH 2 2-Br-Ph 2-Me-Ph 2-Et-Ph 6-(2-CN-PhO)-4-pyrimidinyl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO-4-pyrimidinyl 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidinyl 2-CF 3 -Ph 4-Ph-Ph 3-PhO-Ph 3-(4-pyrimidinyloxy)-Ph 2-I-Ph 3-(2-Cl-PhO)-Ph 3-(2-Et-PhO)-Ph 4-(2-thienyl)Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3-(2-pyridinyloxy)Ph 4-N0 2 -Ph 3,5-d
  • PhCH CHCH 2 PhC ⁇ CCH 2 (c-propyl)CH 2 615
  • compositions of the present invention comprise an effective amount of at least one compound of Formula I as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.
  • Useful formulations can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 weight percent.
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill.
  • Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C, (1988), pp 251-259.
  • Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-148, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, (1963), pp 8"57 and following, and WO 91/13546.
  • Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in DE 3,246,493.
  • Example A Wettable Powder Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example B
  • Compound 1 10.0% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
  • Compound 1 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
  • the compounds of this invention are useful as plant disease control agents.
  • the present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof , or to the plant seed or seedling, an effective amount of a compound of Formula I or a fungicidal composition containing said compound.
  • the compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina,
  • Pseudoperonospora cubensis Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasper
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as acephate, avermectin B, azinphosmethyl, bifenthrin, biphenate, buprofezin, carbofuran, chlordimeform, chlorpyrifos, cyfluthrin, deltamethrin, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, flufenprox, fluvalinate, fonophos, isofenphos, malathion, metaldehyde, metha-midophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,
  • insecticides such as acephate, averme
  • Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing.
  • the compounds can also be applied to the seed to protect the seed and seedling.
  • Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.
  • TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens.
  • the pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-D for compound descriptions.
  • Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following tests.
  • Trem® 014 polyhydric alcohol esters
  • test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f. sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings were made.
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
  • Puccinia recondita the causal agent of wheat leaf rust
  • TEST C The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.
  • Pyricularia oryzae the causal agent of rice blast
  • TEST D The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Phytophthora infestans the causal agent of potato and tomato late blight
  • TEST E The test suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days,and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings were made. 61
  • TEST F The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Botrytis cinerea the causal agent of gray mold on many crops
  • Results for Tests A-F are given in Table 1. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). 5

Landscapes

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

Abstract

L'invention concerne des amides cycliques de formule (I) utilisés comme fongicides. Dans la formule (I), A représente O, S, N, NR?5 ou CR14¿; G représente C ou N; W représente O ou S; X représente OR1, S(O)¿mR?1 ou halogène; R?1, R2 et R5¿ représentent indépendamment, en partie, alkyle C¿1?-C6; Y représente en partie -O-, -S(O)n-, -CHR?6¿O-, -OCHR?6-, -CHR6O-N=C(R7¿)-; Z représente en partie cycloalkyle, phényle, pyridinyle, pyrimidinyle ou naphtyle éventuellement substitués; et R?3, R4, R6, R7, R14¿, m et n sont définis dans la description.
PCT/US1995/005847 1995-05-16 1995-05-16 Amides cycliques fongicides WO1996036615A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/US1995/005847 WO1996036615A1 (fr) 1995-05-16 1995-05-16 Amides cycliques fongicides
JP8534772A JP2771334B2 (ja) 1995-05-16 1995-05-16 殺菌・殺カビ性環状アミド類
KR1019970700264A KR970704709A (ko) 1995-05-16 1997-01-15 살진균성 시클릭 아미드(Fungicidal Cyclic Amides)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1995/005847 WO1996036615A1 (fr) 1995-05-16 1995-05-16 Amides cycliques fongicides

Publications (1)

Publication Number Publication Date
WO1996036615A1 true WO1996036615A1 (fr) 1996-11-21

Family

ID=22249109

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/005847 WO1996036615A1 (fr) 1995-05-16 1995-05-16 Amides cycliques fongicides

Country Status (3)

Country Link
JP (1) JP2771334B2 (fr)
KR (1) KR970704709A (fr)
WO (1) WO1996036615A1 (fr)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997019935A1 (fr) * 1995-12-01 1997-06-05 E.I. Du Pont De Nemours And Company Procedes et composes pour preparer des urees cycliques utiles comme fongicides
WO1998004525A1 (fr) * 1996-07-27 1998-02-05 Agrevo Uk Limited Imides cycliques a cinq membres n-aryle fongicides
WO1998005652A2 (fr) * 1996-08-01 1998-02-12 E.I. Du Pont De Nemours And Company Amides cycliques arthropodicides et fongicides
WO1998020003A1 (fr) * 1996-11-01 1998-05-14 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
WO1998023156A1 (fr) * 1996-11-26 1998-06-04 E.I. Du Pont De Nemours And Company Fongicides et arthropodicides a substitution methyle
WO1998023155A1 (fr) * 1996-11-26 1998-06-04 E.I. Du Pont De Nemours And Company Amides cycliques arthropodicides et fongicides
WO1998037065A1 (fr) * 1997-02-19 1998-08-27 E.I. Du Pont De Nemours And Company Intermediaires d'acide n-arylsulfonamide- et pyrrolidinecarboxylique et leur utilisation pour la preparation de derives herbicides 1,3-dioxo-1h-pyrrolo[1,2-c]imidazole
WO1999007687A1 (fr) * 1997-08-05 1999-02-18 Agrevo Uk Limited Derives pesticides de 4-benzyl-1,2,4-triazolin-5-one
WO1999018102A1 (fr) * 1997-10-08 1999-04-15 E.I. Du Pont De Nemours And Company Amides cycliques fongicides et arthropodicides
EP0909760A1 (fr) * 1997-10-17 1999-04-21 ISAGRO RICERCA S.r.l. Analogues de la srobilurine à propriétés antifongiques et leur utilisation pour lutter contre les champignons phytophatogènes
WO1999028305A1 (fr) * 1997-12-01 1999-06-10 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
WO1999031070A1 (fr) * 1997-12-17 1999-06-24 Basf Aktiengesellschaft Phenylpyrazolones substituees, procede et produits intermediaires permettant de les preparer et leur utilisation pour lutter contre des champignons nuisibles et des parasites animaux
WO1999046246A1 (fr) * 1998-03-09 1999-09-16 Basf Aktiengesellschaft Benzylphenylethers a substitution hetaryle, leur procede de preparation et leur utilisation pour lutter contre les champignons parasites et les parasites animaux
US6200997B1 (en) 1998-02-05 2001-03-13 Basf Aktiengesellschaft Heterocyclyl-substituted phenyl compounds, processes and intermediates for their preparation and their use for controlling harmful fungi and animal pests
WO2001019803A1 (fr) * 1999-09-15 2001-03-22 Basf Aktiengesellschaft Ether oximes insatures et leur utilisation dans la lutte contre la peste fongique et les parasites d'animaux
WO2001028331A1 (fr) * 1999-10-20 2001-04-26 Aventis Cropscience Gmbh Traitement du bois
US6417370B1 (en) 1998-02-27 2002-07-09 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic keto-enols
US6451843B1 (en) 1998-04-27 2002-09-17 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic keto enols
US6458965B1 (en) 1998-03-26 2002-10-01 Bayer Aktiengesellschaft Aryl phenyl substituted cyclic ketoenols
US6489487B1 (en) 1998-08-03 2002-12-03 Sumitomo Chemical Company, Limited Triazolone derivatives, use thereof, and intermediates therefor
US6689776B2 (en) * 1999-06-14 2004-02-10 Syngenta Crop Protection, Inc. Fungicidal combinations
WO2005030199A1 (fr) * 2003-09-25 2005-04-07 Wyeth Derives de l'acide 4-(1-benzofuran-3-yl-methylideneaminoxy-propoxy))-benzoique et composes apparentes utilises comme inhibiteurs de pai-1 pour le traitement d'une deficience du systeme fibrinolytique et de la thrombose
US8119566B2 (en) 2003-08-14 2012-02-21 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives
RU2709732C1 (ru) * 2019-04-22 2019-12-19 ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ НАУКИ ИНСТИТУТ ОРГАНИЧЕСКОЙ ХИМИИ им. Н.Д. ЗЕЛИНСКОГО РОССИЙСКОЙ АКАДЕМИИ НАУК (ИОХ РАН) Замещенные 4-нитропиразолин-5-оны, способ их получения и их применение в качестве фунгицидных средств
US10562887B2 (en) 2016-05-27 2020-02-18 Bristol-Myers Squibb Company Triazolones and tetrazolones as inhibitors of ROCK
EP4242199A1 (fr) * 2022-03-07 2023-09-13 Basf Se Utilisation de composés de type strobilurine pour lutter contre les champignons phytopathogènes contenant une substitution d'acide aminé f129l dans la protéine mitochondriale du cytochrome b conférant une résistance aux inhibiteurs qo vii

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6075182B2 (ja) * 2012-04-27 2017-02-08 住友化学株式会社 テトラゾリノン化合物及びその用途
JP2023025308A (ja) * 2020-01-31 2023-02-22 住友化学株式会社 ＱｏＩ殺菌剤に対して耐性を有するダイズさび病菌の防除方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098896A (en) * 1975-09-29 1978-07-04 Chevron Research Company 1-Halohydrocarbylthio-3-hydrocarbylthio-4-substituted-1,2,4-delta2 -triazolidin-5-ones
EP0508126A1 (fr) * 1991-03-21 1992-10-14 Bayer Ag Dérivés de hydroxy-3-aryl-4-oxo-5-pyrazoline
WO1993007116A1 (fr) * 1991-09-30 1993-04-15 Zeneca Limited Fongicides
DE4413669A1 (de) * 1993-07-05 1995-01-12 Bayer Ag Substituierte Aryl-ketoenolheterocyclen
WO1995014009A1 (fr) * 1993-11-19 1995-05-26 E.I. Du Pont De Nemours And Company Amides cycliques fongicides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098896A (en) * 1975-09-29 1978-07-04 Chevron Research Company 1-Halohydrocarbylthio-3-hydrocarbylthio-4-substituted-1,2,4-delta2 -triazolidin-5-ones
EP0508126A1 (fr) * 1991-03-21 1992-10-14 Bayer Ag Dérivés de hydroxy-3-aryl-4-oxo-5-pyrazoline
WO1993007116A1 (fr) * 1991-09-30 1993-04-15 Zeneca Limited Fongicides
DE4413669A1 (de) * 1993-07-05 1995-01-12 Bayer Ag Substituierte Aryl-ketoenolheterocyclen
WO1995014009A1 (fr) * 1993-11-19 1995-05-26 E.I. Du Pont De Nemours And Company Amides cycliques fongicides

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997019935A1 (fr) * 1995-12-01 1997-06-05 E.I. Du Pont De Nemours And Company Procedes et composes pour preparer des urees cycliques utiles comme fongicides
WO1998004525A1 (fr) * 1996-07-27 1998-02-05 Agrevo Uk Limited Imides cycliques a cinq membres n-aryle fongicides
WO1998005652A2 (fr) * 1996-08-01 1998-02-12 E.I. Du Pont De Nemours And Company Amides cycliques arthropodicides et fongicides
WO1998005652A3 (fr) * 1996-08-01 1998-06-11 E I De Pount De Nemours And Co Amides cycliques arthropodicides et fongicides
WO1998020003A1 (fr) * 1996-11-01 1998-05-14 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
WO1998023156A1 (fr) * 1996-11-26 1998-06-04 E.I. Du Pont De Nemours And Company Fongicides et arthropodicides a substitution methyle
WO1998023155A1 (fr) * 1996-11-26 1998-06-04 E.I. Du Pont De Nemours And Company Amides cycliques arthropodicides et fongicides
WO1998037065A1 (fr) * 1997-02-19 1998-08-27 E.I. Du Pont De Nemours And Company Intermediaires d'acide n-arylsulfonamide- et pyrrolidinecarboxylique et leur utilisation pour la preparation de derives herbicides 1,3-dioxo-1h-pyrrolo[1,2-c]imidazole
US6384234B1 (en) * 1997-02-19 2002-05-07 Degussa Ag N-arylsulfonamide- and pyrrolidinecarboxylic acid intermediates, and their use for the preparation of herbicidal 1,3-dioxo-1h-pyrrolo[1,2-c]imidazole derivatives
US6664400B2 (en) 1997-02-19 2003-12-16 Degussa Ag N-arylsulfonamide and pyrrolidinecarboxylic acid intermediates, and their use for the preparation of herbicidal 1,3-dioxo-1h-pyrrolo[1,2-c]imidazole derivatives
WO1999007687A1 (fr) * 1997-08-05 1999-02-18 Agrevo Uk Limited Derives pesticides de 4-benzyl-1,2,4-triazolin-5-one
WO1999018102A1 (fr) * 1997-10-08 1999-04-15 E.I. Du Pont De Nemours And Company Amides cycliques fongicides et arthropodicides
EP0909760A1 (fr) * 1997-10-17 1999-04-21 ISAGRO RICERCA S.r.l. Analogues de la srobilurine à propriétés antifongiques et leur utilisation pour lutter contre les champignons phytophatogènes
US5994380A (en) * 1997-10-17 1999-11-30 Isagro Ricerca S.R.L. Analogs of strobilurine having fungicidal properties, and their application for controlling phytopathogenous fungi
WO1999028305A1 (fr) * 1997-12-01 1999-06-10 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
WO1999031070A1 (fr) * 1997-12-17 1999-06-24 Basf Aktiengesellschaft Phenylpyrazolones substituees, procede et produits intermediaires permettant de les preparer et leur utilisation pour lutter contre des champignons nuisibles et des parasites animaux
US6200997B1 (en) 1998-02-05 2001-03-13 Basf Aktiengesellschaft Heterocyclyl-substituted phenyl compounds, processes and intermediates for their preparation and their use for controlling harmful fungi and animal pests
US7105471B2 (en) 1998-02-27 2006-09-12 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic ketoenols
US6417370B1 (en) 1998-02-27 2002-07-09 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic keto-enols
US8058210B2 (en) 1998-02-27 2011-11-15 Bayer Cropscience Ag Arylphenyl-substituted cyclic keto-enols
US6716832B2 (en) 1998-02-27 2004-04-06 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic ketoenols
US7718706B2 (en) 1998-02-27 2010-05-18 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic keto-enols
US7288676B2 (en) 1998-02-27 2007-10-30 Bayer Cropscience Ag Arylphenyl-substituted cyclic ketoenols
WO1999046246A1 (fr) * 1998-03-09 1999-09-16 Basf Aktiengesellschaft Benzylphenylethers a substitution hetaryle, leur procede de preparation et leur utilisation pour lutter contre les champignons parasites et les parasites animaux
US6458965B1 (en) 1998-03-26 2002-10-01 Bayer Aktiengesellschaft Aryl phenyl substituted cyclic ketoenols
US6693092B2 (en) 1998-03-26 2004-02-17 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic ketoenols
US6806264B2 (en) 1998-03-26 2004-10-19 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic ketoenols
US6451843B1 (en) 1998-04-27 2002-09-17 Bayer Aktiengesellschaft Arylphenyl-substituted cyclic keto enols
US6489487B1 (en) 1998-08-03 2002-12-03 Sumitomo Chemical Company, Limited Triazolone derivatives, use thereof, and intermediates therefor
US6689776B2 (en) * 1999-06-14 2004-02-10 Syngenta Crop Protection, Inc. Fungicidal combinations
WO2001019803A1 (fr) * 1999-09-15 2001-03-22 Basf Aktiengesellschaft Ether oximes insatures et leur utilisation dans la lutte contre la peste fongique et les parasites d'animaux
US6824830B1 (en) 1999-10-20 2004-11-30 Aventis Cropscience Gmbh Wood treatment
WO2001028331A1 (fr) * 1999-10-20 2001-04-26 Aventis Cropscience Gmbh Traitement du bois
US8119566B2 (en) 2003-08-14 2012-02-21 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives
US8586783B2 (en) 2003-08-14 2013-11-19 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives
US8987500B2 (en) 2003-08-14 2015-03-24 Bayer Cropscience Ag 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives
WO2005030199A1 (fr) * 2003-09-25 2005-04-07 Wyeth Derives de l'acide 4-(1-benzofuran-3-yl-methylideneaminoxy-propoxy))-benzoique et composes apparentes utilises comme inhibiteurs de pai-1 pour le traitement d'une deficience du systeme fibrinolytique et de la thrombose
US10562887B2 (en) 2016-05-27 2020-02-18 Bristol-Myers Squibb Company Triazolones and tetrazolones as inhibitors of ROCK
RU2709732C1 (ru) * 2019-04-22 2019-12-19 ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ НАУКИ ИНСТИТУТ ОРГАНИЧЕСКОЙ ХИМИИ им. Н.Д. ЗЕЛИНСКОГО РОССИЙСКОЙ АКАДЕМИИ НАУК (ИОХ РАН) Замещенные 4-нитропиразолин-5-оны, способ их получения и их применение в качестве фунгицидных средств
EP4242199A1 (fr) * 2022-03-07 2023-09-13 Basf Se Utilisation de composés de type strobilurine pour lutter contre les champignons phytopathogènes contenant une substitution d'acide aminé f129l dans la protéine mitochondriale du cytochrome b conférant une résistance aux inhibiteurs qo vii

Also Published As

Publication number Publication date
JPH10504042A (ja) 1998-04-14
JP2771334B2 (ja) 1998-07-02
KR970704709A (ko) 1997-09-06

Similar Documents

Publication Publication Date Title
EP0729461B1 (fr) Amides cycliques fongicides
WO1996036615A1 (fr) Amides cycliques fongicides
US6057352A (en) Fungicidal cyclic amides
US6096895A (en) Heterocyclic dihydrazole compounds and their use for controlling fungal plant diseases
WO1996036229A1 (fr) Amides cycliques fongicides
US5962436A (en) Fungicidal cyclic amides
EP0836384A1 (fr) Amides cycliques arthropodicides et fongicides
WO1998023155A1 (fr) Amides cycliques arthropodicides et fongicides
EP0944314A1 (fr) Fongicides et arthropodicides a substitution methyle
EP1008589A1 (fr) Imidazolinones fongicides
EP0630370A1 (fr) Oxazolidinones fongicides
WO1999028305A1 (fr) Amides cycliques fongicides
EP0937051A1 (fr) Amides cycliques fongicides
US6022870A (en) Fungicidal cyclic amides
US6255311B1 (en) Fungicidal fused bicyclic pyrimidinones
LT4112B (en) Fungicidal cyclic amides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

WWE Wipo information: entry into national phase

Ref document number: 1019970700264

Country of ref document: KR

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 1019970700264

Country of ref document: KR

122 Ep: pct application non-entry in european phase
WWG Wipo information: grant in national office

Ref document number: 1019970700264

Country of ref document: KR