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): ##STR00135## wherein R.sup.1=hydrogen or fluoro; R.sup.2=hydrogen or fluoro; R.sup.3=methyl, ethyl, iso-propyl, methoxy, ethoxy, methoxyethyl, 2,2,2-trifluoroethyl or cyclopropyl; ZR.sup.4 or R.sup.5, wherein R.sup.4=ethyl, iso-propyl, 2-propen-2-yl (H.sub.2CC(CH.sub.3)), 3-butyn-1-yl (HCCCH.sub.2CH.sub.2), methoxymethyl, 1-methoxyethyl, (difluromethoxy)methyl, 2,2,2-trifluoroethyl, cyclopropyl, 2,2-difluorocyclopropyl, tetrahydrofuran-2-yl; and R.sup.5NR.sup.6R.sup.7, wherein R.sup.6=hydrogen or methyl; and R.sup.7=methyl, iso-propyl, methoxy, ethoxy, allyl (H.sub.2CCHCH.sub.2), propargyl (HCCCH.sub.2), 2,2,2-trifluoroethyl, cyclopropyl or (cyclopropyl)methyl, or salt 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: N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (compound X.01), N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pent-4-ynamide (compound X.02), N-methoxy-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]prop-2-enamide (compound X.03), N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (compound X.04), N-cyclopropyl-3,3,3-trifluoro-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (compound X.05), 2,2-difluoro-N-(2-methoxyethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclo propanecarboxamide (compound X.06), N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (compound X.07), N-[[3-floro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-propanamide (compound X.08), 2-methoxy-N-(2,2,2-trifluoroethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl] acetamide (compound X.09), N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-cyclopropane carboxamide (compound X.10), 2-(difluoromethoxy)-N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide (compound X.11), N-ethoxy-2-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (compound X.12), N-isopropyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]tetrahydrofuran-2-carboxamide (compound X.13), 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.14), 3-cyclopropyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.15), 3-ethoxy-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.16), 3-allyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.17), 1-cyclopropyl-3-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.18), 3-isopropyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.19), 1-methoxy-3-prop-2-ynyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.20), 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1-methoxy-3-methyl-urea (compound X.21), 3-(cyclopropylmethyl)-1-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.22), 1-ethyl-3-(2,2,2-trifluoroethyl)-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.23); 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.24); or a salt, enantiomer, tautomer or N-oxide thereof.

3. A fungicidal composition according to claim 1, wherein component (A) is: N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (compound X.01), or N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (compound X.04), or N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (compound X.07) or 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.14); or 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.24), or a salt, enantiomer, tautomer or N-oxide thereof.

4. A fungicidal composition according to claim 1, wherein component (A) is: N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (compound X.01), or 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (compound X.14); or a salt, enantiomer, tautomer or N-oxide thereof.

5. 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.

6. 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.

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

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

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

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

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

12. A fungicidal composition according to claim 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, 5 S)-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 bactericides 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.

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

14. 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.

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

Description

EXAMPLES

[0285] The Examples which follow serve to illustrate the invention. 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).

[0286] 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 and B) is as follows:

The Description of the LC/MS Apparatus and the Method A is:

[0287] SQ Detector 2 from Waters [0288] Ionisation method: Electrospray [0289] Polarity: positive and negative ions [0290] 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 [0291] Mass range: 100 to 900 Da [0292] DAD Wavelength range (nm): 210 to 500
Method Waters ACQUITY UPLC with the Following HPLC Gradient Conditions:

(Solvent A: Water/Methanol 20:1+0.05% Formic Acid and Solvent B: Acetonitrile+0.05% Formic Acid)

[0293]

TABLE-US-00002 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
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.

The Description of the LC/MS Apparatus and the Method B is:

[0294] SQ Detector 2 from Waters [0295] Ionisation method: Electrospray [0296] Polarity: positive ions

[0297] 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 [0298] Mass range: 140 to 800 Da [0299] DAD Wavelength range (nm): 210 to 400
Method Waters ACQUITY UPLC with the Following HPLC Gradient Conditions

(Solvent A: Water/Methanol 9:1+0.1% Formic Acid and Solvent B: Acetonitrile+0.1% Formic Acid)

[0300]

TABLE-US-00003 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.

[0301] 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.

A Representative Description of a Chiral Analysis Apparatus is:

[0302] Supercritical Fluid Chromatography: [0303] Waters Acquity UPC.sup.2/QDa [0304] PDA Detector Waters Acquity UPC.sup.2 [0305] Column: Daicel SFC CHIRALPAK IC, 3 m, 0.3 cm10 cm, 40 C. [0306] Mobile phase: A: CO.sub.2 B: iPr gradient: 05% B in 3.8 min [0307] ABPR: 1800 psi [0308] Flow rate: 2.0 mL/min [0309] Detection: 247 nm [0310] Sample concentration: 1 mg/mL in Acetonitril/iPrpanol 50/50 [0311] Injection: 1 L

FORMULATION EXAMPLES

[0312]

TABLE-US-00004 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-00005 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%

[0313] 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-00006 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-00007 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-00008 Extruder granules 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-00009 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-00010 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-00011 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% solution in 0.5%.sup. water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%.sup. 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

[0314] 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

[0315] AIBN=azobisisobutyronitrile [0316] BOP-Cl=phosphoric acid bis(2-oxooxazolidide) chloride [0317] CDI=carbonyl diimidazole [0318] DCE=1,2-dichloroethane [0319] DCM=dichloromethane [0320] DIPEA=N,N-diisopropylethylamine [0321] DMA=dimethylacetamide [0322] DMF=dimethylformamide [0323] EdCl=3-(ethyliminomethyleneamino)-N,N-dimethylpropan-1-amine [0324] EtOAc=ethyl acetate [0325] EtOH=ethyl alcohol [0326] HCl=hydrochloric acid [0327] HOAt=1-hydroxy-7-azabenzotriazole [0328] HATU=1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid-hexafluorophosphate [0329] mp=melting point [0330] MeOH=methyl alcohol [0331] NaOH=sodium hydroxide [0332] NBS=N-bromosuccinimide [0333] rh=relative humidity [0334] TFAA=trifluoroacetic acid anhydride

[0335] THF=tetrahydrofuran

PREPARATION EXAMPLES

[0336] The below 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, as are the syntheses of closely-related compounds described in accordance with the present invention.

##STR00062##

[0337] 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/).

[0338] Using the synthetic techniques described both above and below, compounds of formula (I) may be prepared accordingly.

Example 1

[0339] This example illustrates the preparation of 2-(difluoromethoxy)-N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide (Compound X.11 of Table T1)

##STR00063##

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

[0340] ##STR00064##

[0341] To a suspension of 4-methylbenzonitrile (35 g, 0.29 mol) in ethanol (220 mL) and water (440 mL) was added at room temperature 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, then cooled to room temperature, and diluted with 2N HCl until pH 8. The volatiles were removed under reduced pressure and the reaction contents were filtered, washed with water, and dried under vacuum to afford 39.1 g of 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

[0342] ##STR00065##

[0343] To a solution of N-hydroxy-4-methyl-benzamidine (38.7 g, 0.25 mol) in 2-methyltetrahydrofuran (750 mL) was added TFAA at 0 C. The reaction mixture was stirred at 15 C. for two hours then diluted with water. The organic layer was separated, washed successively with a saturated aqueous sodium bicarbonate solution, a saturated aqueous ammonium chloride solution, and water then dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude residue was purified by flash chromatography over silica gel (heptane/EtOAc eluent gradient 99:1 to 90:10) to afford 54.1 g of the title compound as clear oil, which solidified after storage. LC/MS (Method A) retention time=1.15 minutes, mass not detected.

[0344] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.00 (d, 2H), 7.32 (d, 2H), 2.45 (s, 3H).

[0345] .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

[0346] ##STR00066##

[0347] 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. AIBN (4.03 g, 24 mmol) was added and the reaction mixture was stirred at 65 C. for 18 hours. The mixture was then cooled to room temperature and diluted with dichloromethane and water. The layers were separated and the 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 (cyclohehane/EtOAc eluent gradient 100:0 to 95:5) to afford 44.7 g of the title compound as a white solid. mp: 58-63 C.

[0348] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.11 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).

[0349] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.32 (s).

[0350] 3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole was isolated as by-product as white solid. mp: 61-66 C.

[0351] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.15 (d, 2H), 7.73 (d, 2H), 6.68 (s, 1H).

[0352] .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

[0353] ##STR00067##

[0354] 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, aqueous 1M HCl was added, and volatiles were removed under reduced pressure. The resultant white slurry was extracted with dichloromethane and the total combined organic layer was 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 9:1) to afford 7.10 g of the title compound as a white solid. mp: 58-63 C.

[0355] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.11 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).

[0356] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.32 (s).

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

[0357] ##STR00068##

[0358] A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (15 g, 46.9 mmol) in THF (20 mL) was added dropwise at room temperature to a solution of methylamine (2M in THF, 120 mL, 234.5 mmol) and stirred at room temperature for 24 hours. The solvent was removed under reduced pressure and the resultant crude material was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to give 10.3 g of the title compound as a clear oil. LC/MS (Method A) retention time=0.58 minutes, 258 (M+H).

[0359] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.08 (d, 2H), 7.47 (d, 2H), 3.84 (s, 2H), 2.48 (s, 3H).

[0360] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.39 (s).

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

[0361] ##STR00069##

[0362] To a suspension of N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]methanamine (0.50 g, 1.94 mmol) in DMF (7.8 mL) under nitrogen atmosphere was added DIPEA (1.0 mL, 5.83 mmol) followed by 2-hydroxy acetic acid (0.22 g, 2.92 mmol), HATU (1.1 g, 2.92 mmol). After the reaction stirred overnight, the contents were diluted with an aqueous saturated sodium bicarbonate solution and extracted with ethyl acetate. The total combined organic layer was dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 95:5 to 9:1) to afford 442 mg of the title compound as a clear oil. LC/MS (Method A) retention time=0.90 minutes, 316 (M+H).

[0363] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.34 (s).

Step 6: Preparation of 2-(difluoromethoxy)-N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide

[0364] 2-hydroxy-N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide (442 mg, 1.40 mmol) was suspended in dry acetonitrile (3.4 mL, dried over 2 molecular sieves) and CuI (0.07 g, 0.34 mmol) was introduced. The contents were heated at 45 C. and 2,2-difluoro-2-fluorosulfonyl-acetic acid (0.20 mL, 1.89 mmol) in acetonitrile (2 mL) was introduced via syringe pump over 40 minutes. The reaction mixture was heated for 30 minutes, cooled to room temperature, quenched with water (30 mL), and extracted with ethyl acetate. The total combined organic layer was washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to give 22 mg of the title compound as a clear oil. LC/MS (Method A) retention time=1.02 minutes, 366 (M+H).

[0365] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.12 (m, 2H), 7.40 (m, 2H), 6.44 (t, 1H), 4.69 (m, 2H), 4.58 (m, 2H), 2.96 (m, 3H).

[0366] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.34 (s), 85.92 (s).

Example 2

[0367] This example illustrates the preparation of 1-cyclopropyl-3-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (Compound X.18 of Table X)

##STR00070##

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

[0368] ##STR00071##

[0369] A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (2.50 g, 8.1 mmol) in dichloromethane (5 mL) was added over 2 hours at room temperature to a solution of cyclopropanamine (3.7 g, 65 mmol) and N-ethyl-N-isopropyl-propan-2-amine (1.4 mL, 8.1 mmol) in dichloromethane (10 mL). The mixture was stirred at room temperature for 30 minutes, poured into water and then extracted with dichloromethane. The total combined organic layer was washed with brine, 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 1:0 to 1:1) to give 1.18 g of the title compound as a white solid, LC/MS (Method A) retention time=0.71 minutes, 300 (M+H).

[0370] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.06 (d, 2H), 7.49 (d, 2H), 3.92 (s, 2H), 2.18 (m, 1H), 1.85 (brs, 1H), 0.42 (m, 2H), 0.39 (m, 2H).

[0371] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.36 (s).

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

[0372] To a stirred suspension of N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanamine (0.15 g, 0.53 mmol) in dichloromethane (3 mL) at 0 C. was added triethylamine (0.15 mL, 1.06 mmol) followed by N-methoxy-N-methylcarbamoyl chloride (0.07 g, 0.58 mmol). After 4 hours, the reaction mixture volatiles were removed under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 95:5 to 9:1) to afford 183 mg of the desired product as a light yellow oil. LC/MS (Method A) retention time=1.10 minutes, 371 (M+H).

[0373] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.08 (d, 2H), 7.44 (d, 2H), 4.62 (s, 2H), 3.68 (s, 3H), 3.08 (s, 3H), 2.68 (m, 1H), 0.74 (m, 4H).

Example 3

[0374] This example illustrates the preparation of 2-methoxy-N-(2,2,2-trifluoroethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide (Compound X.09 of Table X)

##STR00072##

Step 1: Preparation of the intermediate 2,2,2-trifluoro-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]ethanamine

[0375] ##STR00073##

[0376] To a solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (1.5 g, 4.69 mmol) in dichloromethane (10 mL) was introduced dropwise DIPEA (0.82 mL, 4.69 mmol) followed by 2,2,2-trifluoroethanamine (2.94 mL, 37.5 mmol). The reaction mixture was stirred at room temperature for 24 hours then poured into water and extracted with dichloromethane. 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 1:0 to 0:1) to give 1.53 g of the title compound as a clear oil.

[0377] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (d, 2H), 7.51 (d, 2H), 4.00 (s, 2H), 3.22 (q, 2H), 1.71 (s, 1H).

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

[0378] To a suspension of 2,2,2-trifluoro-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]ethanamine (0.1 g, 0.31 mmol) in dichloromethane (6 mL) at 0 C. was added triethylamine (0.09 mL, 0.62 mmol) followed by 2-methoxyacetyl chloride (0.03 mL, 0.32 mmol). The reaction mixture stirred overnight, was reduced under reduced pressure, and the resultant crude residue was subjected to flash chromatography over silica gel (heptane/EtOAc eluent gradient 9:1 to 1:9) to afford 116 mg of the desired product as a white solid mp: 92-95 C. LC/MS (Method A) retention time=1.08 minutes, 398 (M+H).

[0379] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.12 (m, 2H), 7.36 (m, 2H), 4.82 (s, 2H), 4.08 (m, 2H), 3.98 (m, 2H), 3.45 (s, 3H).

Example 4

[0380] This example illustrates the preparation of intermediate N-propoxy-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine

##STR00074##

[0381] A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (1.30 g, 4.06 mmol) in dichloromethane (10 mL) was added dropwise to a solution of O-propylhydroxylamine hydrochloride (3.74 g, 32.5 mmol) and DIPEA (6.40 mL, 36.6 mmol) in dichloromethane (6 mL). The reaction mixture was stirred at room temperature for 24 hours then poured onto water and the layers were separated. The aqueous layer was extracted with dichloromethane and the total combined organic layer was washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to give 0.92 g of the title compound as a clear oil. LC/MS (Method A) retention time=1.12 minutes, 302 (M+H).

[0382] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (d, 2H), 7.02 (d, 2H), 5.70 (sbr, 1H), 4.11 (s, 2H), 3.59 (m, 2H), 1.52 (m, 2H), 0.86 (s, 3H).

[0383] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.33 (s).

Example 5

[0384] This example illustrates the preparation 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1-methoxy-3-methyl-urea (Compound X.21 of Table X)

##STR00075##

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

[0385] ##STR00076##

[0386] 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 the reaction mixture was heated at 80 C. for 2 hours. After cooling to room temperature the volatiles were removed under reduced pressure thus affording a white solid that was used in the next transformation without additional purification. LC/MS (Method A) retention time=1.14 minutes, 169.2 (M+H).

[0387] 1H NMR (400 MHz, CDCl.sub.3) ppm: 7.96 (t, 1H), 7.11 (m, 2H), 2.45 (s, 3H).

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

[0388] ##STR00077##

[0389] To a solution of 2-fluoro-N-hydroxy-4-methyl-benzamidine (37 mmol) in tetrahydrofuran (122 mL) cooled via an ice bath was added TFAA (7.71 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, and water then 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).

[0390] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.00 (d, 1H), 7.32 (d, 2H), 2.45 (s, 3H).

[0391] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.3 (s), 108.1 (s).

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

[0392] ##STR00078##

[0393] 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. AIBN (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 removed via filtration and the solvent was removed under reduced pressure to afford a brown gum. This residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc 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.

[0394] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (t, 1H), 7.34 (m, 2H), 4.49 (s, 2H).

[0395] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.18 (s), 106.2 (s).

[0396] 3-[4-(dibromomethyl)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.

[0397] 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 33-[4-(dibromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole

[0398] ##STR00079##

[0399] 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) at 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 aqueous 1M HCl were added. Volatiles were removed under reduced pressure and the resultant white slurry was extracted with dichloromethane. The total 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. LC/MS (Method A) retention time=1.13 minutes, (M+H) not detected.

[0400] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (t, 1H), 7.34 (m, 2H), 4.49 (s, 2H).

[0401] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.18 (s), 106.2 (s).

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

[0402] ##STR00080##

[0403] To a solution of O-methylhydroxylamine hydrochloride (4.9 g, 59 mmol) in dichloromethane (15 mL) was introduced dropwise DIPEA (12 mL, 66 mmol) followed by a solution of 3-[4-(bromomethyl)-2-fluorophenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (1.2 g, 3.7 mmol) in dichloromethane (5 mL). After 18 hours, water was introduced (10 mL) and the reaction contents were extracted twice with dichloromethane and the total combined organic layer was dried over sodium sulfate then filtered. The resultant residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to afford 410 mg of the title compound as a colorless oil LC/MS (Method A) retention time=1.01 minutes, (M+H) not detected.

[0404] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.05 (t, 1H), 7.45 (m, 2H), 5.85 (brs, 1H), 4.12 (s, 2H), 3.50 (s, 3H).

[0405] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.21 (s), 107.33 (s).

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

[0406] To a solution of 1-[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-N-methoxy-methanamine (20 mg, 0.07 mmol) in dichloromethane (0.23 mL) was added N-methylcarbamoyl chloride (0.012 g, 0.14 mmol) and triethylamine (0.02 mL, 0.13 mmol). After 1 hour, the reaction mixture was concentrated under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 1:1) to provide 12 mg of the desired product as a gum. LC/MS (Method A) retention time=0.97 minutes, 349 (M+H).

[0407] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.04 (t, 1H), 7.31 (m, 2H), 5.81 (m, 1H), 4.71 (s, 2H), 3.60 (s, 3H), 2.87 (d, 3H).

[0408] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.17 (s), 107.10 (s).

Example 6

[0409] This example illustrates the preparation of N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-cyclopropanecarboxamide (Compound X.10 of Table X)

##STR00081##

Step 1: Preparation of 2,3-difluoro-N-hydroxy-4-methyl-benzamidine

[0410] ##STR00082##

[0411] To a suspension of 2,3-difluoro-4-methylbenzonitrile (5.0 g, 32.6 mmol) in ethanol (111 mL) at 25 C. was added hydroxylamine hydrochloride (4.5 g, 65.3 mmol). The reaction mixture was heated at 80 C. for 2 hours. After cooling to room temperature, the volatiles were removed under reduced pressure thus affording a white solid that was used in the next transformation without purification.

[0412] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.30 (m, 1H), 6.95 (m, 1H), 6.50 (brs, 1H), 5.05 (brs, 2H), 2.30 (s, 3H).

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

[0413] ##STR00083##

[0414] To a solution of 2,3-difluoro-N-hydroxy-4-methyl-benzamidine (2.6 mmol) in tetrahydrofuran (108 mL) cooled via an ice bath was added TFAA (6.9 mL, 49 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, and water then dried over sodium sulfate, filtered, and concentrated under reduced pressure. The title compound (6.6 g) was isolated as a light brown solid that was used in the next transformation without further purification. LC/MS (Method A) retention time=1.16 minutes, 265 (M+H).

[0415] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.76 (d, 1H), 7.12 (d, 1H), 2.41 (s, 3H).

[0416] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.41 (s), 133.3 (s), 140.1 (s).

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

[0417] ##STR00084##

[0418] A mixture of 3-(2,3-difluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1,2,4-oxadiazole (6.0 g, 22.6 mmol) and NBS (7.17 g, 10.0 mmol) in tetrachloromethane (79 mL) under argon was heated to 70 C. AIBN (0.68 g, 3.95 mmol) was added and the reaction mixture stirred at 65 C. for 36 hours. The mixture was cooled to 25 C., diluted with dichloromethane, water, and the layers were separated. The succinimide by-product was removed via filtration and volatiles were removed under reduced pressure. The resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 100:0 to 4:1) to afford 4.8 g of the title compound as a white solid. LC/MS (Method A) retention time=1.16 minutes, 344 (M+H).

[0419] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.80 (m, 1H), 7.37 (m, 1H), 4.55 (s, 2H).

[0420] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.1 (s), 131.2 (s), 139.1 (s).

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

[0421] ##STR00085##

[0422] A solution of O-methylhydroxylamine hydrochloride (3.5 g, 42 mmol) in dichloromethane (8 mL) was treated dropwise with DIPEA (8.3 mL, 47 mmol) followed by a solution of 3-[4-(bromomethyl)-2,3-difluoro-phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (2.0 g, 5.2 mmol) in dichloromethane (5 mL). After 18 hours, water was introduced (10 mL), the reaction contents were extracted twice with dichloromethane, and the total combined organic layer was dried over sodium sulfate and filtered. The resultant residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to afford 1.10 g of the title compound as a pale yellow oil. LC/MS (Method A) retention time=1.03 minutes, 310 (M+H).

[0423] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.84 (t, 1H), 7.38 (t, 1H), 5.87 (brs, 1H), 4.20 (s, 2H), 3.52 (s, 3H).

[0424] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.21 (s), 132.53 (s), 147.50 (s).

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

[0425] To a solution of 1-[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-N-methoxy-methanamine (0.18 g, 0.58 mmol) in dichloromethane (2.9 mL) was added cyclopropanecarbonyl chloride (0.06 mL, 0.61 mmol) followed by triethylamine (0.16 mL, 1.16 mmol). After 1 hour, the reaction mixture was concentrated under reduced pressure and the crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 1:1) to provide 207 mg of the title compound as a gum. LC/MS (Method A) retention time=1.11 minutes, 378 (M+H).

Example 7a

[0426] This example illustrates the preparation of N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (Compound X.07 of Table X)

##STR00086##

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

[0427] ##STR00087##

[0428] A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (1.50 g, 4.69 mmol) in dichloromethane (9.4 mL) was added dropwise at room temperature to a solution of ethylamine 2M in MeOH (12 mL, 24.0 mmol). The mixture was stirred at room temperature for 24 hours then poured into water and the layers were separated. The aqueous layer was extracted with dichloromethane and the total combined organic layer was washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to give 0.92 g of the title compound as a white solid mp: 102-112 C., LC/MS (Method A) retention time=0.66 minutes, 272 (M+H).

[0429] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.01 (d, 2H), 7.57 (d, 2H), 3.86 (q, 2H), 3.29 (brs, 1H), 2.53 (q, 2H), 1.05 (t, 3H).

[0430] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 64.77 (s).

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

[0431] To a suspension of N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]ethanamine (4.8 g, 18 mmol) in dichloromethane (58 mL) at 0 C. was added triethylamine (4.9 mL, 35 mmol) followed by 2-methylpropanoyl chloride (2.0 mL, 19 mmol). The reaction mixture stirred for 1 hour, then a saturated aqueous ammonia chloride solution was introduced followed by extraction with ethyl acetate. 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 subjected to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 9:1 to 1:9) to afford 5.1 g of the desired product as an orange oil. LC/MS (Method A) retention time=1.11 minutes, 342.6 (M+H).

[0432] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.07 (m, 2H), 7.36 (m, 2H), 4.66 (m, 2H), 3.36 (m, 2H), 2.87 (m, 1H), 1.15 (m, 9H).

[0433] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 64.36 (s).

Example 7b

[0434] This example illustrates an alternative preparation of N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (Compound X.07 of Table X)

Step 1: Preparation of 4-(ethylaminomethyl)benzonitrile

[0435] ##STR00088##

[0436] To a solution of 4-(chloromethyl)benzonitrile (3.0 g, 19.4 mmol) in tetrahydrofuran (30 mL) heated at 40 C. was added a 70% aqueous ethylamine solution (4 equiv., 77.6 mmol) and the reaction was heated at 40 C. for 16 hours. Upon cooling to 25 C., the reaction contents were diluted with water (25 mL) and tert-butyl methyl ether (50 mL) and the layers were separated. The aqueous layer was extracted with tert-butyl methyl ether and the total combined organic fraction was washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure to give 3.05 g of the title compound as a yellow gum that was used in the next transformation without further purification.

[0437] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.61 (d, 2H), 7.42 (d, 2H), 3.85 (s, 2H), 2.53 (q, 2H), 1.13 (t, 3H).

Step 2: Preparation of N-[(4-cyanophenyl)methyl]-N-ethyl-2-methyl-propanamide

[0438] ##STR00089##

[0439] To a suspension of 4-(ethylaminomethyl)benzonitrile (2.0 g, 11.2 mmol) in toluene (13 mL) at 0 C. was added sodium hydroxide (0.50 g, 12.3 mmol) as a water solution (6.6 mL) followed by 2-methylpropanoyl chloride (1.38 g, 12.3 mmol). The ice bath was removed and the reaction mixture stirred for 24 hours. After, the reaction contents were diluted water (100 mL) and tert-butyl methyl ether (100 mL) then the layers were separated. The aqueous layer was extracted with tert-butyl methyl ether and the total combined organic fraction was dried over sodium sulfate and filtered. The solvent was removed under reduced pressure to afford 2.65 g of the desired product as an orange oil that was used in the next transformation without further purification.

[0440] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.58 (m, 2H), 7.30 (m, 2H), 4.61 (m, 2H), 3.49 (m, 2H), 2.85 (m, 1H), 1.17 (m, 9H).

[0441] Step 3: Preparation of N-ethyl-N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-2-methyl-propanamide

##STR00090##

[0442] To a solution of N-[(4-cyanophenyl)methyl]-N-ethyl-2-methyl-propanamide (2.80 g, 11 mmol) and ethanol (28 mL) was introduced a 50% aqueous hydroxylamine solution (1.5 equiv., 17 mmol). After 18 hours, the reaction contents were concentrated under reduced pressure and dried under vacuum. Water (10 mL) was introduced and the contents were stirred for 15 minutes. The resultant white solid was filtered and dried under vacuum to afford 2.52 mg of the title compound as a white solid that was used in the next transformation without further purification.

[0443] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm: 9.60 (sbr, 1H), 7.63 (m, 2H), 7.17 (m, 2H), 4.55 (m, 2H), 3.31 (m, 1H), 3.27 (m, 2H), 1.07 (m, 9H).

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

[0444] A 30 mL Schlenk tube, connected to trap-1 (empty) followed by trap-2 (filled with an 4N NaOH aqueous solution), was charged with N-ethyl-N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-2-methyl-propanamide (2.00 g, 7.22 mmol), ethyl acetate (20 mL), and pyridine (0.88 mL, 10.8 mmol). The contents were stirred for 10 minutes, then to the resultant white suspension was introduced 2,2,2-trifluoroacetyl chloride (1.05 g, 7.94 mmol) by gentle bubbling. The reaction media became colorless upon stirring at 25 C. and after 1 hour the reaction contents were diluted with ethyl acetate, washed with water, dried over sodium sulfate, and concentrated under reduced pressure to afford 2.5 g of the title compound as an orange oil. LC/MS (Method A) retention time=1.11 minutes, 342.6 (M+H).

[0445] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.07 (m, 2H), 7.36 (m, 2H), 4.66 (m, 2H), 3.36 (m, 2H), 2.87 (m, 1H), 1.15 (m, 9H).

[0446] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 64.36 (s).

Example 8a

[0447] This example illustrates the preparation of N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (Compound X.01 of Table X)

##STR00091##

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

[0448] ##STR00092##

[0449] To a solution of O-methylhydroxylamine hydrochloride (11.2 g, 131.3 mmol) in dichloromethane (91 mL) was introduced DIPEA (19.1 g, 147.7 mmol) via dropwise addition. After 20 minutes, 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1,2,4-oxadiazole (14.0 g, 16.4 mmol) was introduced as a dichloromethane (4 mL) solution. The reaction mixture was stirred at room temperature for 24 hours, then poured into water and the layers were separated. The organic layer was washed with water, the organic fraction was concentrated under reduced pressure, and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 7:3) to give 4.4 g of the title compound as a yellowish oil.

[0450] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (d, 2H), 7.53 (d, 2H), 5.33 (brs, 1H), 4.12 (s, 2H), 3.50 (s, 3H).

[0451] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.32 (s).

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

[0452] To a suspension of N-methoxy-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine (0.11 g, 0.38 mmol) in dichloromethane (2.8 mL) was introduced triethylamine (0.16 mL, 1.14 mmol) followed by cyclopropanecarboxylic acid (0.4 mL, 0.49 mmol) and EDCl (0.15 g, 0.76 mmol). After 18 hours, the contents were diluted with an aqueous 1M HCl solution and extracted with dichloromethane. 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 8:2) to afford 126 mg of the title compound as a white solid, mp: 35-38 C., LC/MS (Method A) retention time=0.99 minutes, 316.3 (M+H).

[0453] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (d, 2H), 7.53 (d, 2H), 4.87 (s, 2H), 3.73 (s, 3H), 2.19 (m, 1H), 1.05 (m, 2H), 0.86 (m, 2H).

[0454] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.33 (s).

Example 8b

[0455] This example illustrates an alternative preparation of N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (Compound X.01 of Table X)

Step 1: Preparation of N-methoxycyclopropanecarboxamide

[0456] ##STR00093##

[0457] To a solution of O-methylhydroxylamine (0.80 g, 21.8 mmol) and potassium carbonate (0.52 mL, 2.88 mmol) in ethyl acetate (7.7 mL) cooled via ice bath was introduced dropwise cyclopropanecarbonyl chloride (2.0 g, 18.2 mmol) over 30 minutes. The ice bath was removed and after the contents were stirred for 2 hours EtOH (5 mL) was introduced and the contents were stirred for an additional 30 minutes. The solids were filtered then dried under vacuum to afford 2.14 g of the title compound as a white solid.

[0458] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm: 11.13 (s, 1H), 3.57 (s, 3H), 1.34 (m, 1H), 0.87 (m, 1H), 0.68 (m, 3H).

Step 2: Preparation of N-[(4-cyanophenyl)methyl]-N-methoxy-cyclopropanecarboxamide

[0459] ##STR00094##

[0460] To a solution of N-methoxycyclopropanecarboxamide (0.67 g, 5.50 mmol) in acetonitrile (10 mL) was introduced potassium carbonate (0.80 g, 5.50 mmol) followed by 4-(bromomethyl)benzonitrile (1.0 g, 5.50 mmol). The reaction was heated at 60 C. during 8 hours then cooled to 25 C. and quenched with water. The contents were extracted with ethyl acetate and the total combined organic layer was dried with sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 7:3) to give 1.0 g of the title compound as a yellowish oil.

[0461] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.61 (d, 2H), 7.42 (d, 2H), 4.84 (s, 2H), 3.74 (s, 3H), 2.18 (m, 1H), 1.04 (m, 2H), 0.89 (m, 2H).

Step 3: Preparation of N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-N-methoxy-cyclopropanecarboxamide

[0462] ##STR00095##

[0463] To a solution of N-[(4-cyanophenyl)methyl]-N-methoxy-cyclopropanecarboxamide (0.50 g, 2.30 mmol) and ethanol (2.5 mL) was introduced a 50% aqueous hydroxylamine solution (0.18 mL, 2.99 mmol). The reaction was then heated at 80 C. for 2 hours, cooled to 25 C., and concentrated under reduced pressure. The contents were basified to pH 8 with using an aqueous 30% NaOH solution, extracted with EtOAc, and then the total combined organic fraction was concentrated under reduced pressure and dried under vacuum to afford 270 mg of the title compound as a white solid.

[0464] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm: 9.60 (s, 1H), 7.62 (d, 2H), 7.28 (d, 2H), 5.77 (s, 2H), 4.55 (s, 2H), 3.71 (s, 3H), 2.17 (m, 1H), 0.82 (m, 4H).

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

[0465] To a 30 mL Schlenk tube connected to trap-1 (empty) followed by trap-2 (filled with an 4N NaOH aqueous solution) was added N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-N-methoxy-cyclopropanecarboxamide (1.05 g, 4.00 mmol), ethyl acetate (20 mL), and pyridine (0.49 mL, 6.0 mmol). The contents were stirred for 10 minutes then cooled to 0 C. To the resultant white suspension was introduced 2,2,2-trifluoroacetyl chloride (0.58 g, 4.40 mmol) by gentle bubbling. The reaction media became colorless upon stirring at 25 C. and after 1 hour the contents were diluted with ethyl acetate, washed with water, dried over sodium sulfate, filtered and then concentrated under reduced pressure to afford 1.26 g of the title compound as an orange oil which solidified upon storage. mp: 35-38 C., LC/MS (Method A) retention time=0.99 minutes, 316.3 (M+H).

[0466] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (d, 2H), 7.53 (d, 2H), 4.87 (s, 2H), 3.73 (s, 3H), 2.19 (m, 1H), 1.05 (m, 2H), 0.86 (m, 2H).

[0467] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.33 (s).

Example 9a

[0468] This example illustrates the preparation of N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (Compound X.04 of Table X)

##STR00096##

[0469] To a solution of 2-methoxypropanoic acid (0.2 g, 1.92 mmol) in DMF (7.7 mL) was added HATU (0.80 g, 2.11 mmol) and DIPEA (0.52 mL, 2.88 mmol). After the contents stirred for 20 minutes, N-methoxy-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine (0.524 g, 1.92 mmol) was introduced. After 2 hours, the contents were diluted with water and ethyl acetate, the layers were separated, and the aqueous phase was extracted with ethyl acetate. 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 4:1 to 1:9) to afford 418 mg of the title compound as a white solid, mp: 62-65 C., LC/MS (Method A) retention time=1.02 minutes, 360.6 (M+H). A single enantiomeric form, i.e., (R)- or (S)-enantiomer, of 2-methoxypropanoic acid can be introduced, using identical conditions, to afford the corresponding single enantiomeric form of Compound X.04.

[0470] 1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (d, 2H), 7.48 (d, 2H), 4.98 (m, 1H), 4.80 (m, 1H), 4.27 (m, 1H), 3.71 (s, 3H), 3.34 (s, 3H), 1.37 (d, 3H).

[0471] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.35 (s).

Example 9b

[0472] This example illustrates an alternative preparation of N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (Compound X.04 of Table X)

##STR00097##

Step 1: Preparation of 2-methoxypropanoyl chloride

[0473] ##STR00098##

[0474] To a solution of 2-methoxypropanoic acid (0.70 g, 6.72 mmol), dimethylformamide (0.005 mL) and dichloromethane cooled via ice bath was introduced oxalyl chloride (0.90 mL, 10.1 mmol). After 30 minutes, the ice bath was removed and stirring continued for 3.5 hours. The contents were then concentrated under slightly reduced pressure (ca. 500 mbar) to afford 200 mg of the title compound that was used directly in the next transformation. A single enantiomeric form, i.e., (R)- or (S)-enantiomer, of 2-methoxypropanoic acid can be introduced, using identical conditions, to afford the corresponding single enantiomeric form of 2-methoxypropanoyl chloride.

Step 2: Preparation of 4-[(methoxyamino)methyl]benzonitrile hydrochloride

[0475] ##STR00099##

[0476] To a solution of 4-(bromomethyl)benzonitrile (2.0 g, 10.2 mmol) in acetonitrile (10 mL) was added O-methylhydroxylamine hydrochloride (1.7 g, 20.4 mmol) and potassium carbonate (3.0 g, 21.4 mmol). After 17 hours, the reaction mixture was poured into water and extracted with ethyl acetate. The total combined organic layer was washed with water and brine then dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude residue was taken up in tert-butyl methyl ether (15 mL), cooled to via ice bath, and 4M HCl in dioxane (2.2 mL) was introduced dropwise. After 10 minutes, the ice bath was removed and the crude contents were stirred for 2 hours. After, all solids were collected via filtration, rinsed with tert-butyl methyl ether, and dried under vacuum to afford 1.6 g of the title compound as a white solid that was used in the next transformation without further purification.

[0477] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm: 7.90 (d, 2H), 7.72 (d, 2H), 4.41 (s, 2H), 3.75 (s, 3H).

Step 3: Preparation of N-[(4-cyanophenyl)methyl]-N,2-dimethoxy-propanamide

[0478] ##STR00100##

[0479] To a suspension of 4-[(methoxyamino)methyl]benzonitrile hydrochloride (0.33 g, 1.63 mmol) and sodium hydrogen carbonate (0.42 g, 4.90 mmol) in dichloromethane (25 mL) at cooled via ice bath was introduced dropwise 2-methoxypropanoyl chloride (0.20 g, 1.63 mmol) as a dichloromethane solution (10 mL). After 10 minutes, the ice bath was removed and the reaction mixture stirred for 15 minutes. After, the solids were removed via filtration and the filtrate solution was 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 provide 155 mg of the title compound as a colorless oil. A single enantiomeric form, i.e., (R)- or (S)-enantiomer, of 2-methoxypropanoyl chloride can be introduced, using identical conditions, to afford the corresponding single enantiomeric form of N-[(4-cyanophenyl)methyl]-N,2-dimethoxy-propanamide.

[0480] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.65 (d, 2H), 7.45 (d, 2H), 4.95 (m, 1H), 4.72 (m, 1H), 4.25 (q, 1H), 3.70 (s, 3H), 3.36 (s, 3H), 1.35 (d, 3H).

Step 4: Preparation of N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-N,2-dimethoxy-propanamide

[0481] ##STR00101##

[0482] To a solution of N-[(4-cyanophenyl)methyl]-N,2-dimethoxy-propanamide (1.0 g, 4.03 mmol) and ethanol (5 mL) was introduced a 50% aqueous hydroxylamine solution (0.3 mL, 4.29 mmol). The reaction was heated at 60 C. for 3 hours, cooled to 25 C., and then concentrated under reduced pressure. The contents were basified to pH 8 with using an aqueous 30% NaOH solution, extracted with EtOAc, and the total combined organic phase was concentrated under reduced pressure then oven dried to afford 270 mg of the title compound as a white solid that was use in the next transformation without further purification. A single enantiomeric form, i.e., (R)- or (S)-enantiomer, of N-[(4-cyanophenyl)methyl]-N,2-dimethoxy-propanamide can be introduced, using identical conditions, to afford the corresponding single enantiomeric form of N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-N,2-dimethoxy-propanamide.

[0483] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm: 9.59 (s, 1H), 7.63 (d, 2H), 7.25 (d, 2H), 5.77 (s, 2H), 4.88 (s, 1H), 4.71 (m, 1H), 4.25 (q, 1H), 3.69 (m, 3H), 3.21 (s, 3H), 1.20 (d, 3H).

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

[0484] To a 30 mL Schlenk tube connected to trap-1 (empty) followed by trap-2 (filled with an 4N NaOH aqueous solution) was added N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-N,2-dimethoxy-propanamide (1.0 g, 3.34 mmol), ethyl acetate (20 mL), and pyridine (0.41 mL, 5.0 mmol). The contents were stirred for 10 minutes and then cooled via ice bath. To the resultant white suspension was introduced 2,2,2-trifluoroacetyl chloride (0.49 g, 3.68 mmol) by gentle bubbling. The ice bath was removed and the reaction media became colorless solution upon stirring at room temperature. After 1 hour, the reaction contents were diluted with ethyl acetate, washed with water, dried over sodium sulfate, and concentrated under reduced pressure to afford 1.26 g of the title compound as white solid. mp: 62-65 C., LC/MS (Method A) retention time=1.02 minutes, 360.6 (M+H). A single enantiomeric form, i.e., (R)- or (S)-enantiomer, of N-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-N,2-dimethoxy-propanamide can be introduced, using identical conditions, to afford the corresponding single enantiomeric form of Compound X.04.

[0485] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.09 (d, 2H), 7.48 (d, 2H), 4.98 (m, 1H), 4.80 (m, 1H), 4.27 (m, 1H), 3.71 (s, 3H), 3.34 (s, 3H), 1.37 (d, 3H).

[0486] .sup.19F NMR (400 MHz, CDCl.sub.3) ppm: 65.35 (s).

Example 10a

[0487] This example illustrates the preparation of 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (Compound X.14 of Table X)

##STR00102##

[0488] To a solution of N-methoxy-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine (0.10 g, 0.37 mmol) in dichloromethane (1.23 mL) was added N-methylcarbamoyl chloride (0.07 g, 0.73 mmol) and triethylamine (0.10 mL, 0.73 mmol). After 1 hour, the reaction mixture was concentrated under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 1:1) to provide 79 mg of the title compound as a white solid, mp: 75-78 C. LC/MS (Method A) retention time=0.96 minutes, (M+H) not observed.

[0489] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.00 (d, 2H), 7.45 (d, 2H), 5.72 (m, 1H), 4.61 (s, 2H), 3.50 (s, 3H), 2.79 (d, 3H).

Example 10b

[0490] This example illustrates an alternative preparation of 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (Compound X.14 of Table X)

Step 1: Preparation of 1-methoxy-3-methyl-urea

[0491] ##STR00103##

[0492] A 250 mL reactor equipped with mechanical stirrer and a condenser charged with water (10 mL), N-methoxyamine hydrochloride (9.0 g, 106.9 mmol), and sodium bicarbonate (20.0 g, 253.3 mmol), cooled via an ice bath, was stirred with cooling via ice bath for 15 minutes. Then, N-methyl carbamoyl chloride (10.0 g, 106.9 mmol) was introduced dropwise as a solution in EtOAc (15 mL) over 1 hour, keeping the temperature between 0 C. to 10 C. The contents were stirred an additional 2 hours at 0 C., then the ice bath was removed. After 4 hours, THF (25 mL) and EtOAc (10 mL) were added to the reaction mixture. After 15 minutes, stirring was stopped and the phases were allowed to separate. The organic layer was concentrated under reduced pressure to give a crude solid that was dried under vacuum. To the reactor was introduced a EtOAc/THF solution (1:1, 40 mL) and the contents stirred for 15 minutes. The solution was then concentrated under reduced pressure and the resultant crude solid was dried under vacuum. The two crude solid fractions were combined and triturated using pentane (50 mL), filtered, and dried under vacuum to afford 10.8 g of the title compound as a white solid that was used in the next transformation without further purification.

[0493] .sup.1H NMR (400 MHz, DMSO-d6) ppm: 9.00 (s, 1H), 6.78 (sbr, 1H), 3.50 (s, 3H), 2.61 (m, 3H).

Step 2: Preparation of 1-[(4-cyanophenyl)methyl]-1-methoxy-3-methyl-urea

[0494] ##STR00104##

[0495] To a solution of 1-methoxy-3-methyl-urea (765 mg, 7.26 mmol), 4-(chloromethyl)benzonitrile (1.0 g, 6.60 mmol), tetrabutylammonium sulfate (0.113 g, 0.33 mmol), and acetonitrile (10 mL) was added potassium carbonate (1.02 g, 7.26 mmol). The contents were heated at 80 C. for 4 hours, cooled to 25 C., and the solids were removed via filtration, rinsed with EtOAc, and the filtrate was concentrated under reduced pressure. The resultant crude residue was dissolved in EtOAc (50 mL), washed sequentially with an aqueous 1N NaOH solution, water, and brine then dried with sodium sulfate and concentrated under reduced pressure to afford 1.4 g of the title compound as a yellow crystalline solid that was used in the next transformation without further purification.

[0496] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 7.61 (d, 2H), 7.47 (d, 2H), 5.74 (brs, 1H), 4.67 (s, 2H), 3.54 (s, 3H), 2.82 (s, 3H).

Step 3: Preparation of 1-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-1-methoxy-3-methyl-urea

[0497] ##STR00105##

[0498] To a solution of 1-[(4-cyanophenyl)methyl]-1-methoxy-3-methyl-urea (1.00 g, 4.56 mmol) and ethanol (5 mL) was added hydroxylamine hydrochloride (0.380 g, 5.47 mmol) followed by the dropwise introduction of triethylamine (0.77 mL, 5.47 mmol). The reaction media was heated at 80 C. for 2 hours, cooled to 25 C., and then concentrated under reduced pressure. The reaction contents were basified to pH 8 with using an aqueous 30% NaOH solution, extracted with EtOAc, and the total combined organic phase was concentrated under reduced pressure then oven dried to afford 970 mg of the title compound as a yellow solid.

[0499] .sup.1H NMR (400 MHz, DMSO-d6) ppm: 7.60 (d, 2H), 7.25 (d, 2H), 7.12 (m, 1H), 5.75 (s, 2H), 4.50 (s, 3H), 3.50 (s, 3H), 2.50 (d, 3H).

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

[0500] A 30 mL Schlenk tube, connected to trap-1 (empty) followed by trap-2 (filled with an 4N NaOH aqueous solution), was charged with 1-[[4-(N-hydroxycarbamimidoyl)phenyl]methyl]-1-methoxy-3-methyl-urea (1.00 g, 3.75 mmol), ethyl acetate (20 mL), and pyridine (0.46 mL, 5.62 mmol). After 10 minutes, to the resultant white suspension was introduced 2,2,2-trifluoroacetyl fluoride (0.57 g, 4.12 mmol) by gentle bubbling. The reaction media became colorless and after 4.5 hours the reaction contents were diluted with ethyl acetate, washed with water, dried over sodium sulfate, and concentrated under reduced pressure to afford 1.21 g of the title compound as a white solid, mp: 75-78 C. LC/MS (Method A) retention time=0.96 minutes, (M+H) not observed.

[0501] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.00 (d, 2H), 7.45 (d, 2H), 5.72 (m, 1H), 4.61 (s, 2H), 3.50 (s, 3H), 2.79 (d, 3H).

Example 11

[0502] This example illustrates an alternative preparation 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (Compound X.25 of Table X)

##STR00106##

[0503] Triphosgene (130 mg) was dissolved in 1,2-dichloroethane (5 mL) and cooled via ice bath. To this colorless solution was added N-methoxy-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine (300 mg) dissolved in 1,2-dichloroethane (2.5 mL) and triethylamine (0.38 mL). After 1 hour, a solution of ethylamine hydrochloride (179 mg) dissolved in 1,2-dichloroethane (2.5 mL) was introduced to the reaction mixture followed by triethylamine (0.38 mL) and the mixture stirred for 24 hours. Then sodium hydrogen carbonate and dichloromethane were added to the mixture and the aqueous layer was extracted twice with dichloromethane. The total combined organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a cyclohexane/ethyl acetate eluent gradient to afford 0.084 g of the title compound as a white solid. mp: 58-63 C. LC/MS (Method A) retention time=1.02 minutes, 345 (M+H).

[0504] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.12 (d, 2H), 7.50 (d, 2H), 5.85 (m, 1H), 4.7 (s, 2H), 3.60 (s, 3H), 3.35 (m, 2H), 1.15 (t, 3H)

Example 12

[0505] This example illustrates an alternative preparation of 1,3-dimethoxy-1-[[4-[5(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (Compound X.24 of Table X)

##STR00107##

[0506] N-methoxy-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanamine (140 mg) was dissolved in tetrahydrofuran (1.54 mL) and to this suspension was introduced CDI (111 mg) in one portion. The suspension slowly turned into a clear solution as the mixture was stirred for 1.5 hours at ambient temperature. Then O-methylhydroxylamine hydrochloride (131 mg) was added followed by triethylamine (0.21 mL). After 24 hours, the reaction contents were concentrated under reduced pressure and the crude residue was purified by flash chromatography on silica gel using a cyclohexane/ethyl acetate gradient to afford 0.14 g of the title compound as a white solid. mp: 88-91 C. LC/MS (Method A) retention time=0.95 minutes, 347 (M+H).

[0507] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm: 8.32 (s, 1H), 8.12 (d, 2H), 7.50 (d, 2H), 4.72 (s, 2H), 3.80 (s, 3H), 3.60 (s, 3H).

[0508] The following procedure was used in a combinatorial fashion to provide the compounds of Formula (I), wherein Z represents R.sup.4, using appropriate building blocks (compounds (II) and (III)). The compounds prepared via the following combinatorial protocol were analyzed using LC/MS Method B.

##STR00108##

[0509] By way of exemplification, acid derivatives of formula (III) (0.038 mmol in DMA (375 L) were transferred to a 96 slot deep well plate (DWP96) containing the [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]aryl]methanamine derivative of formula (II) (0.03 mmol) and DIPEA (0.09 mmol) in DMA (250 L), followed by the addition of BOP-Cl (0.06 mmol) dissolved in DMA (250 L). The DWP was sealed and stirred at 50 C. for 18 hours. 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) in 10-85% yields.

[0510] Alternatively, the following procedures (protocol A and protocol B) were used in a combinatorial fashion to provide the compounds of Formula (I), wherein Z represents NR.sup.6R.sup.7, using appropriate building blocks (compounds (II) and (IV)). The compounds prepared via the following combinatorial protocols were analyzed using LC/MS Method B.

##STR00109##

[0511] Protocol A: Portions of triphosgene (6 mg) in DCE (0.3 mL) were transferred at 0 C. to a 96 slot deep well plate (DWP96) containing compounds of formula (IV) (0.05 mmol), wherein Z-Nu is an amine derivative [HNR.sup.6R.sup.7], and triethylamine (0.12 mmol) in DMA (200 L). The reaction mixtures were stirred at room temperature for 30 minutes. Then, [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]aryl]methanamine derivatives of formula (II) (0.05 mmol) and triethylamine (0.12 mmol) in DMA (200 L)were added. The DWP was sealed and stirred at room temperature for 18 hours. DCE was removed under the Barkey station. The crude residues were solubilized in a mixture of MeOH (200 L) and DMA (600 L) and directly submitted for preparative LC/MS purification which provided the compounds of formula (I) in 3-45% yields.

[0512] Protocol B: The amine derivative [HNR.sup.6R.sup.7] of formula (IV) (0.05 mmol) and DIPEA (0.25 mmol) in DMA (300 L) were transferred at room temperature to a 96 slot deep well plate (DWP96). CDI (0.10 mmol) in DMA (300 L) were added and the contents stirred until solubilization. [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]aryl]methanamine derivatives of formula (II) (0.05 mmol) and triethylamine (0.12 mmol) in DMA (200 L) were then introduced. The DWP was sealed and stirred at room temperature for 18 hours. The DCE was removed under the Barkey station. The crude residues were solubilized in a mixture of MeOH (200 L) and DMA (600 L) and directly submitted for preparative LC/MS purification which provided the compounds of formula (I) in 5-47% yields.

[0513] 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-00012 TABLE T1 Melting point (mp) data and/or retention times (R.sub.t) for compounds X.01 to X.25 according to Formula (I): Compound RT [M + H] mp Entry name Structure (min) (measured) Method C. X.01 N-methoxy-N-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] cyclopropanecarboxamide [00110] 0.99 316.3 A 38-41 X.02 N-methoxy-N-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] pent-4-ynamide [00111] 1.73 354.2 B X.03 N-methoxy-2- methyl-N-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] prop-2-enamide [00112] 1.74 342.2 B X.04 N,2-dimethoxy-N- [[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] propanamide [00113] 1.62 360.2 B 62-65 X.05 N-cyclopropyl- 3,3,3-trifluoro-N- [[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] propanamide [00114] 1.84 394.2 B X.06 2,2-difluoro-N-(2- methoxyethyl)-N- [[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] cyclopropanecarboxamide [00115] 1.73 406.3 B X.07 N-ethyl-2-methyl- N-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] propanamide [00116] 1.78 342.3 B X.08 N-[[3-fluoro-4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]- N-methoxy- propanamide [00117] 1.05 348 A X.09 2-methoxy-N- (2,2,2- trifluoroethyl)-N- [[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] acetamide [00118] 92.6-94.3 X.10 N-[[2,3-difluoro-4- [5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]- N-methoxy- cyclopropanecarboxamide [00119] 1.11 378 A X.11 2- (difluoromethoxy)- N-methyl-N-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] acetamide [00120] 1.02 366 A X.12 N-ethoxy-2- methoxy-N-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] propanamide [00121] 1.67 374.17 B X.13 N-isopropyl-N-[[4- [5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl] tetrahydrofuran-2- carboxamide [00122] 1.67 374.17 B X.14 1-methoxy-3- methyl-1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00123] 75-78 X.15 3-cyclopropyl-1- methoxy-1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00124] 84-87 X.16 3-ethoxy-1- methoxy-1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00125] 107-110 X.17 3-allyl-1-methoxy- 1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00126] 64-70 X.18 1-cyclopropyl-3- methoxy-3-methyl- 1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00127] 1.1 371 A X.19 3-isopropyl-1- methoxy-1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00128] 106-107.3 X.20 1-methoxy-3-prop- 2-ynyl-1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00129] 88.9-90.6 X.21 1-[[3-fluoro-4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]- 1-methoxy-3- methyl-urea [00130] 0.98 349 A X.22 3- (cyclopropylmethyl)- 1-methyl-1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00131] 1.63 355.2 B X.23 1-ethyl-3-(2,2,2- trifluoroethyl)-1- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00132] 1.7 397.2 B X.24 1,3-dimethoxy-1- [[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00133] 88-91 X.25 3-ethyl-1-methoxy- 1-[[4-[5- (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]urea [00134] 58-63

BIOLOGICAL EXAMPLES

General Examples of Leaf Disk Tests in Well Plates:

[0514] 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:

[0515] 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)

[0516] 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).

[0517] 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.

[0518] Compounds (from Table T1) X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11, X.12, and X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, X.21, X.22, X.23, X.24, and X.25.

Example A2

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

[0519] 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).

[0520] 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.

[0521] Compounds (from Table T1) X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11, X.12, and X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, X.21, X.22, X.23, X.24, and X.25.

Example A3

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

[0522] 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).

[0523] 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.

[0524] Compounds (from Table T1) X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11, X.12, and X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, X.21, X.22, X.23, X.24, and X.25.

Example A4

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

[0525] 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.

[0526] 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.

[0527] Compounds (from Table T1) X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11, X.12, and X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, X.21, X.22, X.23, X.24, and X.25.

[0528] Further biolgical test examples relating to fungicidal composition comprising a mixture of components (A) and (B) as active ingredients:

Example B1

Preventative Activity Against Phakopsora Pachyrhizi on Soybean

[0529] 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).

[0530] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test.

TABLE-US-00013 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.01 Benzovindiflupyr 1:3 40:120 X.01 Benzovindiflupyr 1:1 40:40 X.01 Benzovindiflupyr 1:1 120:120 X.01 Benzovindiflupyr 3:1 120:40 X.14 Benzovindiflupyr 1:3 40:120 X.14 Benzovindiflupyr 1:2 10:20 X.14 Benzovindiflupyr 1:1 20:20 X.14 Benzovindiflupyr 1:1 120:120 X.14 Benzovindiflupyr 3:1 120:40 X.04 Benzovindiflupyr 1:1 9:9 X.04 Benzovindiflupyr 2:1 9:4.5 X.04 Benzovindiflupyr 1:3 3:9 X.07 Benzovindiflupyr 1:1 9:9 X.07 Benzovindiflupyr 2:1 9:4.5 X.07 Benzovindiflupyr 1:3 3:9 X.07 Benzovindiflupyr 1:1.5 3:4.5 X.25 Benzovindiflupyr 1:1 9:9 X.25 Benzovindiflupyr 2:1 9:4.5 X.25 Benzovindiflupyr 1:3 3:9 X.25 Benzovindiflupyr 1:1.5 3:4.5 X.24 Benzovindiflupyr 1:1 9:9 X.24 Benzovindiflupyr 2:1 9:4.5 X.24 Benzovindiflupyr 1:3 3:9 X.24 Benzovindiflupyr 1:1.5 3:4.5 X.01 Fluxapyroxad 1:3 40:120 X.01 Fluxapyroxad 1:1 40:40 X.01 Fluxapyroxad 1:1 120:120 X.01 Fluxapyroxad 3:1 120:40 X.14 Fluxapyroxad 1:3 40:120 X.14 Fluxapyroxad 1:1 120:120 X.14 Fluxapyroxad 3:1 120:40 X.04 Fluxapyroxad 1:1 9:9 X.04 Fluxapyroxad 2:1 9:4.5 X.04 Fluxapyroxad 1:1.5 3:4.5 X.07 Fluxapyroxad 1:1 9:9 X.07 Fluxapyroxad 2:1 9:4.5 X.07 Fluxapyroxad 1:1.5 3:4.5 X.25 Fluxapyroxad 1:1 9:9 X.25 Fluxapyroxad 2:1 9:4.5 X.25 Fluxapyroxad 1:3 3:9 X.25 Fluxapyroxad 1:1.5 3:4.5 X.24 Fluxapyroxad 1:1 9:9 X.24 Fluxapyroxad 2:1 9:4.5 X.24 Fluxapyroxad 1:3 3:9 X.24 Fluxapyroxad 1:1.5 3:4.5 X.01 Pydiflumetofen 1:5 120:600 X.01 Pydiflumetofen 1:3 120:300 X.14 Pydiflumetofen 1:15 40:600 X.14 Pydiflumetofen 1:7.5 40:300 X.14 Pydiflumetofen 1:5 120:600 X.14 Pydiflumetofen 1:3 120:300 X.04 Pydiflumetofen .sup.1:6.67 9:60 X.04 Pydiflumetofen 3:1 9:3 X.04 Pydiflumetofen 1:20 3:60 X.04 Pydiflumetofen 1:1 3:3 X.07 Pydiflumetofen .sup.1:6.67 9:60 X.07 Pydiflumetofen 3:1 9:3 X.07 Pydiflumetofen 1:20 3:60 X.07 Pydiflumetofen 1:1 3:3 X.25 Pydiflumetofen .sup.1:6.67 9:60 X.25 Pydiflumetofen 3:1 9:3 X.25 Pydiflumetofen 1:20 3:60 X.25 Pydiflumetofen 1:1 3:3 X.24 Pydiflumetofen .sup.1:6.67 9:60 X.24 Pydiflumetofen 3:1 9:3 X.24 Pydiflumetofen 1:20 3:60 X.24 Pydiflumetofen 1:1 3:3 X.01 Fluopyram 1:15 120:600 X.01 Fluopyram 1:7.5 120:300 X.14 Fluopyram 1:15 40:600 X.14 Fluopyram 1:7.5 40:300 X.14 Fluopyram 1:5 120:600 X.14 Fluopyram 1:3 120:300 X.04 Fluopyram .sup.1:6.67 9:60 X.04 Fluopyram 3:1 9:3 X.04 Fluopyram 1:20 3:60 X.04 Fluopyram 1:1 3:3 X.07 Fluopyram .sup.1:6.67 9:60 X.07 Fluopyram 3:1 9:3 X.07 Fluopyram 1:20 3:60 X.07 Fluopyram 1:1 3:3 X.25 Fluopyram .sup.1:6.67 9:60 X.25 Fluopyram 3:1 9:3 X.25 Fluopyram 1:20 3:60 X.25 Fluopyram 1:1 3:3 X.24 Fluopyram .sup.1:6.67 9:60 X.24 Fluopyram 3:1 9:3 X.24 Fluopyram 1:1 3:3 X.01 Penthiopyrad 1:6 40:240 X.01 Penthiopyrad 1:3 40:120 X.01 Penthiopyrad 1:2 120:240 X.01 Penthiopyrad 1:1 120:120 X.14 Penthiopyrad 1:6 40:240 X.14 Penthiopyrad 1:2 120:240 X.14 Penthiopyrad 1:1 120:120 X.04 Penthiopyrad .sup.1:3.33 9:30 X.04 Penthiopyrad .sup.1:1.67 9:15 X.04 Penthiopyrad 1:10 3:30 X.04 Penthiopyrad 1:5 3:15 X.07 Penthiopyrad .sup.1:3.33 9:30 X.07 Penthiopyrad .sup.1:1.67 9:15 X.07 Penthiopyrad 1:10 3:30 X.07 Penthiopyrad 1:5 3:15 X.25 Penthiopyrad .sup.1:3.33 9:30 X.25 Penthiopyrad .sup.1:1.67 9:15 X.25 Penthiopyrad 1:10 3:30 X.25 Penthiopyrad 1:5 3:15 X.24 Penthiopyrad .sup.1:3.33 9:30 X.24 Penthiopyrad .sup.1:1.67 9:15 X.24 Penthiopyrad 1:10 3:30 X.24 Penthiopyrad 1:5 3:15 X.01 Difenoconazole 1:30 40:1200 X.01 Difenoconazole 1:10 120:1200 X.01 Difenoconazole 1:6 40:240 X.01 Difenoconazole 1:2 120:240 X.14 Difenoconazole 1:60 10:600 X.14 Difenoconazole 1:30 40:1200 X.14 Difenoconazole 1:30 10:300 X.14 Difenoconazole 1:30 20:600 X.14 Difenoconazole 1:15 20:300 X.14 Difenoconazole 1:10 120:1200 X.14 Difenoconazole 1:6 40:240 X.14 Difenoconazole 1:2 120:240 X.04 Difenoconazole .sup.1:6.67 9:60 X.04 Difenoconazole .sup.1:1.33 9:12 X.04 Difenoconazole 1:20 3:60 X.04 Difenoconazole 1:4 3:12 X.07 Difenoconazole .sup.1:6.67 9:60 X.07 Difenoconazole .sup.1:1.33 9:12 X.07 Difenoconazole 1:20 3:60 X.07 Difenoconazole 1:4 3:12 X.25 Difenoconazole .sup.1:6.67 9:60 X.25 Difenoconazole .sup.1:1.33 9:12 X.25 Difenoconazole 1:20 3:60 X.25 Difenoconazole 1:4 3:12 X.24 Difenoconazole .sup.1:6.67 9:60 X.24 Difenoconazole .sup.1:1.33 9:12 X.24 Difenoconazole 1:20 3:60 X.24 Difenoconazole 1:4 3:12 X.01 Cyproconazole 1:30 40:1200 X.01 Cyproconazole 1:10 120:1200 X.01 Cyproconazole 1:6 40:240 X.01 Cyproconazole 1:2 120:240 X.14 Cyproconazole 1:30 10:300 X.14 Cyproconazole 1:30 40:1200 X.14 Cyproconazole 1:15 10:150 X.14 Cyproconazole 1:15 20:300 X.14 Cyproconazole 1:10 120:1200 X.14 Cyproconazole 1:7.5 20:150 X.14 Cyproconazole 1:6 40:240 X.14 Cyproconazole 1:2 120:240 X.04 Cyproconazole .sup.1:6.67 9:60 X.04 Cyproconazole .sup.1:1.33 9:12 X.04 Cyproconazole 1:20 3:60 X.04 Cyproconazole 1:4 3:12 X.07 Cyproconazole .sup.1:6.67 9:60 X.07 Cyproconazole .sup.1:1.33 9:12 X.07 Cyproconazole 1:20 3:60 X.07 Cyproconazole 1:4 3:12 X.25 Cyproconazole .sup.1:6.67 9:60 X.25 Cyproconazole .sup.1:1.33 9:12 X.25 Cyproconazole 1:20 3:60 X.25 Cyproconazole 1:4 3:12 X.24 Cyproconazole .sup.1:6.67 9:60 X.24 Cyproconazole .sup.1:1.33 9:12 X.24 Cyproconazole 1:20 3:60 X.24 Cyproconazole 1:4 3:12 X.01 Tebuconazole 1:30 40:1200 X.01 Tebuconazole 1:15 20:300 X.01 Tebuconazole 1:10 120:1200 X.01 Tebuconazole 1:7.5 20:150 X.01 Tebuconazole 1:6 40:240 X.01 Tebuconazole 1:2 120:240 X.14 Tebuconazole 1:60 5:300 X.14 Tebuconazole 1:30 40:1200 X.14 Tebuconazole 1:30 10:300 X.14 Tebuconazole 1:15 20:300 X.14 Tebuconazole 1:15 10:150 X.14 Tebuconazole 1:10 120:1200 X.14 Tebuconazole 1:7.5 20:150 X.14 Tebuconazole 1:6 40:240 X.14 Tebuconazole 1:2 120:240 X.04 Tebuconazole .sup.1:6.67 9:60 X.04 Tebuconazole .sup.1:1.33 9:12 X.04 Tebuconazole 1:20 3:60 X.04 Tebuconazole 1:4 3:12 X.07 Tebuconazole .sup.1:6.67 9:60 X.07 Tebuconazole .sup.1:1.33 9:12 X.07 Tebuconazole 1:20 3:60 X.07 Tebuconazole 1:4 3:12 X.25 Tebuconazole .sup.1:6.67 9:60 X.25 Tebuconazole .sup.1:1.33 9:12 X.25 Tebuconazole 1:20 3:60 X.25 Tebuconazole 1:4 3:12 X.24 Tebuconazole .sup.1:6.67 9:60 X.24 Tebuconazole .sup.1:1.33 9:12 X.24 Tebuconazole 1:20 3:60 X.24 Tebuconazole 1:4 3:12 X.01 Hexaconazole 1:30 40:1200 X.01 Hexaconazole 1:10 120:1200 X.01 Hexaconazole 1:6 40:240 X.01 Hexaconazole 1:2 120:240 X.14 Hexaconazole 1:30 40:1200 X.14 Hexaconazole 1:10 120:1200 X.14 Hexaconazole 1:6 40:240 X.14 Hexaconazole 1:2 120:240 X.04 Hexaconazole .sup.1:6.67 9:60 X.04 Hexaconazole .sup.1:1.33 9:12 X.04 Hexaconazole 1:20 3:60 X.04 Hexaconazole 1:4 3:12 X.07 Hexaconazole .sup.1:6.67 9:60 X.07 Hexaconazole .sup.1:1.33 9:12 X.07 Hexaconazole 1:20 3:60 X.07 Hexaconazole 1:4 3:12 X.25 Hexaconazole .sup.1:6.67 9:60 X.25 Hexaconazole .sup.1:1.33 9:12 X.25 Hexaconazole 1:20 3:60 X.25 Hexaconazole 1:4 3:12 X.24 Hexaconazole .sup.1:6.67 9:60 X.24 Hexaconazole .sup.1:1.33 9:12 X.24 Hexaconazole 1:20 3:60 X.24 Hexaconazole 1:4 3:12 X.01 Prothioconazole 1:60 5:300 X.01 Prothioconazole 1:30 40:1200 X.01 Prothioconazole 1:30 10:300 X.01 Prothioconazole 1:15 20:300 X.01 Prothioconazole 1:10 120:1200 X.01 Prothioconazole 1:7.5 20:150 X.01 Prothioconazole 1:6 40:240 X.01 Prothioconazole 1:2 120:240 X.14 Prothioconazole 1:60 5:300 X.14 Prothioconazole 1:30 40:1200 X.14 Prothioconazole 1:30 10:300 X.14 Prothioconazole 1:15 10:150 X.14 Prothioconazole 1:15 20:300 X.14 Prothioconazole 1:10 120:1200 X.14 Prothioconazole 1:7.5 20:150 X.14 Prothioconazole 1:6 40:240 X.14 Prothioconazole 1:2 120:240 X.04 Prothioconazole .sup.1:6.67 9:60 X.04 Prothioconazole .sup.1:1.33 9:12 X.04 Prothioconazole 1:20 3:60 X.04 Prothioconazole 1:4 3:12 X.07 Prothioconazole .sup.1:6.67 9:60 X.07 Prothioconazole .sup.1:1.33 9:12 X.07 Prothioconazole 1:20 3:60 X.07 Prothioconazole 1:4 3:12 X.25 Prothioconazole .sup.1:6.67 9:60 X.25 Prothioconazole .sup.1:1.33 9:12 X.25 Prothioconazole 1:20 3:60 X.25 Prothioconazole 1:4 3:12 X.24 Prothioconazole .sup.1:6.67 9:60 X.24 Prothioconazole .sup.1:1.33 9:12 X.24 Prothioconazole 1:20 3:60 X.01 Azoxystrobin 1:25 20:500 X.01 Azoxystrobin 1:25 10:250 X.01 Azoxystrobin .sup.1:12.5 20:250 X.14 Azoxystrobin 1:100 5:500 X.14 Azoxystrobin 1:50 10:500 X.14 Azoxystrobin 1:50 5:250 X.14 Azoxystrobin 1:25 20:500 X.14 Azoxystrobin 1:25 10:250 X.14 Azoxystrobin .sup.1:12.5 20:250 X.04 Azoxystrobin 1:10 9:90 X.04 Azoxystrobin 1:5 9:45 X.04 Azoxystrobin 1:30 3:90 X.04 Azoxystrobin 1:15 3:45 X.07 Azoxystrobin 1:10 9:90 X.07 Azoxystrobin 1:5 9:45 X.07 Azoxystrobin 1:30 3:90 X.07 Azoxystrobin 1:15 3:45 X.25 Azoxystrobin 1:10 9:90 X.25 Azoxystrobin 1:5 9:45 X.25 Azoxystrobin 1:30 3:90 X.25 Azoxystrobin 1:15 3:45 X.24 Azoxystrobin 1:10 9:90 X.24 Azoxystrobin 1:5 9:45 X.24 Azoxystrobin 1:30 3:90 X.24 Azoxystrobin 1:15 3:45 X.01 Trifloxystrobin 1:100 5:500 X.01 Trifloxystrobin 1:50 10:500 X.01 Trifloxystrobin 1:25 20:500 X.01 Trifloxystrobin 1:25 10:250 X.14 Trifloxystrobin 1:200 2.5:500 X.14 Trifloxystrobin 1:100 5:500 X.14 Trifloxystrobin 1:50 5:250 X.14 Trifloxystrobin 1:50 10:500 X.14 Trifloxystrobin 1:25 10:250 X.14 Trifloxystrobin .sup.1:12.5 20:250 X.14 Trifloxystrobin .sup.1:12.5 10:125 X.14 Trifloxystrobin .sup.1:6.25 20:125 X.04 Trifloxystrobin 1:10 9:90 X.04 Trifloxystrobin 1:5 9:45 X.04 Trifloxystrobin 1:30 3:90 X.04 Trifloxystrobin 1:15 3:45 X.07 Trifloxystrobin 1:10 9:90 X.07 Trifloxystrobin 1:5 9:45 X.07 Trifloxystrobin 1:30 3:90 X.07 Trifloxystrobin 1:15 3:45 X.25 Trifloxystrobin 1:10 9:90 X.25 Trifloxystrobin 1:5 9:45 X.25 Trifloxystrobin 1:30 3:90 X.25 Trifloxystrobin 1:15 3:45 X.24 Trifloxystrobin 1:10 9:90 X.24 Trifloxystrobin 1:5 9:45 X.24 Trifloxystrobin 1:30 3:90 X.24 Trifloxystrobin 1:15 3:45 X.01 Picoxystrobin 1:100 5:500 X.01 Picoxystrobin 1:50 10:500 X.01 Picoxystrobin 1:25 20:500 X.01 Picoxystrobin 1:25 10:250 X.01 Picoxystrobin .sup.1:12.5 20:250 X.04 Picoxystrobin 1:10 9:90 X.04 Picoxystrobin 1:5 9:45 X.04 Picoxystrobin 1:30 3:90 X.04 Picoxystrobin 1:15 3:45 X.07 Picoxystrobin 1:10 9:90 X.07 Picoxystrobin 1:5 9:45 X.07 Picoxystrobin 1:30 3:90 X.07 Picoxystrobin 1:15 3:45 X.25 Picoxystrobin 1:10 9:90 X.25 Picoxystrobin 1:5 9:45 X.25 Picoxystrobin 1:30 3:90 X.25 Picoxystrobin 1:15 3:45 X.24 Picoxystrobin 1:10 9:90 X.24 Picoxystrobin 1:5 9:45 X.24 Picoxystrobin 1:30 3:90 X.24 Picoxystrobin 1:15 3:45 X.04 Pyraclostrobin 1:10 9:90 X.04 Pyraclostrobin 1:5 9:45 X.04 Pyraclostrobin 1:30 3:90 X.04 Pyraclostrobin 1:15 3:45 X.07 Pyraclostrobin 1:10 9:90 X.07 Pyraclostrobin 1:5 9:45 X.07 Pyraclostrobin 1:30 3:90 X.07 Pyraclostrobin 1:15 3:45 X.25 Pyraclostrobin 1:10 9:90 X.25 Pyraclostrobin 1:5 9:45 X.25 Pyraclostrobin 1:30 3:90 X.25 Pyraclostrobin 1:15 3:45 X.24 Pyraclostrobin 1:10 9:90 X.24 Pyraclostrobin 1:5 9:45 X.24 Pyraclostrobin 1:30 3:90 X.24 Pyraclostrobin 1:15 3:45 X.01 Metalaxyl-M 1:150 40:6000 X.01 Metalaxyl-M 1:50 120:6000 X.01 Metalaxyl-M 1:50 40:2000 X.01 Metalaxyl-M .sup.1:16.7 120:2000 X.14 Metalaxyl-M 1:150 40:6000 X.14 Metalaxyl-M 1:100 20:2000 X.14 Metalaxyl-M 1:100 10:1000 X.14 Metalaxyl-M 1:50 20:1000 X.14 Metalaxyl-M 1:50 120:6000 X.14 Metalaxyl-M 1:50 40:2000 X.14 Metalaxyl-M .sup.1:16.7 120:2000 X.04 Metalaxyl-M 1:33.33 9:300 X.04 Metalaxyl-M 1:11.11 9:100 X.04 Metalaxyl-M 1:100 3:300 X.04 Metalaxyl-M 1:33.33 3:100 X.07 Metalaxyl-M 1:33.33 9:300 X.07 Metalaxyl-M 1:11.11 9:100 X.07 Metalaxyl-M 1:100 3:300 X.07 Metalaxyl-M 1:33.33 3:100 X.25 Metalaxyl-M 1:33.33 9:300 X.25 Metalaxyl-M 1:11.11 9:100 X.25 Metalaxyl-M 1:100 3:300 X.25 Metalaxyl-M 1:33.33 3:100 X.24 Metalaxyl-M 1:33.33 9:300 X.24 Metalaxyl-M 1:11.11 9:100 X.24 Metalaxyl-M 1:100 3:300 X.24 Metalaxyl-M 1:33.33 3:100 X.01 Fenpropidin 1:400 5:2000 X.01 Fenpropidin 1:100 20:2000 X.01 Fenpropidin 1:100 10:1000 X.01 Fenpropidin 1:50 20:1000 X.14 Fenpropidin 1:200 10:2000 X.14 Fenpropidin 1:200 5:1000 X.14 Fenpropidin 1:100 20:2000 X.14 Fenpropidin 1:100 10:1000 X.14 Fenpropidin 1:50 20:1000 X.04 Fenpropidin 1:33.33 9:300 X.04 Fenpropidin 1:11.11 9:100 X.04 Fenpropidin 1:100 3:300 X.04 Fenpropidin 1:33.33 3:100 X.07 Fenpropidin 1:33.33 9:300 X.07 Fenpropidin 1:11.11 9:100 X.07 Fenpropidin 1:100 3:300 X.07 Fenpropidin 1:33.33 3:100 X.25 Fenpropidin 1:33.33 9:300 X.25 Fenpropidin 1:11.11 9:100 X.25 Fenpropidin 1:100 3:300 X.25 Fenpropidin 1:33.33 3:100 X.24 Fenpropidin 1:33.33 9:300 X.24 Fenpropidin 1:11.11 9:100 X.24 Fenpropidin 1:100 3:300 X.24 Fenpropidin 1:33.33 3:100 X.01 Fenpropimorph 1:600 5:3000 X.01 Fenpropimorph 1:300 10:3000 X.01 Fenpropimorph 1:150 20:3000 X.04 Fenpropimorph 1:33.33 9:300 X.04 Fenpropimorph 1:11.11 9:100 X.04 Fenpropimorph 1:100 3:300 X.04 Fenpropimorph 1:33.33 3:100 X.07 Fenpropimorph 1:33.33 9:300 X.07 Fenpropimorph 1:11.11 9:100 X.07 Fenpropimorph 1:100 3:300 X.07 Fenpropimorph 1:33.33 3:100 X.25 Fenpropimorph 1:33.33 9:300 X.25 Fenpropimorph 1:11.11 9:100 X.25 Fenpropimorph 1:100 3:300 X.25 Fenpropimorph 1:33.33 3:100 X.24 Fenpropimorph 1:33.33 9:300 X.24 Fenpropimorph 1:11.11 9:100 X.24 Fenpropimorph 1:100 3:300 X.24 Fenpropimorph 1:33.33 3:100 X.01 Cyprodinil 1:6000 5:30000 X.01 Cyprodinil 1:3000 10:30000 X.01 Cyprodinil 1:1500 10:15000 X.01 Cyprodinil 1:750 20:15000 X.14 Cyprodinil 1:6000 5:30000 X.14 Cyprodinil 1:6000 .sup.2.5:15000 X.14 Cyprodinil 1:3000 10:30000 X.14 Cyprodinil 1:1500 10:15000 X.04 Cyprodinil 1:100 9:900 X.04 Cyprodinil 1:33.33 9:300 X.04 Cyprodinil 1:300 3:900 X.04 Cyprodinil 1:100 3:300 X.07 Cyprodinil 1:100 9:900 X.07 Cyprodinil 1:33.33 9:300 X.07 Cyprodinil 1:300 3:900 X.07 Cyprodinil 1:100 3:300 X.25 Cyprodinil 1:100 9:900 X.25 Cyprodinil 1:33.33 9:300 X.25 Cyprodinil 1:300 3:900 X.25 Cyprodinil 1:100 3:300 X.24 Cyprodinil 1:100 9:900 X.24 Cyprodinil 1:33.33 9:300 X.24 Cyprodinil 1:300 3:900 X.24 Cyprodinil 1:100 3:300 X.04 Fludioxinil 1:200 9:1800 X.04 Fludioxinil 1:66.67 9:600 X.04 Fludioxinil 1:600 3:1800 X.04 Fludioxinil 1:200 3:600 X.07 Fludioxinil 1:200 9:1800 X.07 Fludioxinil 1:66.67 9:600 X.07 Fludioxinil 1:600 3:1800 X.25 Fludioxinil 1:200 9:1800 X.25 Fludioxinil 1:66.67 9:600 X.25 Fludioxinil 1:600 3:1800 X.25 Fludioxinil 1:200 3:600 X.24 Fludioxinil 1:200 9:1800 X.24 Fludioxinil 1:66.67 9:600 X.01 Spiroxamine 1:1200 5:6000 X.01 Spiroxamine 1:600 10:6000 X.01 Spiroxamine 1:300 20:6000 X.01 Spiroxamine 1:300 10:3000 X.01 Spiroxamine 1:150 20:3000 X.14 Spiroxamine 1:2400 2.5:6000 X.14 Spiroxamine 1:1200 2.5:3000 X.14 Spiroxamine 1:1200 5:6000 X.14 Spiroxamine 1:600 10:6000 X.14 Spiroxamine 1:600 5:3000 X.14 Spiroxamine 1:300 10:3000 X.04 Spiroxamine 1:33.33 9:300 X.04 Spiroxamine 1:11.11 9:100 X.04 Spiroxamine 1:100 3:300 X.04 Spiroxamine 1:33.33 3:100 X.07 Spiroxamine 1:33.33 9:300 X.07 Spiroxamine 1:11.11 9:100 X.07 Spiroxamine 1:100 3:300 X.04 Spiroxamine 1:33.33 3:100 X.25 Spiroxamine 1:33.33 9:300 X.25 Spiroxamine 1:11.11 9:100 X.25 Spiroxamine 1:100 3:300 X.25 Spiroxamine 1:33.33 3:100 X.24 Spiroxamine 1:33.33 9:300 X.24 Spiroxamine 1:11.11 9:100 X.24 Spiroxamine 1:100 3:300 X.24 Spiroxamine 1:33.33 3:100 X.01 Mancozeb 1:500 20:10000 X.01 Mancozeb 1:250 20:5000 X.01 Mancozeb 1:1000 5:5000 X.14 Mancozeb 1:500 20:10000 X.14 Mancozeb 1:500 10:5000 X.14 Mancozeb 1:250 20:5000 X.14 Mancozeb 1:1000 10:10000 X.04 Mancozeb 1:100 9:900 X.04 Mancozeb 1:33.33 9:300 X.04 Mancozeb 1:300 3:900 X.04 Mancozeb 1:100 3:300 X.07 Mancozeb 1:100 9:900 X.07 Mancozeb 1:33.33 9:300 X.07 Mancozeb 1:300 3:900 X.07 Mancozeb 1:100 3:300 X.25 Mancozeb 1:100 9:900 X.25 Mancozeb 1:33.33 9:300 X.25 Mancozeb 1:300 3:900 X.25 Mancozeb 1:100 3:300 X.24 Mancozeb 1:100 9:900 X.24 Mancozeb 1:33.33 9:300 X.24 Mancozeb 1:300 3:900 X.24 Mancozeb 1:100 3:300 X.01 Chlorothalonil 1:1500 40:60000 X.01 Chlorothalonil 1:500 120:60000 X.01 Chlorothalonil 1:500 40:20000 X.01 Chlorothalonil 1:166.7 120:20000 X.14 Chlorothalonil 1:4000 10:40000 X.14 Chlorothalonil 1:2000 20:40000 X.14 Chlorothalonil 1:1500 40:60000 X.14 Chlorothalonil 1:1000 20:20000 X.14 Chlorothalonil 1:500 120:60000 X.14 Chlorothalonil 1:500 40:20000 X.14 Chlorothalonil 1:166.7 120:20000 X.04 Chlorothalonil 1:200 9:1800 X.04 Chlorothalonil 1:66.67 9:600 X.04 Chlorothalonil 1:600 3:1800 X.04 Chlorothalonil 1:200 3:600 X.07 Chlorothalonil 1:200 9:1800 X.07 Chlorothalonil 1:66.67 9:600 X.07 Chlorothalonil 1:600 3:1800 X.07 Chlorothalonil 1:200 3:600 X.25 Chlorothalonil 1:200 9:1800 X.25 Chlorothalonil 1:66.67 9:600 X.25 Chlorothalonil 1:600 3:1800 X.25 Chlorothalonil 1:200 3:600 X.24 Chlorothalonil 1:200 9:1800 X.24 Chlorothalonil 1:66.67 9:600 X.24 Chlorothalonil 1:600 3:1800 X.24 Chlorothalonil 1:200 3:600 X.04 Fenhexamid 1:100 9:900 X.04 Fenhexamid 1:33.33 9:300 X.04 Fenhexamid 1:300 3:900 X.04 Fenhexamid 1:100 3:300 X.07 Fenhexamid 1:100 9:900 X.07 Fenhexamid 1:33.33 9:300 X.07 Fenhexamid 1:300 3:900 X.07 Fenhexamid 1:100 3:300 X.25 Fenhexamid 1:100 9:900 X.25 Fenhexamid 1:33.33 9:300 X.25 Fenhexamid 1:300 3:900 X.25 Fenhexamid 1:100 3:300 X.24 Fenhexamid 1:100 9:900 X.24 Fenhexamid 1:33.33 9:300 X.24 Fenhexamid 1:300 3:900 X.24 Fenhexamid 1:100 3:300 X.04 Prochloraz 1:100 9:900 X.04 Prochloraz 1:33.33 9:300 X.04 Prochloraz 1:300 3:900 X.04 Prochloraz 1:100 3:300 X.07 Prochloraz 1:100 9:900 X.07 Prochloraz 1:33.33 9:300 X.07 Prochloraz 1:100 3:300 X.25 Prochloraz 1:100 9:900 X.25 Prochloraz 1:33.33 9:300 X.25 Prochloraz 1:300 3:900 X.25 Prochloraz 1:100 3:300 X.24 Prochloraz 1:100 9:900 X.24 Prochloraz 1:33.33 9:300 X.24 Prochloraz 1:300 3:900 X.24 Prochloraz 1:100 3:300 X.01 Oxathiapiprolin 1:5 120:600 X.01 Oxathiapiprolin 1:1.7 120:200 X.14 Oxathiapiprolin 1:15 40:600 X.14 Oxathiapiprolin 1:5 120:600 X.14 Oxathiapiprolin 1:5 40:200 X.14 Oxathiapiprolin 1:1.7 120:200 X.04 Oxathiapiprolin .sup.1:3.33 9:30 X.04 Oxathiapiprolin .sup.1:1.11 9:10 X.04 Oxathiapiprolin 1:10 3:30 X.04 Oxathiapiprolin .sup.1:3.33 3:10 X.07 Oxathiapiprolin .sup.1:3.33 9:30 X.07 Oxathiapiprolin .sup.1:1.11 9:10 X.07 Oxathiapiprolin 1:10 3:30 X.07 Oxathiapiprolin .sup.1:3.33 3:10 X.25 Oxathiapiprolin .sup.1:3.33 9:30 X.25 Oxathiapiprolin .sup.1:1.11 9:10 X.25 Oxathiapiprolin 1:10 3:30 X.25 Oxathiapiprolin .sup.1:3.33 3:10 X.24 Oxathiapiprolin .sup.1:3.33 9:30 X.24 Oxathiapiprolin .sup.1:1.11 9:10 X.24 Oxathiapiprolin 1:10 3:30 X.24 Oxathiapiprolin .sup.1:3.33 3:10 X.01 Mandipropamid 120:6000 120:6000 X.01 Mandipropamid 120:2000 120:2000 X.14 Mandipropamid 1:150 40:6000 X.14 Mandipropamid 1:50 120:6000 X.14 Mandipropamid 1:50 40:2000 X.14 Mandipropamid .sup.1:16.7 120:2000 X.04 Mandipropamid 1:33.33 9:300 X.04 Mandipropamid 1:11.11 9:100 X.04 Mandipropamid 1:100 3:300 X.04 Mandipropamid 1:33.33 3:100 X.07 Mandipropamid 1:33.33 9:300 X.07 Mandipropamid 1:11.11 9:100 X.07 Mandipropamid 1:100 3:300 X.07 Mandipropamid 1:33.33 3:100 X.25 Mandipropamid 1:33.33 9:300 X.25 Mandipropamid 1:11.11 9:100 X.25 Mandipropamid 1:100 3:300 X.25 Mandipropamid 1:33.33 3:100 X.24 Mandipropamid 1:33.33 9:300 X.24 Mandipropamid 1:11.11 9:100 X.24 Mandipropamid 1:100 3:300 X.24 Mandipropamid 1:33.33 3:100 X.01 Fluazinam 1:375 40:15000 X.01 Fluazinam 1:125 120:15000 X.01 Fluazinam .sup.1:41.7 120:5000 X.14 Fluazinam 1:375 40:15000 X.14 Fluazinam 1:125 40:5000 X.14 Fluazinam 1:125 120:15000 X.14 Fluazinam .sup.1:41.7 120:5000 X.04 Fluazinam 1:90 9:810 X.04 Fluazinam 1:30 9:270 X.04 Fluazinam 1:270 3:810 X.04 Fluazinam 1:90 3:270 X.07 Fluazinam 1:90 9:810 X.07 Fluazinam 1:30 9:270 X.07 Fluazinam 1:270 3:810 X.07 Fluazinam 1:90 3:270 X.25 Fluazinam 1:90 9:810 X.25 Fluazinam 1:30 9:270 X.25 Fluazinam 1:270 3:810 X.25 Fluazinam 1:90 3:270 X.24 Fluazinam 1:90 9:810 X.24 Fluazinam 1:30 9:270 X.24 Fluazinam 1:270 3:810 X.24 Fluazinam 1:90 3:270 X.01 (N-[5-bromo-2-methyl- 1:3 40:120 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.01 (N-[5-bromo-2-methyl- 1:1 120:120 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.01 (N-[5-bromo-2-methyl- 1:1 40:40 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.01 (N-[5-bromo-2-methyl- 3:1 120:40 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.14 (N-[5-bromo-2-methyl- 1:3 40:120 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.14 (N-[5-bromo-2-methyl- 1:1 120:120 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.14 (N-[5-bromo-2-methyl- 1:1 40:40 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.14 (N-[5-bromo-2-methyl- 3:1 120:40 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.04 (N-[5-bromo-2-methyl- 1.5:1 9:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.04 (N-[5-bromo-2-methyl- 3:1 9:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.04 (N-[5-bromo-2-methyl- 1:2 3:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.04 (N-[5-bromo-2-methyl- 1:1 3:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1.5:1 9:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 3:1 9:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:2 3:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.07 (N-[5-bromo-2-methyl- 1:1 3:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.25 (N-[5-bromo-2-methyl- 1.5:1 9:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.25 (N-[5-bromo-2-methyl- 3:1 9:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.25 (N-[5-bromo-2-methyl- 1:2 3:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.25 (N-[5-bromo-2-methyl- 1:1 3:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.24 (N-[5-bromo-2-methyl- 1.5:1 9:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.24 (N-[5-bromo-2-methyl- 3:1 9:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.24 (N-[5-bromo-2-methyl- 1:2 3:6 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.24 (N-[5-bromo-2-methyl- 1:1 3:3 6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N- ethyl-N-methyl- formamidine) X.01 fosetyl-aluminium 1:1500 40:60000 X.01 fosetyl-aluminium 1:500 120:60000 X.01 fosetyl-aluminium 1:500 40:20000 X.01 fosetyl-aluminium 3:167 120:20000 X.14 fosetyl-aluminium 1:1500 40:60000 X.14 fosetyl-aluminium 1:500 120:60000 X.14 fosetyl-aluminium 1:500 40:20000 X.14 fosetyl-aluminium 3:167 120:20000 X.04 fosetyl-aluminium 1:666.67 9:6000 X.04 fosetyl-aluminium 1:333.33 9:3000 X.04 fosetyl-aluminium 1:2000 3:6000 X.04 fosetyl-aluminium 1:1000 3:3000 X.07 fosetyl-aluminium 1:666.67 9:6000 X.07 fosetyl-aluminium 1:333.33 9:3000 X.07 fosetyl-aluminium 1:2000 3:6000 X.07 fosetyl-aluminium 1:1000 3:3000 X.25 fosetyl-aluminium 1:333.33 9:3000 X.25 fosetyl-aluminium 1:166.67 9:1500 X.25 fosetyl-aluminium 1:1000 3:3000 X.25 fosetyl-aluminium 1:500 3:1500 X.24 fosetyl-aluminium 1:333.33 9:3000 X.24 fosetyl-aluminium 1:166.67 9:1500 X.24 fosetyl-aluminium 1:1000 3:3000 X.24 fosetyl-aluminium 1:500 3:1500 X.01 Trinexapac-ethyl 1:250 20:5000 X.01 Trinexapac-ethyl 1:150 40:6000 X.01 Trinexapac-ethyl 1:125 20:2500 X.01 Trinexapac-ethyl 1:50 120:6000 X.01 Trinexapac-ethyl 1:50 40:2000 X.01 Trinexapac-ethyl .sup.1:16.7 120:2000 X.14 Trinexapac-ethyl 1:500 10:5000 X.14 Trinexapac-ethyl 1:150 40:6000 X.14 Trinexapac-ethyl 1:50 120:6000 X.14 Trinexapac-ethyl 1:50 40:2000 X.14 Trinexapac-ethyl .sup.1:16.7 120:2000 X.04 Trinexapac-ethyl 1:33.33 9:300 X.04 Trinexapac-ethyl 1:16.67 9:150 X.04 Trinexapac-ethyl 1:100 3:300 X.04 Trinexapac-ethyl 1:50 3:150 X.07 Trinexapac-ethyl 1:33.33 9:300 X.07 Trinexapac-ethyl 1:16.67 9:150 X.07 Trinexapac-ethyl 1:100 3:300 X.07 Trinexapac-ethyl 1:50 3:150 X.25 Trinexapac-ethyl 1:33.33 9:300 X.25 Trinexapac-ethyl 1:16.67 9:150 X.25 Trinexapac-ethyl 1:100 3:300 X.25 Trinexapac-ethyl 1:50 3:150 X.24 Trinexapac-ethyl 1:33.33 9:300 X.24 Trinexapac-ethyl 1:16.67 9:150 X.24 Trinexapac-ethyl 1:100 3:300 X.24 Trinexapac-ethyl 1:50 3:150 X.01 Acibenzolar-S-methyl 1:15 40:600 X.01 Acibenzolar-S-methyl 1:5 120:600 X.01 Acibenzolar-S-methyl 1:5 40:200 X.01 Acibenzolar-S-methyl 1:1.7 120:200 X.14 Acibenzolar-S-methyl 1:15 40:600 X.14 Acibenzolar-S-methyl 1:5 120:600 X.14 Acibenzolar-S-methyl 1:5 40:200 X.14 Acibenzolar-S-methyl 1:1.7 120:200 X.04 Acibenzolar-S-methyl 1:10 9:90 X.04 Acibenzolar-S-methyl 1:30 3:90 X.07 Acibenzolar-S-methyl 1:10 9:90 X.07 Acibenzolar-S-methyl 1:5 9:45 X.07 Acibenzolar-S-methyl 1:30 3:90 X.07 Acibenzolar-S-methyl 1:15 3:45 X.25 Acibenzolar-S-methyl 1:10 9:90 X.25 Acibenzolar-S-methyl 1:5 9:45 X.25 Acibenzolar-S-methyl 1:30 3:90 X.25 Acibenzolar-S-methyl 1:15 3:45 X.24 Acibenzolar-S-methyl 1:10 9:90 X.24 Acibenzolar-S-methyl 1:5 9:45 X.24 Acibenzolar-S-methyl 1:30 3:90 X.24 Acibenzolar-S-methyl 1:15 3:45 X.01 Glyphosate 1:2400 5:12000 X.01 Glyphosate 1:1200 10:12000 X.01 Glyphosate 1:600 20:12000 X.01 Glyphosate 1:300 20:6000 X.14 Glyphosate 1:2400 5:12000 X.14 Glyphosate 1:1200 10:12000 X.14 Glyphosate 1:1200 5:6000 X.14 Glyphosate 1:600 10:6000 X.04 Glyphosate 1:20 9:180 X.04 Glyphosate .sup.1:6.67 9:60 X.04 Glyphosate 1:60 3:180 X.04 Glyphosate 1:20 3:60 X.07 Glyphosate 1:20 9:180 X.07 Glyphosate .sup.1:6.67 9:60 X.07 Glyphosate 1:60 3:180 X.07 Glyphosate 1:20 3:60 X.25 Glyphosate 1:20 9:180 X.25 Glyphosate .sup.1:6.67 9:60 X.25 Glyphosate 1:60 3:180 X.25 Glyphosate 1:20 3:60 X.24 Glyphosate 1:20 9:180 X.24 Glyphosate .sup.1:6.67 9:60 X.24 Glyphosate 1:60 3:180 X.24 Glyphosate 1:20 3:60 X.04 2,4-D 1:20 9:180 X.04 2,4-D .sup.1:6.67 9:60 X.04 2,4-D 1:60 3:180 X.04 2,4-D 1:20 3:60 X.07 2,4-D 1:20 9:180 X.07 2,4-D .sup.1:6.67 9:60 X.07 2,4-D 1:60 3:180 X.07 2,4-D 1:20 3:60 X.25 2,4-D 1:20 9:180 X.25 2,4-D .sup.1:6.67 9:60 X.25 2,4-D 1:60 3:180 X.25 2,4-D 1:20 3:60 X.24 2,4-D 1:20 9:180 X.01 Timorex Gold 1:4500 40:180000 X.01 Timorex Gold 1:1500 120:180000 X.01 Timorex Gold 1:1500 40:60000 X.01 Timorex Gold 1:500 120:60000 X.14 Timorex Gold 1:4500 40:180000 X.14 Timorex Gold 1:1500 120:180000 X.14 Timorex Gold 1:1500 40:60000 X.14 Timorex Gold 1:500 120:60000 X.04 Timorex Gold 1:1000 9:9000 X.04 Timorex Gold 1:500 9:4500 X.04 Timorex Gold 1:3000 3:9000 X.04 Timorex Gold 1:1500 3:4500 X.07 Timorex Gold 1:1000 9:9000 X.07 Timorex Gold 1:500 9:4500 X.07 Timorex Gold 1:3000 3:9000 X.07 Timorex Gold 1:1500 3:4500 X.25 Timorex Gold 1:1000 9:9000 X.25 Timorex Gold 1:500 9:4500 X.25 Timorex Gold 1:3000 3:9000 X.25 Timorex Gold 1:1500 3:4500 X.24 Timorex Gold 1:1000 9:9000 X.24 Timorex Gold 1:500 9:4500 X.24 Timorex Gold 1:3000 3:9000 X.24 Timorex Gold 1:1500 3:4500 X.14 Thiamethoxam 1:250 10:2500 X.04 Thiamethoxam 1:33.33 9:300 X.04 Thiamethoxam 1:16.67 9:150 X.04 Thiamethoxam 1:100 3:300 X.04 Thiamethoxam 1:50 3:150 X.07 Thiamethoxam 1:33.33 9:300 X.07 Thiamethoxam 1:16.67 9:150 X.07 Thiamethoxam 1:100 3:300 X.07 Thiamethoxam 1:50 3:150 X.25 Thiamethoxam 1:33.33 9:300 X.25 Thiamethoxam 1:16.67 9:150 X.25 Thiamethoxam 1:100 3:300 X.25 Thiamethoxam 1:50 3:150 X.24 Thiamethoxam 1:33.33 9:300 X.24 Thiamethoxam 1:16.67 9:150 X.24 Thiamethoxam 1:100 3:300 X.24 Thiamethoxam 1:50 3:150

Example B2

Uncinula Necator/Grape/Preventive (Powdery Mildew on Grape)UNCIVIT/fo-pr-P

[0531] 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.

[0532] 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.01 Benzovindiflupyr 1000:1 60:0.06 X.01 Benzovindiflupyr 3000:1 60:0.02 X.14 Benzovindiflupyr 1000:1 60:0.06 X.14 Benzovindiflupyr 3000:1 60:0.02 X.14 Benzovindiflupyr 333:1 20:0.06 X.14 Benzovindiflupyr 1000:1 20:0.02 X.04 Benzovindiflupyr 1000:1 60:0.06 X.04 Benzovindiflupyr 3000:1 60:0.02 X.04 Benzovindiflupyr 333.33:1 20:0.06 X.04 Benzovindiflupyr 1000:1 20:0.02 X.07 Benzovindiflupyr 1000:1 60:0.06 X.07 Benzovindiflupyr 3000:1 60:0.02 X.07 Benzovindiflupyr 333.33:1 20:0.06 X.07 Benzovindiflupyr 1000:1 20:0.02 X.25 Benzovindiflupyr 3:1 60:20 X.25 Benzovindiflupyr 10:1 60:6 X.25 Benzovindiflupyr 1:1 20:20 X.25 Benzovindiflupyr 3.3:1 20:6 X.24 Benzovindiflupyr 3:1 60:20 X.24 Benzovindiflupyr 10:1 60:6 X.24 Benzovindiflupyr 1:1 20:20 X.24 Benzovindiflupyr 3.3:1 20:6 X.01 Isopyrazam 10:1 60:6 X.01 Isopyrazam 30:1 60:2 X.01 Isopyrazam 3.3:1 20:6 X.01 Isopyrazam 10:1 20:2 X.14 Isopyrazam 1:1 6:6 X.14 Isopyrazam 3:1 6:2 X.14 Isopyrazam 1:3 2:6 X.14 Isopyrazam 1:1 2:2 X.01 Penthiopyrad 10:1 60:6 X.01 Penthiopyrad 30:1 60:2 X.01 Penthiopyrad 3.3:1 20:6 X.14 Penthiopyrad 1:1 6:6 X.14 Penthiopyrad 3:1 6:2 X.14 Penthiopyrad 1:3 2:6 X.01 Pydiflumetofen 10:1 60:6 X.01 Pydiflumetofen 30:1 60:2 X.01 Pydiflumetofen 3.3:1 20:6 X.01 Pydiflumetofen 10:1 20:2 X.14 Pydiflumetofen 10:1 60:6 X.14 Pydiflumetofen 30:1 60:2 X.14 Pydiflumetofen 3.3:1 20:6 X.14 Pydiflumetofen 10:1 20:2 X.04 Pydiflumetofen 10:1 60:6 X.04 Pydiflumetofen 30:1 60:2 X.04 Pydiflumetofen 3.33:1.sup. 20:6 X.04 Pydiflumetofen 10:1 20:2 X.07 Pydiflumetofen 10:1 60:6 X.07 Pydiflumetofen 30:1 60:2 X.07 Pydiflumetofen 3.33:1.sup. 20:6 X.07 Pydiflumetofen 10:1 20:2 X.25 Pydiflumetofen 3:1 60:20 X.25 Pydiflumetofen 10:1 60:6 X.25 Pydiflumetofen 1:1 20:20 X.25 Pydiflumetofen 3.3:1 20:6 X.24 Pydiflumetofen 3:1 60:20 X.24 Pydiflumetofen 10:1 60:6 X.24 Pydiflumetofen 1:1 20:20 X.24 Pydiflumetofen 3.3:1 20:6 X.01 Fluopyram 10:1 60:6 X.01 Fluopyram 30:1 60:2 X.14 Fluopyram 10:1 60:6 X.14 Fluopyram 30:1 60:2 X.14 Fluopyram 3.3:1 20:6 X.14 Fluopyram 10:1 20:2 X.04 Fluopyram 10:1 60:6 X.04 Fluopyram 30:1 60:2 X.04 Fluopyram 3.33:1.sup. 20:6 X.04 Fluopyram 10:1 20:2 X.07 Fluopyram 10:1 60:6 X.07 Fluopyram 30:1 60:2 X.07 Fluopyram 3.33:1.sup. 20:6 X.07 Fluopyram 10:1 20:2 X.25 Fluopyram 3:1 60:20 X.25 Fluopyram 10:1 60:6 X.25 Fluopyram 1:1 20:20 X.25 Fluopyram 3.3:1 20:6 X.24 Fluopyram 3:1 60:20 X.24 Fluopyram 10:1 60:6 X.24 Fluopyram 1:1 20:20 X.24 Fluopyram 3.3:1 20:6 X.01 Azoxystrobin 1000:1 60:0.06 X.01 Azoxystrobin 3000:1 60:0.02 X.01 Azoxystrobin 333:1 20:0.06 X.14 Azoxystrobin 1000:1 60:0.06 X.14 Azoxystrobin 3000:1 60:0.02 X.14 Azoxystrobin 333:1 20:0.06 X.14 Azoxystrobin 1000:1 20:0.02 X.04 Azoxystrobin 1000:1 60:0.06 X.04 Azoxystrobin 3000:1 60:0.02 X.04 Azoxystrobin 333.33:1 20:0.06 X.04 Azoxystrobin 1000:1 20:0.02 X.07 Azoxystrobin 1000:1 60:0.06 X.07 Azoxystrobin 3000:1 60:0.02 X.07 Azoxystrobin 333.33:1 20:0.06 X.07 Azoxystrobin 1000:1 20:0.02 X.25 Azoxystrobin 100:1 .sup.60:0.6 X.25 Azoxystrobin 300:1 .sup.60:0.2 X.25 Azoxystrobin 33.33:1 .sup.20:0.6 X.25 Azoxystrobin 100:1 .sup.20:0.2 X.24 Azoxystrobin 100:1 .sup.60:0.6 X.24 Azoxystrobin 300:1 .sup.60:0.2 X.24 Azoxystrobin 33.33:1 .sup.20:0.6 X.24 Azoxystrobin 100:1 .sup.20:0.2 X.01 Trifloxystrobin 1000:1 60:0.06 X.01 Trifloxystrobin 3000:1 60:0.02 X.01 Trifloxystrobin 333:1 20:0.06 X.01 Trifloxystrobin 1000:1 20:0.02 X.14 Trifloxystrobin 1000:1 60:0.06 X.14 Trifloxystrobin 3000:1 60:0.02 X.14 Trifloxystrobin 333:1 20:0.06 X.14 Trifloxystrobin 1000:1 20:0.02 X.04 Trifloxystrobin 1000:1 60:0.06 X.04 Trifloxystrobin 3000:1 60:0.02 X.04 Trifloxystrobin 333.33:1 20:0.06 X.04 Trifloxystrobin 1000:1 20:0.02 X.07 Trifloxystrobin 1000:1 60:0.06 X.07 Trifloxystrobin 3000:1 60:0.02 X.07 Trifloxystrobin 333.33:1 20:0.06 X.07 Trifloxystrobin 1000:1 20:0.02 X.25 Trifloxystrobin 100:1 .sup.60:0.6 X.25 Trifloxystrobin 300:1 .sup.60:0.2 X.25 Trifloxystrobin 33.33:1 .sup.20:0.6 X.25 Trifloxystrobin 100:1 .sup.20:0.2 X.24 Trifloxystrobin 100:1 .sup.60:0.6 X.24 Trifloxystrobin 300:1 .sup.60:0.2 X.24 Trifloxystrobin 33.33:1 .sup.20:0.6 X.24 Trifloxystrobin 100:1 .sup.20:0.2 X.01 Pyraclostrobin 100:1 .sup.60:0.6 X.01 Pyraclostrobin 300:1 .sup.60:0.2 X.01 Pyraclostrobin 33:1 .sup.20:0.6 X.01 Pyraclostrobin 100:1 .sup.20:0.2 X.14 Pyraclostrobin 10:1 6:0.6 X.14 Pyraclostrobin 30:1 6:0.2 X.14 Pyraclostrobin 3.3:1 2:0.6 X.14 Pyraclostrobin 10:1 2:0.2 X.04 Pyraclostrobin 100:1 .sup.60:0.6 X.04 Pyraclostrobin 300:1 .sup.60:0.2 X.04 Pyraclostrobin 33.33:1 .sup.20:0.6 X.04 Pyraclostrobin 100:1 .sup.20:0.2 X.07 Pyraclostrobin 100:1 .sup.60:0.6 X.07 Pyraclostrobin 300:1 .sup.60:0.2 X.07 Pyraclostrobin 33.33:1 .sup.20:0.6 X.07 Pyraclostrobin 100:1 .sup.20:0.2 X.25 Pyraclostrobin 100:1 .sup.60:0.6 X.25 Pyraclostrobin 300:1 .sup.60:0.2 X.25 Pyraclostrobin 33.33:1 .sup.20:0.6 X.25 Pyraclostrobin 100:1 .sup.20:0.2 X.24 Pyraclostrobin 100:1 .sup.60:0.6 X.24 Pyraclostrobin 300:1 .sup.60:0.2 X.24 Pyraclostrobin 33.33:1 .sup.20:0.6 X.24 Pyraclostrobin 100:1 .sup.20:0.2 X.01 Cyproconazole 100:1 .sup.60:0.6 X.01 Cyproconazole 300:1 .sup.60:0.2 X.01 Cyproconazole 33.3:1.sup. .sup.20:0.6 X.14 Cyproconazole 100:1 .sup.60:0.6 X.14 Cyproconazole 300:1 .sup.60:0.2 X.14 Cyproconazole 33.3:1.sup. .sup.20:0.6 X.14 Cyproconazole 100:1 .sup.20:0.2 X.04 Cyproconazole 100:1 .sup.60:0.6 X.04 Cyproconazole 300:1 .sup.60:0.2 X.04 Cyproconazole 33.33:1 .sup.20:0.6 X.04 Cyproconazole 100:1 .sup.20:0.2 X.07 Cyproconazole 100:1 .sup.60:0.6 X.07 Cyproconazole 300:1 .sup.60:0.2 X.07 Cyproconazole 33.33:1 .sup.20:0.6 X.07 Cyproconazole 100:1 .sup.20:0.2 X.25 Cyproconazole 10:1 60:6 X.25 Cyproconazole 30:1 60:2 X.25 Cyproconazole 3.33:1.sup. 20:6 X.25 Cyproconazole 10:1 20:2 X.24 Cyproconazole 10:1 60:6 X.24 Cyproconazole 30:1 60:2 X.24 Cyproconazole 3.33:1.sup. 20:6 X.24 Cyproconazole 10:1 20:2 X.01 Difenoconazole 10:1 60:6 X.01 Difenoconazole 30:1 60:2 X.01 Difenoconazole 3.3:1 20:6 X.01 Difenoconazole 10:1 20:2 X.14 Difenoconazole 1:1 6:6 X.14 Difenoconazole 3:1 6:2 X.14 Difenoconazole 1:3 2:6 X.14 Difenoconazole 1:1 2:2 X.04 Difenoconazole 10:1 60:6 X.04 Difenoconazole 30:1 60:2 X.04 Difenoconazole 3.33:1.sup. 20:6 X.04 Difenoconazole 10:1 20:2 X.07 Difenoconazole 10:1 60:6 X.07 Difenoconazole 30:1 60:2 X.07 Difenoconazole 3.33:1.sup. 20:6 X.07 Difenoconazole 10:1 20:2 X.25 Difenoconazole 10:1 60:6 X.25 Difenoconazole 30:1 60:2 X.25 Difenoconazole 3.33:1.sup. 20:6 X.25 Difenoconazole 10:1 20:2 X.24 Difenoconazole 10:1 60:6 X.24 Difenoconazole 30:1 60:2 X.24 Difenoconazole 3.33:1.sup. 20:6 X.24 Difenoconazole 10:1 20:2 X.01 Hexaconazole 10:1 60:6 X.01 Hexaconazole 30:1 60:2 X.01 Hexaconazole 3.3:1 20:6 X.01 Hexaconazole 10:1 20:2 X.14 Hexaconazole 1:1 6:6 X.14 Hexaconazole 3:1 6:2 X.14 Hexaconazole 1:3 2:6 X.14 Hexaconazole 1:1 2:2 X.04 Hexaconazole 10:1 60:6 X.04 Hexaconazole 30:1 60:2 X.04 Hexaconazole 3.33:1.sup. 20:6 X.04 Hexaconazole 10:1 20:2 X.07 Hexaconazole 10:1 60:6 X.07 Hexaconazole 30:1 60:2 X.07 Hexaconazole 3.33:1.sup. 20:6 X.07 Hexaconazole 10:1 20:2 X.25 Hexaconazole 10:1 60:6 X.25 Hexaconazole 30:1 60:2 X.25 Hexaconazole 3.33:1.sup. 20:6 X.25 Hexaconazole 10:1 20:2 X.24 Hexaconazole 10:1 60:6 X.24 Hexaconazole 30:1 60:2 X.24 Hexaconazole 3.33:1.sup. 20:6 X.24 Hexaconazole 10:1 20:2 X.01 Propiconazole 10:1 60:6 X.01 Propiconazole 30:1 60:2 X.01 Propiconazole 3.3:1 20:6 X.01 Propiconazole 10:1 20:2 X.14 Propiconazole 1:1 6:6 X.14 Propiconazole 3:1 6:2 X.14 Propiconazole 1:3 2:6 X.14 Propiconazole 1:1 2:2 X.01 Mefentrifluconazole 10:1 60:6 X.01 Mefentrifluconazole 30:1 60:2 X.01 Mefentrifluconazole 3.3:1 20:6 X.01 Mefentrifluconazole 10:1 20:2 X.14 Mefentrifluconazole 1:1 6:6 X.14 Mefentrifluconazole 3:1 6:2 X.14 Mefentrifluconazole 1:3 2:6 X.14 Mefentrifluconazole 1:1 2:2 X.04 Mefentrifluconazole 10:1 60:6 X.04 Mefentrifluconazole 30:1 60:2 X.04 Mefentrifluconazole 3.33:1.sup. 20:6 X.04 Mefentrifluconazole 10:1 20:2 X.07 Mefentrifluconazole 10:1 60:6 X.07 Mefentrifluconazole 30:1 60:2 X.07 Mefentrifluconazole 3.33:1.sup. 20:6 X.07 Mefentrifluconazole 10:1 20:2 X.25 Mefentrifluconazole 10:1 60:6 X.25 Mefentrifluconazole 30:1 60:2 X.25 Mefentrifluconazole 3.33:1.sup. 20:6 X.25 Mefentrifluconazole 10:1 20:2 X.24 Mefentrifluconazole 10:1 60:6 X.24 Mefentrifluconazole 30:1 60:2 X.24 Mefentrifluconazole 3.33:1.sup. 20:6 X.24 Mefentrifluconazole 10:1 20:2 X.01 Prothioconazole 10:1 60:6 X.01 Prothioconazole 30:1 60:2 X.01 Prothioconazole 3.3:1 20:6 X.14 Prothioconazole 10:1 60:6 X.14 Prothioconazole 30:1 60:2 X.14 Prothioconazole 3.3:1 20:6 X.14 Prothioconazole 10:1 20:2 X.04 Prothioconazole 10:1 60:6 X.04 Prothioconazole 30:1 60:2 X.04 Prothioconazole 3.33:1.sup. 20:6 X.04 Prothioconazole 10:1 20:2 X.07 Prothioconazole 10:1 60:6 X.07 Prothioconazole 30:1 60:2 X.07 Prothioconazole 3.33:1.sup. 20:6 X.07 Prothioconazole 10:1 20:2 X.25 Prothioconazole 10:1 60:6 X.25 Prothioconazole 30:1 60:2 X.25 Prothioconazole 3.33:1.sup. 20:6 X.25 Prothioconazole 10:1 20:2 X.24 Prothioconazole 10:1 60:6 X.24 Prothioconazole 30:1 60:2 X.24 Prothioconazole 3.33:1.sup. 20:6 X.24 Prothioconazole 10:1 20:2 X.01 Chlorothalonil 1:1 60:60 X.01 Chlorothalonil 3:1 60:20 X.01 Chlorothalonil 1:3 20:60 X.01 Chlorothalonil 1:1 20:20 X.14 Chlorothalonil 1:1 60:60 X.14 Chlorothalonil 3:1 60:20 X.14 Chlorothalonil 1:3 20:60 X.14 Chlorothalonil 1:1 20:20 X.04 Chlorothalonil 1:1 60:60 X.04 Chlorothalonil 3:1 60:20 X.04 Chlorothalonil 1:3 20:60 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.25 Chlorothalonil 1:1 60:60 X.25 Chlorothalonil 3:1 60:20 X.25 Chlorothalonil 1:3 20:60 X.25 Chlorothalonil 1:1 20:20 X.24 Chlorothalonil 1:1 60:60 X.24 Chlorothalonil 3:1 60:20 X.24 Chlorothalonil 1:3 20:60 X.24 Chlorothalonil 1:1 20:20 X.01 Mancozeb 1:1 60:60 X.01 Mancozeb 3:1 60:20 X.14 Mancozeb 1:1 60:60 X.14 Mancozeb 3:1 60:20 X.14 Mancozeb 1:3 20:60 X.14 Mancozeb 1:1 20:20 X.04 Mancozeb 1:1 60:60 X.04 Mancozeb 3:1 60:20 X.04 Mancozeb 1:3 20:60 X.04 Mancozeb 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.25 Mancozeb 1:1 60:60 X.25 Mancozeb 3:1 60:20 X.25 Mancozeb 1:3 20:60 X.25 Mancozeb 1:1 20:20 X.24 Mancozeb 1:1 60:60 X.24 Mancozeb 3:1 60:20 X.24 Mancozeb 1:3 20:60 X.24 Mancozeb 1:1 20:20 X.01 fosetyl-aluminium 1:3.3 60:200 X.01 fosetyl-aluminium 1:1 60:60 X.14 fosetyl-aluminium 1:33 6:200 X.14 fosetyl-aluminium 1:10 6:60 X.01 Acibenzolar-S-methyl 1:3.3 60:200 X.01 Acibenzolar-S-methyl 1:1 60:60 X.01 Acibenzolar-S-methyl 1:10 20:200 X.14 Acibenzolar-S-methyl 1:33.3 6:200 X.14 Acibenzolar-S-methyl 1:10 6:60 X.14 Acibenzolar-S-methyl 1:100 2:200 X.14 Acibenzolar-S-methyl 1:30 2:60 X.04 Acibenzolar-S-methyl 1:3.3 60:200 X.04 Acibenzolar-S-methyl 1:1 60:60 X.04 Acibenzolar-S-methyl 1:3.3 20:60 X.07 Acibenzolar-S-methyl 1:3.3 60:200 X.07 Acibenzolar-S-methyl 1:1 60:60 X.07 Acibenzolar-S-methyl 1:10 20:200 X.07 Acibenzolar-S-methyl 1:3.3 20:60 X.25 Acibenzolar-S-methyl 1:3.3 60:200 X.25 Acibenzolar-S-methyl 1:1 60:60 X.25 Acibenzolar-S-methyl 1:10 20:200 X.25 Acibenzolar-S-methyl 1:3.3 20:60 X.24 Acibenzolar-S-methyl 1:3.3 60:200 X.24 Acibenzolar-S-methyl 1:1 60:60 X.24 Acibenzolar-S-methyl 1:10 20:200 X.24 Acibenzolar-S-methyl 1:3.3 20:60

Example B3

Glomerella Lagenarium (Colletotrichum Lagenarium)/Cucumber/PreventiveCOLLCUM/fo-pr-S

[0533] 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.

[0534] The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test.

TABLE-US-00015 Component A Conc. (ppm) (Compound) Component B Ratio A:B (A:B) X.01 Benzovindiflupyr 1000:1 .sup.60:0.06 X.01 Benzovindiflupyr 3000:1 .sup.60:0.02 X.14 Benzovindiflupyr 1000:1 .sup.60:0.06 X.14 Benzovindiflupyr 3000:1 .sup.60:0.02 X.25 Benzovindiflupyr 3:1 60:20 X.25 Benzovindiflupyr 10:1 60:6 X.25 Benzovindiflupyr 1:1 20:20 X.24 Benzovindiflupyr 3:1 60:20 X.24 Benzovindiflupyr 10:1 60:6 X.24 Benzovindiflupyr 1:1 20:20 X.24 Benzovindiflupyr 3.3:1.sup. 20:6 X.01 Isopyrazam 10:1 60:6 X.01 Isopyrazam 30:1 60:2 X.14 Isopyrazam 1:1 6:6 X.14 Isopyrazam 3:1 6:2 X.14 Isopyrazam 1:3 2:6 X.01 Penthiopyrad 10:1 60:6 X.01 Penthiopyrad 30:1 60:2 X.14 Penthiopyrad 1:1 6:6 X.14 Penthiopyrad 3:1 6:2 X.14 Penthiopyrad 1:3 2:6 X.01 Pydiflumetofen 10:1 60:6 X.01 Pydiflumetofen 30:1 60:2 X.14 Pydiflumetofen 10:1 60:6 X.25 Pydiflumetofen 10:1 60:6 X.24 Pydiflumetofen 3:1 60:20 X.24 Pydiflumetofen 10:1 60:6 X.01 Fluopyram 10:1 60:6 X.01 Fluopyram 30:1 60:2 X.14 Fluopyram 10:1 60:6 X.14 Fluopyram 30:1 60:2 X.25 Fluopyram 3:1 60:20 X.25 Fluopyram 10:1 60:6 X.24 Fluopyram 3:1 60:20 X.24 Fluopyram 10:1 60:6 X.24 Fluopyram 1:1 20:20 X.01 Azoxystrobin 1000:1 .sup.60:0.06 X.14 Azoxystrobin 1000:1 .sup.60:0.06 X.07 Azoxystrobin 1000:1 .sup.60:0.06 X.25 Azoxystrobin 100:1 60:0.6 X.25 Azoxystrobin 300:1 60:0.2 X.25 Azoxystrobin 33.33:1 20:0.6 X.25 Azoxystrobin 100:1 20:0.2 X.24 Azoxystrobin 100:1 60:0.6 X.24 Azoxystrobin 300:1 60:0.2 X.24 Azoxystrobin 33.33:1 20:0.6 X.24 Azoxystrobin 100:1 20:0.2 X.01 Trifloxystrobin 1000:1 .sup.60:0.06 X.14 Trifloxystrobin 1000:1 .sup.60:0.06 X.14 Trifloxystrobin 3000:1 .sup.60:0.02 X.25 Trifloxystrobin 100:1 60:0.6 X.24 Trifloxystrobin 300:1 60:0.2 X.24 Trifloxystrobin 100:1 60:0.6 X.01 Pyraclostrobin 100:1 60:0.6 X.01 Pyraclostrobin 300:1 60:0.2 X.01 Pyraclostrobin 33:1 20:0.6 X.01 Pyraclostrobin 100:1 20:0.2 X.14 Pyraclostrobin 10:1 .sup.6:0.6 X.14 Pyraclostrobin 30:1 .sup.6:0.2 X.14 Pyraclostrobin 3.3:1.sup. .sup.2:0.6 X.14 Pyraclostrobin 10:1 .sup.2:0.2 X.25 Pyraclostrobin 100:1 60:0.6 X.25 Pyraclostrobin 300:1 60:0.2 X.24 Pyraclostrobin 100:1 60:0.6 X.24 Pyraclostrobin 300:1 60:0.2 X.01 Cyproconazole 100:1 60:0.6 X.01 Cyproconazole 300:1 60:0.2 X.14 Cyproconazole 100:1 60:0.6 X.14 Cyproconazole 300:1 60:0.2 X.25 Cyproconazole 100:1 60:0.6 X.25 Cyproconazole 300:1 60:0.2 X.24 Cyproconazole 100:1 60:0.6 X.24 Cyproconazole 300:1 60:0.2 X.01 Difenoconazole 10:1 60:6 X.01 Difenoconazole 30:1 60:2 X.01 Difenoconazole 3.3:1.sup. 20:6 X.14 Difenoconazole 1:1 6:6 X.24 Difenoconazole 10:1 60:6 X.24 Difenoconazole 30:1 60:2 X.01 Hexaconazole 10:1 60:6 X.01 Hexaconazole 30:1 60:2 X.01 Hexaconazole 3.3:1.sup. 20:6 X.25 Hexaconazole 10:1 60:6 X.24 Hexaconazole 10:1 60:6 X.24 Hexaconazole 30:1 60:2 X.01 Propiconazole 10:1 60:6 X.01 Propiconazole 30:1 60:2 X.25 Mefentrifluconazole 30:1 60:2 X.24 Mefentrifluconazole 10:1 60:6 X.24 Mefentrifluconazole 30:1 60:2 X.14 Prothioconazole 10:1 60:6 X.14 Prothioconazole 30:1 60:2 X.14 Prothioconazole 3.3:1.sup. 20:6 X.25 Prothioconazole 30:1 60:2 X.24 Prothioconazole 10:1 60:6 X.24 Prothioconazole 30:1 60:2 X.01 Chlorothalonil 1:1 60:60 X.01 Chlorothalonil 3:1 60:20 X.01 Chlorothalonil 1:3 20:60 X.01 Chlorothalonil 1:1 20:20 X.14 Chlorothalonil 1:1 60:60 X.14 Chlorothalonil 3:1 60:20 X.14 Chlorothalonil 1:3 20:60 X.04 Chlorothalonil 60:60 60:60 X.04 Chlorothalonil 60:20 60:20 X.07 Chlorothalonil 60:60 60:60 X.25 Chlorothalonil 1:1 60:60 X.25 Chlorothalonil 3:1 60:20 X.25 Chlorothalonil 1:3 20:60 X.24 Chlorothalonil 1:1 60:60 X.24 Chlorothalonil 3:1 60:20 X.24 Chlorothalonil 1:3 20:60 X.24 Chlorothalonil 1:1 20:20 X.01 Mancozeb 1:1 60:60 X.01 Mancozeb 3:1 60:20 X.01 Mancozeb 1:3 20:60 X.01 Mancozeb 1:1 20:20 X.14 Mancozeb 1:1 60:60 X.14 Mancozeb 3:1 60:20 X.14 Mancozeb 1:3 20:60 X.14 Mancozeb 1:1 20:20 X.04 Mancozeb 1:1 60:60 X.04 Mancozeb 3:1 60:20 X.04 Mancozeb 1:3 20:60 X.04 Mancozeb 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.25 Mancozeb 1:1 60:60 X.25 Mancozeb 3:1 60:20 X.25 Mancozeb 1:3 20:60 X.25 Mancozeb 1:1 20:20 X.24 Mancozeb 1:1 60:60 X.24 Mancozeb 3:1 60:20 X.24 Mancozeb 1:3 20:60 X.24 Mancozeb 1:1 20:20 X.01 fosetyl-aluminium .sup.1:3.3 60:200 X.01 fosetyl-aluminium 1:1 60:60 X.01 fosetyl-aluminium 1:10 20:200 X.14 fosetyl-aluminium .sup.1:3.3 60:200 X.14 fosetyl-aluminium 1:1 60:60 X.14 fosetyl-aluminium 1:10 20:200 X.01 Acibenzolar-S-methyl .sup.1:3.3 60:200 X.01 Acibenzolar-S-methyl 1:1 60:60 X.01 Acibenzolar-S-methyl 1:10 20:200 X.01 Acibenzolar-s-methyl 1:3 20:60 X.14 Acibenzolar-S-methyl 1:33.3 6:200 X.14 Acibenzolar-S-methyl 1:10 6:60 X.14 Acibenzolar-S-methyl 1:100 2:200 X.14 Acibenzolar-S-methyl 1:30 2:60 X.04 Acibenzolar-S-methyl .sup.1:3.3 60:200 X.04 Acibenzolar-S-methyl 1:1 60:60 X.04 Acibenzolar-S-methyl 1:10 20:200 X.04 Acibenzolar-s-methyl .sup.1:3.3 20:60 X.07 Acibenzolar-S-methyl .sup.1:3.3 60:200 X.07 Acibenzolar-S-methyl 1:1 60:60 X.07 Acibenzolar-S-methyl 1:10 20:200 X.07 Acibenzolar-S-methyl .sup.1:3.3 20:60 X.25 Acibenzolar-S-methyl .sup.1:3.3 60:200 X.25 Acibenzolar-S-methyl 1:1 60:60 X.25 Acibenzolar-S-methyl 1:10 20:200 X.25 Acibenzolar-S-methyl .sup.1:3.3 20:60 X.24 Acibenzolar-S-methyl .sup.1:3.3 60:200 X.24 Acibenzolar-S-methyl 1:1 60:60 X.24 Acibenzolar-S-methyl 1:10 20:200 X.24 Acibenzolar-S-methyl .sup.1:3.3 20:60

Example B4

Puccinia recondita/Wheat/Preventive (Brown Rust on Wheat)PUCCTRZ/fo-pr-P+PUCCTRZ/fo-pr-S

[0535] 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.

[0536] 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.01 Benzovindiflupyr 1000:1 60:0.06 X.01 Benzovindiflupyr 3000:1 60:0.02 X.14 Benzovindiflupyr 1000:1 60:0.06 X.14 Benzovindiflupyr 3000:1 60:0.02 X.04 Benzovindiflupyr 1000:1 60:0.06 X.25 Benzovindiflupyr 3:1 60:20 X.25 Benzovindiflupyr 10:1 60:6 X.25 Benzovindiflupyr 1:1 20:20 X.24 Benzovindiflupyr 3:1 60:20 X.24 Benzovindiflupyr 10:1 60:6 X.24 Benzovindiflupyr 1:1 20:20 X.24 Benzovindiflupyr 3.3:1 20:6 X.01 Isopyrazam 10:1 60:6 X.01 Isopyrazam 30:1 60:2 X.01 Isopyrazam 3.3:1 20:6 X.01 Isopyrazam 10:1 20:2 X.14 Isopyrazam 1:1 6:6 X.14 Isopyrazam 3:1 6:2 X.14 Isopyrazam 1:3 2:6 X.14 Isopyrazam 1:1 2:2 X.01 Penthiopyrad 10:1 60:6 X.01 Penthiopyrad 30:1 60:2 X.01 Penthiopyrad 3.3:1 20:6 X.01 Penthiopyrad 10:1 20:2 X.14 Penthiopyrad 1:1 6:6 X.14 Penthiopyrad 3:1 6:2 X.14 Penthiopyrad 1:3 2:6 X.14 Penthiopyrad 1:1 2:2 X.01 Pydiflumetofen 10:1 60:6 X.01 Pydiflumetofen 30:1 60:2 X.14 Pydiflumetofen 10:1 60:6 X.04 Pydiflumetofen 1000:1 60:0.06 X.25 Pydiflumetofen 10:1 60:6 X.24 Pydiflumetofen 3:1 60:20 X.24 Pydiflumetofen 10:1 60:6 X.24 Pydiflumetofen 1:1 20:20 X.24 Pydiflumetofen 3.3:1 20:6 X.01 Fluopyram 10:1 60:6 X.01 Fluopyram 30:1 60:2 X.14 Fluopyram 10:1 60:6 X.14 Fluopyram 30:1 60:2 X.25 Fluopyram 3:1 60:20 X.25 Fluopyram 10:1 60:6 X.24 Fluopyram 3:1 60:20 X.24 Fluopyram 10:1 60:6 X.24 Fluopyram 1:1 20:20 X.24 Fluopyram 3.3:1 20:6 X.01 Azoxystrobin 1000:1 60:0.06 X.14 Azoxystrobin 1000:1 60:0.06 X.04 Azoxystrobin 1000:1 60:0.06 X.04 Azoxystrobin 3000:1 60:0.02 X.07 Azoxystrobin 1000:1 60:0.06 X.07 Azoxystrobin 333.33:1 20:0.06 X.25 Azoxystrobin 100:1 .sup.60:0.6 X.25 Azoxystrobin 300:1 .sup.60:0.2 X.25 Azoxystrobin 33.33:1 .sup.20:0.6 X.25 Azoxystrobin 100:1 .sup.20:0.2 X.24 Azoxystrobin 100:1 .sup.60:0.6 X.24 Azoxystrobin 300:1 .sup.60:0.2 X.24 Azoxystrobin 33.33:1 .sup.20:0.6 X.24 Azoxystrobin 100:1 .sup.20:0.2 X.01 Trifloxystrobin 1000:1 60:0.06 X.14 Trifloxystrobin 1000:1 60:0.06 X.14 Trifloxystrobin 3000:1 60:0.02 X.04 Trifloxystrobin 3000:1 60:0.02 X.25 Trifloxystrobin 100:1 .sup.60:0.6 X.25 Trifloxystrobin 300:1 .sup.60:0.2 X.24 Trifloxystrobin 100:1 .sup.60:0.6 X.24 Trifloxystrobin 300:1 .sup.60:0.2 X.24 Trifloxystrobin 33.33:1 .sup.20:0.6 X.24 Trifloxystrobin 100:1 .sup.20:0.2 X.01 Pyraclostrobin 100:1 .sup.60:0.6 X.01 Pyraclostrobin 300:1 .sup.60:0.2 X.01 Pyraclostrobin 33:1 .sup.20:0.6 X.07 Pyraclostrobin .sup.60:0.6 .sup.60:0.6 X.07 Pyraclostrobin .sup.60:0.2 .sup.60:0.2 X.25 Pyraclostrobin 100:1 .sup.60:0.6 X.25 Pyraclostrobin 300:1 .sup.60:0.2 X.24 Pyraclostrobin 100:1 .sup.60:0.6 X.24 Pyraclostrobin 300:1 .sup.60:0.2 X.24 Pyraclostrobin 33.33:1 .sup.20:0.6 X.24 Pyraclostrobin 100:1 .sup.20:0.2 X.01 Cyproconazole 100:1 .sup.60:0.6 X.01 Cyproconazole 300:1 .sup.60:0.2 X.14 Cyproconazole 100:1 .sup.60:0.6 X.14 Cyproconazole 300:1 .sup.60:0.2 X.04 Cyproconazole .sup.60:0.6 .sup.60:0.6 X.04 Cyproconazole .sup.60:0.2 .sup.60:0.2 X.07 Cyproconazole 100:1 .sup.60:0.6 X.07 Cyproconazole 300:1 .sup.60:0.2 X.07 Cyproconazole 33.33:1 .sup.20:0.6 X.07 Cyproconazole 100:1 .sup.20:0.2 X.25 Cyproconazole 10:1 60:6 X.25 Cyproconazole 30:1 60:2 X.24 Cyproconazole 10:1 60:6 X.24 Cyproconazole 30:1 60:2 X.24 Cyproconazole 3.33:1.sup. 20:6 X.24 Cyproconazole 10:1 20:2 X.01 Difenoconazole 10:1 60:6 X.01 Difenoconazole 30:1 60:2 X.01 Difenoconazole 3.3:1 20:6 X.01 Difenoconazole 10:1 20:2 X.14 Difenoconazole 1:1 6:6 X.14 Difenoconazole 3:1 6:2 X.14 Difenoconazole 1:3 2:6 X.14 Difenoconazole 1:1 2:2 X.04 Difenoconazole 10:1 60:6 X.04 Difenoconazole 30:1 60:2 X.04 Difenoconazole 3.33:1.sup. 20:6 X.04 Difenoconazole 10:1 20:2 X.07 Difenoconazole 10:1 60:6 X.07 Difenoconazole 30:1 60:2 X.07 Difenoconazole 3.33:1.sup. 20:6 X.07 Difenoconazole 10:1 20:2 X.25 Difenoconazole 10:1 60:6 X.25 Difenoconazole 30:1 60:2 X.25 Difenoconazole 3.33:1.sup. 20:6 X.25 Difenoconazole 10:1 20:2 X.24 Difenoconazole 10:1 60:6 X.24 Difenoconazole 30:1 60:2 X.24 Difenoconazole 3.33:1.sup. 20:6 X.24 Difenoconazole 10:1 20:2 X.01 Hexaconazole 10:1 60:6 X.01 Hexaconazole 30:1 60:2 X.01 Hexaconazole 3.3:1 20:6 X.14 Hexaconazole 1:1 6:6 X.04 Hexaconazole 10:1 60:6 X.04 Hexaconazole 30:1 60:2 X.04 Hexaconazole 3.33:1.sup. 20:6 X.07 Hexaconazole 10:1 60:6 X.07 Hexaconazole 30:1 60:2 X.07 Hexaconazole 3.33:1.sup. 20:6 X.25 Hexaconazole 10:1 60:6 X.25 Hexaconazole 30:1 60:2 X.25 Hexaconazole 3.33:1.sup. 20:6 X.24 Hexaconazole 10:1 60:6 X.24 Hexaconazole 30:1 60:2 X.24 Hexaconazole 3.33:1.sup. 20:6 X.24 Hexaconazole 10:1 20:2 X.01 Propiconazole 30:1 60:2 X.01 Mefentrifluconazole 10:1 60:6 X.01 Mefentrifluconazole 30:1 60:2 X.01 Mefentrifluconazole 3.3:1 20:6 X.01 Mefentrifluconazole 10:1 20:2 X.14 Mefentrifluconazole 1:1 6:6 X.14 Mefentrifluconazole 3:1 6:2 X.14 Mefentrifluconazole 1:3 2:6 X.14 Mefentrifluconazole 1:1 2:2 X.04 Mefentrifluconazole 10:1 60:6 X.04 Mefentrifluconazole 30:1 60:2 X.04 Mefentrifluconazole 3.33:1.sup. 20:6 X.04 Mefentrifluconazole 10:1 20:2 X.07 Mefentrifluconazole 10:1 60:6 X.07 Mefentrifluconazole 30:1 60:2 X.07 Mefentrifluconazole 3.33:1.sup. 20:6 X.07 Mefentrifluconazole 10:1 20:2 X.25 Mefentrifluconazole 10:1 60:6 X.25 Mefentrifluconazole 30:1 60:2 X.24 Mefentrifluconazole 10:1 60:6 X.24 Mefentrifluconazole 30:1 60:2 X.24 Mefentrifluconazole 3.33:1.sup. 20:6 X.24 Mefentrifluconazole 10:1 20:2 X.01 Prothioconazole 10:1 60:6 X.01 Prothioconazole 30:1 60:2 X.01 Prothioconazole 3.3:1 20:6 X.14 Prothioconazole 10:1 60:6 X.14 Prothioconazole 30:1 60:2 X.14 Prothioconazole 3.3:1 20:6 X.25 Prothioconazole 10:1 60:6 X.25 Prothioconazole 30:1 60:2 X.24 Prothioconazole 10:1 60:6 X.24 Prothioconazole 30:1 60:2 X.24 Prothioconazole 3.33:1.sup. 20:6 X.24 Prothioconazole 10:1 20:2 X.01 Chlorothalonil 1:1 60:60 X.01 Chlorothalonil 3:1 60:20 X.01 Chlorothalonil 1:3 20:60 X.01 Chlorothalonil 1:1 20:20 X.14 Chlorothalonil 1:1 60:60 X.14 Chlorothalonil 3:1 60:20 X.14 Chlorothalonil 1:3 20:60 X.25 Chlorothalonil 1:1 60:60 X.25 Chlorothalonil 3:1 60:20 X.25 Chlorothalonil 1:3 20:60 X.24 Chlorothalonil 1:1 60:60 X.24 Chlorothalonil 3:1 60:20 X.24 Chlorothalonil 1:3 20:60 X.24 Chlorothalonil 1:1 20:20 X.01 Mancozeb 1:1 60:60 X.01 Mancozeb 3:1 60:20 X.01 Mancozeb 1:3 20:60 X.01 Mancozeb 1:1 20:20 X.14 Mancozeb 1:1 60:60 X.14 Mancozeb 3:1 60:20 X.14 Mancozeb 1:3 20:60 X.14 Mancozeb 1:1 20:20 X.25 Mancozeb 3:1 60:20 X.24 Mancozeb 1:1 60:60 X.24 Mancozeb 3:1 60:20 X.24 Mancozeb 1:3 20:60 X.24 Mancozeb 1:1 20:20 X.01 fosetyl-aluminium 1:3.3 60:200 X.01 fosetyl-aluminium 1:1 60:60 X.24 Acibenzolar-S-methyl 1:3.3 60:200 X.24 Acibenzolar-S-methyl 1:1 60:60 X.24 Acibenzolar-S-methyl 1:10 20:200 X.24 Acibenzolar-S-methyl 1:3.3 20:60