Fungicidal pyrazole mixtures

Abstract

Disclosed is a fungicidal composition comprising (a) at least one compound selected from the compounds of Formula 1, N-oxides, and salts thereof, wherein R 1 is F, Cl or Br; R 2 is H or F; and R 3 is Cl or Br; and (b) at least one fungicidal compound selected from (b1) through (b13) as disclosed herein. Also disclosed is a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Formula 1, an N-oxide, or salt thereof (e.g., as a component in the aforesaid composition). Also disclosed are process intermediate compounds useful for preparing compounds of Formula 1.

What is claimed is: 
     
         1 . A fungicidal composition comprising:
 (a) at least one compound selected from the compounds of Formula 1, N-oxides, and salts thereof:   
       
         
           
           
               
               
           
         
         wherein
 R 1  is F, Cl or Br; 
 R 2  is H or F; and 
 R 3  is Cl or Br; and 
 
         (b) at least one fungicidal compound selected from 
         (b1) 
       
       
         
           
           
               
               
           
         
         
           wherein R b20  and R b21  are independently CH 3 , CF 2 H or CF 3 ; each R b22  is independently halogen or cyano; n is 0, 1, 2 or 3; and L is a direct bond or —CH 2 O— wherein the left bond is connected to the dihydroisoxazole ring and the right bond is connected to the phenyl ring; 
         
         (b2) 
       
       
         
           
           
               
               
           
         
         
           wherein R b1  is 
         
       
       
         
           
           
               
               
           
         
         
           wherein R b2  is —CH 2 OC(O)CH(CH 3 ) 2 , —C(O)CH 3 , —CH 2 OC(O)CH 3 , —C(O)OCH 2 CH(CH 3 ) 2  or 
         
       
       
         
           
           
               
               
           
         
         
           wherein R b3  is CH 3  or F; 
         
       
       
         
           
           
               
               
           
         
         
           wherein R b4  is —(CH 2 ) 4 CH 3 , —C(CH 3 ) 3  or —(CH 2 ) 2 C≡CH; 
         
       
       
         
           
           
               
               
           
         
         
           wherein R b5  is H or F, and R b6  is —CF 2 CHFCF 3  or —CF 2 CF 2 H; 
         
       
       
         
           
           
               
               
           
         
         
           wherein 
           R b7  is 
         
       
       
         
           
           
               
               
           
         
         
           R b8  is H, halogen or C 1 -C 2  alkyl; 
           R b9  is C 1 -C 8  alkyl, C 1 -C 8  haloalkyl or C 2 -C 8  alkoxyalkyl; 
           R b10  is halogen, C 1 -C 2  alkyl or C 1 -C 2  haloalkyl; 
           R b11  is halogen, C 1 -C 2  alkyl or C 1 -C 2  haloalkyl; 
           R b12  is C 1 -C 2  alkyl; 
           R b13  is H, halogen or C 1 -C 2  alkyl; 
           R b14  is C 1 -C 2  alkyl or C 1 -C 2  haloalkyl; 
           R b15  is H, C 1 -C 2  alkyl or C 1 -C 2  haloalkyl; 
           W is CH or N; 
           Y is CH or N; and 
           Z is CH or N; 
         
       
       
         
           
           
               
               
           
         
         and salts thereof. 
       
     
     
         2 . The composition of  claim 1  wherein component (a) comprises a compound of Formula 1 or salt thereof. 
     
     
         3 . The composition of  claim 1  wherein component (a) comprises a compound selected from the group consisting of
 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluoromethyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 
 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, and 
 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine. 
 
     
     
         4 . The composition of  claim 1  further comprising (c) at least one additional compound or agent that is biologically active. 
     
     
         5 . The composition of  claim 4  wherein component (c) comprises at least one fungicidal compound selected from the group consisting of:
 (c1) methyl benzimidazole carbamate fungicides; 
 (c2) dicarboximide fungicides; 
 (c3) demethylation inhibitor fungicides; 
 (c4) phenylamide fungicides; 
 (c5) amine/morpholine fungicides; 
 (c6) phospholipid biosynthesis inhibitor fungicides; 
 (c7) carboxamide fungicides; 
 (c8) hydroxy(2-amino-)pyrimidine fungicides; 
 (c9) anilinopyrimidine fungicides; 
 (c10) N-phenyl carbamate fungicides; 
 (c1) quinone outside inhibitor fungicides; 
 (c12) phenylpyrrole fungicides; 
 (c13) quinoline fungicides; 
 (c14) lipid peroxidation inhibitor fungicides; 
 (c15) melanin biosynthesis inhibitors-reductase fungicides; 
 (c16) melanin biosynthesis inhibitors-dehydratase fungicides; 
 (c17) hydroxyanilide fungicides; 
 (c18) squalene-epoxidase inhibitor fungicides; 
 (c19) polyoxin fungicides; 
 (c20) phenylurea fungicides; 
 (c21) quinone inside inhibitor fungicides; 
 (c22) benzamide fungicides; 
 (c23) enopyranuronic acid antibiotic fungicides; 
 (c24) hexopyranosyl antibiotic fungicides; 
 (c25) glucopyranosyl antibiotic: protein synthesis fungicides; 
 (c26) glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides; 
 (c27) cyanoacetamideoxime fungicides; 
 (c28) carbamate fungicides; 
 (c29) oxidative phosphorylation uncoupling fungicides; 
 (c30) organo tin fungicides; 
 (c31) carboxylic acid fungicides; 
 (c32) heteroaromatic fungicides; 
 (c33) phosphonate fungicides; 
 (c34) phthalamic acid fungicides; 
 (c35) benzotriazine fungicides; 
 (c36) benzene-sulfonamide fungicides; 
 (c37) pyridazinone fungicides; 
 (c38) thiophene-carboxamide fungicides; 
 (c39) pyrimidinamide fungicides; 
 (c40) carboxylic acid amide fungicides; 
 (c41) tetracycline antibiotic fungicides; 
 (c42) thiocarbamate fungicides; 
 (c43) benzamide fungicides; 
 (c44) host plant defense induction fungicides; 
 (c45) multi-site contact activity fungicides; 
 (c46) fungicidal compounds other than fungicidal compounds of component (a) and components (c1) through (c45); and salts of compounds of (c1) through (c46). 
 
     
     
         6 . The composition of  claim 4  wherein component (c) includes at least one compound selected from acibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl-M, benodanil, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper salts, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, dithianon, dodemorph, dodine, edifenphos, enestroburin, epoxiconazole, etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazol, guazatine, imazalil, imibenconazole, iminoctadine, iodocarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, metiram, metominostrobin, mepanipyrim, metrafenone, myclobutanil, naftifine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, penflufen, penthiopyrad, pefurazoate, phosphorous acid and salts thereof, phthalide, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyrrolnitrin, quinconazole, quinomethionate, quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triarimol, triazoxide, tricyclazole, tridemorph, triflumizole, tricyclazole, trifloxystrobin, triforine, trimorphamide, triticonazole, uniconazole, validamycin, valifenalate, vinclozolin, zineb, ziram, zoxamide, N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, 5-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-1-yl)[1,2,4]triazolo[1,5-a]-pyrimidine (BAS600), N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxy-phenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, N-[2-[4-[[3-(4-chloro-phenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]-butanamide, 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine, 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]-sulfonyl]methyl]propyl]carbamate, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide, α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide, N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide, 2-[[[[3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzene-acetamide, 1-[(2-propenylthio)carbonyl]-2-(1-methylethyl)-4-(2-methylphenyl)-5-amino-1H-pyrazol-3-one, ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, pentyl N-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate, pentyl N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]-carbamate, 2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide, 2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide, N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide and N′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide. 
     
     
         7 . A composition comprising the composition of  claim 1  and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. 
     
     
         8 . A method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of the composition of  claim 1  to the plant or plant seed. 
     
     
         9 . (canceled) 
     
     
         10 . A compound of Formula 17, 
       
         
           
           
               
               
           
         
         wherein
 R 1  is F, Cl or Br; 
 R 2  is H or F; 
 R 3  is Cl or Br; and 
 R 32  is H, CH 3 , CH 2 CH 3  or (CH 2 ) 2 CH 3 ; 
 
         provided that when R 1  is H, or when R 1  and R 2  are each F, then R 32  is H. 
       
     
     
         11 . (canceled) 
     
     
         12 . A compound of Formula 22, 
       
         
           
           
               
               
           
         
         wherein
 R 1  is F, Cl or Br; 
 R 2  is H or F; 
 R 3  is Cl or Br; and 
 M is Na or K.