Fungicidal compositions

Abstract

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

Claims

1. A fungicidal composition comprising a mixture of components (A) and (B), wherein component (A) is a compound of formula (I) ##STR00079## wherein R.sup.1 represents hydrogen, chloro, bromo, cyano, C.sub.1-C.sub.2 alkyl, CO.sub.2(C.sub.1-C.sub.2 alkyl), CO.sub.2H, CONH.sub.2, CONH(C.sub.1-C.sub.4 alkyl), CON(C.sub.1-C.sub.4 alkyl).sub.2, C.sub.1-C.sub.4 haloalkyl, or C.sub.1-C.sub.4 haloalkoxy; R.sup.2 represents C.sub.3-C.sub.6alkyl, C.sub.3-C.sub.6alkenyl; R.sup.3 and R.sup.4 independently of each other represent hydrogen, methyl, ethyl, isopropyl or cyclopropyl; or R.sup.3 and R.sup.4 together with the nitrogen atom to which they are attached form a 3-, 4- or 5-membered saturated cyclic group; R.sup.5 represents C.sub.1-C.sub.3 alkyl, or C.sub.1-C.sub.2 alkoxyC.sub.1-C.sub.2 alkyl; 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 aldimorph, dodemorph, fenpropimorph and tridemorph; (B4) a carboxamide fungicide selected from 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 cyprodinil, mepanipyrim and pyrimethanil; (B6) an phenylpyrrole fungicide selected from fludioxonil and fenpiclonil; (B7) a phenylamide fungicide selected from benalaxyl, benalaxyl-M, furalaxyl, mefenoxam (metalaxyl-M) 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 ##STR00080## a compound of the formula ##STR00081## and a compound of the formula: ##STR00082## (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 -terpinene; and (B11) glyphosate, wherein the weight ratio of component (A) to component (B) is from 30:1 to 1:40.

2. A fungicidal composition according to claim 1 wherein component (A) is a compound of formula (I) wherein R.sup.1 is chloro, bromo, cyano, methyl or C.sub.1 fluoroalkyl; R.sup.2 is n-propyl, iso-propyl or allyl; R.sup.3 is methyl; R.sup.4 is ethyl or iso-propyl; and R.sup.5 is methyl; or a salt, enantiomer, tautomer or N-oxide thereof.

3. A fungicidal composition according to either claim 1 wherein component (B) is a compound selected from the group consisting of azoxystrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, cyproconazole, difenoconazole, epoxiconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, bixafen, fluopyram, fluxapyroxad, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, acibenzolar-S-methyl, chlorothalonil, mancozeb, dithianon, a compound of the formula ##STR00083## a compound of the formula ##STR00084## and a compound of the formula ##STR00085##

4. A fungicidal composition according to claim 1 wherein component (A) is a compound selected from N-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.002), N-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.003), N-[5-cyano-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.007), N-[5-(difluoromethyl)-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.009), N-[2,5-dimethyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.011), N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.013), N-[6-(2-allyloxy-1-methyl-ethoxy)-5-chloro-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.014), N-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.015), and N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (compound 67.018); or a salt, enantiomer, tautomer or N-oxide thereof.

5. A fungicidal composition according to claim 1 wherein component (A) is N-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.002); or a salt, enantiomer, tautomer or N-oxide thereof.

6. A fungicidal composition according to claim 1 wherein component (A) is N-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.003); or a salt, enantiomer, tautomer or N-oxide thereof.

7. A fungicidal composition according to claim 1 wherein component (A) is N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.013); or a salt, enantiomer, tautomer or N-oxide thereof.

8. A fungicidal composition according to claim 1 wherein component (A) is N-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (compound 67.015); or a salt, enantiomer, tautomer or N-oxide thereof.

9. A fungicidal composition according to claim 1 wherein component (A) is N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (compound 67.018); or a salt, enantiomer, tautomer or N-oxide thereof.

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

Description

SYNTHETIC EXAMPLES

(1) Using techniques described below and techniques analogous to those described in WO 12/146125 (pp. 370-378) and further techniques known to the person skilled in the art, for example as found in WO 08/101682 (pp. 22-33), compounds of formula (I) may be prepared.

Preparation of (2R)-1-propoxypropan-2-ol

(2) ##STR00023##

(3) To an ice-bath cooled solution of THF (400 mL) under inert atmosphere (Ar) charged with sodium hydride (12 g, 490 mmol, 5 equiv.) 1-propanol (40 mL, 490 mmol, 5 equiv) was added dropwise. The ice bath was removed and the reaction mixture was stirred at room temperature for 30 minutes then (2R)-2-methyloxirane (5.8 g, 99 mmol) was added dropwise and the reaction was stirred for 18h under heating at 50 C. After this time, GC-MS and NMR indicated that the starting material was consumed and the reaction mixture was allowed to reach room temperature before quenching with aqueous NH.sub.4Cl solution and extracting with dichloromethane. The organic layer was dried over anhydrous Na.sub.2SO.sub.4 and filtered. The solvent was removed in vacuo (not dropping below 200 mbar) at 30 C. and provided the title compound (4.4 g, 38% yield) as a yellow liquid.

(4) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 4.00-3.87 (1H, m) 3.50-3.40 (m, 3H), 3.30-3.20 (m, 1H), 2.64 (d, 1H), 1.61 (m, 2H), 1.12 (d, 3H), 0.95 (t, 3H)

Preparation of N-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine

(5) ##STR00024##

(6) To a stirring suspension of N-(5-bromo-6-hydroxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (0.75 g, 2.8 mmol) in THF (15 mL), (2R)-1-propoxypropan-2-ol (0.36 g, 3 mmol, 1.1 equiv) and triphenylphosphine (0.80 g, 3 mmol, 1.1 equiv) were added at room temperature under inert atmosphere (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (0.60 mL, 3 mmol, 1.1 equiv) was added dropwise over 10 minutes while keeping the temperature below 40 C. The reaction mixture was stirred for 24h at room temperature. After this time, LC-MS indicated that the starting material had been nearly consumed and the reaction mixture was quenched with water (40 mL). The water phase was extracted with ethyl acetate (350 mL). The organic layer was dried over anhydrous Na.sub.2SO.sub.4 and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by preparative reverse phase chromatography to afford the desired (0.10 g, 10% yield).

(7) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.45-7.30 (broad s, 1H), 7.24 (s, 1H), 5.40-5.30 (m, 1H), 3.70-3.60 (m, 1H), 3.55-3.45 (m, 3H), 3.45-3.30 (broad m, 2H), 3.00 (s, 3H), 2.35 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Preparation of N-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine

(8) ##STR00025##

(9) To an ice-bath cooled solution of (2R)-1-propoxypropan-2-ol (0.103 g, 0.88 mmol, 1.2 equiv) in DMF (4 mL) under inert atmosphere (Ar), potassium tertbutoxide (0.25 g, 2.19 mmol, 3 equiv) and triphenylphosphine (0.14 g, 0.55 mmol, 1.5 equiv) were added. The reaction mixture was stirred for 20 minutes before N-(5-bromo-6-fluoro-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (0.20 g, 0.73 mmol) was added. The reaction mixture was stirred for 4h at room temperature and was quenched with water upon completion. The water phase was extracted with ethyl acetate (250 mL). The organic layers were combined, washed with water (350 mL), dried over anhydrous Na.sub.2SO.sub.4, and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by preparative reverse phase chromatography to afford the desired compound (0.130 g, 13% yield).

(10) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.45-7.30 (broad s, 1H), 7.24 (s, 1H), 5.40-5.30 (m, 1H), 3.70-3.60 (m, 1H), 3.55-3.45 (m, 3H), 3.50-3.30 (broad m, 2H), 3.00 (s, 3H), 2.35 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Preparation of N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine

(11) ##STR00026##

(12) To a stirring suspension of N-(5-bromo-6-hydroxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (6.0 g, 22.05 mmol) in THF (30 mL), 1-propoxypropan-2-ol (3.53 mL, 26.46 mmol, 1.2 equiv) and triphenylphosphine (6.94 g, 26.46 mmol, 1.2 equiv) were added at room temperature under inert atmosphere (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (5.21 mL, 26.46 mmol, 1.2 equiv) was added dropwise over 10 minutes while keeping the temperature below 40 C. The reaction mixture was stirred for 1.5 h at room temperature. After this time, LC-MS indicated that the starting material had been consumed and the reaction mixture was concentrated in vacuo. Heptane was added to the residue and the mixture was cooled with an ice bath to recrystallize triphenylphosphine oxide. The brown residue was purified by combiflash column chromatography (silica gel, heptanelethyl acetate, v/v=90/10 to 4/1). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (7.80 g, 95% yield) as a light yellow oil.

(13) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.45-7.30 (broad s, 1H), 7.24 (s, 1H), 5.40-5.30 (m, 1H), 3.70-3.60 (m, 1H), 3.55-3.45 (m, 3H), 3.45-3.30 (broad m, 2H), 3.00 (s, 3H), 2.35 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Preparation of N-[5-cyano-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine

(14) ##STR00027##

(15) To a stirred solution of N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (0.25 g, 0.67 mmol) in DMF (1 mL) under inert atmosphere (Ar), zinc cyanide (0.087 g, 0.74 mmol, 1.1 equiv) and tetrakis(triphenylphosphine)palladium (0.23 g, 0.20 mmol, 0.3 equiv) were added and the reaction mixture was stirred for 18h under heating at 120 C. After this time, TLC and LC-MS indicated that the starting material was consumed and the reaction mixture was allowed to reach room temperature before quenching with water. The water phase was extracted with ethyl acetate (230 mL). The organic layer was washed with brine (350 mL), dried over anhydrous Na.sub.2SO.sub.4 and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate, v/v=90/10 to 70/30). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.207 g, 97% yield) as a colorless oil.

(16) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.45-7.30 (broad s, 1H), 7.20 (s, 1H), 5.50-5.40 (m, 1H), 3.70-3.60 (m, 1H), 3.55-3.40 (m, 3H), 3.45-3.30 (broad m, 2H), 3.00 (s, 3H), 2.40 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Preparation of 3-chloro-6-methyl-5-nitro-pyridin-2-ol

(17) ##STR00028##

(18) To an ice-bath cooled suspension of 6-methyl-5-nitro-pyridin-2-ol (0.50 g, 3.24 mmol) in acetonitrile (5 mL) under inert atmosphere (Ar), was added N-chlorosuccinimide (0.43 g, 3.24 mmol, 1 equiv) was added portionwise. The reaction mixture was stirred for 20h under heating at 67 C. At this time, LC-MS indicated that the starting material was consumed and the reaction mixture was cooled to 0 C. and the precipitate was filtered to give the title compound (0.36 g, 48% yield) as a beige-white solid.

(19) .sup.1H NMR (400 MHz, CD.sub.3OD): (ppm) 8.5 (s, 1H), 2.7 (s, 3H).

Preparation of 5-chloro-2-methyl-3-nitro-6-(o-tolylmethoxy)pyridine

(20) ##STR00029##

(21) To a stirred solution of o-tolylmethanol (3.99 g, 32.1 mmol, 1.2 equiv) in THF (100 mL), 3-chloro-6-methyl-5-nitro-pyridin-2-ol (5.30 g, 26.7 mmol) and triphenylphosphine (8.41 g, 32.1 mmol, 1.2 equiv) were added at room temperature under inert atmosphere (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (6.58 mL, 33.4 mmol, 1.25 equiv) was added dropwise over 10 minutes while keeping the temperature below 40 C. The reaction mixture was stirred for 16 h at room temperature. At this time, LC-MS indicated that the starting material was consumed and the reaction mixture was quenched with water (20 mL). A precipitate formed and was filtered and washed with a mixture of methanol/water (v/v=5/1), suspended in toluene and concentrated in vacuo to give the title compound (5.28 g, 47% yield) as a yellow solid.

(22) .sup.1H NMR (400 MHz, DMSO): (ppm)=8.60 (s, 1H), 7.45 (d, 1H), 7.30-7.20 (m, 3H), 5.50 (s, 2H), 2.70 (s, 3H), 2.35 (s, 3H).

Preparation of 6-benzyloxy-5-chloro-2-methyl-pyridin-3-amine

(23) ##STR00030##

(24) A solution of 2-benzyloxy-3-chloro-6-methyl-5-nitro-pyridine (250 mg, 0.90 mmol), 10% platinum on carbon (12 mg, 0.062 mmol) in THF (5 mL) was placed under hydrogen (3 equiv., 2.70 mmol) pressure of 3 bar and the reaction was stirred for 18 h at 37 C. After this time, TLC indicated that the starting material has been consumed. The reaction mixture was filtered and the residue was washed with methanol. The organic layer was concentrated to give the title compound (0.216 g, 97% yield) which was used without further purification.

(25) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.50-7.45 (m, 1H), 7.25-7.15 (m, 3H), 7.0 (s, 1H), 5.35 (s, 2H), 3.40-3.10 (broad s, 2H), 2.42 (s, 3H), 2.30 (s, 3H).

Preparation of N-(5-chloro-6-hydroxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine

(26) ##STR00031##

(27) To a solution of N-ethyl-N-methyl-formamide (1.29 g, 14.76 mmol, 1.1 equiv) in dichloromethane (70 mL) was added phosphorus oxychloride (1.38 mL, 14.76 mmol, 1.1 equiv). The solution was stirred for 1.5 h at room temperature and then a solution of 5-chloro-2-methyl-6-(o-tolylmethoxy)pyridin-3-amine (3.52 g, 13.41 mmol) in dichloromethane (10 mL) was added dropwise. After being stirred for 20 h at room temperature the solid was filtered and washed with dichloromethane. The residue was purified by combiflash column chromatography (silica gel, dichloromethane/methanol+5% triethylamine v/v=10/0 to 9/1). Fractions containing the compound were collected and concentrated in vacuo to give the title compound (2.52 g, 82% yield) as a yellow solid.

(28) .sup.1H NMR (400 MHz, CD.sub.3OD): (ppm) 7.65-7.50 (broad s, 1H), 3.50-3.30 (broad s, 1H), 3.0 (s, 2H), 2.25 (s, 3H), 1.35 (m, 3H), 1.25 (m, 3H).

Preparation of N-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine

(29) ##STR00032##

(30) To a stirred solution of N-(5-chloro-6-hydroxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (0.25 g, 1.10 mmol) in THF (10 mL), 1-propoxypropan-2-ol (0.14 g, 1.21 mmol, 1.1 equiv) and triphenylphosphine (0.32 g, 1.21 mmol, 1.1 equiv) were added at room temperature under inert atmosphere (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (0.24 mL, 1.21 mmol, 1.1 equiv) was added dropwise over 10 minutes while keeping the temperature below 40 C. The reaction mixture was stirred for 16h under heating at 60 C. After this time, triphenylphosphine (0.15 g, 0.55 mmol, 0.5 equiv) and DIAD (diisopropyl diazodicarboxylate) (0.11 mL, 0.55 mmol, 0.5 equiv) were added again and the reaction mixture wasfurther stirred for 9 h. The reaction mixture was allowed to reach room temperature before quenching with water (10 mL) and 2M NaOH aqueous solution (2 mL).

(31) The water phase was extracted with ethyl acetate (125 mL). The organic layers were combined, dried over anhydrous Na.sub.2SO.sub.4 and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate, v/v=9/1 to 1/1). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.19 g, 53% yield) as an yellow oil.

(32) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.45-7.30 (broad s, 1H), 7.05 (s, 1H), 5.40-5.30 (m, 1H), 3.70-3.60 (m, 1H), 3.55-3.40 (m, 3H), 3.45-3.30 (broad m, 2H), 3.00 (s, 3H), 2.35 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.85 (t, 3H).

Preparation of 5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-nitro-pyridine

(33) ##STR00033##

(34) To a stirred suspension of 3-bromo-6-methyl-5-nitro-pyridin-2-ol (0.23 g, 1 mmol) in THF (0.08 mL), 1-propoxypropan-2-ol (0.15 g, 1.2 mmol, 1.2 equiv) and triphenylphosphine (0.32 g, 1.2 mmol, 1.2 equiv) were added at room temperature under inert atmosphere (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (0.24 mL, 1.2 mmol, 1.2 equiv) was added dropwise over 10 minutes while keeping the temperature below 40 C. The reaction mixture was stirred for 12h under heating at 65 C. After this time, LC-MS still showed remaining starting material but the reaction mixture was allowed to reach room temperature and the solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/triethylamine, v/v=95/5). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.20 g, 60% yield) as a beige oil.

(35) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 8.45 (s, 1H), 5.50-5.40 (m, 1H), 3.65-3.60 (m, 1H), 3.65-3.50 (m, 1H), 3.50-3.35 (m, 2H), 2.70 (s, 3H), 1.50 (m, 2H), 1.30 (m, 3H), 0.80 (t, 3H).

Preparation of 5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)pyridin-3-amine

(36) ##STR00034##

(37) To a stirred suspension of 5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-nitro-pyridine (0.47 g, 1.41 mmol) in ethanol (10 mL) were added ammonium chloride (0.15 g, 2.82 mmol, 2 equiv), water (2.8 mL) and then iron powder (0.32 g, 5.64 mmol, 4 equiv). The reaction mixture was stirred for 4h under heating at 85 C. As reaction monitoring still showed remaining starting material, ammonium chloride (0.75 g, 1.41 mmol, 1 equiv) and iron powder (0.16 g, 2.82 mmol, 2 equiv) were added and reaction mixture was further stirred for 10 h under heating at 85 C. After this time, LC-MS indicated that the starting material has been consumed and the reaction mixture was allowed to reach room temperature before filtering it over celite. The solvent was removed in vacuo and the residue was redissolved with ethyl acetate (15 mL). The organic phase was washed with a 2N aqueous NaOH solution (225 mL), dried over anhydrous Na.sub.2SO.sub.4 and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate+10% triethylamine, v/v=10/0 to 1/1). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.27 g, 63% yield) as an orange-brown oil.

(38) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.10 (s, 1H), 5.25-5.15 (m, 1H), 3.65-3.60 (m, 1H), 3.55-3.50 (m, 3H), 3.50-3.35 (broad m, 2H), 2.20 (s, 3H), 1.50 (m, 2H), 1.25 (m, 3H), 0.80 (t, 3H).

Preparation of N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-formamidine

(39) ##STR00035##

(40) To a solution of N-ethylformamide (0.070 mL, 0.91 mmol, 1.1 equiv) in dichloromethane (6.6 mL) was added phosphorus oxychloride (0.085 mL, 0.91 mmol, 1.1 equiv). The solution was stirred for 1 h at room temperature. Then a solution of 5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)pyridin-3-amine (0.25 g, 0.83 mmol) in dichloromethane (3 mL) was added dropwise. The suspension was stirred for 2 h at room temperature then poured onto a mixture of 2N aqueous NaOH solution (25 mL) and ice. The aqueous layer was separated, extracted with dichloromethane (215 mL). The organic phase was washed with 2N aqueous NaOH solution (25 mL) and brine (25 mL), dried over anhydrous Na.sub.2SO.sub.4 and filtered. The solvent was removed in vacuo to give a dark yellow residue, which was purified by reverse phase preparative HPLC to give the title compound (0.09 g, 29% yield) as an orange-brown oil.

(41) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.45 (s, 1H), 7.25 (s, 1H), 5.40-5.30 (m, 1H), 4.70-4.50 (broad s, 1H), 3.75-3.60 (m, 1H), 3.55-3.45 (m, 3H), 3.50-3.35 (broad m, 2H), 2.30 (s, 3H), 1.60-1.50 (m, 2H), 1.35 (m, 3H), 1.25 (m, 3H), 0.80 (t, 3H).

Preparation of N-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-methyl-formamidine

(42) ##STR00036##

(43) To a solution of N-methyl N-ethylformamide (0.30 g, 2.37 mmol, 1.1 equiv, 80% wt.) in dichloromethane (4.0 mL) was added phosphorus oxychloride (0.20 mL, 2.2 mmol, 1.1 equiv). The solution was stirred for 1 h at room temperature. Then a solution of 5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)pyridin-3-amine (0.60 g, 2.0 mmol) in dichloromethane (0.5 mL) was added dropwise. The suspension was stirred for 2h at room temperature, then poured onto a mixture of 2N aqueous NaOH solution (25 mL) and ice. The aqueous layer was separated, extracted with dichloromethane (215 mL). The organic phase was washed with 2N aqueous NaOH solution (25 mL) and brine (25 mL), dried over anhydrous Na.sub.2SO.sub.4 and filtered. The solvent was removed in vacuo to give a dark yellow residue, which was purified by reverse phase preparative HPLC to give the title compound (0.30 g, 40% yield) as an orange oil.

(44) .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm) 7.47 (broad s, 1H), 7.25 (s, 1H), 5.40-5.30 (m, 2H), 3.70-3.64 (m, 3H), 3.60-3.40 (m, 3H), 2.94 (broad s, 2H) 2.35 (d, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.25 (m, 6H), 0.90 (t, 3H).

(45) TABLE-US-00011 TABLE 67 This table gives analytical data for compounds of formula (I) prepared using techniques analogous to those above, as well as those described in WO 12/146125 (pp. 370-378) and further techniques known to the person skilled in the art, for example as found in WO 08/101682 (pp. 22-33). LC-Method: R.sub.t (min); Compound MS-ESI No. Structural formula (m/z; (M + H).sup.+); 67.001 Method 1 0.9 min.; 337 67.002 Method 1 0.76 min.; 372 67.003 Method 1 0.76 min.; 372 67.004 0 Method 1 0.8 min.; 361 67.005 Method 1 0.8 min.; 351 67.006 Method 1 0.7 min.; 338 67.007 Method 1 0.78 min.; 319 67.008 oil 67.009 Method 2 13.04 min.; 342 67.010 Method 1 0.85 min.; 360 67.011 Method 1 0.79 min.; 308 67.012 Method 1 0.67 min.; 294 67.013 Method 1 0.76 min.; 372 67.014 0 Method 3 1.08 min.; 326 67.015 Method 1 1.11 min.; 328 67.016 Method 3 1.02 min.; 400 67.017 Method 3 0.96 min.; 317 67.018 oil 67.019 Method 1 0.80 min.; 352 67.020 Method 3 1.33 min.; 422 67.021 Method 3 1.29 min.; 387 67.022 Method 3 1.21 min.; 353 67.023 Method 3 1.38 min.; 430 67.024 0 Method 3 1.38 min.; 396 67.025 Method 3 1.23 min.; 362 67.026 Method 3 1.37 min.; 440 67.027 Method 3 1.42 min.; 474 67.028 Method 3 1.25 min.; 406 67.029 Method 1 0.77 min.; 371 67.030 Method 1 0.76 min.; 385

(46) Analytical Methods Used

(47) Method 1: Mass spectra were recorded on a Mass Spectrometer from Waters (SQD 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 m, 302.1 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: 0 min 0% B, 100% A; 1.2-1.5 min 100% B: Flow (ml/min) 0.85.

(48) Method 2: Mass spectra were recorded on a Mass Spectrometer from Shimadzu (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 1.5 kV, Cone range: unknown, Extractor: 5.00 V, Source Temperature: 200 C., Desolvation Temperature: 250 C., Cone Gas Flow: 90 L/Hr, Desolvation Gas Flow: 90 L/Hr, Mass range: 50 to 900 Da) and an SPD-20A from LC from Shimadzu: Solvent degasser, binary pump, heated column compartment and ultraviolet detector. Column: Diamonsil C.sub.18 (2) 5u 150*4.6 mm, Temp: 40 C., SPD-20A Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+0.1% F.sub.3CCOOH, B=Acetonitrile+0.1% F.sub.3CCOOH; Gradient: 0 min 10% B, 90% A; 15 min 100% B; Flow 1.00 (ml/min)

(49) Method 3: Mass spectra were recorded on a ZQ2000 Mass Spectrometer from Waters (Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive ions, Capillary (kV) 3.5, Cone (V) 60.00, Extractor (V) 3.00, Source Temperature ( C.) 150, Desolvation Temperature ( C.) 350, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 800, Mass range: 140 to 800 Da) DAD Wavelength range (nm): 210 to 400, Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60 C. Solvent Gradient: A=water+10% MeOH+0.1% HCOOH, B=Acetonitrile+0.1% HCOOH. Gradient: 0 min 0% B, 100% A; 2.5-2.8 min 100% B; 0% A; 3.0 min 100% A, 0% B: Flow (ml/min) 0.85.

(50) Biological Examples for Compounds of Formula (I)

(51) 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.

(52) Blumeria graminis f. Sp. Tritici (Erysiphe qraminis f. Sp. Tritici)/Wheat/Leaf Disc Preventative (Powdery Mildew on Wheat)

(53) 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).

(54) 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:

(55) 67.002, 67.003, 67.007, 67.008, 67.009, 67.010, 67.011, 67.013, 67.014, 67.015, 67.016, 67.017, 67.018, 67.020, 67.021, 67.022, 67.023, 67.024, 67.025, 67.026, 67.027, 67.028, 67.029, 67.030.

(56) Puccinia recondita f. sp. tritici/wheat/leaf disc preventative (brown rust)

(57) 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).

(58) 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:

(59) 67.002, 67.003, 67.007, 67.008, 67.009, 67.010, 67.011, 67.013, 67.014, 67.015, 67.016, 67.017, 67.018, 67.020, 67.021, 67.022, 67.023, 67.024, 67.025, 67.026, 67.028, 67.029, 67.030.

(60) Puccinia recondita f. Sp. Tritici/Wheat/Leaf Disc Curative (Brown Rust)

(61) 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).

(62) 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:

(63) 67.002, 67.003, 67.007, 67.008, 67.009, 67.010, 67.011, 67.012, 67.013, 67.014, 67.015, 67.016, 67.017, 67.018, 67.019, 67.020, 67.021, 67.022, 67.023, 67.024, 67.025, 67.026, 67.027, 67.028, 67.029, 67.030.

(64) Phakopsora pachyrhizi on Soybean, Preventive Treatment

(65) The compound or mixture composition activity was tested under 1 day preventive conditions. Soybean plants with a fully enfolded first trifoliate leaf were sprayed with a track sprayer and 50 l/ha spray volume with the test compounds or mixture composition, either solo or in tankmix as shown in the table below.

(66) 1 day after application leaf discs were cut from the first trifoliate leaf and placed in multiwell plates on water-agar. 5 leaf discs per treatment where infested with spores of a triazole tolerant soybean rust strain. The multiwell plates where sealed and placed in an incubator 48 h in darkness and 12 h light/dark cycle afterwards. Rust infestation on leaf discs was evaluated visually 11 days after application and average activity calculated in relation to disease severity on untreated check leaf discs.

(67) 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:

(68) 67.002, 67.003, 67.007, 67.008, 67.009, 67.010, 67.011, 67.012, 67.013, 67.014, 67.015, 67.016, 67.017, 67.018, 67.019 67.020, 67.023, 67.024, 67.025, 67.026, 67.027, 67.028, 67.029, 67.030.

(69) Further Biological Test Examples:

Example B1

Preventative Activity Against Blumeria Graminis f. Sp. Tritici (Erysiphe Graminis f. Sp. Tritici) on Wheat

(70) 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)

(71) 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

(72) 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).

(73) 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:

(74) TABLE-US-00012 Conc. Ratio (ppm) Component A Component B A:B (A:B) Azoxystrobin 1:1 66:66 Compound 67.013 Azoxystrobin 1:1 22:22 Compound 67.013 Azoxystrobin 1:1 7.3:7.3 Compound 67.013 Azoxystrobin 1:3 66:200 Compound 67.013 Azoxystrobin 1:3 22:66 Compound 67.013 Azoxystrobin 3:1 200:66 Compound 67.013 Azoxystrobin 3:1 66:22 Compound 67.013 Azoxystrobin 3:1 22:7.33 Compound 67.013 Azoxystrobin 3:1 7.3:2.44 Compound 67.013 Azoxystrobin 3:1 2.44:0.8 Compound 67.013 Azoxystrobin 3:1 0.8:0.27 Compound 67.013 Trifloxystrobin 1:1 66:66 Compound 67.013 Trifloxystrobin 1:1 22:22 Compound 67.013 Trifloxystrobin 1:3 66:200 Compound 67.013 Trifloxystrobin 1:3 22:66 Compound 67.013 Trifloxystrobin 1:3 7.33:22 Compound 67.013 Trifloxystrobin 3:1 200:66 Compound 67.013 Trifloxystrobin 3:1 66:22 Compound 67.013 Trifloxystrobin 3:1 22:7.33 Compound 67.013 Trifloxystrobin 3:1 7.3:2.44 Compound 67.013 Trifloxystrobin 3:1 2.44:0.8 Compound 67.013 Cyproconazole 1:1 66:66 Compound 67.013 Cyproconazole 1:3 66:200 Compound 67.013 Cyproconazole 3:1 200:66 Compound 67.013 Cyproconazole 3:1 66:22 Compound 67.013 Cyproconazole 3:1 22:7.33 Compound 67.013 Cyproconazole 3:1 7.3:2.44 Compound 67.013 Cyproconazole 3:1 2.44:0.8 Compound 67.013 Difenoconazole 1:1 66:66 Compound 67.013 Difenoconazole 1:1 22:22 Compound 67.013 Difenoconazole 1:3 66:200 Compound 67.013 Difenoconazole 1:3 22:66 Compound 67.013 Difenoconazole 3:1 200:66 Compound 67.013 Difenoconazole 3:1 66:22 Compound 67.013 Difenoconazole 3:1 22:7.33 Compound 67.013 Difenoconazole 3:1 7.3:2.44 Compound 67.013 Prothioconazole 1:1 66:66 Compound 67.013 Prothioconazole 1:1 22:22 Compound 67.013 Prothioconazole 1:3 66:200 Compound 67.013 Prothioconazole 1:3 22:66 Compound 67.013 Prothioconazole 1:3 7.33:22 Compound 67.013 Prothioconazole 3:1 200:66 Compound 67.013 Prothioconazole 3:1 66:22 Compound 67.013 Prothioconazole 3:1 22:7.33 Compound 67.013 Prothioconazole 3:1 7.3:2.44 Compound 67.013 Mefentrifluconazole 1:1 66:66 Compound 67.013 Mefentrifluconazole 1:3 66:200 Compound 67.013 Mefentrifluconazole 1:3 22:66 Compound 67.013 Mefentrifluconazole 3:1 200:66 Compound 67.013 Mefentrifluconazole 3:1 66:22 Compound 67.013 Mefentrifluconazole 3:1 22:7.33 Compound 67.013 Mefentrifluconazole 3:1 7.3:2.44 Compound 67.013 Bixafen 1:1 66:66 Compound 67.013 Bixafen 1:1 22:22 Compound 67.013 Bixafen 1:3 66:200 Compound 67.013 Bixafen 1:3 22:66 Compound 67.013 Bixafen 1:3 7.33:22 Compound 67.013 Bixafen 3:1 200:66 Compound 67.013 Bixafen 3:1 66:22 Compound 67.013 Bixafen 3:1 22:7.33 Compound 67.013 Bixafen 3:1 7.3:2.44 Compound 67.013 Fluxapyroxad 3:1 66:22 Compound 67.013 Fluxapyroxad 3:1 22:7.3 Compound 67.013 Fluxapyroxad 1:1 66:66 Compound 67.013 Fluxapyroxad 1:1 22:22 Compound 67.013 Fluxapyroxad 9:1 200:22 Compound 67.013 Fluxapyroxad 9:1 66:7.33 Compound 67.013 lsopyrazam 9:1 66:7.3 Compound 67.013 lsopyrazam 3:1 66:22 Compound 67.013 lsopyrazam 3:1 22:7.3 Compound 67.013 lsopyrazam 55:2 200:7.33 Compound 67.013 lsopyrazam 55:2 66:2.44 Compound 67.013 lsopyrazam 55:2 22:0.8 Compound 67.013 lsopyrazam 55:2 7.3:0.27 Compound 67.013 Sedaxane 9:1 66:7.3 Compound 67.013 Sedaxane 3:1 66:22 Compound 67.013 Sedaxane 55:2 200:7.33 Compound 67.013 Sedaxane 55:2 66:2.44 Compound 67.013 Sedaxane 55:2 22:0.8 Compound 67.013 Sedaxane 55:2 7.3:0.27 Compound 67.013 Benzovindifupyr 9:1 66:7.3 Compound 67.013 Benzovindifupyr 9:1 22:2.44 Compound 67.013 Benzovindifupyr 9:1 7.3:0.8 Compound 67.013 Benzovindifupyr 3:1 66:22 Compound 67.013 Benzovindifupyr 3:1 22:7.3 Compound 67.013 Benzovindifupyr 3:1 7.33:2.44 Compound 67.013 Benzovindifupyr 3:1 2.44:0.8 Compound 67.013 Benzovindifupyr 55:2 200:7.33 Compound 67.013 Benzovindifupyr 55:2 66:2.44 Compound 67.013 Benzovindifupyr 55:2 22:0.8 Compound 67.013 Benzovindifupyr 55:2 7.3:0.27 Compound 67.013 9:1 66:7.3 Compound 67.013 9:1 22:2.44 Compound 67.013 0 3:1 66:22 Compound 67.013 3:1 22:7.3 Compound 67.013 3:1 7.33:2.44 Compound 67.013 55:2 200:7.33 Compound 67.013 55:2 66:2.44 Compound 67.013 55:2 22:0.8 Compound 67.013 55:2 7.3:0.27 Compound 67.013 3:1 22:7.3 Compound 67.013 Fuindapyr 1:1 66:66 Compound 67.013 Fuindapyr 1:1 22:22 Compound 67.013 Fuindapyr 1:1 7.3:7.3 Compound 67.013 Fuindapyr 9:1 200:22 Compound 67.013 Fuindapyr 9:1 66:7.33 Compound 67.013 Fuindapyr 9:1 22:2.44 Compound 67.013 Fuindapyr 9:1 7.3:0.8 Compound 67.013 3:1 66:22 Compound 67.013 UK-2A procide 3:1 22:7.3 Compound 67.013 UK-2A procide 1:1 66:66 Compound 67.013 UK-2A procide 1:1 22:22 Compound 67.013 UK-2A procide 1:1 7.3:7.3 Compound 67.013 UK-2A procide 9:1 200:22 Compound 67.013 UK-2A procide 9:1 66:7.33 Compound 67.013 UK-2A procide 9:1 22:2.44 Compound 67.013 UK-2A procide 9:1 7.3:0.8 Compound 67.013 Chlorothalonil 1:1 66:66 Compound 67.013 Chlorothalonil 1:3 66:200 Compound 67.013 Chlorothalonil 3:1 200:66 Compound 67.013 Chlorothalonil 3:1 66:22 Compound 67.013 Chlorothalonil 3:1 22:7.33 Compound 67.013 Chlorothalonil 3:1 7.3:2.44 Compound 67.013 Chlorothalonil 3:1 2.44:0.8 Compound 67.013 Mancozeb 1:1 66:66 Compound 67.013 Mancozeb 1:3 66:200 Compound 67.013 Mancozeb 3:1 200:66 Compound 67.013 Mancozeb 3:1 66:22 Compound 67.013 Mancozeb 3:1 22:7.33 Compound 67.013 Mancozeb 3:1 7.3:2.44

Example B4

Preventative Activity Against Phakopsora pachyrhizi on Soybean

(75) 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

(76) 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

(77) 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)

(78) 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.