WO1998033382A1 - Fungicidal compositions - Google Patents

Fungicidal compositions Download PDF

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Publication number
WO1998033382A1
WO1998033382A1 PCT/US1998/001382 US9801382W WO9833382A1 WO 1998033382 A1 WO1998033382 A1 WO 1998033382A1 US 9801382 W US9801382 W US 9801382W WO 9833382 A1 WO9833382 A1 WO 9833382A1
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chr
alkyl
haloalkyl
phenyl
alkoxy
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PCT/US1998/001382
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French (fr)
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John Anthony Bruhn
Martina Cajnar Crompton
Stephen Ray Foor
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E.I. Du Pont De Nemours And Company
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Priority to AU60403/98A priority Critical patent/AU6040398A/en
Publication of WO1998033382A1 publication Critical patent/WO1998033382A1/en

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    • 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

Definitions

  • TITLE FUNGICIDAL COMPOSITIONS BACKGROUND OF THE INVENTION Fungicides that effectively control plant diseases are in constant demand by growers. Plant diseases are highly destructive, difficult to control and quickly develop resistance to commercial fungicides. Combinations of pesticides are often used to facilitate disease control, to broaden spectrum of control and to retard resistance development. It is recognized in the art that the advantages of particular pesticide combinations can often vary, depending on such factors as the particular plant and plant disease to be treated, and the treatment conditions.
  • International Patent Application WO 95/14009 discloses certain triazolone compounds as fungicides including 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one (Formula la, an example ofthe compounds of Formula I defined herein).
  • International Patent Application WO 90/12791 discloses certain oxazolidinone compounds as fungicides including 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone (Formula Ila, an example ofthe compounds of Formula II defined herein).
  • European Patent Application EP-A-551048 discloses 3,5-dihydro 5-methyl-2-(methylthio)-5- phenyl-3-(phenylamino)-4H-imidazol-4-one (Formula lib, an example ofthe compounds of Formula II defined herein).
  • European Patent Application EP-A-68813 discloses certain triazole compounds as fungicides (e.g., flusilazole).
  • European Patent Application EP-A-40345 discloses certain triazole compounds as fungicides (e.g., tebuconazole).
  • This invention is directed to fungicidal combinations (e.g., mixtures) comprising
  • E is selected from: i) 1 ,2-phenylene optionally substituted with R 3 or both R 3 and R 4 ; ii) naphthalenediyl, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalenediyl optionally substituted with R 3 or both R 3 and R 4 ; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from
  • G is attached to an aromatic ring, and when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with R 3 or both R 3 and R 4 ;
  • A is O, S, N, NR 5 or CR 14 ;
  • 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 14 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 H, OR 1 , SCO ⁇ R 1 , halogen, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl, cyano, NH 2 , NHR 1 , N(C r C 6 alky ⁇ R 1 , NH(C r C 6 alkoxy) or N(C 1 -C 6 alkoxy)R 1 ;
  • 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 -Cg alkyl; C Cg haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -Cg alkynyl; C 2 -Cg haloalkynyl; C ⁇ -C 6 alkoxy; Ci-Cg haloalkoxy; C 2 -Cg alkenyloxy; C 2 -C 6 alkynyloxy; Cj-C 6 alkylthio; Ci-Cg alkylsulfmyl; C ⁇ -C 6 alkyls
  • R 3 and R 4 can be taken together as C 3 -C 5 alkylene, C 3 -C 5 haloalkylene, C 3 -C 5 alkenylene or C 3 -C 5 haloalkenylene each optionally substituted with 1-2 C r C 3 alkyl; R 5 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl,
  • W 1 is O or S
  • a 1 is O, S, NR 15 or a direct bond
  • a 2 is O, NR 15 or a direct bond
  • each Z is independently selected from: i) CJ-CJO alkyl, C -C 10 alkenyl and C 2 -CJO alkynyl each substituted with R 9 and optionally substituted with one or more R 10 ; ii) C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkenyl and phenyl each substituted with R 9 and optionally substituted with one or more R 10 ; iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to 14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system
  • R 8 is H, 1-2 halogen, C r C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy,
  • R 9 is H; 1-2 halogen; Cj-Cg alkyl; C r C 6 haloalkyl; C j -Cg alkoxy;
  • 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 1 1 and R 12 ; each R 10 is independently halogen, C j -C alkyl, C j -C haloalkyl, C ⁇ -C alkoxy, nitro or cyano; or * when R 9 and an R 10 are attached to adjacent atoms on Z, R 9 and said adjacently attached R 10 can be taken together as -OCH 2 O- or -OCH 2 CH 2 O-; each CH 2 group of said taken together R 9 and R 10 optionally substitute
  • R 7 and said adjacently attached R 10 can be taken together as -(CH 2 ) r -J- such that J is attached to Z; J is -CH 2 -, -CH 2 CH 2 -, -OCH 2 -, -CH 2 0-, -SCH 2 -, -CH 2 S-, -N(R 16 )CH 2 - or
  • R 1 i and R 12 are each independently 1-2 halogen; C j -C alkyl; C j -C 4 haloalkyl;
  • each R 25 is independently C j -C alkyl, C J -C4 haloalkyl, C 2 -C alkenyl, C J -C4 alkoxy or phenyl; each R 26 is independently H; C j -C 6 alkyl; C j -Cg haloalkyl; C 2 -C 6 alkenyl;
  • each R 27 is independently Cj-Cg alkyl; C j -Cg haloalkyl; C 2 -Cg alkenyl;
  • C -C 6 haloalkenyl C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C 3 -Cg cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C alkyl, Cj-C 4 haloalkyl, C j -C alkoxy, C j -C haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2; r is 0 or 1 ; and s is 2 or 3; and (2) at least one compound selected from (a) compounds of Formula II (including all geometric and stereoisomers), N-oxides, and agriculturally suitable salts thereof,
  • the directionally ofthe E 1 linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to carbon and the moiety on the right side is bonded to nitrogen; and R 28 is H or phenoxy; and (b) compounds that control fungal disease by inhibiting the sterol biosynthesis pathway.
  • This invention provides agricultural compositions containing these combinations and the use ofthe combinations as fungicides.
  • Advantageous compositions include those where component (1) and component (2) are present in a fungicidally effective amount and the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15.
  • Advantageous methods include those where component ( 1 ) and component (2) are added in amounts sufficient to provide a fungicidal effectiveness greater than the sum ofthe fungicidal effectivenesses provided by those amounts of said components taken independently.
  • this invention also provides methods 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 one ofthe following:
  • A) an effective amount of a fungicidal composition comprising component (1), component (2), and at least one of a surfactant, a solid diluent or a liquid diluent;
  • the mole ratio ofthe compound(s) of component (1) to the compound(s) of component (2) applied is normally from about 15:1 to 1 :15, and the compound(s) of component (1) and the compound(s) of component (2) are normally applied in amounts effective to provide control ofthe fungal disease which is greater than the additive control of that fungal disease provided by the compound(s) of component (1) and the compound(s) of component (2) individually.
  • alkyl used in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, ⁇ -propyl, z ' -propyl, or the different butyl, pentyl or hexyl isomers.
  • alkyl used alone includes straight-chain or branched alkyl, such as, methyl, ethyl, «- ⁇ ropyl, i-propyl, or the different butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl 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, hexynyl, heptynyl, octynyl, nonynyl and decynyl 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 and CH 2 CH 2 CH 2 CH 2 CH 2 .
  • Haloalkylene denotes a halogen substituted alkylene.
  • haloalkylene examples include CH 2 CH(CF 3 ), CH 2 CF 2 CH 2 and CH 2 CH(CC1 3 ).
  • Haloalkenylene denotes a halogen substituted alkenylene.
  • Alkoxy includes, for example, methoxy, ethoxy, ⁇ -propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy. Examples of “alkoxyalkoxy” include CH 3 OCH 2 0, (CH 3 ) 3 COCH 2 O and CH 3 OCH 2 CH 2 O.
  • 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.
  • Alkoxyalkynyl denotes alkoxy substitution of alkynyl.
  • Alkoxyalkynyl includes straight-chain or branched alkoxyalkynyl moieties. Examples of “alkoxyalkynyl” include (CH 3 ) 2 CHOCH 2 C ⁇ C and CH 3 OCH 2 C ⁇ C.
  • Alkoxyalkynyl include (CH 3 ) 2 CHOCH 2 C ⁇ C and CH 3 OCH 2 C ⁇ C.
  • 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 .
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy. Examples of “alkylthioalkoxy” include CH 3 SCH 2 O and CH 3 CH 2 SCH 2 CH 2 O.
  • Alkylthioalkylthio denotes alkylthio substitution on alkylthio. Examples of “alkylthioalkylthio” include CH 3 SCH 2 S and CH 3 SCH 2 CH 2 S.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl 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 butylsulfmyl, pentylsulfinyl and hexylsulfmyl isomers.
  • alkylsulfonyl include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 ,
  • alkenylthio is defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohepyl and cyclooctyl.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1 ,4-cyclohexadienyl.
  • Tetrahydropyranyloxyalkynyl denotes a tetrahydropyranyl group on oxygen which in turn is substituted on an alkynyl group.
  • An example of “tetrahydropyranyloxyalkynyl” is 2-[(tetrahydro-2H-pyranyl)oxy]ethynyl.
  • aromatic carbocyclic ring system includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Huckel rule is satisfied).
  • nonaromatic carbocyclic ring system denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Huckel rule is not satisfied by any ofthe rings in the ring system.
  • aromatic heterocyclic ring system includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Huckel rule is satisfied).
  • aromatic heterocyclic ring systems include furanyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said ring attached through any available carbon or nitrogen.
  • the aromatic heterocyclic ring when it is furanyl, it can be 2-furanyl or 3 -furanyl, for pyrrolyl, the aromatic heterocyclic ring is 1 -pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, for pyridyl, the aromatic ring is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for other aromatic heterocyclic rings.
  • nonaromatic heterocyclic ring system denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Huckel rule is not satisfied by any ofthe rings in the ring system.
  • the heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • 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 ofthe 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”.
  • haloalkynyloxy examples include CF 3 C ⁇ CCH 2 O, CCl 3 C ⁇ CCH 2 O and FCH 2 C ⁇ CCH 2 O. Examples of
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfmyl include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl 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 .
  • Alkoxycarbonylamino denotes alkoxycarbonyl substituted on nitrogen.
  • Trialkylsilylalkoxyalkoxy denotes trialkylsilyl substitution on alkoxy substituted in turn on alkoxy.
  • Examples of “trialkylsilylalkoxyalkoxy” include (CH 3 ) 3 SiCH 2 OCH 2 O and (CH 3 ) 3 SiCH 2 CH 2 OCH 2 O.
  • Cj-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.
  • Cj-C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl.
  • R 13 when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
  • a group is optionally substituted with a substituent, for example with R 7 , then, when the group is not substituted with that substituent, it is recognized that this is equivalent to said group having a hydrogen substituent.
  • Compounds used in this invention often 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).
  • Compounds of Formula II contain a chiral center. Enantiomers of Formula II with the S configuration (i.e., as defined by Cahn-Ingold-Prelog rules) are preferred.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds ofthe invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the salts ofthe compounds which may be used in 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 ofthe compounds which may be used in 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.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • compositions for reasons of ease of synthesis or greater fungicidal activity are:
  • a fungicidal composition comprising a fungicidally effective amount of (1) a compound of Formula I (including all geometric and stereoisomers), N-oxides, and agriculturally suitable salts thereof, wherein
  • E is selected from the group 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2-, and 2, 3 -naphthalenediyl; lH-pyrrole-1,2-, 2,3- and
  • R 1 is C j -C 3 alkyl or C r C 3 haloalkyl
  • R 2 is H, C j -Cg alkyl, C r C 6 haloalkyl or C 3 -C 6 cycloalkyl
  • R 3 and R 4 are each independently halogen, cyano, nitro, C j -Cg alkyl, C j -Cg haloalkyl, C j -Cg alkoxy, C j -Cg haloalkoxy, C j -C 6 alkylthio, Cj-Cg alkylsulfonyl, C 2 -Cg alkylcarbonyl, C 2 -Cg alkoxycarbonyl, (C r C 4 alkyl)NHC(O), (C r C 4 alkyl) 2 NC(O), benzoyl or phenylsulfonyl; Y is -0-, -S(O) n
  • R 7 is H, Cj-Cg alkyl, C r C 6 haloalkyl, C,-C 6 alkoxy, C r C 6 alkylthio,
  • R 7 and said adjacently attached R 10 can be taken together as -(CH 2 ) r -J- such that J is attached to Z;
  • Z is selected from the group CJ-CJ Q alkyl; C 3 -Cg cycloalkyl; phenyl; naphthalenyl; anthracenyl; phenanthrenyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2 /-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl;
  • 1,3,4-thiadiazolyl 1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl;
  • the fungicidal composition of Preferred 1 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4- triazol-3-one (sometimes referred to hereafter as the Formula la compound) and (2) at least one compound selected from (a) 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)-2,4-oxazolidinedione (sometimes referred to hereafter as the Formula Ila compound) and 3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H- imidazol-4-one (sometimes referred to hereafter as the Formula lib compound) and (b) epoxiconazole, fenpropimorph, flusilazole, propiconazole
  • the fungicidal composition of Preferred 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4- triazol-3-one and (2) flusilazole.
  • the fungicidal composition of Preferred 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4- triazol-3-one and (2) both 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)- 2,4-oxazolidinedione and flusilazole.
  • the fungicidal compositions of this invention in addition to comprising fungicidally effective amounts ofthe mixtures ofthe invention also optionally comprise at least one of a surfactant, a solid diluent or a liquid diluent.
  • the preferred compositions ofthe present invention are those which comprise the above preferred component (1) and component (2) 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 ofthe mixtures ofthe invention (e.g., as a composition described herein).
  • the preferred methods of use include those involving the above preferred compositions.
  • the Sterol Biosynthesis Inhibitor Fungicides include those involving the above preferred compositions.
  • the class of sterol biosynthesis inhibitors includes DMI and non-DMI compounds, that control fungi by inhibiting enzymes in the sterol biosynthesis pathway.
  • DMI fungicides have a common site of action within the fungal sterol biosynthesis pathway; that is, an inhibition of demethylation at position 14 of lanosterol or 24- methylene dihydrolanosterol, which are precursors to sterols in fungi.
  • Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs.
  • the demethylase enzyme is sometimes referred to by other names in the biochemical literature, including cytochrome P-450 (14DM). The demethylase enzyme is described in, for example, J.
  • DMI fungicides fall into several classes: triazoles, imidazoles, pyrimidines, piperazines and pyridines.
  • the triazoles includes bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, penconazole, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.
  • the imidazoles include clotrimazole, econazole, imazalil, isoconazole, miconazole and prochloraz.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the piperazines include triforine.
  • the pyridines include buthiobate and pyrifenox. Biochemical investigations have shown that all ofthe above mentioned fungicides are DMI fungicides as described by K. H. Kuck, et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 205-258.
  • the DMI fungicides have been grouped together to distinguish them from other sterol biosynthesis inhibitors, such as, the morpholine and piperidine fungicides.
  • the morpholines and piperidines are also sterol biosynthesis inhibitors but have been shown to inhibit later steps in the sterol biosynthesis pathway.
  • the morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide.
  • the piperidines include fenpropidin.
  • Biochemical investigations have shown that all ofthe above mentioned morpholine and piperidine fungicides are sterol biosynthesis inhibitor fungicides as described by K. H. Kuck, et al.
  • the presence of a synergistic interaction between two active ingredients is established by first calculating the predicted activity, p, ofthe mixture based on activities ofthe two components applied alone. If p is lower than the experimentally established effect, synergism has occurred.
  • A is the fungicidal activity in percentage control of one component applied alone at rate x.
  • the B term is the fungicidal activity in percentage control ofthe second component applied at rate y.
  • the equation estimates p, the fungicidal activity ofthe mixture of A at rate x with B at rate y if their effects are strictly additive and no interaction has occurred.
  • compositions of Formula la, Formula Ila and flusilazole alone are compared with that of compositions ofthe compounds of Formula la and Formula Ila together and with that of compositions ofthe compounds of Formula la and flusilazole together.
  • compositions ofthe present invention are considered to be synergistically useful. Accordingly, this invention provides an improved method of combating fungi, such as the control wheat powdery mildew (Erysiphe graminis) and the preventative control of wheat glume blotch (Septoria nodorum), in crops, especially cereals.
  • compositions are provided in accordance with this invention which comprise proportions of component (1) and component (2) which are especially useful for controlling particular fungal diseases.
  • the compositions of this invention include those wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15.
  • Compositions including the compounds of Formula II are considered especially useful for controlling wheat powdery mildew (Erysiphe graminis) and compositions including the sterol biosynthesis inhibitor fungicides are considered especially useful for the preventative control of wheat glume blotch (Septoria nodorum).
  • Preferred component (1) compounds for these compositions include 2,4-dihydro-5- methoxy-2-methyl-4-[2-[[[[[l-[3-
  • Preferred component (2) compounds for these compositions include 5-methyl-5-(4- phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone; 3,5-dihydro 5-methyl-2-
  • compositions of this type include compositions comprising 2,4- dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone in a mole ratio of the compound of Formula la to the compound of Formula Ila of from about 4:1 to 1 :4; and compositions comprising 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]
  • This invention also provides processes for the control of wheat powdery mildew and the preventative control of wheat glume blotch which comprises 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 fungicidal combination including component (1) and component (2) wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15 (preferably from about 4:1 to 1 :15).
  • Component (1) can, for example, be applied at a rate of 0.2 g/ha or more. Typically component (1) is applied at a rate of 125 g/ha.
  • Component (2) may be applied simultaneously (e.g., in the form of a composition comprising component (1) and component (2) in an appropriate mole ratio); or component (1) and component (2) can be applied separately in an appropriate mole ratio (e.g., as a tank mix).
  • Compositions wherein component (2) is selected from the group consisting of compounds of Formula II; and wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15 are considered especially useful for controlling wheat powdery mildew.
  • Preferred component (1) compounds for these compositions include 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H- 1 ,2,4-triazol-3-one.
  • component (2) compounds for these compositions include 5-methyl-5-(4- phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone and 3,5-dihydro 5-methyl-2- (methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one; with 5-methyl-5-(4- phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone being particularly preferred.
  • the mole ratio of component (1) to component (2) for these compositions is from about 4:1 to 1 :4.
  • Example compositions of this type include compositions comprising 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[[l -[3-
  • This invention also provides a process for controlling wheat powdery mildew which comprises 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 fungicidal combination including component (1) and component (2) wherein the mole ratio of component (1) to component (2) is from about 4:1 to 1:4.
  • Component (1) can, for example, be applied at a rate of 0.2 g/ha or more. Typically component (1) is applied at a rate of 125 g/ha.
  • Component (2) may be applied simultaneously (e.g., in the form of a composition comprising component (1) and component (2) in an appropriate mole ratio); or component (1) and component (2) can be applied separately in an appropriate mole ratio (e.g., as a tank mix).
  • component (2) is selected from the group consisting of 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone; 3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one; flusilazole; epoxiconazole; fenpropimorph; propiconazole; and tebuconazole; and wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1:15 are considered especially useful for the preventative control of wheat glume blotch.
  • Preferred component (1) compounds for these compositions include 2,4-dihydro-5- methoxy-2-methyl-4-[2-[[[[[l-[3-
  • component (2) compounds for these compositions include sterol biosynthesis inhibitor fungicides; with epoxiconazole, flusilazole, propiconazole and tebuconazole being particularly preferred.
  • the mole ratio of component (1) to component (2) for these compositions is from about 4 : 1 to 1 : 15.
  • Example compositions of this type include compositions comprising 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and flusilazole in a mole ratio ofthe compound of Formula la to flusilazole of from about 4:1 to 1:15.
  • This invention also provides a process for the preventative control of wheat glume blotch, which comprises 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 fungicidal combination including component (1) and component (2) wherein the mole ratio of component (1) to component (2) is from about 4:1 to 1 :15.
  • Component (1) can, for example, be applied at a rate of 5 g/ha or more. Typically component (1) is applied at a rate of 125 g/ha.
  • Component (2) may be applied simultaneously (e.g., in the form of a composition comprising component (1) and component (2) in an appropriate mole ratio); or component (1) and component (2) can be applied separately in an appropriate mole ratio (e.g., as a tank mix).
  • the compounds of Formula I can be prepared by one or more ofthe following methods and variations as described in Schemes 1-2 and International Patent Application WO 95/14009.
  • the definitions of A, E, G, W, X, Y, Z, R 1 and R 2 in the compounds of Formulae 1-5 below are as defined above in the Summary ofthe Invention.
  • the compound of Formula la is a subset ofthe compounds of Formula I.
  • Compounds of Formula I can be prepared as described in International Patent Application WO 95/14009.
  • a synthesis ofthe compounds of Formula I involves treating a compound 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, dimethoxyethane, 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, dimethoxyethane, or diethyl ether
  • ketones such as acetone or 2-butanone
  • hydrocarbons such as toluene or benzene
  • halocarbons such as dichloromethane or chloroform.
  • a protic cosolvent such as methanol.
  • compounds of Formula I can also be prepared by contacting carbonyl a compound of Formula 1 with alkyl trichloroacetimidates of
  • 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. H ⁇ nig, Synth. Commun., (1990), 20, 203).
  • Compound 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.,
  • alkylating agents which can convert compounds of Formula 1 to compounds of Formula I 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.
  • Compounds of Formula I where A, G, E, W, X, Y, Z, R 1 and R 2 are defined as above, can also be prepared by reaction of Formula 5 compounds with alkali metal alkoxides (RiO ⁇ M " ) (Scheme 2).
  • the leaving group Lg 1 in the amides of Formula 5 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.
  • M K or Na 2,4-Dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one,
  • the compounds of Formula II can be prepared by one or more ofthe following methods and variations as described in Scheme 3, International Patent Application WO 94/11359 and European Patent Application EP-A-551048.
  • the compounds of Formulae Ila and lib are various subsets ofthe compounds of Formula II.
  • R 2 9 is -C4 alkyl
  • Lg' is 1-imidazolyl or 1 ,2,4-triazolyl Reaction conditions suitable for preparing the compound of Formula Ila are as follows.
  • the suitable solvents include inert organic solvents.
  • Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, hexanes, tetrahydrofuran, tert-butyl methyl ether, dioxanes, chlorobenzene, o-dichlorobenzene (ODCB), toluene, xylenes, and suitable combinations thereof.
  • the most preferred solvents are selected from the group consisting of chlorobenzene, ODCB, toluene, and xylenes.
  • the reaction temperatures can range from about 10°C to about 75°C. Preferred temperatures are from about 40°C to about 60°C.
  • Suitable reaction pressures are from about 1.0 x 10 5 to about 5.1 x 10 5 Pascals. The preferred pressure is 1 x 10 5 Pascals.
  • the reaction times are typically 1 to 24 hours, preferably 3 to 6 hours.
  • a suitable ratio of Formula 7 to 6 is from about 1 :1 to 2:1. The preferred ratio is from about 1.1 :1 to 1.8:1.
  • Suitable bases for this reaction include trialkylamines, imidazole, pyridine, picolines or other substituted pyridine derivatives. For the conversion of compounds of Formula 8 to the 2,4-oxazolidinedione of
  • suitable solvents are as noted above for the condensation of Formulae 6 and 7.
  • the preferred solvents are those disclosed above as preferred.
  • the reaction temperatures are from about 0°C to about 75°C. Preferred temperatures are from about 10°C to about 50°C.
  • Reaction pressures are from about 1.0 x 10 5 to about 5.1 x 10 5 Pascals. The preferred pressure is 1 x 10 5 Pascals.
  • the reaction times are typically 1 to 24 hours, preferably 2 to 6 hours.
  • the acids suitable for catalyzing the reaction are selected from the group consisting of alkyl and aryl carboxylic acids, trialkylammonium halides and combinations thereof. The preferred acids are acetic acid and triethylammonium chloride. The most preferred acid is triethylammonium chloride.
  • Suitable ratios of phenylhydrazine to Formula 8 is from about 2:1 to 1 : 1. The preferred ratio is from about 1.6:1 to 1.1 :1.
  • the carbonylating agent of Formula 7 may be added as a pure compound, a solution ofthe pure compound in an inert solvent, or prepared in situ in the presence of the ester of Formula 6.
  • the preferred process involves preparation ofthe carbonylating agent in situ.
  • Phase transfer catalysts are preferably added to reactions wherein the triazole salt has low solubility in the solvent.
  • phase transfer catalysts are preferred when xylenes or toluene is used. Any phase transfer catalyst known to one skilled in the art is suitable. Tetraalkylammonium halides are preferred.
  • the triazole salt is prepared by treating triazole with a suitable base, such as sodium hydroxide or sodium ethoxide. The preferred relative amount of alkali metal base to triazole to phosgene is 0.5:1.0:0.6.
  • Base is also necessary to catalyze the condensation of Formulae 6 and 7.
  • suitable base catalysts are trialkylamines, imidazole, pyridine, picolines or other substituted pyridines.
  • l,l'-carbonyldiimidazole is used
  • Compounds of Formula 8 may be isolated and purified, or treated in situ with phenylhydrazine and acid to form the 2,4-oxazolidinedione of Formula Ila.
  • the preferred method involves treatment of Formula 8 in situ with phenylhydrazine. After the formation ofthe carbamate of Formula 8 is complete, excess carbonylating agent can be decomposed by the addition of water.
  • compositions ofthe present invention comprise an effective amount of a mixture ofthe compounds(s) of component (1) (e.g., 2,4-dihydro-5- methoxy-2-methyl-4-[2-[[[[l-[3-
  • the mixtures of this invention will typically 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 ofthe 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 ofthe 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 ingredients, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • 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, N,N-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-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, com, 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.
  • 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. Patent No. 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
  • Pellets can be prepared as described in U.S. Patent No. 4,172,714.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. Patent No. 4,144,050, U.S. Patent No. 3,920,442 and German Patent Publication DE 3,246,493.
  • Tablets can be prepared as taught in
  • Active ingredient(s) 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example B Granule Active ingredient(s) 10.0% attapulgite granules (low volatile matter
  • Example C Extruded Pellet Active ingredient(s) 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Extruded Pellet Active ingredient(s) 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Extruded Pellet Active ingredient(s) 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • 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 ofthe 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.
  • insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene
  • insecticides such as abamectin, acep
  • 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 this composition can be influenced by many factors ofthe 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 aggregate active ingredient. Aggregate active ingredient is defined as the total combined weight of active ingredients. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g of aggregate active ingredient per kilogram of seed.
  • the following Examples demonstrate the composition and method ofthe present invention and provide experimental evidence for synergy between the compound of Formula la and flusilazole in preventative control of wheat glume blotch caused by Septoria nodorum.
  • the experimental also provides evidence for synergy between the compound of Formula la and Ila in preventative and curative control of wheat powdery mildew caused by Erysiphe graminis.
  • the experimental also provides evidence for synergy between the compound of Formula la and Ila in preventative and curative control of grape downy mildew caused by Plasmopara viticola.
  • BIOLOGICAL EXAMPLES OF THE INVENTION Test compounds were first dissolved in acetone in an amount equal to 50% ofthe final volume and then suspended at a concentrations from 0.08 to 200 ppm in purified water containing 250 ppm ofthe surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following test protocols. Spraying these test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha.
  • Protocol # 1 - WPM Preventive The test compounds were 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). Seedlings were incubated in a growth chamber at 20°C for 6 days, after which disease ratings were made.
  • Protocol # 2 - WPM Curative Wheat seedlings were inoculated with a spore dust of Erysiphe graminis f sp. tritici, (the causal agent of wheat powdery mildew). The following day a test compounds were sprayed to the point of run-off on and seedlings incubated in a growthchamber at 20°C for 7 days, after which disease ratings were made.
  • Protocol # 3 WLR Preventive The test compounds were 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 compounds (the causal agent of wheat leaf rust).
  • test compounds were sprayed to the point of run-off on and incubated in a saturated atmosphere at 20°C for 24 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
  • Protocol # 5 - WFR Preventive
  • test compounds were sprayed to the point of run-off on wheat seedlings.
  • Protocol # 6 - WGB Preventive The test compounds were sprayed to the point of run-off on wheat seedlings.
  • Protocol # 7 - WGB Curative Wheat seedlings were inoculated with a spore suspension Septoria nodorum (the causal agent of wheat glume blotch). Two days later test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
  • Protocol # 8 - RCB Curative Wheat seedlings were inoculated with a spore suspension Pyricularia oryzae (the causal agent of rice Blast). The following day test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to greenhouse at 27°C for 8 days, after which disease ratings were made.
  • Protocol # 9 - RSB Preventive The test compounds were sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Rizoctonia solani (the causal agent of rice sheath blight ) and incubated in a saturated atmosphere at 20°C for 48 h, and then moved to a greenhouse at 27°C for 8 days, after which disease ratings were made.
  • Rizoctonia solani the causal agent of rice sheath blight
  • Protocol # 10 - PLB Preventive 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. Protocol # 11 - PLB Curative
  • test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made. Protocol # 12 - GDM Preventive The test suspension was sprayed to the point of run-off on tomato seedlings.
  • Protocol # 13 - GDM Curative Wheat seedlings were inoculated with a spore Plasmopara viticola (the causal agent of grape downy mildew). The following day test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
  • Results for protocols 1 - 13 are given in Tables A-F.
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls).
  • An (nt) indicates no test results and (--) indicates no estimate of activity.
  • rates are given in parts per million (ppm) and/or grams active ingredient per hectare (g a.i./ha).
  • Actual stands for the experimental value.
  • the abbreviation "Exp.” stands for "Expected” (i.e., the predicted activity, p, from the Colby equation).
  • WLR Wheat Leaf Rust
  • WFR Wheat Foot Rot
  • WGB Wheat Glume Blotch
  • WLR Wheat Leaf Rust
  • WFR Wheat Foot Rot
  • WGB Wheat Glume Blotch
  • WLR Wheat Leaf Rust
  • WGB Wheat Glume Blotch
  • WLR Wheat Leaf Rust
  • WGB Wheat Glume Blotch
  • PLB Potato Late Blight
  • GDM Grape Downy Mildew
  • PLB Potato Late Blight
  • GDM Grape Downy Mildew

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Abstract

Advantageous fungicidal combinations are disclosed comprising (1) at least one compound selected from the compounds of Formula (I), N-oxides and agriculturally suitable salts thereof, and (2) at least one compound selected from (a) compounds of Formula (II), N-oxides, and agriculturally suitable salts thereof, wherein E1 is (i) or (ii); and R28 is H or phenoxy; and (b) compounds that control fungal disease by inhibiting the sterol biosynthesis pathway; wherein A, E, W, X, Y, Z and R2 are as defined in the disclosure. Included are fungicidal compositions comprising fungicidally effective amounts of the compound combinations of the invention and 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 compound combinations of the invention.

Description

TITLE FUNGICIDAL COMPOSITIONS BACKGROUND OF THE INVENTION Fungicides that effectively control plant diseases are in constant demand by growers. Plant diseases are highly destructive, difficult to control and quickly develop resistance to commercial fungicides. Combinations of pesticides are often used to facilitate disease control, to broaden spectrum of control and to retard resistance development. It is recognized in the art that the advantages of particular pesticide combinations can often vary, depending on such factors as the particular plant and plant disease to be treated, and the treatment conditions.
International Patent Application WO 95/14009 discloses certain triazolone compounds as fungicides including 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one (Formula la, an example ofthe compounds of Formula I defined herein). International Patent Application WO 90/12791 discloses certain oxazolidinone compounds as fungicides including 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone (Formula Ila, an example ofthe compounds of Formula II defined herein). European Patent Application EP-A-551048 discloses 3,5-dihydro 5-methyl-2-(methylthio)-5- phenyl-3-(phenylamino)-4H-imidazol-4-one (Formula lib, an example ofthe compounds of Formula II defined herein). European Patent Application EP-A-68813 discloses certain triazole compounds as fungicides (e.g., flusilazole). European Patent Application EP-A-40345 discloses certain triazole compounds as fungicides (e.g., tebuconazole).
Research Disclosure 1996, No. 38829, 487-490 discloses synergistic mixtures of 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-2,4-oxazolidinedione with fungicides, insecticides and herbicides. International Patent Application WO 96/03044 discloses synergistic mixtures of 3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)- 4H-imidazol-4-one with fungicides.
SUMMARY OF THE INVENTION This invention is directed to fungicidal combinations (e.g., mixtures) comprising
(1) at least one compound selected from the compounds of Formula I (including all geometric and stereoisomers), N-oxides, and agriculturally suitable salts thereof,
Figure imgf000004_0001
I wherein
E is selected from: i) 1 ,2-phenylene optionally substituted with R3 or both R3 and R4; ii) naphthalenediyl, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalenediyl optionally substituted with R3 or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from
C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with R3 or both R3 and R4; A is O, S, N, NR5 or CR14;
G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A; W is O, S, NH, N(CrC6 alkyl) or NO(CrC6 alkyl); X is H, OR1, SCO^R1, halogen, CrC6 alkyl, CrC6 haloalkyl, C3-C6 cycloalkyl, cyano, NH2, NHR1, N(CrC6 alky^R1, NH(CrC6 alkoxy) or N(C1-C6 alkoxy)R1; R1 is CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-Cg alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, 2-C4 alkylcarbonyl or C2-C4 alkoxy carbonyl;
R2 is H, CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-Cg alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C2-C4 alkylcarbonyl, C2-C4 alkoxy carbonyl, hydroxy, C C2 alkoxy or acetyloxy; R3 and R4 are each independently halogen; cyano; nitro; hydroxy; Cj-Cg alkyl; C Cg haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-Cg alkynyl; C2-Cg haloalkynyl; Cι-C6 alkoxy; Ci-Cg haloalkoxy; C2-Cg alkenyloxy; C2-C6 alkynyloxy; Cj-C6 alkylthio; Ci-Cg alkylsulfmyl; Cι-C6 alkylsulfonyl; formyl; C2-C6 alkylcarbonyl; C -C6 alkoxycarbonyl;
NH2C(O); (CrC4 alkyl)NHC(O); (CrC4 alkyl)2NC(O); Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1 ,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2 CrC3 alkyl; R5 is H, CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C3-Cg cycloalkyl, C2-C alkylcarbonyl or C -C4 alkoxycarbonyl; Y is -O-, -S(O)n-, -NR15-, -C(=O)-, -CH(OR15)-, -CHR6-, -CHR6CHR6-,
-CR6=CR6-, -G≡C-, -CHR15O-, -OCHR15-, -CHR^S^ , -S(O)nCHR15-, -CHR15O-N=C(R7)-, -(R7)C=N-OCH(R15)-, -C(R7)=N-O-, -O-N=C(R7)-, -CHR15OC(=O)N(R15)-, -CHR15OC(=S)N(R15)-, -CHR15OC(=O)O-,
-CHR15OC(=S)O-, -CHR15OC(-O)S-, -CHR15OC(=S)S-, -CHR15SC(=O)N(R15)-, -CHR15SC(=S)N(R15)-, -CHR15SC(=O)O-, -CHR15SC(=S)O-, -CHR15SC(=O)S-, -CHR15SC(=S)S-, -CHR15SC(=NR! 5)S-, -CHR15N(Ri 5)C(=O)N(R15)-, -CHR15O-N(R15)C(=O)N(R15)-, -CHR15O-N(R15)C(=S)N(R15)-,
-CHR15θ-N-C(R7)NR15-, -CHR15O-N=C(R7)OCH2-, -CHR150-N=C(R7)-N=N-, -CHR15O-N=C(R7)-C(=O)-, -CHR15O-N=C(R7)-C(=N-A2-Z1)-A1-, -CHR15O-N=C(R7)-C(R7)=N-A2-A3-, -CHR15O-N=C(-C(R7)=N-A2-Z1)-, -CHR15O-N=C(R7)-CH20-, -CHR15O-N=C(R7)-CH2S-,
-O-CH2CH2O-N=C(R7)-, -CHR15O-C(R15)=C(R7)-, -CHR15θ-C(R7)-N-, -CHR15S-C(R7)=N-, -C(R7)=N-NR15-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)-, -CHR15N(COCH3)-N=C(R7)-, -OC(=S)NR15C(=O)-, -CHR6-C(=W1)-A1-, -CHR6CHR6-C(=W1)-A1-,
Figure imgf000005_0001
direct bond; and the directionality ofthe Y linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to E and the moiety on the right side ofthe linkage is bonded to Z; Z1 is H or -A3-Z;
W1 is O or S;
A1 is O, S, NR15 or a direct bond;
A2 is O, NR15 or a direct bond; A3 is -C(=O , -S(O)2- or a direct bond; each R6 is independently H, 1-2 CH3, C2-C3 alkyl, C j-C3 alkoxy, C3-Cg cycloalkyl, formylamino, C2-C alkylcarbonylamino, C2-C4 alkoxycarbonylamino, NH2C(O)NH, (CrC3 alkyl)NHC(O)NH, (CrC3 alkyl)2NC(O)NH, N(CrC3 alkyl)2, piperidinyl, morpholinyl, 1-2 halogen, cyano or nitro; each R7 is independently H, Cι-C6 alkyl, Cj-Cg haloalkyl, Cj-C6 alkoxy, Ci-Cg haloalkoxy, Cι-C6 alkylthio, Cj-Cg alkylsulfinyl, C]-C6 alkylsulfonyl, Cj-Cg haloalkylthio, Cj-Cg haloalkylsulfinyl, Cj-Cg haloalkylsulfonyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C2-C4 alkylcarbonyl,
C2-C4 alkoxycarbonyl, halogen, cyano, nitro, hydroxy, amino, NH(CrC6 alkyl), N(CrC6 alkyl)2 or morpholinyl; each Z is independently selected from: i) CJ-CJO alkyl, C -C10 alkenyl and C2-CJO alkynyl each substituted with R9 and optionally substituted with one or more R10; ii) C3-C8 cycloalkyl, C3-C8 cycloalkenyl and phenyl each substituted with R9 and optionally substituted with one or more R10; iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to 14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10; iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and v) adamantyl substituted with R9 and optionally substituted with one or more R10; each Q is independently selected from the group -CHR13-, -NR13-, -O- and -S(O)p-;
R8 is H, 1-2 halogen, CrC6 alkyl, CrC6 haloalkyl, CrC6 alkoxy,
Cj-Cg haloalkoxy, C2-C6 alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl,
Cj-Cg alkylthio, Cj-Cg haloalkylthio, Cj-Cg alkylsulfinyl,
Cj-Cg alkylsulfonyl, C3-Cg cycloalkyl, C3-Cg alkenyloxy, C02(Cj-C6 alkyl), NH(Cj-C6 alkyl), N(Cj-C6 alkyl)2, cyano, nitro,
SiR1 R20R21 or GeR19R 0R21; R9 is H; 1-2 halogen; Cj-Cg alkyl; CrC6 haloalkyl; Cj-Cg alkoxy;
Cj-Cg haloalkoxy; C2-Cg alkenyl; C2-Cg haloalkenyl; C2-Cg alkynyl;
Cj-Cg alkylthio; Cj-Cg haloalkylthio; Cj-Cg alkylsulfinyl; Cj-Cg alkylsulfonyl; C3-C6 cycloalkyl; C3-Cg alkenyloxy;
CO2(Cj-C6 alkyl);
Figure imgf000007_0001
cyano; nitro; SF5; SiR22R23R24; or GeR22R23R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R11, R12, or both R1 1 and R12; each R10 is independently halogen, Cj-C alkyl, Cj-C haloalkyl, Cι-C alkoxy, nitro or cyano; or * when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR15O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-,
-CHR15O-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)- or -CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; J is -CH2-, -CH2CH2-, -OCH2-, -CH20-, -SCH2-, -CH2S-, -N(R16)CH2- or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2
CH3; R1 i and R12 are each independently 1-2 halogen; Cj-C alkyl; Cj-C4 haloalkyl;
C2-Cg alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-Cg haloalkynyl;
C2-Cg alkoxyalkyl; C2-Cg alkylthioalkyl; C3-C6 alkoxy alkynyl;
C7-Cjo tetrahydropyranyloxyalkynyl; benzyloxymethyl; Cj-C alkoxy; CJ-C4 haloalkoxy; C3-Cg alkenyloxy; C -Cg haloalkenyloxy; C3-Cg alkynyloxy; C3-C6 haloalkynyloxy; C2-Cg alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-Cg alkylthioalkoxy; Cj-C alkylthio; C1-C4 haloalkylthio; Cj-C alkylsulfinyl; CJ-C4 haloalkylsulfinyl; Cj-C4 alkylsulfonyl; CJ-C4 haloalkylsulfonyl; C3-C6 alkenylthio;
C3-Cg haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R26)2; SF5; Si(R25)3; Ge(R25)3; (R25)3Si-G≡C-; OSi(R 5)3; OGe(R 5)3; C(=O)R26; C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR26; C(=S)SR26; C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R 6; SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26;
OC(=O)OR27; OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26; S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, Cj-C4 alkyl, ]-C4 haloalkyl, CJ-C4 alkoxy, CJ-C4 haloalkoxy, nitro or cyano; each R13 is independently H; Cj-Cg alkyl; Cj-Cg haloalkyl; or phenyl optionally substituted with halogen, C J-C4 alkyl, CJ-C4 haloalkyl, C1-C4 alkoxy, CJ-C4 haloalkoxy, nitro or cyano; R14 is H, halogen, Cj-Cg alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl or C3-C6 cycloalkyl; each R15 is independently H; C j-C3 alkyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, CJ-C4 alkyl, C1-C4 haloalkyl, CJ-C4 alkoxy, CJ-C4 haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)S-; or when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)S-, -O-(CH2)s-, -S-(CH2)S- or -N(Cj-C3 alkyl)-(CH2)s-; with the directionality of said linkage defined such that the moiety depicted on the left side ofthe linkage is bonded to the carbon and the moiety on the right side ofthe linkage is bonded to the nitrogen; R16, R17 and R18 are each independently H; Cj-C3 alkyl; C3-C6 cycloalkyl; or phenyl optionally substituted with halogen, Cj-C4 alkyl, C j-C4 haloalkyl, CJ-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; R19, R », R 1 , R22, R23 and R24 are each independently C j -C6 alkyl,
C2-C6 alkenyl, CJ-C4 alkoxy or phenyl; each R25 is independently Cj-C alkyl, CJ-C4 haloalkyl, C2-C alkenyl, CJ-C4 alkoxy or phenyl; each R26 is independently H; Cj-C6 alkyl; Cj-Cg haloalkyl; C2-C6 alkenyl;
C2-Cg haloalkenyl; C2-Cg alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C alkyl, Cj-C haloalkyl, Cj-C alkoxy, Cj-C4 haloalkoxy, nitro or cyano; each R27 is independently Cj-Cg alkyl; Cj-Cg haloalkyl; C2-Cg alkenyl;
C -C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-Cg cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C alkyl, Cj-C4 haloalkyl, Cj-C alkoxy, Cj-C haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2; r is 0 or 1 ; and s is 2 or 3; and (2) at least one compound selected from (a) compounds of Formula II (including all geometric and stereoisomers), N-oxides, and agriculturally suitable salts thereof,
Figure imgf000009_0001
wherein E1 is
Figure imgf000009_0002
the directionally ofthe E1 linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to carbon and the moiety on the right side is bonded to nitrogen; and R28 is H or phenoxy; and (b) compounds that control fungal disease by inhibiting the sterol biosynthesis pathway. This invention provides agricultural compositions containing these combinations and the use ofthe combinations as fungicides. Advantageous compositions include those where component (1) and component (2) are present in a fungicidally effective amount and the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15. Advantageous methods include those where component ( 1 ) and component (2) are added in amounts sufficient to provide a fungicidal effectiveness greater than the sum ofthe fungicidal effectivenesses provided by those amounts of said components taken independently.
DETAILS OF THE INVENTION Combinations of fungicides are used in accordance with this invention to facilitate disease control and to retard resistance development. Suitable compositions and methods are provided.
For example, this invention also provides methods 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 one ofthe following:
A) an effective amount of a fungicidal composition comprising component (1), component (2), and at least one of a surfactant, a solid diluent or a liquid diluent;
B) (i) an effective amount of a first composition comprising component (1), and at least one of a surfactant, solid or liquid diluent; and (ii) an effective amount of a second composition comprising component (2), and at least one of a surfactant, a solid diluent or a liquid diluent; said first and second compositions applied sequentially in any order; or
C) an effective amount of a physical mixture ofthe first and second compositions as defined in B above. The mole ratio ofthe compound(s) of component (1) to the compound(s) of component (2) applied is normally from about 15:1 to 1 :15, and the compound(s) of component (1) and the compound(s) of component (2) are normally applied in amounts effective to provide control ofthe fungal disease which is greater than the additive control of that fungal disease provided by the compound(s) of component (1) and the compound(s) of component (2) individually.
In the above recitations, the term "alkyl", used in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, ^-propyl, z'-propyl, or the different butyl, pentyl or hexyl isomers. The term "alkyl", used alone includes straight-chain or branched alkyl, such as, methyl, ethyl, «-ρropyl, i-propyl, or the different butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl isomers. The term "1-2 CH3" indicates that the substituent can be methyl (i.e., Me) or, when there is a hydrogen attached to the same atom, the substituent and said hydrogen can both be methyl. "Alkenyl" includes straight-chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl 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, hexynyl, heptynyl, octynyl, nonynyl and decynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
"Alkylene" denotes a straight-chain alkanediyl. Examples of "alkylene" include CH2CH2CH2, CH2CH2CH2CH2 and CH2CH2CH2CH2CH2. "Haloalkylene" denotes a halogen substituted alkylene. Examples of "haloalkylene" include CH2CH(CF3), CH2CF2CH2 and CH2CH(CC13). "Alkenylene" denotes a straight-chain alkenediyl containing one olefmic bond. Examples of "alkenylene" include CH2CH=CH, CH2CH2CH=CH, CH2CH=CHCH2 and CH2CH=CHCH2CH2. "Haloalkenylene" denotes a halogen substituted alkenylene. Examples of "haloalkenylene" include CH2CC1=CC1 and CH=C(CF3).
"Alkoxy" includes, for example, methoxy, ethoxy, π-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy. Examples of "alkoxyalkoxy" include CH3OCH20, (CH3)3COCH2O and CH3OCH2CH2O. "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O and CH2=CHCH2CH2O. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH2O, CH3C≡CCH2O and CH3C≡CCH2CH2O. "Alkoxyalkynyl" denotes alkoxy substitution of alkynyl. "Alkoxyalkynyl" includes straight-chain or branched alkoxyalkynyl moieties. Examples of "alkoxyalkynyl" include (CH3)2CHOCH2C≡C and CH3OCH2C≡C. "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. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylthioalkoxy" denotes alkylthio substitution on alkoxy. Examples of "alkylthioalkoxy" include CH3SCH2O and CH3CH2SCH2CH2O. "Alkylthioalkylthio" denotes alkylthio substitution on alkylthio. Examples of "alkylthioalkylthio" include CH3SCH2S and CH3SCH2CH2S. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfmyl, pentylsulfinyl and hexylsulfmyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2,
(CH3)2CHS(O)2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkenylthio" is defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohepyl and cyclooctyl. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1 ,4-cyclohexadienyl. "Tetrahydropyranyloxyalkynyl" denotes a tetrahydropyranyl group on oxygen which in turn is substituted on an alkynyl group. An example of "tetrahydropyranyloxyalkynyl" is 2-[(tetrahydro-2H-pyranyl)oxy]ethynyl.
The term "aromatic carbocyclic ring system" includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Huckel rule is satisfied). The term "nonaromatic carbocyclic ring system" denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Huckel rule is not satisfied by any ofthe rings in the ring system. The term "aromatic heterocyclic ring system" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Huckel rule is satisfied). Examples of "aromatic heterocyclic ring systems" include furanyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said ring attached through any available carbon or nitrogen. For example, when the aromatic heterocyclic ring is furanyl, it can be 2-furanyl or 3 -furanyl, for pyrrolyl, the aromatic heterocyclic ring is 1 -pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, for pyridyl, the aromatic ring is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for other aromatic heterocyclic rings. The term "nonaromatic heterocyclic ring system" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Huckel rule is not satisfied by any ofthe rings in the ring system. The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. One skilled in the art will appreciate that not all 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.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "1-2 halogen" indicates that one or two ofthe available positions for that substituent may be halogen which are independently selected. 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 F3C, C1CH2, CF3CH2 and CF3CC12. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy" and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C=CHCH2 and CF3CH2CH-CHCH2. Examples of "haloalkenyloxy" include (Cl)2C=CHCH2O and CF3CH2CH=CHCH2O. Examples of "haloalkenylthio" include (C1)2C=CHCH2S and CF3CH2CH=CHCH2S. Examples of "haloalkynyl" include HCsCCHCl, CF3C=C, CC13C≡C and FCH2C≡CCH2. Examples of "haloalkynyloxy" include CF3C≡CCH2O, CCl3C≡CCH2O and FCH2C≡CCH2O. Examples of
"haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkylsulfmyl" include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O). Examples of "haloalkylsulfonyl" include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2.
"Alkylcarbonyl" denotes alkyl substituted carbonyl. Examples of "alkylcarbonyl" include CH3C(=O) and (CH3)2CHC(=O). "Alkoxycarbonyl denotes alkoxy substituted carbonyl. Examples of "alkoxycarbonyl" include CH3OC(=O) and (CH3)2CHOC(=O). "Alkylcarbonylamino" denotes alkylcarbonyl substituted on nitrogen. Examples of "alkylcarbonylamino" include CH3C(=O)NH and CH3CH2C(=O)NH.
"Alkoxycarbonylamino" denotes alkoxycarbonyl substituted on nitrogen. Examples of "alkoxycarbonylamino" include CH3OC(=O)NH and CH3CH2OC(=O)NH.
"Trialkylsilylalkoxyalkoxy" denotes trialkylsilyl substitution on alkoxy substituted in turn on alkoxy. Examples of "trialkylsilylalkoxyalkoxy" include (CH3)3SiCH2OCH2O and (CH3)3SiCH2CH2OCH2O.
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. For example, Cj-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl. Examples of "alkylcarbonyl" include CH3C(=O), CH3CH2CH2C(=O) and (CH3)2CHC(=O). Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O),
CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. When a group contains a substituent which can be hydrogen, for example R9 or
R13, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a group is optionally substituted with a substituent, for example with R7, then, when the group is not substituted with that substituent, it is recognized that this is equivalent to said group having a hydrogen substituent.
Compounds used in this invention often can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that 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). (See, e.g., U.S. Provisional Patent Application Serial No. 60/057917 filed September 4, 1997, which is hereby incorporated by reference in its entirety.) Compounds of Formula II contain a chiral center. Enantiomers of Formula II with the S configuration (i.e., as defined by Cahn-Ingold-Prelog rules) are preferred. Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds ofthe invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. The salts ofthe compounds which may be used in 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 ofthe compounds which may be used in 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 compositions for reasons of ease of synthesis or greater fungicidal activity are:
Preferred 1. A fungicidal composition comprising a fungicidally effective amount of (1) a compound of Formula I (including all geometric and stereoisomers), N-oxides, and agriculturally suitable salts thereof, wherein
E is selected from the group 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2-, and 2, 3 -naphthalenediyl; lH-pyrrole-1,2-, 2,3- and
3,4-diyl; 2,3- and 3,4-furandiyl; 2,3- and 3,4-thiophenediyl; lH-pyrazole-1,5-, 3,4- and 4,5-diyl; lH-imidazole-1,2-, 4,5- and 1,5-diyl; 3,4- and 4,5-isoxazolediyl; 4,5-oxazolediyl; 3,4- and 4,5-isothiazolediyl; 4,5-thiazolediyl; lH-l,2,3-triazole-l,5- and 4,5-diyl; 2H-l,2,3-triazole-4,5-diyl; lH-l,2,4-triazole-l,5-diyl;
4H-1 ,2,4-triazole-3,4-diyl; 1 ,2,3-oxadiazole-4,5-diyl; 1 ,2,5-oxadiazole-3,4-diyl; 1 ,2,3-thiadiazole-4,5-diyl; l,2,5-thiadiazole-3,4-diyl; lH-tetrazole- 1,5-diyl; 2,3- and 3,4-pyridinediyl; 3,4- and 4,5-pyridazinediyl; 4,5-pyrimidinediyl; 2,3-pyrazinediyl; l,2,3-triazine-4,5-diyl; l,2,4-triazine-5,6-diyl; lH-indole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 1,2-, 2,3-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; benzo[6]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-diyl; lH-indazole-1,4-, 1,5-, 1,6-, 1,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; lH-benzimidazole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl;
5 l,2-benzisoxazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-,
2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzoxazolediyl; l,2-benzisothiazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzothiazolediyl; 2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3-, 3,4-, 5,6-,
10 6,7- and 7,8-quinolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 3,5-, 3,6-, 3,7-,
3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-isoquinolinediyl; 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-cinnolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 5,6-, 6,7- and 7,8-phthalazinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-,
15 6,7- and 7,8-quinazolinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 2,3-, 5,6-, 6,7- and 7,8-quinoxalinediyl; l,8,-naphthyridine-2,5-, 2,6-, 2,7-, 3,5-, 3,6-, 4,5-, 2,3- and 3,4-diyl; 2,6-, 2,7-, 4,6-, 4,7-, 6,7-pteridinediyl; pyrazolo[5,l-/3]thiazole-2,6-, 2,7-, 3,6-, 3,7-, 2,3- and 6,7-diyl; thiazolo[2,3-c]-l,2,4-triazole-2,5-, 2,6-, 5,6-diyl;
20 2-oxo-l,3-benzodioxole-4,5- and 5,6-diyl; l,3-dioxo-lH-isoindole-2,4-, 2,5-, 4,5- and 5,6-diyl; 2-oxo-2H-l-benzopyran-3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-diyl; [l,2,4]triazolo[l,5-α]pyridine-2,5-, 2,6-, 2,7-, 2,8-, 5,6-, 6,7- and 7,8-diyl;
25 3,4-dihydro-2,4-dioxo-2H-l,3-benzoxazine-3,5-, 3,6-, 3,7-, 3,8-,
5,6-, 6,7- and 7,8-diyl; 2,3-dihydro-2-oxo-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl; thieno[3,2- ]thiazole-2,5-, 2,6-, and 5,6-diyl; 5,6,7,8-tetrahydro-2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3- and 3,4-quinolinediyl;
30 2,3-dihydro-l,l,3-trioxo-l,2-benzisothiazole-2,4-, 2,5-, 2,6-, 2,7-,
4,5-, 5,6- and 6,7-diyl; l,3-benzodioxole-2,4-, 2,5-, 4,5- and 5,6-diyl; 2,3-dihydro-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl; 2,3-dihydro-l,4-benzodioxin-2,5-, 2,6-, 2,7-, 2,8-, 5,6- and 6,7-diyl; and
35 5,6,7,8-tetrahydro-4H-cyclohepta[/3]thiophene-2,4-, 2,5-, 2,6-, 2,7-,
2,8-, 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, and 2,3-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 and R4; W is O;
R1 is Cj-C3 alkyl or CrC3 haloalkyl; R2 is H, Cj-Cg alkyl, CrC6 haloalkyl or C3-C6 cycloalkyl; R3 and R4 are each independently halogen, cyano, nitro, Cj-Cg alkyl, C j -Cg haloalkyl, C j -Cg alkoxy, Cj-Cg haloalkoxy, C j -C6 alkylthio, Cj-Cg alkylsulfonyl, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, (CrC4 alkyl)NHC(O), (CrC4 alkyl)2NC(O), benzoyl or phenylsulfonyl; Y is -0-, -S(O)n-, -NR15-, -C(=O)-, -CH(OR15)-, -CH2-, -CH2CH2-, -CH=CH-, -C≡C-, -CH20-, -OCH2-, -CH2S(O)n-, -S(O)nCH2-,
-CH2O-N=C(R7)-, -(R7)C=N-OCH(R15)-, -C(R7)=N-O- or a direct bond; R7 is H, Cj-Cg alkyl, CrC6 haloalkyl, C,-C6 alkoxy, CrC6 alkylthio,
C2-Cg alkenyl, C2-Cg alkynyl, C3-Cg cycloalkyl, halogen or cyano; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CH2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; Z is selected from the group CJ-CJQ alkyl; C3-Cg cycloalkyl; phenyl; naphthalenyl; anthracenyl; phenanthrenyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2 /-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl;
1 ,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl;
1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl;
1,2,4,5-tetrazinyl; lH-indolyl; benzofuranyl; benzo[Z?]thiophenyl; lH-indazolyl; lH-benzimidazolyl; benzoxazolyl; benzothiazolyl; quinolinyl; isoquinolinyl; cinnolinyl; phthalazinyl; quinazolinyl; quinoxalinyl; 1,8-naphthyridinyl; pteridinyl;
2,3-dihydro-lH-indenyl; 1,2,3,4-tetrahydronaphthalenyl;
6,7,8,9-tetrahydro-5H-benzocycloheptenyl;
5,6,7,8,9, 10-hexahydrobenzocyclooctenyl; 2,3-dihydro-3-oxobenzofuranyl;
1,3-dihydro-l-oxoisobenzo furanyl;
2,3-dihydro-2-oxobenzofuranyl;
3 ,4-dihydro-4-oxo-2H- 1 -benzopyranyl; 3,4-dihydro-l-oxo-lH-2-benzopyranyl; 3 ,4-dihydro-3 -oxo- 1 H-2-benzopyranyl;
3 ,4-dihydro-2-oxo-2H- 1 -benzopyranyl; 4-oxo-4H- 1 -benzopyranyl ; 2-oxo-2H- 1 -benzopyranyl; 2,3,4,5-tetrahydro-5-oxo-l-benzoxepinyl;
2,3,4,5-tetrahydro-2-oxo- 1 -benzoxepinyl; 2,3 -dihydro- 1 ,3 -dioxo- 1 H-isoindolyl; 1 ,2,3,4-tetrahydro-l ,3-dioxoisoquinolinyl; 3,4-dihydro-2,4-dioxo-2H-l,3-benzoxazinyl; 2-oxo-l,3-benzodioxyl;
2,3-dihydro-l,l,3-trioxo-l,2-benzisothiazolyl; 9H-fluorenyl; azulenyl; and thiazolo[2,3-c]-l,2,4-triazolyl; each group substituted with R9 and optionally substituted with one or more R10; R15 is H, Cj-C3 alkyl or C3-C6 cycloalkyl; and (2) at least one compound selected from compounds of (a)
Formula II, N-oxides and agriculturally suitable salts thereof, and (b) bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenarimol, fenbuconazole, fenpropidin, fenpropimorph, fluquinconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, penconazole, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, tridemorph, triticonazole and uniconazole. Preferred 2. The fungicidal composition of Preferred 1 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4- triazol-3-one (sometimes referred to hereafter as the Formula la compound) and (2) at least one compound selected from (a) 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)-2,4-oxazolidinedione (sometimes referred to hereafter as the Formula Ila compound) and 3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H- imidazol-4-one (sometimes referred to hereafter as the Formula lib compound) and (b) epoxiconazole, fenpropimorph, flusilazole, propiconazole and tebuconazole. Preferred 3. The fungicidal composition of Preferred 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3-
(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3N-l,2,4- triazol-3-one and (2) 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)-2,4- oxazolidinedione. Preferred 4. The fungicidal composition of Preferred 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4- triazol-3-one and (2) flusilazole. Preferred 5. The fungicidal composition of Preferred 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4- triazol-3-one and (2) both 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)- 2,4-oxazolidinedione and flusilazole. The fungicidal compositions of this invention, in addition to comprising fungicidally effective amounts ofthe mixtures ofthe invention also optionally comprise at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions ofthe present invention are those which comprise the above preferred component (1) and component (2) 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 ofthe mixtures ofthe invention (e.g., as a composition described herein). The preferred methods of use include those involving the above preferred compositions. The Sterol Biosynthesis Inhibitor Fungicides
The class of sterol biosynthesis inhibitors includes DMI and non-DMI compounds, that control fungi by inhibiting enzymes in the sterol biosynthesis pathway. DMI fungicides have a common site of action within the fungal sterol biosynthesis pathway; that is, an inhibition of demethylation at position 14 of lanosterol or 24- methylene dihydrolanosterol, which are precursors to sterols in fungi. Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs. The demethylase enzyme is sometimes referred to by other names in the biochemical literature, including cytochrome P-450 (14DM). The demethylase enzyme is described in, for example, J. Biol. Chem. 1992, 267, 13175-79 and references cited therein. DMI fungicides fall into several classes: triazoles, imidazoles, pyrimidines, piperazines and pyridines. The triazoles includes bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, penconazole, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole. The imidazoles include clotrimazole, econazole, imazalil, isoconazole, miconazole and prochloraz. The pyrimidines include fenarimol, nuarimol and triarimol. The piperazines include triforine. The pyridines include buthiobate and pyrifenox. Biochemical investigations have shown that all ofthe above mentioned fungicides are DMI fungicides as described by K. H. Kuck, et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 205-258.
The DMI fungicides have been grouped together to distinguish them from other sterol biosynthesis inhibitors, such as, the morpholine and piperidine fungicides. The morpholines and piperidines are also sterol biosynthesis inhibitors but have been shown to inhibit later steps in the sterol biosynthesis pathway. The morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide. The piperidines include fenpropidin. Biochemical investigations have shown that all ofthe above mentioned morpholine and piperidine fungicides are sterol biosynthesis inhibitor fungicides as described by K. H. Kuck, et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 185-204. Synergistic Effects Fungicides that effectively control plant fungi, such as wheat powdery mildew
(Erysiphe graminis) and wheat glume blotch (Septoria nodorum), are in constant demand by growers. Combinations of fungicides are often used to facilitate disease control and to retard resistance development. Mixtures of fungicides may provide significantly better disease control than could be predicted based on the activity ofthe individual components. This synergism has been described as "the cooperative action of two components of a mixture, such that the total effect is greater or more prolonged than the sum ofthe effects ofthe two (or more) taken independently" (see Tames, P. M. L., Neth. J. Plant Pathology, (1964), 70, 73-80). It has been found that compositions containing the compound of Formula la and flusilazole and compositions containing the compounds of Formula la and Formula Ila exhibit synergistic effects.
The presence of a synergistic effect between two active ingredients is established with the aid ofthe Colby equation (see Colby, S. R. In Calculating Synergistic and Antagonistic Responses of Herbicide Combinations, Weeds, (1967), 15, 20-22):
p = A+ B - A x B
100
Using the methods ofthe Colby, the presence of a synergistic interaction between two active ingredients is established by first calculating the predicted activity, p, ofthe mixture based on activities ofthe two components applied alone. If p is lower than the experimentally established effect, synergism has occurred. In the equation above, A is the fungicidal activity in percentage control of one component applied alone at rate x. The B term is the fungicidal activity in percentage control ofthe second component applied at rate y. The equation estimates p, the fungicidal activity ofthe mixture of A at rate x with B at rate y if their effects are strictly additive and no interaction has occurred.
In this application, fungicidal activities provided by compositions of Formula la, Formula Ila and flusilazole alone are compared with that of compositions ofthe compounds of Formula la and Formula Ila together and with that of compositions ofthe compounds of Formula la and flusilazole together. Based on the description of synergism developed by Colby, compositions ofthe present invention are considered to be synergistically useful. Accordingly, this invention provides an improved method of combating fungi, such as the control wheat powdery mildew (Erysiphe graminis) and the preventative control of wheat glume blotch (Septoria nodorum), in crops, especially cereals.
Compositions are provided in accordance with this invention which comprise proportions of component (1) and component (2) which are especially useful for controlling particular fungal diseases. For example, the compositions of this invention include those wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15. Compositions including the compounds of Formula II are considered especially useful for controlling wheat powdery mildew (Erysiphe graminis) and compositions including the sterol biosynthesis inhibitor fungicides are considered especially useful for the preventative control of wheat glume blotch (Septoria nodorum). Preferred component (1) compounds for these compositions include 2,4-dihydro-5- methoxy-2-methyl-4-[2-[[[[l-[3-
(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one. Preferred component (2) compounds for these compositions include 5-methyl-5-(4- phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone; 3,5-dihydro 5-methyl-2-
(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one; and flusilazole. Preferably, the mole ratio of component (1) to component (2) for these compositions is from about 4:1 to 1:15. Example compositions of this type include compositions comprising 2,4- dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone in a mole ratio of the compound of Formula la to the compound of Formula Ila of from about 4:1 to 1 :4; and compositions comprising 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and flusilazole in a mole ratio of the compound of Formula la to flusilazole of about 4 : 1 to 1:15.
This invention also provides processes for the control of wheat powdery mildew and the preventative control of wheat glume blotch which comprises 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 fungicidal combination including component (1) and component (2) wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15 (preferably from about 4:1 to 1 :15). Component (1) can, for example, be applied at a rate of 0.2 g/ha or more. Typically component (1) is applied at a rate of 125 g/ha. Component (2) may be applied simultaneously (e.g., in the form of a composition comprising component (1) and component (2) in an appropriate mole ratio); or component (1) and component (2) can be applied separately in an appropriate mole ratio (e.g., as a tank mix). Compositions wherein component (2) is selected from the group consisting of compounds of Formula II; and wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1 :15 are considered especially useful for controlling wheat powdery mildew. Preferred component (1) compounds for these compositions include 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H- 1 ,2,4-triazol-3-one. Preferred component (2) compounds for these compositions include 5-methyl-5-(4- phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone and 3,5-dihydro 5-methyl-2- (methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one; with 5-methyl-5-(4- phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone being particularly preferred. Preferably, the mole ratio of component (1) to component (2) for these compositions is from about 4:1 to 1 :4. Example compositions of this type include compositions comprising 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l -[3-
(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone in a mole ratio of the compound of Formula la to the compound of Formula Ila of from about 4:1 to 1 :4. This invention also provides a process for controlling wheat powdery mildew which comprises 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 fungicidal combination including component (1) and component (2) wherein the mole ratio of component (1) to component (2) is from about 4:1 to 1:4. Component (1) can, for example, be applied at a rate of 0.2 g/ha or more. Typically component (1) is applied at a rate of 125 g/ha. Component (2) may be applied simultaneously (e.g., in the form of a composition comprising component (1) and component (2) in an appropriate mole ratio); or component (1) and component (2) can be applied separately in an appropriate mole ratio (e.g., as a tank mix).
Compositions wherein component (2) is selected from the group consisting of 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinone; 3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one; flusilazole; epoxiconazole; fenpropimorph; propiconazole; and tebuconazole; and wherein the mole ratio of component (1) to component (2) is from about 15:1 to 1:15 are considered especially useful for the preventative control of wheat glume blotch. Preferred component (1) compounds for these compositions include 2,4-dihydro-5- methoxy-2-methyl-4-[2-[[[[l-[3-
(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one. Preferred component (2) compounds for these compositions include sterol biosynthesis inhibitor fungicides; with epoxiconazole, flusilazole, propiconazole and tebuconazole being particularly preferred. Preferably, the mole ratio of component (1) to component (2) for these compositions is from about 4 : 1 to 1 : 15. Example compositions of this type include compositions comprising 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and flusilazole in a mole ratio ofthe compound of Formula la to flusilazole of from about 4:1 to 1:15. This invention also provides a process for the preventative control of wheat glume blotch, which comprises 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 fungicidal combination including component (1) and component (2) wherein the mole ratio of component (1) to component (2) is from about 4:1 to 1 :15. Component (1) can, for example, be applied at a rate of 5 g/ha or more. Typically component (1) is applied at a rate of 125 g/ha. Component (2) may be applied simultaneously (e.g., in the form of a composition comprising component (1) and component (2) in an appropriate mole ratio); or component (1) and component (2) can be applied separately in an appropriate mole ratio (e.g., as a tank mix). Synthesis of Compounds of Formula I
The compounds of Formula I can be prepared by one or more ofthe following methods and variations as described in Schemes 1-2 and International Patent Application WO 95/14009. The definitions of A, E, G, W, X, Y, Z, R1 and R2in the compounds of Formulae 1-5 below are as defined above in the Summary ofthe Invention. The compound of Formula la is a subset ofthe compounds of Formula I. Compounds of Formula I can be prepared as described in International Patent Application WO 95/14009. A synthesis ofthe compounds of Formula I involves treating a compound 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, dimethoxyethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; and halocarbons such as dichloromethane or chloroform. Scheme 1
Figure imgf000023_0001
Method 1 : V-CH=N2 (V = H or (CH3)3Si)
2
NH
Method 2: JL
C13C7 OCH3 ; Lewis acid 3
Method 3: (CH3)30+ BF4-
4
Method 4: (CH3) SC>4; R1OS02V; or CH3-hal; optional base
(hal = F, Cl, Br, or I)
(V = Cj-Cg alkyl, Cj-Cg haloalkyl)
For example, compounds of Formula I can be prepared by the action of diazoalkane reagents of Formula 2 such as diazomethane (V = H) or trimethylsilyldiazomethane (V = (CH3)3Si) on compounds of Formula 1 (Method 1). Use of trimethylsilyldiazomethane requires a protic cosolvent such as methanol. For examples of these procedures, see Chem. Pharm. Bull., (1984), 32, 3759.
As indicated in Method 2, compounds of Formula I can also be prepared by contacting carbonyl a compound 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. Hδnig, Synth. Commun., (1990), 20, 203).
Compound 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). The use of trialkyloxonium salts as powerful alkylating agents is well known in the art (see U. Schδllkopf, U. Groth, C. Deng, Angew. Chem., Int. Ed. Engl.,
(1981), 20, 798). Other alkylating agents which can convert compounds of Formula 1 to compounds of Formula I 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. See R. E. Benson, T. L. Cairns, J. Am. Chem. Soc, (1948), 70, 2115 for alkylation examples using agents of this type.
Compounds of Formula I, where A, G, E, W, X, Y, Z, R1 and R2 are defined as above, can also be prepared by reaction of Formula 5 compounds with alkali metal alkoxides (RiO^M ") (Scheme 2). The leaving group Lg1 in the amides of Formula 5 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.
Scheme 2
Figure imgf000024_0001
Lg1 = Cl, Br, -S02V, or -OS02V V = Cj-Cg alkyl or Cj-Cg haloalkyl M = K or Na 2,4-Dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one, Formula la, is a compound of Formula I where E is 1 ,2-phenylene, A is N, G is N with the floating double bond attached to A, W is O, X is OR1, R1 is CH3, R2 is CH3, Y is -CHR150-N=C(R7)-, R7 is CH3, R15 is H, Z is phenyl substituted with R9 and R9 is CF3 fixed in the 3 position.
Figure imgf000025_0001
Synthesis of Compounds of Formula II
The compounds of Formula II can be prepared by one or more ofthe following methods and variations as described in Scheme 3, International Patent Application WO 94/11359 and European Patent Application EP-A-551048. The compounds of Formulae Ila and lib are various subsets ofthe compounds of Formula II.
The compound of Formula Ila (where E1 is -OC(=O)CH2- and R28 is phenoxy) can be prepared as depicted in Scheme 3 and described in International Patent Application WO 94/11359.
Scheme 3
Figure imgf000025_0002
Figure imgf000025_0003
wherein: R29 is -C4 alkyl; and Lg' is 1-imidazolyl or 1 ,2,4-triazolyl Reaction conditions suitable for preparing the compound of Formula Ila are as follows. For the conversion of esters of Formula 6 to compounds of Formula 8, the suitable solvents include inert organic solvents. Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, hexanes, tetrahydrofuran, tert-butyl methyl ether, dioxanes, chlorobenzene, o-dichlorobenzene (ODCB), toluene, xylenes, and suitable combinations thereof. The most preferred solvents are selected from the group consisting of chlorobenzene, ODCB, toluene, and xylenes. The reaction temperatures can range from about 10°C to about 75°C. Preferred temperatures are from about 40°C to about 60°C. Suitable reaction pressures are from about 1.0 x 105 to about 5.1 x 105 Pascals. The preferred pressure is 1 x 105 Pascals. The reaction times are typically 1 to 24 hours, preferably 3 to 6 hours. A suitable ratio of Formula 7 to 6 is from about 1 :1 to 2:1. The preferred ratio is from about 1.1 :1 to 1.8:1. Suitable bases for this reaction include trialkylamines, imidazole, pyridine, picolines or other substituted pyridine derivatives. For the conversion of compounds of Formula 8 to the 2,4-oxazolidinedione of
Formula Ila, suitable solvents are as noted above for the condensation of Formulae 6 and 7. The preferred solvents are those disclosed above as preferred. The reaction temperatures are from about 0°C to about 75°C. Preferred temperatures are from about 10°C to about 50°C. Reaction pressures are from about 1.0 x 105 to about 5.1 x 105 Pascals. The preferred pressure is 1 x 105 Pascals. The reaction times are typically 1 to 24 hours, preferably 2 to 6 hours. The acids suitable for catalyzing the reaction are selected from the group consisting of alkyl and aryl carboxylic acids, trialkylammonium halides and combinations thereof. The preferred acids are acetic acid and triethylammonium chloride. The most preferred acid is triethylammonium chloride. Suitable ratios of phenylhydrazine to Formula 8 is from about 2:1 to 1 : 1. The preferred ratio is from about 1.6:1 to 1.1 :1.
The carbonylating agent of Formula 7 may be added as a pure compound, a solution ofthe pure compound in an inert solvent, or prepared in situ in the presence of the ester of Formula 6. The preferred process involves preparation ofthe carbonylating agent in situ.
Methods for preparing compounds of Formula 7, including in situ methods, from phosgene [or phosgene equivalents such as diphosgene (trichloromethyl chloroformate) or triphosgene (bis(trichloromethyl)carbonate)] and either imidazole or triazole are known in the art (see Org. Syntheses. Coll. Vol. 5, 201, (1973)). Reactions wherein HC1 is liberated require a base to trap the acid. A suitable base is a trialkylamine or imidazole, or combinations thereof. The preferred base is triethylamine. l,l'-Carbonylditriazole (Formula 7 wherein Lg1 = 1,2,4-triazolyl) can also be prepared by treating a metal alkali salt of triazole, preferably the potassium salt, with phosgene (or phosgene equivalent) in a solvent. Phase transfer catalysts are preferably added to reactions wherein the triazole salt has low solubility in the solvent. For example, phase transfer catalysts are preferred when xylenes or toluene is used. Any phase transfer catalyst known to one skilled in the art is suitable. Tetraalkylammonium halides are preferred. The triazole salt is prepared by treating triazole with a suitable base, such as sodium hydroxide or sodium ethoxide. The preferred relative amount of alkali metal base to triazole to phosgene is 0.5:1.0:0.6.
Base is also necessary to catalyze the condensation of Formulae 6 and 7. As previously stated, suitable base catalysts are trialkylamines, imidazole, pyridine, picolines or other substituted pyridines. When l,l'-carbonyldiimidazole is used
(Formula 7 wherein Y=l-imidazolyl), the imidazole which is liberated upon reaction with Formula 6 serves as the catalyst. When l,l'-carbonylditriazole is used, the preferred base is pyridine, a picoline, or a mixture of picoline isomers.
Compounds of Formula 8 may be isolated and purified, or treated in situ with phenylhydrazine and acid to form the 2,4-oxazolidinedione of Formula Ila. The preferred method involves treatment of Formula 8 in situ with phenylhydrazine. After the formation ofthe carbamate of Formula 8 is complete, excess carbonylating agent can be decomposed by the addition of water.
The compound of Formula lib (where E1 is -N=C(SCH3)CH2- and R28 is H) can be prepared as described in European Patent Application EP-A-551048.
Figure imgf000027_0001
lib Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting ofthe disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. *H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d - doublet and m = multiplet. EXAMPLE 1 Preparation of 2,4-dihydro-5-methoxy-2-methyl-4- 2-[ [ l-[3- trifluoromethyl)phenyllethylidenelaminoloxylmethyllphenyll-3H- 2,4-triazol- 3 -one A 100 mL 1 -necked round bottom flask is fitted with a magnetic stirrer and reflux condenser capped with a nitrogen bypass. The flask is charged with 50 mL of tetrahydrofuran, 2.12 g of 5-chloro-2,4-dihydro-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]-ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one (5 mmol) and 1.19 g of 25% sodium methoxide in methanol (5.5 mmol). The mixture is heated to reflux with stirring. After 4 h, 0.10 g of 25% sodium methoxide in methanol is added. After an additional 2 h, 0.30 g of 25% sodium methoxide in methanol is added. The mixture is then stirred at reflux for one additional hour at which time analysis of an aliquot by high pressure liquid chromatography indicates the presence of essentially no starting material. The mixture is allowed to cool to room temperature and left stirring overnight. The mixture is then worked up as in Example 3 to yield 2.06 g of pale yellow oil which crystallized upon seeding with an authentic sample of 2,4- dihydro-5 -methoxy-2-methyl-4- [2 [[[[ 1 - [3 -(trifluoromethyl)phenyl- ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one. Trituration with hexanes followed by filtration and drying gave 1.97 g of white solid, m.p. 97-98.5°C. A portion (1.00 g) of this was recrystallized from 10 mL of 10% ethyl acetate-hexane to yield 0.94 g of white solid, m.p. 101-102°C. HiNMR (CDC13) δ 2.21 (s,3H), 3.40 (s,3H), 3.89 (s,3H), 5.24 (d,2H), 5.28 (d,2H), 7.26 (m,lH), 7.47 (m,3H), 7.58 (m,2H), 7.85 (m,2H). Formulation/Utility The fungicidal compositions ofthe present invention comprise an effective amount of a mixture ofthe compounds(s) of component (1) (e.g., 2,4-dihydro-5- methoxy-2-methyl-4-[2-[[[[l-[3-
(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one) and the compound(s) of component (2) (e.g., 5 -methyl-5 -(4-phenoxyphenyl)-3 -(phenyl-amino)-2 ,4-oxazolidinedione;
3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one; epoxiconazole, fenpropimorph, flusilazole; propiconazole and/or tebuconazole). The mixtures of this invention will typically 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 ofthe 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 ofthe 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 ingredients, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Weight Percent
Active
Ingredients Diluent Surfactant
Water-Dispersible and Water-soluble 5-90 0-94 1-15
Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-15
(including Emulsifiable
Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0-15
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, N,N-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-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, com, 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, including emulsifiable concentrates, 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. Patent No. 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
International Patent Publication WO 91/13546. Pellets can be prepared as described in U.S. Patent No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Patent No. 4,144,050, U.S. Patent No. 3,920,442 and German Patent Publication DE 3,246,493. Tablets can be prepared as taught in
U.S. Patent No. 5,180,587, U.S. Patent No. 5,232,701 and U.S. Patent No. 5,208,030. Films can be prepared as taught in Great Britain Patent Publication GB 2,095,558 and U.S. Patent No. 3,299,566.
For further information regarding the art of formulation, see U.S. Patent No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. Patent No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Patent No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Example A Wettable Powder
Active ingredient(s) 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example B Granule Active ingredient(s) 10.0% attapulgite granules (low volatile matter,
0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example C Extruded Pellet Active ingredient(s) 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. Example D
Emulsifiable Concentrate
Active ingredient(s) 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 ofthe 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. These 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 fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma, Sclerotinia sclerotiorum,
Sclerotium rolfsii, Erysiphe polygoni, Pyrenophora teres, Gaeumannomyces graminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae and other generea and species closely related to these pathogens.
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. Examples of such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methyl 7-chloro- 2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4-
(trifluoromethoxy)pheny 1] amino] carbonyl] indeno [l,2-e][l,3,4] oxadiazine-4a(3H)- carboxylate (DPX-JW062), monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyprodinil (CGA 219417), diclomezine, dicloran, dimethomorph, dodine, edifenphos, famoxadone, fenpiclonil, fluazinam, flutolanil, folpet, fosetyl-aluminum, furalaxyl, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mepronil, metalaxyl, (E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (SSF 126), S-methyl 7-benzothiazolecarbothioate (CGA 245704), myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, pencycuron, probenazole, prochloraz, pyrifenox, pyroquilon, quinoxyfen, spiroxamine (KWG4168), sulfur, thiabendazole, thiophanate-methyl, thiram, tricyclazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi. In certain instances, combinations with other fungicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
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 this composition can be influenced by many factors ofthe 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 aggregate active ingredient. Aggregate active ingredient is defined as the total combined weight of active ingredients. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g of aggregate active ingredient per kilogram of seed. The following Examples demonstrate the composition and method ofthe present invention and provide experimental evidence for synergy between the compound of Formula la and flusilazole in preventative control of wheat glume blotch caused by Septoria nodorum. The experimental also provides evidence for synergy between the compound of Formula la and Ila in preventative and curative control of wheat powdery mildew caused by Erysiphe graminis. The experimental also provides evidence for synergy between the compound of Formula la and Ila in preventative and curative control of grape downy mildew caused by Plasmopara viticola.
The following 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. BIOLOGICAL EXAMPLES OF THE INVENTION Test compounds were first dissolved in acetone in an amount equal to 50% ofthe final volume and then suspended at a concentrations from 0.08 to 200 ppm in purified water containing 250 ppm ofthe surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following test protocols. Spraying these test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha.
Protocol # 1 - WPM Preventive The test compounds were 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). Seedlings were incubated in a growth chamber at 20°C for 6 days, after which disease ratings were made.
Protocol # 2 - WPM Curative Wheat seedlings were inoculated with a spore dust of Erysiphe graminis f sp. tritici, (the causal agent of wheat powdery mildew). The following day a test compounds were sprayed to the point of run-off on and seedlings incubated in a growthchamber at 20°C for 7 days, after which disease ratings were made.
Protocol # 3 WLR Preventive The test compounds were 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.
Protocol # 4 - WLR Curative Wheat seedlings were inoculated with a spore suspension of Puccinia recondita
(the causal agent of wheat leaf rust). The following day the test compounds were sprayed to the point of run-off on and incubated in a saturated atmosphere at 20°C for 24 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made. Protocol # 5 - WFR Preventive
The test compounds were sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Pseudocercosporella herpotrichoides (the causal agent of wheat eye spot or wheat foot rot) and incubated in a saturated atmosphere at 20°C for 72 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made. Protocol # 6 - WGB Preventive The test compounds were sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Septoria nodorum (the causal agent of wheat glume blotch) and incubated in a saturated atmosphere at 20°C for 48 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
Protocol # 7 - WGB Curative Wheat seedlings were inoculated with a spore suspension Septoria nodorum (the causal agent of wheat glume blotch). Two days later test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
Protocol # 8 - RCB Curative Wheat seedlings were inoculated with a spore suspension Pyricularia oryzae (the causal agent of rice Blast). The following day test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to greenhouse at 27°C for 8 days, after which disease ratings were made.
Protocol # 9 - RSB Preventive The test compounds were sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Rizoctonia solani (the causal agent of rice sheath blight ) and incubated in a saturated atmosphere at 20°C for 48 h, and then moved to a greenhouse at 27°C for 8 days, after which disease ratings were made.
Protocol # 10 - PLB Preventive 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. Protocol # 11 - PLB Curative
Wheat seedlings were inoculated with a spore Phytophthora infestans (the causal agent of potato and tomato late blight). The following day test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made. Protocol # 12 - GDM Preventive 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 Plasmopara viticola (the causal agent of grape downy mildew) 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.
Protocol # 13 - GDM Curative Wheat seedlings were inoculated with a spore Plasmopara viticola (the causal agent of grape downy mildew). The following day test compounds were sprayed to the point of run-off on and seedlings incubated in a saturated atmosphere at 20°C for 48 h, then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
Results for protocols 1 - 13 are given in Tables A-F. In the tables, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). An (nt) indicates no test results and (--) indicates no estimate of activity. In Tables A-F rates are given in parts per million (ppm) and/or grams active ingredient per hectare (g a.i./ha). The term "Actual" stands for the experimental value. The abbreviation "Exp." stands for "Expected" (i.e., the predicted activity, p, from the Colby equation).
TABLE A
Synergistic Effects of Compound la / Flusilazole Combinations for Preventive Control of Wheat Powdery Mildew (WPM),
Wheat Leaf Rust (WLR), Wheat Foot Rot (WFR) and Wheat Glume Blotch (WGB)
Percent Disease Control
Test Test Rate Rate Mole WPM(1) WLR(2) WFR(3) WGB(4)
Cmpd l Cmpd 2 (ppm) (ε a.i./ha) Ratio Actual Exp. Actual Exp. Actual Exp. Actual Exp. la ~ 2 5 96 ~ 99 — 17 ~ 64 ~ la ~ 10 25 100 — 99 — 83 ~ 99 —
Flusilazole — 1 2.5 89 ~ 0 — 58 ~ 45 ~
Flusilazole — 5 12.5 92 ~ 88 - 100 — 97 --
Flusilazole — 20 50 100 ~ 100 — 100 — 98 — 00
Flusilazole la 1 + 2 2.5 + 5 1 :1.5 99 99.6 99 99 52 65.1 93 80.2
Flusilazole la 5 + 2 12.5 + 5 3.33:1 99 99.7 98 99.9 100 100 99 98.9
Flusilazole la 20 + 2 50 + 5 13.33:1 100 100 97 100 100 100 99 99.3
Flusilazole la 1 + 10 2.5 + 25 1:7.5 99 100 98 99 54 92.9 97 99.5
Flusilazole la 5 + 10 12.5 + 25 1 :1.5 99 100 99 99.9 100 100 93 100
Flusilazole la 20 + 10 50 + 25 2.67:1 100 100 100 100 100 100 99 100
(1) Wheat powdery mildew activity - Protocol #1
(2) Wheat leaf rust activity - Protocol # 3
Figure imgf000037_0001
(3) Wheat foot rot activity - Protocol # 5
(4) Wheat glume blotch activity - Protocol # 6
TABLE B
Synergistic Effects of Compound la / Compound Ila Combinations for Preventive Control of Wheat Powdery Mildew (WPM),
Wheat Leaf Rust (WLR), Wheat Foot Rot (WFR) and Wheat Glume Blotch (WGB)
Percent Disease Control
Test Test Rate Rate Mole WPM(,) WLR(2) WFR(3) WGB(4)
Cmϋd l Cmpd 2 (PPm (ε a.i./ha) Ratio Actual Exp. Actual Exp. Actual Exp. Actual Exp.
Ila — 0.08 0.2 5 ~ 15 — 0 — 12 ~
Ila — 0.4 1 0 ~ 65 — 0 — 32 —
Ila — 2 5 0 — 64 — 0 — 87 — la — 0.08 0.2 37 — 78 — 0 — 0 — J la ~ 0.4 1 97 — 97 ~ 12 — 0 — cn la — 2 5 100 ~ 99 — 59 — 70 —
Ila la 0.08 + 0.08 0.2 +0.2 1:1.13 55 40.2 51 81.3 0 0 25 12
Ila la 0.4 + 0.4 1 + 1 1:1.13 97 97 94 99 0 12 0 32
Ila la 2 + 2 5 + 5 1 :1.13 100 100 98 99.6 12 59 100 96.1
(1) Wheat powdery mildew activity - Protocol #1
(2) Wheat leaf rust activity - Protocol # 3
(3) Wheat foot rot activity - Protocol # 5
(4) Wheat glume blotch activity - Protocol # 6
TABLE C Synergistic Effects of Compound la / Flusilazole Combinations for Curative Control of Wheat Powdery Mildew (WPM),
Wheat Leaf Rust (WLR) and Wheat Glume Blotch (WGB)
Percent Disease Control
Test Test Rate Rate Mole WPM(1) WLR(2 ) WGB(3)
Cmod l Cmpd 2 (ppm) (ε a.i./ha) Ratio Actual Exp. Actual Exp. Actual Exp. la ~ 2 5 100 — 79 ~ 50 — la ~ 10 25 100 ~ 100 ~ 93 —
Flusilazole — 1 2.5 78 ~ 22 — 10 ~
Flusilazole ~ 5 12.5 99 — 97 ~ 10 ~
CO
Flusilazole — 20 50 100 ~ 100 ~ 68 — ^1
Flusilazole la 1 + 2 2.5 + 5 1 :1.5 68 100 67 83.6 20 55
Flusilazole la 5 + 2 12.5 + 5 3.33:1 99 100 100 99.4 80 55
Flusilazole la 20 + 2 50 + 5 13.33:1 100 100 100 100 84 84
Flusilazole la 1 + 10 2.5 + 25 1:7.5 68 100 67 100 56 100
Flusilazole la 5 + 10 12.5 + 25 1 :1.5 99 100 100 100 29 100
Flusilazole la 20 + 10 50 + 25 2.67:1 100 100 100 100 83 100
(1) Wheat powdery mildew activity - Protocol # 2
(2) Wheat leaf rust activity - Protocol # 4
(3) Wheat glume blotch activity - Protocol # 7
TABLE D Synergistic Effects of Compound la / Compound Ila Combinations for Curative Control of Wheat Powdery Mildew (WPM),
Wheat Leaf Rust (WLR) and Wheat Glume Blotch (WGB)
Percent Disease Control
Test Test Rate Rate Mole WPM(1) WLR(2) WGB(3)
Cmnd l Cmpd 2 (ppm) (ε a.i./ha) Ratio Actual Exp. Actual Exp. Actual Exp
Ila — 0.08 0.2 0 — 0 — 0 —
Ila ~ 0.4 1 0 ~ 0 -- 0 —
Ila — 2 5 64 — 0 ~ 0 — la — 0.08 0.2 0 — 0 — 0 — o
OD la -- 0.4 1 35 — 0 — 0 — la — 2 5 92 — 0 ~ 0 ~
Ila la 0.08 + 0.08 0.2 + 0.2 1 :1.13 73 0 0 0 0 0
Ila la 0.4 + 0.4 1 + 1 1:1.13 80 35 0 0 0 0
Ila la 2 + 2 5 + 5 1:1.13 99 97.1 28 0 0 0
(1) Wheat powdery mildew activity - Protocol # 2
(2) Wheat leaf rust activity - Protocol # 4
(3) Wheat glume blotch activity - Protocol # 7
TABLE E Synergistic Effects of Compound la / Compound Ila Combinations for Preventive Control of Rice Blast (RCB), Rice Sheath Blight (RCB),
Potato Late Blight (PLB) and Grape Downy Mildew (GDM)
Percent Disease Control
Test Test Rate Rate Mole RCB(1) RSB(2) PLB ,(3> GDM(4)
Cmpd l Cmpd 2 (PPm) (ε a.i./ha) Ratio Actual Exp. Actual Exp. Actual Exp. Actual Exp.
Ila ~ 0.08 0.2 0 — 0 — 0 — 43 —
Ila ~ 0.4 1 0 ~ 0 ~ 0 — 43 ~
Ila — 2 5 0 ~ 0 ~ 17 — 100 — la ~ 0.08 0.2 0 — 0 — 0 ~ 7 — la ~ 0.4 1 0 ~ 0 — 0 — 33 -- ω la ~ 2 5 11 ~ 0 ~ 0 — 43 —
Ila la 0.08 + 0.08 0.2 + 0.2 1:1.13 0 0 0 0 0 0 28 47
Ila la 0.4 + 0.4 1 + 1 1 :1.13 0 0 0 0 0 0 88 61.8
Ila la 2 + 2 5 + 5 1 :1.13 0 11 58 0 17 17 100 100
(1) Rice blast - Protocol # 8
(2) Rice sheath blight - Protocol # 9
(3) Potato late blight - Protocol # 10
(4) Grape downy mildew - Protocol # 12
TABLE F Synergistic Effects of Compound la / Compound Ila Combinations for Curative Control of Rice Blast (RCB), Rice Sheath Blight (RCB),
Potato Late Blight (PLB) and Grape Downy Mildew (GDM)
Percent Disease Control
Test Test Rate Rate Mole RCB(I) PLB(2) GDM(3)
Cmpd l Cmpd 2 (ppm) (ε a.i./ha) Ratio Actual Exp. Actual Exp. Actual Exp.
Ila — 0.08 0.2 0 — 0 — 0 —
Ila — 0.4 1 0 — 0 — 0 ~
Ila — 2 5 0 — 0 — 0 ~ la — 0.08 0.2 0 — 0 — 0 -- la — 0.4 1 0 — 0 ~ 0 — o la — 2 5 0 ~ 0 ~ 0 —
Ila la 0.08 + 0.08 0.2 +0.2 1:1.13 0 0 0 0 0 0
Ila la 0.4 + 0.4 1 + 1 1:1.13 0 0 0 0 16 0
Ila la 2 + 2 5 + 5 1:1.13 0 0 0 0 26 0
(1) Rice blast - Protocol # 8
(2) Potato late blight - Protocol # 11
(3) Grape downy mildew - Protocol # 13

Claims

CLAIMS What is claimed is:
1. A fungicidal composition comprising:
(1) at least one compound selected from the compounds of Formula I, N-oxides and agriculturally suitable salts thereof,
Figure imgf000043_0001
I wherein
E is selected from: i) 1 ,2-phenylene optionally substituted with R3 or both R3 and R4; ii) naphthalenediyl, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalenediyl optionally substituted with R3 or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with R3 or both R3 and R4;
A is O, S, Ν, ΝR5 or CR14;
G is C or Ν; provided that when G is C, then A is O, S or ΝR5 and the floating double bond is attached to G; and when G is Ν, then A is Ν or CR1 and the floating double bond is attached to A; W is O, S, ΝH, Ν(CrC6 alkyl) or NO(CrC6 alkyl);
X is H, OR1, S OjmR1, halogen, CrC6 alkyl, CrC6 haloalkyl, C3-C6 cycloalkyl, cyano, NH2, NHR1, N(CrC6 alkyljR1, NH(CrC6 alkoxy) or N(C1-C6 alkoxy)R1; R1 is CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C2-C alkylcarbonyl or C2-C4 alkoxycarbonyl; R2 is H, CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C -C6 haloalkynyl, C3-C6 cycloalkyl, C2-C alkylcarbonyl,
C -C4 alkoxycarbonyl, hydroxy, C1-C2 alkoxy or acetyloxy; R3 and R4 are each independently halogen; cyano; nitro; hydroxy; Cj-Cg alkyl; Cj-Cg haloalkyl; C2-Cg alkenyl; C2-C6 haloalkenyl; C2-Cg alkynyl; C2-C6 haloalkynyl; CrC6 alkoxy; CrC6 haloalkoxy; C2-C6 alkenyloxy; C2-Cg alkynyloxy; Cj-C6 alkylthio; Cj-Cg alkylsulfinyl;
Cj-Cg alkylsulfonyl; formyl; C2-C6 alkylcarbonyl; C2-Cg alkoxycarbonyl; NH2C(O); (CrC4 alkyl)NHC(O); (CrC4 alkyl)2NC(0); Si(R25)3; Ge(R25)3; (R 5)3Si-CΓëíC-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1 ,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2 CrC3 alkyl; R5 is H, CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl; Y is -O-, -S(O)n-, -NR15-, -C(=O)-, -CH(OR15)-, -CHR6-, -CHR6CHR6-,
-CR6=CR6-, -CΓëíC-, -CHR15O-, -OCHR15-, -CHR15S(O)n-, -S(O)nCHR15-, -CHR15O-N=C(R7)-, -(R7)C=N-OCH(R15)-, -C(R7)=N-O-, -O-N=C(R7)-,
-CHR15OC(=O)N(R15)-, -CHR15OC(=S)N(R15)-, -CHR15OC(=O)O-, -CHR150C(=S)0-, -CHR15OC(=0)S-, -CHR15OC(=S)S-, -CHR15SC(=0)N(R15)-, -CHR15SC(=S)N(R15)-, -CHR^SC^O)©-, -CHR15SC(=S)0-, -CHR15SC(=O)S-, -CHR15SC(=S)S-, -CHR15SC(=NR15)S-, -CHR15N(R15)C(=O)N(R15)-,
-CHR15O-N(Ri 5)C(=O)N(R15)-, -CHR15╬╕-N(R15)C(=S)N(R15)-, -CHR15O-N=C(R7)NR15-, -CHR15O-N=C(R7)OCH2-, -CHR15O-N=C(R7)-N=N-, -CHR15O-N=C(R7)-C(-O)-, -CHR150-N=C(R7)-C(=N-A2-Z1)-A1-, -CHR15O-N=C(R7)-C(R7)=N-A2-A -, -CHR15O-N=C(-C(R7)=N-A2-Z1)-,
-CHR15O-N-C(R7)-CH20-, -CHR15O-N=C(R7)-CH2S-, -O-CH2CH2O-N=C(R7)-, -CHR15O-C(R15)=C(R7)-, -CHR15╬╕-C(R7)=N-, -CHR15S-C(R7)=N-, -C(R7)=N-NR15-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)-, -CHR15N(COCH3)-N=C(R7)-, -OC(=S)NR15C(=0)-, -CHR6-C(=W1)-A1-, -CHR6CHR6-C(=W1)-A1-, -CR6=CR6-C(=W1)-A1-, -CΓëíC-C(=W1)-Al-, -N=CR6-C(=W1)-A1- or a direct bond; and the directionality ofthe Y linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to E and the moiety on the right side ofthe linkage is bonded to Z;
Z1 is H or -A3-Z;
W1 is O or S;
A1 is O, S, NR15 or a direct bond; A2 is O, NR15 or a direct bond;
A3 is -C(=O)-, -S(O)2- or a direct bond; each R6 is independently H, 1-2 CH3, C2-C3 alkyl, Cj-C3 alkoxy, C3-Cg cycloalkyl, formylamino, C2-C4 alkylcarbonylamino, C2-C4 alkoxycarbonylamino, NH2C(0)NH, (CrC3 alkyl)NHC(O)NH, (Cj-C3 alkyl)2NC(O)NH, N(CrC3 alkyl)2, piperidinyl, morpholinyl,
1-2 halogen, cyano or nitro; each R7 is independently H, Cj-Cg alkyl, Cj-Cg haloalkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, Cj-C6 alkylthio, Cj-Cg alkylsulfinyl, Cj-Cg alkylsulfonyl, Cj-Cg haloalkylthio, Cj-Cg haloalkylsulfinyl, Cj-Cg haloalkylsulfonyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl,
C2-Cg haloalkynyl, C3-Cg cycloalkyl, C2-C alkylcarbonyl, C2-C4 alkoxycarbonyl, halogen, cyano, nitro, hydroxy, amino, NH(Cj-C6 alkyl), N(Cj-C6 alkyl)2 or morpholinyl; each Z is independently selected from: i) Cj-C}o alkyl, C2-CJQ alkenyl and C2-CJQ alkynyl each substituted with
R9 and optionally substituted with one or more R10; ii) C3-Cg cycloalkyl, C3-C8 cycloalkenyl and phenyl each substituted with R9 and optionally substituted with one or more R10; iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to
14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10; iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and v) adamantyl substituted with R9 and optionally substituted with one or more R10; each Q is independently selected from the group -CHR13-, -NR13-, -O- and
-S(O)p-; R8 is H, 1-2 halogen, Cj-C6 alkyl, Cj-C6 haloalkyl, Cj-C6 alkoxy,
Cj-C6 haloalkoxy, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl,
Cj-Cg alkylthio, Cj-Cg haloalkylthio, Cj-Cg alkylsulfinyl, Cj-Cg alkylsulfonyl, C3-Cg cycloalkyl, C3-Cg alkenyloxy,
CO2(Cj-C6 alkyl), NH(Cj-C6 alkyl), N(Cj-C6 alkyl)2, cyano, nitro,
SiR19R20R21 or GeR19R «R21; R9 is H; 1-2 halogen; CrC6 alkyl; Cj-C6 haloalkyl; Cj-C6 alkoxy;
Cj-Cg haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-Cg alkynyl; C j -C6 alkylthio; C j -Cg haloalkylthio; C j -Cg alkylsulfinyl;
Cj-Cg alkylsulfonyl; C3-Cg cycloalkyl; C3-C6 alkenyloxy;
CO2(Cj-C6 alkyl); NH(Cj-C6 alkyl); N(Cj-C6 alkyl)2; -C(R18)=NOR17; cyano; nitro; SF5; SiR22R23R24; or GeR22R23R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R1 ^
R12, or both R1 1 and R12; each R10 is independently halogen, Cj-C4 alkyl, Cj-C haloalkyl, Cj-C4 alkoxy, nitro or cyano; or when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR15O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-, -CHR150-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)- or
-CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; J is -CH2-, -CH2CH2-, -OCH2-, -CH20-, -SCH2-, -CH2S-, -N(R16)CH2- or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2
CH3; R1 1 and R12 are each independently 1-2 halogen; Cj-C alkyl; Cj-C haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl;
C2-Cg alkoxyalkyl; C2-C6 alkylthioalkyl; C3-C6 alkoxyalkynyl;
C7-Cj0 tetrahydropyranyloxyalkynyl; benzyloxymethyl; Cj-C alkoxy;
Cj-C haloalkoxy; C3-C6 alkenyloxy; C3-Cg haloalkenyloxy;
C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-C6 alkylthioalkoxy; C]-C alkylthio;
Cj-C4 haloalkylthio; Cj-C4 alkylsulfinyl; Cj-C4 haloalkylsulfinyl;
Cj-C4 alkylsulfonyl; Cj-C4 haloalkylsulfonyl; C3-C6 alkenylthio;
C3-Cg haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R 6)2; SF5; Si(R25)3; Ge(R 5)3; (R25)3Si-CΓëíC-; OSi(R25)3; OGe(R25)3; C(=O)R 6; C(=S)R26; C(=0)OR26; C(=S)OR26; C(=O)SR26;
C(=S)SR26; C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26;
SC(=O)R26; SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26;
OC(=O)OR27; OC(=0)SR27; OC(=0)N(R26)2; SC(=0)OR27; SC(=O)SR27;
S(O)2OR26; S(O)2N(R26)2; OS(0)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, Cj-C4 alkyl,
Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; each R13 is independently H; Cj-C6 alkyl; Cj-Cg haloalkyl; or phenyl optionally substituted with halogen, Cj-C alkyl, Cj-C4 haloalkyl, Cj-C alkoxy, Cj-C4 haloalkoxy, nitro or cyano;
R14 is H, halogen, Cj-C6 alkyl, Cj-C6 haloalkyl, C2-C6 alkenyl,
C -C6 haloalkenyl, C -C6 alkynyl, C2-C6 haloalkynyl or C3-C6 cycloalkyl; each R15 is independently H; Cj-C3 alkyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C j-C alkyl, Cj-C haloalkyl, Cj-C4 alkoxy, Cj-C haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)S-; or when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)S-, -0-(CH2)s-, -S-(CH2)S- or -N(Cj-C3 alkyl)-(CH2)s-; with the directionality of said linkage defined such that the moiety depicted on the left side ofthe linkage is bonded to the carbon and the moiety on the right side ofthe linkage is bonded to the nitrogen; R16, R17 and R18 are each independently H; Cj-C3 alkyl; C3-C6 cycloalkyl; or phenyl optionally substituted with halogen, Cj-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; R19, R20, R21, R22, R23 and R24 are each independently C C6 alkyl, C2-Cg alkenyl, C j-C alkoxy or phenyl; each R25 is independently Cj-C4 alkyl, Cj-C4 haloalkyl, C2-C alkenyl,
Cj-C4 alkoxy or phenyl; each R26 is independently H; Cj-C6 alkyl; Cj-C6 haloalkyl; C2-C6 alkenyl;
C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; each R27 is independently Cj-C6 alkyl; Cj-Cg haloalkyl; C2-Cg alkenyl;
C2-C6 haloalkenyl; C2-Cg alkynyl; C2-C6 haloalkynyl; C3-Cg cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2; r is 0 or 1 ; and s is 2 or 3; and
(2) at least one compound selected from (a) compounds of Formula II, N-oxides, and agriculturally suitable salts thereof,
Figure imgf000048_0001
wherein E1 is
Figure imgf000048_0002
the directionally ofthe E1 linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to carbon and the moiety on the right side is bonded to nitrogen; and R28 is H or phenoxy; and (b) compounds that control fungal disease by inhibiting the sterol biosynthesis pathway; and optionally (3) at least one of a surfactant, a solid diluent or a liquid diluent; wherein component (1) and component (2) are present in a fungicidally effective amount and the mole ratio of component ( 1 ) to component (2) is from about 15:1 to 1 :15.
2. The fungicidal composition of Claim 1 comprising a fungicidally effective amount of (1) at least one compound selected from the compounds of Formula I, N-oxides, and agriculturally suitable salts thereof, wherein E is selected from the group 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2-, and 2,3-naphthalenediyl; lH-pyrrole-1,2-, 2,3- and 3,4-diyl; 2,3- and 3,4-furandiyl; 2,3- and 3,4-thiophenediyl; lH-pyrazole-1,5-, 3,4- and 4,5-diyl; \H- imidazole- 1,2-, 4,5- and 1,5-diyl; 3,4- and 4,5-isoxazolediyl; 4,5-oxazolediyl; 3,4- and 4,5-isothiazolediyl; 4,5-thiazolediyl; lH-l,2,3-triazole-l,5- and 4,5-diyl; 2H-l,2,3-triazole-4,5-diyl; lH-l,2,4-triazole-l,5-diyl; 4H-l,2,4-triazole-3,4-diyl; l,2,3-oxadiazole-4,5-diyl; l,2,5-oxadiazole-3,4-diyl; 1 ,2,3-thiadiazole-4,5-diyl; 1 ,2,5-thiadiazole-3,4-diyl; lH-tetrazole-1 ,5-diyl; 2,3- and 3,4-pyridinediyl; 3,4- and 4,5-pyridazinediyl; 4,5-pyrimidinediyl; 2,3-pyrazinediyl; l,2,3-triazine-4,5-diyl; l,2,4-triazine-5,6-diyl; lH-indole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 1,2-, 2,3-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; benzo[╬┤]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-diyl; lH-indazole-1,4-, 1,5-, 1,6-, 1,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; lH-benzimidazole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; l,2-benzisoxazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzoxazolediyl; l,2-benzisothiazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzothiazolediyl; 2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-,
4,7-, 4,8-, 2,3-, 3,4-, 5,6-, 6,7- and 7,8-quinolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-isoquinolinediyl; 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-cinnolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 5,6-, 6,7- and 7,8-phthalazinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and
7,8-quinazolinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 2,3-, 5,6-, 6,7- and 7,8-quinoxalinediyl; l,8,-naphthyridine-2,5-, 2,6-, 2,7-, 3,5-, 3,6-, 4,5-, 2,3- and 3,4-diyl; 2,6-, 2,7-, 4,6-, 4,7-, 6,7-pteridinediyl; pyrazolo[5,l- ]thiazole-2,6-, 2,7-, 3,6-, 3,7-, 2,3- and 6,7-diyl; thiazolo[2,3-c]-l,2,4-triazole-2,5-, 2,6-, 5,6-diyl; 2-oxo-l,3-benzodioxole-4,5- and 5,6-diyl; l,3-dioxo-lH-isoindole-2,4-, 2,5-, 4,5- and 5,6-diyl; 2-oxo-2H-l-benzopyran-3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-diyl; [l,2,4]triazolo[l,5- ]pyridine-2,5-,
2,6-, 2,7-, 2,8-, 5,6-, 6,7- and 7,8-diyl;
3,4-dihydro-2,4-dioxo-2H-l,3-benzoxazine-3,5-, 3,6-, 3,7-, 3,8-, 5,6-, 6,7- and 7,8-diyl; 2,3-dihydro-2-oxo-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl; thieno[3,2-<J|thiazole-2,5-, 2,6-, and 5,6-diyl; 5,6,7,8-tetrahydro-2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-,
4,8-, 2,3- and 3,4-quinolinediyl;
2,3-dihydro-l,l,3-trioxo-l,2-benzisothiazole-2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; l,3-benzodioxole-2,4-, 2,5-, 4,5- and 5,6-diyl; 2,3-dihydro-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl; 2,3-dihydro-l,4-benzodioxin-2,5-, 2,6-, 2,7-, 2,8-, 5,6- and 6,7-diyl; and 5,6,7,8-tetrahydro-4H-cyclohepta[6]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, and 2,3-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 and R4; W is O; R1 is Cj-C3 alkyl or Cj-C3 haloalkyl;
R2 is H, Cj-Cg alkyl, CrC6 haloalkyl or C3-C6 cycloalkyl; R3 and R4 are each independently halogen, cyano, nitro, Cj-Cg alkyl, Cj-Cg haloalkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, Cj-C6 alkylthio, Cj-Cg alkylsulfonyl, C -Cg alkylcarbonyl, C2-C6 alkoxycarbonyl, (Cj-C4 alkyl)NHC(O), (Cj-C4 alkyl)2NC(O), benzoyl or phenylsulfonyl;
Y is -O-, -S(O)n-, -NR15-, -C(=O)-, -CH(OR15)-, -CH2-, -CH2CH2-, -CH=CH-, -CΓëíC-, -CH2O-, -OCH2-, -CH2S(O)n-, -S(O)nCH2-, -CH2O-N=C(R7)-, -(R7)C=N-OCH(R15)-, -C(R7)=N-O- or a direct bond; R7 is H, Cj-Cg alkyl, CrC6 haloalkyl, Cj-C6 alkoxy, Cj-C6 alkylthio, C2-C6 alkenyl, C2-Cg alkynyl, C3-Cg cycloalkyl, halogen or cyano; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CH2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; Z is selected from the group CJ-CJQ alkyl; C3-C8 cycloalkyl; phenyl; naphthalenyl; anthracenyl; phenanthrenyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl; 1 ,2,4-thiadiazolyl; 1,2,5-thiadiazolyl;
1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; 1,2,4,5-tetrazinyl; lH-indolyl; benzofuranyl; benzo[/ ]thiophenyl; lH-indazolyl; lH-benzimidazolyl; benzoxazolyl; benzothiazolyl; quinolinyl; isoquinolinyl; cinnolinyl; phthalazinyl; quinazolinyl; quinoxalinyl;
1,8-naphthyridinyl; pteridinyl; 2,3-dihydro-lH-indenyl;
1 ,2,3 ,4-tetrahydronaphthalenyl; 6,7,8,9-tetrahydro-5H-benzocycloheptenyl;
5,6,7,8,9, 10-hexahydrobenzocyclooctenyl; 2,3-dihydro-3-oxobenzofuranyl; 1,3-dihydro-l-oxoisobenzofuranyl; 2,3-dihydro-2-oxobenzofuranyl;
3,4-dihydro-4-oxo-2H-l -benzopyranyl;
3 ,4-dihydro- 1 -oxo- 1 H-2-benzopyranyl;
3 ,4-dihydro-3 -oxo- 1 H-2-benzopyranyl ;
3 ,4-dihydro-2-oxo-2H- 1 -benzopyranyl ; 4-oxo-4H- 1 -benzopyranyl; 2-oxo-2H-l -benzopyranyl; 2,3,4, 5-tetrahydro-5-oxo-l-benzoxepinyl;
2,3,4,5-tetrahydro-2-oxo- 1 -benzoxepinyl;
2,3-dihydro-l,3-dioxo-lH-isoindolyl;
1 ,2,3,4-tetrahydro-l ,3-dioxoisoquinolinyl;
3,4-dihydro-2,4-dioxo-2H-l,3-benzoxazinyl; 2-oxo-l,3-benzodioxyl; 2,3-dihydro-l,l,3-trioxo-l,2-benzisothiazolyl; 9H-fluorenyl; azulenyl; and thiazolo[2,3-c]-l,2,4-triazolyl; each group substituted with R9 and optionally substituted with one or more R10; R15 is H, Cj-C3 alkyl or C3-C6 cycloalkyl; and
(2) at least one compound selected from the compounds of (a) Formula II, N-oxides, and agriculturally suitable salts thereof, and (b) bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenarimol, fenbuconazole, fenpropidin, fenpropimorph, fluquinconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, penconazole, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, tridemorph, triticonazole and uniconazole.
3. The fungicidal composition of Claim 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3-
(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and (2) of at least one compound selected from the group consisting of (a) 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)-2,4-oxazolidinedione and
3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one and (b) epoxiconazole, fenpropimorph, flusilazole, propiconazole and tebuconazole.
4. The fungicidal composition of Claim 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l ,2,4-triazol-3-one and (2) 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)-2,4-oxazolidinedione.
5. The fungicidal composition of Claim 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3- (trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and (2) flusilazole.
6. The fungicidal composition of Claim 2 comprising a fungicidally effective amount of (1) 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3-
(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-l,2,4-triazol-3-one and (2) both 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)-2,4-oxazolidinedione and flusilazole.
7. 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 a composition of Claim 1.
8. A method of controlling Erysiphe graminis comprising applying to the plant or portion thereof, or to the plant seed or seedling (1) at least one compound selected from the compounds of Formula I, N-oxides, and agriculturally suitable salts thereof,
Figure imgf000052_0001
I wherein
E is selected from: i) 1 ,2-phenylene optionally substituted with R3 or both R3 and R4; ii) naphthalenediyl, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalenediyl optionally substituted with R3 or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when
G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with R3 or both R3 and R4; A is O, S, N, NR5 or CR14; G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A; W is O, S, NH, N(Cj-C6 alkyl) or NO(Cj-C6 alkyl);
X is H, OR1, SCOWt1, halogen, Cj-C6 alkyl, CrC6 haloalkyl, C3-C6 cycloalkyl, cyano, NH2, NHR1 , N(C j -C6 alkyfjR1 , NH(C j -C6 alkoxy) or
N(Cj-C6 alkoxy)R1; R1 is Cj-Cg alkyl, Cj-Cg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-Cg alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl; R2 is H, Cj-Cg alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-Cg alkynyl, C -C6 haloalkynyl, C3-Cg cycloalkyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, hydroxy, Cj-C2 alkoxy or acetyloxy; R3 and R4 are each independently halogen; cyano; nitro; hydroxy; Cj-Cg alkyl; Cj-Cg haloalkyl; C2-Cg alkenyl; C2-Cg haloalkenyl; C2-C6 alkynyl; C2-Cg haloalkynyl; Cj-Cg alkoxy; Cj-Cg haloalkoxy; C2-C6 alkenyloxy;
C2-Cg alkynyloxy; Cj-Cg alkylthio; Cj-Cg alkylsulfinyl; Cj-Cg alkylsulfonyl; formyl; C2-Cg alkylcarbonyl; C2-Cg alkoxycarbonyl; NH2C(O); (Cj-C4 alkyl)NHC(O); (CrC4 alkyl)2NC(O); Si(R25)3; Ge(R 5)3; (R 5)3Si-CΓëíC-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1 ,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C -C5 haloalkylene,
C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2 Cj-C3 alkyl; R5 is H, Cj-Cg alkyl, Cj-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-Cg alkynyl, C -C6 haloalkynyl, C3-Cg cycloalkyl, C2-C alkylcarbonyl or C2-C4 alkoxycarbonyl;
Y is -0-, -S(0)n-, -NR15-, -C(=0)-, -CH(OR1 )-, -CHR6-, -CHR6CHR6-,
-CR6=CR6-, -CΓëíC-, -CHR15O-, -OCHR15-, -CHR15S(O)n-, -S(O)nCHR15-, -CHR15O-N=C(R7)-, -(R )C=N-OCH(R15)-, -C(R7)=N-O-, -O-N=C(R7)-, -CHR15OC(=O)N(R15)-, -CHR15OC(=S)N(R15)-, -CHR15OC(=O)O-, -CHR15OC(=S)O-, -CHR15OC(=O)S-, -CHR15OC(=S)S-,
-CHR15SC(=O)N(R15)-, -CHR15SC(=S)N(R15)-, -CHR15SC(=O)O-, -CHR15SC(=S)O-, -CHR15SC(=O)S-, -CHR15SC(=S)S-, -CHR15SC(=NR15)S-, -CHR15N(R15)C(=0)N(R15)-, -CHR15O-N(R] )C(=O)N(R15)-, -CHR1 O-N(R! )C(=S)N(Ri 5)-, -CHR15O-N=C(R7)NR15-, -CHR150-N=C(R7)OCH2-,
-CHR15O-N=C(R7)-N=N-, -CHR15O-N=C(R7)-C(=O)-, -CHR1 O-N=C(R7)-C(=N-A2-Z1)-A1-,
-CHR15O-N=C(R7)-C(R7)=N-A2-A3-, -CHR15O-N=C(-C(R7)=N-A2-Z1)-, -CHR1 0-N=C(R7)-CH2O-, -CHR15O-N=C(R7)-CH2S-, -O-CH2CH20-N=C(R7)-, -CHR150-C(R15)=C(R7)-, -CHR15O-C(R7)=N-,
-CHR15S-C(R7)=N-, -C(R7)=N-NR15-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)-, -CHR15N(COCH3)-N=C(R7)-, -OC(=S)NR15C(=O)-, -CHR6-C(=W1)-A1-, -CHR6CHR6-C(=W1)-A1-, -CR6=CR6-C(=W1)-A1-, -CΓëíC-C(=W1)-A1-, -N=CR6-C(=W1)-A1- or a direct bond; and the directionality ofthe Y linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to E and the moiety on the right side ofthe linkage is bonded to Z; Z1 is H or -A3-Z; W1 is O or S; A1 is O, S, NR15 or a direct bond;
A2 is O, NR15 or a direct bond; A3 is -C(=O)-, -S(0)2- or a direct bond; each R6 is independently H, 1-2 CH3, C2-C3 alkyl, Cj-C3 alkoxy, C3-C6 cycloalkyl, formylamino, C2-C4 alkylcarbonylamino, C2-C4 alkoxycarbonylamino, NH2C(O)NH, (CrC3 alkyl)NHC(O)NH, (Cj-C3 alkyl)2NC(O)NH, N(CrC3 alkyl)2, piperidinyl, morpholinyl, 1-2 halogen, cyano or nitro; each R7 is independently H, Cj-C6 alkyl, Cj-C6 haloalkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, Cj-Cg alkylthio, Cj-C6 alkylsulfinyl, Cj-Cg alkylsulfonyl, Cj-C6 haloalkylthio, Cj-C6 haloalkylsulfinyl, Cj-Cg haloalkylsulfonyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C2-C alkylcarbonyl,
C2-C4 alkoxycarbonyl, halogen, cyano, nitro, hydroxy, amino, NH(Cj-C6 alkyl), N(Cj-C6 alkyl)2 or morpholinyl; each Z is independently selected from: i) Cj-C]o alkyl, C2-Cj0 alkenyl and C2-C10 alkynyl each substituted with R9 and optionally substituted with one or more R10; ii) C3-Cg cycloalkyl, C3-Cg cycloalkenyl and phenyl each substituted with R9 and optionally substituted with one or more R10; iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to 14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10; iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and v) adamantyl substituted with R9 and optionally substituted with one or more R10; each Q is independently selected from the group -CHR13-, -NR13-, -O- and -S(O)p-; R8 is H, 1-2 halogen, CrC6 alkyl, CrC6 haloalkyl, Cj-C6 alkoxy,
Cj-Cg haloalkoxy, C2-C6 alkenyl, C -C6 haloalkenyl, C2-C6 alkynyl,
Cj-Cg alkylthio, CrC6 haloalkylthio, Cj-C6 alkylsulfinyl,
Cj-Cg alkylsulfonyl, C3-Cg cycloalkyl, C3-C6 alkenyloxy, CO2(Cj-C6 alkyl), NH(Cj-C6 alkyl), N(CrC6 alkyl)2, cyano, nitro,
SiR19R20R21 or GeR19R20R21;
R9 is H; 1-2 halogen; CrC6 alkyl; Cj-C6 haloalkyl; CrC6 alkoxy;
Cj-Cg haloalkoxy; C -Cg alkenyl; C2-C6 haloalkenyl; C -C6 alkynyl;
Cj-C6 alkylthio; Cj-Cg haloalkylthio; Cj-Cg alkylsulfinyl; Cj-Cg alkylsulfonyl; C3-Cg cycloalkyl; C3-C6 alkenyloxy;
CO2(Cj-C6 alkyl); NH(Cj-C6 alkyl); N(Cj-C6 alkyl)2; -C(R18)=NOR17; cyano; nitro; SF5; SiR22R23R24; or GeR R23R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R1 *, R12, or both R11 and R12; each R10 is independently halogen, Cj-C alkyl, Cj-C4 haloalkyl, Cj-C alkoxy, nitro or cyano; or when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR1 O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-,
-CHR1 O-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR1 N(R15)-N=C(R7)- or -CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; J is -CH2-, -CH2CH2-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -N(R16)CH2- or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2
CH3; R1 ΓÇó and R12 are each independently 1-2 halogen; Cj-C4 alkyl; Cj-C4 haloalkyl;
C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C -C6 haloalkynyl;
C2-C6 alkoxyalkyl; C2-Cg alkylthioalkyl; C3-C6 alkoxyalkynyl;
C7-CJO tetrahydropyranyloxyalkynyl; benzyloxymethyl; Cj-C alkoxy;
Cj-C4 haloalkoxy; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy;
C5-C9 trialkylsilylalkoxyalkoxy; C2-C6 alkylthioalkoxy; Cj-C4 alkylthio;
Cj-C4 haloalkylthio; Cj-C alkylsulfinyl; Cj-C4 haloalkylsulfinyl;
Cj-C alkylsulfonyl; Cj-C4 haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C -Cg alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R26)2; SF5; Si(R2 )3; Ge(R25)3; (R )3Si-CΓëíC-; OSi(R25)3; OGe(R 5)3; C(=O)R 6; C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR 6; C(=S)SR26; C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R 6; SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26;
OC(=O)OR27; OC(=O)SR27; OC(=O)N(R 6)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26; S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C j-C4 alkyl, Cj-C haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; each R13 is independently H; Cj-Cg alkyl; Cj-Cg haloalkyl; or phenyl optionally substituted with halogen, Cj-C alkyl, C j-C haloalkyl, C j-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; R14 is H, halogen, CrC6 alkyl, Cj-C6 haloalkyl, C2-C6 alkenyl, C2-Cg haloalkenyl, C -C6 alkynyl, C2-C6 haloalkynyl or C3-Cg cycloalkyl; each R15 is independently H; Cj-C3 alkyl; C3-Cg cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)S-; or when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)S-, -O-(CH2)s-, -S-(CH2)S- or -N(Cj-C3 alkyl)-(CH2)s-; with the directionality of said linkage defined such that the moiety depicted on the left side ofthe linkage is bonded to the carbon and the moiety on the right side ofthe linkage is bonded to the nitrogen; R16, R17 and R18 are each independently H; Cj-C3 alkyl; C3-Cg cycloalkyl; or phenyl optionally substituted with halogen, C j-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; R19, R2┬░, R21 , R22, R23 and R24 are each independently C j -C6 alkyl,
C2-Cg alkenyl, C j-C4 alkoxy or phenyl; each R25 is independently Cj-C4 alkyl, Cj-C haloalkyl, C2-C4 alkenyl,
C j-C4 alkoxy or phenyl; each R26 is independently H; Cj-Cg alkyl; Cj-Cg haloalkyl; C2-C6 alkenyl; C2-Cg haloalkenyl; C2-Cg alkynyl; C2-Cg haloalkynyl; C -Cg cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C alkyl, Cj-C4 haloalkyl, Cj-C alkoxy, Cj-C4 haloalkoxy, nitro or cyano; each R27 is independently Cj-C6 alkyl; Cj-Cg haloalkyl; C2-Cg alkenyl;
C2-Cg haloalkenyl; C2-Cg alkynyl; C -Cg haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2; r is 0 or 1 ; and s is 2 or 3; and
(2) at least one compound selected from compounds of Formula II, N-oxides, and agriculturally suitable salts thereof,
Figure imgf000058_0001
wherein EMs
Figure imgf000058_0002
the directionally ofthe E1 linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to carbon and the moiety on the right side is bonded to nitrogen; and R28 is H or phenoxy; wherein component (1) and component (2) are added in amounts sufficient to provide a fungicidal effectiveness greater than the sum ofthe fungicidal effectivenesses ofthe amounts of said components taken independently.
9. A method of Claim 8 wherein component (1) is 2,4-dihydro-5-methoxy-2- methyl-4-[2-[[[[l-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H- l,2,4-triazol-3-one and component (2) is selected from the group consisting of 5-methyl-5-(4-phenoxyphenyl)-3-(phenyl-amino)-2,4-oxazolidinedione and
3,5-dihydro 5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4N-imidazol-4-one; and wherein the mole ratio of component (1) to component (2) is from 15:1 to 1 :15.
10. A method for the preventative control of Septoria nodorum comprising applying to the plant or portion thereof, or to the plant seed or seedling (1) at least one compound selected from the compounds of Formula I, N-oxides, and agriculturally suitable salts thereof,
E/Y Z I
A — Ν
I wherein
E is selected from: i) 1 ,2-phenylene optionally substituted with R3 or both R3 and R4; ii) naphthalenediyl, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalenediyl optionally substituted with R3 or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with R3 or both R3 and R4; A is O, S, Ν, ΝR5 or CR14;
G is C or Ν; provided that when G is C, then A is O, S or ΝR5 and the floating double bond is attached to G; and when G is Ν, then A is Ν or CR14 and the floating double bond is attached to A; W is O, S, ΝH, Ν(C j-Cg alkyl) or NO(Cj-C6 alkyl);
X is H, OR1, SCOJmR1, halogen, CrC6 alkyl, CrC6 haloalkyl, C3-C6 cycloalkyl, cyano, NH2, NHR1, N(CrC6 alkyfR1, NH(Cj-C6 alkoxy) or N(Cj-C6 alkoxy)R1; R1 is Cj-Cg alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-C6 alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, C2-C alkylcarbonyl or C2-C alkoxycarbonyl; R2 is H, Cj-Cg alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C -C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C2-C alkylcarbonyl,
C2-C4 alkoxycarbonyl, hydroxy, Cj-C2 alkoxy or acetyloxy; R3 and R4 are each independently halogen; cyano; nitro; hydroxy; Cj-Cg alkyl; Cj-Cg haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; Cj-Cg alkoxy; Cj-Cg haloalkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; Cj-Cg alkylthio; Cj-Cg alkylsulfinyl;
Cj-Cg alkylsulfonyl; formyl; C2-Cg alkylcarbonyl; C2-C6 alkoxycarbonyl; NH2C(O); (Cj-C4 alkyl)NHC(O); (CrC4 alkyl)2NC(0); Si(R2 )3; Ge(R25)3; (R25)3Si-CΓëíC-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1 ,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2 Cj-C3 alkyl; R5 is H, Cj-Cg alkyl, Cj-Cg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl,
C2-Cg alkynyl, C2-Cg haloalkynyl, C3-Cg cycloalkyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl; Y is -O-, -S(O)n-, -NR15-, -C(=O)-, -CH(OR15)-, -CHR6-, -CHR6CHR6-,
-CR6=CR6-, -OC-, -CHR150-, -OCHR15-, -CHR15S(O)n-, -S(O)nCHR15-, -CHR15O-N=C(R7)-, -(R7)C=N-OCH(R15)-, -C(R7)=N-0-, -O-N=C(R7)-,
-CHR15OC(=O)N(R15)-, -CHR15OC(=S)N(R15)-, -CHR15OC(=O)O-, -CHR15OC(=S)O-, -CHR15OC(=O)S-, -CHR15OC(=S)S-, -CHR15SC(=O)N(R15)-, -CHR15SC(=S)N(R15)-, -CHR15SC(=O)O-, -CHR15SC(=S)O-, -CHR15SC(=O)S-, -CHR15SC(=S)S-, -CHR15SC(=NR15)S-, -CHR15N(R15)C(=O)N(R15)-,
-CHR15O-N(R! 5)C(=O)N(R! 5)-, -CHR15O-N(R] 5)C(=S)N(Ri 5)-, -CHR15O-N=C(R7)NR15-, -CHR15O-N=C(R7)OCH2-, -CHR15O-N=C(R7)-N=N-, -CHR150-N=C(R7)-C(=O)-, -CHR15O-N=C(R7)-C(=N-A2-Z1)-A1-, -CHR15O-N=C(R7)-C(R7)=N-A2-A3-, -CHR15O-N=C(-C(R7)=N-A2-Z1)-,
-CHR15O-N=C(R7)-CH2O-, -CHR15O-N=C(R7)-CH2S-, -O-CH2CH2O-N=C(R7)-, -CHR15O-C(R15)=C(R7)-, -CHR15O-C(R7)=N-, -CHR15S-C(R7)=N-, -C(R7)=N-NR15-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)-, -CHR15N(COCH3)-N=C(R7)-, -OC(=S)NR15C(=O)-, -CHR -C(=W1)-A1-, -CHR6CHR6-C(=W1)-Al-, -CR6=CR6-C(=W1)-A1-, -CΓëíC-C(=W1)-A1-, -N=CR6-C(=W1)-A1- or a direct bond; and the directionality ofthe Y linkage is defined such that the moiety depicted on the left side ofthe linkage is bonded to E and the moiety on the right side ofthe linkage is bonded to Z;
Z1 is H or -A3-Z;
W1 is O or S;
A1 is O, S, NR15 or a direct bond; A2 is O, NR15 or a direct bond;
A3 is -C(=O)-, -S(O)2- or a direct bond; each R6 is independently H, 1-2 CH3, C2-C3 alkyl, Cj-C3 alkoxy, C3-Cg cycloalkyl, formylamino, C2-C4 alkylcarbonylamino, C2-C4 alkoxycarbonylamino, NH2C(O)NH, (Cj-C3 alkyl)NHC(O)NH, (C j -C3 alkyl)2NC(O)NH, N(C j -C3 alky 1)2, piperidiny 1, morpholinyl,
1-2 halogen, cyano or nitro; each R7 is independently H, Cj-Cg alkyl, Cj-Cg haloalkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, Cj-Cg alkylthio, Cj-Cg alkylsulfinyl, Cj-Cg alkylsulfonyl, Cj-Cg haloalkylthio, Cj-Cg haloalkylsulfinyl, Cj-Cg haloalkylsulfonyl, C2-C6 alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl,
C2-Cg haloalkynyl, C3-Cg cycloalkyl, C2-C alkylcarbonyl, C2-C4 alkoxycarbonyl, halogen, cyano, nitro, hydroxy, amino, NH(Cj-C6 alkyl), N(CrC6 alkyl)2 or morpholinyl; each Z is independently selected from: i) Cj-Cjo alkyl, C2-Cj0 alkenyl and C2-Cj0 alkynyl each substituted with
R9 and optionally substituted with one or more R10; ii) C3-Cg cycloalkyl, C3-Cg cycloalkenyl and phenyl each substituted with R9 and optionally substituted with one or more R10; iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to
14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10; iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and v) adamantyl substituted with R9 and optionally substituted with one or more R10; each Q is independently selected from the group -CHR13-, -NR13-, -O- and
-S(O)p-; R8 is H, 1-2 halogen, Cj-C6 alkyl, CrC6 haloalkyl, Cj-C6 alkoxy,
Cj-Cg haloalkoxy, C2-Cg alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl,
Cj-Cg alkylthio, Cj-Cg haloalkylthio, Cj-Cg alkylsulfinyl, Cj-Cg alkylsulfonyl, C3-Cg cycloalkyl, C3-Cg alkenyloxy,
CO2(Cj-C6 alkyl), NH(Cj-C6 alkyl), N(CrC6 alkyl)2, cyano, nitro,
SiR19R20R21 or GeR R20R21; R9 is H; 1-2 halogen; Cj-Cg alkyl; Cj-Cg haloalkyl; Cj-Cg alkoxy;
Cj-Cg haloalkoxy; C2-C6 alkenyl; C2-Cg haloalkenyl; C2-C6 alkynyl; Cj-Cg alkylthio; Cj-Cg haloalkylthio; Cj-C6 alkylsulfinyl;
Cj-Cg alkylsulfonyl; C3-Cg cycloalkyl; C3-Cg alkenyloxy;
CO2(Cj-C6 alkyl); NH(Cj-C6 alkyl); N(Cj-C6 alkyl)2; -C(R18)=NOR17; cyano; nitro; SF5; SiR22R23R24; or GeR2 R23R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R1 ] ,
R12, or both R1 1 and R12; each R10 is independently halogen, Cj-C alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, nitro or cyano; or when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR15O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-, -CHR15O-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)- or
-CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; J is -CH2-, -CH2CH2-, -OCH2-, -CH20-, -SCH2-, -CH2S-, -N(R16)CH2- or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2
CH3; R11 and R12 are each independently 1-2 halogen; Cj-C4 alkyl; Cj-C4 haloalkyl; C2-C6 alkenyl; C -C6 haloalkenyl; C2-C6 alkynyl; C -C6 haloalkynyl;
C2-C6 alkoxyalkyl; C2-Cg alkylthioalkyl; C3-C6 alkoxyalkynyl;
C7-Cjo tetrahydropyranyloxyalkynyl; benzyloxymethyl; Cj-C alkoxy;
Cj-C4 haloalkoxy; C3-Cg alkenyloxy; C3-Cg haloalkenyloxy;
C3-C6 alkynyloxy; C3-Cg haloalkynyloxy; C2-Cg alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-C6 alkylthioalkoxy; Cj-C alkylthio;
Cj-C4 haloalkylthio; Cj-C4 alkylsulfinyl; Cj-C4 haloalkylsulfinyl;
Cj-C4 alkylsulfonyl; Cj-C4 haloalkylsulfonyl; C3-Cg alkenylthio;
C3-C6 haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R26)2; SF5; Si(R25)3; Ge(R 5)3; (R25)3Si-CΓëíC-; OSi(R25)3; OGe(R25)3; C(=O)R26; C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR26;
C(=S)SR26; C(=O)N(R )2; C(=S)N(R 6)2; OC(=O)R26; OC(=S)R26;
SC(=O)R26; SC(=S)R26; N(R 6)C(=O)R26; N(R 6)C(=S)R26;
OC(=O)OR27; OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27;
S(O)2OR26; S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, Cj-C alkyl,
Cj-C haloalkyl, Cj-C4 alkoxy, Cj-C haloalkoxy, nitro or cyano; each R13 is independently H; Cj-Cg alkyl; Cj-Cg haloalkyl; or phenyl optionally substituted with halogen, Cj-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C haloalkoxy, nitro or cyano;
R14 is H, halogen, Cj-Cg alkyl, Cj-C6 haloalkyl, C2-C6 alkenyl,
C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl or C3-Cg cycloalkyl; each R15 is independently H; Cj-C3 alkyl; C3-Cg cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)S-; or when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)S-, -O-(CH2)s-, -S-(CH2)S- or -N(C j-C3 alkyl)-(CH2)s-; with the directionality of said linkage defined such that the moiety depicted on the left side ofthe linkage is bonded to the carbon and the moiety on the right side ofthe linkage is bonded to the nitrogen; R16, R17 and R18 are each independently H; Cj-C3 alkyl; C3-Cg cycloalkyl; or phenyl optionally substituted with halogen, Cj-C4 alkyl, C j-C haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; R19, R20, R21, R22? R23 and R24 are each independently CrC6 alkyl, C2-Cg alkenyl, Cj-C4 alkoxy or phenyl; each R25 is independently Cj-C4 alkyl, C j-C4 haloalkyl, C2-C4 alkenyl,
Cj-C alkoxy or phenyl; each R26 is independently H; Cj-C6 alkyl; Cj-Cg haloalkyl; C2-Cg alkenyl;
C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, CrC haloalkoxy, nitro or cyano; each R27 is independently Cj-Cg alkyl; Cj-Cg haloalkyl; C -Cg alkenyl;
C2-Cg haloalkenyl; C2-Cg alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C4 alkyl, Cj-C haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2; r is 0 or 1 ; and s is 2 or 3; and
(2) at least one compound selected from compounds that control fungal disease by inhibiting the sterol biosynthesis pathway; wherein component (1) and component (2) are added in amounts sufficient to provide a fungicidal effectiveness greater than the sum ofthe fungicidal effectivenesses ofthe amounts of said components taken independently.
11. A method of Claim 10 wherein component (1) is 2,4-dihydro-5-methoxy-2- methyl-4-[2-[[[[l-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H- l,2,4-triazol-3-one and component (2) is selected from the group consisting of epoxiconazole, fenpropimorph, flusilazole, propiconazole and tebuconazole; and wherein the mole ratio of component ( 1 ) to component (2) is from 15 : 1 to 1 : 15.
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