WO1998020003A1 - Amides cycliques fongicides - Google Patents

Amides cycliques fongicides Download PDF

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Publication number
WO1998020003A1
WO1998020003A1 PCT/US1997/017608 US9717608W WO9820003A1 WO 1998020003 A1 WO1998020003 A1 WO 1998020003A1 US 9717608 W US9717608 W US 9717608W WO 9820003 A1 WO9820003 A1 WO 9820003A1
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Prior art keywords
pho
alkyl
phenyl
dif
haloalkyl
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Michael Paul Walker
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to EP97945385A priority Critical patent/EP0937051A1/fr
Priority to AU46603/97A priority patent/AU4660397A/en
Priority to JP52138398A priority patent/JP2001503424A/ja
Priority to BR9712713-2A priority patent/BR9712713A/pt
Publication of WO1998020003A1 publication Critical patent/WO1998020003A1/fr
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    • 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
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • 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

Definitions

  • This invention relates to certain fungicidal cyclic amides their N-oxides, agriculturally suitable salts and compositions, and methods of their use as fungicides.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides:
  • E is 1,2-phenylene optionally substituted with R 3 or both R 3 and R 4 ;
  • A is O, S, N, NR5 or CR 6 ;
  • G is C or N; provided that when G is C, then A is O, S or NR 5 and the floating double bond is attached to G; and when G is N, then A is N or CR 6 and the floating double bond is attached to A; W is O, S, NH, N(C r C 6 alkyl) or NO(C r C 6 alkyl);
  • X is OR 1 , StO ⁇ 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,
  • R 2 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl,
  • R 3 and R 4 are each independently halogen, cyano, nitro, hydroxy, C j -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 r C 6 alkoxy, C r C 6 haloalkoxy, C 2 -C 6 alkenyloxy,
  • R 5 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl,
  • Y is -O-, -S(O) n -, -NR 7 -, -CH 2 O-, -CH 2 NR 7 -, -CH 2 S(O) n - or a direct bond; and the directionality of the Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z;
  • Z is phenyl, pyrimidinyl or triazinyl, each substituted with R 9 and optionally substituted with one or more R 10 ;
  • R 6 is H, halogen, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkeny
  • R 7 is H, C1-C3 alkyl or C 3 -C 6 cycloalkyl; or R 7 is phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C ⁇ -C alkyl,
  • R 8 is H, 1-2 halogen, Cj-Cg alkyl, Cj-C 6 haloalkyl, C]-C 6 alkoxy,
  • C j -Cg haloalkoxy C -C6 alkenyl, C 2 -Cg haloalkenyl, C 2 -C 6 alkynyl, C j -Cg alkylthio, Ci- haloalkylthio, C ⁇ -C 6 alkylsulfinyl, C j -Cg alkylsulfonyl, C 3 -Cg cycloalkyl, C 3 -Cg alkenyloxy, CO 2 (C r C 6 alkyl), NH(C r C 6 alkyl), N(C r C 6 alkyl) 2 , cyano, nitro,
  • R 9 is phenyl, phenylmethyl, phenoxy, benzoyl, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl or pyrimidinyloxy, each substituted on the aromatic ring with one or more R 1 and with one R 1 ; each R 10 is independently halogen, C ⁇ -C alkyl, C ⁇ -C haloalkyl, C 2 -C 4 alkenyl,
  • each R 1 1 is independently halogen, cyano, nitro, C j -C 4 alkyl, C ⁇ -C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r C 4 alkoxy, Cj-C 4 alkylthio, C ] -C 4 alkylsulfinyl or C ⁇ -C alkylsulfonyl;
  • R 12 is halogen, C j -C alkyl, C ⁇ -C haloalkyl, C -C 6 alkenyl, C 2 -C 6 haloalkenyl,
  • R 14 , R 15 , and R 16 are each independently C r C 6 alkyl, C 2 -C 6 alkenyl, C ⁇ -C 4 alkoxy or phenyl; each R 17 is independently H, C1-C6 alkyl, Cj-Cg haloalkyl, C 2 -C 6 alkenyl,
  • R 18 is C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl,
  • R 18 is phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C j -C alkyl, C1-C4 haloalkyl, C ⁇ -C alkoxy, C1-C4 haloalkoxy, nitro or cyano; and m and n are each independently 0, 1 or 2; provided that i) when E is 1 ,2-phenylene, A is N, G is N, W is O, X is OMe, R 2 is CH 3 and Z substituted with R 9 is 6-[3,5-bis(trifluoromethyl)phenyl]-4-pyrimidinyl,
  • 6-(2,4-dichlorophenyl)-4-pyrimidinyl 4-[3,5-bis(trifiuoromethyl)phenyl]-2-pyrimidinyl, 2-[3,5-bis(trifluoromethyl)phenyl]-4-pyrimidinyl, 3-[2-(methoxycarbonyl)-6-nitrophenoxy]phenyl, 3-(2,6-dicyanophenoxy)phenyl,
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, propyl, 1 -methylethyl or the different butyl, pentyl or hexyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain alkanediyl.
  • alkylene examples include CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 .
  • Alkoxy includes, for example, methoxy, ethoxy, propoxy, 1-methylethoxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxy alkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 O, CH 3 C ⁇ CCH 2 O and CH 3 C ⁇ CCH 2 CH 2 O.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl examples include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkylthio denotes alkylthio substitution on alkylthio.
  • alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl examples include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfmyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Alkenylthio is defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Trialkylsilylalkoxyalkoxy denotes trialkylsilylalkoxy substitution on alkoxy.
  • Examples of “trialkylsilylalkoxyalkoxy” includes, for example, (CH 3 ) 3 SiCH 2 CH 2 OCH 2 O.
  • Phenylene denotes -(C 6 H 4 )-.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected.
  • alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkenyl “haloalkynyl", “haloalkoxy”, and the like, are defined analogously to the term “haloalkyl”.
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfinyl examples include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • C j -C j The total number of carbon atoms in a substituent group is indicated by the "C j -C j " prefix where i and j are numbers from 1 to 10.
  • C j -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl.
  • alkoxycarbonyl when a compound of Formula I is comprised of one or more aromatic or heterocyclic rings, all substituents are attached to these rings through any available carbon by replacement of a hydrogen on said carbon.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia or triethylamine) or inorganic bases (e.g., hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a phenol.
  • Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • R 9 is phenyl, phenylmethyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl or pyrimidinyloxy, each substituted on the aromatic ring with two or more R 1 * and with one R 12 ; and R 12 is halogen, C r C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C j -C 4 alkylthio, C j -C 4 haloalkylthio, C ⁇ -C 4 alkylsulfinyl, C!-C 4 haloalkylsulfinyl, Cj-C alkylsulfonyl, C ⁇ -C 4 haloalkylsulfonyl, nitro, cyano, thiocyanato, hydroxy or
  • R2 is CH 3 ;
  • R 3 and R 4 are each independently halogen or C1-C3 alkyl; and Y is O, CH 2 O or CH 2 S(O) n .
  • Preferred 3. Compounds of Formula I above, and agriculturally suitable salts thereof, wherein: A is N or CR 6 ; G is N; R 9 is phenyl, phenylmethyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl; or pyrimidinyloxy each substituted on the aromatic ring with two or more R 1 !
  • R 12 is halogen, Cj-C 4 alkyl, Cj-C 4 haloalkyl, C ⁇ -C 4 alkoxy, C ⁇ -C haloalkoxy, C j -C 4 alkylthio, C i -C 4 haloalkylthio, C j -C 4 alkylsulfinyl, C r C 4 haloalkylsulfinyl, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C 4 haloalkylsulfonyl, nitro, cyano, thiocyanato, hydroxy or N(R 17 ) 2 ; or R 12 is phenyl optionally substituted with halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, Cj-C alkoxy, C ⁇ -C haloalkoxy, nitro or cyano.
  • A is N; W is O; X is OR 1 ; R 1 is CH 3 ; R 2 is CH 3 ;
  • R 3 and R 4 are each independently halogen or C ⁇ -C 3 alkyl; and Y is O, CH 2 O or CH 2 S(O) n .
  • R 1 J and R 12 are halogen.
  • the 2,3-dihalo, 2,4-dihalo, 2,5-dihalo, 2,6-dihalo, 3,4-dihalo and 3,5-dihalo compounds e.g. 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro, 2-chloro-6-fluoro and 2,6-dichloro
  • 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro, 2-chloro-6-fluoro and 2,6-dichloro are of particular note.
  • R 1 * groups where there are two R 1 * groups, the 2,3,4- trihalo, 2,3,5-trihalo, 2,3,6-trihalo, 2,4,5-trihalo, 2,4,6-trihalo and 3,4,5-trihalo compounds (e.g. 2,4,6-trifluoro, 2,3,4-trifluoro, 2,3,5-trifluoro, 2,3,6-trifluoro, 2,3,6- trifluoro, 2,6-dichloro-4-fluoro and 2,4,6-trichloro) are of particular note.
  • R 1 ! groups where there are three R 1 ! groups, the 2,3,4,5-tetrahalo and 2,3,5,6-tetrahalo compounds (e.g. 2,3,5,6- tetrafluoro and 2,3,5,6-tetrachloro) are of particular note.
  • R 1 ! groups compounds where there are at least two R 1 ! groups. This includes compounds where at least two of the total R 1 ] and R 12 groups are other than halogen (e.g. 2,6-diR 11 -4-R 12 and 2,4-diR 11 -6-R 12 compounds where each R 1 1 is other than halogen or where one R 1 1 and R 12 are other than halogen).
  • Compounds where there are at least two R 11 groups also include compounds having two halogen substituents (e.g. 2,6-dihalo-4-R 12 and 2,4-dihalo-6-R 12 ) where R 12 is other than halogen.
  • R 11 and R 12 groups are 2,6-; 2,5-; 2,4-; and 2,3- positioning.
  • R 1 1 and R 12 groups are 2,3,4-; 2,3,5-; 2,3,6-; 2,4,5-; and 2,4,6- positioning.
  • R 11 and R 12 groups is 2,3,5,6 positioning.
  • This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds.
  • This invention also relates to 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, a fungicidally effective amount of the compounds of the invention (e.g., as a composition described herein).
  • a fungicidally effective amount of the compounds of the invention e.g., as a composition described herein.
  • the preferred methods of use are those involving the above preferred compounds.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-22.
  • One skilled in the art will recognize that compounds of Formula la and lb are encompassed by Formula I and, therefore, can be prepared by these procedures.
  • the definitions of E, A, G, W, X, R, R ⁇ R 20 , Y, Z, m and n in the compounds of Formulae 1-36 below are as defined above (including the Summary of the Invention) or below.
  • Compounds of Formulae la-Ih are various subsets of the compounds of Formula I, and all substituents for Formulae la-Ih are as defined above for Formula I.
  • 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 (E-Y-Z).
  • Procedure 5) describes syntheses of the aryl moiety (E-Y-Z) with the amide ring already in place.
  • the compounds of Formula Ic 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 dimethyl sulfoxide; 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.
  • Use of trimethylsilyldiazomethane requires a protic cosolvent such as methanol.
  • compounds of Formula Ic can also be prepared by contacting 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 Ic 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,
  • alkylating agents which can convert carbonyl compounds of Formula 1 to compounds of Formula Ic are dialkyl sulfates such as dimethyl sulfate, haloalkyl sulfonates such as methyl trifluoromethanesulfonate, and alkyl 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 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), and triethylenediamine.
  • alkali metal alkoxides such as potassium tert-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.
  • X 1 - OH can be prepared by condensation of malonates or malonate derivatives of Formula 5 with an ambident nucleophile of Formula 6 (Scheme 2).
  • Formula 6 are N-substituted hydroxylamines (HO- ⁇ HR 2 ) and substituted hydrazines
  • the malonate esters of Formula 5 can be prepared by methods described hereinafter.
  • Esters of Formula 5 a can be prepared from copper (I)-catalyzed reaction of malonate esters of Formula 7 with substituted aryl halides of Formula 8 according to methods adapted from A. Osuka, T. Kobayashi and H. Suzuki, Synthesis, (1983), 67 and M. S. Malamas, T. C. Hohman, and J. Millen, J. Med. Chem., 1994, 37, 2043-2058, and illustrated in Scheme 3.
  • Malonate esters of Formula 5 a can also be prepared from diester carboxylic acids of Formula 5b after modification of the carboxylic acid functional group to the appropriate Y and Z group.
  • a copper (I)-catalyzed coupling of malonates of Formula 7 with orthobromocarboxylic acids of Formula 8a can be used to prepare compounds of Formula 5b as shown in Scheme 3.
  • Methods to prepare compounds of Formula 8a are common in the art (see P. Beak, V. Snieckus, Ace. Chem. Res., (1982), 15, 306 and Org. React., (1979), 26, 1 and references therein).
  • R C r C 4 alkyl
  • R C j -C 4 alkyl
  • the malonate esters of Formula 5 a can be prepared by treating aryl acetic acid esters of Formula 9 with a dialkyl carbonate or alkyl chloro formate in the presence of a suitable base such as, but not limited to, sodium metal or sodium hydride (Scheme 4).
  • a suitable base such as, but not limited to, sodium metal or sodium hydride (Scheme 4).
  • a suitable base such as, but not limited to, sodium metal or sodium hydride
  • R C r C 4 alkyl
  • Esters of Formula 9 can be prepared from acid-catalyzed alcoholysis of aryl acetonitriles of Formula 10 or esterification of aryl acetic acids of Formula 11 as illustrated in Scheme 5 (see Org. Synth., Coll. Vol. I, (1941), 270).
  • esters of formula 9 can be prepared by palladium (O)-catalyzed cross coupling reaction of aryl iodides of Formula 8 with a Reformatsky reagent or an alkoxy(trialkylstannyl)acetylene followed by hydration (Scheme 5).
  • a Reformatsky reagent or an alkoxy(trialkylstannyl)acetylene followed by hydration (Scheme 5).
  • Scheme 5 for example, see T. Sakamoto, A. Yasuhara, Y. Kondo, H. Yamanaka, Synlett, (1992), 502, and J. F. Fauvarque, A. Jutard, J. Organometal. Chem., (1977), 132, C17.
  • Aryl acetic acid esters of Formula 9 can also be prepared by copper (I)-catalyzed condensation of aryl halides of Formula 12 with compounds of Formula 13 as described in EP-A-307,103 and illustrated below in Scheme 6.
  • R -C 4 alkyl
  • esters of Formula 9 can also be prepared by forming the Y 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 9.
  • a base for example sodium hydride, is used to generate the corresponding alkoxide or thioalkoxide of the compound of Formula 14.
  • R C j -C alkyl
  • Rl9 OH, SFL CH 2 OH, CH 2 SH, NHR 7
  • Y O, S, CH 2 0, CH 2 S, NR 7
  • Compounds of Formula Ic can also be prepared by reaction of Formula 17 compounds with alkali metal alkoxides (R ⁇ O'M " ) or an alkali metal thioalkoxides (R ⁇ S'M " * " ), (Scheme 8).
  • 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 dimethyl sulfoxide, dimethoxy ethane methanol.
  • V C j -C 6 alkyl, C j -C 6 haloalkyl or 4-CH 3 -C 6 H 4
  • Compounds of Formula 17a can be prepared from compounds of Formula lb (compounds of Formula 1 wherein X 1 is OH) by reaction with halogenating agents such as thionyl chloride or phosphorus oxybromide to form the corresponding ⁇ -halo-substituted derivatives (Scheme 9).
  • halogenating agents such as thionyl chloride or phosphorus oxybromide to form the corresponding ⁇ -halo-substituted derivatives (Scheme 9).
  • Compounds of Formula 17a when Lg 2 is chlorine or bromine are also compounds of Formula Id (compounds of Formula I where X is halogen).
  • compounds of Formula lb can be treated with an alkylsulfonyl halide or haloalkylsulfonyl anhydride, such as methanesulfonyl chloride, j9-toluenesulfonyl chloride, and trifluoromethanesulfonyl anhydride, to form the corresponding ⁇ -alkylsulfonate of Formula 17a.
  • the reaction with the sulfonyl halides may be performed in the presence of a suitable base (e.g., triethylamine).
  • Lg 2 Cl, Br or -OS0 2
  • 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-chloroperoxybenzoic acid, hydrogen peroxide and Oxone® (KHSO 5 ).
  • V C ⁇ -C 6 alkyl, -Cg haloalkyl or 4-CH 3 -C 6 H 4
  • the compound of Formula 19 is treated with, for example, excess thionyl chloride, the product formed first is the ring-closed compound of Formula 20.
  • This compound 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 12. Condensation of the isocyanate of Formula 21 with the hydrazine of Formula H 2 NNR R 20 in an inert solvent such as tetrahydrofuran affords the hydrazide.
  • Ketene dithioacetals of Formula 22a can be prepared by condensing arylacetic acid esters of Formula 9 with carbon disulfide in the presence of a suitable base, followed by reaction with two equivalents of an Rl -halide, such as iodomethane or propargyl bromide (Scheme 14).
  • Rl is not C 2 -C alkylcarbonyl or C 2 -C 4 alkoxycarbonyl
  • 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, tertiary amines such as triethylamine and triethylenediamine, pyridine, or 1 ,8-diazabicyclo[5.4.0]undec-7- ene (DBU).
  • Suitable solvents include polar aprotic solvents such as acetonitrile, dimethylformamide, or dimethyl sulfoxide; 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.
  • Tl and T 2 are independently Cl, OCCl 3 , 0(C ⁇ -C 4 alkyl), 1-imidazolyl,
  • N-Amino-ureas of Formula 23 can be prepared as illustrated in Scheme 16.
  • Treatment of an arylamine 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 28 such as 2-halocarboxylic acid chlorides, 2-halocarboxylic acid esters or 2-haloacyl imidazoles.
  • the initial acylation on the arylamino 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 Id compounds can be prepared by reaction of Formula 26 isocyanates with Formula 29 esters. As described above, base may be added to accelerate the reaction and subsequent cyclization to Formula Id compounds.
  • the ureas of Formula 27 can be prepared by either of the methods illustrated in Scheme 18.
  • the arylamine of Formula 25 can be contacted with an isocyanate or isothiocyanate of Formula R 2 N-C-W as described above.
  • an isocyanate or isothiocyanate of Formula 26 can be condensed with an amine of Formula R 2 -NH 2 to form the urea.
  • the arylamine 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), 27, 407. Isocyanates can be prepared as described in March, j.
  • thionating reagents such as P 2 S5 or Lawesson's reagent (2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4- diphosphetane-2,4-disulfide
  • Compounds of Formula I can be prepared by contacting halides of Formula 30 with various nucleophiles (Scheme 20).
  • the appropriate alcohol or thiol is treated with a base, for example sodium hydride, to form the corresponding alkoxide or thioalkoxide which acts as the nucleophile.
  • the halides of Formula 30 can be prepared from the alcohols of Formula 31 with halogenating reagents such as thionyl chloride.
  • the compounds of the present invention are prepared by combinations of reactions as illustrated in the Schemes 1 -20 in which Z is a moiety as described in the summary.
  • Preparation of the compounds containing the radical Z as described in the summary, substituted with R 9 can be accomplished by one skilled in the art by the appropriate combination of reagents and reaction sequences for a particular Z-R 9 .
  • Such reaction sequences can be developed based on known reactions available in the chemical art. For a general reference, see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985) and references therein. See the following paragraphs for some examples of how R 9 is defined in individual schemes, and the preparation of representative Z-R 9 examples.
  • compounds of Formula Ih can be prepared by reacting electrophiles such as those depicted by Formula 34 with nucleophiles such as those generated by reaction of compounds of Formula 35 with the appropriate base as shown in Scheme 22.
  • compounds of Formula Ih can be prepared by reacting compounds of Formula 34 bearing leaving groups such as bromide or iodide with for example aryl boronic acids of Formula 36 in the presence of a palladium catalyst.
  • Step B Preparation of 5-chloro-2.4-dihydro-4-(2-methoxyphenyl)-2-methyl-3H- 2,4-triazol-3-one
  • 29.85 g of triphosgene was added to a stirred solution of 21 g of the title compound of Step A in 800 mL of dichloromethane under nitrogen.
  • the reaction was heated to reflux and allowed to reflux overnight, cooled, and then concentrated under reduced pressure.
  • the resulting residue was dissolved in ethyl acetate, washed with distilled water, and then with saturated aqueous sodium chloride solution.
  • the organic layer was dried (MgSO 4 ), filtered, and concentrated under reduced pressure.
  • Step E Preparation of 4-[2-r(6-chloro-4-pyrimidinyl oxy]phenvn-2,4-dihydro-5- methoxy-2-methyl-3H-l,2,4-triazol-3-one 15 g of the intermediate from Step D above were added to a stirred suspension of potassium carbonate (10.3g) in 150 mL of acetonitrile at room temperature. The suspension stirred at room temperature for 1 h. Then 11.1 g of 4,6-dichloropyrimidine were added at room temperature and the reaction was allowed to stir at room temperature for 16 h. The solvent was then removed under reduced pressure and the crude residue was taken up in 150 mL of water.
  • Step F Preparation of 2,4-dihvdro-5-methoxy-2-methyl-4-r2-[r6-(2.4,6- trifluorophenoxyV4-pyrimidinyl1oxy]phenyl1-3H-L2.4-triazol-3-one 0.34 g 2,4,6-trifluorophenol were added to a stirred suspension of potassium carbonate (0.13 g) in 25 mL acetonitrile at room temperature. The resulting suspension was stirred at room temperature for 1 h. Then 0.5 g of the intermediate from Step E were added and the reaction was heated at reflux overnight. The reaction was cooled to room temperature and the solvent was removed under reduced pressure.
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • 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 percent by weight.
  • High Strength Compositions 90-99 0-10 0-2 Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses.
  • All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, NN-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, N,N-dimethylforrnamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Solutions can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566. For further information regarding the art of formulation, see U.S. 3,235,361,
  • Compound 8 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Compound 8 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium magnesium bentonite 59.0%.
  • Compound 3 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 to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of the invention 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.
  • pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Septoria tritici, 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 fuligine
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos.
  • fungicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
  • Preferred for better control of plant diseases caused by fungal plant pathogens (e.g., lower use rate or broader spectrum of plant pathogens controlled) or resistance management are mixtures of a compound of this invention with a fungicide selected from the group azoxystrobin, benomyl, carbendazim, carpropamid, copper salts, cymoxanil, cyproconazole, cyprodinil, dimethomorph, epoxiconazole, famoxadone, fenpropidin, fenpropimorph, flusilazole, flutolanil, fosetyl-aluminum, kasugamycin, kresoxim-methyl, mancozeb, metalaxyl and oxadixyl, pencycuron, probenazole, propiconazole, pyro
  • Specifically preferred mixtures are selected from the group: compound 8 and azoxystrobin, compound 8 and benomyl, compound 8 and carbendazim, compound 8 and carpropamid, compound 8 and copper salts, compound 8 and cymoxanil, compound 8 and cyproconazole, compound 8 and cyprodinil, compound 8 and epoxiconazole, compound 8 and famoxadone, compound 8 and fenpropidin, compound 8 and fenpropimorph, compound 8 and flusilazole, compound 8 and flutolanil, compound 8 and fosetyl-aluminum, compound 8 and kasugamycin, compound 8 and kresoxim-methyl, compound 8 and mancozeb, compound 8 and metalaxyl, compound 8 and oxadixyl, compound 8 and pencycuron, compound 8 and probenazole, compound 8 and propiconazole, compound 8 and pyro
  • 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.
  • BIOLOGICAL EXAMPLES OF THE INVENTION 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. Spraying these
  • TEST A The 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 B The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the 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. TEST D
  • test suspension was sprayed to the point of run-off on tomato seedlings.
  • 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.
  • TEST E The test suspension was sprayed to the point of run-off on grape seedlings.
  • 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.
  • Plasmopara viticola the causal agent of grape downy mildew
  • 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 o ⁇ 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.
  • a spore suspension o ⁇ Botrytis cinerea the causal agent of gray mold on many crops
  • Results for Tests A-F are given in Table A.
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls).
  • a dash (-) indicates no test results.
  • ND indicates disease control not determined due to phytotoxicity.

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Abstract

Cette invention se rapporte à des composés représentés par la formule (I), à leurs N-oxydes et à leurs sels acceptables en agriculture, qui s'avèrent utiles en tant que fongicides. Dans la formule (I), E est 1,2-phénylène éventuellement substitué par R3 ou à la fois par R?3 et R3 et R4¿; A est O, S, N, NR?5 ou CR6¿; G est C ou N, à condition que lorsque G est C, A est O, S ou NR5 et la double liaison flottante est attachée à G; et lorsque G est N, alors A est N ou CR6 et la double liaison flottante est attachée à A; W est O, S, NH, N (alkyle C¿1?-C6) ou NO (alkyle C1-C6); X est OR?1¿, S(O)¿mR?1 ou halogène; Y est -O-, -S(O)¿n?-, -NR?7¿-, -CH¿2?O-, -CH2NR?7¿-, -CH¿2?S(O)n- ou une liaison directe; et l'orientation de la liaison Y est définie de sorte que la fraction représentée sur le côté gauche de la liaison est liée à E et la fraction sur le côté droit de la liaison est liée à Z; Z est phényle, pyrimidinyle ou triazinyle, chacun des ces composés étant substitué par R?9¿ et éventuellement par un ou plusieurs R10; R2 est H, alkyle C¿1?-C6, haloalkyle C1-C6, alcényle C2-C6, haloalcényle C2-C6, alkynyle C2-C6, haloalkynyle C2-C6, cycloalkyle C3-C6, alkylcarbonyle C2-C4?, alcoxycarbonyle C2-C4, hydroxy, alcoxy C1-C2 ou acétyloxy. Cette invention se rapporte également à des compositions contenant les composés représentés par la formule (I) et à un procédé de lutte contre les maladies des végétaux provoquées par des agents pathogènes fongiques, qui consiste à appliquer une quantité efficace d'un composé représenté par la formule (I).
PCT/US1997/017608 1996-11-01 1997-10-01 Amides cycliques fongicides Ceased WO1998020003A1 (fr)

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EP97945385A EP0937051A1 (fr) 1996-11-01 1997-10-01 Amides cycliques fongicides
AU46603/97A AU4660397A (en) 1996-11-01 1997-10-01 Fungicidal cyclic amides
JP52138398A JP2001503424A (ja) 1996-11-01 1997-10-01 殺菌・殺カビ性の環状アミド類
BR9712713-2A BR9712713A (pt) 1996-11-01 1997-10-01 Composto, composição fungicida e método para controlar as doenças da planta

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JP2000080084A (ja) * 1998-07-14 2000-03-21 American Cyanamid Co 殺ダニ性並びに殺虫性の置換ピリミジン類及びその製造方法
US6489487B1 (en) 1998-08-03 2002-12-03 Sumitomo Chemical Company, Limited Triazolone derivatives, use thereof, and intermediates therefor
US6891071B2 (en) * 2002-10-04 2005-05-10 Corning Incorporated Halogenated styrene compounds and very low-loss polymers made therefrom
US7122544B2 (en) 2000-12-06 2006-10-17 Signal Pharmaceuticals, Llc Anilinopyrimidine derivatives as IKK inhibitors and compositions and methods related thereto
US7129242B2 (en) 2000-12-06 2006-10-31 Signal Pharmaceuticals, Llc Anilinopyrimidine derivatives as JNK pathway inhibitors and compositions and methods related thereto
EP1728428A2 (fr) 1998-06-08 2006-12-06 Bayer CropScience AG Combinaisons fongicides comprenant des dérivés methylester-O-methyloxime d'acide glyoxalique
US7351729B2 (en) 2002-03-08 2008-04-01 Signal Pharmaceuticals, Llc JNK inhibitors for use in combination therapy for treating or managing proliferative disorders and cancers
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WO1996036615A1 (fr) * 1995-05-16 1996-11-21 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
WO1996036616A1 (fr) * 1995-05-17 1996-11-21 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
WO1997000612A1 (fr) * 1995-06-20 1997-01-09 E.I. Du Pont De Nemours And Company Amides cycliques arthropodicides et fongicides

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WO1995014009A1 (fr) * 1993-11-19 1995-05-26 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
WO1996017851A1 (fr) * 1994-12-08 1996-06-13 E.I. Du Pont De Nemours And Company Organosilanes et organogermanes arthropodicides et fongicides
WO1996036615A1 (fr) * 1995-05-16 1996-11-21 E.I. Du Pont De Nemours And Company Amides cycliques fongicides
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EP1728428A2 (fr) 1998-06-08 2006-12-06 Bayer CropScience AG Combinaisons fongicides comprenant des dérivés methylester-O-methyloxime d'acide glyoxalique
EP1728427A2 (fr) 1998-06-08 2006-12-06 Bayer CropScience AG Combinaisons fongicides comprenant des dérivés methylester-O-methyloxime d'acide glyoxalique
JP2000080084A (ja) * 1998-07-14 2000-03-21 American Cyanamid Co 殺ダニ性並びに殺虫性の置換ピリミジン類及びその製造方法
US6489487B1 (en) 1998-08-03 2002-12-03 Sumitomo Chemical Company, Limited Triazolone derivatives, use thereof, and intermediates therefor
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KR20000052948A (ko) 2000-08-25
AU4660397A (en) 1998-05-29
EP0937051A1 (fr) 1999-08-25
ZA978958B (en) 1999-04-07
BR9712713A (pt) 1999-10-26
JP2001503424A (ja) 2001-03-13

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