Fungicidal compositions
11154058 · 2021-10-26
Assignee
Inventors
Cpc classification
A01N37/50
HUMAN NECESSITIES
A01N43/82
HUMAN NECESSITIES
A01N43/82
HUMAN NECESSITIES
A01N43/84
HUMAN NECESSITIES
A01N37/52
HUMAN NECESSITIES
A01N43/713
HUMAN NECESSITIES
A01N37/50
HUMAN NECESSITIES
A01N43/713
HUMAN NECESSITIES
A01N37/52
HUMAN NECESSITIES
A01N43/84
HUMAN NECESSITIES
International classification
Abstract
A fungicidal composition comprising a mixture of a N-phenylamidine defined by formula (I) as component (A) and a further pesticide as component (B) as defined in claim 1, as well as 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) ##STR00176## wherein R.sup.1 is ethyl, isopropyl or cyclopropyl; and R.sup.2 is —CH.sub.2C(═N—OC.sub.2H.sub.5)CH.sub.3, n-butoxymethyl, cyclopropyl, cyclobutylmethoxymethyl, cyclopentoxymethyl, —CH.sub.2C(═CH.sub.2)CH.sub.3, n-butyl, phenyl, 2-methyl-phenyl or 3,5-difluorophenyl; or a salt, enantiomer, tautomer or N-oxide thereof, and component (B) is a compound selected from the group consisting of (B1) a strobilurin fungicide selected from the group consisting of azoxystrobin, picoxystrobin, enoxastrobin, pyraoxystrobin, mandestrobin, flufenoxystrobin, coumoxystrobin, orysastrobin, dimoxystrobin, metominostrobin, fenaminostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, fluoxastrobin, pyribencarb, pyraclostrobin and trifloxystrobin; (B2) an azole fungicide selected from the group consisting of azaconazole, etaconazole, ipconazole, tebuconazole, bitertanol, fenbucoanzole, metconazole, tetraconazole, bromucoanzole, fluquinconazole, myclobutanil, triadimefon, flusilazole, penconazole, triadimenol, triticonazole, simeconazole, imibenconazole, hexaconazole, flutriafol, diniconazole, cyproconazole, difenoconazole, epoxiconazole, propiconazole, prothioconazole, pyrifenox, nuarimol, fenarimol, imizalil, triflumizole, prochloraz, pefurazoate, oxpoconazole, Mefentrifluconazole, 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1,2,4-triazole-3-thione and 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol; (B3) a morpholine fungicide selected from the group consisting of aldimorph, dodemorph, fenpropimorph and tridemorph; (B4) a carboxamide fungicide selected from the group consisting of bixafen, fluopyram, fluxapyroxad, isopyrazam, sedaxane, furametpyr, penflufen, penthiopyrad, benzovindiflupyr, thifluzamide, isofetamid, boscalid, carboxin, oxycarboxin, fenfuram, flutolanil, pyraziflumid, pydiflumetofen, mepronil, benodanil, N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide and (R)-3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide; (B5) an anilinopyrimidine fungicide selected from the group consisting of cyprodinil, mepanipyrim and pyrimethanil; (B6) an phenylpyrrole fungicide selected from the group consisting of fludioxonil and fenpiclonil; (B7) a phenylamide fungicide selected from the group consisting of benalaxyl, benalaxyl-M, furalaxyl, mefenoxam and metalaxyl, ofurace and oxadixyl; (B8) a fungicide selected from the group consisting of ametoctradin, amisulbrom, anilazine, aureofungin, benomyl, benthiavalicarb, benthiazole, bethoxazin, BLAD, blasticidin-S, Bordeaux mixture, bupirimate, calcium polysulfide, captafol, captan, carbaryl, carbendazim, carpropamid, chinomethionate, chitosan, chlobenthiazone, chlorfenazole, chloroneb, chlorothalonil, chlozolinate, climbazole, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, cuprous oxide, cyazofamid, cyclafuramid, cyflufenamid, cymoxanil, dazomet, dichlofluanid, dichlorprop, diclocymet, diclomezine, dicloran, diethofencarb, diflumetorim, dimetachlone, dimethipin, dimethirimol, dimethomorph, dinocap, dinocton, dinobuton, dinopenton, dipymetitrone, ditalimfos, dithianon, dodicin, dodine, doguadine, edifenphos, etem, ethaboxam, ethirimol, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenhexamid, fenoxanil, fenpropidine, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumorph, fluopicolide, fluoroimide, flusulfamide, flutianil, folpet, fosetyl-Al, fuberidazole, gibberellic acid, guazatine, hymexazole, iminoctadine, iodocarb, iprobenfos, iprodione, iprovalicarb, isoprothiolane, kasugamycin, mancozeb, mandipropamid, maneb, metam, meptyldinocap, metiram, metrafenone, nabam, oxathiapiprolin, paclobutrazol, pencycuron, phenamacril, phosdiphen, phthalide, picarbutrazox, polyoxin D, probenazole, procymidone, prohexadione, propamocarb, propineb, proquinazid, pyrazophos, pyrifenox, pyrimorph, pyriofenone, pyroquilon, quinoxyfen, quintozene, silthiofam, spiroxamine, streptomycin, sulphur, tebufloquin, tecloftalam, tecnazene, thiabendazole, thidiazuron, thicyofen, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolprocarb, tolylfluanid, triazoxide, tribufos, tricyclazole, triforine, validamycin, valifenalate, vapam, vinclozolin, zineb, ziram, zoxamide, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, 4,4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine, 2-(difluoromethyl)-N-(1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide, a compound of the formula ##STR00177## a compound of the formula ##STR00178## and a compound of the formula ##STR00179## (B9) a plant-bioregulator selected from the group consisting of acibenzolar-S-methyl, chlormequat chloride, ethephon, isotianil, mepiquat chloride, tiadinil and trinexapac-ethyl; (B10) an insecticide selected from the group consisting of abamectin, acequinocyl, acetamiprid, acrinathrin, afidopyropen, alanycarb, allethrin, alpha-cypermethrin, alphamethrin, amidoflumet, azadirachtin, azocyclotin, Bacillus firmus, Bacillus thuringiensis, bensultap, benzoximate, betacyfluthrin, bifenazate, binapacryl, bioallethrin, bioresmethrin, biphenthrin, broflanilide, brofluthrinate, bromophos-ethyl, buprofezine, cadusafos, carbaryl, carbosulfan, cartap, chlorantraniliprole, chlorfenapyr, chromafenozide, cloethocarb, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cycloxaprid, cyenopyrafen, cyflumetofen, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, deltamethrin, demeton-s-methyl, diafenthiuron, dialifos, dichloromezotiaz, diflovidazine, diflubenzuron, dinactin, dinocap, dinotefuran, d-limonene, emamectin, empenthrin, esfenvalerate, ethion, ethiprole, etofenprox, etoxazole, famphur, fenazaquin, fenfluthrin, fenobucarb, fenoxycarb, fenpropathrin, fenpyroxymate, fenvalerate, fipronil, flometoquin, flonicamid, fluacrypyrim, fluazuron, flubendiamide, flucythrinate, fluensulfone, flufenerim, flufenprox, flufiprole, fluhexafon, flumethrin, flupyradifuron, fluvalinate, fosthiazate, gamma-cyhalothrin, gossyplure, guadipyr, halofenozide, halofenprox, harpin, hexythiazox, hydramethylnon, imicyafos, imidacloprid, imiprothrin, indoxacarb, iodomethane, isothioate, ivermectin, lambda-cyhalothrin, lepimectin, lufenuron, metaflumizone, metaldehyde, methomyl, methoxyfenozide, metofluthrin, milbemectin, niclosamide, nitenpyram, oxamyl, parathion-ethyl, pasteuria nishizawae, p-cymene, permethrin, phenothrin, phosphocarb, piperonylbutoxide, pirimicarb, pirimiphos-ethyl, polyhedrosis virus, prallethrin, profenofos, profenofos, propargite, propetamphos, protrifenbute, pyflubumide, pymetrozine, pyraclofos, pyrafluprole, pyrethrum, pyridaben, pyridalyl, pyrifluquinazon, pyrimidifen, pyriprole, pyriproxyfen, selamectin, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tebufenpyrad, tefluthrin, terpenoid blends, terpenoids, tetradiphon, tetramethrin, tetranactin, tetraniliprole, theta-cypermethrin, thiacloprid, thiamethoxam, thiodicarb, tioxazafen, tolfenpyrad, transfluthrin, trichlorfon, triflumezopyrim, zeta-cypermethrin and α-terpinene; (B11) glyphosate; (B12) a compound selected from the group consisting of azoxystrobin, trifloxystrobin, picoxystrobin, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, coumoxystrobin, cyproconazole, tebuconazole, prothioconazole, hexaconazole, mefentrifluconazole, fenpropidin, fenpropimorph, bixafen, fluxapyroxad, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, isoflucypram, a compound of the structure: ##STR00180## a compound of the structure: ##STR00181## N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, fluindapyr, fenpicoxamid, chlorothalonil, mancozeb, and spiroxamine; (B13) an insecticide selected from the group consisting of 3-(4-chloro-2,6-dimethyl-phenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl] ethyl carbonate, chlorantraniliprole, cyantraniliprole, abamectin, emamectin benzoate, thiamethoxam, acetamiprid, and diafenthiuron; (B14) a herbicide selected from the group consisting of glyphosate, dicamba, 2,4-dichlorophenoxyacetic acid (2,4-D) and glufosinate; (B15) a protein hydrolysate biostimulant; (B16) a biofungicide comprising Bacillus subtilis strains; (B17) a bioinsecticide product that comprises one or more loline alkaloids; (B18) a compound selected from the group consisting of N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pent-4-ynamide, N-methoxy-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]prop-2-enamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propenamide, N-cyclopropyl-3,3,3-trifluoro-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propenamide, 2,2-difluoro-N-(2-methoxyethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, 2,2-difluoro-N-(2-methoxyethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-propanamide, 2-methoxy-N-(2,2,2-trifluoroethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide, N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-cyclopropanecarboxamide, 2-(difluoromethoxy)-N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide, N-ethoxy-2-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propenamide, N-isopropyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]tetrahydrofuran-2-carboxamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-cyclopropyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethoxy-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-allyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1-cyclopropyl-3-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-isopropyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1-methoxy-3-prop-2-ynyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1-methoxy-3-methyl-urea, 3-(cyclopropylmethyl)-1-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, and 1-ethyl-3-(2,2,2-trifluoroethyl)-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea; and (B19) a compound selected from the group consisting of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 4-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]morpholin-3-one, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 1-[[2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, 1-[[2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]oxazinan-3-one, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]oxazolidin-2-one, 1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]imidazolidin-2-one, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3-dimethyl-piperidin-2-one, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, 2-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4,4-dimethyl-isoxazolidin-3-one, 2-[[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 2-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, and 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one; or a salt, enantiomer, tautomer or N-oxide thereof, and wherein the weight ratio of component (A) to component (B) is from 40:1 to 1:40.
2. The composition according to claim 1, wherein component (A) is a compound, or a salt, enantiomer, tautomer or N-oxide thereof, selected from N′-[4-[(3E)-3-ethoxyimino-1-hydroxy-1-(trifluoromethyl)butyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; N′-[4-[1-(butoxymethyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; N′-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine; N′-[4-[1-(cyclobutylmethoxymethyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; N′-[4-[1-(cyclopentoxymethyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; N′-[4-[1-hydroxy-3-methyl-1-(trifluoromethyl)but-3-enyl]-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine; N′-[4-[1-hydroxy-1-(trifluoromethyl)pentyl]-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine; N-isopropyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine; N-ethyl-N′-[5-methoxy-2-methyl-4-[2,2,2-trifluoro-1-hydroxy-1-(o-tolyl)ethyl]phenyl]-N-methyl-formamidine; and N′-[4-[1-(3,5-difluorophenyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine.
3. The fungicidal composition according to claim 2, wherein component (B) is a compound selected from the group consisting of: (B12) a compound selected from the group consisting of azoxystrobin, trifloxystrobin, picoxystrobin, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, coumoxystrobin, cyproconazole, difenoconazole, tebuconazole, prothioconazole, hexaconazole, mefentrifluconazole; (2RS)-2-[4-(4-chlorophenoxy)-α,α,α-trifluoro-o-tolyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol; fenpropidin, fenpropimorph, bixafen, fluxapyroxad, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, isoflucypram, the compound of the structure ##STR00182## the compound of the structure ##STR00183## N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, fluindapyr, fenpicoxamid, chlorothalonil, mancozeb, and spiroxamine; (B13) an insecticide selected from the group consisting of 3-(4-chloro-2,6-dimethyl-phenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl] ethyl carbonate, chlorantraniliprole, cyantraniliprole, abamectin, emamectin benzoate, thiamethoxam, acetamiprid, and diafenthiuron; (B14) a herbicide selected from the group consisting of glyphosate, dicamba, 2,4-dichlorophenoxyacetic acid (2,4-D) and glufosinate; (B15) a protein hydrolysate biostimulant; (B16) a biofungicide comprising Bacillus subtilis strains; (B17) a bioinsecticide product that comprises one or more loline alkaloids; (B18) a compound selected from: N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pent-4-ynamide, N-methoxy-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]prop-2-enamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-cyclopropyl-3,3,3-trifluoro-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 2,2-difluoro-N-(2-methoxyethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-propanamide, 2-methoxy-N-(2,2,2-trifluoroethyl)-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide, N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-cyclopropanecarboxamide, 2-(difluoromethoxy)-N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide, N-ethoxy-2-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-isopropyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]tetrahydrofuran-2-carboxamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-cyclopropyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethoxy-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-allyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1-cyclopropyl-3-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-isopropyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1-methoxy-3-prop-2-ynyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1-methoxy-3-methyl-urea, 3-(cyclopropylmethyl)-1-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, or 1-ethyl-3-(2,2,2-trifluoroethyl)-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea; and (B19) a compound selected from: 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 4-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]morpholin-3-one, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 1-[[2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, 1-[[2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]oxazinan-3-one, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, 3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]oxazolidin-2-one, 1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]imidazolidin-2-one, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3-dimethyl-piperidin-2-one, 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, 2-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4,4-dimethyl-isoxazolidin-3-one, 2-[[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 2-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one or; or a salt, enantiomer, tautomer or N-oxide thereof.
4. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-[(3E)-3-ethoxyimino-1-hydroxy-1-(trifluoromethyl)butyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
5. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-[1-(butoxymethyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
6. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
7. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-[1-(cyclobutylmethoxymethyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
8. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-[1-(cyclopentoxymethyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
9. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-[1-hydroxy-3-methyl-1-(trifluoromethyl)but-3-enyl]-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
10. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-[1-hydroxy-1-(trifluoromethyl)pentyl]-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
11. The fungicidal composition according to claim 3, wherein component (A) is N-isopropyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
12. The fungicidal composition according to claim 3, wherein component (A) is N-ethyl-N′-[5-methoxy-2-methyl-4-[2,2,2-trifluoro-1-hydroxy-1-(o-tolyl)ethyl]phenyl]-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
13. The fungicidal composition according to claim 3, wherein component (A) is N′-[4-[1-(3,5-difluorophenyl)-2,2,2-trifluoro-1-hydroxy-ethyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine; or a salt, enantiomer, tautomer or N-oxide thereof.
14. The fungicidal composition according to claim 3, wherein the composition further comprises one or more components 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′-[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, cyprodinil, mepanipyrim, pyrimethanil, dithianon, aureofungin, blasticidin-S, biphenyl, chloroneb, dicloran, hexachlorobenzene, quintozene, tecnazene, tolclofos-methyl, 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-c′]dipyrrole-1,3,5,7(2H,6H)-tetraone, azithiram, etem, ferbam, mancozeb, maneb, metam, metiram, nabam, propineb, thiram, vapam, zineb, ziram, dithioether, isoprothiolane, ethaboxam, fosetyl, phosetyl-Al, methyl bromide, methyl iodide, methyl isothiocyanate, cyclafuramid, fenfuram, validamycin, streptomycin, (2RS)-2-bromo-2-(bromomethyl)glutaronitrile, 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, α-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, bromuconazole, climbazole, cyproconazole, difenoconazole, dimetconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, mefentrifluconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triazoxide, triticonazole, 2-[[(1R,5S)-5-[(4-fluorophenyl)methyl]-1-hydroxy-2,2-dimethyl-cyclopentyl]methyl]-4H-1,2,4-triazole-3-thione 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1,2,4-triazole-3-thione, ametoctradin, iprovalicarb, valifenalate, 2-benzyl-4-chlorophenol, allyl alcohol, azafenidin, benzalkonium chloride, chloropicrin, cresol, daracide, dichlorophen (dichlorophene), difenzoquat, dipyrithione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, NNF-0721, octhilinone, oxasulfuron, propamidine and propionic acid; 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; a bactericides selected from streptomycin; an acaricide selected from amitraz, chinomethionat, chlorobenzilate, cyenopyrafen, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and a biological agents selected from Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.
15. The fungicidal composition according to claim 3, wherein the composition further comprises an agriculturally acceptable carrier and, optionally, a surfactant and/or formulation adjuvants.
16. A method of controlling or preventing phytopathogenic diseases on useful plants or on propagation material thereof, comprising: applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition as defined in claim 3.
17. The method according to claim 16, wherein the composition components (A) and (B) are applied in a sequential manner.
Description
PREPARATION EXAMPLES
(1) Using techniques described above and below, and also in WO 08/101682 (pp. 22-33) and WO 12/146125 (pp. 370-378), together with further techniques generally known to the person skilled in the art, compounds of formula (I) may be prepared.
Example 1: This example illustrate the preparation N-ethyl-N′-[4-(1-hydroxy-1-phenyl-ethyl)-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine
(2) ##STR00116##
a) Preparation of 4-bromo-5-methoxy-2-methyl-aniline
(3) N-bromosuccinimide (1.28 g, 7.29 mmol) was added portion wise to an ice-cold (0-5° C.) solution of 5-methoxy-2-methyl-aniline (1.0 g, 7.29 mmol) in CHCl.sub.3 (15 mL). The resulting solution was stirred for 60 minutes at 0° C., warmed to room temperature and diluted with CH.sub.2Cl.sub.2. The mixture was washed with aqueous NaHCO.sub.3 (+2 mL Na.sub.2S203 solution), brine and dried over MgSO.sub.4. Solids were removed by filtration and volatiles were removed in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as off white solid.
(4) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.17 (s, 1H), 6.27 (s, 1H), 3.82 (s, 3H), 3.53-3.73 (br. s., 2H), 2.08 (s, 3H).
b) Preparation of N′-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine
(5) To a suspension of 4-bromo-5-methoxy-2-methyl-aniline (1.4 g, 6.48 mmol) and p-toluene sulfonic acid (0.05 g, 0.32 mmol) in toluene (13 mL) was added N-(dimethoxymethyl)-N-methyl-ethanamine (1.3 g, 9.7 mmol) at room temperature. The resulting clear solution was warmed to 50° C. and stirred for 24 h at this temperature. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, washed with aqueous NaHCO.sub.3, brine and dried over MgSO.sub.4. Solids were removed by filtration and volatiles were removed in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as light yellow liquid.
(6) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.40 (br. s., 1H), 7.26 (s, 1H), 6.33 (s, 1H), 3.85 (s, 3H), 3.34 (br. s., 2H), 3.00 (s, 3H), 2.16 (s, 3H), 1.22 (t, 3H).
c) Preparation of N-ethyl-N′-[4-(1-hydroxy-1-phenyl-ethyl)-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine
(7) A solution of N′-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine (0.10 g, 0.35 mmol) in dry tetrahydrofuran (3.5 mL) under N.sub.2-atmosphere was cooled to −78° C. and tert-butyl lithium (1.5 M in pentanes, 0.49 mL, 0.74 mmol) was added slowly. The reaction was aged for 5 min at −78° C. and then 1-phenylethanone (0.044 g, 0.37 mmol) was added drop wise. The cooling bath was removed, the reaction was allowed to warm to room temperature and stirred for an additional 10 min. Aqueous NaHCO.sub.3 was added and the mixture was extracted with EtOAc. The organic layer was washed with brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as white solid.
(8) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.41 (br. s., 1H), 7.28-7.34 (m, 2H), 7.12-7.25 (m, 4H), 6.32 (s, 1H), 4.64 (s, 1H), 3.51 (s, 3H), 3.20-3.47 (br. s, 2H), 3.00 (s, 3H), 2.24 (s, 3H), 1.80 (s, 3H), 1.21 (t, 3H).
Example 2: This example illustrate the preparation of N-ethyl-N′-[4-[1-hydroxy-2-methyl-1-(trifluoromethyl)propyl]-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine
(9) ##STR00117##
a) Preparation of N-ethyl-N′-[5-methoxy-2-methyl-4-(2-methylpropanoyl)phenyl]-N-methyl-formamidine
(10) A solution of N′-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine (2.0 g, 7.01 mmol) in dry tetrahydrofuran (3.5 mL) under N.sub.2-atmosphere was added drop wise to a suspension of LiCl (0.33 g, 7.71 mmol) and Mg-turnings (0.26 g, 7.02 mmol) in dry tetrahydrofuran (3.5 mL) at a temperature between 20° C. to 40° C. (temperature controlled by addition rate). Upon completed addition, the reaction was aged for 1 h at 40° C. and then the mixture was then cooled to 0° C. N-methoxy-N,2-dimethyl-propanamide (1.01 g, 7.33 mmol) was added drop wise and the reaction was mixture was gradually warmed to RT over 1 h. Aqueous NH.sub.4Cl solution was added and the mixture was extracted with EtOAc. The organic layer was washed with water, brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as light yellow oil.
(11) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.47 (br. s, 2H), 6.30 (s, 1H), 3.85 (s, 3H), 3.25-3.60 (m, 3H), 3.02 (s, 3H), 2.18 (s, 3H), 1.59 (s, 1H), 1.23 (t, 3H), 1.13 (d, 6H).
b) Preparation of N-ethyl-N′-[4-[1-hydroxy-2-methyl-1-(trifluoromethyl)propyl]-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine
(12) Trimethyl(trifluoromethyl)silane (0.26 g, 1.81 mmol) was added drop wise to a solution of N-ethyl-N′-[5-methoxy-2-methyl-4-(2-methylpropanoyl)phenyl]-N-methyl-formamidine (0.50 g, 1.81 mmol) and CsF (0.03 g, 0.18 mmol) in toluene (9 mL) at 40° C. The resulting mixture was aged for 3 h at 40° C., a second portion of trimethyl(trifluoromethyl)silane (0.13 g, 0.91 mmol) was then added and the reaction was stirred for additional 30 min before being concentrated in vacuo to a brown oil.
(13) This residue was taken up in methanol (7 mL), treated with potassium carbonate (0.37 g, 2.71 mmol) and aq. sodium hydroxide (2 M, 3 drops), warmed to 40° C. and stirred for 24 h at this temperature. Aqueous NaHCO.sub.3 solution was then added and the emulsion was extracted with EtOAc. The organic layer was washed with water, brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as light brown solid (m.p. 57-59° C.).
(14) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.47 (br s, 1H), 7.07 (s, 1H), 6.56 (br s, 1H), 6.40 (s, 1H), 3.90 (s, 3H), 3.22-3.66 (m, 2H), 3.03 (s, 3H), 2.46-2.66 (m, 1H), 2.22 (s, 3H), 1.25 (t, 3H), 1.16 (d, 3H), 0.87 (d, 3H).
Preparation of N-ethyl-N′-[5-methoxy-2-methyl-4-[2,2,2-trifluoro-1-hydroxy-1-(isobutoxymethyl)-ethyl]phenyl]-N-methyl-formamidine
Preparation of 4-bromo-5-methoxy-2-methyl-aniline
(15) N-bromosuccinimide (1.28 g, 7.29 mmol) was added portion wise to an ice-cold (0-5° C.) solution of 5-methoxy-2-methyl-aniline (1.0 g, 7.29 mmol) in CHCl.sub.3 (15 mL). The resulting solution was stirred for 60 minutes at 0° C., warmed to room temperature and diluted with CH.sub.2C.sub.2. The mixture was washed with aqueous NaHCO.sub.3 (+2 mL Na.sub.2S203 solution), brine and dried over MgSO.sub.4. Solids were removed by filtration and volatiles were removed in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as off white solid.
(16) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.17 (s, 1H), 6.27 (s, 1H), 3.82 (s, 3H), 3.53-3.73 (br. s., 2H), 2.08 (s, 3H).
Preparation of N′-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine
(17) To a suspension of 4-bromo-5-methoxy-2-methyl-aniline (1.4 g, 6.48 mmol) and p-toluene sulfonic acid (0.05 g, 0.32 mmol) in toluene (13 mL) was added N-(dimethoxymethyl)-N-methyl-ethanamine (1.3 g, 9.7 mmol) at room temperature. The resulting clear solution was warmed to 50° C. and stirred for 24 h at this temperature. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, washed with aqueous NaHCO.sub.3, brine and dried over MgSO.sub.4. Solids were removed by filtration and volatiles were removed in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as light yellow liquid.
(18) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.40 (br. s., 1H), 7.26 (s, 1H), 6.33 (s, 1H), 3.85 (s, 3H), 3.34 (br. s., 2H), 3.00 (s, 3H), 2.16 (s, 3H), 1.22 (t, 3H).
Preparation of N-ethyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoroacetyl)phenyl]-N-methyl-formamidine
(19) A solution of N′-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine (0.94 g, 3.30 mmol) in THE (7 mL) under inert atmosphere was cooled to −78° C. and n-butyl lithium (2.5 M in hexanes, 2.5 mL, 3.96 mmol) was added drop wise. The resulting solution was aged for 30 min at −78° C., then ethyl 2,2,2-trifluoroacetate (1.40 g, 9.89 mmol) was added, the flask was removed from the cooling bath and was allowed to reach room temperature. The mixture was quenched with aq. NH.sub.4Cl and extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo to yellow oil. Purification by flash chromatography on silica gel to afford the title compound as light yellow solid.
(20) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.55 (s, 1H), 7.36-7.54 (m, 1H), 6.32 (s, 1H), 3.89 (s, 3H), 3.27-3.64 (m, 2H), 3.05 (s, 3H), 2.20 (s, 3H), 1.16-1.35 (m, 3H).
Preparation of N-ethyl-N′-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)oxiran-2-yl]phenyl]-N-methyl-formamidine
(21) Trimethyl sulfonium iodide (0.52 g, 2.48 mmol) was added in small portions to an ice-cold suspension of sodium hydride (60% in oil, 0.11 g, 2.48 mmol) in tetrahydrofuran (8 mL) and dimethylsulfoxide (6 mL). The cooling bath was removed and the mixture was stirred for 30 min at room temperature. A solution of N-ethyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoroacetyl)phenyl]-N-methyl-formamidine (0.50 g, 1.65 mmol) in tetrahydrofuran (5 mL) was added and the reaction was stirred at room temperature until HPLC indicated full conversion of the starting material. The mixture was cooled with an ice bath, carefully quenched with aq. NH.sub.4Cl solution and was extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo to a light brown solid which was purified by flash chromatography on silica gel to afford the title compound as light brown solid
(22) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.43 (br.s, 1H), 7.20 (s, 1H), 6.31 (s, 1H), 3.81 (s, 3H), 3.40 (d, 1H), 3.15-3.66 (m, 2H), 3.00 (s, 3H), 2.95-2.93 (m, 1H), 2.18 (s, 3H), 1.21 (t, 3H).
Preparation of N-ethyl-N′-[5-methoxy-2-methyl-4-[2,2,2-trifluoro-1-hydroxy-1-(isobutoxymethyl)-ethyl]phenyl]-N-methyl-formamidine
(23) 2-methylpropan-1-ol (0.11 g, 1.52 mmol) was added slowly to a suspension of sodium hydride (60%, 0.04 g, 1.0 mmol) in DMF (1 mL) at 0° C. and the mixture was aged for 5 min at 0° C. A solution of N-ethyl-N′-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)oxiran-2-yl]phenyl]-N-methyl-formamidine (0.20 g, 0.51 mmol) in DMF (1 mL) was added, the resulting solution was warmed to 65° C. and stirred at this temperature until HPLC indicated full conversion of the starting material. The reaction was cooled to room temperature, diluted with aq. NH.sub.4C solution and extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo to brown oil. Purification by flash chromatography on silica gel to afford the title compound as light yellow liquid.
(24) .sup.1H NMR (400 MHz, CDCl.sub.3-d) δ 7.43 (br.s, 1H), 7.31 (s, 1H), 6.34 (s, 1H), 5.49 (s, 1H), 4.13 (d, 1H), 3.89 (d, 1H), 3.83 (s, 3H), 3.17-3.59 (m, 4H), 3.00 (s, 3H), 2.19 (s, 3H), 1.81-1.98 (m, 1H), 1.21 (t, 3H), 0.88 (dd, 6H).
Preparation of N′-[4-[3-ethoxyimino-1-hydroxy-1-(trifluoromethyl)butyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine (Q.001)
Step 1. Preparation of N-ethoxypropan-2-imine
(25) To a suspension of sodium hydroxide (9.44 g, 236 mmol) in DMSO (40 mL) was added propan-2-one oxime (15.0 g, 205 mmol) at 23° C. The reaction mixture was stirred for 5 min at this temperature and bromoethane (22.8 mL, 308 mmol) was added dropwise over approx. 15 min. Upon completed addition, the reaction was warmed to 60° C. and aged for 60 min at this temperature. The mixture was cooled to 20° C., diluted with water and petroleum ether. The layers were separated, the organic layer was washed with brine, dried over MgSO.sub.4 and filtrated. Fractional distillation at ambient pressure afforded the title compound as colorless liquid, b.p. 90° C.
(26) .sup.1H NMR (400 MHz, DMSO) 3.96 (q, 2H), 1.79 (s, 3H), 1.77 (s, 3H), 1.16 (t, 3H).
Step 2. Preparation of N′-[4-[3-ethoxyimino-1-hydroxy-1-(trifluoromethyl)butyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine
(27) A solution of N-ethoxypropan-2-imine (4.3 g, 39 mmol) in dry oxolane (10 mL) was added dropwise to lithium diisopropyl amide (0.8 M solution in oxolane, 44 mL, 39 mmol) at −78° C. and the reaction was aged for 60 min at this temperature. Then a solution of N-ethyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoroacetyl)phenyl]-N-methyl-formamidine (7.8 g, 26 mmol) in dry oxolane (30 mL) was added. The reaction was stirred for 10 min at −78° C., the cooling bath was removed and the reaction warmed to 20° C. Aqueous NaHCO.sub.3 (saturated) was added and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The oily residue was purified by medium pressure chromatography on silica gel to afford the title compound as colorless oil.
(28) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.43 (br s, 1H), 7.15 (s, 1H), 6.39 (s, 1H), 6.13 (s, 1H), 4.08-4.17 (m, 2H), 3.88 (s, 3H), 3.83 (d, 1H), 3.22-3.63 (m, 2H), 3.02 (s, 3H), 2.75 (d, 1H), 2.16 (s, 3H), 1.70 (s, 3H), 1.32 (t, 3H), 1.23 (t, 3H).
(29) Table Q′: Physical Data of Compounds of Formula (I)
(30) The compounds of formula (I) in Table Q′ were prepared using techniques analogous to those described above and/or common synthetic techniques generally known to the person skilled in the art, as well as those described in WO 12/146125 (pp. 370-378) and WO 08/101682 (pp. 22-33).
(31) TABLE-US-00014 TABLE Q′ [M + H] Comp. Structural formula RT (min) (measured) MP °C. Q.001
HPLC Method Used
(32) Method A:
(33) Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters 10 (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. 15 Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 mm, 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
(34) Method B:
(35) Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150° C., Desolvation Temperature: 400° C., Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da), DAD Wavelength range (nm): 210 to 400, and an Acquity UPLC from Waters: 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/Methanol 9:1, 0.1% formic acid, B=Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75
Biological Examples for Compounds of Formula (I)
(36) Certain compositions of the invention can be distinguished from known compositions and compounds by virtue of displaying a 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 and/or 0.2 ppm. The use of “concentration/dilution factors” in biological testing to determine the intrinsic biological efficacy of bioactive molecules is known in the art.
(37) Blumeria graminis f. Sp. Tritici (Erysiphe graminis f. Sp. Tritici)/Wheat/Leaf Disc Preventative (Powdery Mildew on Wheat)
(38) Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound or mixture composition diluted in water. The leaf disks were inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks were incubated at 20° C. and 60% rh under a light regime of 24 h darkness followed by 12 h light/12 h darkness in a climate chamber and the activity of a compound or mixture composition was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6-8 days after application).
(39) The following compounds gave at 200 ppm 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:
(40) Q.001, Q.002, Q.003, Q.004, Q.006, Q.007, Q.009, Q.010
(41) Puccinia recondita f. Sp. Tritici/Wheat/Leaf Disc Preventative (Brown Rust)
(42) Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound or mixture composition 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% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound or mixture composition was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7-9 days after application).
(43) The following compounds gave at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development:
(44) Q.001, Q.002, Q.003, Q.004, Q.006, Q.007, Q.008, Q.009, Q.010
(45) Puccinia recondita f. Sp. Tritici/Wheat/Leaf Disc Curative (Brown Rust)
(46) Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19° C. and 75% rh. The formulated test compound or mixture composition diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19° C. and 75% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound or mixture composition was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6-8 days after application).
(47) The following compounds gave at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development:
(48) Q.001, Q.002, Q.003, Q.004, Q.006, Q.007, Q.008, Q.009, Q.010
(49) Phakopsora pachyrhizi/Soybean/Preventative (Soybean Rust)
(50) 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 (12-14 days after application).
(51) The following compounds gave at least 80% control of Phakopsora pachyrhizi at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
(52) Q.001, Q.002, Q.003, Q.004, Q.005, Q.006, Q.007, Q.008, Q.009, Q.010
Further Biological Test Examples
Example B1: Preventative Activity Against Blumeria graminis f. Sp. Tritici (Erysiphe graminis f. Sp. Tritici) on Wheat
(53) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound or mixture composition diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are incubated at 20° C. and 60% rh under a light regime of 24 h darkness followed by 12 h light/12 h darkness in a climate chamber and the activity of a compound or mixture composition is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6-8 days after application).
Example B2: Activity Against Mycosphaerella arachidis (Cercospora arachidicola)
(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 or mixture composition 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.
Example B3: Preventative Activity Against Phakopsora pachyrhizi on Soybean
(55) Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound or mixture composition 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 or mixture composition is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (10-12 days after application).
(56) The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development:
(57) TABLE-US-00015 A:B conc. A:B Component A Component B (ppm) Ratio
Example B4: Preventative Activity Against Phakopsora pachyrhizi on Soybean
(58) 4-week old soybean plants are sprayed in a spray chamber with the formulated test compound or mixture composition 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 (12-14 days after application).
Example B5: Preventative Activity Against Puccinia recondita on Wheat
(59) Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound or mixture composition diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments are incubated at 19° C. and 75% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound or mixture composition is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7-9 days after application).
Examples B6: Preventative Activity Against Pyrenophora teres on Barley
(60) Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound or mixture composition 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 or mixture composition 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).
Example B7: Activity Against Thanatephorus cucumeris (Rhizoctonia solani)
(61) Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compound or mixture composition into a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 3-4 days after application.
Example B8: Preventative Activity Against Phakopsora pachyrhizi on Genetically Modified Soybean (e.g. Comprising Event MON87701; Intacta RR2 PRO™ Soybean)
(62) Genetically modified soybean (e.g. comprising event MON87701; Intacta RR2 PRO™ soybean) leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with a compound selected from compound Q.001, Q.002, Q.003, Q.004, Q.005, Q.006, Q.007, Q.008, Q.009 and Q.010, as defined in Table Q above, or a fungicidal composition comprising a mixture of components (A) and (B) (as described above and claimed below) 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 or mixture composition is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (10-12 days after application).