FUNGICIDAL COMPOSITIONS

Abstract

A fungicidal composition comprising a mixture of components (A) and (B), wherein components (A) and (B) are as defined in claim 1, and use of the compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Claims

1. A fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I): ##STR00086## wherein R.sup.1=hydrogen or fluoro; R.sup.2=hydrogen or methyl; and Z=Z.sup.1, Z.sup.2 or Z.sup.3; wherein Z.sup.1 is ##STR00087## wherein Z.sup.1 is optionally substituted by 1 group selected from cyano, trifluoromethyl, dimethylamino or ethylthio; Z.sup.2 is ##STR00088## wherein Z.sup.2 is optionally substituted by 1 group selected from C(O)OR.sup.3, wherein R.sup.3 is selected from methyl, ethyl or n-propyl; C(O)NR.sup.4(R.sup.5), wherein R.sup.4 is selected from hydrogen, methyl, ethyl and R.sup.5 is selected from hydrogen, methyl, ethyl, methoxy or cyclopropyl; or C(H)NOCH.sub.3; and Z.sup.3 is ##STR00089## or a salt, enantiomer, tautomer or N-oxide thereof, and component (B) is a compound selected from the group consisting of: benzovindiflupyr, fluxapyroxad, pydiflumetofen, isopyrazam, fluopyram, penthiopyrad, sedaxane, bixafen, difenoconazole, cyproconazole, tebuconazole, hexaconazole, prothioconazole, propiconazole, epoxiconazole, flutriafol, mefentrifluconazole, ipconazole, paclobutrazol, azoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, metalaxyl-M, fenpropidin, fenpropimorph, cyprodinil, spiroxamine, mancozeb, chlorothalonil, oxathiapiprolin, mandipropamid, fluazinam, fludioxinil, fosetyl-aluminium, acibenzolar-S-methyl, procymidone, carbendazim, fenhexamid, prochloraz, prohexadione-calcium, Timorex Gold (plant extract comprising tea tree oil), N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine), N-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine, N-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, calcium phosphonate, cis-jasmone, trinexapac-ethyl, glyphosate, 2,4-D (2,4-dichlorophenoxyacetic acid) and thiamethoxam.

2. A fungicidal composition according claim 1, wherein component (A) is a compound selected from: 5-(trifluoromethyl)-3-[4-[[3-(trifluoromethyl)-1,2,4-triazol-1-yl]methyl]phenyl]-1,2,4-oxadiazole (compound X.01), 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazole-3-carbonitrile (compound X.02), ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (compound X.03), N-cyclopropyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.04), N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.05), N-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.06), N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (compound X.07), 3-[4-[(5-ethylsulfanyl-1,2,4-triazol-1-yl)methyl]phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (compound X.08), 3-[4-(triazolo[4,5-b]pyridin-1-ylmethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (compound X.09), 3-[4-(triazolo[4,5-b]pyridin-2-ylmethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (compound X.10), 3-[4-(triazolo[4,5-b]pyridin-3-ylmethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (compound X.11), methyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (compound X.12), ethyl 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (compound X.13), N,N-diethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.14), N-methoxy-N-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.15), propyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (compound X.16), N-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.17), N-ethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.18), 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.19), N-methoxy-1-[1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]methanimine (compound X.20), ethyl 1-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]pheny f lethyl]pyrazole-4-carboxylate (compound X.21); or a salt, enantiomer, tautomer or N-oxide thereof.

3. A fungicidal composition according to claim 1, wherein component (A) is: ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (compound X.03), N-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.06), N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (compound X.07), N-methoxy-N-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.15), propyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (compound X.16), N-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (compound X.17), or a salt, enantiomer, tautomer or N-oxide thereof.

4. A fungicidal composition according to claim 1, wherein component (B) is a compound selected from the group consisting of benzovindiflupyr, fluxapyroxad, pydiflumetofen, isopyrazam, fluopyram, penthiopyrad, difenoconazole, cyproconazole, tebuconazole, hexaconazole, prothioconazole, mefentrifluconazole, azoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, fenpropidin, fenpropimorph, mancozeb, chlorothalonil or N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine.

5. A fungicidal composition according to claim 1, wherein component (B) is a compound selected from the group consisting of benzovindiflupyr, pydiflumetofen, difenoconazole, cyproconazole, hexaconazole, prothioconazole, azoxystrobin, fenpropidin, or N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine.

6. A fungicidal composition according to claim 1, wherein the weight ratio of component (A) to component (B) is from 100:1 to 1:100.

7. A fungicidal composition according to claim 1, wherein the weight ratio of component (A) to component (B) is from 20:1 to 1:40.

8. A fungicidal composition according to claim 1, wherein the weight ratio of component (A) to component (B) is from 12:1 to 1:25.

9. A fungicidal composition according to claim 1, wherein the weight ratio of component (A) to component (B) is from 5:1 and 1:15.

10. A fungicidal composition according to claim 1, wherein the weight ratio of component (A) to component (B) is from 2:1 to 1:5.

11. A fungicidal composition according to 1, wherein the composition comprises one or more further pesticides selected from the group consisting of: a fungicide, selected from etridiazole, fluazinam, benzovindiflupyr, pydiflumetofen, benalaxyl, benalaxyl-M (kiralaxyl), furalaxyl, metalaxyl, metalaxyl-M (mefenoxam), dodicin, N-(2,5-Dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N-[4-(4,5-Dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, N-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, ethirimol, 3-chloro-2-methoxy-N-[(3RS)-tetrahydro-2-oxofuran-3-yl]acet-2,6-xylidide (clozylacon), cyprodinil, mepanipyrim, pyrimethanil, dithianon, aureofungin, blasticidin-S, biphenyl, chloroneb, dicloran, hexachlorobenzene, quintozene, tecnazene, (TCNB), tolclofos-methyl, metrafenone, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, fluopicolide (flupicolide), tioxymid, flusulfamide, benomyl, carbendazim, carbendazim chlorhydrate, chlorfenazole, fuberidazole, thiabendazole, thiophanate-methyl, benthiavalicarb, chlobenthiazone, probenazole, acibenzolar, bethoxazin, pyriofenone (IKF-309), acibenzolar-S-methyl, pyribencarb (KIF-7767), butylamine, 3-iodo-2-propinyl n-butylcarbamate (IPBC), iodocarb (isopropanyl butylcarbamate), isopropanyl butylcarbamate (iodocarb), picarbutrazox, polycarbamate, propamocarb, tolprocarb, 3-(difluoromethyl)-N-(7-fluoro-1,1,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide diclocymet, N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1-methyl-pyrazole-4-carboxamide carpropamid, chlorothalonil, flumorph, oxine-copper, cymoxanil, phenamacril, cyazofamid, flutianil, thicyofen, chlozolinate, iprodione, procymidone, vinclozolin, bupirimate, dinocton, dinopenton, dinobuton, dinocap, meptyldinocap, diphenylamine, phosdiphen, 2,6-dimethyl-[1,4]dithiino[2,3-c:5,6-c]dipyrrole-1,3,5,7(2H,6H)-tetraone, azithiram, etem, ferbam, mancozeb, maneb, metam, metiram (polyram), metiram-zinc, nabam, propineb, thiram, vapam (metam sodium), zineb, ziram, dithioether, isoprothiolane, ethaboxam, fosetyl, fosetyl-aluminium (fosetyl-al), methyl bromide, methyl iodide, methyl isothiocyanate, cyclafuramid, fenfuram, validamycin, streptomycin, (2RS)-2-bromo-2-(bromomethyl)glutaronitrile (bromothalonil), dodine, doguadine, guazatine, iminoctadine, iminoctadine triacetate, 2,4-D, 2,4-DB, kasugamycin, dimethirimol, fenhexamid, hymexazole, hydroxyisoxazole imazalil, imazalil sulphate, oxpoconazole, pefurazoate, prochloraz, triflumizole, fenamidone, Bordeaux mixture, calcium polysulfide, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, cuprous oxide, sulphur, carbaryl, phthalide (fthalide), dingjunezuo (Jun Si Qi), oxathiapiprolin, fluoroimide, mandipropamid, KSF-1002, benzamorf, dimethomorph, fenpropimorph, tridemorph, dodemorph, diethofencarb, fentin acetate, fentin hydroxide, carboxin, oxycarboxin, drazoxolon, famoxadone, m-phenylphenol, p-phenylphenol, tribromophenol (TBP), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, cyflufenamid, ofurace, oxadixyl, flutolanil, mepronil, isofetamid, fenpiclonil, fludioxonil, pencycuron, edifenphos, iprobenfos, pyrazophos, phosphorus acids, tecloftalam, captafol, captan, ditalimfos, triforine, fenpropidin, piperalin, osthol, 1-methylcyclopropene, 4-CPA, chlormequat, clofencet, dichlorprop, dimethipin, endothal, ethephon, flumetralin, forchlorfenuron, gibberellic acid, gibberellins, hymexazol, maleic hydrazide, mepiquat, naphthalene acetamide, paclobutrazol, prohexadione, prohexadione-calcium, thidiazuron, tribufos (tributyl phosphorotrithioate), trinexapac, uniconazole, -naphthalene acetic acid, polyoxin D (polyoxrim), BLAD, chitosan, fenoxanil, folpet, 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, bixafen, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, fenpyrazamine, diclomezine, pyrifenox, boscalid, fluopyram, diflumetorim, fenarimol, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine ferimzone, dimetachlone (dimethaclone), pyroquilon, proquinazid, ethoxyquin, quinoxyfen, 4,4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline 4,4-difluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline 5-fluoro-3,3,4,4-tetramethyl-1-(3-quinolyl)isoquinoline 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1,4-benzoxazepine, tebufloquin, oxolinic acid, chinomethionate (oxythioquinox, quinoxymethionate), spiroxamine, (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide, (mandestrobin), azoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, pyriotrobin, fenamistrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metaminostrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, triclopyricarb, trifloxystrobin, amisulbrom, dichlofluanid, tolylfluanid, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, dazomet, isotianil, tiadinil, thifluzamide, benthiazole (TCMTB), silthiofam, zoxamide, anilazine, tricyclazole, (.+.)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol (huanjunzuo), 1-(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)-1,1-difluoro-3-(1,2,4-triazol-1-yl)propan-2-ol 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol (TCDP), (N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine), azaconazole, bitertanol (biloxazol), bromuconazole, climbazole, cyproconazole, difenoconazole, dimetconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, mefentrifluconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triazoxide, triticonazole, 2-[[(1R,5S)-5-[(4-fluorophenyl)methyl]-1-hydroxy-2,2-dimethyl-cyclopentyl]methyl]-4H-1,2,4-triazole-3-thione 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1,2,4-triazole-3-thione, ametoctradin (imidium), iprovalicarb, valifenalate, 2-benzyl-4-chlorophenol (Chlorophene), allyl alcohol, azafenidin, benzalkonium chloride, chloropicrin, cresol, daracide, dichlorophen (dichlorophene), difenzoquat, dipyrithione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, NNF-0721, octhilinone, oxasulfuron, Timorex Gold (plant extract comprising tea tree oil), propamidine and propionic acid; or an insecticide selected from abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, trichlorfon and triflumuron; or a bactericide selected from streptomycin; or an acaricide selected from amitraz, chinomethionat, chlorobenzilate, cyenopyrafen, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; or a biological agent selected from Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

12. A fungicidal composition according to claim 1, wherein the composition further comprises an agriculturally acceptable carrier and, optionally, a surfactant and/or formulation adjuvants.

13. A method of controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition as defined in claim 1.

14. A method according to claim 13, wherein the composition components (A) and (B) are applied in a sequential manner.

Description

EXAMPLES

[0237] The Examples which follow serve to illustrate the invention.

[0238] The compounds (and compositions) of the invention may be distinguished from known compounds (and compositions) by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm or 0.2 ppm of active ingredient(s).

[0239] Throughout this description, temperatures are given in degrees Celsius ( C.) and mp. means melting point. LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method (Methods A, B and C) is as follows: [0240] The description of the LC/MS apparatus and the method A is: [0241] SQ Detector 2 from Waters [0242] Ionisation method: Electrospray [0243] Polarity: positive and negative ions [0244] Capillary (kV) 3.0, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature ( C.) 150, Desolvation Temperature ( C.) 350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650 [0245] Mass range: 100 to 900 Da [0246] DAD Wavelength range (nm): 210 to 500 [0247] Method Waters ACQUITY UPLC with the following HPLC gradient conditions:

TABLE-US-00002 (Solvent A: Water/Methanol 20:1 + 0.05% formic acid and Solvent B: Acetonitrile + 0.05% formic acid) Time (minutes) A (%) B (%) Flow rate (ml/min) 0 100 0 0.85 1.2 0 100 0.85 1.5 0 100 0.85 [0248] Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60 C. [0249] The description of the LC/MS apparatus and the method B is: [0250] SQ Detector 2 from Waters [0251] Ionisation method: Electrospray [0252] Polarity: positive ions [0253] Capillary (kV) 3.5, Cone (V) 30.00, Extractor (V) 3.00, Source Temperature ( C.) 150, Desolvation Temperature ( C.) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700 [0254] Mass range: 140 to 800 Da [0255] DAD Wavelength range (nm): 210 to 400 [0256] Method Waters ACQUITY UPLC with the following HPLC gradient conditions

TABLE-US-00003 (Solvent A: Water/Methanol 9:1 + 0.1% formic acid and Solvent B: Acetonitrile + 0.1% formic acid) Time (minutes) A (%) B (%) Flow rate (ml/min) 0 100 0 0.75 2.5 0 100 0.75 2.8 0 100 0.75 3.0 100 0 0.75 Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60 C. [0257] The description of the LC/MS apparatus and the method C is: [0258] SQ Detector 2 from Waters [0259] Ionisation method: Electrospray [0260] ACQUITY H Class UPLC, Mass Spectrometer from Waters [0261] Polarity: positive and Negative Polarity Switch [0262] Scan Type MS1 Scan [0263] Capillary (kV) 3.00, Cone (V) 40.00, Desolvation Temperature ( C.) 500, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 1000 [0264] Mass range: 0 to 2000 Da [0265] DAD Wavelength range (nm): 200 to 350 [0266] Method Waters ACQUITY UPLC with the following HPLC gradient conditions

TABLE-US-00004 (Solvent A: Water +, 0.1% formic acid and Solvent B: Acetonitrile) Time (minutes) A (%) B (%) Flow rate (ml/min) 0 70 30 0.5 0.05 70 30 0.5 0.8 5 95 0.5 1.8 5 95 0.5 2.45 70 30 0.5 2.50 70 30 0.5 Type of column: Waters ACQUITY UPLC BEH C18; Column length: 50 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.7 micron; Temperature: 35 C.

[0267] Where necessary, enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.

Formulation Examples

[0268]

TABLE-US-00005 Wettable powders a) b) c) active ingredients [components (A) and (B)] 25% 50% 75% sodium lignosulfonate 5% 5% sodium lauryl sulfate 3% 5% sodium diisobutylnaphthalenesulfonate 6% 10% phenol polyethylene glycol ether 2% (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27%
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

TABLE-US-00006 Powders for dry seed treatment a) b) c) active ingredients [components (A) and (B)] 25% 50% 75% light mineral oil 5% 5% 5% highly dispersed silicic acid 5% 5% Kaolin 65% 40% Talcum 20%

[0269] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

TABLE-US-00007 Emulsifiable concentrate active ingredients [components (A) and (B)] 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% xylene mixture 50%
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

TABLE-US-00008 Dusts a) b) c) active ingredients [components (A) and (B)] 5% 6% 4% talcum 95% Kaolin 94% mineral filler 96%
Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

TABLE-US-00009 Extruder dranules active ingredients [components (A) and (B)] 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

TABLE-US-00010 Coated granules active ingredients [components (A) and (B)] 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

TABLE-US-00011 Suspension concentrate active ingredients [components (A) and (B)] 40% propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (in the form of a 75% emulsion in water) 1% Water 32%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

TABLE-US-00012 Flowable concentrate for seed treatment active ingredients [components (A) and (B)] 40% propylene glycol 5% copolymer butanol PO/EO 2% tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (in the form of a 20% 0.5% solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension

[0270] 28 parts of a combination of the active ingredients [components (A) and (B)] is mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

List of Abbreviations:

[0271] AIBN=azobisisobutyronitrile [0272] DIBAL-H=diisobutylaluminium hydride [0273] DIPEA=N,N-diisopropylethylamine [0274] DMF=dimethylformamide [0275] EtOAc=ethyl acetate [0276] HCl=hydrochloric acid [0277] mp=melting point [0278] MeOH=methyl alcohol [0279] NaOH=sodium hydroxide [0280] NBS=N-bromosuccinimide [0281] TFAA=trifluoroacetic acid anhydride [0282] THF=tetrahydrofuran

Preparation Examples

[0283] The compound of component (B) N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine and its synthesis is known from WO 2015/155075.

[0284] The compound of component (B) Timorex Gold (active ingredient tea tree (Melaleuca alternifolia) oil) is a plant extract available from the Stockton Group (http://www.stockton-ag.com/products/timorex-gold/).

[0285] Using the synthetic techniques described both above and below, compounds of formula (I) may be prepared accordingly.

Preparation Examples

Example 1

This Example Illustrates the Preparation of N,N-dimethyl-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (Compound X.07 of Table T1)

[0286] ##STR00038##

Step 1: Preparation of N-hydroxy-4-methyl-benzamidine

[0287] ##STR00039##

[0288] To a suspension of 4-methylbenzonitrile (35 g, 0.29 mol) in ethanol (220 mL) and water (440 mL) at room temperature was added hydroxylamine hydrochloride (41.1 g, 0.58 mol), potassium carbonate (65.4 g, 0.47 mol) and 8-hydroxyquinoline (0.22 g, 1.5 mmol). The reaction mixture was heated at 80 C. for 4 hours. The mixture was cooled to room temperature and diluted with 2N HCl until pH 8 and volatiles were then removed under reduced pressure. The reaction contents were filtered, washed with water, and dried under reduced pressure to afford the title compound. LC/MS (Method A) retention time=0.23 minutes, 151.0 (M+H).

Step 2: Preparation of 3-(p-tolyl)-5-(trifluoromethyl)-1,2,4-oxadiazole

[0289] ##STR00040##

[0290] To a solution of N-hydroxy-4-methyl-benzamidine (38.7 g, 0.25 mol) in 2-methyltetrahydrofuran (750 mL) was added TFAA (49.9 mL, 349.9 mmol) at 0 C. The reaction mixture was stirred at 15 C. for two hours and then diluted with water. The organic layer was separated, washed successively with a saturate sodium bicarbonate solution, a saturated aqueous ammonium chloride solution, water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel (heptane:EtOAc eluent gradient 99:1 to 90:10) to afford the title compound as a clear oil, which solidified upon storage. LC/MS (Method A) retention time=1.15 minutes, mass not detected.

[0291] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.00 (d, 2H), 7.32 (d, 2H), 2.45 (s, 3H).

[0292] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.41 (s).

Step 3a: Preparation of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0293] ##STR00041##

[0294] A mixture of 3-(p-tolyl)-5-(trifluoromethyl)-1,2,4-oxadiazole (56.0 g, 0.24 mol) and NBS (45.4 g, 0.25 mol) in tetrachloromethane (480 mL) under argon was heated to 70 C. AlBN (4.03 g, 24 mmol) was added and the reaction mixture was stirred at 65 C. for 18 hours, cooled to room temperature, and then diluted with dichloromethane and water. The fractions were separated and the combined organic layer was washed with a saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 100:0 to 95:5) to afford the title compound as a white solid mp: 58-63 C.

[0295] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.11 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).

[0296] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.32 (s).

[0297] 3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole was isolated as by-product as a white solid mp: 61-66 C.

[0298] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.15 (d, 2H), 7.73 (d, 2H), 6.68 (s, 1H).

[0299] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.34 (s).

Step 3b: Preparation of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole from 3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0300] ##STR00042##

[0301] To a 1:9 ratio mixture of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole and 3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (10.2 g) in acetonitrile (95 mL), water (1.9 mL) and DIPEA (6.20 ml, 35.7 mmol) was added diethylphosphite (4.7 mL, 35.7 mmol) at 5 C. The mixture was stirred at 5-10 C. for two hours, water and 1M HCl were added and volatiles were removed under reduced pressure. The white slurry was extracted with dichloromethane and the total combined organic layer was dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99:1 to 9:1) to afford the title compound as a white solid. mp: 58-63 C.

[0302] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.11 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).

[0303] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.32 (s).

Step 4: Preparation of N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine

[0304] 3-[4-(Bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (550 mg, 1.71 mmol), N,N-dimethyl-4H-1,2,4-triazol-3-amine (0.23 g, 2.04 mmol), and potassium carbonate (0.48 g, 3.40 mmol) in acetonitrile (17.0 mL) were sealed in a vial and heated at room temperature overnight. Solids were removed by filtration, rinsed with ethyl acetate, and the mother liquors were concentrated under reduced pressure. The resultant residue purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 95:5 to 1:1) to afford 362 mg of the title compound as a yellow solid. LC/MS (Method A) retention time=0.97 minutes, 339 (M+H). mp: 106-111 C.

[0305] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.11 (d, 2H), 7.77 (s, 1H), 7.40 (d, 2H), 5.24 (s, 2H), 3.00 (s, 6H).

Example 2

This Example Illustrates the Preparation of N-methoxy-1-[1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]methanimine (Compound X.20 of Table T1)

[0306] ##STR00043##

Step 1: Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carbaldehyde

[0307] ##STR00044##

[0308] A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (5.0 g, 15.5 mmol), 1H-pyrazole-4-carbaldehyde (2.35 g, 23.2 mmol), and potassium carbonate (4.32 g, 30.9 mmol) in acetonitrile (62 mL) were sealed in a vial. The contents were irradiated with microwaves at 130 C. for 1 hour. Solids were removed by filtration, washed with ethyl acetate, and the mother liquors were concentrated under reduced pressure. The resultant residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 1:0 to 0:1) to afford 362 mg of the title compound as a white solid. LC/MS (Method A) retention time=1.06 minutes, 352 (M+H). mp: 91-96 C.

[0309] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 9.78 (s, 1H), 8.22 (d, 2H), 8.05 (s, 1H), 7.98 (s, 1H), 7.40 (d, 2H), 5.40 (s, 2H).

Step 2: Preparation of N-methoxy-1-[1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]methanimine

[0310] A solution of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carbaldehyde (0.12 g, 0.36 mmol), triethylamine (0.15 mL, 1.08 mmol), and methoxyamine hydrochloride (0.077 g, 0.90 mmol) in methanol (3.6 mL) was stirred at room temperature overnight. The reaction was concentrated under reduced pressure, 1M HCl was added, and the contents were extracted with dichloromethane. The total combined organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The resultant residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 1:0 to 0:1) to afford 0.095 g of the title compound as a white solid. LC/MS (Method A) retention time=0.97 minutes, 322 (M+H). mp: 88-98 C.

[0311] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.20 (m, 2H), 7.98 (s, 1H), 7.78 (s, 1H), 7.65 (d, 1H), 7.35 (d, 2H), 5.38 (s, 2H), 3.88 (s, 3H).

Example 3

This Example Illustrates the Preparation of ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (Compound X.03 of Table T1)

[0312] ##STR00045##

Step 1: ethyl 1-[(4-cyanophenyl)methyl]pyrazole-4-carboxylate

[0313] ##STR00046##

[0314] A solution of 4-(chloromethyl)benzonitrile (10.0 g, 64.65 mmol), ethyl 1H-pyrazole-4-carboxylate (9.24 g, 64.65 mmol), and potassium carbonate (10.03 g, 71.1 mmol) in acetonitrile (100.0 mL) was heated for 4 hours at 80 C. The contents were cooled to room temperature and the volatiles removed under reduced pressure. To the resultant white solid mass was added 150 mL of water which was stirred for 15 minutes. Solids were collected by filtration and dried under high vacuum to afford 16.8 g of the title compound as a white solid. LC/MS (Method A) retention time=0.69 minutes, 295 (M+H). mp: 45-55 C.

[0315] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.95 (d, 2H), 7.64 (d, 2H), 7.29 (d, 2H), 5.38 (s, 2H), 4.29 (q, 2H), 1.33 (t, 3H).

Step 2: ethyl 1-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]pyrazole-4-carboxylate

[0316] ##STR00047##

[0317] To a suspension of ethyl 1-[[(4-cyanophenyl)methyl]pyrazole-4-carboxylate (20 g, 74.0 mmol) in ethanol (200 mL) at room temperature was added hydroxylamine hydrochloride (6.3 g, 88.0 mmol), triethylamine (12.4 mL, 88.8 mmol). The reaction mixture was heated at 80 C. for 2 hours. The mixture was cooled to room temperature and volatiles were then removed under reduced pressure. The contents were filtered, washed with water, and dried under vacuum to afford 21 g of the title compound that was used directly in the next transformation without further purification.

[0318] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm: 9.67 (s, 1H), 8.47 (s, 1H), 7.88 (s, 1H), 7.67 (d, 2H), 7.27 (d, 2H), 5.81 (brs, 2H), 5.38 (s, 2H), 4.19 (q, 2H), 1.25 (t, 3H).

Step 3: ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate

[0319] To a solution of ethyl 1-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]pyrazole-4-carboxylate (10.0 g, 33.3 mol) in 2-methyltetrahydrofuran (100 mL) was added TFAA (5.11 mL, 35.5 mmol). The reaction mixture was stirred for 6 hours then poured into 100 mL of ice water and basified by slow addition of aqueous saturated NaHCO.sub.3 solution. The reaction mixture was extracted with ethyl acetate, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford 11.8 g of the title compound as a white solid. mp: 120-125 C.

[0320] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.11 (d, 2H), 7.96 (d, 2H), 7.37 (d, 2H), 5.39 (s, 2H), 4.30 (q, 2H), 1.34 (t, 3H).

[0321] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.32 (s).

Example 4

This Example Illustrates the Preparation propyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (Compound X.16 of Table T1)

[0322] ##STR00048##

Step 1: Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid

[0323] ##STR00049##

[0324] To a solution of ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (5.0 g, 13.7 mmol) dissolved in concentrated hydrochloric acid (130 mL) was added trifluoroacetic acid (52 mL). The reaction was heated at 55 C. for 50 hours, cooled to room temperature and poured into ice water (400 mL), and basified by slow addition of aqueous saturated NaHCO.sub.3 solution. The reaction mixture was extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99:1 to 9:1) to afford 4.62 g of the title compound as an off-white solid. mp: 182-192 C.

[0325] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.05 (d, 2H), 7.60 (d, 2H), 7.39 (d, 2H), 5.39 (d, 2H).

[0326] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.39 (s).

Step 2: Preparation of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carbonyl chloride

[0327] ##STR00050##

[0328] To a solution of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid (0.63 g, 1.800 mmol) dissolved in dichloromethane (9 mL) and dimethylformamide (0.001 mL) was added oxalyl dichloride (0.18 mL, 2.070 mmol). The mixture was heated at reflux (33-38 C.) for 2 hours then cooled to room temperature. The contents were concentrated under reduced pressure to afford 0.64 g of the title compound as a yellow oil which was used directly in the next transformation without further purification. LC/MS (Method A) retention time=1.03 minutes, (M+H) not detected.

Step 3: Preparation of propyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate

[0329] To a solution of triethylamine (0.084 mL, 0.60 mmol) and n-propanol (3.0 mL) was added 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carbonyl chloride (0.11 g, 0.30 mmol) and the contents were stirred overnight. 1M Hydrochloric acid (2 mL) was added to the mixture and extracted with dichloromethane. The total combined organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (dichloromethane:methanol eluent gradient 99:1 to 95:5) to afford 81 mg of the title compound as a white solid. mp: 105-115 C. LC/MS (Method A) retention time=1.14 minutes, 381 (M+H).

[0330] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.21 (d, 2H), 7.95 (d, 2H), 7.38 (d, 2H), 5.39 (s, 2H), 4.40 (q, 2H), 1.72 (m, 2H), 0.98 (t, 3H).

[0331] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.40 (s).

Example 5

This Example Illustrates the Preparation N-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (Compound X.06 of Table T1)

[0332] ##STR00051##

[0333] To a solution of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carbonyl chloride (0.073 g, 0.21 mmol) in dichloromethane (3.1 mL) was added methylamine (2.0 M MeOH solution, 0.26 mL, 0.513 mmol) and the contents were stirred overnight. 1M Hydrochloric acid (2 mL) was added to the mixture followed by extraction with dichloromethane. The total combined organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (dichloromethane:methanol eluent gradient 99:1 to 95:5) to afford 73 mg of the title compound as a white solid. mp: 156-161 C. LC/MS (Method A) retention time=0.88 minutes, 351 (M+H).

[0334] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.11 (d, 2H), 7.92 (s, 1H), 7.69 (s, 1H), 7.35 (d, 2H), 5.99 (brs, 1H), 5.37 (s, 2H), 2.94 (d, 3H).

[0335] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.35 (s).

Example 6

This Example Illustrates the Preparation ethyl 1-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]pyrazole-4-carboxylate (Compound X.21 of Table T1)

[0336] ##STR00052##

Step 1: Preparation of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoyl chloride

[0337] ##STR00053##

[0338] 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoic acid (4.00 g, 15.0 mmol) was suspended in dichloromethane (90 mL) and DMF (0.01 mL, 0.150 mmol) then oxalyl chloride (1.46 mL, 16.5 mmol) was added. The reaction mixture was heated at reflux for 2 hours then evaporated under reduced pressure to afford 4.15 g of the titled compound as a yellow solid that was used directly in the next transformation without further purification.

Step 2: Preparation of N-methoxy-N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide

[0339] ##STR00054##

[0340] A solution of crude 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoyl chloride (4.15 g, 14.6 mmol) in dichloromethane (20 mL) was added drop wise at room temperature to a stirred solution of N-methoxymethanamine (1.10 g, 17.5 mmol) and triethylamine (3.10 mL, 21.8 mmol) in dichloromethane (80 mL). The mixture was stirred at room temperature for 18 hours then poured into water and extracted twice with dichloromethane. The combined organic layers was washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (heptane: EtOAc eluent gradient 9:1 to 65:35) to afford 4.12 g of the title compound as a solid. LC/MS (Method A) retention time=0.97 minutes, 302 (M+H).

[0341] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.18 (d, 2H), 7.84 (d, 2H), 3.56 (s, 3H), 3.40 (s, 3H).

Step 3: Preparation of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzaldehyde

[0342] ##STR00055##

[0343] To a 75 mL multi neck flask equipped with stirrer and thermometer at 78 C. under argon, to DIBAL-H, 1.0M in toluene (16 mL, 16.0 mmol) was added drop-wise a solution of N-methoxy-N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (4.10 g, 13.3 mmol) in 2-methyltetrahydrofuran (90 mL). The mixture was stirred for two hours at 78 C. and for one hour temperature was increased to 0 C. via ice bath. The mixture was quenched by drop-wise addition of a saturated ammonium chloride solution. Precipitation of a white solid resulted and 4M HCl was added until full solubilisation occurred. The mixture was extracted with ethyl acetate and the combined organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The crude residue was subject to combiflash chromatography over silica gel (heptane: EtOAc eluent gradient 99:1 to 90:10) to afford 2.93 g of the title compound as a white solid. mp: 40-50 C.

[0344] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 10.12 (s, 1H), 8.31 (d, 2H), 8.05 (d, 2H).

[0345] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.29 (s).

Step 4: Preparation of 1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethanol

[0346] ##STR00056##

[0347] In a 50 mL flask dried and under argon, 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzaldehyde (1.36 mol) was dissolved in THF (10 mL) and cooled to 78 C. via a dry ice acetone bath. To this solution was introduced dropwise methyl magnesium bromide (0.70 mL, 2.0M in diethyl ether). The mixture was stirred for 1 hour at 78 C. then quenched with a saturated aqueous ammonium chloride solution. The dry ice bath was removed and the reaction was stirred at room temperature for 5 minutes then extracted with ethyl acetate. The total combined organic layer was dried over sodium sulfate and concentrated under reduced pressure. The resultant crude residue was subject to combiflash chromatography over silicagel (heptane: EtOAc eluent gradient 99:1 to 1:1) to afford the title compound as a white solid.

[0348] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.12 (d, 2H), 7.54 (d, 2H), 5.00 (s, 1H), 1.54 (d, 3H).

[0349] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.31 (s).

Step 5: Preparation of 1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethanone

[0350] ##STR00057##

[0351] In a 50 mL flask dried and under argon, 1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethanol (1.36 mol) was dissolved in dichloromethane (10 mL). To this solution was introduced manganese oxide (40.6 mmol) and the heterogenous mixture was stirred overnight at room temperature.

[0352] The reaction solution was filtered over a pad of celite, rinsed with dichloromethane, and the total combined organic layer was concentrated under reduced pressure to afford the title compound as a white solid which was used directly without further purification.

[0353] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.24 (d, 2H), 8.12 (d, 2H), 2.67 (d, 3H).

[0354] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.39 (s).

Step 6: Preparation of 3-[4-(1-bromoethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0355] ##STR00058##

[0356] To a solution of 1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethanol (1.15 g, 4.45 mmol) in dichloromethane (15 mL) cooled to 0 C. via an ice bath was added tribromophosphane (0.465 mL, 4.90 mmol) over 30 minutes and the reaction mixture was stirred for 1.5 hours. Then, a 10% sodium metabisulphite (50 ml) was introduced and after 15 minutes the aqueous layer was extracted with dichloromethane. The total combined organic layer was washed with water, dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The resultant crude residue was purified by combiflash chromatography over silica gel using cyclohexane as eluent to afford 1.0 g of the title compound pure as white solid.

[0357] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm: 8.07 (m, 2H), 7.75 (m, 2H), 5.59 (q, 1H), 2.02 (d, 3H).

Step 7: Preparation of ethyl 1-[1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl]pyrazole-4-carboxylate

[0358] Ethyl 1H-pyrazole-4-carboxylate (0.061 g, 0.46 mmol), potassium carbonate (0.13 g, 0.93 mmol), 3 44-(1-bromoethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (0.15 g, 0.47 mmol), and acetonitrile (1.5 mL) were reacted at room temperature overnight then concentrated under reduced pressure. Water was added and the organics were extracted twice with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, and filtered. Volatiles was removed under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 93:7) to afford 0.115 g of the title compound. LC/MS (Method C) retention time=1.61 minutes, 385 (M+H).

[0359] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.12 (d, 2H), 7.98 (d, 2H), 7.37 (d, 2H), 5.61 (q, 1H), 4.31 (q, 2H), 1.97 (d, 3H), 1.35 (t, 3H).

[0360] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.33 (s).

Example 7

This Example Illustrates the Preparation ethyl 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (Compound X.13 of Table T1)

[0361] ##STR00059##

Step 1: Preparation of 2-fluoro-N-hydroxy-4-methyl-benzamidine

[0362] ##STR00060##

[0363] To a suspension of 2-fluoro-4-methylbenzonitrile (5 g, 37.0 mmol) in ethanol (125 mL) at 25 C. was added hydroxylamine hydrochloride (7.7 g, 111 mmol) and triethylamine (15.5 mL, 111 mmol). The reaction mixture was heated at 80 C. for 2 hours. After cooling to room temperature, volatiles were removed under reduced pressure thus affording a white solid that was used in the next step without any purification. LC/MS (Method A) retention time=0.25 minutes, 169.2 (M+H).

[0364] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.96 (t, 1H), 7.11 (m, 2H), 2.45 (s, 3H).

[0365] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.26 (s), 108.12 (s).

Step 2: Preparation of 3-(2-fluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1,2,4-oxadiazole

[0366] ##STR00061##

[0367] To a solution of 2-fluoro-N-hydroxy-4-methyl-benzamidine (37 mmol) in tetrahydrofuran (122 mL) cooled via an ice bath to 0 C. was added TFAA (7.7 mL, 55.5 mmol). The reaction mixture was stirred at 25 C. overnight and then diluted with water. The organic layer was separated, washed successively with a saturated aqueous sodium bicarbonate solution, a saturated aqueous ammonium chloride solution, water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99:1 to 1:1) to afford 6.6 g of the title compound as an amorphous white solid. LC/MS (Method A) retention time=1.14 minutes, 247 (M+H).

[0368] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.00 (d, 1H), 7.32 (d, 2H), 2.45 (s, 3H).

[0369] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.3 (s), 108.1 (s).

Step 3a: Preparation of 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0370] ##STR00062##

[0371] A mixture of 3-(2-fluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1,2,4-oxadiazole (4.2 g, 17.1 mmol) and NBS (3.11 g, 17.1 mmol) in tetrachloromethane (34.3 mL) was heated to 70 C. AlBN (0.29 g, 1.71 mmol) was introduced and the reaction mixture stirred at 65 C. for 18 hours. The contents were cooled to 25 C., diluted with dichloromethane and water, and the layers were separated. A succinimide by-product was filtrated off the organic fraction and the solvent was removed under reduced pressure to afford a brown gum. The crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 100:0 to 4:1) to afford 1.7 g of the title compound as a white solid. LC/MS (Method A) retention time=1.13 minutes, (M+H) not detected.

[0372] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (t, 1H), 7.34 (m, 2H), 4.49 (s, 2H).

[0373] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.18 (s), 106.2 (s).

[0374] 3-[4-(dibromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole was isolated as by-product in the form of a beige solid (4.0 g, 58% yield) LC/MS (Method A) retention time=1.20 minutes, (M+H) not detected.

[0375] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.14 (d, 1H), 7.52 (dd, 2H), 6.63 (s, 1H).

Step 3b: Preparation of 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole from 3-[4-(dibromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0376] ##STR00063##

[0377] To a 1:20 mixture of 3 -[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole and 3-[4-(dibromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (4.0 g, 9.9 mmol) in acetonitrile (37 mL), water (0.8 mL) and DIPEA (2.59 mL, 14.8 mmol) cooled to 5 C. was added diethylphosphite (2.0 mL, 14.8 mmol). The mixture was stirred at 5-10 C. for 2 hours, then water and 1M HCl were added and volatiles were removed under reduced pressure. The resultant white slurry was extracted with dichloromethane and the combined organic layer was dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the resultant light orange colored crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99:1 to 1:1) to afford 2.2 g of the title compound as a white solid.

[0378] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (t, 1H), 7.34 (m, 2H), 4.49 (s, 2H).

[0379] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.18 (s), 106.2 (s).

Step 4: Preparation of 2-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4,4-dimethyl-isoxazolidin-3-one

[0380] Ethyl 1H-pyrazole-4-carboxylate (0.066 g, 0.46 mmol), potassium carbonate (0.086 g, 0.62 mmol), 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (0.10 g, 0.31 mmol), and acetonitrile (1.5 mL) were sealed in a vial. The reaction contents were irradiated with microwaves and heated at 130 C. for 0.5 hour. After cooling to 25 C., all solids were filtered off, rinsed with ethyl acetate, and the volatiles were removed under reduced pressure. The resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 1:1) to afford 0.075 g of the title compound. LC/MS (Method C) retention time=1.61 minutes, 381 (M+H).

[0381] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.19 (t, 1H), 7.98 (d, 2H), 7.36 (m, 1H), 7.18 (m, 1H), 5.36 (s, 2H), 4.30 (q, 2H), 1.32 (t, 3H).

[0382] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.18 (s), 105.62 (s).

[0383] The following general procedure was performed in a combinatorial fashion using appropriate building blocks (compounds of Formula (II) and (III)) to provide the compounds of Formula (I). The compounds prepared via the following combinatorial protocol were analyzed using LC/MS Method B.

##STR00064##

[0384] By way of exemplification, 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (0.03 mmol in 1000 L acetonitrile) were transferred to microwave vials containing amine derivative of formula (II) (0.03 mmol), potassium carbonate (0.06 mmol), and were stirred under microwaves irradiation at 120 C. for 20 minutes in the parallel microwave apparatus. The solvent was removed under a stream of nitrogen. The resultant crude residues were solubilized in a mixture of MeOH (250 L) and DMA (500 L) and directly submitted for preparative LC/MS purification which provided the compounds of formula (I). Structures of Isomers were assigned by NMR techniques.

[0385] Where necessary, enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, (eg, by using chiral starting materials).

TABLE-US-00013 TABLE T1 Melting point (mp) data and/or retention times (t.sub.R) for compounds X.01 to X.21 according to Formula (I): Mass t.sub.R charge LCMS mp Entry Compound name Structure (min) [M + H].sup.+ Method ( C.) X.01 5-(trifluoromethyl)-3-[4- [[3-(trifluoromethyl)-1,2,4- triazol-1- yl]methyl]phenyl]-1,2,4- oxadiazole [00065] 68.2- 70.1 X.02 2-[[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]-1,2,4- triazole-3-carbonitrile [00066] 1.56 321.1 B X.03 ethyl 1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxylate [00067] 120- 130 X.04 N-cyclopropyl-1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00068] 189- 194 X.05 N,N-dimethyl-1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00069] 124- 129 X.06 N-methyl-1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00070] 0.88 351 A 156- 161 X.07 N,N-dimethyl-1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]-1,2,4- triazol-3-amine [00071] 0.97 339 A 106.2- 110.5 X.08 3-[4-[(5-ethylsulfanyl- 1,2,4-triazol-1- yl)methyl]phenyl]-5- (trifluoromethyl)-1,2,4- oxadiazole [00072] 1.82 370.1 B X.09 3-[4-(triazolo[4,5- b]pyridin-1- ylmethyl)phenyl]-5- (trifluoromethyl)-1,2,4- oxadiazole [00073] 1.42 347.1 B X.10 3-[4-(triazolo[4,5- b]pyridin-2- ylmethyl)phenyl]-5- (trifluoromethyl)-1,2,4- oxadiazole [00074] 121- 122 X.11 3-[4-(triazolo[4,5- b]pyridin-3- ylmethyl)phenyl]-5- (trifluoromethyl)-1,2,4- oxadiazole [00075] 143- 144 X.12 methyl 1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxylate [00076] 122- 129 X.13 ethyl 1-[[3-fluoro-4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxylate [00077] 131- 135 X.14 N,N-diethyl-1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00078] 86- 96 X.15 N-methoxy-N-methyl-1- [[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00079] 102- 112 X.16 propyl 1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxylate [00080] 1.14 381 A 105- 115 X.17 N-methoxy-1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00081] 128- 138 X.18 N-ethyl-1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00082] 166- 176 X.19 1-[[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]pyrazole- 4-carboxamide [00083] 0.86 338 A X.20 N-methoxy-1-[1-[[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]methyl]pyrazol- 4-yl]methanimine [00084] 0.97 322 A 88- 98 X.21 ethyl 1-[1-[4-[5- (trifluoromethyl)-1,2,4- oxadiazol-3- yl]phenyl]ethyl]pyrazole- 4-carboxylate [00085] 1.61 381 C

Biological Examples

General Examples of Leaf Disk Tests in Well Plates

[0386] Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse. The cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar. The leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation. Compounds to be tested are prepared as DMSO solutions (max. 10 mg/mL) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying. The inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system. A single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.

General Examples of Liquid Culture Tests in Well Plates

[0387] Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth. DMSO solutions of the test compound (max. 10 mg/mL) are diluted with 0.025% Tween20 by a factor of 50 and 10 L of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound. The test plates are incubated in the dark at 24 C. and 96% relative humidity. The inhibition of fungal growth is determined photometrically after 2 to 7 days, depending on the pathosystem, and percent antifungal activity relative to the untreated check is calculated.

Example A1

Fungicidal Activity Against Puccinia recondita f. sp. tritici/Wheat/Leaf Disc Preventative (Brown Rust)

[0388] Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19 C. and 75% relative humidity (rh) under a light regime of 12 hours light/12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 to 9 days after application).

[0389] The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

[0390] Compounds (from Table T1) X.1, X.2, X.3, X.4, X.5, X.6, X.7, X.8, X.9, X.10, X.11, X.12, X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, and X.21.

Example A2

Fungicidal Activity Against Puccinia recondita f. sp. tritici/Wheat/Leaf Disc Curative (Brown Rust)

[0391] Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are then inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19 C. and 75% relative humidity. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19 C. and 75% relative humidity under a light regime of 12 hours light/12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 to 8 days after application).

[0392] The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

[0393] Compounds (from Table T1) X.1, X.2, X.3, X.4, X.5, X.6, X.7, X.8, X.9, X.10, X.11, X.12, X.14, X.15, X.16, X.17, X.18, X.19, X.20, and X.21.

Example A3

Fungicidal Activity Against Phakopsora pachrhizi/Soybean/Leaf Disc Preventative (Asian Soybean Rust)

[0394] Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20 C. and 75% rh leaf disc are kept at 20 C. with 12 h light/day and 75% rh. The activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 to 14 days after application).

[0395] The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

[0396] Compounds (from Table T1) X.1, X.2, X.3, X.4, X.5, X.6, X.7, X.8, X.9, X.10, X.11, X.12, X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, and X.21.

Example A4

Fungicidal Activity Against Glomerella lagenarium (Colletotrichum lagenarium) Liquid Culture/Cucumber/Preventative (Anthracnose)

[0397] Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDBpotato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C. and the inhibition of growth is measured photometrically 3 to 4 days after application.

[0398] The following compounds at 20 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.

[0399] Compounds (from Table T1) X.1, X.2, X.3, X.4, X.5, X.6, X.7, X.8, X.9, X.10, X.11, X.12, X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, and X.21.

[0400] Further biolgical test examples relating to fungicidal compositions comprising a mixture of components (A) and (B) as active ingredients:

Example B1a

Preventative Activity Against Phakopsora pachyrhizi on Soybean

[0401] 4-week old soybean plants are sprayed in a spray chamber with a tank-mix of formulated test compounds (WP10) diluted in water. Leaf disks are cut from treated plants and placed on agar into 24-well plates one day after application. Leaf disks are inoculated by spraying them with a spore suspension on their lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20 C. and 75% rh, the leaf disks are then kept at 20 C. with 12 h light/day and 75% rh. The percentage leaf disk area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (10-14 days after application).

[0402] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test.

TABLE-US-00014 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.03 Benzovindiflupyr 1:1 180:180 X.03 Benzovindiflupyr 2:1 180:90 X.03 Benzovindiflupyr 1:3 60:180 X.03 Benzovindiflupyr 1:1.5 60:90 X.03 Fluxapyroxad 2:1 180:90 X.03 Fluxapyroxad 1:1.5 60:90 X.03 Pydiflumetofen 1:6.67 180:1200 X.03 Pydiflumetofen 1:3.33 180:600 X.03 Pydiflumetofen 1:20 60:1200 X.03 Pydiflumetofen 1:10 60:600 X.03 Fluopyram 1:6.67 180:1200 X.03 Fluopyram 1:3.33 180:600 X.03 Fluopyram 1:20 60:1200 X.03 Fluopyram 1:10 60:600 X.03 Penthiopyrad 1:3.33 180:600 X.03 Penthiopyrad 1:1.67 180:300 X.03 Penthiopyrad 1:10 60:600 X.03 Penthiopyrad 1:5 60:300 X.03 Difenoconazole 1:6.67 180:1200 X.03 Difenoconazole 1:1.33 180:240 X.03 Difenoconazole 1:20 60:1200 X.03 Difenoconazole 1:4 60:240 X.03 Cyproconazole 1:6.67 180:1200 X.03 Cyproconazole 1:1.33 180:240 X.03 Cyproconazole 1:20 60:1200 X.03 Cyproconazole 1:4 60:240 X.03 Tebuconazole 1:6.67 180:1200 X.03 Tebuconazole 1:1.33 180:240 X.03 Tebuconazole 1:20 60:1200 X.03 Tebuconazole 1:4 60:240 X.03 Hexaconazole 1:6.67 180:1200 X.03 Hexaconazole 1:1.33 180:240 X.03 Hexaconazole 1:20 60:1200 X.03 Hexaconazole 1:4 60:240 X.03 Prothioconazole 1:6.67 180:1200 X.03 Prothioconazole 1:1.33 180:240 X.03 Prothioconazole 1:20 60:1200 X.03 Prothioconazole 1:4 60:240 X.03 Azoxystrobin 1:6.67 180:1200 X.03 Azoxystrobin 1:3.33 180:600 X.03 Azoxystrobin 1:20 60:1200 X.03 Azoxystrobin 1:10 60:600 X.03 Trifloxystrobin 1:6.67 180:1200 X.03 Trifloxystrobin 1:3.33 180:600 X.03 Trifloxystrobin 1:20 60:1200 X.03 Trifloxystrobin 1:10 60:600 X.03 Picoxystrobin 1:6.67 180:1200 X.03 Picoxystrobin 1:3.33 180:600 X.03 Picoxystrobin 1:20 60:1200 X.03 Picoxystrobin 1:10 60:600 X.03 Pyraclostrobin 1:6.67 180:1200 X.03 Pyraclostrobin 1:3.33 180:600 X.03 Pyraclostrobin 1:20 60:1200 X.03 Pyraclostrobin 1:10 60:600 X.03 Metalaxyl-M 1:33.33 180:6000 X.03 Metalaxyl-M 1:11.11 180:2000 X.03 Metalaxyl-M 1:100 60:6000 X.03 Metalaxyl-M 1:33.33 60:2000 X.03 Fenpropidin 1:33.33 180:6000 X.03 Fenpropidin 1:11.11 180:2000 X.03 Fenpropidin 1:100 60:6000 X.03 Fenpropidin 1:33.33 60:2000 X.03 Fenpropimorph 1:33.33 180:6000 X.03 Fenpropimorph 1:11.11 180:2000 X.03 Fenpropimorph 1:100 60:6000 X.03 Fenpropimorph 1:33.33 60:2000 X.03 Cyprodinil 1:33.33 180:6000 X.03 Fludioxonil 1:200 180:36000 X.03 Fludioxonil 1:66.67 180:12000 X.03 Fludioxonil 1:600 60:36000 X.03 Fludioxonil 1:200 60:12000 X.03 Spiroxamine 1:33.33 180:6000 X.03 Spiroxamine 1:11.11 180:2000 X.03 Spiroxamine 1:100 60:6000 X.03 Spiroxamine 1:33.33 60:2000 X.03 Mancozeb 1:100 180:18000 X.03 Mancozeb 1:33.33 180:6000 X.03 Mancozeb 1:300 60:18000 X.03 Mancozeb 1:100 60:6000 X.03 Chlorothalonil 1:200 180:36000 X.03 Chlorothalonil 1:66.67 180:12000 X.03 Chlorothalonil 1:600 60:36000 X.03 Chlorothalonil 1:200 60:12000 X.03 Fenhexamid 1:100 180:18000 X.03 Fenhexamid 1:33.33 180:6000 X.03 Fenhexamid 1:300 60:18000 X.03 Fenhexamid 1:100 60:6000 X.03 Prochloraz 1:100 180:18000 X.03 Prochloraz 1:33.33 180:6000 X.03 Prochloraz 1:300 60:18000 X.03 Prochloraz 1:100 60:6000 X.03 Oxathiapiprolin 1:3.33 180:600 X.03 Oxathiapiprolin 1:1.11 180:200 X.03 Oxathiapiprolin 1:10 60:600 X.03 Oxathiapiprolin 1:3.33 60:200 X.03 Mandipropamid 1:33.33 180:6000 X.03 Mandipropamid 1:11.11 180:2000 X.03 Mandipropamid 1:100 60:6000 X.03 Fluazinam 1:90 180:16200 X.03 Fluazinam 1:30 180:5400 X.03 Fluazinam 1:270 60:16200 X.03 Fluazinam 1:90 60:5400 X.03 N-[5-bromo-2-methyl- 1.5:1 180:120 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.03 (N-[5-bromo-2-methyl- 3:1 180:60 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.03 (N-[5-bromo-2-methyl- 1:2 60:120 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.03 (N-[5-bromo-2-methyl- 1:1 60:60 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.03 fosetyl-aluminium 1:333.33 180:60000 X.03 fosetyl-aluminium 1:166.67 180:30000 X.03 fosetyl-aluminium 1:1000 60:60000 X.03 fosetyl-aluminium 1:500 60:30000 X.03 Trinexapac-ethyl 1:33.33 180:6000 X.03 Trinexapac-ethyl 1:1.67 180:300 X.03 Trinexapac-ethyl 1:100 60:6000 X.03 Trinexapac-ethyl 1:50 60:3000 X.03 Acibenzolar-S-methyl 1:3.33 180:600 X.03 Acibenzolar-S-methyl 1:1.67 180:300 X.03 Acibenzolar-S-methyl 1:10 60:600 X.03 Acibenzolar-S-methyl 1:5 60:300 X.03 Glyphosate 1:20 180:3600 X.03 Glyphosate 1:6.67 180:1200 X.03 Glyphosate 1:60 60:3600 X.03 Glyphosate 1:20 60:1200 X.03 2,4-D 1:20 180:3600 X.03 2,4-D 1:6.67 180:1200 X.03 2,4-D 1:60 60:3600 X.03 2,4-D 1:20 60:1200 X.03 Timorex Gold 1:1000 180:180000 X.03 Timorex Gold 1:500 180:90000 X.03 Timorex Gold 1:3000 60:180000 X.03 Timorex Gold 1:1500 60:90000 X.03 Thiamethoxam 1:33.33 180:6000 X.03 Thiamethoxam 1:16.67 180:3000 X.03 Thiamethoxam 1:100 60:6000

Example B1b

Preventative Activity Against Phakopsora pachyrhizi on Soybean

[0403] Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20 C. and 75% relative humidity leaf disc are kept at 20 C. with 12 hours light/day and 75% relative humidity. The activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 to 14 days after application).

[0404] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

TABLE-US-00015 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.07 Benzovindiflupyr 10:1 60:6 X.07 Benzovindiflupyr 30:1 60:2 X.07 Benzovindiflupyr 3.3:1 20:6 X.07 Benzovindiflupyr 10:1 20:2 X.07 Fluxapyroxad 3:1 60:20 X.07 Fluxapyroxad 10:1 60:6 X.07 Fluxapyroxad 1:1 20:20 X.07 Fluxapyroxad 3.3:1 20:6 X.07 Pydiflumetofen 1:1 60:60 X.07 Pydiflumetofen 3:1 60:20 X.07 Pydiflumetofen 1:3 20:60 X.07 Pydiflumetofen 1:1 20:20 X.07 Fluopyram 3:1 60:20 X.07 Fluopyram 10:1 60:6 X.07 Fluopyram 1:1 20:20 X.07 Fluopyram 3.3:1 20:6 X.07 Difenoconazole 1:1 60:60 X.07 Difenoconazole 3:1 60:20 X.07 Difenoconazole 1:3 20:60 X.07 Difenoconazole 1:1 20:20 X.07 Cyproconazole 1:1 60:60 X.07 Cyproconazole 3:1 60:20 X.07 Cyproconazole 1:3 20:60 X.07 Cyproconazole 1:1 20:20 X.07 Tebuconazole 1:1 60:60 X.07 Tebuconazole 3:1 60:20 X.07 Tebuconazole 1:3 20:60 X.07 Tebuconazole 1:1 20:20 X.07 Mefentrifluconazole 1:1 60:60 X.07 Mefentrifluconazole 3:1 60:20 X.07 Mefentrifluconazole 1:3 20:60 X.07 Mefentrifluconazole 1:1 20:20 X.07 Hexaconazole 1:1 60:60 X.07 Hexaconazole 3:1 60:20 X.07 Hexaconazole 1:3 20:60 X.07 Hexaconazole 1:1 20:20 X.07 Prothioconazole 1:1 60:60 X.07 Prothioconazole 3:1 60:20 X.07 Prothioconazole 1:3 20:60 X.07 Prothioconazole 1:1 20:20 X.07 Azoxystrobin 1:1 60:60 X.07 Azoxystrobin 3:1 60:20 X.07 Azoxystrobin 1:3 20:60 X.07 Azoxystrobin 1:1 20:20 X.07 Trifloxystrobin 1:1 60:60 X.07 Trifloxystrobin 3:1 60:20 X.07 Trifloxystrobin 1:3 20:60 X.07 Trifloxystrobin 1:1 20:20 X.07 Picoxystrobin 1:1 60:60 X.07 Picoxystrobin 3:1 60:20 X.07 Picoxystrobin 1:3 20:60 X.07 Picoxystrobin 1:1 20:20 X.07 Pyraclostrobin 1:1 60:60 X.07 Pyraclostrobin 3:1 60:20 X.07 Pyraclostrobin 1:3 20:60 X.07 Pyraclostrobin 1:1 20:20 X.07 Metalaxyl-M 1:1 60:60 X.07 Metalaxyl-M 3:1 60:20 X.07 Metalaxyl-M 1:3 20:60 X.07 Metalaxyl-M 1:1 20:20 X.07 Fenpropidin 3:1 60:20 X.07 Fenpropidin 10:1 60:6 X.07 Fenpropidin 1:1 20:20 X.07 Fenpropidin 3.3:1 20:6 X.07 Fenpropimorph 3:1 60:20 X.07 Fenpropimorph 10:1 60:6 X.07 Fenpropimorph 1:1 20:20 X.07 Fenpropimorph 3.3:1 20:6 X.07 Mancozeb 1:1 60:60 X.07 Mancozeb 3:1 60:20 X.07 Mancozeb 1:3 20:60 X.07 Mancozeb 1:1 20:20 X.07 Chlorothalonil 1:1 60:60 X.07 Chlorothalonil 3:1 60:20 X.07 Chlorothalonil 1:3 20:60 X.07 Chlorothalonil 1:1 20:20 X.07 Oxathiapiprolin 1:1 60:60 X.07 Oxathiapiprolin 3:1 60:20 X.07 Oxathiapiprolin 1:3 20:60 X.07 Oxathiapiprolin 1:1 20:20 X.07 Mandipropamid 1:1 60:60 X.07 Mandipropamid 3:1 60:20 X.07 Mandipropamid 1:3 20:60 X.07 Mandipropamid 1:1 20:20 X.07 (N-[5-bromo-2-methyl- 1:1 60:60 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 3:1 60:20 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:3 20:60 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:1 20:20 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 fosetyl-aluminium 1:1 60:60 X.07 fosetyl-aluminium 3:1 60:20 X.07 fosetyl-aluminium 1:3 20:60 X.07 fosetyl-aluminium 1:1 20:20 X.07 Trinexapac-ethyl 1:1 60:60 X.07 Trinexapac-ethyl 3:1 60:20 X.07 Trinexapac-ethyl 1:3 20:60 X.07 Trinexapac-ethyl 1:1 20:20 X.07 Acibenzolar-S-methyl 1:1 60:60 X.07 Acibenzolar-S-methyl 3:1 60:20 X.07 Acibenzolar-S-methyl 1:3 20:60 X.07 Acibenzolar-S-methyl 1:1 20:20 X.07 Glyphosate 3:1 60:20 X.07 Glyphosate 10:1 60:6 X.07 Glyphosate 1:1 20:20 X.07 Glyphosate 3.3:1 20:6 X.07 2,4-D 3:1 60:20 X.07 2,4-D 10:1 60:6 X.07 2,4-D 1:1 20:20 X.07 2,4-D 3.3:1 20:6 X.07 Timorex Gold 3:1 60:20 X.07 Timorex Gold 10:1 60:6 X.07 Timorex Gold 1:3 20:60 X.07 Timorex Gold 1:1 20:20 X.07 Thiamethoxam 1:1 60:60 X.07 Thiamethoxam 3:1 60:20 X.07 Thiamethoxam 1:3 20:60 X.07 Thiamethoxam 1:1 20:20

Example B2

Uncinula necator/Grape/Preventive (Powdery Mildew on Grape)

[0405] 5-week old grape seedlings cv. Gutedel were treated with the formulated test compounds in a spray chamber. One day after application grape plants were inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 24/22 C. and 70% r. h. under a light regime of 14/10 h (light/dark) the percentage leaf area covered by disease was assessed.

[0406] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test.

TABLE-US-00016 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.03 Benzovindiflupyr 1000:1 60:0.06 X.03 Benzovindiflupyr 3000:1 60:0.02 X.03 Benzovindiflupyr 333.33:1 20:0.06 X.03 Benzovindiflupyr 1000:1 20:0.02 X.03 Pydiflumetofen 10:1 60:6 X.03 Pydiflumetofen 30:1 60:2 X.03 Pydiflumetofen 3.33:1 20:6 X.03 Pydiflumetofen 10:1 20:2 X.03 Isopyrazam 10:1 60:6 X.03 Isopyrazam 30:1 60:2 X.03 Isopyrazam 3.33:1 20:6 X.03 Isopyrazam 10:1 20:2 X.03 Penthiopyrad 10:1 60:6 X.03 Penthiopyrad 30:1 60:2 X.03 Penthiopyrad 3.33:1 20:6 X.03 Penthiopyrad 10:1 20:2 X.03 Fluopyram 10:1 60:6 X.03 Fluopyram 30:1 60:2 X.03 Fluopyram 3.33:1 20:6 X.03 Fluopyram 10:1 20:2 X.03 Azoxystrobin 1000:1 60:0.06 X.03 Azoxystrobin 3000:1 60:0.02 X.03 Azoxystrobin 333.33:1 20:0.06 X.03 Azoxystrobin 1000:1 20:0.02 X.03 Trifloxystrobin 1000:1 60:0.06 X.03 Trifloxystrobin 3000:1 60:0.02 X.03 Trifloxystrobin 333.33:1 20:0.06 X.03 Trifloxystrobin 1000:1 20:0.02 X.03 Pyraclostrobin 100:1 60:0.6 X.03 Pyraclostrobin 300:1 60:0.2 X.03 Pyraclostrobin 33.33:1 20:0.6 X.03 Pyraclostrobin 100:1 20:0.2 X.03 Cyproconazole 100:1 60:0.6 X.03 Cyproconazole 300:1 60:0.2 X.03 Cyproconazole 33.33:1 20:0.6 X.03 Cyproconazole 100:1 20:0.2 X.03 Difenoconazole 10:1 60:6 X.03 Difenoconazole 30:1 60:2 X.03 Difenoconazole 3.33:1 20:6 X.03 Difenoconazole 10:1 20:2 X.03 Hexaconazole 10:1 60:6 X.03 Hexaconazole 30:1 60:2 X.03 Hexaconazole 3.33:1 20:6 X.03 Hexaconazole 10:1 20:2 X.03 Propiconazole 10:1 60:6 X.03 Propiconazole 30:1 60:2 X.03 Propiconazole 3.33:1 20:6 X.03 Propiconazole 10:1 20:2 X.03 Mefentrifluconazole 10:1 60:6 X.03 Mefentrifluconazole 30:1 60:2 X.03 Mefentrifluconazole 3.33:1 20:6 X.03 Mefentrifluconazole 10:1 20:2 X.03 Prothioconazole 10:1 60:6 X.03 Prothioconazole 30:1 60:2 X.03 Prothioconazole 3.33:1 20:6 X.03 Prothioconazole 10:1 20:2 X.03 Chlorothalonil 1:1 60:60 X.03 Chlorothalonil 3:1 60:20 X.03 Chlorothalonil 1:3 20:60 X.03 Chlorothalonil 1:1 20:20 X.03 Mancozeb 1:1 60:60 X.03 Mancozeb 3:1 60:20 X.03 Mancozeb 1:3 20:60 X.03 Mancozeb 1:1 20:20 X.03 fosetyl-aluminium 1:3.3 60:200 X.03 fosetyl-aluminium 1:1 60:60 X.03 fosetyl-aluminium 1:10 20:200 X.03 fosetyl-aluminium 1:3.3 20:60 X.03 Acibenzolar-S-methyl 1:3.3 60:200 X.03 Acibenzolar-S-methyl 1:1 60:60 X.03 Acibenzolar-S-methyl 1:10 20:200 X.03 Acibenzolar-S-methyl 1:3.3 20:60

Example B3a

Glomerella lagenarium (Colletotrichum lagenarium)/Cucumber/Preventive

[0407] 1-week old cucumber plants cv. Wisconsin were treated with the formulated test compounds in a spray chamber. One day after application wheat plants were inoculated by spraying a spore suspension (110.sup.5 spores/ml) on the test plants. After an incubation period of 30 h in darkness at 23 C. and 100% r. h. plants were kept for 6 days 23 C./21 C. (day/night) and 70% r.h. in a greenhouse. The percentage leaf area covered by disease was assessed 7 days after inoculation.

[0408] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test.

TABLE-US-00017 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.03 Benzovindiflupyr 1000:1 60:0.06 X.03 Benzovindiflupyr 3000:1 60:0.02 X.03 Isopyrazam 10:1 60:6 X.03 Isopyrazam 30:1 60:2 X.03 Isopyrazam 3.33:1 20:6 X.03 Isopyrazam 10:1 20:2 X.03 Azoxystrobin 1000:1 60:0.06 X.03 Triflooxystrobin 1000:1 60:0.06 X.03 Pyraclostrobin 100:1 60:0.6 X.03 Pyraclostrobin 300:1 60:0.2 X.03 Pyraclostrobin 33.33:1 20:0.6 X.03 Pyraclostrobin 100:1 20:0.2 X.03 Difenoconazole 10:1 60:6 X.03 Difenoconazole 30:1 60:2 X.03 Difenoconazole 3.33:1 20:6 X.03 Difenoconazole 10:1 20:2 X.03 Hexaconazole 10:1 60:6 X.03 Hexaconazole 30:1 60:2 X.03 Hexaconazole 10:1 20:2 X.03 Propiconazole 10:1 60:6 X.03 Propiconazole 30:1 60:2 X.03 Propiconazole 3.33:1 20:6 X.03 Propiconazole 10:1 20:2 X.03 Prothioconazole 10:1 60:6 X.03 Prothioconazole 3.33:1 20:6 X.03 Mefentrifluconazole 10:1 60:6 X.03 Mefentrifluconazole 30:1 60:2 X.03 Mefentrifluconazole 3.33:1 20:6 X.03 Mefentrifluconazole 10:1 20:2 X.03 Chlorothalonil 1:1 60:60 X.03 Chlorothalonil 3:1 60:20 X.03 Chlorothalonil 1:3 20:60 X.03 Chlorothalonil 1:1 20:20 X.03 Mancozeb 1:1 60:60 X.03 Mancozeb 3:1 60:20 X.03 Mancozeb 1:3 20:60 X.03 Mancozeb 1:1 20:20 X.03 fosetyl-aluminium 1:3.3 60:200 X.03 fosetyl-aluminium 1:1 60:60 X.03 fosetyl-aluminium 1:10 20:200 X.03 fosetyl-aluminium 1:3 20:60 X.03 Acibenzolar-S-methyl 1:3.3 60:200 X.03 Acibenzolar-S-methyl 1:1 60:60 X.03 Acibenzolar-S-methyl 1:10 20:200 X.03 Acibenzolar-s-methyl 1:3 20:60

Example B3b

Glomerella lagenarium (Colletotrichum lagenarium)/Cucumber

[0409] Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDBpotato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C. and the inhibition of growth is measured photometrically 3 to 4 days after application.

[0410] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.

TABLE-US-00018 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.07 Benzovindiflupyr 10:1 6:0.6 X.07 Benzovindiflupyr 30:1 6:0.2 X.07 Benzovindiflupyr 3.3:1 2:0.6 X.07 Benzovindiflupyr 10:1 2:0.2 X.07 Fluxapyroxad 3:1 6:2 X.07 Fluxapyroxad 10:1 6:0.6 X.07 Fluxapyroxad 1:1 2:2 X.07 Fluxapyroxad 3.3:1 2:0.6 X.07 Pydiflumetofen 1:1 6:6 X.07 Pydiflumetofen 3:1 6:2 X.07 Pydiflumetofen 1:3 2:6 X.07 Pydiflumetofen 1:1 2:2 X.07 Fluopyram 3:1 6:2 X.07 Fluopyram 10:1 6:0.6 X.07 Fluopyram 1:1 2:2 X.07 Fluopyram 3.3:1 2:0.6 X.07 Difenoconazole 1:1 6:6 X.07 Difenoconazole 3:1 6:2 X.07 Difenoconazole 1:3 2:6 X.07 Difenoconazole 1:1 2:2 X.07 Cyproconazole 1:1 6:6 X.07 Cyproconazole 3:1 6:2 X.07 Cyproconazole 1:3 2:6 X.07 Cyproconazole 1:1 2:2 X.07 Tebuconazole 1:1 6:6 X.07 Tebuconazole 3:1 6:2 X.07 Tebuconazole 1:3 2:6 X.07 Tebuconazole 1:1 2:2 X.07 Mefentrifluconazole 1:1 6:6 X.07 Mefentrifluconazole 3:1 6:2 X.07 Mefentrifluconazole 1:3 2:6 X.07 Mefentrifluconazole 1:1 2:2 X.07 Hexaconazole 1:1 6:6 X.07 Hexaconazole 3:1 6:2 X.07 Hexaconazole 1:3 2:6 X.07 Hexaconazole 1:1 2:2 X.07 Prothioconazole 1:1 6:6 X.07 Prothioconazole 3:1 6:2 X.07 Prothioconazole 1:3 2:6 X.07 Prothioconazole 1:1 2:2 X.07 Azoxystrobin 1:1 6:6 X.07 Azoxystrobin 3:1 6:2 X.07 Azoxystrobin 1:3 2:6 X.07 Azoxystrobin 1:1 2:2 X.07 Trifloxystrobin 1:1 6:6 X.07 Trifloxystrobin 3:1 6:2 X.07 Trifloxystrobin 1:3 2:6 X.07 Trifloxystrobin 1:1 2:2 X.07 Picoxystrobin 1:1 6:6 X.07 Picoxystrobin 3:1 6:2 X.07 Picoxystrobin 1:3 2:6 X.07 Picoxystrobin 1:1 2:2 X.07 Pyraclostrobin 1:1 6:6 X.07 Pyraclostrobin 3:1 6:2 X.07 Pyraclostrobin 1:3 2:6 X.07 Pyraclostrobin 1:1 2:2 X.07 Metalaxyl-M 1:1 6:6 X.07 Metalaxyl-M 3:1 6:2 X.07 Metalaxyl-M 1:3 2:6 X.07 Metalaxyl-M 1:1 2:2 X.07 Fenpropidin 3:1 6:2 X.07 Fenpropidin 10:1 6:0.6 X.07 Fenpropidin 1:1 2:2 X.07 Fenpropidin 3.3:1 2:0.6 X.07 Fenpropimorph 3:1 6:2 X.07 Fenpropimorph 10:1 6:0.6 X.07 Fenpropimorph 1:1 2:2 X.07 Fenpropimorph 3.3:1 2:0.6 X.07 Mancozeb 1:1 6:6 X.07 Mancozeb 3:1 6:2 X.07 Mancozeb 1:3 2:6 X.07 Mancozeb 1:1 2:2 X.07 Chlorothalonil 1:1 6:6 X.07 Chlorothalonil 3:1 6:2 X.07 Chlorothalonil 1:3 2:6 X.07 Chlorothalonil 1:1 2:2 X.07 Oxathiapiprolin 1:1 6:6 X.07 Oxathiapiprolin 3:1 6:2 X.07 Oxathiapiprolin 1:3 2:6 X.07 Oxathiapiprolin 1:1 2:2 X.07 Mandipropamid 1:1 6:6 X.07 Mandipropamid 3:1 6:2 X.07 Mandipropamid 1:3 2:6 X.07 Mandipropamid 1:1 2:2 X.07 (N-[5-bromo-2-methyl- 1:1 6:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 3:1 6:2 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:3 2:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:1 2:2 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 fosetyl-aluminium 1:1 6:6 X.07 fosetyl-aluminium 3:1 6:2 X.07 fosetyl-aluminium 1:3 2:6 X.07 fosetyl-aluminium 1:1 2:2 X.07 Trinexapac-ethyl 1:1 6:6 X.07 Trinexapac-ethyl 3:1 6:2 X.07 Trinexapac-ethyl 1:3 2:6 X.07 Trinexapac-ethyl 1:1 2:2 X.07 Acibenzolar-S-methyl 1:1 6:6 X.07 Acibenzolar-S-methyl 3:1 6:2 X.07 Acibenzolar-S-methyl 1:3 2:6 X.07 Acibenzolar-S-methyl 1:1 2:2 X.07 Glyphosate 3:1 6:2 X.07 Glyphosate 10:1 6:0.6 X.07 Glyphosate 1:1 2:2 X.07 Glyphosate 3.3:1 2:0.6 X.07 2,4-D 3:1 6:2 X.07 2,4-D 10:1 6:0.6 X.07 2,4-D 1:1 2:2 X.07 2,4-D 3.3:1 2:0.6 X.07 Timorex Gold 3:1 6:2 X.07 Timorex Gold 10:1 6:0.6 X.07 Timorex Gold 1:3 2:6 X.07 Timorex Gold 1:1 2:2 X.07 Thiamethoxam 1:1 6:6 X.07 Thiamethoxam 3:1 6:2 X.07 Thiamethoxam 1:3 2:6 X.07 Thiamethoxam 1:1 2:2

Example B4a

Puccinia recondita/Wheat/Preventive (Brown Rust on Wheat)

[0411] 13-day old wheat plants cv. Arina were treated with the formulated test compounds in a spray chamber. One day after application wheat plants were inoculated by spraying a spore suspension (110.sup.5 uredospores/ml) on the test plants. After an incubation period of 1 day at 20 C. and 95% r. h. plants were kept for 10 days 20 C./18 C. (day/night) and 60% r.h. in a greenhouse. The percentage leaf area covered by disease was assessed 11 days after inoculation.

[0412] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test.

TABLE-US-00019 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.03 Benzovindiflupyr 1000:1 60:0.06 X.03 Benzovindiflupyr 3000:1 60:0.02 X.03 Benzovindiflupyr 333.33:1 20:0.06 X.03 Benzovindiflupyr 1000:1 20:0.02 X.03 Pydiflumetofen 10:1 60:6 X.03 Azoxystrobin 1000:1 60:0.06 X.03 Azoxystrobin 3000:1 60:0.02 X.03 Cyproconazole 100:1 60:0.6 X.03 Cyproconazole 300:1 60:0.2 X.03 Isopyrazam 10:1 60:6 X.03 Isopyrazam 30:1 60:2 X.03 Isopyrazam 3.3:1 20:6 X.03 Isopyrazam 10:1 20:2 X.03 Penthiopyrad 10:1 60:6 X.03 Penthiopyrad 30:1 60:2 X.03 Penthiopyrad 3.3:1 20:6 X.03 Pyraclostrobin 100:1 60:0.6 X.03 Pyraclostrobin 300:1 60:0.2 X.03 Pyraclostrobin 33.33:1 20:0.6 X.03 Difenoconazole 10:1 60:6 X.03 Difenoconazole 30:1 60:2 X.03 Difenoconazole 3.3:1 20:6 X.03 Difenoconazole 10:1 20:2 X.03 Hexaconazole 10:1 60:6 X.03 Hexaconazole 30:1 60:2 X.03 Mefentrifluconazole 10:1 60:6 X.03 Mefentrifluconazole 30:1 60:2 X.03 Mefentrifluconazole 3.3:1 20:6 X.03 Mefentrifluconazole 10:1 20:2 X.03 Chlorothalonil 1:1 60:60 X.03 Chlorothalonil 3:1 60:20 X.03 Chlorothalonil 1:3 20:60 X.03 Mancozeb 1:1 60:60 X.03 Mancozeb 3:1 60:20 X.03 Mancozeb 1:3 20:60 X.03 Acibenzolar-S-methyl 1:3.3 60:200

Example B4b

Puccinia recondita/Wheat/Preventive (Brown Rust on Wheat)

[0413] Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19 C. and 75% relative humidity under a light regime of 12 hours light/12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 to 9 days after application).

[0414] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

TABLE-US-00020 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.07 Benzovindiflupyr 10:1 60:6 X.07 Benzovindiflupyr 30:1 60:2 X.07 Benzovindiflupyr 3.3:1 20:6 X.07 Benzovindiflupyr 10:1 20:2 X.07 Fluxapyroxad 3:1 60:20 X.07 Fluxapyroxad 10:1 60:6 X.07 Fluxapyroxad 1:1 20:20 X.07 Fluxapyroxad 3.3:1 20:6 X.07 Pydiflumetofen 1:1 60:60 X.07 Pydiflumetofen 3:1 60:20 X.07 Pydiflumetofen 1:3 20:60 X.07 Pydiflumetofen 1:1 20:20 X.07 Fluopyram 3:1 60:20 X.07 Fluopyram 10:1 60:6 X.07 Fluopyram 1:1 20:20 X.07 Fluopyram 3.3:1 20:6 X.07 Difenoconazole 1:1 60:60 X.07 Difenoconazole 3:1 60:20 X.07 Difenoconazole 1:3 20:60 X.07 Difenoconazole 1:1 20:20 X.07 Cyproconazole 1:1 60:60 X.07 Cyproconazole 3:1 60:20 X.07 Cyproconazole 1:3 20:60 X.07 Cyproconazole 1:1 20:20 X.07 Tebuconazole 1:1 60:60 X.07 Tebuconazole 3:1 60:20 X.07 Tebuconazole 1:3 20:60 X.07 Tebuconazole 1:1 20:20 X.07 Mefentrifluconazole 1:1 60:60 X.07 Mefentrifluconazole 3:1 60:20 X.07 Mefentrifluconazole 1:3 20:60 X.07 Mefentrifluconazole 1:1 20:20 X.07 Hexaconazole 1:1 60:60 X.07 Hexaconazole 3:1 60:20 X.07 Hexaconazole 1:3 20:60 X.07 Hexaconazole 1:1 20:20 X.07 Prothioconazole 1:1 60:60 X.07 Prothioconazole 3:1 60:20 X.07 Prothioconazole 1:3 20:60 X.07 Prothioconazole 1:1 20:20 X.07 Azoxystrobin 1:1 60:60 X.07 Azoxystrobin 3:1 60:20 X.07 Azoxystrobin 1:3 20:60 X.07 Azoxystrobin 1:1 20:20 X.07 Trifloxystrobin 1:1 60:60 X.07 Trifloxystrobin 3:1 60:20 X.07 Trifloxystrobin 1:3 20:60 X.07 Trifloxystrobin 1:1 20:20 X.07 Picoxystrobin 1:1 60:60 X.07 Picoxystrobin 3:1 60:20 X.07 Picoxystrobin 1:3 20:60 X.07 Picoxystrobin 1:1 20:20 X.07 Pyraclostrobin 1:1 60:60 X.07 Pyraclostrobin 3:1 60:20 X.07 Pyraclostrobin 1:3 20:60 X.07 Pyraclostrobin 1:1 20:20 X.07 Metalaxyl-M 1:1 60:60 X.07 Metalaxyl-M 3:1 60:20 X.07 Fenpropidin 3:1 60:20 X.07 Fenpropidin 10:1 60:6 X.07 Fenpropidin 1:1 20:20 X.07 Fenpropidin 3.3:1 20:6 X.07 Fenpropimorph 3:1 60:20 X.07 Fenpropimorph 10:1 60:6 X.07 Fenpropimorph 1:1 20:20 X.07 Mancozeb 1:1 60:60 X.07 Mancozeb 3:1 60:20 X.07 Mancozeb 1:3 20:60 X.07 Mancozeb 1:1 20:20 X.07 Chlorothalonil 1:1 60:60 X.07 Chlorothalonil 3:1 60:20 X.07 Oxathiopiprolin 1:1 60:60 X.07 Oxathiopiprolin 3:1 60:20 X.07 Oxathiopiprolin 1:3 20:60 X.07 Mandipropamid 1:1 60:60 X.07 Mandipropamid 3:1 60:20 X.07 (N-[5-bromo-2-methyl- 1:1 60:60 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 3:1 60:20 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:3 20:60 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:1 20:20 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 fosetyl-aluminium 1:1 60:60 X.07 fosetyl-aluminium 3:1 60:20 X.07 fosetyl-aluminium 1:3 20:60 X.07 Trinexapac-ethyl 1:1 60:60 X.07 Trinexapac-ethyl 3:1 60:20 X.07 Acibenzolar-S-methyl 1:1 60:60 X.07 Acibenzolar-S-methyl 3:1 60:20 X.07 Acibenzolar-S-methyl 1:3 20:60 X.07 Acibenzolar-S-methyl 1:1 20:20 X.07 Glyphosate 3:1 60:20 X.07 Glyphosate 10:1 60:6 X.07 Glyphosate 1:1 20:20 X.07 Glyphosate 3.3:1 20:6 X.07 2,4-D 3:1 60:20 X.07 2,4-D 10:1 60:6 X.07 2,4-D 1:1 20:20 X.07 Timorex Gold 3:1 60:20 X.07 Timorex Gold 10:1 60:6 X.07 Thiamethoxam 1:1 60:60 X.07 Thiamethoxam 3:1 60:20 X.07 Thiamethoxam 1:3 20:60