Fungicidal compositions

Abstract

A fungicidal composition comprising a mixture of components (A) and (B), wherein component (A) defined by formula (I) is a 3,4-dihydroisoquinoline having a 1-benzimidazolyl substituent and component (B) is selected from difenoconazole, hexaconazole, azoxystrobin, fludioxonil, cyprodinil, fluazinam, isopyrazam, pyroquilon, tricyclazole, chlorothalonil, propiconazole, penconazole, fenpropimorph, fenpropidin, sulphur and Bacillus subtilis var. amyloliquefacien s Strain FZB24. The use of the composition 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), wherein component (A) is a compound of formula (I) ##STR00098## wherein R.sup.1 is fluoro or methyl; R.sup.2 is fluoro or methyl; R.sup.3 is hydrogen or fluoro; R.sup.4 is hydrogen, fluoro or chloro; R.sup.5 is hydrogen, methyl or fluoro; or a salt, enantiomer, tautomer, or N-oxide thereof; and component (B) is a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Pyroquilon, Tricyclazole, Chlorothalonil, Propiconazole, Penconazole, Fenpropimorph, Fenpropidin, Sulfur, and Bacillus subtilis var. amyloliquefaciens Strain FZB24, wherein the weight ratio of component (A) to component (B) is from 20:1 to 1:40.

2. A fungicidal composition according claim 1 wherein component (A) is a compound selected from 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 6-chloro-1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 4,4,5-trifluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-5-fluoro-3,3,4,4-tetramethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, and 5-fluoro-3,3,4,4-tetramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline; or a salt, enantiomer, tautomer or N-oxide of one of those compounds.

3. A fungicidal composition according to claim 1 wherein component (A) is 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline; or a salt, enantiomer, tautomer or N-oxide thereof.

4. A fungicidal composition according to claim 1 wherein component (A) is 6-chloro-1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-; or a salt, enantiomer, tautomer or N-oxide thereof.

5. A fungicidal composition according to claim 1 wherein component (A) is 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-di methyl-isoquinoline; or a salt, enantiomer, tautomer or N-oxide thereof.

6. A fungicidal composition according to claim 1 wherein component (A) is 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline; or a salt, enantiomer, tautomer or N-oxide thereof.

7. A fungicidal composition according to claim 1 wherein component (B) is a compound selected from the group consisting of Pydiflumetofen, Benzovindiflupyr, Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Pyroquilon, Tricyclazole, Chlorothalonil, Propiconazole, Bacillus subtilis var. amyloliquefaciens Strain FZB24.

8. A fungicidal composition according to claim 1 wherein component (B) is a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr and Bacillus subtilis var. amyloliquefaciens Strain FZB24.

9. A fungicidal composition according to claim 1 wherein component (B) is pydiflumetofen or benzovindiflupyr.

10. 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, benalaxyl, benalaxyl M, furalaxyl, metalaxyl, metalaxyl-M, dodicin, N′-(2,5-Dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N′44-(4,5-Dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, N′444[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, ethirimol, clozylacon, cyprodinil, mepanipyrim, pyrimethanil, dithianon, aureofungin, blasticidin-S, biphenyl, chloroneb, dicloran, hexachlorobenzene, quintozene, tecnazene, tolclofos-methyl, aminopyrifen, metrafenone, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, fluopicolide, tioxymid, flusulfamide, benomyl, carbendazim, carbendazim chlorhydrate, chlorfenazole, fuberidazole, thiabendazole, thiophanate-methyl, benthiavalicarb, chlobenthiazone, probenazole, acibenzolar, bethoxazin, pyriofenone, acibenzolar-S-methyl, pyribencarb, butylamine, 3-iodo-2-propinyl n-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-cldipyrrole-1,3,5,7(2H,6H)-tetraone, azithiram, etem, ferbam, mancozeb, maneb, metam, metiram, metiram-zinc, nabam, propineb, thiram, (metam sodium), zineb, ziram, dithioether, isoprothiolane, ethaboxam, fosetyl, phosetyl-Al, methyl bromide, methyl iodide, methyl isothiocyanate, cyclafuramid, fenfuram, validamycin, streptomycin, 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, dingjunezuo, oxathiapiprolin, fluoroimide, mandipropamid, KSF-1002, benzamorf, dimethomorph, fenpropimorph, tridemorph, dodemorph, diethofencarb, fentin acetate, fentin hydroxide, carboxin, oxycarboxin, drazoxolon, famoxadone, m-phenylphenol, p-phenylphenol, tribromophenol, 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, trinexapac, uniconazole, a-naphthalene acetic acid, polyoxin D, 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, 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,_spiroxamine, (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, mandestrobin, azoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrobin 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, silthiofam, zoxamide, anilazine, tricyclazole, (+-)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, 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, 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, Mmefentrifluconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triazoxide, triticonazole, 2-[[(1R,5S)-5-[(4-fluorophenyl)methyl]-1-hydroxy-2,2-dimethyl-cyclopentyl]methyl]-4H-1,2,4-triazole-3-thione 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1,2,4-triazole-3-thione, ametoctradin, iprovalicarb, valifenalate, 2-benzyl-4-chlorophenol, allyl alcohol, azafenidin, benzalkonium chloride, chloropicrin, cresol, daracide, dichlorophen, difenzoquat, dipyrithione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, NNF-0721, octhilinone, oxasulfuron, propamidine and propionic acid; or an insecticides selected from abamectin, acephate, acetamiprid, amidoflumet, avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole, 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, flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron, 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, 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 agents selected from Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

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

12. A method of controlling or preventing phytopathogens 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 wherein the phytopathogen-is Botryotinia fuceliana, Fusarium culmorum, Gaeumannomyces Graminis, Glomerella Lagenarium, Monographella nivalis, Mycosphaerella graminicola, Magnaporthe grisea, Pyrenophora teres, Sclerotinia sclerotiorum, Pyricularia orzyae, Botrytis cinerea, Glomerella lagenarium, Septoria tritici, or Venturia inequalis.

13. A method according to claim 12 wherein the composition components (A) and (B) are applied in a sequential manner.

14. A fungicidal composition according claim 1 wherein component (A) is compound of formula (I) ##STR00099## wherein R.sup.1 is fluoro or methyl; R.sup.2 is fluoro or methyl; R.sup.3 is hydrogen or fluoro; R.sup.4 is hydrogen, fluoro or chloro; R.sup.5 is hydrogen, methyl or fluoro.

15. A fungicidal composition according claim 14 wherein component (A) is a compound selected from 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 6-chloro-1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 4,4,5-trifluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-5-fluoro-3,3,4,4-tetramethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, and 5-fluoro-3,3,4,4-tetramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline.

16. A fungicidal composition according to claim 14 wherein component (A) is 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline.

17. A fungicidal composition according to claim 14 wherein component (A) is 6-chloro-1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline.

18. A fungicidal composition according to claim 14 wherein component (A) is 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline.

19. A fungicidal composition according to claim 14 wherein component (A) is 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline.

20. A fungicidal composition according to claim 14 wherein component (B) is chlorothalonil, tricyclazole, pyroquilon, propiconazole, isopyrazam, fluazinam, cyprodinil, fludioxonil, azoxystrobin, hexaconazole, difenoconazole, benzovindiflupyr, or pydiflumetofen.

21. A fungicidal composition, comprising: (A) 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline; and (B) a component selected from the group consisting of: chlorothalonil, tricyclazole, pyroquilon, aminopyrifen, propiconazole, isopyrazam, fluazinam, cyprodinil, fludioxonil, azoxystrobin, hexaconazole, difenoconazole, benzovindiflupyr, and pydiflumetofen, wherein the weight ratio of (A) to (B) is from 20:1 to 1:40.

Description

EXAMPLES

(1) The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds 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, 0.8 ppm or 0.2 ppm.

(2) Throughout this description, temperatures are given in degrees Celsius and “m.p.” means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the methods are:

(3) Method G:

(4) Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters (SQD, SQDII or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2 min; Flow (ml/min) 0.85

(5) Method H:

(6) Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters (SQD, SQDII or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 2.7 min; Flow (ml/min) 0.85

FORMULATION EXAMPLES

(7) TABLE-US-00003 Wettable powders a) b) c) active ingredient [compound of formula (I)] 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% —

(8) 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.

(9) TABLE-US-00004 Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25% 50% 75% light mineral oil 5% 5%  5% highly dispersed silicic acid 5% 5% — Kaolin 65% 40% — Talcum — 20

(10) 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.

(11) TABLE-US-00005 Emulsifiable concentrate active ingredient [compound of formula (I)] 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%

(12) Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

(13) TABLE-US-00006 Dusts a) b) c) Active ingredient  5%  6%  4% [compound of formula (I)] talcum 95% — — Kaolin — 94% — mineral filler — — 96%

(14) 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.

(15) TABLE-US-00007 Extruder granules Active ingredient [compound of formula (I)] 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%

(16) 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.

(17) TABLE-US-00008 Coated granules Active ingredient [compound of formula (I)] 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%

(18) 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.

(19) TABLE-US-00009 Suspension concentrate active ingredient [compound of formula (I)] 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%

(20) 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.

(21) TABLE-US-00010 Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 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 0.5%   in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%   Water 45.3%  

(22) 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.

(23) Slow Release Capsule Suspension

(24) 28 parts of a combination of the compound of formula I are 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.

(25) 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.

(26) The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

PREPARATION EXAMPLES

Example 1

(27) This example illustrates the preparation of 5-fluoro-3,3,4,4-tetramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline.

Step 1: Preparation of ethyl-2-(2-fluorophenyl)-2-methyl-propanoate

(28) To a suspension of sodium hydride (0.69 mol, 27.4 g) in tetrahydrofuran (220 mL) at room temperature was added dropwise a solution of ethyl-2-(2-fluorophenyl)acetate (0.27 mol, 50.0 g) and iodomethane (0.82 mmol, 117.9 g) in tetrahydrofuran (60 mL, conc. Total 1 M) and the mixture was stirred at room temperature overnight. The reaction was quenched by the slow addition of a saturated aqueous solution ammonium chloride and then poured into 300 mL of ice-water mixture. The aqueous phase was extracted with ethyl acetate, and the combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (heptane/ethyl acetate=19:1) to give ethyl-2-(2-fluorophenyl)-2-methyl-propanoate as a pale yellow oil: LC-MS (Method H) UV Detection: 220 nm, Rt=1.60; MS: (M+1)=211.2; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.16-1.23 (m, 3H) 1.57 (s, 6H) 4.17 (d, J=6.97 Hz, 2H) 6.99-7.05 (m, 1H) 7.11-7.17 (m, 1H) 7.22-7.28 (m, 1H) 7.33 (td, J=7.89, 1.83 Hz, 1H); .sup.19F NMR (377 MHz, CHLOROFORM-d) δ ppm −113.26 (s, 1 F).

Step 2: Preparation of 3-(2-fluorophenyl)-2,3-dimethyl-butan-2-ol

(29) A solution of ethyl-2-(2-fluorophenyl)-2-methyl-propanoate (0.25 mol, 52.1 g) and lanthanum(III) chloride bis(lithium chloride) complex (0.6 M in THF, 0.50 equiv., 0.12 mol, 207 mL) in tetrahydrofuran (1.2 M) was stirred at room temperature for 1.5 h. The reaction was then cooled to 0° C. and a solution of methyl magnesium bromide (3.0 M in diethyl ether, 3.0 equiv, 0.74 mol, 248 mL) was subsequently added dropwise. The reaction mixture was stirred at room temperature overnight, cooled to 0° C. and then quenched by the dropwise addition of a saturated aqueous solution of ammonium chloride solution. Water was added and the reaction mixture was stirred for an additional 30 min. The reaction mixture was filtered over Celite and the two phases were separated. The aqueous phase was extracted with tert-butyl methyl ether, and the combined organic phases were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give 3-(2-fluorophenyl)-2,3-dimethyl-butan-2-ol as a yellowish solid: LC-MS (Method H) UV Detection: 220 nm, Rt=1.46; MS: (M-OH)=179.3; m.p. 42-43° C.; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.19 (d, J=1.10 Hz, 6H) 1.50 (d, J=2.93 Hz, 6H) 6.97-7.04 (m, 1H) 7.07-7.12 (m, 1H) 7.18-7.24 (m, 1H) 7.40 (td, J=8.25, 1.83 Hz, 1H); .sup.19F NMR (377 MHz, CHLOROFORM-d) δ ppm −104.04 (s, 1 F).

Step 3: Preparation of 5-fluoro-3,3,4,4-tetramethyl-1-methylsulfanyl-isoquinoline

(30) To cooled (0° C.) sulfuric acid (98% w/w, 133 mL, 1M) was added a mixture of methyl thiocyanate (133 mmol, 9.73 g) and 3-(2-fluorophenyl)-2,3-dimethyl-butan-2-ol (1.00 equiv., 133 mmol, 26.1 g) portion-wise over 15 min, and the mixture was stirred at room temperature for additional 20 min. The reaction mixture was carefully poured into 600 ml ice water and the pH of the water layer was adjusted to ˜8 using an aqueous solution of NaOH (30% w/w). The aqueous phase was extracted with ethyl acetate and the combined organic phases were dried with Na.sub.2SO.sub.4, filtered and concentrated in vacuo to afford (25.1 g, 75%) of 5-fluoro-3,3,4,4-tetramethyl-1-methylsulfanyl-isoquinoline as a pale yellow oil: LC-MS (Method G) UV Detection: 220 nm, Rt=; MS: (M+1)=; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.10 (s, 6H) 1.24 (d, J=2.93 Hz, 6H) 2.34 (s, 3H) 7.00 (ddd, J=12.20, 8.34, 1.10 Hz, 1H) 7.07-7.21 (m, 1H) 7.32-7.42 (m, 1H); .sup.19F NMR (377 MHz, CHLOROFORM-d) δ ppm −111.06 (s, 1 F).

Step 4: Preparation of 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1-one

(31) To a solution of 5-fluoro-3,3,4,4-tetramethyl-1-methylsulfanyl-isoquinoline (99.8 mmol, 25.1 g) in a mixture of acetic acid (160 mL, 0.25 M) and water (40 mL) was added sodium acetate (0.10 equiv., 9.98 mmol, 0.818 g) and the mixture was heated at reflux for 2 h. The reaction mixture was then cooled down to room temperature and most of the acetic acid solution was removed under vacuo. The residue was then carefully added to a mixture of saturated aqueous NaHCO.sub.3 and ethyl acetate. The two layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic phases were washed with saturated aqueous NaHCO.sub.3, water and brine, dried with Na.sub.2SO.sub.4, filtered and concentrated in vacuo to afford 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1-one (21.4 g, 97%) as a pale yellow oil: LC-MS (Method G) UV Detection: 220 nm, Rt=1.28; MS: (M+1)=222.2; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.21 (s, 6H) 1.36 (d, J=1.00 Hz, 6H) 6.19 (br. s, 1H) 7.12 (ddd, J=12.38, 8.34, 1.28 Hz, 1H) 7.20-7.26 (m, 1H) 7.85 (dd, J=7.52, 1.28 Hz, 1H); .sup.19F NMR (377 MHz, CHLOROFORM-d) δ ppm −111.05 (s, 1 F).

Step 5: Preparation of 1-chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline

(32) To a solution of N,N-dimethylformamide (6.3 mmol, 0.49 mL) in dichloromethane (8 mL, 0.8 M) at room temperature was added oxalyl chloride (1.3 equiv., 6.01 mmol, 0.53 mL) dropwise and the white suspension was vigorously stirred for 30 min. A solution of 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1-one (4.52 mmol, 1.00 g) in dichloromethane (9 mL, 0.5 M) was then added dropwise and the mixture was stirred at room temperature for 2 h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHCO.sub.3 solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated to give 1-chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline (1.02 g, 94% yield) as a colourless oil: LC-MS (Method G) UV Detection: 220 nm, Rt=1.16; MS: (M+1)=240-242; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.27 (s, 6H) 1.38 (s, 6H) 7.15-7.20 (m, 1H) 7.26-7.36 (m, 1H) 7.62 (d, 1H).

Step 6: Preparation of 5-fluoro-3,3,4,4-tetramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline

(33) To a solution of 1-chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline (1.67 mmol, 0.430 g) in pyridine (0.20 M, 9.0 mL) at room temperature was added 4-methyl-1H-benzimidazole (1.5 equiv., 2.69 mmol, 0.356 g) and the mixture was stirred at 90° C. for 15 hours. The reaction mixture was allowed to cool down to room temperature and then concentrated under vacuo. The residue obtained was purified by flash chromatography to give 5-fluoro-3,3,4,4-tetramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline (0.525 g, 87% yield) as a beige solid: mp=118-120° C., LC-MS (Method G) UV Detection: 220 nm, Rt=1.19, MS: (M+1)=336; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.32 (s, 6H) 1.47 (s, 6H) 2.71 (s, 3H) 6.91-6.95 (m, 1H) 7.10-7.25 (m, 5H) 8.18 (s, 1H).

Example 2: This example illustrates the preparation of 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline

Step 1: Preparation of 3,3-dimethyl-2H-isoquinoline-1,4-dione

(34) To a solution of 3,3-dimethyl-2,4-dihydroisoquinolin-1-one (57.1 mmol, 10.0 g) in CCl.sub.4 (0.20 M, 285 mL) at room temperature was added N-bromosuccinimide (3.0 equiv., 171 mmol, 30.5 g) and AIBN (0.15 equiv., 8.5 mmol, 1.43 g) and the reaction mixture was stirred at 70° C. for 3 hours. The reaction mixture was allowed to cool down to room temperature, concentrated under vacuo and diluted with EtOAc, washed with water and brine, dried over Na.sub.2SO.sub.4, filtered and concentrated to give 4,4-dibromo-3,3-dimethyl-2H-isoquinolin-1-one (25.2 g) as a light yellow solid which was used directly in the next step without further purification: LC-MS (Method H) UV Detection: 220 nm, Rt=1.34; MS: (M+1)=332-334-336; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.57 (s, 6H) 7.21 (br. s, 1H) 7.70-7.77 (m, 1H) 7.78-7.85 (m, 1H) 8.06-8.14 (m, 1H) 8.23-8.30 (m, 1H).

(35) To a solution of 4,4-dibromo-3,3-dimethyl-2H-isoquinolin-1-one (20.0 g) in a mixture of water (450 mL) and tetrahydrofuran (225 mL) was added sodium carbonate (3.0 equiv., 135 mmol, 14.3 g) and the mixture was stirred at room temperature for 12 h and at 70° C. for 4 h 30 min. The reaction mixture was allowed to cool down to room temperature, diluted with water, acidified to PH 3-4 with 90 mL of a 2 M solution of hydrochloric acid and extracted with dichloromethane. The combined organic extracts were dried over Na.sub.2SO.sub.4, filtered and concentrated to give 3,3-dimethyl-2H-isoquinoline-1,4-dione (9.95 g) as a yellow solid: LC-MS (Method H) UV Detection: 220 nm, Rt=0.81; MS: (M+1)=190; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.77 (s, 3H) 1.97 (s, 3H) 7.39 (s, 1H) 7.46-7.58 (m, 1H) 7.60-7.71 (m, 1H) 7.98-8.22 (m, 2H).

Step 2: Preparation of 1-chloro-3,3-dimethyl-isoquinolin-4-one

(36) To a solution of N,N-dimethylformamide (2.3 mL, 30 mmol) in dichloromethane (52 mL, 0.6 M) at room temperature was added oxalyl chloride (0.67 equiv., 20 mmol, 1.8 mL) dropwise over a period of 35 min and the white suspension was vigorously stirred for 15 min until the gas evolution stopped. A solution of 3,3-dimethyl-2H-isoquinoline-1,4-dione (2.5 g, 13 mmol) in dichloromethane (25 mL) was then added dropwise and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHCO.sub.3 solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated to give 1-chloro-3,3-dimethyl-isoquinolin-4-one (2.5 g, 91% yield) as a yellow solid: LC-MS (Method H) UV Detection: 220 nm, Rt=1.34; MS: (M+1)=208-210; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.47 (s, 6H) 7.62-7.69 (m, 1H) 7.73-7.81 (m, 1H) 7.90 (dd, J=8.07, 0.73 Hz, 1H) 8.04 (dd, J=7.50, 0.90 Hz, 1H).

Step 3: Preparation of 3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinolin-4-one

(37) To a solution of 1-chloro-3,3-dimethyl-isoquinolin-4-one (3.61 mmol, 0.750 g) in pyridine (0.07 M, 50 mL) at room temperature was added 4-methyl-1H-benzimidazole (1.5 equiv., 0.716 g, 5.42 mmol) and the mixture was stirred at 100° C. for 15 hours. The reaction mixture was allowed to cool down to room temperature and then concentrated under vacuo. The residue obtained was purified by flash chromatography to give 3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinolin-4-one (0.569 g, 52% yield) as a brown oil: LC-MS (Method G) UV Detection: 220 nm, Rt=0.98, MS: (M+1)=305; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.63 (s, 6H) 2.75 (s, 3H) 7.15-7.27 (m, 3H) 7.36-7.42 (m, 1H) 7.70-7.82 (m, 2H) 8.18-8.25 (m, 1H) 8.28 (s, 1H).

Step 4: Preparation of 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline

(38) A solution of 3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinolin-4-one (1.85 mmol, 560 mg) in 2,2-difluoro-1,3-dimethyl-imidazolidine (10.0 equiv., 18.5 mmol, 2.4 mL) was stirred at 105° C. overnight. The reaction mixture was allowed to cool down to room temperature, diluted with DCM then quenched by slow addition to a saturated aqueous NaHCO.sub.3 solution. The 2 phases were separated, and the aqueous phase was extracted with DCM. The combined organic phases were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated. The residue was purified by flash chromatography to give 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline (36 mg, 60% yield) as a white solid: LC-MS (Method G) UV Detection: 220 nm, Rt=1.12; MS: (M+1)=326; mp 142-149° C.; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.49 (s, 6H) 2.76 (s, 3H) 7.15-7.27 (m, 2H) 7.34-7.42 (m, 2H) 7.57-7.64 (m, 1H) 7.71-7.79 (m, 1H) 7.90-7.97 (m, 1H) 8.31 (s, 1H); .sup.19F NMR (377 MHz, CHLOROFORM-d) δ ppm-112.38 (br. s., 1 F).

Example 3

(39) This example illustrates the preparation of 1′-(benzimidazol-1-yl)-3′,3′-dimethyl-spiro(cyclopropane-1,4′-isoquinoline)

Step 1: Preparation of 3,3-dimethylspiro(2H-isoquinoline-4,1′-cyclopropane)-1-one

(40) In an autoclave was added a solution of 2-(1-phenylcyclopropyl)propan-2-amine (120 mg, 0.685 mmol), benzoquinone (2.0 equiv., 1.37 mmol, 153 mg) and palladium (II) acetate (0.05 equiv., 0.034 mmol, 7.6 mg) in acetic acid (4.6 mL, 0.15 M) and the high pressure reactor was pressurized with carbon monoxide (3 bars) and heated at 110° C. overnight. The reaction vessel was allowed to cool down to room temperature, depressurized and the reaction mixture was diluted with dichloromethane and quenched by the addition of an aqueous NaOH solution (2.0 M) to reach pH>9. The two phases were separated and the aqueous phase was extracted with dichloromethane twice. The combined organic phases were washed with brine, dried over Na.sub.2SO.sub.4, filtered, concentrated and purified by flash chromatography to give 3,3-dimethylspiro(2H-isoquinoline-4,1′-cyclopropane)-1-one (27 mg, 20% yield) as a yellowish gum: LC-MS (Method G), Rt=0.80; MS: (M+1)=202; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.96 (t, 2H) 1.10 (t, 2H) 1.18 (s, 6H) 6.21 (NH, 1H) 6.91 (d, 1H) 7.20 (t, 1H) 7.45 (t, 1H) 8.09 (d, 1H).

Step 2: Preparation of 1′-chloro-3′,3′-dimethyl-spiro(cyclopropane-1,4′-isoquinoline)

(41) To a solution of N,N-dimethylformamide (0.63 mmol, 0.049 mL) in dichloromethane (1 mL, 0.5 M) at room temperature was added oxalyl chloride (1.3 equiv., 0.63 mmol, 0.056 mL) dropwise and the white suspension was vigorously stirred for 30 min. A solution of 3,3-dimethylspiro(2H-isoquinoline-4,1′-cyclopropane)-1-one (0.423 mmol, 85 mg) in dichloromethane (0.8 mL, conc. total 0.25 M) was then added dropwise and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHCO.sub.3 solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated to give 1′-chloro-3′,3′-dimethyl-spiro(cyclopropane-1,4′-isoquinoline) (101 mg, 98% yield) as a beige liquid: LC-MS (Method G), Rt=1.06; MS: (M+1)=220-222.

Step 3: Preparation of 1′-(benzimidazol-1-yl)-3′,3′-dimethyl-spiro(cyclopropane-1,4′-isoquinoline)

(42) To a solution of 1′-chloro-3′,3′-dimethyl-spiro(cyclopropane-1,4′-isoquinoline) (0.064 mmol, 14 mg) in pyridine (1.3 mL, 0.05M) was added benzimidazole (5 equiv., 0.32 mmol, 38 mg) and the mixture was stirred at 90° C. for 1 h. The reaction mixture was allowed to cool down to room temperature and then concentrated under vacuo. The residue obtained was purified by flash chromatography to give 1′-(benzimidazol-1-yl)-3′,3′-dimethyl-spiro(cyclopropane-1,4′-isoquinoline) (9 mg, 50% yield) as a yellow gum: LC-MS (Method G), Rt=1.04; MS: (M+1)=302; .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.01 (t, 2H) 1.17 (t, 2H) 1.23 (s, 6H) 7.08 (d, 1H) 7.15-7.24 (m, 2H) 7.27-7.35 (m, 2H) 7.48 (t, 1H) 7.52 (d, 1H) 7.84 (d, 1H) 8.30 (s, 1H).

(43) TABLE-US-00011 TABLE E Physical data of compounds of formula I RT [M + H] Entry STRUCTURE (min) (measured) Method MP ° C. E-1 1.15 336.4 G 45-46 E-2 1.13 322.5 G E-3 1.04 302 G E-4 0 1.22 401.3 G 48-49 E-5 1.25 390.5 G E-6 1.13 352.5 G E-7 1.17 340.4 G E-8 1.26 362.5 G E-9 1.10 316 G E-10 0.96 304 G 123-125 E-11 1.30 362.5 G E-12 1.31 364.5 G 113-114 E-13 1.25 348.4 G 70-71 E-14 0 1.25 350.5 G 87-88 E-15 1.10 326 G E-16 1.14 318 G E-17 1.21 356.4 G 50-51 E-18 1.19 350.6 G E-19 1.13 358 G 157-159 E-20 1.08 344 G E-21 1.14 340.5 G E-22 1.18 354.5 G E-23 1.13 340.5 G 132-133 E-24 0 1.10 380.4 G 178-179 E-25 0.99 318.4 G 159-161 E-26 1.03 318.5 G  96-101 E-27 1.07 332.5 G 145-149 E-28 1.81 347 H 199-202 E-29 1.51 325 H E-30 1.21 351 G E-31 1.92 362 H E-32 1.16 344 G 118-121 E-33 1.23 361 G E-34 0 1.71 339 H 129-133 E-35 1.80 357 H 133-136 E-36 1.83 353 H 196-199 E-37 2.00 381 H 197-200 E-38 1.19 369 G 52-54 E-39 1.32 391 G 126-127 E-40 1.17 324 G E-41 1.33 415 G 122-124 E-42 1.31 370 G 102-103 E-43 1.12 302 G 132-133 E-44 0 1.07 290 G E-45 1.27 370 G 147-151 E-46 1.21 354 G 122-125 E-47 1.99 361 H E-48 2.06 379 H E-49 2.10 375 H E-50 1.23 358 G 112-114 E-51 1.27 362 G 177-178 E-52 1.27 330 G E-53 1.20 316 G E-54 0 0.81 302 G E-55 1.88 352 H E-56 1.92 358 H E-57 1.75 322 H 143-145 E-58 1.14 328 G 141-143 E-59 1.06 288 G E-60 1.24 354 G E-61 1.11 314 G

BIOLOGICAL EXAMPLES

(44) Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

(45) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels 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 determined photometrically 3-4 days after application.

(46) The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1, E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-29, E-30, E-31, E-32, E-33, E-34, E-35, E-36, E-37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61

(47) Fusarium culmorum/Liquid Culture (Head Blight)

(48) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato 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 determined photometrically 3-4 days after application.

(49) The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1, E-2, E-4, E-7, E-9, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-30, E-31, E-32, E-33, E-34, E-35, E-36, E-41, E-42, E-45, E-46, E-47, E-48, E-49, E-50, E-51, E-55, E-56, E-57, E-58, E-59, E-60, E-61

(50) Gaeumannomyces Graminis/Liquid Culture (Take-all of Cereals)

(51) Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato 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 determined photometrically 4-5 days after application.

(52) The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1, E-3, E-4, E-7, E-8, E-9, E-14, E-15, E-16, E-17, E-18, E-19, E-21, E-23, E-30, E-31, E-32, E-33, E-37, E-41, E-47, E-48, E-49, E-51, E-58, E-59, E-60, E-61

(53) Glomerella Lagenarium (Colletotrichum Lagenarium)/Liquid Culture (Anthracnose)

(54) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato 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 3-4 days after application.

(55) The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1, E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-30, E-31, E-32, E-33, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-49, E-50, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61

(56) Monographella nivalis (Microdochium Nivale)/Liquid Culture (Foot Rot Cereals)

(57) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato 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 determined photometrically 4-5 days after application.

(58) The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1, E-2, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-30, E-31, E-32, E-33, E-34, E-37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-49, E-50, E-51, E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61

(59) Mycosphaerella graminicola (Septoria tritici)/Liquid Culture (Septoria Blotch)

(60) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato 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 determined photometrically 4-5 days after application.

(61) The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1, E-18, E-21, E-22, E-30, E-32, E-33, E-34, E-35, E-36, E-50, E-53, E-54, E-55, E-56, E-57, E-60

(62) Magnaporthe grisea (Pyricularia oryzae)/Rice/Leaf Disc Preventative (Rice Blast)

(63) Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 22° C. and 80% r.h. under a light regime of 24 h darkness followed by 12 h light/12 h darkness in a climate cabinet and 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 segments (5-7 days after application).

(64) The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-21, E-42, E-49, E-50

(65) Magnaporthe grisea (Pyricularia oryzae)/Liquid Culture (Rice Blast)

(66) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato 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 determined photometrically 3-4 days after application.

(67) The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-1, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-24, E-25, E-26, E-27, E-30, E-31, E-32, E-33, E-34, E-35, E-36, E-37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61

(68) Fusarium culmorum/Wheat/Spikelet Preventative (Head Blight)

(69) Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The spikelets are inoculated with a spore suspension of the fungus 1 day after application. The inoculated spikelets are incubated at 20° C. and 60% rh under a light regime of 72 h semi darkness followed by 12 h light/12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6-8 days after application).

(70) The following compounds gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-20, E-46, E-49, E-56, E-58

(71) Pyrenophora teres/Barley/Leaf Disc Preventative (Net Blotch)

(72) Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20° C. and 65% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5-7 days after application).

(73) The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-16

(74) Pyrenophora teres/Liquid Culture (Net Blotch)

(75) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels 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 determined photometrically 3-4 days after application.

(76) The following compounds gave at least 80% control of Pyrenophora teres at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-1, E-4, E-5, E-6, E-7, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27

(77) Sclerotinia sclerotiorum/Liquid Culture (Cottony Rot)

(78) Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added.

(79) The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 3-4 days after application.

(80) The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-1, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-30, E-31, E-32, E-33, E-37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-55, E-56, E-57, E-58, E-61

FURTHER BIOLOGICAL TEST EXAMPLES

Example B1: Pyricularia orzyae (Rice Blast)

(81) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hrs.

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

(83) TABLE-US-00012 Conc. (ppm) Ratio Composition (B + A) (B:A) (B:A) Pydiflumetofen + Compound X.006 0.8 + 0.2   4:1 Pydiflumetofen + Compound X.006 0.16 + 0.04   4:1 Pydiflumetofen + Compound X.006 0.032 + 0.008   4:1 Pydiflumetofen + Compound X.006 0.2 + 0.2   1:1 Pydiflumetofen + Compound X.006 0.04 + 0.04   1:1 Pydiflumetofen + Compound X.006 0.008 + 0.008   1:1 Pydiflumetofen + Compound X.006 0.2 + 0.8   1:4 Pydiflumetofen + Compound X.006 0.04 + 0.16   1:4 Pydiflumetofen + Compound X.006 0.008 + 0.032   1:4 Benzovindiflupyr + Compound X.006 0.8 + 0.2   4:1 Benzovindiflupyr + Compound X.006 0.16 + 0.04   4:1 Benzovindiflupyr + Compound X.006 0.032 + 0.008   4:1 Benzovindiflupyr + Compound X.006 0.2 + 0.2   1:1 Benzovindiflupyr + Compound X.006 0.04 + 0.04   1:1 Benzovindiflupyr + Compound X.006 0.008 + 0.008   1:1 Benzovindiflupyr + Compound X.006 0.2 + 0.8   1:4 Benzovindiflupyr + Compound X.006 0.04 + 0.16   1:4 Benzovindiflupyr + Compound X.006 0.008 + 0.032   1:4 Difenoconazole + Compound X.006  8 + 0.2 40:1 Difenoconazole + Compound X.006 1.6 + 0.04 40:1 Difenoconazole + Compound X.006 0.32 + 0.008 40:1 Difenoconazole + Compound X.006  2 + 0.2 10:1 Difenoconazole + Compound X.006 0.4 + 0.04 10:1 Difenoconazole + Compound X.006 0.08 + 0.008 10:1 Difenoconazole + Compound X.006  2 + 0.8  5:2 Difenoconazole + Compound X.006 0.4 + 0.16  5:2 Difenoconazole + Compound X.006 0.08 + 0.032  5:2 Hexaconazole + Compound X.006  8 + 0.2 40:1 Hexaconazole + Compound X.006 1.6 + 0.04 40:1 Hexaconazole + Compound X.006 0.32 + 0.008 40:1 Hexaconazole + Compound X.006  2 + 0.2 10:1 Hexaconazole + Compound X.006 0.4 + 0.04 10:1 Hexaconazole + Compound X.006 0.08 + 0.008 10:1 Hexaconazole + Compound X.006  2 + 0.8  5:2 Hexaconazole + Compound X.006 0.4 + 0.16  5:2 Hexaconazole + Compound X.006 0.08 + 0.032  5:2 Azoxystrobin + Compound X.006 0.8 + 0.2   4:1 Azoxystrobin + Compound X.006 0.16 + 0.04   4:1 Azoxystrobin + Compound X.006 0.032 + 0.008   4:1 Azoxystrobin + Compound X.006 0.2 + 0.2   1:1 Azoxystrobin + Compound X.006 0.04 + 0.04   1:1 Azoxystrobin + Compound X.006 0.008 + 0.008   1:1 Azoxystrobin + Compound X.006 0.2 + 0.8   1:4 Azoxystrobin + Compound X.006 0.04 + 0.16   1:4 Azoxystrobin + Compound X.006 0.008 + 0.032   1:4 Fludioxonil + Compound X.006  8 + 0.2 40:1 Fludioxonil + Compound X.006 1.6 + 0.04 40:1 Fludioxonil + Compound X.006 0.32 + 0.008 40:1 Fludioxonil + Compound X.006  2 + 0.2 10:1 Fludioxonil + Compound X.006 0.4 + 0.04 10:1 Fludioxonil + Compound X.006 0.08 + 0.008 10:1 Fludioxonil + Compound X.006  2 + 0.8  5:2 Fludioxonil + Compound X.006 0.4 + 0.16  5:2 Fludioxonil + Compound X.006 0.08 + 0.032  5:2 Cyprodinil + Compound X.006  8 + 0.2 40:1 Cyprodinil + Compound X.006 1.6 + 0.04 40:1 Cyprodinil + Compound X.006 0.32 + 0.008 40:1 Cyprodinil + Compound X.006  2 + 0.2 10:1 Cyprodinil + Compound X.006 0.4 + 0.04 10:1 Cyprodinil + Compound X.006 0.08 + 0.008 10:1 Cyprodinil + Compound X.006  2 + 0.8  5:2 Cyprodinil + Compound X.006 0.4 + 0.16  5:2 Cyprodinil + Compound X.006 0.08 + 0.032  5:2 Fluazinam + Compound X.006  8 + 0.2 40:1 Fluazinam + Compound X.006 1.6 + 0.04 40:1 Fluazinam + Compound X.006 0.32 + 0.008 40:1 Fluazinam + Compound X.006  2 + 0.2 10:1 Fluazinam + Compound X.006 0.4 + 0.04 10:1 Fluazinam + Compound X.006 0.08 + 0.008 10:1 Fluazinam + Compound X.006  2 + 0.8  5:2 Fluazinam + Compound X.006 0.4 + 0.16  5:2 Fluazinam + Compound X.006 0.08 + 0.032  5:2 Isopyrazam + Compound X.006  8 + 0.2 40:1 Isopyrazam + Compound X.006 1.6 + 0.04 40:1 Isopyrazam + Compound X.006 0.32 + 0.008 40:1 Isopyrazam + Compound X.006  2 + 0.2 10:1 Isopyrazam + Compound X.006 0.4 + 0.04 10:1 Isopyrazam + Compound X.006 0.08 + 0.008 10:1 Isopyrazam + Compound X.006  2 + 0.8  5:2 Isopyrazam + Compound X.006 0.4 + 0.16  5:2 Isopyrazam + Compound X.006 0.08 + 0.032  5:2 Propiconazole + Compound X.006  8 + 0.2 40:1 Propiconazole + Compound X.006 1.6 + 0.04 40:1 Propiconazole + Compound X.006 0.32 + 0.008 40:1 Propiconazole + Compound X.006  2 + 0.2 10:1 Propiconazole + Compound X.006 0.4 + 0.04 10:1 Propiconazole + Compound X.006 0.08 + 0.008 10:1 Propiconazole + Compound X.006  2 + 0.8  5:2 Propiconazole + Compound X.006 0.4 + 0.16  5:2 Propiconazole + Compound X.006 0.08 + 0.032  5:2 Aminopyrifen + Compound X.006  8 + 0.2 40:1 Aminopyrifen + Compound X.006 1.6 + 0.04 40:1 Aminopyrifen + Compound X.006 0.32 + 0.008 40:1 Aminopyrifen + Compound X.006  2 + 0.2 10:1 Aminopyrifen + Compound X.006 0.4 + 0.04 10:1 Aminopyrifen + Compound X.006 0.08 + 0.008 10:1 Aminopyrifen + Compound X.006  2 + 0.8  5:2 Aminopyrifen + Compound X.006 0.4 + 0.16  5:2 Aminopyrifen + Compound X.006 0.08 + 0.032  5:2 Pyroquilon + Compound X.006 30 + 0.2  150:1  Pyroquilon + Compound X.006   6 + 0.04 150:1  Pyroquilon + Compound X.006  1.2 + 0.008 150:1  Pyroquilon + Compound X.006  8 + 0.2 40:1 Pyroquilon + Compound X.006 1.6 + 0.04 40:1 Pyroquilon + Compound X.006 0.32 + 0.008 40:1 Pyroquilon + Compound X.006  2 + 0.2 10:1 Pyroquilon + Compound X.006 0.4 + 0.04 10:1 Pyroquilon + Compound X.006 0.08 + 0.008 10:1 Tricyclazole + Compound X.006 30 + 0.2  150:1  Tricyclazole + Compound X.006   6 + 0.04 150:1  Tricyclazole + Compound X.006  1.2 + 0.008 150:1  Tricyclazole + Compound X.006  8 + 0.2 40:1 Tricyclazole + Compound X.006 1.6 + 0.04 40:1 Tricyclazole + Compound X.006 0.32 + 0.008 40:1 Tricyclazole + Compound X.006  2 + 0.2 10:1 Tricyclazole + Compound X.006 0.4 + 0.04 10:1 Tricyclazole + Compound X.006 0.08 + 0.008 10:1 Chlorothalonil + Compound X.006 30 + 0.2  150:1  Chlorothalonil + Compound X.006   6 + 0.04 150:1  Chlorothalonil + Compound X.006  1.2 + 0.008 150:1  Chlorothalonil + Compound X.006  8 + 0.2 40:1 Chlorothalonil + Compound X.006 1.6 + 0.04 40:1 Chlorothalonil + Compound X.006 0.32 + 0.008 40:1 Chlorothalonil + Compound X.006  2 + 0.2 10:1 Chlorothalonil + Compound X.006 0.4 + 0.04 10:1 Chlorothalonil + Compound X.006 0.08 + 0.008 10:1

Example B2: Botrytis cinerea (Gray Mould)

(84) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hrs.

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

(86) TABLE-US-00013 Conc. (ppm) Ratio Composition (B + A) (B:A) (B:A) Pydiflumetofen + Compound X.006 0.8 + 0.2 4:1 Pydiflumetofen + Compound X.006 0.16 + 0.04 4:1 Pydiflumetofen + Compound X.006 0.032 + 0.008 4:1 Pydiflumetofen + Compound X.006 0.2 + 0.2 1:1 Pydiflumetofen + Compound X.006 0.04 + 0.04 1:1 Pydiflumetofen + Compound X.006 0.008 + 0.008 1:1 Pydiflumetofen + Compound X.006 0.2 + 0.8 1:4 Pydiflumetofen + Compound X.006 0.04 + 0.16 1:4 Pydiflumetofen + Compound X.006 0.008 + 0.032 1:4 Benzovindiflupyr + Compound X.006 0.8 + 0.2 4:1 Benzovindiflupyr + Compound X.006 0.16 + 0.04 4:1 Benzovindiflupyr + Compound X.006 0.2 + 0.2 1:1 Benzovindiflupyr + Compound X.006 0.04 + 0.04 1:1 Benzovindiflupyr + Compound X.006 0.2 + 0.8 1:4 Benzovindiflupyr + Compound X.006 0.04 + 0.16 1:4 Benzovindiflupyr + Compound X.006 0.008 + 0.032 1:4 Difenoconazole + Compound X.006   8 + 0.2 40:1  Difenoconazole + Compound X.006  1.6 + 0.04 40:1  Difenoconazole + Compound X.006   2 + 0.2 10:1  Difenoconazole + Compound X.006  0.4 + 0.04 10:1  Difenoconazole + Compound X.006   2 + 0.8 5:2 Difenoconazole + Compound X.006  0.4 + 0.16 5:2 Difenoconazole + Compound X.006  0.08 + 0.032 5:2 Hexaconazole + Compound X.006   8 + 0.2 40:1  Hexaconazole + Compound X.006  1.6 + 0.04 40:1  Hexaconazole + Compound X.006  0.32 + 0.008 40:1  Hexaconazole + Compound X.006   2 + 0.2 10:1  Hexaconazole + Compound X.006  0.4 + 0.04 10:1  Hexaconazole + Compound X.006  0.08 + 0.008 10:1  Hexaconazole + Compound X.006   2 + 0.8 5:2 Hexaconazole + Compound X.006  0.4 + 0.16 5:2 Hexaconazole + Compound X.006  0.08 + 0.032 5:2 Azoxystrobin + Compound X.006 0.8 + 0.2 4:1 Azoxystrobin + Compound X.006 0.16 + 0.04 4:1 Azoxystrobin + Compound X.006 0.2 + 0.2 1:1 Azoxystrobin + Compound X.006 0.04 + 0.04 1:1 Azoxystrobin + Compound X.006 0.2 + 0.8 1:4 Azoxystrobin + Compound X.006 0.04 + 0.16 1:4 Fludioxonil + Compound X.006   8 + 0.2 40:1  Fludioxonil + Compound X.006  1.6 + 0.04 40:1  Fludioxonil + Compound X.006   2 + 0.2 10:1  Fludioxonil + Compound X.006  0.4 + 0.04 10:1  Fludioxonil + Compound X.006   2 + 0.8 5:2 Fludioxonil + Compound X.006  0.4 + 0.16 5:2 Cyprodinil + Compound X.006   8 + 0.2 40:1  Cyprodinil + Compound X.006  1.6 + 0.04 40:1  Cyprodinil + Compound X.006  0.32 + 0.008 40:1  Cyprodinil + Compound X.006   2 + 0.2 10:1  Cyprodinil + Compound X.006  0.4 + 0.04 10:1  Cyprodinil + Compound X.006  0.08 + 0.008 10:1  Cyprodinil + Compound X.006   2 + 0.8 5:2 Cyprodinil + Compound X.006  0.4 + 0.16 5:2 Cyprodinil + Compound X.006  0.08 + 0.032 5:2 Fluazinam + Compound X.006   8 + 0.2 40:1  Fluazinam + Compound X.006  1.6 + 0.04 40:1  Fluazinam + Compound X.006  0.32 + 0.008 40:1  Fluazinam + Compound X.006   2 + 0.2 10:1  Fluazinam + Compound X.006  0.4 + 0.04 10:1  Fluazinam + Compound X.006  0.08 + 0.008 10:1  Fluazinam + Compound X.006   2 + 0.8 5:2 Fluazinam + Compound X.006  0.4 + 0.16 5:2 Fluazinam + Compound X.006  0.08 + 0.032 5:2 Isopyrazam + Compound X.006   8 + 0.2 40:1  Isopyrazam + Compound X.006  1.6 + 0.04 40:1  Isopyrazam + Compound X.006   2 + 0.2 10:1  Isopyrazam + Compound X.006  0.4 + 0.04 10:1  Isopyrazam + Compound X.006  0.08 + 0.008 10:1  Isopyrazam + Compound X.006   2 + 0.8 5:2 Isopyrazam + Compound X.006  0.4 + 0.16 5:2 Isopyrazam + Compound X.006  0.08 + 0.032 5:2 Propiconazole + Compound X.006   8 + 0.2 40:1  Propiconazole + Compound X.006  1.6 + 0.04 40:1  Propiconazole + Compound X.006   2 + 0.2 10:1  Propiconazole + Compound X.006  0.4 + 0.04 10:1  Propiconazole + Compound X.006   2 + 0.8 5:2 Propiconazole + Compound X.006  0.4 + 0.16 5:2 Propiconazole + Compound X.006  0.08 + 0.032 5:2 Aminopyrifen + Compound X.006   8 + 0.2 40:1  Aminopyrifen + Compound X.006  1.6 + 0.04 40:1  Aminopyrifen + Compound X.006  0.32 + 0.008 40:1  Aminopyrifen + Compound X.006   2 + 0.2 10:1  Aminopyrifen + Compound X.006  0.4 + 0.04 10:1  Aminopyrifen + Compound X.006  0.08 + 0.008 10:1  Aminopyrifen + Compound X.006   2 + 0.8 5:2 Aminopyrifen + Compound X.006  0.4 + 0.16 5:2 Aminopyrifen + Compound X.006  0.08 + 0.032 5:2 Pyroquilon + Compound X.006  30 + 0.2 150:1  Pyroquilon + Compound X.006   6 + 0.04 150:1  Pyroquilon + Compound X.006   8 + 0.2 40:1  Pyroquilon + Compound X.006  1.6 + 0.04 40:1  Pyroquilon + Compound X.006   2 + 0.2 10:1  Pyroquilon + Compound X.006  0.4 + 0.04 10:1  Tricyclazole + Compound X.006  30 + 0.2 150:1  Tricyclazole + Compound X.006   6 + 0.04 150:1  Tricyclazole + Compound X.006   8 + 0.2 40:1  Tricyclazole + Compound X.006  1.6 + 0.04 40:1  Tricyclazole + Compound X.006   2 + 0.2 10:1  Tricyclazole + Compound X.006  0.4 + 0.04 10:1  Chlorothalonil + Compound X.006  30 + 0.2 150:1  Chlorothalonil + Compound X.006   6 + 0.04 150:1  Chlorothalonil + Compound X.006  1.2 + 0.008 150:1  Chlorothalonil + Compound X.006   8 + 0.2 40:1  Chlorothalonil + Compound X.006  1.6 + 0.04 40:1  Chlorothalonil + Compound X.006  0.32 + 0.008 40:1  Chlorothalonil + Compound X.006   2 + 0.2 10:1  Chlorothalonil + Compound X.006  0.4 + 0.04 10:1 

Example B3: Glomerella lagenarium (Syn. Colletotrichum lagenarium), Anthracnose of Cucurbits

(87) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hrs at 620 nm

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

(89) TABLE-US-00014 Conc. (ppm) Ratio Composition (B + A) (B:A) (B:A) Pydiflumetofen + Compound X.006 0.8 + 0.2  4:1 Pydiflumetofen + Compound X.006 0.16 + 0.04  4:1 Pydiflumetofen + Compound X.006 0.2 + 0.2  1:1 Pydiflumetofen + Compound X.006 0.04 + 0.04  1:1 Pydiflumetofen + Compound X.006 0.2 + 0.8  1:4 Pydiflumetofen + Compound X.006 0.04 + 0.16  1:4 Benzovindiflupyr + Compound X.006 0.8 + 0.2  4:1 Benzovindiflupyr + Compound X.006 0.16 + 0.04  4:1 Benzovindiflupyr + Compound X.006 0.2 + 0.2  1:1 Benzovindiflupyr + Compound X.006 0.04 + 0.04  1:1 Benzovindiflupyr + Compound X.006 0.2 + 0.8  1:4 Benzovindiflupyr + Compound X.006 0.04 + 0.16  1:4 Benzovindiflupyr + Compound X.006 0.008 + 0.032  1:4 Difenoconazole + Compound X.006  8 + 0.2 40:1  Difenoconazole + Compound X.006 1.6 + 0.04 40:1  Difenoconazole + Compound X.006  2 + 0.2 10:1  Difenoconazole + Compound X.006 0.4 + 0.04 10:1  Difenoconazole + Compound X.006  2 + 0.8 5:2 Difenoconazole + Compound X.006 0.4 + 0.16 5:2 Difenoconazole + Compound X.006 0.08 + 0.032 5:2 Hexaconazole + Compound X.006  8 + 0.2 40:1  Hexaconazole + Compound X.006  2 + 0.2 10:1  Hexaconazole + Compound X.006 0.4 + 0.04 10:1  Hexaconazole + Compound X.006  2 + 0.8 5:2 Hexaconazole + Compound X.006 0.4 + 0.16 5:2 Azoxystrobin + Compound X.006 0.8 + 0.2  4:1 Azoxystrobin + Compound X.006 0.16 + 0.04  4:1 Azoxystrobin + Compound X.006 0.032 + 0.008  4:1 Azoxystrobin + Compound X.006 0.2 + 0.2  1:1 Azoxystrobin + Compound X.006 0.04 + 0.04  1:1 Azoxystrobin + Compound X.006 0.2 + 0.8  1:4 Azoxystrobin + Compound X.006 0.04 + 0.16  1:4 Azoxystrobin + Compound X.006 0.008 + 0.032  1:4 Fludioxonil + Compound X.006  8 + 0.2 40:1  Fludioxonil + Compound X.006 1.6 + 0.04 40:1  Fludioxonil + Compound X.006  2 + 0.2 10:1  Fludioxonil + Compound X.006 0.4 + 0.04 10:1  Fludioxonil + Compound X.006  2 + 0.8 5:2 Fludioxonil + Compound X.006 0.4 + 0.16 5:2 Fludioxonil + Compound X.006 0.08 + 0.032 5:2 Cyprodinil + Compound X.006  8 + 0.2 40:1  Cyprodinil + Compound X.006  2 + 0.2 10:1  Cyprodinil + Compound X.006 0.4 + 0.04 10:1  Cyprodinil + Compound X.006  2 + 0.8 5:2 Cyprodinil + Compound X.006 0.4 + 0.16 5:2 Fluazinam + Compound X.006  8 + 0.2 40:1  Fluazinam + Compound X.006 1.6 + 0.04 40:1  Fluazinam + Compound X.006 0.32 + 0.008 40:1  Fluazinam + Compound X.006  2 + 0.2 10:1  Fluazinam + Compound X.006 0.4 + 0.04 10:1  Fluazinam + Compound X.006 0.08 + 0.008 10:1  Fluazinam + Compound X.006  2 + 0.8 5:2 Fluazinam + Compound X.006 0.4 + 0.16 5:2 Fluazinam + Compound X.006 0.08 + 0.032 5:2 Isopyrazam + Compound X.006  8 + 0.2 40:1  Isopyrazam + Compound X.006  2 + 0.2 10:1  Isopyrazam + Compound X.006 0.4 + 0.04 10:1  Isopyrazam + Compound X.006  2 + 0.8 5:2 Isopyrazam + Compound X.006 0.4 + 0.16 5:2 Propiconazole + Compound X.006  8 + 0.2 40:1  Propiconazole + Compound X.006 1.6 + 0.04 40:1  Propiconazole + Compound X.006  2 + 0.2 10:1  Propiconazole + Compound X.006 0.4 + 0.04 10:1  Propiconazole + Compound X.006  2 + 0.8 5:2 Propiconazole + Compound X.006 0.4 + 0.16 5:2 Propiconazole + Compound X.006 0.08 + 0.032 5:2 Aminopyrifen + Compound X.006  8 + 0.2 40:1  Aminopyrifen + Compound X.006 1.6 + 0.04 40:1  Aminopyrifen + Compound X.006 0.32 + 0.008 40:1  Aminopyrifen + Compound X.006  2 + 0.2 10:1  Aminopyrifen + Compound X.006 0.4 + 0.04 10:1  Aminopyrifen + Compound X.006  2 + 0.8 5:2 Aminopyrifen + Compound X.006 0.4 + 0.16 5:2 Aminopyrifen + Compound X.006 0.08 + 0.032 5:2 Pyroquilon + Compound X.006 30 + 0.2  150:1  Pyroquilon + Compound X.006   6 + 0.04 150:1  Pyroquilon + Compound X.006  8 + 0.2 40:1  Pyroquilon + Compound X.006 1.6 + 0.04 40:1  Pyroquilon + Compound X.006  2 + 0.2 10:1  Pyroquilon + Compound X.006 0.4 + 0.04 10:1  Tricyclazole + Compound X.006 30 + 0.2  150:1  Tricyclazole + Compound X.006   6 + 0.04 150:1  Tricyclazole + Compound X.006  8 + 0.2 40:1  Tricyclazole + Compound X.006 1.6 + 0.04 40:1  Tricyclazole + Compound X.006  2 + 0.2 10:1  Chlorothalonil + Compound X.006 30 + 0.2  150:1  Chlorothalonil + Compound X.006   6 + 0.04 150:1  Chlorothalonil + Compound X.006  1.2 + 0.008 150:1  Chlorothalonil + Compound X.006  8 + 0.2 40:1  Chlorothalonil + Compound X.006 1.6 + 0.04 40:1  Chlorothalonil + Compound X.006 0.32 + 0.008 40:1  Chlorothalonil + Compound X.006  2 + 0.2 10:1  Chlorothalonil + Compound X.006 0.4 + 0.04 10:1 

Example B4: Septoria tritici (Leaf Blotch)

(90) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). A DMSO solution of the test compounds was placed into a microtiter plate (96-well format) and the nutrient broth containing the fungal spores was added to it. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hrs.

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

(92) TABLE-US-00015 Conc. (ppm) Ratio Composition (B + A) (B:A) (B:A) Pydiflumetofen + Compound X.006 0.8 + 0.2  4:1 Pydiflumetofen + Compound X.006 0.16 + 0.04  4:1 Pydiflumetofen + Compound X.006 0.032 + 0.008  4:1 Pydiflumetofen + Compound X.006 0.2 + 0.2  1:1 Pydiflumetofen + Compound X.006 0.04 + 0.04  1:1 Pydiflumetofen + Compound X.006 0.008 + 0.008  1:1 Pydiflumetofen + Compound X.006 0.2 + 0.8  1:4 Pydiflumetofen + Compound X.006 0.04 + 0.16  1:4 Pydiflumetofen + Compound X.006 0.008 + 0.032  1:4 Benzovindiflupyr + Compound X.006 0.8 + 0.2  4:1 Benzovindiflupyr + Compound X.006 0.2 + 0.8  1:4 Difenoconazole + Compound X.006  8 + 0.2 40:1  Difenoconazole + Compound X.006 1.6 + 0.04 40:1  Difenoconazole + Compound X.006 0.32 + 0.008 40:1  Difenoconazole + Compound X.006  2 + 0.2 10:1  Difenoconazole + Compound X.006 0.4 + 0.04 10:1  Difenoconazole + Compound X.006 0.08 + 0.008 10:1  Difenoconazole + Compound X.006  2 + 0.8 5:2 Difenoconazole + Compound X.006 0.4 + 0.16 5:2 Difenoconazole + Compound X.006 0.08 + 0.032 5:2 Hexaconazole + Compound X.006  8 + 0.2 40:1  Hexaconazole + Compound X.006 1.6 + 0.04 40:1  Hexaconazole + Compound X.006 0.32 + 0.008 40:1  Hexaconazole + Compound X.006  2 + 0.2 10:1  Hexaconazole + Compound X.006 0.4 + 0.04 10:1  Hexaconazole + Compound X.006  2 + 0.8 5:2 Hexaconazole + Compound X.006 0.4 + 0.16 5:2 Azoxystrobin + Compound X.006 0.8 + 0.2  4:1 Azoxystrobin + Compound X.006 0.16 + 0.04  4:1 Azoxystrobin + Compound X.006 0.2 + 0.2  1:1 Azoxystrobin + Compound X.006 0.2 + 0.8  1:4 Azoxystrobin + Compound X.006 0.04 + 0.16  1:4 Fludioxonil + Compound X.006  8 + 0.2 40:1  Fludioxonil + Compound X.006 1.6 + 0.04 40:1  Fludioxonil + Compound X.006  2 + 0.2 10:1  Fludioxonil + Compound X.006 0.4 + 0.04 10:1  Fludioxonil + Compound X.006  2 + 0.8 5:2 Fludioxonil + Compound X.006 0.4 + 0.16 5:2 Cyprodinil + Compound X.006  2 + 0.8 5:2 Fluazinam + Compound X.006  8 + 0.2 40:1  Fluazinam + Compound X.006 1.6 + 0.04 40:1  Fluazinam + Compound X.006 0.32 + 0.008 40:1  Fluazinam + Compound X.006  2 + 0.2 10:1  Fluazinam + Compound X.006 0.4 + 0.04 10:1  Fluazinam + Compound X.006 0.08 + 0.008 10:1  Fluazinam + Compound X.006  2 + 0.8 5:2 Fluazinam + Compound X.006 0.4 + 0.16 5:2 Fluazinam + Compound X.006 0.08 + 0.032 5:2 Isopyrazam + Compound X.006  8 + 0.2 40:1  Isopyrazam + Compound X.006 1.6 + 0.04 40:1  Isopyrazam + Compound X.006  2 + 0.2 10:1  Isopyrazam + Compound X.006 0.4 + 0.04 10:1  Isopyrazam + Compound X.006  2 + 0.8 5:2 Isopyrazam + Compound X.006 0.4 + 0.16 5:2 Propiconazole + Compound X.006  8 + 0.2 40:1  Propiconazole + Compound X.006 1.6 + 0.04 40:1  Propiconazole + Compound X.006  2 + 0.2 10:1  Propiconazole + Compound X.006 0.4 + 0.04 10:1  Aminopyrifen + Compound X.006  8 + 0.2 40:1  Aminopyrifen + Compound X.006 1.6 + 0.04 40:1  Aminopyrifen + Compound X.006  2 + 0.2 10:1  Aminopyrifen + Compound X.006  2 + 0.8 5:2 Chlorothalonil + Compound X.006 30 + 0.2  150:1  Chlorothalonil + Compound X.006   6 + 0.04 150:1  Chlorothalonil + Compound X.006  1.2 + 0.008 150:1  Chlorothalonil + Compound X.006  8 + 0.2 40:1  Chlorothalonil + Compound X.006 1.6 + 0.04 40:1  Chlorothalonil + Compound X.006 0.32 + 0.008 40:1  Chlorothalonil + Compound X.006  2 + 0.2 10:1  Chlorothalonil + Compound X.006 0.4 + 0.04 10:1 

Example B5: Fusarium culmorum (Root Rot)

(93) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). A DMSO solution of the test compounds was placed into a microtiter plate (96-well format) and the nutrient broth containing the fungal spores was added to it. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 48 hrs.

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

(95) TABLE-US-00016 Conc. (ppm) Ratio Composition (B + A) (B:A) (B:A) Pydiflumetofen + Compound X.006 0.8 + 0.2  4:1 Pydiflumetofen + Compound X.006 0.2 + 0.2  1:1 Pydiflumetofen + Compound X.006 0.2 + 0.8  1:4 Pydiflumetofen + Compound X.006 0.04 + 0.16  1:4 Benzovindiflupyr + Compound X.006 0.8 + 0.2  4:1 Benzovindiflupyr + Compound X.006 0.2 + 0.2  1:1 Benzovindiflupyr + Compound X.006 0.2 + 0.8  1:4 Benzovindiflupyr + Compound X.006 0.04 + 0.16  1:4 Difenoconazole + Compound X.006  8 + 0.2 40:1  Difenoconazole + Compound X.006  2 + 0.2 10:1  Difenoconazole + Compound X.006  2 + 0.8 5:2 Hexaconazole + Compound X.006  8 + 0.2 40:1  Hexaconazole + Compound X.006  2 + 0.2 10:1  Hexaconazole + Compound X.006  2 + 0.8 5:2 Azoxystrobin + Compound X.006 0.8 + 0.2  4:1 Azoxystrobin + Compound X.006 0.2 + 0.2  1:1 Azoxystrobin + Compound X.006 0.2 + 0.8  1:4 Azoxystrobin + Compound X.006 0.04 + 0.16  1:4 Fludioxonil + Compound X.006  8 + 0.2 40:1  Fludioxonil + Compound X.006 1.6 + 0.04 40:1  Fludioxonil + Compound X.006 0.32 + 0.008 40:1  Fludioxonil + Compound X.006  2 + 0.2 10:1  Fludioxonil + Compound X.006 0.4 + 0.04 10:1  Fludioxonil + Compound X.006  2 + 0.8 5:2 Fludioxonil + Compound X.006 0.4 + 0.16 5:2 Fludioxonil + Compound X.006 0.08 + 0.032 5:2 Cyprodinil + Compound X.006  8 + 0.2 40:1  Cyprodinil + Compound X.006  2 + 0.2 10:1  Cyprodinil + Compound X.006  2 + 0.8 5:2 Cyprodinil + Compound X.006 0.4 + 0.16 5:2 Fluazinam + Compound X.006  8 + 0.2 40:1  Fluazinam + Compound X.006 1.6 + 0.04 40:1  Fluazinam + Compound X.006  2 + 0.2 10:1  Fluazinam + Compound X.006 0.4 + 0.04 10:1  Fluazinam + Compound X.006  2 + 0.8 5:2 Fluazinam + Compound X.006 0.4 + 0.16 5:2 Isopyrazam + Compound X.006  8 + 0.2 40:1  Isopyrazam + Compound X.006  2 + 0.2 10:1  Isopyrazam + Compound X.006  2 + 0.8 5:2 Isopyrazam + Compound X.006 0.4 + 0.16 5:2 Propiconazole + Compound X.006  8 + 0.2 40:1  Propiconazole + Compound X.006  2 + 0.8 5:2 Aminopyrifen + Compound X.006  8 + 0.2 40:1  Aminopyrifen + Compound X.006 1.6 + 0.04 40:1  Aminopyrifen + Compound X.006  2 + 0.2 10:1  Aminopyrifen + Compound X.006 0.4 + 0.04 10:1  Aminopyrifen + Compound X.006  2 + 0.8 5:2 Aminopyrifen + Compound X.006 0.4 + 0.16 5:2 Pyroquilon + Compound X.006 30 + 0.2  150:1  Pyroquilon + Compound X.006  8 + 0.2 40:1  Pyroquilon + Compound X.006  2 + 0.2 10:1  Tricyclazole + Compound X.006 30 + 0.2  150:1  Tricyclazole + Compound X.006  8 + 0.2 40:1  Tricyclazole + Compound X.006  2 + 0.2 10:1  Chlorothalonil + Compound X.006 30 + 0.2  150:1  Chlorothalonil + Compound X.006   6 + 0.04 150:1  Chlorothalonil + Compound X.006  1.2 + 0.008 150:1  Chlorothalonil + Compound X.006  8 + 0.2 40:1  Chlorothalonil + Compound X.006 1.6 + 0.04 40:1  Chlorothalonil + Compound X.006  2 + 0.2 10:1 

Example B6: Venturia inequalis (Apple Scab)

(96) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). A DMSO solution of the test compounds was placed into a microtiter plate (96-well format) and the nutrient broth containing the fungal spores was added to it. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 7 days at 620 nm.

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

(98) TABLE-US-00017 Conc. (ppm) Ratio Composition (B + A) (B:A) (B:A) Pydiflumetofen + Compound X.006 0.8 + 0.2  4:1 Pydiflumetofen + Compound X.006 0.16 + 0.04  4:1 Pydiflumetofen + Compound X.006 0.032 + 0.008  4:1 Pydiflumetofen + Compound X.006 0.2 + 0.2  1:1 Pydiflumetofen + Compound X.006 0.04 + 0.04  1:1 Pydiflumetofen + Compound X.006 0.008 + 0.008  1:1 Pydiflumetofen + Compound X.006 0.2 + 0.8  1:4 Pydiflumetofen + Compound X.006 0.04 + 0.16  1:4 Pydiflumetofen + Compound X.006 0.008 + 0.032  1:4 Benzovindiflupyr + Compound X.006 0.8 + 0.2  4:1 Benzovindiflupyr + Compound X.006 0.16 + 0.04  4:1 Benzovindiflupyr + Compound X.006 0.032 + 0.008  4:1 Benzovindiflupyr + Compound X.006 0.2 + 0.2  1:1 Benzovindiflupyr + Compound X.006 0.04 + 0.04  1:1 Benzovindiflupyr + Compound X.006 0.2 + 0.8  1:4 Benzovindiflupyr + Compound X.006 0.04 + 0.16  1:4 Benzovindiflupyr + Compound X.006 0.008 + 0.032  1:4 Difenoconazole + Compound X.006  8 + 0.2 40:1  Difenoconazole + Compound X.006 1.6 + 0.04 40:1  Difenoconazole + Compound X.006 0.32 + 0.008 40:1  Difenoconazole + Compound X.006  2 + 0.2 10:1  Difenoconazole + Compound X.006 0.4 + 0.04 10:1  Difenoconazole + Compound X.006 0.08 + 0.008 10:1  Difenoconazole + Compound X.006  2 + 0.8 5:2 Difenoconazole + Compound X.006 0.4 + 0.16 5:2 Difenoconazole + Compound X.006 0.08 + 0.032 5:2 Hexaconazole + Compound X.006  8 + 0.2 40:1  Hexaconazole + Compound X.006 1.6 + 0.04 40:1  Hexaconazole + Compound X.006 0.32 + 0.008 40:1  Hexaconazole + Compound X.006  2 + 0.2 10:1  Hexaconazole + Compound X.006 0.4 + 0.04 10:1  Hexaconazole + Compound X.006 0.08 + 0.008 10:1  Hexaconazole + Compound X.006  2 + 0.8 5:2 Hexaconazole + Compound X.006 0.4 + 0.16 5:2 Hexaconazole + Compound X.006 0.08 + 0.032 5:2 Azoxystrobin + Compound X.006 0.8 + 0.2  4:1 Azoxystrobin + Compound X.006 0.16 + 0.04  4:1 Azoxystrobin + Compound X.006 0.032 + 0.008  4:1 Azoxystrobin + Compound X.006 0.2 + 0.2  1:1 Azoxystrobin + Compound X.006 0.04 + 0.04  1:1 Azoxystrobin + Compound X.006 0.2 + 0.8  1:4 Azoxystrobin + Compound X.006 0.04 + 0.16  1:4 Fludioxonil + Compound X.006  8 + 0.2 40:1  Fludioxonil + Compound X.006 1.6 + 0.04 40:1  Fludioxonil + Compound X.006  2 + 0.2 10:1  Fludioxonil + Compound X.006 0.4 + 0.04 10:1  Fludioxonil + Compound X.006  2 + 0.8 5:2 Fludioxonil + Compound X.006 0.4 + 0.16 5:2 Cyprodinil + Compound X.006  8 + 0.2 40:1  Cyprodinil + Compound X.006 1.6 + 0.04 40:1  Cyprodinil + Compound X.006 0.32 + 0.008 40:1  Cyprodinil + Compound X.006  2 + 0.2 10:1  Cyprodinil + Compound X.006 0.4 + 0.04 10:1  Cyprodinil + Compound X.006 0.08 + 0.008 10:1  Cyprodinil + Compound X.006  2 + 0.8 5:2 Cyprodinil + Compound X.006 0.4 + 0.16 5:2 Cyprodinil + Compound X.006 0.08 + 0.032 5:2 Fluazinam + Compound X.006  8 + 0.2 40:1  Fluazinam + Compound X.006 1.6 + 0.04 40:1  Fluazinam + Compound X.006 0.32 + 0.008 40:1  Fluazinam + Compound X.006  2 + 0.2 10:1  Fluazinam + Compound X.006 0.4 + 0.04 10:1  Fluazinam + Compound X.006 0.08 + 0.008 10:1  Fluazinam + Compound X.006  2 + 0.8 5:2 Fluazinam + Compound X.006 0.4 + 0.16 5:2 Fluazinam + Compound X.006 0.08 + 0.032 5:2 Isopyrazam + Compound X.006  8 + 0.2 40:1  Isopyrazam + Compound X.006 1.6 + 0.04 40:1  Isopyrazam + Compound X.006 0.32 + 0.008 40:1  Isopyrazam + Compound X.006  2 + 0.2 10:1  Isopyrazam + Compound X.006 0.4 + 0.04 10:1  Isopyrazam + Compound X.006  2 + 0.8 5:2 Isopyrazam + Compound X.006 0.4 + 0.16 5:2 Isopyrazam + Compound X.006 0.08 + 0.032 5:2 Propiconazole + Compound X.006  8 + 0.2 40:1  Propiconazole + Compound X.006 1.6 + 0.04 40:1  Propiconazole + Compound X.006 0.32 + 0.008 40:1  Propiconazole + Compound X.006  2 + 0.2 10:1  Propiconazole + Compound X.006 0.4 + 0.04 10:1  Propiconazole + Compound X.006  2 + 0.8 5:2 Propiconazole + Compound X.006 0.4 + 0.16 5:2 Propiconazole + Compound X.006 0.08 + 0.032 5:2 Aminopyrifen + Compound X.006  8 + 0.2 40:1  Aminopyrifen + Compound X.006  2 + 0.2 10:1  Aminopyrifen + Compound X.006  2 + 0.8 5:2 Aminopyrifen + Compound X.006 0.4 + 0.16 5:2 Pyroquilon + Compound X.006 30 + 0.2  150:1  Pyroquilon + Compound X.006   6 + 0.04 150:1  Pyroquilon + Compound X.006  8 + 0.2 40:1  Pyroquilon + Compound X.006 1.6 + 0.04 40:1  Pyroquilon + Compound X.006  2 + 0.2 10:1  Tricyclazole + Compound X.006 30 + 0.2  150:1  Tricyclazole + Compound X.006   6 + 0.04 150:1  Tricyclazole + Compound X.006  1.2 + 0.008 150:1  Tricyclazole + Compound X.006  8 + 0.2 40:1  Tricyclazole + Compound X.006 1.6 + 0.04 40:1  Tricyclazole + Compound X.006 0.32 + 0.008 40:1  Tricyclazole + Compound X.006  2 + 0.2 10:1  Tricyclazole + Compound X.006 0.4 + 0.04 10:1  Chlorothalonil + Compound X.006 30 + 0.2  150:1  Chlorothalonil + Compound X.006   6 + 0.04 150:1  Chlorothalonil + Compound X.006  1.2 + 0.008 150:1  Chlorothalonil + Compound X.006  8 + 0.2 40:1  Chlorothalonil + Compound X.006 1.6 + 0.04 40:1  Chlorothalonil + Compound X.006 0.32 + 0.008 40:1  Chlorothalonil + Compound X.006  2 + 0.2 10:1  Chlorothalonil + Compound X.006 0.4 + 0.04 10:1  Chlorothalonil + Compound X.006 0.08 + 0.008 10:1