WO2013011010A1 - Fungizide mixtures - Google Patents

Fungizide mixtures Download PDF

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Publication number
WO2013011010A1
WO2013011010A1 PCT/EP2012/063968 EP2012063968W WO2013011010A1 WO 2013011010 A1 WO2013011010 A1 WO 2013011010A1 EP 2012063968 W EP2012063968 W EP 2012063968W WO 2013011010 A1 WO2013011010 A1 WO 2013011010A1
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Prior art keywords
compound
methyl
chlorophenyl
isoxazole
formula
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PCT/EP2012/063968
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French (fr)
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Camilla Corsi
Carla Bobbio
Peter Schneiter
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Syngenta Participations Ag
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Publication of WO2013011010A1 publication Critical patent/WO2013011010A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to novel compositions of fungicides comprising isoxazole containing compounds and a further fungicidial active ingredient, their use and methods for the control and/or prevention of microbial infection, particularly fungal infection, in plants and to processes for the preparation of these compounds.
  • Fungicides are compounds, of natural or synthetic origin, which act to protect plants against damage caused by fungi.
  • Current methods of agriculture rely heavily on the use of fungicides. In fact, some crops cannot be grown usefully without the use of fungicides.
  • Using fungicides allows a grower to increase the yield of the crop and consequently, increase the value of the crop. Numerous fungicidal agents have been developed. However, the treatment of fungal infestations continues to be a major problem. Furthermore, fungicide resistance has become a serious problem, rendering these agents ineffective for some agricultural uses. As such, a need exists for the development of new fungicidal compositions with optionally synergistical effect.
  • the present invention provides a fungicidal composition
  • a fungicidal composition comprising (A) at least one compound of formula I:
  • Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;
  • R 2 is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;
  • R 3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano, nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro; or alkylsilyl; and
  • R4 is H or acyl, benzoyl and phenylacetyl and
  • dimethyldithiocarbamate dimethyldithiocarbamate, mefenoxam, mepronil, mercuric chloride, mercury, metalaxyl, methasulfocarb, metiram, metrafenone, nabam, neem oil (hydrophobic extract), nuarimol, octhilinone, ofurace, oxadixyl, oxine copper, oxolinic acid, oxycarboxin, oxytetracycline, paclobutrazole, paraffin oil, paraformaldehyde, pencycuron, pentachloronitrobenzene, pentachlorophenol, penthiopyrad, perfurazoate, phosphoric acid, polyoxin, polyoxin D zinc salt, potassium bicarbonate, probenazole, procymidone, propamocarb, propineb, proquinazid, prothiocarb, pyrazophos, pyrifenox, pyr
  • X is a bivalent group selected from
  • Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R 2 is bromine, R 3 is methyl, R ⁇ s CN and X is 3 ⁇ 4;
  • Ri is methyl substituted by cyclopropyl, R 2 is CF 3 , R 3 is methyl, R 4 is CI and X is Xi; c) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R 2 is CF 3 , R 3 is methyl, R 4 is Cl and X is Xi;
  • Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R 2 is CF , R is methyl, R 4 is CN and X is 3 ⁇ 4;
  • Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R 2 is OCH 2 CF 3 , R 3 is methyl, R 4 is CN and X is Xi;
  • Ri is isopropyl, R 2 is methoxy; R 3 is methyl, R 4 is hydrogen and X is X 8 ;
  • Ri is isopropyl, R 2 is trifluoromethyl, R 3 is chlorine, R 4 is hydrogen and X is Xs;
  • Ri is isopropyl, R 2 is trifluoromethyl, R 3 is methyl, R 4 is hydrogen and X is Xs;
  • Ri is methyl, R 2 is bromine, R 3 is methyl, R 4 is CN and X is Xi ;
  • Ri is methyl
  • R 2 is bromine
  • R 3 is methyl
  • R 4 is CI
  • X is Xi
  • nd (B8) glyphosate a compound of formula V
  • compositions comprising (A) a compound of formula I and
  • a strobilurin fungicide (B2) an azole fungicide, (B3) a morpholine fungicide, (B4) an anilinopyrimidine fungicide, (B5) a fungicide selected from the group consisting of anilazine (878), arsenates, benalaxyl (56), benalaxyl-M, benodanil (896), benomyl (62), benthiavalicarb, benthiavalicarb-isopropyl (68), biphenyl (81), bitertanol (84), blasticidin-S (85), bordeaux mixture (87), boscalid (88), bupirimate (98), cadmium chloride, captafol (113), captan (114), carbendazim (116), carbon disulfide (945), carboxin (120), carpropamid (122), cedar leaf oil, chinomethionat (126), chlorine, chlorone
  • dichloropropene (233), diclocymet (237), diclomezine (239), dicloran (240), diethofencarb (245), diflumetorim (253), dimethirimol (1082), dimethomorph (263), dinocap (270), dithianon (279), dodine (289), edifenphos (290), ethaboxam (304), ethirimol (1133), etridiazole (321), famoxadone (322), fenamidone (325), fenaminosulf (1144), fenamiphos (326), fenarimol (327), fenfuram (333), fenhexamid (334), fenoxanil (338), fenpiclonil (341), fentin acetate (347), fentin chloride, fentin hydroxide (347), ferbam (350), ferimzone (351), fluazinam (363),
  • Examples of especially suitable compounds as component (B) are compounds selected from the following group P:
  • Group P especially suitable compounds as component (B) in the compositions according to the invention:
  • a strobilurin fungicide selected from azoxystrobin (47), dimoxystrobin (226), fluoxastrobin (382), kresoxim-methyl (485), metominostrobin (551), orysastrobin, picoxystrobin (647), pyraclostrobin (690); trifloxystrobin (832), a compound of formula B-1.1
  • an azole fungicide selected from azaconazole (40), bromuconazole (96), cyproconazole (207), difenoconazole (247), diniconazole (267), diniconazole-M (267), epoxiconazole (298), fenbuconazole (329), fluquinconazole (385), flusilazole (393), flutriafol (397), hexaconazole (435), imazalil (449), imibenconazole (457), ipconazole (468), metconazole (525), myclobutanil (564), oxpoconazole (607), pefurazoate (618), penconazole (619), prochloraz (659), propiconazole (675), prothioconazole (685), simeconazole (731), tebuconazole (761), tetraconazole (778), triadimefon (814), triadimenol
  • an anilino-pyrimidine fungicide selected from cyprodinil (208), mepanipyrim (508) and pyrimethanil (705);
  • a fungicide selected from the group consisting of
  • dichloropropene (233), diclocymet (237), diclomezine (239), dicloran (240), diethofencarb (245), diflumetorim (253), dimethirimol (1082), dimethomorph (263), dinocap (270), dithianon (279), dodine (289), edifenphos (290), ethaboxam (304), ethirimol (1133), etridiazole (321), famoxadone (322), fenamidone (325), fenaminosulf (1144), fenamiphos (326), fenarimol (327), fenfuram (333), fenhexamid (334), fenoxanil (338), fenpiclonil (341), fentin acetate (347), fentin chloride, fentin hydroxide (347), ferbam (350), ferimzone (351), fluazinam (363),
  • a plant-bioregulator selected from the group consisting of
  • an insecticide selected from the group consisting of
  • compositions selected from the following group Q are compounds selected from the following group Q:
  • Group Q especially suitable compounds as component (B) in the compositions according to the invention:
  • a strobilurin fungicide selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,
  • an azole fungicide selected from the group consisting of azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate, penconazole, prochloraz,
  • prothioconazole simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, diclobutrazol, etaconazole, furconazole, furconazole- cis and quinconazole;
  • a morpholine fungicide selected from the group consisting of aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine, piperalin and a compound of formula B-3.1;
  • an anilino-pyrimidine fungicide selected from the group consisting of cyprodinil,
  • a fungicide selected from the group consisting of benalaxyl, benalaxyl-M, benomyl, bitertanol, boscalid, captan, carboxin, carpropamid, chlorothalonil, copper, cyazofamid, cymoxanil, diethofencarb, dithianon, famoxadone, fenamidone, fenhexamide, fenoxycarb, fenpiclonil, fluazinam, fludioxonil, flutolanil, folpet, guazatine, hymexazole, iprodione, lufenuron, mancozeb, metalaxyl, mefenoxam, metrafenone, nuarimol, paclobutrazol, pencycuron, penthiopyrad, procymidone, proquinazid, pyroquilon, quinoxyfen
  • a plant-bioregulator selected from acibenzolar-S-methyl, chlormequat chloride, ethephon, mepiquat chloride and trinexapc-ethyl;
  • an insecticide selected from abamectin, emamectin benzoate, tefluthrin, thiamethoxam, and glyphosate, a compound of formula V
  • component (B) in combination with component (A) surprisingly and substantially may enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely.
  • the weight ratio of component (A) to component (B) is from 2000 : 1 to 1 : 1000.
  • a non-limiting example for such weight ratios is compound of formula I : compound of formula B-2 is 10: 1.
  • the weight ratio of component (A) to component (B) is preferably from 100 : 1 to 1 : 100; more preferably from 20 : 1 to 1 : 50; and the weight ratio of component (A) to component (C) is from 2000 : 1 to 1 : 1000.
  • a non-limiting example for such weight ratios is compound of formula I : compound of formula B-2 is 10: 1.
  • the weight ratio of component (A) to component (C) is preferably from 100 : 1 to 1 : 100; more preferably from 20 : 1 to 1 : 50;
  • the active ingredient mixture of component (A) to component (B) comprises compounds of formula I and a further, other biocidally active ingredients or compositions preferably in a mixing ratio of from 1000: 1 to 1 : 1000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5 : 1 and 1 :5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 : 1 , or 5 : 1 , or 5 :2, or 5:3, or 5:4, or 4: 1, or 4:2, or 4:3, or 3: 1, or 3:2, or 2: 1, or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1
  • the active ingredient mixture of component (A) to component (C) comprises compounds of formula I and a further, other biocidally active ingredients or compositions preferably in a mixing ratio of from 1000: 1 to 1 : 1000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5 : 1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 : 1 , or 5 : 1 , or 5:2, or 5:3, or 5:4, or 4: 1, or 4:2, or 4:3, or 3: 1, or 3:2, or 2: 1, or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150
  • Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios. It has been found, surprisingly, that certain weight ratios of component (A) to component (B) together with certain weight ratios of component (A) to component (C) are able to give rise to synergistic activity. Therefore, a further aspect of the invention are compositions, wherein component (A) and component (B) and component (C) are present in the composition in amounts producing a synergistic effect.
  • This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component (A) and component (B) and component (C) is greater than the sum of the fungicidal activities of component (A) and of component (B) and component (C).
  • This synergistic activity extends the range of action of component (A) and component (B) and component (C) in two ways. Firstly, the rates of application of component (A) and component (B) and component (C) are lowered whilst the action remains equally good, meaning that the active ingredient mixture still achieves a high degree of phytopathogen control even where the two individual components have become totally ineffective in such a low application rate range.
  • compositions according to the invention can also have further surprising advantageous properties.
  • advantageous properties are: more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination.
  • compositions according to the invention have a systemic action and can be
  • compositions according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms.
  • compositions according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack.
  • compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms.
  • a further aspect of the present invention is a method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention.
  • Preferred is a method, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, more preferably to the useful plants.
  • Further preferred is a method, which comprises applying to the propagation material of the useful plants a composition according to the invention.
  • the components (B) are known for example from "The Pesticide Manual" [The Pesticide
  • aldimorph (CAS 91315-15-0); arsenates (CAS 1327-53-3); benalaxyl -M (CAS 98243-83-5); benthiavalicarb (CAS 413615-35-7); cadmium chloride (CAS 10108-64-2); cedar leaf oil (CAS 8007-20-3); chlorine (CAS 7782-50-5); cinnamaldehyde (CAS: 104-55-2); copper ammoniumcarbonate (CAS 33113-08-5); copper oleate (CAS 1120-44-1); iodocarb (3-Iodo- 2-propynyl butyl carbamate) (CAS 55406-53-6); hymexazole (CAS 10004-44-1); manganous dimethyldithiocarbamate (CAS 15339-36-3); mercury (CAS 7487-94-7; 21908-53-2; 7546- 30-7); metrafenone (CAS 220899-03-6); neem oil (hydrophobic extract) (CAS 800
  • Compound B-1.1 (“enestrobin”) is described in EP-0-936-213; compound B-3.1 (“flumorph”) in US-6,020,332, CN-1-167-568, CN-1-155-977 and in EP-0-860-438; compound B-5.1 (“mandipropamid”) in WO 01/87822; compound B-5.2 in WO 98/46607; compound B-5.3 (“fluopicolide”) in WO 99/42447; compound B-5.4 (“cyflufenamid”) in WO 96/19442;
  • compound B-5.9 (3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid (9-isopropyp- l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide) is described in WO 04/35589 and in WO 06/37632; compound B-5.10 (l,3-dimethyl-5-fluoro-lH-pyrazole-4-carboxylic acid [2- (l,3-dimethylbutyl)phenyl]-amide) is described in WO 03/10149; compound B-5.11 (3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid (3 ' ,4' -dichloro-5-fluoro- 1, 1 '- biphenyl-2-yl)-amide; "bixafen”) is registered under CAS-Reg.
  • Isopyraxam (3-(difluoromethyl)- 1 -methyl -N-[ 1 ,2,3,4-tetrahydro-9-(l -methylethyl)-l ,4- methanonaphthalen-5-yl]-lH-pyrazole-4-carboxamide) is described in WO 2004/035589, in WO 2006/037632 and in EP1556385B1 and is registered under the CAS-Reg. 881685-58-1.
  • Sedaxane N-[2-[l,l '-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-l-methyl-lH-pyrazole- 4-carboxamide
  • WO 2003/074491 is described in WO 2003/074491 and is registered under the CAS-Reg.
  • the compound of formula (VI) is described in WO 2008/014870; the compound of formula (Via) is described in WO 2010/063700; a compound of formula (VIb) (Fluxapyroxad) is described in WO2006087343 and WO2009007344 and is registered under the CAS-RegNr.: 907204-31-3,; a compound of formula (Vic) which is 3-(difluoromethyl)-N- methoxy-1 -methyl -N-[l-methyl-2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide is described in WO2010063700;
  • composition stands for the various mixtures or combinations of components (A) and (B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the components (A) and (B) is not essential for working the present invention.
  • the compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component (A).
  • An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.
  • the Mixtures of the present invention may also act as plant grow regulators.
  • Plant growth regulators can, for example, reduce plant height, stimulate seed germination, induce flowering, darken leaf coloring, change the rate of plant growth and modify the timing and efficiency of fruiting.
  • PGRs may exhibit pronounced growth-regulating properties which can result in an increase in the yield of cultivated plants or harvested crops.
  • PGRs may also have a growth inhibiting action which is dependent on concentration.
  • the growth of both monocots and dicots may be inhibited.
  • Inhibition of the vegetative growth of many cultivated plants permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area.
  • Inhibition of the vegetative growth of monocot plants, e.g. cultivated plants such as cereals, is sometimes desirable and advantageous. Such a growth inhibition is of economic interest.
  • PGRs for inhibiting the growth in height of cereals is also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting.
  • compositions comprising the isoxazole derivatives of the present invention that improve plants, a process which is commonly and hereinafter referred to as "plant health".
  • plant health a process which is commonly and hereinafter referred to as "plant health”.
  • characteristics including: emergence, crop yield, protein content, increased vigour, faster/delayed maturation, increased speed of seed emergence, improved nutrient utilization efficiency, improved nitrogen utilization efficiency, improved water use efficiency, improved oil content and /or quality, improved digestibility, faster/more even ripening, improved flavor, improved starch content, more developed root system (improved root growth), improved stress tolerance (e.g.
  • tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination.
  • Advantageous properties obtained, especially from treated seeds include, for example, improved germination and field establishment, better vigor and more homogeneous field establishment.
  • Advantageous properties obtained, especially from foliar and/or in-furrow application include, for example, improved plant growth and plant development, better growth, more tillers, greener leafes, largers leaves, more biomass, better roots, improved stress tolerance of the plants, more grain yield, more biomass harvested, improved quality of the harvest (content of fatty acids, metabolites, oil etc), more marketable products (e.g. improved size), improved process (e.g. longer shelf-life, better extraction of compounds), improved quality of seeds (for being seeded in the following seasons for seed production); or any other advantages familiar to a person skilled in the art. It is therefore an object of the present invention to provide compositions and methods suitable for addressing the opportunities outlined above.
  • the present invention provides plant-protecting active ingredients that are isoxazole compounds of formula (I) according to the invention, in particular the individual isoxazole compounds described in the description as being preferred, and mixtures with increased efficacy and to a method of improving the health of plants by applying said compounds and mixtures to the plants or the locus thereof.
  • the action of the compounds of formula (I) is separate to any fungicidal action.
  • the isoxazole compounds of formula (I) according to the invention in particular the individual isoxazole compounds described in the above description as being preferred compounds exhibit plant health properties.
  • compositions comprising or consisting essentially of an active compound as described herein in combination with a suitable carrier (e.g., an agricultural carrier).
  • a suitable carrier e.g., an agricultural carrier.
  • Alkyl refers to a saturated hydrocarbon radical which may be straight-chain or branched-chain or cyclic (cycloalkyl) and contains from 1 to 24 carbon atoms. This definition applies both when the term is used alone and when it is used as part of a compound term, such as haloalkyl and similar terms.
  • Preferred straight chain and branched alkyl groups may contain 1 to 8 carbon atoms, more preferably 1 to 4 carbons, even more preferably, 1 to 4 carbon atoms.
  • Representative alkyl groups include, for example, methyl, ethyl, isopropyl, n- propyl, n-butyl, t-butyl, t-amyl, and 2,5-dimethylhexyl.
  • Preferred cycloalkyl groups may contain 3 to 12 carbon atoms, more preferably 4 to 10 carbons, even more preferably, 5 to 8 carbon atoms and most preferably 5 or 6 carbon atoms.
  • Preferred cycloalkyl groups include, for example, cyclobutyl, cyclopropyl, cyclopentyl and cyclohexyl.
  • alkenyl refers to a straight or branched chain hydrocarbon containing from 2 to 24 carbons, more preferably 2 to 8 carbons, yet more preferably, 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and containing at least one carbon-carbon double bond.
  • Representative alkenyl groups include, for example, ethenyl, 2-propenyl, 2 -methyl -2- propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-l-heptenyl and 3-decenyl.
  • Alkynyl refers to a straight or branched chain hydrocarbon group containing from 2 to 24 carbons, more preferably 2 to 8 carbons, yet more preferably, 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and containing at least one carbon-carbon triple bond.
  • Representative alkynyl groups include, for example, acetylenyl, 1-propynyl, 2- propynyl, 3-butynyl, 2-pentynyl and 1-butynyl.
  • alkoxy groups include, for example, methoxy, ethoxy and t-butoxy.
  • alkylthio groups include, for example, methylthio, ethylthio, t-butylthio and hexylthio.
  • Heterocyclyl refers to a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 10 ring-atoms up to 4 of which may be hetero-atoms such as nitrogen, oxygen and sulfur.
  • heterocyclyl groups are oxiranyl, azetidinyl,
  • Aryl refers to an aromatic substituent which may be a single ring or multiple rings which are fused together, linked covalently or linked to a common group such as an ethylene or methylene moiety.
  • the aromatic rings may each contain heteroatoms and hence aryl encompasses heteroaryl as used herein.
  • Aryl moieties may be optionally substituted with 1 to 4 substituents independently selected from halogen, nitro, alkylcarboxyl, alkoxy and phenoxy.
  • aryl include phenyl azulenyl, indanyl, indenyl, naphthyl, tetrahydronaphthyl, biphenyl, diphenylmethyl, 2,2-diphenyl-l -ethyl, thienyl, pyridyl and quinoxalyl. Most preferably, aryl is phenyl.
  • Heteroaryl means a cyclic, aromatic hydrocarbon containing 3 to 10 ring-atoms including 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur. Preferred heteroaryl groups are five and six membered rings and contain from one to three heteroatoms independently selected from nitrogen, oxygen and sulphur. Heteroaryl moieties may be optionally substituted with 1 to 4 substituents independently selected from halogen, nitro, alkylcarboxyl, alkoxy and phenoxy.
  • heteroaryl groups include furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyranyl, pyridazinyl, tetrazolyl, triazinyl.
  • heteroaryl includes fused heteroaryl groups, for example benzimidazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl, benzothiazinyl, oxazolopyridinyl,
  • Acyl includes any readily hydrolysable acyl groups, and comprises, for example, C(0)R 5 , C(0)OR 5 , C(0)NHR 5 and C(0)NR 5 R 6 , wherein R 5 and R 6 are each independently selected from alkyl, alkenyl, akynyl, heterocyclyl, aryl and heteroaryl.
  • Acyl groups may be optionally substituted with one or more, for example 1, 2, 3 or 4, halo or OR 5 groups.
  • Preferred acyl groups are acetyl, benzoyl and phenylacetyl.
  • Halo or "halogen” means fluoro, chloro, bromo and iodo and is preferably fluoro or chloro.
  • Haloalkyl includes monohaloalkyl, polyhaloalkyl and perhaloalkyl, for example, chloromethyl, 2-bromoethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, chlorodifluoromethyl, trichloromethyl, trifluoromethyl, pentafluoroethyl and 2-chloro-3-fluoropentyl.
  • Organic base as used herein includes, for example, triethylamine, triisobutylamine, triiooctylamine, triisodecylamine, diethanolamine, triethanolamine, pyridine, morpholine, and mixtures thereof.
  • a preferred category of organic base is organic amines.
  • Organic base as used herein includes, for example, sodium carbonate, sodium
  • Inert solvent as used herein includes any suitable inert solvent including, for example, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, toluene, dimethyl ether, methyl t-butyl ether and dioxane, methylene chloride, chloroform, 1 ,2-dichloroethane, and mixtures thereof.
  • Protic solvent as used herein may be any suitable protic solvent including, for example, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, methyl Cellosolve, ethyl
  • Cellosolve cyclohexanol, glycerol, diethylene glycol, triethanolamine, polyethylene glycol, sec-butanol, n-propanol and tert-butanol.
  • Optionally substituted means substituted by one or more substituents, in particular, one, two, three or four substituents. In the case where groups may be selected from a number of alternative groups, the selected groups may be the same or different.
  • Agriculturally acceptable salt means a salt the cation of which is known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably the salts are water-soluble.
  • the compounds of formula (I) may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula (I) may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers.
  • Suitable salts of the compounds of formula (I) include acid addition salts such as those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid.
  • organic carboxylic acids include haloacids such as trifluoroacetic acid.
  • N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991.
  • the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein.
  • Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, nitro; or heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro.
  • Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen.
  • Ri is phenyl optionally substituted with halogen, Ci-C 6 -alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -alkynyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -alkylthio, Ci-C 6 -haloalkoxy, phenoxy, methoxypropargyl, cyano, or nitro; or furanyl, thienyl, pyridyl, or benzothienyl, each optionally substituted with halogen.
  • Ri is 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 4-trifluoro-methylphenyl, 4-trifluoromethoxyphenyl, 2-fluoro-4-chlorophenyl or 2-thienyl.
  • R 2 is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro.
  • R 2 is pyridyl, pyrimidinyl or isoquinolyl, each optionally substituted with halogen, Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 - alkylthio, Ci-C 6 -haloalkoxy, cyano, or nitro.
  • R 2 is 2-, 3- or 4-pyridyl or 5-pyrimidinyl, each optionally substituted with halogen, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or Ci-C 6 -alkylthio.
  • R 2 is 3-pyridyl, 4-pyridyl, or 5-pyrimidinyl, each optionally substituted with methyl, chloro, fluoro, methoxy, thiomethoxy or trifluoromethyl.
  • R3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano or nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro; or alkylsilyl.
  • R 3 is phenyl optionally substituted with halogen, Ci-C 6 -alkyl, Ci-C 6 - haloalkyl, Ci-C 6 -alkoxy, Ci-C6-alkylthio, methoxypropargyl, cyano or nitro; furanyl, thienyl or pyridyl, each optionally substituted with halogen, Ci-C 6 -alkyl or Ci-C 6 -alkoxy; or Ci-C 6 - alkylsilyl.
  • R3 is phenyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl,
  • R 4 is H, acetyl.
  • R 4 is H.
  • Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen;
  • R 2 is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro
  • R 3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano, nitro
  • heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro
  • or alkylsilyl or alkylsilyl
  • R 4 is H or acetyl.
  • R 4 is H.
  • Ri is phenyl optionally substituted with halogen, Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, C2-C 6 -alkynyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -alkylthio, Ci-C 6 -haloalkoxy, phenoxy,
  • R 2 is pyridyl or pyrimidinyl, each optionally substituted with halogen, Ci-C 6 -alkyl,
  • R3 is Ci-C 6 -alkyl; Ci-C 6 -alkoxy; phenyl optionally substituted with halogen, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -alkylthio, methoxypropargyl, cyano or nitro; furanyl, thienyl or pyridyl, each optionally substituted with halogen, Ci-C 6 -alkyl or Ci-C 6 -alkoxy; or Ci-C 6 -alkylsilyl; and R4 is H.
  • Ri is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen, haloalkyl, haloalkoxy and cyano;
  • R 2 is pyridyl; wherein R 3 is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen, haloalkyl, haloalkoxy and cyano, and;
  • Ri is phenyl, which is substituted with 1 , 2 or 3 substituents selected from F or CI;
  • R 2 is pyridyl
  • R 3 is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from from F or CI, and;
  • R4 is H
  • Preferred compounds of formula (I) for use according to the methods of the present invention are selected from:
  • the compound of formula (I) is 3-(4-Chloro-2-fluoro-phenyl)-5 - (2,4-difluoro-phenyl)-isoxazol-4-yl]-pyridin-3-yl-methanol.
  • the compound of formula (I) is (3 ⁇ 4)-[3-(4-Chloro-2-fluoro-phenyl)- 5 -(2,4-difluoro-phenyl)-isoxazol-4-yl]-pyridin-3-yl-methanol and
  • the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein, wherein said method comprises one or more applications of one or more compounds as defined herein alone or in conjunction with one or more customary plant protection formulating auxiliaries.
  • the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein, wherein two or more applications are carried out in sequence, and wherein the two or more applications have the same or different concentration or combinations of compounds as defined herein or both.
  • the crops of useful plants are selected from cereals, rice, beets, leguminous plants, oil plants, cucumber plants, fibre plants, vegetables, plantation crops, ornamentals, vines, bushberries, caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses.
  • the plant growth regulating effect is an inhibition or a retardation of the plant growth.
  • the present invention provides an agricultural composition comprising one or more compounds of formula (I) as defined herein and one or more customary plant protection auxiliaries.
  • the compound of formula (I) exists as racemate comprising (R) and (S)-enantiomers.
  • the (S)-enantiomer has been found to have significantly greater fungicidal activity compared to the (R)-enantiomer
  • the present invention is directed to the (5)-enantiomers of the compounds of formula (I), designated (S)-(I)
  • R l s R 2 , R 3 and R 4 are as defined herein; and salts thereof.
  • the present invention provides the compound of formula (5)-( ⁇ ) as a single enantiomer having an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%>, 70%> or 80%>, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%.
  • Preferred compounds of formula include the (S)-enantiomers of compounds 1 to 153 of Table 1.
  • the present invention also relates to an agricultural composition
  • the present invention also relates to an isoxazole compounds of formula (II), derived from compound 146, exhibit unexpected fungicidal activity and are therefore suitable for use in agriculture as crop protection agents to combat or prevent fungal infestations, or to control other pests such as weeds, insects, or acarids that are harmful to crops.
  • the present invention provides a compound of formula (II)
  • R 4 is H or acyl, preferably H
  • the present invention provides the compound formula (iS)-(II)
  • R 4 is H or acyl
  • the present invention provides the compound (5)-[3-(4-chloro-2- fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyridin-3-yl-methanol (compound (S)- (146)).
  • the compounds of formula (S)-(II), and preferably (5)-(146), are provided as single enantiomers having an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%.
  • compositions comprising a compound of formula (5)-(II), and preferably (5)-(146), and an agriculturally acceptable diluent or carrier.
  • the compound of formula (S)-(II), and preferably (S)-(146), and compositions thereof are suitable for controlling and preventing plant pathogenic microorganisms, especially fungal organisms, including those disclosd in International Patent Application WO 2006/031631.
  • the present invention provides a method for controlling or preventing infestation of cultivated plants by pathogenic microorganisms, comprising applying a compound of formula (S)-(II), and preferably (5)-(146), to said plants, parts thereof or the locus thereof in an amount effective to control said microorganisms.
  • the organism is a fungal organism and more preferably, said fungal organism is selected from the group consisting of Septoria tritici, Stagonospora nodorum, Phytophthora infestans, Botrytis cinerea, Sclerotinia homoeocarpa and Puccinia recondita.
  • the fungal organism is Botryotinia fuckeliana ⁇ Botrytis cinerea) (Gray mould). In a further embodiment the fungal organism is Glomerella lagenarium
  • the fungal organism is F urium culmorum (Head blight). In a further embodiment the fungal organism is
  • Gaeum an n omyces graminis Take-all of cereals.
  • the fungal organism is Mycosphaerella arachidis (Cercospora arachidicola) (early leaf spot).
  • the fungal organism is Mycosphaerella graminicola (Septoria tritici) (Septoria blotch)
  • compositions according to the invention are suitable for controlling the following plant diseases: Alternaria species on vegetables, oilseed rape, sugar beet and fruit and rice, such as, for example, A. solani or A. alternata on potatoes and tomatoes;
  • chlamydosporium Ph. Aleophilum and Formitipora punctata (syn. Phellinus punctatus); Exserohilum species on corn; Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumbers; Fusarium and Verticillium species on various plants, such as, for example, F. graminearum or F. culmorum on cereals or F. oxysporum on a multitude of plants, such as, for example, tomatoes; Gaeumanomyces graminis on cereals; Gibberella species on cereals and rice (for example Gibberella fujikuroi on rice); Grainstaining complex on rice;
  • capsici on bell pepper Plasmopara viticola on grapevines; Podosphaera leucotricha on apples; Pseudocercosporella herpotrichoides on cereals; Pseudoperonospora on various plants, such as, for example, P. cubensis on cucumber or P. humili on hops; Puccinia species on various plants, such as, for example, P. triticina, P. strifor- mins, P. hordei or P. graminis on cereals or P.
  • inventive compositions are furthermore suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • materials for example wood, paper, paint dispersions, fibers or fabrics
  • harmful fungi Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp.,
  • Zygomycetes such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • the present invention also encompasses compositions, combinations and plants as described herein and in International Patent Application WO 2006/031631.
  • Plant propagation material means the generative parts of a plant including seeds of all kinds (fruit, tubers, bulbs, grains etc), roots, rhizomes, cuttings, cut shoots and the like. Plant propagation material may also include plants and young plants which are to be transplanted after germination or after emergence from the soil.
  • Locus means the fields on which the plants to be treated are growing, or where the seeds of cultivated plants are sown, or the place where the seed will be placed into the soil.
  • the crops of useful plants to be protected typically comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, maize (including field corn, pop corn and sweet corn), rice, sorghum and related crops); beet (sugar beet and fodder beet); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, sunflowers); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, carrots, eggplants, onions, pepper, tomatoes, potatoes, paprika, okra); plantation crops (bananas, fruit trees, rubber trees, tree nurseries), ornamentals
  • turf grasses including, for example, cool-season turf grasses (for example, bluegrasses ⁇ Poa L.), such as Kentucky bluegrass ⁇ Poa pratensis L.), rough bluegrass ⁇ Poa trivialis L.), Canada bluegrass ⁇ Poa compressa L.) and annual bluegrass ⁇ Poa annua L.); bentgrasses ⁇ Agrostis L.), such as creeping bentgrass ⁇ Agrostis palustris Huds.), colonial bentgrass ⁇ Agrostis tenius Sibth.), velvet bentgrass ⁇ Agrostis canina L.) and redtop ⁇ Agrostis alba L.); fescues ⁇ Fest
  • ryegrasses ⁇ Lolium L. such as perennial ryegrass ⁇ Lolium perenne L.) and annual (Italian) ryegrass ⁇ Lolium multiflorum Lam.)) and warm-season turf grasses (for example, Bermudagrasses ⁇ Cynodon L. C. Rich), including hybrid and common Bermudagrass; Zoysiagrasses ⁇ Zoysia Willd.), St.
  • useful plants is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and
  • EPSPS 5-enol-pyrovyl-shikimate-3-phosphate-synthase
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate -resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresse
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so- called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil.
  • An example for such a locus is a field, on which crop plants are growing.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material” is understood to denote seeds.
  • the compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.
  • plant or “useful plants” as used herein includes seedlings, bushes and trees.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae
  • Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect- specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome- inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdy
  • ⁇ -endotoxins for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced
  • Truncated toxins for example a truncated CrylAb
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
  • YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus®
  • transgenic crops are:
  • Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ⁇ Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Btl 76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/ES/96/02.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cryl Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • the agrochemical compositions of the present invention will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
  • the agrochemical compositions of the present invention are applied prior to disease development.
  • Rates and frequency of use of the formulations are those conventionally used in the art and factors such as the developmental stage of the plant and on the location, timing and application method.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient rates of application are from lOmg to lg of active substance per kg of seeds.
  • the agrochemical compositions comprising a compound of formula (I) are applied as a formulation containing the various adjuvants and carriers known to or used in the industry. They may therefore be formulated as granules, wettable or soluble powders, emulsifiable concentrates, coatable pastes, dusts, flowables, solutions, suspensions or emulsions, or as controlled release forms such as microcapsules. These formulations are described in more detail below and may contain from 0.5% to 95% or more by weight of the active ingredient. The optimum amount will depend on formulation, application equipment and nature of the plant to be treated.
  • Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti- foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non- volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter.
  • Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers,
  • polyacrylonitriles polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions of the invention include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, ⁇ , ⁇ -dimethyl formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol di
  • Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
  • alcohol-alkylene oxide addition products such as tridecyl alcohol-C.sub. 16 ethoxylate
  • soaps such as sodium stearate
  • alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compound of formula (I) and used in the methods of the invention and applied
  • these further active ingredients may be formulated together with the compound of formula (I) or mixed in, for example, the spray tank.
  • These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • the present invention provides a composition comprising a compound of formula (I), which is selected from compounds 1 to 156 of Table 1 , and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is selected from compounds 1 to 156 of Table 1 , and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • a composition comprising a compound of formula (I), which is selected from compounds 1 to 156 of Table 1 , and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • the present invention provides a composition comprising a compound of formula (I), which is the (5)-enantiomer of formula (iS)-(I) and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • a compound of formula (I) which is the (5)-enantiomer of formula (iS)-(I) and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is the (S)- enantiomer of formula (5)-(I), and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • the compounds of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No.
  • US 6,919,298 include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the present invention relates additionally to mixtures comprising at least a compound of formula I and at least a further, other biocidally active ingredient and optionally further ingredients.
  • the further, other biocidally active ingredient are known for example from "The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition (New edition (02 Nov 2003)); Editor: C. D. S.
  • TX means a compound encompassed by the compounds of formula I, or preferably the term “TX” refers to a compound selected from the Table 1 which lists the compounds 1 to 156 preferrably the compounds 144, 145, 146, 147, 148, 149, 150, 151, or 153, or (S)-146 (or 154)) and defines the group NIX provided that the compounds TX and the further active ingredient (B) are not the same; therefore mixtures of the compounds TX with a further active ingredient (B) defines the group NIX.
  • TX has the meaning of [3-(4-chloro-2-fluorophenyl)-5-(2,4- difluorophenyl)isoxazol-4-yl]pyridin-3-yl-methanol.
  • TX has the meaning of (5)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yl]pyridin-3-yl -methanol (Table 1, compound 153: (S)- 146)).
  • an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
  • an acaricide selected from the group of substances consisting of l,l-bis(4-chlorophenyl)-2- ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate
  • TX isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (
  • an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4 -amine (IUPAC name) (23) and strychnine (745) + TX,
  • a bactericide selected from the group of substances consisting of 1 -hydroxy- lH-pyridine-2- thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) ( 170) + TX, copper hydroxide (IUPAC name) ( 169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483)
  • a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX,
  • a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate
  • an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-l-yl acetate with (E)-dec-5-en-l-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)- tetradeca-4,10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-l 1-enal (IUPAC name) (436) + TX, (Z)-hexadec- 1 1 -en- 1 -yl acetate (IUPAC name) (437) + TX, (Z)-hexa
  • an insecticide selected from the group of substances consisting of 1-dichloro-l-nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l ,l-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (IUPAC name) (1063) + TX, 1 - bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-l- (3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (IUPAC name) (1066)
  • methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofiuthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] +
  • development code 723 + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite
  • spirotetrmat CCN + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphonyl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tef uthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, teralle
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide -olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) +
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1, 1 -dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenyla
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-l,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421
  • an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imanin (alternative name)
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
  • azaconazole 60207- 31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fiuquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol
  • TX is the compound 144; In a further preferred embodiment TX is the compound 145; In a further preferred embodiment TX is the compound 146; In a further preferred embodiment TX is the compound 147; In a further preferred embodiment TX is the compound 148; In a further preferred embodiment TX is the compound 149; In a further preferred embodiment TX is the compound 150; In a further preferred embodiment TX is the compound 151; In a further preferred embodiment TX is the compound 153; In a further preferred embodiment TX is the compound (S)-146; In a further preferred embodiment TX is the compound 154.
  • a binary mixture selected from the group of NIX and 3-(difluoromethyl)-N-methoxy-l- methyl-N-[l -methyl -2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide;
  • a binary mixture selected from the group of NIX and Cyproconazole A binary mixture selected from the group of NIX and Epoxiconazole;
  • a binary mixture selected from the group of NIX and famoxadone A binary mixture selected from the group of NIX and Cyprodinil;
  • a binary mixture selected from the group of NIX and Metrafenone
  • a binary mixture selected from the group of NIX and Proquinazid A binary mixture selected from the group of NIX and Fenpropidin; A binary mixture selected from the group of NIX and Fenpropimorph;
  • a binary mixture selected from the group of NIX and spiroxamine
  • a binary mixture selected from the group of NIX and tefluthrin;
  • the mixtures comprising a TX (a compound encompassed by the compounds of formula I) preferrably selected from Table 1 especially the compounds 144, 145, 146, 147, 148, 149, 150, 151, or 153, or (S)-146 (or 154) and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank- mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • composition stands for the various mixtures or combinations of components TX and (B) and (C), for example in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the components TX and (B) and (C) is not essential for working the present invention.
  • compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component TX.
  • An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.
  • the compound of the formula I is preferably a compound of Tables 1.
  • the mixing ratios can vary over a large range and are, preferably 100: 1 to 1 :6000, especially 50: 1 to 1 :50, more especially 20: 1 to 1 :20, even more especially 10: 1 to 1 :10.
  • Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of TX with the mixing partner).
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • Compounds of formula (I) may be prepared using the methods below or according to WO2006031631, WO2010069881 and/or WO2010069882.
  • the reaction may be carried out in the presence of an organic base such as triethylamine in an inert solvent such as DCE (1,2-dichloroethane), or an inorganic base such as sodium bicarbonate in a protic solvent such as isopropanol.
  • an organic base such as triethylamine in an inert solvent such as DCE (1,2-dichloroethane)
  • an inorganic base such as sodium bicarbonate in a protic solvent such as isopropanol.
  • Time and temperature of the reaction is not critical but may be at temperatures ranging from 20 to 60° C for 1 to 24h.
  • the carboximidoyl chlorides (II) may be prepared from the corresponding oximes using chlorinating reagents such as N-chlorosuccinimide or sodium hypochlorite (bleach), or may be obtained from commercial sources.
  • the regioisomer (VIII) is produced along with (I) in the [3+2]-cycloaddition.
  • This regioisomer (VIII) generally is less active than (I) in bioevaluation.
  • Acetylenic ketone (VI) can be prepared from (III) by oxidation, for example with IBX (o-iodosobenzoic acid) in an inert solvent such as DMSO (dimethylsulfoxide) at any suitable time and temperature (e.g. 20°C for 1 to 2h).
  • IBX o-iodosobenzoic acid
  • DMSO dimethylsulfoxide
  • Acylations may be carried out using either acid anhydrides (e.g. acetic anhydride, propionic anhydride) or acid chlorides (e.g. benzoyl chloride) in the presence of an organic base in an inert solvent (e.g. ether, dichloromethane).
  • Carbamoylations are effected by treating alcohols (I) with a strong base such as sodium hydride followed by a carbamoyl chloride (e.g. N,N-dimethylcarbamoyl chloride) in an inert solvent such as DMF (dimethylformamide).
  • a strong base such as sodium hydride
  • a carbamoyl chloride e.g. N,N-dimethylcarbamoyl chloride
  • DMF dimethylformamide
  • racemate or the racemate of a salt or derivative
  • HPLC high performance liquid chromatography
  • the racemate or a racemic precursor
  • a suitable optically active compound for example, a carboxylic acid, or, in the case where the compound of formula (I) contains an acidic or basic moiety, a base or acid such as 1-phenylethylamine or tartaric acid.
  • the resulting diastereomeric mixture may be separated by chromatography and/or fractional crystallization and one or both of the diastereoisomers converted to the corresponding pure enantiomer(s) by means well known to a skilled person.
  • Example 1 3-(2,6-Dichlorophenyl)-4-r(3-pyridyl)-hvdroxymethyl1-5-trimethylsilyl-isoxazole (Table 1, compound 1) and
  • Example 7 5-(2-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-r(3-pyridyl)hvdroxymethyl1- isoxazole (Table 1, compound 14) A mixture of 56mg (0.25mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 60mg (0.25mmol) of 3-(2-chlorophenyl)-l-(3-pyridyl)-2-propyn-l-one, and 30mg (0.36mmol) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C overnight with shaking.
  • Example 8 5-(2-Chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3-pyridyl)hydroxymethyll- isoxazole (Table 1, compound 15)
  • a solution of 59mg (0.25mmol) of 2,4-dichlorobenzylcarboximidoyl chloride prepared according to G. Kumaran and G. H. Kulkarni, J. Org. Chem.
  • the first eluting enantiomer is the ( ?)-enantiomer.
  • the second eluting enantiomer is the (iS)-enantiomer.
  • the compounds of formula (I) in Table 1 may be prepared by analogous methods.
  • Botrytis cinerea (Gray mould): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours. Compound (5)-(146) gave at least 80% control of Botrytis cinerea at 200 ppm.
  • Mycosphaerella arachidis (syn. Cercospora arachidicola), Brown leaf spot of groundnut (peanut): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours at 620nm. Compound (S)-(146) gave at least 80% control of Mycosphaerella arachidis at 200 ppm.
  • DMSO DMSO
  • Septoria tritici (leaf blotch): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours. Compound (5)-(146) gave at least 80% control of Septoria tritici at 200 ppm.
  • Monographella nivalis (syn. Microdochium nivale, Fusarium nivale), snow mould, foot rot of cereals: Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours at 620nm. Compound (S)-(146) gave at least 80% control of Monographella nivalis at 200 ppm.
  • DMSO DMSO
  • Fusarium culmorum (root rot): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 48 hours. Compound (5)-(146) gave at least 80%> control of Fusarium culmorum at 200 ppm.
  • Rhizoctonia solani foot rot, damping -off: Mycelial fragments of the fungus, prepared from a fresh liquid culture, were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal mycelium was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 48h. Compound (S)-(146) gave at least 80%> control of Rhizoctonia solani at 200 ppm.

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Abstract

A composition suitable for control of diseases caused by phytopathogens comprising (A) a compound of formula (I) wherein the substituents have the definitions as defined in claim 1 or a salt or a N-oxide thereof and (B) at least one compound selected from compounds known for their fungicidal activity and (C) at least one further compound selected from the compounds (B) provided that none of the compounds are the same; and a method of controlling diseases on useful plants.

Description

FUNGIZIDE MIXTURES
The present invention relates to novel compositions of fungicides comprising isoxazole containing compounds and a further fungicidial active ingredient, their use and methods for the control and/or prevention of microbial infection, particularly fungal infection, in plants and to processes for the preparation of these compounds.
The incidence of serious microbial infections, particularly fungal infections, either systemic or topical, continues to increase for plants.
Fungicides are compounds, of natural or synthetic origin, which act to protect plants against damage caused by fungi. Current methods of agriculture rely heavily on the use of fungicides. In fact, some crops cannot be grown usefully without the use of fungicides. Using fungicides allows a grower to increase the yield of the crop and consequently, increase the value of the crop. Numerous fungicidal agents have been developed. However, the treatment of fungal infestations continues to be a major problem. Furthermore, fungicide resistance has become a serious problem, rendering these agents ineffective for some agricultural uses. As such, a need exists for the development of new fungicidal compositions with optionally synergistical effect.
Accordingly, the present invention provides a fungicidal composition comprising (A) at least one compound of formula I:
Figure imgf000002_0001
wherein:
Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;
R2 is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;
R3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano, nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro; or alkylsilyl; and
R4 is H or acyl, benzoyl and phenylacetyl and
(B) at least one compound selected from the group consisting of
(Bl) a strobilurin fungicide,
(B2) an azole fungicide,
(B3) a morpholine fungicide,
(B4) an anilinopyrimidine fungicide,
(B5) a fungicide selected from the group consisting of
anilazine, arsenates, benalaxyl, benalaxyl-M, benodanil, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, biphenyl, bitertanol, blasticidin-S, bordeaux mixture, boscalid, bupirimate, cadmium chloride, captafol, captan, carbendazim, carbon disulfide, carboxin, carpropamid, cedar leaf oil, chinomethionat, chlorine, chloroneb, chlorothalonil, chlozolinate, cinnamaldehyde, copper, copper ammoniumcarbonate, copper hydroxide, copper octanoate, copper oleate, copper sulphate, cyazofamid, cycloheximide, cymoxanil, dichlofluanid, dichlone, dichloropropene, diclocymet, diclomezine, dicloran, diethofencarb, diflumetorim, dimethirimol, dimethomorph, dinocap, dithianon, dodine, edifenphos, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenaminosulf, fenamiphos, fenarimol, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flusulfamide, flusulfamide, flutolanil, folpet,
formaldehyde, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furametpyr, flyodin, fuazatine, hexachlorobenzene, hymexazole, iminoctadine, iodocarb, iprobenfos, iprodione, iprovalicarb, isoprothiolane, kasugamycin, mancozeb, maneb, manganous
dimethyldithiocarbamate, mefenoxam, mepronil, mercuric chloride, mercury, metalaxyl, methasulfocarb, metiram, metrafenone, nabam, neem oil (hydrophobic extract), nuarimol, octhilinone, ofurace, oxadixyl, oxine copper, oxolinic acid, oxycarboxin, oxytetracycline, paclobutrazole, paraffin oil, paraformaldehyde, pencycuron, pentachloronitrobenzene, pentachlorophenol, penthiopyrad, perfurazoate, phosphoric acid, polyoxin, polyoxin D zinc salt, potassium bicarbonate, probenazole, procymidone, propamocarb, propineb, proquinazid, prothiocarb, pyrazophos, pyrifenox, pyroquilon, quinoxyfen, quintozene, silthiofam, sodium bicarbonate, sodium diacetate, sodium propionate, streptomycin, sulphur, TCMTB, tecloftalam, tecnazene, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tolclofos-methyl, tolyfluanid, triazoxide, trichoderma harzianum, tricyclazole, triforine, triphenyltin hydroxide, validamycin, vinclozolin, zineb, ziram, zoxamide, l,l-bis(4- chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N- 1-naphthylacetamide, 4-chlorophenyl phenyl sulfone,
a compound of formula -5.1
Figure imgf000004_0001
a compound of formula B-5.2
Figure imgf000004_0002
a compound of formula B-5.3
Figure imgf000005_0001
a compound of formula B-5.4
Figure imgf000005_0002
a compound of formula B-5.5
Figure imgf000005_0003
a compound of formula B-5.6
Figure imgf000005_0004
a compound of formula B-5.7
Figure imgf000005_0005
3 -difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid (2-bicyclopropyl-2-yl-phenyl)- amide (compound B-5.8), 3 -difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid (9- isopropyp-l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide (compound B-5.9), 1,3- dimethyl-5-fluoro-lH-pyrazole-4-carboxylic acid [2-(l ,3-dimethylbutyl)phenyl]-amide (compound B-5.10), 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid (3',4'- dichloro-5-fluoro-l, -biphenyl-2-yl)-amide (compound B-5.11), N-{2-[3-chloro-5- (trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamid (compound B-5.12), 3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid N-[2-( 1 , 1 ,2,2- tetrafluoroethoxy)phenyl] -amide (compound B-5.13), 3-difluoromethyl-l -methyl- 1H- pyrazole-4-carboxylic acid N-[2-(l, 1,2,3, 3,3-hexafluoropropoxy)phenyl]-amide (compound B-5.14), 3 -difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid N-[2-(2-chloro-l,l,2- trifluoroethoxy)phenyl] -amide (compound B-5.15), 3 -difluoromethyl-l -methyl- lH-pyrazole- 4-carboxylic acid N-(4'-trif uoromethyl-biphen-2-yl)-amide (compound B-5.16), 3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid N-(2 ' -trifluoromethyl-biphen-2-yl)- amide (compound B-5.17) and 3 -difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid N- (2'-trifluoromethyl-biphen-2-yl)-amide (compound B-5.18); (B6) a plant-bioregulator selected from the group consisting of
acibenzolar-S-methyl, chlormequat chloride, ethephon, mepiquat chloride and trinexapc- ethyl;
(B7) an insecticide selected from the group consisting of
abamectin, clothianidin, emamectin benzoate, imidacloprid, tefluthrin, thiamethoxam, and a compound of formula IV
Figure imgf000006_0001
wherein X is a bivalent group selected from
Figure imgf000007_0001
wherein
a) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is bromine, R3 is methyl, R^s CN and X is ¾;
b) Ri is methyl substituted by cyclopropyl, R2 is CF3, R3 is methyl, R4 is CI and X is Xi; c) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is CF3, R3 is methyl, R4 is Cl and X is Xi;
d) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is CF , R is methyl, R4 is CN and X is ¾;
e) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is OCH2CF3, R3 is methyl, R4 is CN and X is Xi;
f) Ri is isopropyl, R2 is methoxy; R3 is methyl, R4 is hydrogen and X is X8 ;
g) Ri is isopropyl, R2 is trifluoromethyl, R3 is chlorine, R4 is hydrogen and X is Xs;
h) Ri is isopropyl, R2 is trifluoromethyl, R3 is methyl, R4 is hydrogen and X is Xs;
i) Ri is methyl, R2 is bromine, R3 is methyl, R4 is CN and X is Xi ;
j) Ri is methyl, R2 is bromine, R3 is methyl, R4 is CI and X is Xi; nd (B8) glyphosate, a compound of formula V
Figure imgf000008_0001
fomesafen, and (B9) Isopyrazam, Sedaxane, l-[4-[4-[5-(2,6-Difluorophenyl)-4,5-dihydro-l,2- oxazol-3 -yl] -1,3 -thiazol-2-yl]piperidin- 1 -yl]-2-[5 -methyl-3 -(trifluoromethyl)- 1 H-pyrazol- 1 - yljethanone,
a compound of formula (Via)
Figure imgf000008_0002
, a compound of formula VIb) (Fluxapyroxad)
Figure imgf000008_0003
a compound of formula (Vic) which is 3-(difluoromethyl)-N-methoxy-l-methyl-N-[l-methyl- 2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide; a compound of formula (VI d) which is 3 -Difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid methoxy-[l-methyl-2- (2,4,5 -trichloro-thiophen-3 -yl)-ethy 1] -amide a compound of formula (VII)
Figure imgf000009_0001
Preferred compositions comprising (A) a compound of formula I and
(B) a compound selected from the group consisting of
(Bl) a strobilurin fungicide, (B2) an azole fungicide, (B3) a morpholine fungicide, (B4) an anilinopyrimidine fungicide, (B5) a fungicide selected from the group consisting of anilazine (878), arsenates, benalaxyl (56), benalaxyl-M, benodanil (896), benomyl (62), benthiavalicarb, benthiavalicarb-isopropyl (68), biphenyl (81), bitertanol (84), blasticidin-S (85), bordeaux mixture (87), boscalid (88), bupirimate (98), cadmium chloride, captafol (113), captan (114), carbendazim (116), carbon disulfide (945), carboxin (120), carpropamid (122), cedar leaf oil, chinomethionat (126), chlorine, chloroneb (139), chlorothalonil (142), chlozolinate (149), cinnamaldehyde, copper, copper ammoniumcarbonate, copper hydroxide (169), copper octanoate (170), copper oleate, copper sulphate (87), cyazofamid (185), cycloheximide (1022), cymoxanil (200), dichlofluanid (230), dichlone (1052),
dichloropropene (233), diclocymet (237), diclomezine (239), dicloran (240), diethofencarb (245), diflumetorim (253), dimethirimol (1082), dimethomorph (263), dinocap (270), dithianon (279), dodine (289), edifenphos (290), ethaboxam (304), ethirimol (1133), etridiazole (321), famoxadone (322), fenamidone (325), fenaminosulf (1144), fenamiphos (326), fenarimol (327), fenfuram (333), fenhexamid (334), fenoxanil (338), fenpiclonil (341), fentin acetate (347), fentin chloride, fentin hydroxide (347), ferbam (350), ferimzone (351), fluazinam (363), fiudioxonil (368), flusulfamide (394), fiutolanil (396), folpet (400), formaldehyde (404), fosetyl-aluminium (407), fthalide (643), fuberidazole (419), furalaxyl (410), furametpyr (411), flyodin (1205), fuazatine (422), hexachlorobenzene (434), hymexazole, iminoctadine (459), iodocarb (3-Iodo-2-propynyl butyl carbamate), iprobenfos (IBP) (469), iprodione (470), iprovalicarb (471), isoprothiolane (474), kasugamycin (483), mancozeb (496), maneb (497), manganous dimethyldithiocarbamate, mefenoxam (Metalaxyl- M) (517), mepronil (510), mercuric chloride (511), mercury, metalaxyl (516), methasulfocarb (528), metiram (546), metrafenone, nabam (566), neem oil (hydrophobic extract), nuarimol (587), octhilinone (590), ofurace (592), oxadixyl (601), oxine copper (605), oxolinic acid (606), oxycarboxin (608), oxytetracycline (611), paclobutrazole (612), paraffin oil (628), paraformaldehyde, pencycuron (620), pentachloronitrobenzene (716), pentachlorophenol (623), penthiopyrad, perfurazoate, phosphoric acid, polyoxin (654), polyoxin D zinc salt (654), potassium bicarbonate, probenazole (658), procymidone (660), propamocarb (668), propineb (676), proquinazid (682), prothiocarb (1361), pyrazophos (693), pyrifenox (703), pyroquilon (710), quinoxyfen (715), quintozene (PCNB) (716), silthiofam (729), sodium bicarbonate, sodium diacetate, sodium propionate, streptomycin (744), sulphur (754), TCMTB, tecloftalam, tecnazene (TCNB) (767), thiabendazole (790), thifluzamide (796), thiophanate (1435), thiophanate-methyl (802), thiram (804), tolclofos-methyl (808), tolylfluanid (810), triazoxide (821), trichoderma harzianum (825), tricyclazole (828), triforine (838), triphenyltin hydroxide (347), validamycin (846), vinclozolin (849), zineb (855), ziram (856), zoxamide (857), l,l-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC-Name) (910), 2,4- dichlorophenyl benzenesulfonate (IUPAC- / Chemical Abstracts-Name) (1059), 2-fluoro-N- methyl-N-l-naphthylacetamide (IUPAC-Name) (1295), 4-chlorophenyl phenyl sulfone (IUPAC-Name) (981),
a compound of formula B-5.1
Figure imgf000010_0001
a compound of formula B-5.2
Figure imgf000010_0002
a compound of formula B-5.3
Figure imgf000011_0001
a compound of formula B-5.4
Figure imgf000011_0002
a compound of formula B-5.5
Figure imgf000011_0003
a compound of formula B-5.6
Figure imgf000011_0004
a compound of formula B-5.7
Figure imgf000011_0005
3 -difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid (2-bicyclopropyl-2-yl-phenyl)- amide (compound B-5.8), 3 -difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid (9- isopropyp-l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide (compound B-5.9), 1,3- dimethyl-5-fiuoro-lH-pyrazole-4-carboxylic acid [2-(l ,3-dimethylbutyl)phenyl]-amide (compound B-5.10), 3-difiuoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid (3',4'- dichloro-5-fiuoro-l, -biphenyl-2-yl)-amide (compound B-5.11), N-{2-[3-chloro-5- (trifiuoromethyl)pyridin-2-yl]ethyl}-2-(trifiuoromethyl)benzamid (compound B-5.12), 3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid N-[2-( 1 , 1 ,2,2- tetrafiuoroethoxy)phenyl] -amide (compound B-5.13), 3-difiuoromethyl-l -methyl- 1H- pyrazole-4-carboxylic acid N-[2-(l, 1,2,3, 3,3-hexafiuoropropoxy)phenyl]-amide (compound B-5.14), 3 -difluoromethyl- 1 -methyl- lH-pyrazole-4-carboxylic acid N-[2-(2-chloro-l,l,2- trifiuoroethoxy)phenyl] -amide (compound B-5.15), 3 -difluoromethyl- 1 -methyl- lH-pyrazole- 4-carboxylic acid N-(4'-trifiuoromethyl-biphen-2-yl)-amide (compound B-5.16), 3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid N-(2 ' -trifluoromethyl-biphen-2-yl)- amide (compound B-5.17) and 3 -difluoromethyl- 1 -methyl- lH-pyrazole-4-carboxylic acid N- (2'-trifiuoromethyl-biphen-2-yl)-amide (compound B-5.18);
(B6) a plant-bioregulator selected from the group consisting of
acibenzolar-S-methyl (6), chlormequat chloride (137), ethephon (307), mepiquat chloride (509) and trinexapc-ethyl (841);
(B7) an insecticide selected from the group consisting of
abamectin (1), clothianidin (165), emamectin benzoate (291), imidacloprid (458), tefiuthrin (769), thiamethoxam (792), a compound of formula B-7.1
Figure imgf000012_0001
H
(B-7.1);
and a compound of formula B-7.2;
Figure imgf000013_0001
and (B8) glyphosate (419);
and (C) at least one further compound selected from the compounds (B) provided that the compounds are the same.
Examples of especially suitable compounds as component (B) are compounds selected from the following group P:
Group P: especially suitable compounds as component (B) in the compositions according to the invention:
a strobilurin fungicide selected from azoxystrobin (47), dimoxystrobin (226), fluoxastrobin (382), kresoxim-methyl (485), metominostrobin (551), orysastrobin, picoxystrobin (647), pyraclostrobin (690); trifloxystrobin (832), a compound of formula B-1.1
Figure imgf000013_0002
an azole fungicide selected from azaconazole (40), bromuconazole (96), cyproconazole (207), difenoconazole (247), diniconazole (267), diniconazole-M (267), epoxiconazole (298), fenbuconazole (329), fluquinconazole (385), flusilazole (393), flutriafol (397), hexaconazole (435), imazalil (449), imibenconazole (457), ipconazole (468), metconazole (525), myclobutanil (564), oxpoconazole (607), pefurazoate (618), penconazole (619), prochloraz (659), propiconazole (675), prothioconazole (685), simeconazole (731), tebuconazole (761), tetraconazole (778), triadimefon (814), triadimenol (815), triflumizole (834), triticonazole (842), diclobutrazol (1068), etaconazole (1129), furconazole (1198), furconazole-cis (1199) and quinconazole (1378); a morpholine fungicide selected from aldimorph, dodemorph (288), fenpropimorph (344), tridemorph (830), fenpropidin (343), spiroxamine (740), piperalin (648) and a compound of formula B-3.1
Figure imgf000014_0001
an anilino-pyrimidine fungicide selected from cyprodinil (208), mepanipyrim (508) and pyrimethanil (705);
a fungicide selected from the group consisting of
anilazine (878), arsenates, benalaxyl (56), benalaxyl-M, benodanil (896), benomyl (62), benthiavalicarb, benthiavalicarb-isopropyl (68), biphenyl (81), bitertanol (84), blasticidin-S (85), bordeaux mixture (87), boscalid (88), bupirimate (98), cadmium chloride, captafol (113), captan (114), carbendazim (116), carbon disulfide (945), carboxin (120), carpropamid (122), cedar leaf oil, chinomethionat (126), chlorine, chloroneb (139), chlorothalonil (142), chlozolinate (149), cinnamaldehyde, copper, copper ammoniumcarbonate, copper hydroxide (169), copper octanoate (170), copper oleate, copper sulphate (87), cyazofamid (185), cycloheximide (1022), cymoxanil (200), dichlofluanid (230), dichlone (1052),
dichloropropene (233), diclocymet (237), diclomezine (239), dicloran (240), diethofencarb (245), diflumetorim (253), dimethirimol (1082), dimethomorph (263), dinocap (270), dithianon (279), dodine (289), edifenphos (290), ethaboxam (304), ethirimol (1133), etridiazole (321), famoxadone (322), fenamidone (325), fenaminosulf (1144), fenamiphos (326), fenarimol (327), fenfuram (333), fenhexamid (334), fenoxanil (338), fenpiclonil (341), fentin acetate (347), fentin chloride, fentin hydroxide (347), ferbam (350), ferimzone (351), fluazinam (363), fiudioxonil (368), flusulfamide (394), fiutolanil (396), folpet (400), formaldehyde (404), fosetyl-aluminium (407), fthalide (643), fuberidazole (419), furalaxyl (410), furametpyr (411), flyodin (1205), fuazatine (422), hexachlorobenzene (434), hymexazole, iminoctadine (459), iodocarb (3-Iodo-2-propynyl butyl carbamate), iprobenfos (IBP) (469), iprodione (470), iprovalicarb (471), isoprothiolane (474), kasugamycin (483), mancozeb (496), maneb (497), manganous dimethyldithiocarbamate, mefenoxam (Metalaxyl- M) (517), mepronil (510), mercuric chloride (511), mercury, metalaxyl (516), methasulfocarb (528), metiram (546), metrafenone, nabam (566), neem oil (hydrophobic extract), nuarimol (587), octhilinone (590), ofurace (592), oxadixyl (601), oxine copper (605), oxolinic acid (606), oxycarboxin (608), oxytetracycline (611), paclobutrazole (612), paraffin oil (628), paraformaldehyde, pencycuron (620), pentachloronitrobenzene (716), pentachlorophenol (623), penthiopyrad, perfurazoate, phosphoric acid, polyoxin (654), polyoxin D zinc salt (654), potassium bicarbonate, probenazole (658), procymidone (660), propamocarb (668), propineb (676), proquinazid (682), prothiocarb (1361), pyrazophos (693), pyrifenox (703), pyroquilon (710), quinoxyfen (715), quintozene (PCNB) (716), silthiofam (729), sodium bicarbonate, sodium diacetate, sodium propionate, streptomycin (744), sulphur (754), TCMTB, tecloftalam, tecnazene (TCNB) (767), thiabendazole (790), thifluzamide (796), thiophanate (1435), thiophanate-methyl (802), thiram (804), tolclofos-methyl (808), tolylfluanid (810), triazoxide (821), trichoderma harzianum (825), tricyclazole (828), triforine (838), triphenyltin hydroxide (347), validamycin (846), vinclozolin (849), zineb (855), ziram (856), zoxamide (857), l,l-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC-Name) (910), 2,4- dichlorophenyl benzenesulfonate (IUPAC- / Chemical Abstracts-Name) (1059), 2-fluoro-N- methyl-N-l-naphthylacetamide (IUPAC-Name) (1295), 4-chlorophenyl phenyl sulfone (IUPAC-Name) (981),
a compound of formula B-5.1, a compound of formula B-5.2, a compound of formula B-5.3, a compound of formula B-5.4, a compound of formula B-5.5, a compound of formula B-5.6, a compound of formula B-5.7, compound B-5.8, compound B-5.9, compound B-5.10, compound B-5.11, compound B-5.12, compound B-5.13, compound B-5.14, compound B- 5.15, compound B-5.16, compound B-5.17 and compound B-5.18;
a plant-bioregulator selected from the group consisting of
acibenzolar-S-methyl (6), chlormequat chloride (137), ethephon (307), mepiquat chloride
(509) and trinexapc-ethyl (841);
an insecticide selected from the group consisting of
abamectin (1), clothianidin (165), emamectin benzoate (291), imidacloprid (458), tefluthrin (769), thiamethoxam (792), and glyphosate (419), a compound of formula V
Figure imgf000016_0001
fomesafen, and (B9) Isopyrazam, Sedaxane, l-[4-[4-[5-(2,6-Difluorophenyl)-4,5-dihydro-l,2- oxazol-3 -yl] -1,3 -thiazol-2-yl]piperidin- 1 -yl]-2-[5 -methyl-3 -(trifluoromethyl)- 1 H-pyrazol- 1 - yljethanone, a compound of formula (Via)
Figure imgf000016_0002
a compound of formula (VIb) (Fluxapyroxad)
Figure imgf000016_0003
a compound of formula (Vic) which is 3-(difluoromethyl)-N-methoxy-l-methyl-N-[l-methyl- 2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide; a compound of formula (VId) which is 3 -Difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid methoxy-[l-methyl-2- (2,4,5 -trichloro-thiophen-3 -yl)-ethy 1] -amide
a compound of formula (VII)
Figure imgf000017_0001
Further examples of especially suitable compounds as component (B) are compounds selected from the following group Q:
Group Q: especially suitable compounds as component (B) in the compositions according to the invention:
a strobilurin fungicide selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,
pyraclostrobin; trifloxystrobin and a compound of formula B-l .l;
an azole fungicide selected from the group consisting of azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate, penconazole, prochloraz,
propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, diclobutrazol, etaconazole, furconazole, furconazole- cis and quinconazole;
a morpholine fungicide selected from the group consisting of aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine, piperalin and a compound of formula B-3.1;
an anilino-pyrimidine fungicide selected from the group consisting of cyprodinil,
mepanipyrim and pyrimethanil;
a fungicide selected from the group consisting of benalaxyl, benalaxyl-M, benomyl, bitertanol, boscalid, captan, carboxin, carpropamid, chlorothalonil, copper, cyazofamid, cymoxanil, diethofencarb, dithianon, famoxadone, fenamidone, fenhexamide, fenoxycarb, fenpiclonil, fluazinam, fludioxonil, flutolanil, folpet, guazatine, hymexazole, iprodione, lufenuron, mancozeb, metalaxyl, mefenoxam, metrafenone, nuarimol, paclobutrazol, pencycuron, penthiopyrad, procymidone, proquinazid, pyroquilon, quinoxyfen, silthiofam, sulfur, thiabendazole, thiram, triazoxide, tricyclazole, a compound of formula B-5.1, a compound of formula B-5.2, a compound of formula B-5.3, a compound of formula B-5.4, a compound of formula B-5.5, a compound of formula B-5.6, a compound of formula B-5.7, a compound of formula B-5.8, a compound of formula B-5.9, a compound of formula B-5.10 and a compound of formula B-5.12;
a plant-bioregulator selected from acibenzolar-S-methyl, chlormequat chloride, ethephon, mepiquat chloride and trinexapc-ethyl;
an insecticide selected from abamectin, emamectin benzoate, tefluthrin, thiamethoxam, and glyphosate, a compound of formula V
Figure imgf000018_0001
fomesafen, and (B9) Isopyrazam, Sedaxane, l-[4-[4-[5-(2,6-Difluorophenyl)-4,5-dihydro-l oxazol-3 -yl] -1,3 -thiazol-2-yl]piperidin- 1 -yl]-2-[5 -methyl-3 -(trifluoromethyl)- 1 H-pyrazol- 1 yljethanone and TX,
a compound of formula (Via)
Figure imgf000018_0002
, a compound of formula (VIb) (Fluxapyroxad)
Figure imgf000019_0001
a compound of formula (Vic) which is 3-(difluoromethyl)-N-methoxy-l-methyl-N-[l-methyl- 2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide; a compound of formula (VI d) which is 3 -Difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid methoxy-[l-methyl-2- (2,4,5 -trichloro-thiophen-3 -yl)-ethy 1] -amide
a compound of formula (VII)
Figure imgf000019_0002
It has been found that the use of component (B) in combination with component (A) surprisingly and substantially may enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely.
In general, the weight ratio of component (A) to component (B) is from 2000 : 1 to 1 : 1000. A non-limiting example for such weight ratios is compound of formula I : compound of formula B-2 is 10: 1. The weight ratio of component (A) to component (B) is preferably from 100 : 1 to 1 : 100; more preferably from 20 : 1 to 1 : 50; and the the weight ratio of component (A) to component (C) is from 2000 : 1 to 1 : 1000. A non-limiting example for such weight ratios is compound of formula I : compound of formula B-2 is 10: 1. The weight ratio of component (A) to component (C) is preferably from 100 : 1 to 1 : 100; more preferably from 20 : 1 to 1 : 50;
The active ingredient mixture of component (A) to component (B) comprises compounds of formula I and a further, other biocidally active ingredients or compositions preferably in a mixing ratio of from 1000: 1 to 1 : 1000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5 : 1 and 1 :5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 : 1 , or 5 : 1 , or 5 :2, or 5:3, or 5:4, or 4: 1, or 4:2, or 4:3, or 3: 1, or 3:2, or 2: 1, or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. The active ingredient mixture of component (A) to component (C) comprises compounds of formula I and a further, other biocidally active ingredients or compositions preferably in a mixing ratio of from 1000: 1 to 1 : 1000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5 : 1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 : 1 , or 5 : 1 , or 5:2, or 5:3, or 5:4, or 4: 1, or 4:2, or 4:3, or 3: 1, or 3:2, or 2: 1, or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios. It has been found, surprisingly, that certain weight ratios of component (A) to component (B) together with certain weight ratios of component (A) to component (C) are able to give rise to synergistic activity. Therefore, a further aspect of the invention are compositions, wherein component (A) and component (B) and component (C) are present in the composition in amounts producing a synergistic effect. This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component (A) and component (B) and component (C) is greater than the sum of the fungicidal activities of component (A) and of component (B) and component (C). This synergistic activity extends the range of action of component (A) and component (B) and component (C) in two ways. Firstly, the rates of application of component (A) and component (B) and component (C) are lowered whilst the action remains equally good, meaning that the active ingredient mixture still achieves a high degree of phytopathogen control even where the two individual components have become totally ineffective in such a low application rate range. Secondly, there is a substantial broadening of the spectrum of phytopathogens that can be controlled. A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated according to COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967.
However, besides the actual synergistic action with respect to fungicidal activity, the compositions according to the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination.
Some compositions according to the invention have a systemic action and can be
used as foliar, soil and seed treatment fungicides.
With the compositions according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms.
The compositions according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack.
The compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms.
A further aspect of the present invention is a method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention. Preferred is a method, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, more preferably to the useful plants. Further preferred is a method, which comprises applying to the propagation material of the useful plants a composition according to the invention. The components (B) are known for example from "The Pesticide Manual" [The Pesticide
Manual - A World Compendium; Thirteenth Edition (New edition (02 Nov 2003)); Editor: C. D. S. Tomlin; The British Crop Protection Council, ISBN- 10: 1901396134; ISBN-13: 978- 1901396133] or its electronic version "e-Pesticide Manual V4.2" or from the website http://www.alanwood.net/pesticides/. Where the components (B) are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition;
Editor: C. D. S. Tomlin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular component (B); for example, the compound "abamectin" is described under entry number (1). Most of the components (B) are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular component (B); in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a
"develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed.
The following components (B) are registered under a CAS-Reg. No.
aldimorph (CAS 91315-15-0); arsenates (CAS 1327-53-3); benalaxyl -M (CAS 98243-83-5); benthiavalicarb (CAS 413615-35-7); cadmium chloride (CAS 10108-64-2); cedar leaf oil (CAS 8007-20-3); chlorine (CAS 7782-50-5); cinnamaldehyde (CAS: 104-55-2); copper ammoniumcarbonate (CAS 33113-08-5); copper oleate (CAS 1120-44-1); iodocarb (3-Iodo- 2-propynyl butyl carbamate) (CAS 55406-53-6); hymexazole (CAS 10004-44-1); manganous dimethyldithiocarbamate (CAS 15339-36-3); mercury (CAS 7487-94-7; 21908-53-2; 7546- 30-7); metrafenone (CAS 220899-03-6); neem oil (hydrophobic extract) (CAS 8002-65-1); orysastrobin CAS 248593-16-0); paraformaldehyde (CAS 30525-89-4); penthiopyrad (CAS 183675-82-3); phosphoric acid (CAS 7664-38-2); potassium bicarbonate (CAS 298-14-6); sodium bicarbonate (CAS 144-55-8); sodium diacetate (CAS 127-09-3); sodium propionate (CAS 137-40-6);TCMTB (CAS 21564-17-0); and tolyfiuanid (CAS 731-27-1).
Compound B-1.1 ("enestrobin") is described in EP-0-936-213; compound B-3.1 ("flumorph") in US-6,020,332, CN-1-167-568, CN-1-155-977 and in EP-0-860-438; compound B-5.1 ("mandipropamid") in WO 01/87822; compound B-5.2 in WO 98/46607; compound B-5.3 ("fluopicolide") in WO 99/42447; compound B-5.4 ("cyflufenamid") in WO 96/19442;
compound B-5.5 in WO 99/14187; compound B-5.6 ("pyribencarb") is registered under CAS- Reg. No. 325156-49-8; compound B-5.7 ("amisulbrom" or "ambromdole") is registered under CAS-Reg. No. 348635-87-0; compound B-5.8 (3 -difiuoromethyl-1 -methyl- lH-pyrazole-4- carboxylic acid (2-bicyclopropyl-2-yl-phenyl)-amide) is described in WO 03/74491;
compound B-5.9 (3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid (9-isopropyp- l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide) is described in WO 04/35589 and in WO 06/37632; compound B-5.10 (l,3-dimethyl-5-fluoro-lH-pyrazole-4-carboxylic acid [2- (l,3-dimethylbutyl)phenyl]-amide) is described in WO 03/10149; compound B-5.11 (3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid (3 ' ,4' -dichloro-5-fluoro- 1, 1 '- biphenyl-2-yl)-amide; "bixafen") is registered under CAS-Reg. No.: 581809-46-3 and described in WO 03/70705; compound B-5.12 (N-{2-[3-Chloro-5-(trifluoromethyl)pyridin-2- yl]ethyl}-2-(trifluoromethyl)benzamid; "fluopyram") is registered under CAS-Reg. No:
658066-35-4 and described in WO 04/16088; compounds B-5.13, B-5.14 and B-5.15 are described in WO 2007/17450; compounds B-5.16, B-5.17 and B-5.18 are described in WO 2006/120219; The compounds of formula IV are for example described in WO 04/067528, WO 2005/085234, WO 2006/111341 , WO 03/015519, WO 2007/020050, WO 2006/040113, and WO 2007/093402. The compound of formula V is described in WO 2001/094339.
Isopyraxam (3-(difluoromethyl)- 1 -methyl -N-[ 1 ,2,3,4-tetrahydro-9-(l -methylethyl)-l ,4- methanonaphthalen-5-yl]-lH-pyrazole-4-carboxamide) is described in WO 2004/035589, in WO 2006/037632 and in EP1556385B1 and is registered under the CAS-Reg. 881685-58-1. Sedaxane (N-[2-[l,l '-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-l-methyl-lH-pyrazole- 4-carboxamide) is described in WO 2003/074491 and is registered under the CAS-Reg.
874967-67-6; l-[4-[4-[5-(2,6-Difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2- yl]piperidin-l-yl]-2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone is described in WO2010123791, WO2008013925 and WO2008013622 and is registered under the CAS- RegNr.: 1003318-67-9. The compound of formula (VI) is described in WO 2008/014870; the compound of formula (Via) is described in WO 2010/063700; a compound of formula (VIb) (Fluxapyroxad) is described in WO2006087343 and WO2009007344 and is registered under the CAS-RegNr.: 907204-31-3,; a compound of formula (Vic) which is 3-(difluoromethyl)-N- methoxy-1 -methyl -N-[l-methyl-2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide is described in WO2010063700;
and the compounds of formula (VII) is described in WO 2007/048556. Fomesafen is registered under the CAS-Reg. No. 72178-02-0.
Throughout this document the expression "composition" stands for the various mixtures or combinations of components (A) and (B), for example in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components (A) and (B) is not essential for working the present invention. The compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component (A). An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.
The Mixtures of the present invention may also act as plant grow regulators. Plant growth regulators can, for example, reduce plant height, stimulate seed germination, induce flowering, darken leaf coloring, change the rate of plant growth and modify the timing and efficiency of fruiting. In addition, PGRs may exhibit pronounced growth-regulating properties which can result in an increase in the yield of cultivated plants or harvested crops.
PGRs may also have a growth inhibiting action which is dependent on concentration. The growth of both monocots and dicots may be inhibited. Inhibition of the vegetative growth of many cultivated plants permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area. Inhibition of the vegetative growth of monocot plants, e.g. cultivated plants such as cereals, is sometimes desirable and advantageous. Such a growth inhibition is of economic interest.
The use of PGRs for inhibiting the growth in height of cereals is also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting.
Additionally, PGRs are able to bring about a strengthening of the stalks in crops of cereals and this too counteracts lodging. Furthermore, the present invention also provides compositions comprising the isoxazole derivatives of the present invention that improve plants, a process which is commonly and hereinafter referred to as "plant health". For example, advantageous properties that may be mentioned are improved crop
characteristics including: emergence, crop yield, protein content, increased vigour, faster/delayed maturation, increased speed of seed emergence, improved nutrient utilization efficiency, improved nitrogen utilization efficiency, improved water use efficiency, improved oil content and /or quality, improved digestibility, faster/more even ripening, improved flavor, improved starch content, more developed root system (improved root growth), improved stress tolerance (e.g. against drought, heat, salt, light, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination.
Advantageous properties obtained, especially from treated seeds, include, for example, improved germination and field establishment, better vigor and more homogeneous field establishment.
Advantageous properties obtained, especially from foliar and/or in-furrow application include, for example, improved plant growth and plant development, better growth, more tillers, greener leafes, largers leaves, more biomass, better roots, improved stress tolerance of the plants, more grain yield, more biomass harvested, improved quality of the harvest (content of fatty acids, metabolites, oil etc), more marketable products (e.g. improved size), improved process (e.g. longer shelf-life, better extraction of compounds), improved quality of seeds (for being seeded in the following seasons for seed production); or any other advantages familiar to a person skilled in the art. It is therefore an object of the present invention to provide compositions and methods suitable for addressing the opportunities outlined above. The present invention provides plant-protecting active ingredients that are isoxazole compounds of formula (I) according to the invention, in particular the individual isoxazole compounds described in the description as being preferred, and mixtures with increased efficacy and to a method of improving the health of plants by applying said compounds and mixtures to the plants or the locus thereof.
The action of the compounds of formula (I) is separate to any fungicidal action. The isoxazole compounds of formula (I) according to the invention, in particular the individual isoxazole compounds described in the above description as being preferred compounds exhibit plant health properties.
The present invention also concerns compositions comprising or consisting essentially of an active compound as described herein in combination with a suitable carrier (e.g., an agricultural carrier). The foregoing and other objects and aspects of the present invention are explained in greater detail below. Unless otherwise stated, the substituents are unsubstituted or substituted, preferably the substituents are unsubstituted or substituted by the substituents given below. Unless otherwise stated, the following terms used in the specification and claims have the meanings given below:
"Alkyl" as used herein refers to a saturated hydrocarbon radical which may be straight-chain or branched-chain or cyclic (cycloalkyl) and contains from 1 to 24 carbon atoms. This definition applies both when the term is used alone and when it is used as part of a compound term, such as haloalkyl and similar terms. Preferred straight chain and branched alkyl groups may contain 1 to 8 carbon atoms, more preferably 1 to 4 carbons, even more preferably, 1 to 4 carbon atoms. Representative alkyl groups include, for example, methyl, ethyl, isopropyl, n- propyl, n-butyl, t-butyl, t-amyl, and 2,5-dimethylhexyl. Preferred cycloalkyl groups may contain 3 to 12 carbon atoms, more preferably 4 to 10 carbons, even more preferably, 5 to 8 carbon atoms and most preferably 5 or 6 carbon atoms. Preferred cycloalkyl groups include, for example, cyclobutyl, cyclopropyl, cyclopentyl and cyclohexyl.
"Alkenyl" as used herein, refers to a straight or branched chain hydrocarbon containing from 2 to 24 carbons, more preferably 2 to 8 carbons, yet more preferably, 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and containing at least one carbon-carbon double bond. Representative alkenyl groups include, for example, ethenyl, 2-propenyl, 2 -methyl -2- propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-l-heptenyl and 3-decenyl.
"Alkynyl" as used herein, refers to a straight or branched chain hydrocarbon group containing from 2 to 24 carbons, more preferably 2 to 8 carbons, yet more preferably, 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and containing at least one carbon-carbon triple bond. Representative alkynyl groups include, for example, acetylenyl, 1-propynyl, 2- propynyl, 3-butynyl, 2-pentynyl and 1-butynyl.
Representative alkoxy groups include, for example, methoxy, ethoxy and t-butoxy.
Representative alkylthio groups include, for example, methylthio, ethylthio, t-butylthio and hexylthio.
"Heterocyclyl", as used herein refers to a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 10 ring-atoms up to 4 of which may be hetero-atoms such as nitrogen, oxygen and sulfur. Examples of heterocyclyl groups are oxiranyl, azetidinyl,
tetrahydrofuranyl, thiolanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, sulfolanyl, dioxolanyl, dihydropyranyl, tetrahydropyranyl, piperidinyl, pyrazolinyl, pyrazolidinyl, dioxanyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, azepinyl, oxazepinyl, thiazepinyl, thiazolinyl and diazapanyl. "Aryl" refers to an aromatic substituent which may be a single ring or multiple rings which are fused together, linked covalently or linked to a common group such as an ethylene or methylene moiety. The aromatic rings may each contain heteroatoms and hence aryl encompasses heteroaryl as used herein. Aryl moieties may be optionally substituted with 1 to 4 substituents independently selected from halogen, nitro, alkylcarboxyl, alkoxy and phenoxy. Representative examples of aryl include phenyl azulenyl, indanyl, indenyl, naphthyl, tetrahydronaphthyl, biphenyl, diphenylmethyl, 2,2-diphenyl-l -ethyl, thienyl, pyridyl and quinoxalyl. Most preferably, aryl is phenyl.
"Heteroaryl" means a cyclic, aromatic hydrocarbon containing 3 to 10 ring-atoms including 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur. Preferred heteroaryl groups are five and six membered rings and contain from one to three heteroatoms independently selected from nitrogen, oxygen and sulphur. Heteroaryl moieties may be optionally substituted with 1 to 4 substituents independently selected from halogen, nitro, alkylcarboxyl, alkoxy and phenoxy. Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyranyl, pyridazinyl, tetrazolyl, triazinyl.
In addition, the term heteroaryl includes fused heteroaryl groups, for example benzimidazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl, benzothiazinyl, oxazolopyridinyl,
benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, benzothiazolyl, phthalimido, benzofuranyl, benzodiazepinyl, indolyl, isoindolyl, isobenzofuranyl, chromenyl, xanthenyl, indolizinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, phthalazinyl, naphthyridinyl and benzo[b]thienyl.
Acyl includes any readily hydrolysable acyl groups, and comprises, for example, C(0)R5, C(0)OR5, C(0)NHR5 and C(0)NR5R6, wherein R5 and R6 are each independently selected from alkyl, alkenyl, akynyl, heterocyclyl, aryl and heteroaryl. Acyl groups may be optionally substituted with one or more, for example 1, 2, 3 or 4, halo or OR5 groups. Preferred acyl groups are acetyl, benzoyl and phenylacetyl.
"Halo" or "halogen" means fluoro, chloro, bromo and iodo and is preferably fluoro or chloro.
"Haloalkyl" includes monohaloalkyl, polyhaloalkyl and perhaloalkyl, for example, chloromethyl, 2-bromoethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, chlorodifluoromethyl, trichloromethyl, trifluoromethyl, pentafluoroethyl and 2-chloro-3-fluoropentyl. "Organic base" as used herein includes, for example, triethylamine, triisobutylamine, triiooctylamine, triisodecylamine, diethanolamine, triethanolamine, pyridine, morpholine, and mixtures thereof. A preferred category of organic base is organic amines.
"Inorganic base" as used herein includes, for example, sodium carbonate, sodium
bicarbonate, potassium carbonate, and mixtures thereof.
"Inert solvent" as used herein includes any suitable inert solvent including, for example, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, toluene, dimethyl ether, methyl t-butyl ether and dioxane, methylene chloride, chloroform, 1 ,2-dichloroethane, and mixtures thereof.
"Protic solvent" as used herein may be any suitable protic solvent including, for example, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, methyl Cellosolve, ethyl
Cellosolve, cyclohexanol, glycerol, diethylene glycol, triethanolamine, polyethylene glycol, sec-butanol, n-propanol and tert-butanol.
"Optionally substituted" means substituted by one or more substituents, in particular, one, two, three or four substituents. In the case where groups may be selected from a number of alternative groups, the selected groups may be the same or different. "Agriculturally acceptable salt" means a salt the cation of which is known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably the salts are water-soluble. The compounds of formula (I) may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula (I) may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds present in the molecule, such as C=C or C=N bonds, in which case compounds of formula (I) may exist as single isomers of mixtures of isomers. Centres of tautomerisation may be present. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
Suitable salts of the compounds of formula (I), include acid addition salts such as those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid. Other examples of organic carboxylic acids include haloacids such as trifluoroacetic acid. N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991.
In another aspect, the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein.
The preferred embodiments of the invention as defined below apply equally to each aspect and preferred aspects thereof of the invention as defined herein. In a preferred embodiment, Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, nitro; or heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro.
Preferably, Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen.
More preferably, Ri is phenyl optionally substituted with halogen, Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-haloalkoxy, phenoxy, methoxypropargyl, cyano, or nitro; or furanyl, thienyl, pyridyl, or benzothienyl, each optionally substituted with halogen.
Most preferably, Ri is 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 4-trifluoro-methylphenyl, 4-trifluoromethoxyphenyl, 2-fluoro-4-chlorophenyl or 2-thienyl.
In a preferred embodiment, R2 is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro.
Preferably, R2 is pyridyl, pyrimidinyl or isoquinolyl, each optionally substituted with halogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6- alkylthio, Ci-C6-haloalkoxy, cyano, or nitro.
More preferably, R2 is 2-, 3- or 4-pyridyl or 5-pyrimidinyl, each optionally substituted with halogen, Ci-C6-haloalkyl, Ci-C6-alkoxy or Ci-C6-alkylthio. Most preferably, R2 is 3-pyridyl, 4-pyridyl, or 5-pyrimidinyl, each optionally substituted with methyl, chloro, fluoro, methoxy, thiomethoxy or trifluoromethyl.
Preferably, R3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano or nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro; or alkylsilyl.
More preferably, R3 is phenyl optionally substituted with halogen, Ci-C6-alkyl, Ci-C6- haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, methoxypropargyl, cyano or nitro; furanyl, thienyl or pyridyl, each optionally substituted with halogen, Ci-C6-alkyl or Ci-C6-alkoxy; or Ci-C6- alkylsilyl.
More preferably, R3 is phenyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl,
3,5-difluorophenyl, 4-methylphenyl, 2,4-difluorophenyl, 2-thienyl, 5-chloro-2-thienyl, 5- methyl-2-thienyl, 3-thienyl, t-butyl or trimethylsilyl.
In a preferred embodiment, R4 is H, acetyl.
Most preferably, R4 is H.
In one preferred aspect of the present invention:
Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen;
R2 is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro; R3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano, nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro; or alkylsilyl; and
R4 is H or acetyl.
Most preferably, R4 is H.
In a more preferred aspect of the present invention;
Ri is phenyl optionally substituted with halogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-haloalkoxy, phenoxy,
methoxypropargyl, cyano, or nitro; or furanyl, thienyl, pyridyl, or benzothienyl, each optionally substituted with halogen;
R2 is pyridyl or pyrimidinyl, each optionally substituted with halogen, Ci-C6-alkyl,
C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6- haloalkoxy, cyano, or nitro; R3 is Ci-C6-alkyl; Ci-C6-alkoxy; phenyl optionally substituted with halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, methoxypropargyl, cyano or nitro; furanyl, thienyl or pyridyl, each optionally substituted with halogen, Ci-C6-alkyl or Ci-C6-alkoxy; or Ci-C6-alkylsilyl; and R4 is H.
In the more preferred embodiment
Ri is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen, haloalkyl, haloalkoxy and cyano;
R2 is pyridyl; wherein R3 is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen, haloalkyl, haloalkoxy and cyano, and;
P IS H
In the even more preferred embodiment
Ri is phenyl, which is substituted with 1 , 2 or 3 substituents selected from F or CI;
R2 is pyridyl;
wherein R3 is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from from F or CI, and;
R4 is H
Preferred compounds of formula (I) for use according to the methods of the present invention are selected from:
3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]- isoxazole (compound 144);
3-(4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole (compound 145);
3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole (compound 146);
3-(2,4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole
(compound 147);
3-(2-fluoro-4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole (compound 148);
3-(4-chlorophenyl)-5-(2-methoxypyridine)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole (compound 149);
3-(4-chlorophenyl)-5-(4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole
(compound 150); 3-(4-chlorophenyl)-5-(2,4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole
(compound 151);
3-(2,4-fluoro-4-chlorophenyl)-5-(2-chloro-4-fluorophenyl)-4-[(3pyridyl)hydroxymethyl]- isoxazole (compound 152); and
(5)-3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole (compound 154);
and salts thereof.
In a preferred embodiment the compound of formula (I) is 3-(4-Chloro-2-fluoro-phenyl)-5 - (2,4-difluoro-phenyl)-isoxazol-4-yl]-pyridin-3-yl-methanol.
In a preferred embodiment the compound of formula (I) is (¾)-[3-(4-Chloro-2-fluoro-phenyl)- 5 -(2,4-difluoro-phenyl)-isoxazol-4-yl]-pyridin-3-yl-methanol and
In a further aspect, the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein, wherein said method comprises one or more applications of one or more compounds as defined herein alone or in conjunction with one or more customary plant protection formulating auxiliaries.
In a further aspect, the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein, wherein two or more applications are carried out in sequence, and wherein the two or more applications have the same or different concentration or combinations of compounds as defined herein or both.
In a preferred embodiment of the invention, the crops of useful plants are selected from cereals, rice, beets, leguminous plants, oil plants, cucumber plants, fibre plants, vegetables, plantation crops, ornamentals, vines, bushberries, caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses.
In a preferred embodiment of the invention, the plant growth regulating effect is an inhibition or a retardation of the plant growth.
In a further aspect, the present invention provides an agricultural composition comprising one or more compounds of formula (I) as defined herein and one or more customary plant protection auxiliaries.
The compound of formula (I) exists as racemate comprising (R) and (S)-enantiomers. The (S)-enantiomer has been found to have significantly greater fungicidal activity compared to the (R)-enantiomer In a further aspect, the present invention is directed to the (5)-enantiomers of the compounds of formula (I), designated (S)-(I)
Figure imgf000037_0001
wherein Rl s R2, R3 and R4 are as defined herein; and salts thereof.
The stereo center described in the expression "(¾)-enantiomer of the compound of formula (I)" is the carbon atom in the methanol moiety which is marked with a star (*) in the formula
(S)-(i).
The present invention provides the compound of formula (5)-(Ι) as a single enantiomer having an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%>, 70%> or 80%>, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%.
Preferred compounds of formula include the (S)-enantiomers of compounds 1 to 153 of Table 1.
In a further aspect, the present invention also relates to an agricultural composition
comprising a compound of formula (5)-(Ι) a defined herein, or an agrochemically acceptable salt thereof, and an agrochemically acceptable diluent or carrier.
In a further aspect, the present invention also relates to an isoxazole compounds of formula (II), derived from compound 146, exhibit unexpected fungicidal activity and are therefore suitable for use in agriculture as crop protection agents to combat or prevent fungal infestations, or to control other pests such as weeds, insects, or acarids that are harmful to crops.
Accordingly, in an additional aspect, the present invention provides a compound of formula (II)
Figure imgf000038_0001
wherein R4 is H or acyl, preferably H;
or an agrochemically acceptable salt thereof.
In a preferred embodiment, the present invention provides the compound formula (iS)-(II)
Figure imgf000039_0001
wherein R4 is H or acyl;
or an agrochemically acceptable salt thereof. Most preferably, the present invention provides the compound (5)-[3-(4-chloro-2- fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyridin-3-yl-methanol (compound (S)- (146)).
Figure imgf000039_0002
Preferably, the compounds of formula (S)-(II), and preferably (5)-(146), are provided as single enantiomers having an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%.
Accordingly there is provided a composition comprising a compound of formula (5)-(II), and preferably (5)-(146), and an agriculturally acceptable diluent or carrier. The compound of formula (S)-(II), and preferably (S)-(146), and compositions thereof are suitable for controlling and preventing plant pathogenic microorganisms, especially fungal organisms, including those disclosd in International Patent Application WO 2006/031631. In particular, the present invention provides a method for controlling or preventing infestation of cultivated plants by pathogenic microorganisms, comprising applying a compound of formula (S)-(II), and preferably (5)-(146), to said plants, parts thereof or the locus thereof in an amount effective to control said microorganisms. Preferably, the organism is a fungal organism and more preferably, said fungal organism is selected from the group consisting of Septoria tritici, Stagonospora nodorum, Phytophthora infestans, Botrytis cinerea, Sclerotinia homoeocarpa and Puccinia recondita.
In a further embodiment the fungal organism is Botryotinia fuckeliana {Botrytis cinerea) (Gray mould). In a further embodiment the fungal organism is Glomerella lagenarium
(Colletotrichum lagenarium) (Anthracnose). In a further embodiment the fungal organism is F urium culmorum (Head blight). In a further embodiment the fungal organism is
Gaeum an n omyces graminis (Take-all of cereals). In a further embodiment the fungal organism is Mycosphaerella arachidis (Cercospora arachidicola) (early leaf spot). In a further embodiment the fungal organism is Mycosphaerella graminicola (Septoria tritici) (Septoria blotch)
Furthermore, the compositions according to the invention are suitable for controlling the following plant diseases: Alternaria species on vegetables, oilseed rape, sugar beet and fruit and rice, such as, for example, A. solani or A. alternata on potatoes and tomatoes;
Aphanomyces species on sugar beet and vegetables; Ascochyta species on cereals and vegetables; Bipolaris and Drechslera species on corn, cereals, rice and lawns, such as, for example, D. maydis on corn; Blumeria graminis (powdery mildew) on cereals; Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and grapevines; Bremia lactucae on lettuce; Cercospora species on corn, soybeans, rice and sugar beet; Cochliobolus species on corn, cereals, rice, such as, for example, Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice; Colletotricum species on soybeans and cotton; Drechslera species, Pyrenophora species on corn, cereals, rice and lawns, such as, for example, D. teres on barley or D. tritici-repentis on wheat; Esca on grapevines, caused by Phaeoacremonium
chlamydosporium, Ph. Aleophilum and Formitipora punctata (syn. Phellinus punctatus); Exserohilum species on corn; Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumbers; Fusarium and Verticillium species on various plants, such as, for example, F. graminearum or F. culmorum on cereals or F. oxysporum on a multitude of plants, such as, for example, tomatoes; Gaeumanomyces graminis on cereals; Gibberella species on cereals and rice (for example Gibberella fujikuroi on rice); Grainstaining complex on rice;
Helminthosporium species on corn and rice; Michrodochium nivale on cereals;
Mycosphaerella species on cereals, bananas and groundnuts, such as, for example, M.
graminicola on wheat or M.fijiensis on bananas; Peronospora species on cabbage and bulbous plants, such as, for example, P. brassicae on cabbage or P. destructor on onions; Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans; Phomopsis species on soybeans and sunflowers; Phytophthora infestans on potatoes and tomatoes; Phytophthora species on various plants, such as, for example, P. capsici on bell pepper; Plasmopara viticola on grapevines; Podosphaera leucotricha on apples; Pseudocercosporella herpotrichoides on cereals; Pseudoperonospora on various plants, such as, for example, P. cubensis on cucumber or P. humili on hops; Puccinia species on various plants, such as, for example, P. triticina, P. strifor- mins, P. hordei or P. graminis on cereals or P. asparagi on asparagus; Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Entyloma oryzae on rice; - Pyricularia grisea on lawns and cereals; Pythium spp. on lawns, rice, corn, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants, such as, for example, P. ultiumum on various plants, P. aphanidermatum on lawns; Rhizoctonia species on cotton, rice, potatoes, lawns, corn, oilseed rape, potatoes, sugar beet, vegetables and on various plants, such as, for example, R. solani on beet and various plants; Rhynchosporium secalis on barley, rye and triticale; Sclerotinia species on oilseed rape and sunflowers; Septoria tritici and Stagonospora nodorum on wheat; Erysiphe (syn. Uncinula) necator on grapevines; Setospaeria species on corn and lawns; Sphacelotheca reilinia on corn; Thievaliopsis species on soybeans and cotton; Tilletia species on cereals; Ustilago species on cereals, corn and sugar cane, such as, for example, U. maydis on corn; Venturia species (scab) on apples and pears, such as, for example, V. inaequalis on apples. The inventive compositions are furthermore suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In the protection of wood, particular attention is paid to the following harmful fungi: Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp.,
Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and
Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae. The present invention also encompasses compositions, combinations and plants as described herein and in International Patent Application WO 2006/031631.
"Plant propagation material" means the generative parts of a plant including seeds of all kinds (fruit, tubers, bulbs, grains etc), roots, rhizomes, cuttings, cut shoots and the like. Plant propagation material may also include plants and young plants which are to be transplanted after germination or after emergence from the soil.
"Locus" means the fields on which the plants to be treated are growing, or where the seeds of cultivated plants are sown, or the place where the seed will be placed into the soil.
The crops of useful plants to be protected typically comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, maize (including field corn, pop corn and sweet corn), rice, sorghum and related crops); beet (sugar beet and fodder beet); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, sunflowers); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, carrots, eggplants, onions, pepper, tomatoes, potatoes, paprika, okra); plantation crops (bananas, fruit trees, rubber trees, tree nurseries), ornamentals
(flowers, shrubs, broad-leaved trees and evergreens, such as conifers); as well as other plants such as vines, bushberries (such as blueberries), caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses including, for example, cool-season turf grasses (for example, bluegrasses {Poa L.), such as Kentucky bluegrass {Poa pratensis L.), rough bluegrass {Poa trivialis L.), Canada bluegrass {Poa compressa L.) and annual bluegrass {Poa annua L.); bentgrasses {Agrostis L.), such as creeping bentgrass {Agrostis palustris Huds.), colonial bentgrass {Agrostis tenius Sibth.), velvet bentgrass {Agrostis canina L.) and redtop {Agrostis alba L.); fescues {Festuca L.), such as tall fescue {Festuca arundinacea Schreb.), meadow fescue {Festuca elatior L.) and fine fescues such as creeping red fescue {Festuca rubra L.), chewings fescue {Festuca rubra var. commutata Gaud.), sheep fescue {Festuca ovina L.) and hard fescue {Festuca longifolia); and ryegrasses {Lolium L.), such as perennial ryegrass {Lolium perenne L.) and annual (Italian) ryegrass {Lolium multiflorum Lam.)) and warm-season turf grasses (for example, Bermudagrasses {Cynodon L. C. Rich), including hybrid and common Bermudagrass; Zoysiagrasses {Zoysia Willd.), St.
Augustinegrass {Stenotaphrum secundatum (Walt.) Kuntze); and centipedegrass {Eremochloa ophiuroides (Munro.) Hack.)).
The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and
trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate -resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate -tolerant trait), Agrisure® CB Advantage (Btl 1 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so- called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.
The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.
The compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation. The term "plant" or "useful plants" as used herein includes seedlings, bushes and trees. The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect- specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome- inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the context of the present invention there are to be understood by δ-endotoxins, for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced
recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl- type deoxyribonucleic acids and their preparation are known, for example, from WO
95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin);
YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus®
(maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a CrylFa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cryl Ac toxin); Bollgard I® (cotton variety that expresses a Cryl Ac toxin); Bollgard II® (cotton variety that expresses a Cryl Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cryl Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Btl 1 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1. Bill Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cryl Ab toxin. Btl 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Btl 76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-l 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry IF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cryl Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
The agrochemical compositions of the present invention will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
Suitably, the agrochemical compositions of the present invention are applied prior to disease development. Rates and frequency of use of the formulations are those conventionally used in the art and factors such as the developmental stage of the plant and on the location, timing and application method. Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient rates of application are from lOmg to lg of active substance per kg of seeds. In practice, as indicated above, the agrochemical compositions comprising a compound of formula (I) are applied as a formulation containing the various adjuvants and carriers known to or used in the industry. They may therefore be formulated as granules, wettable or soluble powders, emulsifiable concentrates, coatable pastes, dusts, flowables, solutions, suspensions or emulsions, or as controlled release forms such as microcapsules. These formulations are described in more detail below and may contain from 0.5% to 95% or more by weight of the active ingredient. The optimum amount will depend on formulation, application equipment and nature of the plant to be treated.
Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti- foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non- volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins. Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers. Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers,
polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used. Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethyl formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1- trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n- hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o- xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2 -pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.
Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride;
polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents. In addition, further, other biocidally active ingredients or compositions may be combined with the compound of formula (I) and used in the methods of the invention and applied
simultaneously or sequentially with the compound of formula (I). When applied
simultaneously, these further active ingredients may be formulated together with the compound of formula (I) or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
Accordingly, in one aspect, the present invention provides a composition comprising a compound of formula (I), which is selected from compounds 1 to 156 of Table 1 , and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
Additionally, the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is selected from compounds 1 to 156 of Table 1 , and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator. In a further aspect, the present invention provides a composition comprising a compound of formula (I), which is the (5)-enantiomer of formula (iS)-(I) and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator. Additionally, the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is the (S)- enantiomer of formula (5)-(I), and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator. In addition, the compounds of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl. The present invention relates additionally to mixtures comprising at least a compound of formula I and at least a further, other biocidally active ingredient and optionally further ingredients. The further, other biocidally active ingredient are known for example from "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition (New edition (02 Nov 2003)); Editor: C. D. S. Tomlin; The British Crop Protection Council, ISBN- 10: 1901396134; ISBN-13 : 978-1901396133] or its electronic version "e-Pesticide Manual V4.2" or from the website http://www.alanwood.net/pesticides/ or preferably one of the further pesticides listed below.
The following mixtures of the compounds TX with a further active ingredient (B) are preferred (the abbreviation "TX" means a compound encompassed by the compounds of formula I, or preferably the term "TX" refers to a compound selected from the Table 1 which lists the compounds 1 to 156 preferrably the compounds 144, 145, 146, 147, 148, 149, 150, 151, or 153, or (S)-146 (or 154)) and defines the group NIX provided that the compounds TX and the further active ingredient (B) are not the same; therefore mixtures of the compounds TX with a further active ingredient (B) defines the group NIX.
In a preferred embodiment "TX" has the meaning of [3-(4-chloro-2-fluorophenyl)-5-(2,4- difluorophenyl)isoxazol-4-yl]pyridin-3-yl-methanol. In a further preferred embodiment "TX" has the meaning of (5)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yl]pyridin-3-yl -methanol (Table 1, compound 153: (S)- 146)). an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
an acaricide selected from the group of substances consisting of l,l-bis(4-chlorophenyl)-2- ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate
(IUP AC/Chemical Abstracts name) (1059) + TX, 2-fhioro-N-methyl-N- 1 -naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidofiumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (IUP AC name) ( 111 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971) + TX, chlorfenvinphos ( 131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton ( 1038) + TX, demeton-methyl (224) + TX, demeton-0 ( 1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton- S -methyl (224) + TX, demeton-S- methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1102) + TX, diphenyl sulfone (IUP AC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1113) + TX, doramectin
(alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate- methyl ( 1134) + TX, etoxazole (320) + TX, etrimfos ( 1142) + TX, fenazaflor (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX,
flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, f uorbenside (1174) + TX, fiuvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, gamma- HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos
(alternative name) (473) + TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 : 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250
(compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (711) + TX, quintiofos ( 1381 ) + TX, R- 1492 (development code) ( 1382) + TX, RA- 17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime ( 1431 ) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos ( 1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX, an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne
[CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,
an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4 -amine (IUPAC name) (23) and strychnine (745) + TX,
a bactericide selected from the group of substances consisting of 1 -hydroxy- lH-pyridine-2- thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) ( 170) + TX, copper hydroxide (IUPAC name) ( 169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,
a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX,
Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis
(alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide
(scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,
a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,
a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate
[CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,
an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-l-yl acetate with (E)-dec-5-en-l-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)- tetradeca-4,10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-l 1-enal (IUPAC name) (436) + TX, (Z)-hexadec- 1 1 -en- 1 -yl acetate (IUPAC name) (437) + TX, (Z)-hexadec- 13 -en- 1 1 -yn- 1 -yl acetate (IUPAC name) (438) + TX, (Z)-icos-13-en-10-one (IUPAC name) (448) + TX, (Z)- tetradec-7-en- 1 -al (IUPAC name) (782) + TX, fZ)-tetradec-9-en- 1 -ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-l-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-l- yl acetate (IUPAC name) (283) + TX, (9Z,1 lE)-tetradeca-9,l 1 -dien-l-yl acetate (IUPAC name) (780) + TX, (9 12E)-tetradeca-9,12-dien-l-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-l-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4- methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name)
[CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-l -yl acetate (IUPAC name) (286) + TX, dodec-9- en-l-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-l-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-l-yl acetate (IUPAC name) (588) + TX, octadeca-3,13-dien-l-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-1 1-en-l-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
an insecticide selected from the group of substances consisting of 1-dichloro-l-nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l ,l-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (IUPAC name) (1063) + TX, 1 - bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-l- (3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(l ,3-dithiolan-2- yl)phenyl dimethylcarbamate (IUPAC/ Chemical Abstracts name) (1 109) + TX, 2-(2- butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-l ,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-l ,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2- ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-l-chloroprop-l-ene (IUPAC name) (917) + TX, 3- methyl-l-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop- 2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-l-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide
(IUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT
(alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl ( 115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945) + TX, carbon
tetrachloride (IUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX,
chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin
(alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos ( 1010) + TX, crufomate ( 1011 ) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, (i-limonene (alternative name) [CCN] + TX, -tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton- O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S- methyl (224) + TX, demeton- S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin ( 1070) + TX, diethyl 5 -methylpyrazol-3 -yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diofenolan (1099) + TX, dioxabenzofos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfoton (278) + TX, dithicrofos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos
(alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1134) + TX, ethoprophos (312) + TX, ethyl formate (IUP AC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos ( 1142) + TX, EXD ( 1143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenethacarb (1149) + TX, fenfiuthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpirithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, fhibendiamide (CAS. Reg. No.: 272451-65-7) + TX, flucofuron (1168) + TX, flucycloxuron (366) + TX, fiucythrinate (367) + TX, fluenetil (1169) + TX, f ufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, fhimethrin (372) + TX, fiuvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos ( 1191 ) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furathiocarb (412) + TX, furethrin ( 1200) + TX, gamma-cyhalothrin ( 197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda- cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metafiumizone (CCN) + TX, metam (519) + TX, metam- potassium (alternative name) (519) + TX, metam- sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulphonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX,
methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofiuthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifiuridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb ( 1313) + TX, nitrilacarb 1 : 1 zinc chloride complex ( 1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl 0-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, 0,0-diethyl <3-4-methyl-2-oxo-2H- chromen-7-yl phosphorothioate (IUPAC name) ( 1074) + TX, O, O-diethyl <3-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (IUPAC name) ( 1075) + TX, 0, 0, 0 O'-tetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525
(development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite
[CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX,
spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphonyl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tef uthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin
(alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfiuthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin
[84937-88-2] + TX,
a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide -olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71 -3] + TX,
a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1, 1 -dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran ( 118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX,
tetrachlorothiophene (IUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox
(alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
a rodenticide selected from the group of substances consisting of 2-isovalerylindan-l,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, fiocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX,
scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fiuoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421
(development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imanin (alternative name)
[CCN] and ribavirin (alternative name) [CCN] + TX,
a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
and biologically active compounds selected from the group consisting of azaconazole (60207- 31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fiuquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol
[76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole
[125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283- 41-4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX,
simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole
[112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771-68- 5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483- 43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61- 2] + TX, mepanipyrim [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17-3] + TX, fiudioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878- 19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX,
dichlozoline [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471-44-8] + TX, boscalid
[188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173- 90-6] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX,
trifloxystrobin [141517-21-7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin
[117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid
[1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731 -27- 1 ] + TX, bordeaux mixture [8011 -63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60- 3] + TX, cymoxanil [57966-95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920- 32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867- 47-9] + ΎΧ, dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52- 6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb
[25606-41-1] + TX, proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulphur [7704-34-9] + TX, tiadinil [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, 3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid (9-dichloromethylene-l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid [2- (2,4-dichlorophenyl)-2-methoxy-l-methyl-ethyl]-amide (disclosed in WO 2008/148570) + TX, l-[4-[4-[(5S)5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2- yl]piperidin-l-yl]-2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone + TX, l-[4-[4- [5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl]piperidin-l-yl]-2-[5- methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone [1003318-67-9], both disclosed in WO 2010/123791, WO 2008/013925, WO 2008/013622 and WO 2011/051243 page 20) +TX, and 3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2- yl)-amide (dislosed in WO 2006/087343) + TX, 3-(difluoromethyl)-N-methoxy-l-methyl-N- [l-methyl-2-(2,4,6-trichlorophenyl)ethyl]-lH-Pyrazole-4-carboxamide + TX, 4-[(5<S)-5-(3,5- dichlorophenyl)-5 -(trifluoromethyl)-4H-isoxazol-3 -yl] -2-methyl-N-(thietan-3 -yl)benzamide (WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-2-methyl-N-(thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(cis-l-oxo-thietan-3- yl)benzamide (WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)- 4H-isoxazol-3-yl]-2-methyl-N-(cis-l-oxo-thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(trans-l- oxo-thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3 -yl] -2-methyl-N-(trans- 1 -oxo-thietan-3 -yl)benzamide
(WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-N-(l,l-dioxothietan-3-yl)-2-methyl-benzamide (WO2011/104089) + TX, 4-[(5R)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-( 1,1 -dioxothietan-3 -yl)-2-methyl- benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide
(WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide (WO2011/104089) + TX, Penflufen [494793-67-8] and TX, 5-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-(l,2,4-triazol-l-yl)benzonitrile (WO2007/075459) + TX, 5-[(5R)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-(l,2,4-triazol-l-yl)benzonitrile (WO2007/075459) + TX.
In a preferred embodiment TX is the compound 144; In a further preferred embodiment TX is the compound 145; In a further preferred embodiment TX is the compound 146; In a further preferred embodiment TX is the compound 147; In a further preferred embodiment TX is the compound 148; In a further preferred embodiment TX is the compound 149; In a further preferred embodiment TX is the compound 150; In a further preferred embodiment TX is the compound 151; In a further preferred embodiment TX is the compound 153; In a further preferred embodiment TX is the compound (S)-146; In a further preferred embodiment TX is the compound 154.
The following ternary mixtures are preferred with the proviso that none of the at least three composition components are the same:
A binary mixture selected from the group of NIX and Isopyrazam;
A binary mixture selected from the group of NIX and 3 -Difluoromethyl-1 -methyl- 1H- pyrazole-4-carboxylic acid ((1 R,4S)-9-dichloromethylene- 1 ,2,3 ,4-tetrahydro- 1 ,4-methano- naphthalen-5 -yl)-amide;
A binary mixture selected from the group of NIX and 3-(difluoromethyl)-N-methoxy-l- methyl-N-[l -methyl -2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide;
A binary mixture selected from the group of NIX and Bixafen; A binary mixture selected from the group of NIX and Boscalid;
A binary mixture selected from the group of NIX and Fluxapyroxad;
A binary mixture selected from the group of NIX and Penthiopyrad;
A binary mixture selected from the group of NIX and Fluopyram;
A binary mixture selected from the group of NIX and Prothioconazole;
A binary mixture selected from the group of NIX and Propiconazole;
A binary mixture selected from the group of NIX and Difenconazole;
A binary mixture selected from the group of NIX and Ipconazole;
A binary mixture selected from the group of NIX and Cyproconazole; A binary mixture selected from the group of NIX and Epoxiconazole;
A binary mixture selected from the group of NIX and Metconazole;
A binary mixture selected from the group of NIX and Tebuconazole;
A binary mixture selected from the group of NIX and Prochloraz;
A binary mixture selected from the group of NIX and flusilazole;
A binary mixture selected from the group of NIX and flutriafol;
A binary mixture selected from the group of NIX and fluquinconazole;
A binary mixture selected from the group of NIX and Azoxystrobin;
A binary mixture selected from the group of NIX and Trifloxystrobin;
A binary mixture selected from the group of NIX and Pyraclostrobin; A binary mixture selected from the group of NIX and Fluoxastrobin;
A binary mixture selected from the group of NIX and Picoxystrobin;
A binary mixture selected from the group of NIX and Kresoxim-methyl;
A binary mixture selected from the group of NIX and dimoxystrobin;
A binary mixture selected from the group of NIX and famoxadone; A binary mixture selected from the group of NIX and Cyprodinil;
A binary mixture selected from the group of NIX and Chlorothalonil;
A binary mixture selected from the group of NIX and fludioxonil;
A binary mixture selected from the group of NIX and Metrafenone;
A binary mixture selected from the group of NIX and Proquinazid; A binary mixture selected from the group of NIX and Fenpropidin; A binary mixture selected from the group of NIX and Fenpropimorph;
A binary mixture selected from the group of NIX and quinoxyfen;
A binary mixture selected from the group of NIX and spiroxamine;
A binary mixture selected from the group of NIX and Thiamethoxam;
A binary mixture selected from the group of NIX and clothianidin;
A binary mixture selected from the group of NIX and tefluthrin;
A binary mixture selected from the group of NIX and imidaclodprid;
The mixtures comprising a TX (a compound encompassed by the compounds of formula I) preferrably selected from Table 1 especially the compounds 144, 145, 146, 147, 148, 149, 150, 151, or 153, or (S)-146 (or 154) and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank- mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from Table 1 especially the compounds 144, 145,147,148, 149, 150, 151, or 153, or (S)- 146 (or 154), and the active ingredients as described above is not essential for working the present invention. Throughout this document the expression "composition" stands for the various mixtures or combinations of components TX and (B) and (C), for example in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components TX and (B) and (C) is not essential for working the present invention.
The compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component TX. An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.
In the above different lists of active ingredients to be mixed with a TX, the compound of the formula I is preferably a compound of Tables 1.
In the above-mentioned mixtures of compounds of formula I, in particular a compound selected from said Table 1, with other insecticides, fungicides, herbicides, safeners, adjuvants and the like, the mixing ratios can vary over a large range and are, preferably 100: 1 to 1 :6000, especially 50: 1 to 1 :50, more especially 20: 1 to 1 :20, even more especially 10: 1 to 1 :10.
Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of TX with the mixing partner).
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
Compounds of formula (I) may be prepared using the methods below or according to WO2006031631, WO2010069881 and/or WO2010069882. Compounds of formula (I) wherein R4 = H may be prepared by a [3+2]-cycloaddition of a carboximidoyl chloride (II) with an acetylenic carbinol (III):
Figure imgf000079_0001
(II) (in) (I) (R4 = H)
The reaction may be carried out in the presence of an organic base such as triethylamine in an inert solvent such as DCE (1,2-dichloroethane), or an inorganic base such as sodium bicarbonate in a protic solvent such as isopropanol. Time and temperature of the reaction is not critical but may be at temperatures ranging from 20 to 60° C for 1 to 24h.
The carboximidoyl chlorides (II) may be prepared from the corresponding oximes using chlorinating reagents such as N-chlorosuccinimide or sodium hypochlorite (bleach), or may be obtained from commercial sources.
The acetylenic carbinols (III) may be obtained by addition of an organometallic acetylene (IV) (M = Li, MgX; X = CI, Br) to an aldehyde R2CHO (V), as shown below:
Figure imgf000079_0002
(IV) (V) (III)
In certain cases, the [3+2]-cycloaddition proceeds more rapidly and in higher yield when the corresponding ketone (VI) of acetylenic carbinol (III) is used:
Figure imgf000080_0001
(II) (VI) (VII)
Compounds of formula (VII) are useful for making compounds of formula (I) as described below wherin the isoxazole (VII) is reduced (e.g. with sodium borohydride) to give (I).
In some cases, the regioisomer (VIII) is produced along with (I) in the [3+2]-cycloaddition. This regioisomer (VIII) generally is less active than (I) in bioevaluation.
Figure imgf000080_0002
(VIII)
Acetylenic ketone (VI) can be prepared from (III) by oxidation, for example with IBX (o-iodosobenzoic acid) in an inert solvent such as DMSO (dimethylsulfoxide) at any suitable time and temperature (e.g. 20°C for 1 to 2h). Reduction of isoxazole (VII) with sodium borohydride in an alcoholic solvent (e.g. ethanol) at 0°C for 0.3 to 2h produces the isoxazole (I) (R4 = H).
Isoxazoles in which R4≠ H may be prepared from (I) (R4 = H) using standard acylation or carbamoylation conditions. For example, the acetate derivative of (I) (R4 = COCH3) is synthesized from the alcohol (I) (R = H) by reaction with acetic anhydride and pyridine in ether solvent at room temperature overnight. Acylations may be carried out using either acid anhydrides (e.g. acetic anhydride, propionic anhydride) or acid chlorides (e.g. benzoyl chloride) in the presence of an organic base in an inert solvent (e.g. ether, dichloromethane). Carbamoylations are effected by treating alcohols (I) with a strong base such as sodium hydride followed by a carbamoyl chloride (e.g. N,N-dimethylcarbamoyl chloride) in an inert solvent such as DMF (dimethylformamide).
Conventional techniques for the preparation or isolation of individual enantiomers include chiral synthesis from a suitable optically pure precursor or resolution of the racemate (or the racemate of a salt or derivative) using, for example, chiral high performance liquid chromatography (HPLC). Alternatively, the racemate (or a racemic precursor) may be reacted with a suitable optically active compound, for example, a carboxylic acid, or, in the case where the compound of formula (I) contains an acidic or basic moiety, a base or acid such as 1-phenylethylamine or tartaric acid. The resulting diastereomeric mixture may be separated by chromatography and/or fractional crystallization and one or both of the diastereoisomers converted to the corresponding pure enantiomer(s) by means well known to a skilled person. Conventional techniques known to those skilled in the art -are disclosed in, for example, Stereochemistry of Organic Compounds by E. L. Eliel and S. H. Wilen (Wiley, New York, 1994).
The invention is illustrated by the following Examples.
Example 1 : 3-(2,6-Dichlorophenyl)-4-r(3-pyridyl)-hvdroxymethyl1-5-trimethylsilyl-isoxazole (Table 1, compound 1) and
3-(2,6-dichlorophenyl)-5-[(3-pyridyl)-hydroxymethyll-4-trimethylsilylisoxazole (Table 1 , compound 2)
A mixture of 55mg (0.24mmol) of 2,6-dichloro-N-hydroxybenzenecarboximidoyl chloride, 50mg (0.24mmol) of l-(3-pyridyl)-3-trimethylsilyl-2-propyn-l-ol, and 20mg (0.24mmol) of sodium bicarbonate in 2mL of isopropyl alcohol was heated at 55°C for 24h. The reaction mixture was diluted with ether. The ether layer was washed with saturated sodium chloride solution, and was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by preparative thin layer chromatography (prep TLC), and two products were isolated. The less polar product (lOmg, 0.025mmol) was identified as 3-(2,6-dichlorophenyl)-4-[(3- pyridyl)hydroxy-methyl]-5-trimethylsilylisoxazole. 1H NMR (CDC13): δ 0.45 (br s, 9), 5.82 (s, 1), and 7.40ppm (d, 1). MS m/z: 393.0 (M+H).
The more polar product was 3-(2,6-dichlorophenyl)-5-[(3-pyridyl)hydroxymethyl]-4- trimethylsilylisoxazole. 1H NMR (CDCI3): δ 0.20 (m, 9), 6.12 (s, 1), 7.80 (d, 1), and 7.87ppm (d, 1). MS m/z: 393.0 (M+H). Example 2: 5-(3-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl) hydroxymethyl]- isoxazole (Table 1 , compound 4)
A mixture of 53mg (0.24mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 50mg (0.21mmol) of l-(3-pyridyl)-3-(3-chlorophenyl)-2-propyn-l-ol, and 26mg (0.31mmol) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C on a rotary table shaker equipped with a heated sand bath. After 20h, an additional 20mg of 2,4-dichloro-N- hydroxybenzenecarboximidoyl chloride and lOmg of sodium bicarbonate was added, and the reaction mixture was stirred and heated for another 16h. The mixture was then diluted with ether, and the solution was washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 15mg (0.035mmol) of 5-(3-chlorophenyl)-3- (2,4-dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]isoxazole.
1H NMR (CDC13): δ 5.92 (br s, 1), 7.04 (d of d, 1), 7.12 (d, 1), 7.72 (m, 1), 8.86 (br s, 1), and 8.29ppm (br s, 2). MS m/z: 430.9 (M+H).
Example 3 : 5-(3-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-r(3-pyridyl)- acetoxymethyllisoxazole
To a solution of 43mg (O.lOmmol) of 5-(3-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl]isoxazole in 2mL of pyridine was added \9 iL (0.20mmol) of acetic anhydride. The reaction was stirred overnight at room temperature, and then the pyridine was removed under vacuum. The residue was taken up in ethyl acetate, washed with saturated sodium chloride, and the ethyl acetate fraction dried over magnesium sulfate. The drying agent was filtered off, and the ethyl acetate was removed by rotoevaporation. The crude product was purified by preparative thin layer chromatography (prep TLC) to give 35mg (0.074mmol) of 5-(3-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)acetoxymethyl]- isoxazole.
Example 4: 3-(2,4-Dichlorophenyl)-5-(lJ-dimethylethyl)-4-r(3- pyridyDcarbonyllisoxazole
To a solution of 200mg (1.06mmol) of 4,4-dimethyl-l-pyridyl-2-pentyn-l-ol in 2.5mL of dimethyl sulfoxide (DMSO) was added 443mg (1.58mmol) of o-iodosobenzoic acid (IBX). The reaction mixture was stirred overnight at room temperature, and then the solid was removed by filtration. The filtrate was diluted with ether, and washed with saturated sodium chloride solution. The organic fraction was separated and dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The ketonic product, 4,4-dimethyl-l-(3-pyridyl)-2-pentyn-l-one (182mg) was used directly without any purification.
A mixture of 72mg (0.32mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 60mg (0.32mmol) of 4,4-dimethyl-l-(3-pyridyl)-2-pentyn-l-one, and 32mg (0.38mmol, 1.2 equivalents) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C for 16h on a rotary table shaker. A second addition of 25mg of carboximidoyl chloride and lOmg of sodium bicarbonate was followed by another 20h at 55 °C. The reaction mixture was cooled, diluted with ether, and then washed with saturated sodium bicarbonate. The ether fraction was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 92mg of oily product, 3-(2,4-dichlorophenyl)-5-(l,l-dimethylethyl)-4-[(3-pyridyl)carbonyl]-isoxazole. 1H NMR (CDCU): δ 1.47 (s, 9), 7.90 (m, 1), 7.60 (br s, 1) and 8.72ppm (br s, 1). MS m/z: 375.0 (M+H).
Example 5 : 3-(2,4-Dichlorophenyl)-5-(lJ-dimethylethyl)-4-r(3- pyridvPhydroxymethyll - isoxazole (Table 1 , compound 7)
To a solution of 92mg (0.24mmol) of 3-(2,4-dichlorophenyl)-5-(l,l-dimethylethyl)-4-[(3- pyridyl)carbonyl]isoxazole in 5mL of ethanol at 0°C was added 20mg (0.53mmol) of sodium borohydride. After 2h, the reaction mixture was poured into water, and the product was extracted several times with ethyl acetate. The combined ethyl acetate fractions were washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and the ethyl acetate was removed by rotoevaporation. The crude product was purified by prep TLC to yield 68mg (0.18mmol) 3-(2,4-d.ichlorophenyl)-5-(l,l- dimethylethyl)-4-[(3-pyridyl)hydroxy-methyl]isoxazole. 1H NMR (CDC13): δ 1.52 (s, 9), 6.14 (br s, 1), 6.86 (d, 1), 7.38 (m, 1), 8.27 (br s, 1) and 8.33ppm (m, 1). MS m/z: 377.0 (M+H).
Example 6: 5-(2-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-r(3-pyridyl)hvdroxymethyl1- isoxazole (Table 1, compound 14)
To a solution of 655mg (4.8mmol) of 2-chlorophenylacetylene in lOmL of tetrahydrofuran (THF) cooled to -78°C under a nitrogen atmosphere was added 3.0mL (4.8mmol) of 1.6M n-butyllithium in hexane. The solution was stirred at -78°C for 2h, and then a solution of 514mg (4.8mmol) of 3-pyridinecarboxaldehyde in 2.5mL of tetrahydrofuran (THF) was added. After 3.5h, the reaction mixture was poured into water. The organic product was extracted with ether several times. Combined ether extracts were washed with saturated sodium bicarbonate and dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation to give the oily 3-(2-chlorophenyl)-l-(3-pyridyl)-2- propyn-l-ol. A mixture of 52mg (0.23mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 50mg (0.21mmol) of 3-(2-chlorophenyl)-l-(3-pyridyl)-2-propyn-l-ol, and 30mg (0.36mmol) of sodium bicarbonate in 3mL of isopropyl alcohol was heated at 55°C overnight with shaking. The reaction mixture was cooled, diluted with ether, and then washed with saturated sodium bicarbonate. The ether fraction was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 15mg (0.035mmol) of 5-(2-chlorophenyl)-3-(2,4- dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]isoxazole. 1H NMR (CDC13): δ 5.80 (br s, 1). MS m/z: 431.0 (M+H).
Example 7: 5-(2-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-r(3-pyridyl)hvdroxymethyl1- isoxazole (Table 1, compound 14) A mixture of 56mg (0.25mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 60mg (0.25mmol) of 3-(2-chlorophenyl)-l-(3-pyridyl)-2-propyn-l-one, and 30mg (0.36mmol) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C overnight with shaking. An additional 30mg of carboximidoyl chloride and 15mg of sodium bicarbonate was then added, and the mixture was heated for another 20h.The reaction mixture was cooled, diluted with ether, and then washed with saturated sodium bicarbonate. The ether fraction was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 90mg (0.2 lmmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)carbonyl]isoxazole. 1H NMR (CDC13): 6 7.16 (m, 1), 7.60 (m,2), 7.92 (m, 1), 8.53 (br d, 1), and 8.74ppm (br s, 1). MS m/z: 428.9 (M+H).
To a solution of 80mg (0.19mmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)carbonyl]isoxazole in 3mL of ethanol at 0°C was added 40mg (1.06mmol) of sodium borohydride. The mixture was stirred for 2h and then diluted with ethyl acetate. The ethyl acetate solution was washed with saturated sodium chloride solution and dried over magnesium sulfate. The drying agent was filtered off, and the ethyl acetate was removed by rotoevaporation. The crude product was purified by prep TLC to give 65mg (0.15mmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole.
1H NMR (CDCU): δ 5.80 (br s, 1), 6.97 (m, l), 8.23 (br s, 1), and 8.28ppm (br s, 1).
MS m/z: 431.0 (M+H).
Example 8: 5-(2-Chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3-pyridyl)hydroxymethyll- isoxazole (Table 1, compound 15) A solution of 59mg (0.25mmol) of 2,4-dichlorobenzylcarboximidoyl chloride (prepared according to G. Kumaran and G. H. Kulkarni, J. Org. Chem. 1997, 62, 1516), 50mg (0.21mmol) of 3-(2-chlorophenyl)-l-(3-pyridyl)-2-propyn-l-one, and 43μί (0.31mmol) of triethylamine in mL of dichlorom ethane was heated at 55°C in a sealed vial overnight. The reaction mixture was cooled and diluted with ether, washed with saturated sodium chloride, and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The crude product was purified by prep TLC to give 50mg (0.1 lmmol) 5-(2-chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3-pyridyl)carbonyl]isoxazole. 1H NMR (CDCI3): δ 4.23 (s, 2), 7.48 (d, 1), 7.88 (d of d, 1), 8.66 (br d, 1), 8.70ppm (br s, 1). MS m/z: 442.9 (M+H).
To a solution of 50mg (0.1 lmmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3- pyridyl)carbonyl]isoxazole in 15mL of THF was added 21mg (0.56mmol) of sodium borohydride at room temperature. After 2h, the solution was diluted with ethyl acetate, washed with saturated sodium chloride, and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The crude product was purified by prep TLC to give 39mg (0.088mmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3- pyridyl)hydroxymethyl]isoxazole. 1H NMR (CDC13): δ 3.91 (d, 1), 4.00 (d, 1), 6.97 (br s, 1), 7.64 (d, 1), 8.42ppm (br m, 2). MS m/z: 445.0 (M+H). Example 9: 5-(3-Chlorophenyl)-3-(2-fluoro-5-trifluorometh^
methyl"|isoxazole (Table 1, compound 29)
To a solution of 643mg (3.10mmol) of 2-fluoro-5-trifluoromethylbenzaldehyde oxime in 5mL of dimethyl formamide (DMF) was added 456mg (3.41mmol) of N-chlorosuccinimide (see K.-C. Liu, B. R. Shelton, and R. K. Howe, J. Org. Chem. 1980, 45, 3916). The reaction mixture was stirred at room temperature overnight, and then diluted with ethyl acetate. The ethyl acetate solution was washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation to give 675mg (2.79mmol) of pure white crystalline 2-fluoro-5-trifluoromethyl-N- hydroxybenzene-carboximidoyl chloride.
A mixture of 60mg (0.25mmol) of 2-fluoro-5-trifluoromethyl-N-hydroxybenzenecarbox- imidoyl chloride, 50mg (0.21mmol) of 3-(3-chlorophenyl) l-(3-pyridyl)-2-propyn-l-one (prepared similarly to procedures noted above from lithio 3-chlorophenylacetylide and 3-pyridinecarboxaldehyde, followed by IBX oxidation), and 26mg (0.36mmol) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C overnight with shaking. An additional 30mg of carboximidoyl chloride and 15mg of sodium bicarbonate were added, and the reaction was heated for another 24h. The mixture was cooled and diluted with ether. The ether fraction was washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The residue was purified by prepTLC to give 56mg (0.13mmol) of 5-(3-chlorophenyl)-3-(2-fluoro-5- trifluoromethylphenyl)-4-[(3-pyridyl)carbonyl]isoxazole. 1H NMR (CDC13): δ 7.10 (t, 1), 7.41 (m, 1), 7.52 (m, 1), 8.65 (br s, 1), and 8.86ppm (br s, 1). MS m/z: 447.0 (M+H).
To a solution of 56mg (0.13mmol) of 5-(3-chlorophenyl)-3-(2-fluoro-5-trifluoromethyl- phenyl)-4-[(3-pyridyl)carbonyl]isoxazole in 2mL of ethanol was added 24mg (0.63mmol) of sodium borohydride. After 2 h at room temperature, the reaction mixture was diluted with ethyl acetate. The solution was washed with saturated sodium chloride and was dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The residue was purified by prepTLC to give 44mg (0.098mmol) of 5-(3- chlorophenyl)-3-(2-fluoro-5-trifluoromethylphenyl)-4-[(3-pyridyl)hydroxymethyl]isoxazole. 1H NMR (CDCI3): δ 6.01 (s, 1), 7.01 (m, 1), 7.83 (m, 1), 8.27 (m, 1), and 8.35ppm (br s, 1). MS m/z: 449.0 (M+H).
Example 10: [3-(4-Chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yllpyridin- 3-yl-methanol (Table 1, compound 146)
Preparation of 3-(2,4-difluorophenyl)-l-pyridin-3-yl-propynone (3)
Figure imgf000088_0001
1 2 3 l-Ethynyl-2,4-difluorobenzene (24g, 0.17mol) was dissolved in THF (350ml) and the reaction mixture was cooled at -78°C. A solution of n-BuLi, 2.5 M in hexane, (76.5ml, 0.19mol) was added dropwise over 70 minutes maintaining the temperature below -70°C. The mixture was stirred at this temperature for a further 10 minutes after the addition was finished. A solution of the Weinreb amide 2 (prepared according to WO 05/097760, Letters in Organic Chemistry, 4, 20, 2007) (28.9g, 0.17mol) in THF (100ml) was added dropwise over 20 minutes to the solution above keeping the temperature below -70°C. The mixture was now warmed to -50°C obtaining a solution that was further stirred for 1 hour at this temperature. The reaction mixture was quenched with a saturated solution of ammonium chloride (100ml) and allowed to warm to room temperature. The reaction was then poured into a mixture of ethyl acetate/water. Successively, the aqueous phase was washed twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulphate, filtered and concentrated. The crude was recrystallised from diethyl ether obtaining 28g of the desired product. The mother liquors were concentrated and the residue was purified by column chromatography on alumina using a mixture of cyclohexane/ethyl acetate 3: 1. Totally, 29.8g (70%) of brown compound were obtained.
1H NMR (CDC13): δ 7. 02 (m, 1), 7.58 (m, 1), 7.71 (m, 1), 8.56 (m, 1) 8.90 (m, 1) and 9.48 ppm (m, 1). MS m/z: 244.0 (M+H).
(ii) Preparation of [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yl]pyridin-3-yl-methanone (5)
Figure imgf000089_0001
3 4 5
A mixture of 46.7g (0.22mol) of 2-fluoro-4-chloro-N-hydroxybenzenecarboximidoyl chloride (prepared by analogy to the method of preparation of 2-fluoro-5-trifluoromethyl-N- hydroxybenzene-carboximidoyl chloride Example 9), 42g (0.17mol) of 3-(2,4- difluorophenyl)-l-pyridin-3-yl-propynone (3), and 21.76g (0.26mol) of sodium bicarbonate in 500mL of isopropyl alcohol was heated at 85 °C for 21 hours. The reaction mixture was diluted with ethyl acetate and washed successively with saturated ammonium chloride, water, and saturate sodium chloride solution, and was dried over magnesium sulfate. The drying agent was filtered off and the ethyl acetate was removed by rotoevaporation. The crude was recrystallised from diethyl ether obtaining the desired product as a yellowish solid (50.28g, 70.2%). 1H NMR (CDCI3): δ 6.75 (m, 1), 7.05 (m, 2), 7.27 (m, 2), 7.67 (t, 1), 7.80 (m, 1), 8.03 (m, 1), 8.66 (m, 1) and 8.82 ppm (d, 1). MS m/z: 415 (M+H).
(iii) Preparation of [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yl]pyridin-3-yl -methanol (6)
Figure imgf000090_0001
To a solution of 5 (26.5g, 63.9mmol) in a mixture of THF/methanol (400ml/40ml) at 0°C was added 2.42g (63.7mmol) of sodium borohydride. The mixture was stirred for 1.5 hours and then diluted with ethyl acetate. The ethyl acetate solution was washed with saturated sodium chloride solution and dried over magnesium sulfate. The drying agent was filtered off and the ethyl acetate was removed by rotoevaporation. The reaction mixture was purified by column chromatography using a mixture of heptane/ethyl acetate 1 : 1. The desired compound was obtained as white crystals (17.5g, 66%). mp= 138-140°C.
1H NMR (CDC13): δ 4.19 (bs, 1), 5.89 (s, 1), 6.99 (m, 5), 7.28 (t, 1), 7.43 (d, 1), 7.59 (q, 1), and 8.19 (d, 1) and 8.23 ppm (d, 1). MS m/z: 417 (M+H).
Example 11 : (6 -r3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yllpyridin-3-yl -methanol (Table 1, compound 153: (5 146V)
Figure imgf000090_0002
Each enantiomer was isolated by preparative chromatography using the racemic mixture 6 starting material.
Preparative method:
Column: 250x76 mm CHIRALPAK® AD 20 μιη; Mobil phase: n-heptane/ethanol 70/30 (v/v)
Flow rate: 270 ml/min
Detection: UV 280 nm
Temperature: 25°C
Analytical method:
Column: 250x4.6 mm CHIRALPAK® AD-H 5 μιη;
Mobil phase: n-heptane/ethanol/diethylamine 70/30/0.1 (v/v/v)
Flow rate: 1 ml/min
Detection: UV 230 nm
Temperature: 25°C
The first eluting enantiomer had a retention time of 7.6 min ([a]= +58.07, C= 0.025 M, TFiF) while the second enantiomer had a retention time of 9.9 min ([a]= -57.59, C= 0.025 M, THF). The first eluting enantiomer is the ( ?)-enantiomer. The second eluting enantiomer is the (iS)-enantiomer. The compounds of formula (I) in Table 1 may be prepared by analogous methods.
Table 1
Chemical Name
5-(3-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- phenylisoxazole
3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-thienyl)isoxazole
Figure imgf000091_0001
3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3 -thienyl)isoxazole
5-(2-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(2- trifluoromethylphenyl)-isoxazole
4-[(3 -Pyridyl)hydroxymethyl] -3 -(4- trifluoromethoxyphenyl)-5-(2-trifluoromethylphenyl)- isoxazole
4-[(3 -Pyridyl)hydroxymethyl] -3 -(3 - trifluoromethylphenyl)-5-(2-trifluoromethylphenyl)- isoxazole
3-(3,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-trifluoromethylphenyl)-isoxazole
3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-trifluoromethylphenyl)-isoxazole
3 -(4-Chlorophenyl)-5 -(4-methylphenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
5-(4-Methylphenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethoxyphenyl)-isoxazole
5-(4-Methylphenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- trifluoromethylphenyl)-isoxazole
Figure imgf000092_0001
3-(3,4-Dichlorophenyl)-5-(4-methylphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(2,4-Dichlorophenyl)-5-(4-methylphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(2-fluoro-5- trifluoromethylphenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole
5 -(3 -Chlorophenyl)-3 -(4-cyanophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
5 -(2-Chlorophenyl)-3 -(4-cyanophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
5-(4-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(3- trifluoromethylphenyl)-isoxazole
4-[(3 -Pyridyl)hydroxymethyl] -3 -(4- trifluoromethoxyphenyl) -5 -(3 -trifluoromethylphenyl) - isoxazole
4-[(3 -Pyridyl)hydroxymethyl] -3 -(3 - trifluoromethylphenyl)-5-(3-trifluorometliylplienyl)- isoxazole
3-(3,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3-trifluoromethylphenyl)-isoxazole
Figure imgf000093_0001
3-(4-Chlorophenyl)-5-phenyl-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-Phenyl-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethoxyphenyl)-isoxazole
5-Phenyl-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethylphenyl)-isoxazole
3-(2,4-Dichlorophenyl)-5-phenyl-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(3,4-Dichlorophenyl)-5-phenyl-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethoxyphenyl)-isoxazole
5-(3-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- trifluoromethylphenyl)-isoxazole
5-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(2- thienyl)isoxazole
5-(4-Chlorophenyl)-3-(2-fluoro-4- trifluoromethylphenyl)-4-[(3-pyridyl)liydroxymetliyl]- isoxazole
3-(2-Fluoro-4-trifluoromethylphenyl)-4-[(3- pyridyl)hydroxymethyl] -5 -(3 -thienyl)isoxazole
Figure imgf000094_0001
4-[(3 -Pyridyl)hydroxymethyl] -3 -(2-thienyl)-5 -(3 - thienyl)-isoxazole
5-(3 -Chlorophenyl)-3 -phenyl-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
5-(4-Methylphenyl)-3-phenyl-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(4-Methylphenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- thienyl)isoxazole
5-(3-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- thienyl)isoxazole
5-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- thienyl)isoxazole
3 -(4-Chlorophenyl)-5 -(3 -chlorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
3-(2-Fluoro-5-trifluoromethylphenyl)-4-[(3- pyridyl)hydroxymethyl] -5 -(3 -thienyl)isoxazole
5-(4-Chlorophenyl)-3-(2-fluoro-5- trifluoromethylphenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole
3-(4-Chlorophenyl)-5-phenyl-4-[(2- pyridyl)hydroxymethyl] -isoxazole
Figure imgf000095_0001
5-(3-Chloro-4-methylphenyL)-3-(4-chlorophenyl pyridyl)hydroxymetliyL]-isoxazole
5-(3-Chloro-4-fluorophenyl)-3-(4-chlorophenyl) pyridyl)hydroxymethyl]-isoxazole
3-(4-Chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyL]-isoxazole
3-(4-Chlorophenyl)-5-(2-methoxyphenyl)-4 pyridyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(4-methylphenyl-4- pyridyl)hydroxymethyL] -isoxazole
3-(4-?er?-Butylphenyl)-5-(3-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(4-isopropoxyphenyl)-4-[(3- pyridyl)hydro ymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(4-butoxyoxyphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(4-phenoxyphenyl)-4-[(3- pyridyl)hydro ymetliyl] -isoxazole
3 -(4-Chlorophenyl)-5 -(5-methyl-3 -thienyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
Figure imgf000096_0001
3-(2,4-Dichlorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(2-Chlorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5 -(4-Chlorophenyl)-3 -(4-fluorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
5 -(2-Chlorophenyl)-3 -(4-fluorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
3 -(4-Chlorophenyl)-5 -(4-chlorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
3 -(4-Chlorophenyl)-5 -(2-chlorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
3-(4-Fluorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(3- thienyl)isoxazole
5-(4-Chlorophenyl)-3-(5-chloro-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
Figure imgf000097_0001
5-(3-Chlorophenyl)-3-(5-chloro-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(5-Chloro-2-thienyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3 -thienyl)isoxazole
5-(4-Chlorophenyl)-3-(5-chloro-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(3 -Chlorophenyl)-3 -(5-chloro-3 -thienyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(2,5-dichloro-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(4-Chlorophenyl)-3-(2,5-dichloro-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(3,5-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3 -(5 -Chloro-2-thienyl)-5 -(3 ,5 -difluorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(3-chlorophenyl)-4-[(5- pyrimidinyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(5-chloro-2-thienyl)-4-[(5- pyrimidinyl)hydroxymethyl] -isoxazole
Figure imgf000098_0001
3-(5-Bromo-2-thienyl)-5-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(5-Bromo-2-thienyl)-5-(3-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole
3 -(2-Chlorophenyl)-5 -(4-chlorophenyl)-4-[(3 - pyridyl)hydroxymetliyL] -isoxazole
3 -(2-Chloropheny l)-5 -(3 -chlorophenyl)-4-[(3 - pyridyl)hydroxymethyl]-isoxazole
3 -(3 -Chlorophenyl)-5 -(4-chlorophenyl)-4-[(3 - pyridyl)hydroxymetliyL] -isoxazole
3 -(3 -Chlorophenyl)-5 -(3 -chlorophenyl)-4-[(3 - pyridyl)hydroxymethyl]-isoxazole
5-(4-Butylphenyl)-3-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymetliyL] -isoxazole
3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(2- thienyl)isoxazole
5-(3-Clilorophenyl)-4-[(3-pyridyL)liydroxymethyl]-3-(4- trifluorophenyl)isoxazole
5-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluorophenyl)isoxazole
Figure imgf000099_0001
5-(3-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(3-Chlorophenyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(4-Chlorophenyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(5-chloro-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3 -(5 -Chloro-2-thienyl)-5 -(5-chloro-2-thienyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole
5-(4-Chlorophenyl)-3-(3,5-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(5-methyl-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(2,4-Difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-thienyl)isoxazole
5-(5-Chloro-2-thienyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(2,4-Difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3 -thienyl)isoxazole
Figure imgf000100_0001
3 -(2 ,4 -Difluorophenyl) -5 -(4 - fluorophenyl)-4 - [(3 - pyridyl)hydroxymethyl]-isoxazoLe
3-(4-Chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
3-(5-Chloro-2-thienyl)-5-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(2,4-Difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3- (3 -thienyl)isoxazole
5-(5-Bromo-2-thienyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(5-Bromo-2-thienyl)-3-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymetliyl] -isoxazole
5-(4-Chlorophenyl)-3-(2-fluorophenyl)-4-[(3- pyridy l)hy dro xy met hy L] - i so xazo le
5-(3,5-Diflorophenyl)-3-(2-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
5-(5-Chloro-2-thienyl)-3-(2-fluorophenyl)-4-[(3- pyridyl)hydroxymethyL] -isoxazole
5-(5-Bromo-2-thienyl)-3-(2-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole
Figure imgf000101_0001
3-(2-Fluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(2- thienyl)isoxazole
3-(2-Fluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(3- thienyl)isoxazole
3-(2-Fluoro-4-Chlorophenyl)-5-(2,4-difluorophenyl)-4- [(3 -pyrimidyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3- pyrimidyl)hydroxymethyl] -isoxazole
3-(2-Fluoro-4-Chlorophenyl)-5-(2,4-difluorophenyl)-4- [(3 -pyridyl)hydroxymethyl] -isoxazole
3-(2,4-Chlorophenyl)-5-(2-Chlorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl] -isoxazole
3-(2-Fluoro-4-Chlorophenyl)-5-(2-Chlorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl] -isoxazole
3 -(4-Chlorophenyl)-5 -(2-Methoxypyridine)- 4-[(3 - pyrimidyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(4-Fluorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl] -isoxazole
3-(4-Chlorophenyl)-5-(2,4-Fluorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl] -isoxazole
Figure imgf000102_0001
3-(2,4-Diluoro)-5-(2-Chloro-4-Fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole
(5)-3-(2-Fluoro-4-Chlorophenyl)-5-(2,4-difluorophenyl)- 4-[(3-pyridyl)hydroxymethyl] -isoxazole
Figure imgf000103_0001
Further Biological examples: This fungicidal properties of compound (S)-(146) were demonstrated in the following examples.
Botrytis cinerea (Gray mould): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours. Compound (5)-(146) gave at least 80% control of Botrytis cinerea at 200 ppm.
Mycosphaerella arachidis (syn. Cercospora arachidicola), Brown leaf spot of groundnut (peanut): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours at 620nm. Compound (S)-(146) gave at least 80% control of Mycosphaerella arachidis at 200 ppm.
Septoria tritici (leaf blotch): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours. Compound (5)-(146) gave at least 80% control of Septoria tritici at 200 ppm.
Monographella nivalis (syn. Microdochium nivale, Fusarium nivale), snow mould, foot rot of cereals: Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 72 hours at 620nm. Compound (S)-(146) gave at least 80% control of Monographella nivalis at 200 ppm.
Fusarium culmorum (root rot): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 48 hours. Compound (5)-(146) gave at least 80%> control of Fusarium culmorum at 200 ppm.
Rhizoctonia solani (foot rot, damping -off): Mycelial fragments of the fungus, prepared from a fresh liquid culture, were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal mycelium was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically after 48h. Compound (S)-(146) gave at least 80%> control of Rhizoctonia solani at 200 ppm.

Claims

Claims
1. A composition suitable for control of diseases caused by phytopathogens comprising (A) a compound of formula I
Figure imgf000105_0001
wherein:
Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;
R2 is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;
R3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano, nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro; or alkylsilyl; and
R4 is H or acyl; and (B) at least one compound selected from the group consisting of
(Bl) a strobilurin fungicide,
(B2) an azole fungicide, (B3) a morpholine fungicide,
(B4) an anilinopyrimidine fungicide,
(B5) a fungicide selected from the group consisting of
anilazine, arsenates, benalaxyl, benalaxyl-M, benodanil, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, biphenyl, bitertanol, blasticidin-S, bordeaux mixture, boscalid, bupirimate, cadmium chloride, captafol, captan, carbendazim, carbon disulfide, carboxin, carpropamid, cedar leaf oil, chinomethionat, chlorine, chloroneb, chlorothalonil, chlozolinate, cinnamaldehyde, copper, copper ammoniumcarbonate, copper hydroxide, copper octanoate, copper oleate, copper sulphate, cyazofamid, cycloheximide, cymoxanil, dichlofluanid, dichlone, dichloropropene, diclocymet, diclomezine, dicloran, diethofencarb, diflumetorim, dimethirimol, dimethomorph, dinocap, dithianon, dodine, edifenphos, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenaminosulf, fenamiphos, fenarimol, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flusulfamide, flusulfamide, flutolanil, folpet,
formaldehyde, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furametpyr, flyodin, fuazatine, hexachlorobenzene, hymexazole, iminoctadine, iodocarb, iprobenfos, iprodione, iprovalicarb, isoprothiolane, kasugamycin, mancozeb, maneb, manganous
dimethyldithiocarbamate, mefenoxam, mepronil, mercuric chloride, mercury, metalaxyl, methasulfocarb, metiram, metrafenone, nabam, neem oil (hydrophobic extract), nuarimol, octhilinone, ofurace, oxadixyl, oxine copper, oxolinic acid, oxycarboxin, oxytetracycline, paclobutrazole, paraffin oil, paraformaldehyde, pencycuron, pentachloronitrobenzene, pentachlorophenol, penthiopyrad, perfurazoate, phosphoric acid, polyoxin, polyoxin D zinc salt, potassium bicarbonate, probenazole, procymidone, propamocarb, propineb, proquinazid, prothiocarb, pyrazophos, pyrifenox, pyroquilon, quinoxyfen, quintozene, silthiofam, sodium bicarbonate, sodium diacetate, sodium propionate, streptomycin, sulphur, TCMTB, tecloftalam, tecnazene, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tolclofos-methyl, tolyfluanid, triazoxide, trichoderma harzianum, tricyclazole, triforine, triphenyltin hydroxide, validamycin, vinclozolin, zineb, ziram, zoxamide, l,l-bis(4- chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-JV- 1-naphthylacetamide, 4-chlorophenyl phenyl sulfone, a compound of formula B-5.1
Figure imgf000107_0001
a compound of formula B-5.2
Figure imgf000107_0002
a compound of formula B-5.
Figure imgf000107_0003
a compound of formula B-5.4
Figure imgf000107_0004
a compound of formula B-5.5
Figure imgf000107_0005
a compound of formula B-5.6
Figure imgf000108_0001
a compound of formula B-5
Figure imgf000108_0002
3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid (2-bicyclopropyl-2-yl-phenyl)- amide (compound B-5.8), 3-difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid (9- isopropyp-l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide (compound B-5.9), 1,3- dimethyl-5-fluoro-lH-pyrazole-4-carboxylic acid [2-(l,3-dimethylbutyl)phenyl]-amide (compound B-5.10), 3-difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid (3',4'- dichloro-5-fluoro-l,l'-biphenyl-2-yl)-amide (compound B-5.11), N-{2-[3-chloro-5- (trifluoromethyl)pyridin-2-yl]ethyl } -2-(trifluoromethyl)benzamid (compound B-5.12), 3 - difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid N-[2-( 1 , 1 ,2,2- tetrafluoroethoxy)phenyl] -amide (compound B-5.13), 3 -difluoromethyl-1 -methyl- 1H- pyrazole-4-carboxylic acid N-[2-(l,l,2,3,3,3-hexafluoropropoxy)phenyl]-amide (compound B-5.14), 3-difluoromethyl-l -methyl- 1 H-pyrazole-4-carboxylic acid N-[2-(2-chloro- 1,1,2- trifluoroethoxy)phenyl]-amide (compound B-5.15), 3-difluoromethyl-l-methyl-lH-pyrazole-
4- carboxylic acid N-(4'-trifluoromethyl-biphen-2-yl)-amide (compound B-5.16), 3- difiuoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid N-(2'-trifluoromethyl-biphen-2-yl)- amide (compound B-5.17) and 3-difluoromethyl-l -methyl- lH-pyrazole-4-carboxylic acid N- (2'-trifluoromethyl-biphen-2-yl)-amide (compound B-5.18); (B6) a plant-bioregulator selected from the group consisting of acibenzolar-S-methyl, chlormequat chloride, ethephon, mepiquat chloride and trinexapc- ethyl;
(B7) an insecticide selected from the group consisting of
abamectin, clothianidin, emamectin benzoate, imidacloprid, tefluthrin, thiamethoxam, and a compound of formula IV
Figure imgf000109_0001
wherein X is a bivalent roup selected from
Figure imgf000109_0002
wherein a) Rj is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is bromine, R3 is methyl, Rt is CN and X is Xi;
b) Ri is methyl substituted by cyclopropyl, R2 is CF3, R3 is methyl, R4 is CI and X is Xi; c) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is CF3, R3 is methyl, R4 is Cl and X is Xi;
d) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is CF3, R3 is methyl, R4 is CN and X is Xi;
e) Ri is cyclopropyl substituted by cyclopropyl at the 1 -position, R2 is OCH2CF3, R3 is methyl, R4 is CN and X is Xi;
f) Ri is isopropyl, R2 is methoxy; R3 is methyl, R4 is hydrogen and X is Xg ;
g) R] is isopropyl, R2 is trifluoromethyl, R3 is chlorine, R4 is hydrogen and X is X8;
h) R\ is isopropyl, R2 is trifluoromethyl, R3 is methyl, R4 is hydrogen and X is X8;
i) Ri is methyl, R2 is bromine, R3 is methyl, R4 is CN and X is Xi ;
j) Ri is methyl, R2 is bromine, R3 is methyl, R4 is CI and X is Xr,
and (B8) glyphosate, a compound of formula V
Figure imgf000110_0001
fomesafen, and (B9) Isopyrazam, Sedaxane, l-[4-[4-[5-(2,6-Difluorophenyl)-4,5-dihydro-l oxazol-3-yl]-l ,3-thiazol-2-yl]piperidin- 1 -yl]-2-[5-methyl-3-(trifluoromethyl)- 1 H-pyrazol-1 yl]ethanone,
a compound of formula (Via)
(Via),
Figure imgf000110_0002
, a compound of formula VIb) (Fluxapyroxad)
Figure imgf000111_0001
a compound of formula (Vic) which is 3-(difluoromethyl)-N-methoxy-l-methyl-N-[l-methyl- 2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide; a compound of formula (VId) which is 3-Difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid methoxy-[ 1 -methyl-2- (2,4,5-trichloro-thiophen-3-yl)-ethyl]-amide a compound of formula (VII)
Figure imgf000111_0002
And/or (B) a compound selected from the group consisting of
(Bl) a strobilurin fungicide, (B2) an azole fungicide, (B3) a morpholine fungicide, (B4) an anilinopyrimidine fungicide, (B5) a fungicide selected from the group consisting of anilazine (878), arsenates, benalaxyl (56), benalaxyl-M, benodanil (896), benomyl (62), benthiavalicarb, benthiavalicarb-isopropyl (68), biphenyl (81), bitertanol (84), blasticidin-S (85), bordeaux mixture (87), boscalid (88), bupirimate (98), cadmium chloride, captafol (1 13), captan (1 14), carbendazim (1 16), carbon disulfide (945), carboxin (120), carpropamid (122), cedar leaf oil, chinomethionat (126), chlorine, chloroneb (139), chlorothalonil (142), chlozolinate (149), cinnamaldehyde, copper, copper ammoniumcarbonate, copper hydroxide (169), copper octanoate (170), copper oleate, copper sulphate (87), cyazofamid (185), cycloheximide (1022), cymoxanil (200), dichlofluanid (230), dichlone (1052),
dichloropropene (233), diclocymet (237), diclomezine (239), dicloran (240), diethofencarb (245), diflumetorim (253), dimethirimol (1082), dimethomorph (263), dinocap (270), dithianon (279), dodine (289), edifenphos (290), ethaboxam (304), ethirimol (1 133), etridiazole (321), famoxadone (322), fenamidone (325), fenaminosulf (1144), fenamiphos (326), fenarimol (327), fenfuram (333), fenhexamid (334), fenoxanil (338), fenpiclonil (341), fentin acetate (347), fentin chloride, fentin hydroxide (347), ferbam (350), ferimzone (351), fluazinam (363), fludioxonil (368), flusulfamide (394), flutolanil (396), folpet (400), formaldehyde (404), fosetyl-aluminium (407), fthalide (643), Albendazole (419), furalaxyl (410), furametpyr (411), flyodin (1205), fuazatine (422), hexachlorobenzene (434), hymexazole, iminoctadine (459), iodocarb (3-Iodo-2-propynyl butyl carbamate), iprobenfos (IBP) (469), iprodione (470), iprovalicarb (471), isoprothiolane (474), kasugamycin (483), mancozeb (496), maneb (497), manganous dimethyldithiocarbamate, mefenoxam (Metalaxyl- M) (517), mepronil (510), mercuric chloride (511), mercury, metalaxyl (516), methasulfocarb (528), metiram (546), metrafenone, nabam (566), neem oil (hydrophobic extract), nuarimol (587), octhilinone (590), ofurace (592), oxadixyl (601), oxine copper (605), oxolinic acid (606), oxycarboxin (608), oxytetracycline (611), paclobutrazole (612), paraffin oil (628), paraformaldehyde, pencycuron (620), pentachloronitrobenzene (716), pentachlorophenol (623), penthiopyrad, perfurazoate, phosphoric acid, polyoxin (654), polyoxin D zinc salt (654), potassium bicarbonate, probenazole (658), procymidone (660), propamocarb (668), propineb (676), proquinazid (682), prothiocarb (1361), pyrazophos (693), pyrifenox (703), pyroquilon (710), quinoxyfen (715), quintozene (PCNB) (716), silthiofam (729), sodium bicarbonate, sodium diacetate, sodium propionate, streptomycin (744), sulphur (754), TCMTB, tecloftalam, tecnazene (TCNB) (767), thiabendazole (790), thifluzamide (796), thiophanate (1435), thiophanate-methyl (802), thiram (804), tolclofos-methyl (808), tolylfluanid (810), triazoxide (821), trichoderma harzianum (825), tricyclazole (828), triforine (838), triphenyltin hydroxide (347), validamycin (846), vinclozolin (849), zineb (855), ziram (856), zoxamide (857), l,l-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC-Name) (910), 2,4- dichlorophenyl benzenesulfonate (IUPAC- / Chemical Abstracts-Name) (1059), 2-fluoro-JV- methyl-N-l-naphthylacetamide (IUPAC-Name) (1295), 4-chlorophenyl phenyl sulfone
(IUPAC-Name) (981),
a compound of formula -5.1
Figure imgf000113_0001
a compound of formula B-5.2
Figure imgf000113_0002
a compound of formula B-5.4
Figure imgf000113_0003
a compound of formula B-5.5
(B-5.5),
Figure imgf000113_0004
a compound of formula B-
Figure imgf000114_0001
a compound of formula B-5
Figure imgf000114_0002
3-difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid (2-bicyclopropyl-2-yl-phenyl)- amide (compound B-5.8), 3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid (9- isopropyp-l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide (compound B-5.9), 1,3- dimethyl-5-fluoro-lH-pyrazole-4-carboxylic acid [2-(l ,3-dimethylbutyl)phenyl]-amide (compound B-5.10), 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid (3',4'- dichloro-5-fluoro-l,l '-biphenyl-2-yl)-amide (compound B-5.1 1), N-{2-[3-chloro-5-
(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamid (compound B-5.12), 3- difluoromethyl- 1 -methyl- 1 H-pyrazole-4-carboxylic acid N-[2-(l , 1 ,2,2- tetrafluoroethoxy)phenyl]-amide (compound B-5.13), 3-difluoromethyl- 1 -methyl- 1H- pyrazole-4-carboxylic acid N-[2-(l,l,2,3,3,3-hexafluoropropoxy)phenyl]-amide (compound B-5.14), 3 -difluoromethyl-1 -methyl- 1 H-pyrazole-4-carboxylic acid N-[2-(2-chloro-l,l,2- trifluoroethoxy)phenyl]-amide (compound B-5.15), 3 -difluoromethyl-1 -methyl- lH-pyrazole- 4-carboxylic acid N-(4'-trifluoromethyl-biphen-2-yl)-amide (compound B-5.16), 3- difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid N-(2'-trifluoromethyl-biphen-2-yl)- amide (compound B-5.17) and 3-difluoromethyl- 1 -methyl- lH-pyrazole-4-carboxylic acid N- (2'-trifluoromethyl-biphen-2-yl)-amide (compound B-5.18); (B6) a plant-bioregulator selected from the group consisting of
acibenzolar-S-methyl (6), chlormequat chloride (137), ethephon (307), mepiquat chloride (509) and trinexapc-ethyl (841);
(B7) an insecticide selected from the group consisting of
abamectin (1), clothianidin (165), emamectin benzoate (291), imidacloprid (458), tefluthrin (769), thiamethoxam (792), a compound of formula B-7.1
and a compound of formul
Figure imgf000115_0001
and (B8) glyphosate (419); and (C) at least one further compound selected from the compounds (B) provided that none of the compounds are the same.
2. A composition suitable for control of diseases caused by phytopathogens according to claim 1 wherein Rj is phenyl optionally substituted with halogen, Ci-C6-alkyl, CrCe-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-Ce-alkoxy, C|-C6-alkylthio, Ci-Ce-haloalkoxy, phenoxy, methoxypropargyl, cyano, or nitro; or furanyl, thienyl, pyridyl, or benzothienyl, each optionally substituted with halogen.
3. A composition suitable for control of diseases caused by phytopathogens according to claim 2 wherein Ri is 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 4-trifluoro-methylphenyl, 4-trifluoromethoxyphenyl, 2-fluoro-4-chlorophenyl or 2-thienyl.
4. A composition suitable for control of diseases caused by phytopathogens according to any one of claims 1 or 3 wherein R2 is pyridyl, pyrimidinyl or isoquinolyl, each optionally substituted with halogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce-haloalkyl, Ci-C6- alkoxy, d-Ce-alkylthio, Ci-C6-haloalkoxy, cyano, or nitro.
5. A composition suitable for control of diseases caused by phytopathogens according to claim 1 to 4 wherein R2 is 3-pyridyl, 4-pyridyl, or 5-pyrimidinyl, each optionally substituted with methyl, chloro, fiuoro, methoxy, thiomethoxy or trifluoromethyl 6. A composition suitable for control of diseases caused by phytopathogens according to claim 1 to 5 wherein R3 is phenyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 3,5- difluorophenyl, 4-methylphenyl, 2,4-difluorophenyl, 2-thienyl, 5-chloro-2-thienyl, 5-methyl-
2- thienyl, 3-thienyl, or trimethylsilyl.
7. A composition suitable for control of diseases caused by phytopathogens according to claims 1 to 6 wherein R4 is H.
8. A composition suitable for control of diseases caused by phytopathogens according to claim 1 wherein the compound of formula (I) is selected from:
3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]- isoxazole;
3- (4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole; 3 -(2 ,4-chloropheny l)-5 -(2-chloropheny l)-4- [(3 -pyrimidyl)hydroxymethy I] -isoxazo le ;
3-(2-fluoro-4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole; 3-(4-chlorophenyl)-5-(2-memoxypyridine)-4-[(3-pyrimidyl)hyckoxymethyl]-i
3-(4-chlorophenyl)-5-(4-fluorophenyl)-4-[(3-pyrimidyl)hydroxyrnethyl]-isoxazole;
3-(4-chlorophenyl)-5-(2,4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(2,4-difluorophenyl)-5-(2-cWoro-4-fluorophenyl)-4-[(3pyridyl)hydroxymethyl]-isoxazole; and
(5)-3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole;
and salts thereof.
9. A composition suitable for control of diseases caused by phytopathogens according to claim 1 wherein the compound of formula (I) is selected from:
3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]- isoxazole;
3-(4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole;
3-(2,4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(2-fluoro-4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(4-chlorophenyl)-5-(2-methoxypyridine)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(4-chlorophenyl)-5-(4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(4-chlorophenyl)-5-(2,4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;
3-(2,4-difluorophenyl)-5-(2-chloro-4-fluorophenyl)-4-[(3pyridyl)hydroxymethyl]-isoxazole; and
(-S)-3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole;
and salts thereof.
10. A method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a mixtures as defined in any one of claims 1 to 9.
1 1. A method according to claim 10, which comprises one or more applications of one of more compounds of formula (I) alone or in conjunction with one or more customary plant protection formulating auxiliaries.
12. A method according to claim 10 wherein two or more applications are carried out in sequence, and wherein the two or more applications have the same or different concentration or combinations of mixtures as defined in any one of claims 1 to 9 or both.
13. A method according to any one of claims 10 to 12 wherein the useful crop plants are selected from the group consting of cereals, rice, beets, leguminous plants, oil plants, cucumber plants, fibre plants, vegetables, plantation crops, ornamentals, vines, bushberries, caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses.
14. An agricultural composition comprising mixtures as defined in any one of claims 1 to 9, and one or more customary plant protection auxiliaries.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017121810A1 (en) * 2016-01-13 2017-07-20 Bayer Cropscience Aktiengesellschaft Use of active substances for controlling virus infection in plants
US10130095B2 (en) 2014-02-19 2018-11-20 BASF Agro B.V. Fungicidal compositions of pyrazolecarboxylic acid alkoxyamides
CN111518702A (en) * 2020-04-17 2020-08-11 南京农业大学 Helminthosporium umbilicalis strain, screening and identifying method and application thereof

Citations (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0353191A2 (en) 1988-07-29 1990-01-31 Ciba-Geigy Ag DNA sequences encoding polypeptides having beta-1,3-glucanase activity
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0392225A2 (en) 1989-03-24 1990-10-17 Ciba-Geigy Ag Disease-resistant transgenic plants
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995033818A2 (en) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes for the synthesis of antipathogenic substances
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO1996019442A1 (en) 1994-12-19 1996-06-27 Nippon Soda Co., Ltd. Benzamidoxime derivative, process for production thereof, and agrohorticultural bactericide
CN1155977A (en) 1995-08-28 1997-08-06 化学工业部沈阳化工研究院 Acrylamide germicide containing fluoro-diphenyl
CN1167568A (en) 1995-08-28 1997-12-17 化学工业部沈阳化工研究院 Fungicide contg. fluorodiphenyl acrylamides
EP0860438A1 (en) 1997-02-21 1998-08-26 Shenyang Research Institute of Chemical Industry Fluorine-containing diphenyl acrylamide antimicrobial agents
WO1998046607A1 (en) 1997-04-14 1998-10-22 American Cyanamid Company Fungicidal trifluorophenyl-triazolopyrimidines
WO1999014187A1 (en) 1997-09-18 1999-03-25 Basf Aktiengesellschaft Benzamidoxim derivatives, intermediate products and methods for preparing and using them as fungicides
EP0936213A1 (en) 1998-02-10 1999-08-18 Rohm And Haas Company Unsaturated oxime ethers and their use as fungicides and insecticides
WO1999042447A1 (en) 1998-02-19 1999-08-26 Aventis Cropscience Uk Limited 2-pyridylmethylamine derivatives useful as fungicides
US6020332A (en) 1997-02-20 2000-02-01 Shenyang Research Institute Of Chemical Industry Fluorine-containing diphenyl acrylamide antimicrobial agents
WO2001087822A1 (en) 2000-05-17 2001-11-22 Syngenta Participations Ag Novel phenyl-propargylether derivatives
WO2001094339A1 (en) 2000-06-09 2001-12-13 Syngenta Participations Ag Substituted pyridine herbicides
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003010149A1 (en) 2001-07-25 2003-02-06 Bayer Cropscience Ag Pyrazolylcarboxanilides as fungicides
WO2003015519A1 (en) 2001-08-13 2003-02-27 E.I. Du Pont De Nemours And Company Arthropodicidal anthranilamides
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2003070705A1 (en) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Disubstituted pyrazolyl carboxanilides
WO2003074491A1 (en) 2002-03-05 2003-09-12 Syngenta Participations Ag O-cyclopropyl-carboxanilides and their use as fungicides
WO2004016088A2 (en) 2002-08-12 2004-02-26 Bayer Cropscience S.A. Novel 2-pyridylethylbenzamide derivative
WO2004035589A1 (en) 2002-10-18 2004-04-29 Syngenta Participations Ag Heterocyclocarboxamide derivatives
WO2004067528A1 (en) 2003-01-28 2004-08-12 E.I. Du Pont De Nemours And Company Cyano anthranilamide insecticides
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2005085234A2 (en) 2004-03-03 2005-09-15 Syngenta Participations Ag Bycyclic anthranilamide derivatives useful as insecticides
WO2005097760A1 (en) 2004-03-26 2005-10-20 Rigel Pharmaceuticals, Inc. Heterocyclic anti-viral compounds comprising metabolizable moieties and their uses
WO2006031631A1 (en) 2004-09-10 2006-03-23 Syngenta Limited Substituted isoxazoles as fungicides
WO2006037632A1 (en) 2004-10-08 2006-04-13 Syngenta Participations Ag Synergistic fungicidal compositions
WO2006040113A2 (en) 2004-10-11 2006-04-20 Syngenta Participations Ag Heterocyclic diamide insecticidal agents
WO2006087343A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Pyrazole carboxylic acid anilides, method for the production thereof and agents containing them for controlling pathogenic fungi
WO2006111341A1 (en) 2005-04-20 2006-10-26 Syngenta Participations Ag Cyano anthranilamide insecticides
WO2006120219A1 (en) 2005-05-11 2006-11-16 Basf Aktiengesellschaft Pyrazolocarboxamides as fungicides
WO2007017450A1 (en) 2005-08-05 2007-02-15 Basf Se Fungicidal n-[2-(haloalkoxy)phenyl]heteroarylcarboxamides
WO2007020050A2 (en) 2005-08-15 2007-02-22 Syngenta Participations Ag Bicyclic bisamide derivatives and use thereof as insecticides
WO2007048556A1 (en) 2005-10-25 2007-05-03 Syngenta Participations Ag Heterocyclic amide derivatives useful as microbiocides
WO2007075459A2 (en) 2005-12-16 2007-07-05 E. I. Du Pont De Nemours And Company 5-aryl isoxazolines for controlling invertebrate pests
WO2007093402A1 (en) 2006-02-16 2007-08-23 Syngenta Participations Ag Pesticides containing a bicyclic bisamide structure
WO2007131678A1 (en) * 2006-05-16 2007-11-22 Bayer Cropscience Ag Fungicidal active substance combinations
WO2008013622A2 (en) 2006-07-27 2008-01-31 E. I. Du Pont De Nemours And Company Fungicidal azocyclic amides
WO2008014870A1 (en) 2006-08-02 2008-02-07 A. Raymond Et Cie Device for securing a camera to a carrier
WO2008148859A2 (en) * 2007-06-06 2008-12-11 Basf Se Fungicidal mixtures
WO2008148570A1 (en) 2007-06-08 2008-12-11 Syngenta Participations Ag Pyrazole carboxylic acid amides useful as microbiocides
WO2009007344A1 (en) 2007-07-12 2009-01-15 Basf Se Novel crystalline form of 3-(difluormethyl)-1-methyl-n -(3',4',5'-trifluor[1,1'-biphenyl]-2-yl)-1h-pyrazol-4-carboxamide
WO2010063700A2 (en) 2008-12-05 2010-06-10 Syngenta Participations Ag Novel microbiocides
WO2010069882A1 (en) 2008-12-17 2010-06-24 Syngenta Participations Ag Isoxazole derivatives for use as fungicides
WO2010123791A1 (en) 2009-04-22 2010-10-28 E. I. Du Pont De Nemours And Company Solid forms of an azocyclic amide
CN101946775A (en) * 2010-09-03 2011-01-19 江苏七洲绿色化工股份有限公司 Sterilization compound containing triazole fungicide and azoxystrobin
WO2011051243A1 (en) 2009-10-29 2011-05-05 Bayer Cropscience Ag Active compound combinations
WO2011104089A1 (en) 2010-02-25 2011-09-01 Syngenta Participations Ag Process for the preparation of isoxazoline derivatives

Patent Citations (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0353191A2 (en) 1988-07-29 1990-01-31 Ciba-Geigy Ag DNA sequences encoding polypeptides having beta-1,3-glucanase activity
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0392225A2 (en) 1989-03-24 1990-10-17 Ciba-Geigy Ag Disease-resistant transgenic plants
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995033818A2 (en) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes for the synthesis of antipathogenic substances
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO1996019442A1 (en) 1994-12-19 1996-06-27 Nippon Soda Co., Ltd. Benzamidoxime derivative, process for production thereof, and agrohorticultural bactericide
CN1155977A (en) 1995-08-28 1997-08-06 化学工业部沈阳化工研究院 Acrylamide germicide containing fluoro-diphenyl
CN1167568A (en) 1995-08-28 1997-12-17 化学工业部沈阳化工研究院 Fungicide contg. fluorodiphenyl acrylamides
US6020332A (en) 1997-02-20 2000-02-01 Shenyang Research Institute Of Chemical Industry Fluorine-containing diphenyl acrylamide antimicrobial agents
EP0860438A1 (en) 1997-02-21 1998-08-26 Shenyang Research Institute of Chemical Industry Fluorine-containing diphenyl acrylamide antimicrobial agents
WO1998046607A1 (en) 1997-04-14 1998-10-22 American Cyanamid Company Fungicidal trifluorophenyl-triazolopyrimidines
WO1999014187A1 (en) 1997-09-18 1999-03-25 Basf Aktiengesellschaft Benzamidoxim derivatives, intermediate products and methods for preparing and using them as fungicides
EP0936213A1 (en) 1998-02-10 1999-08-18 Rohm And Haas Company Unsaturated oxime ethers and their use as fungicides and insecticides
WO1999042447A1 (en) 1998-02-19 1999-08-26 Aventis Cropscience Uk Limited 2-pyridylmethylamine derivatives useful as fungicides
WO2001087822A1 (en) 2000-05-17 2001-11-22 Syngenta Participations Ag Novel phenyl-propargylether derivatives
WO2001094339A1 (en) 2000-06-09 2001-12-13 Syngenta Participations Ag Substituted pyridine herbicides
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003010149A1 (en) 2001-07-25 2003-02-06 Bayer Cropscience Ag Pyrazolylcarboxanilides as fungicides
WO2003015519A1 (en) 2001-08-13 2003-02-27 E.I. Du Pont De Nemours And Company Arthropodicidal anthranilamides
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2003070705A1 (en) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Disubstituted pyrazolyl carboxanilides
WO2003074491A1 (en) 2002-03-05 2003-09-12 Syngenta Participations Ag O-cyclopropyl-carboxanilides and their use as fungicides
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2004016088A2 (en) 2002-08-12 2004-02-26 Bayer Cropscience S.A. Novel 2-pyridylethylbenzamide derivative
WO2004035589A1 (en) 2002-10-18 2004-04-29 Syngenta Participations Ag Heterocyclocarboxamide derivatives
EP1556385B1 (en) 2002-10-18 2010-03-10 Syngenta Participations AG Heterocyclocarboxamide derivatives
WO2004067528A1 (en) 2003-01-28 2004-08-12 E.I. Du Pont De Nemours And Company Cyano anthranilamide insecticides
WO2005085234A2 (en) 2004-03-03 2005-09-15 Syngenta Participations Ag Bycyclic anthranilamide derivatives useful as insecticides
WO2005097760A1 (en) 2004-03-26 2005-10-20 Rigel Pharmaceuticals, Inc. Heterocyclic anti-viral compounds comprising metabolizable moieties and their uses
WO2006031631A1 (en) 2004-09-10 2006-03-23 Syngenta Limited Substituted isoxazoles as fungicides
WO2006037632A1 (en) 2004-10-08 2006-04-13 Syngenta Participations Ag Synergistic fungicidal compositions
WO2006040113A2 (en) 2004-10-11 2006-04-20 Syngenta Participations Ag Heterocyclic diamide insecticidal agents
WO2006087343A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Pyrazole carboxylic acid anilides, method for the production thereof and agents containing them for controlling pathogenic fungi
WO2006111341A1 (en) 2005-04-20 2006-10-26 Syngenta Participations Ag Cyano anthranilamide insecticides
WO2006120219A1 (en) 2005-05-11 2006-11-16 Basf Aktiengesellschaft Pyrazolocarboxamides as fungicides
WO2007017450A1 (en) 2005-08-05 2007-02-15 Basf Se Fungicidal n-[2-(haloalkoxy)phenyl]heteroarylcarboxamides
WO2007020050A2 (en) 2005-08-15 2007-02-22 Syngenta Participations Ag Bicyclic bisamide derivatives and use thereof as insecticides
WO2007048556A1 (en) 2005-10-25 2007-05-03 Syngenta Participations Ag Heterocyclic amide derivatives useful as microbiocides
WO2007075459A2 (en) 2005-12-16 2007-07-05 E. I. Du Pont De Nemours And Company 5-aryl isoxazolines for controlling invertebrate pests
WO2007093402A1 (en) 2006-02-16 2007-08-23 Syngenta Participations Ag Pesticides containing a bicyclic bisamide structure
WO2007131678A1 (en) * 2006-05-16 2007-11-22 Bayer Cropscience Ag Fungicidal active substance combinations
WO2008013622A2 (en) 2006-07-27 2008-01-31 E. I. Du Pont De Nemours And Company Fungicidal azocyclic amides
WO2008013925A2 (en) 2006-07-27 2008-01-31 E. I. Du Pont De Nemours And Company Fungicidal azocyclic amides
WO2008014870A1 (en) 2006-08-02 2008-02-07 A. Raymond Et Cie Device for securing a camera to a carrier
WO2008148859A2 (en) * 2007-06-06 2008-12-11 Basf Se Fungicidal mixtures
WO2008148570A1 (en) 2007-06-08 2008-12-11 Syngenta Participations Ag Pyrazole carboxylic acid amides useful as microbiocides
WO2009007344A1 (en) 2007-07-12 2009-01-15 Basf Se Novel crystalline form of 3-(difluormethyl)-1-methyl-n -(3',4',5'-trifluor[1,1'-biphenyl]-2-yl)-1h-pyrazol-4-carboxamide
WO2010063700A2 (en) 2008-12-05 2010-06-10 Syngenta Participations Ag Novel microbiocides
WO2010069882A1 (en) 2008-12-17 2010-06-24 Syngenta Participations Ag Isoxazole derivatives for use as fungicides
WO2010069881A2 (en) 2008-12-17 2010-06-24 Syngenta Participations Ag Isoxazole derivatives for use as plant growth regulators
WO2010123791A1 (en) 2009-04-22 2010-10-28 E. I. Du Pont De Nemours And Company Solid forms of an azocyclic amide
WO2011051243A1 (en) 2009-10-29 2011-05-05 Bayer Cropscience Ag Active compound combinations
WO2011104089A1 (en) 2010-02-25 2011-09-01 Syngenta Participations Ag Process for the preparation of isoxazoline derivatives
CN101946775A (en) * 2010-09-03 2011-01-19 江苏七洲绿色化工股份有限公司 Sterilization compound containing triazole fungicide and azoxystrobin

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"The Pesticide Manual - A World Compendium", 2 November 2003, THE BRITISH CROP PROTECTION COUNCIL
"The Pesticide Manual - A World Compendium", THE BRITISH CROP PROTECTION COUNCIL
ANGELO ALBINI; SILVIO PIETRA: "Heterocyclic N-oxides", 1991, CRC PRESS
COLBY, S.R.: "Calculating synergistic and antagonistic responses of herbicide combination", WEEDS, vol. 15, 1967, pages 20 - 22, XP001112961
E. L. ELIEL; S. H. WILEN: "Stereochemistry of Organic Compounds", 1994, WILEY
G. KUMARAN; G. H. KULKARNI, J. ORG. CHEM., vol. 62, 1997, pages 1516
K.-C. LIU; B. R. SHELTON; R. K. HOWE, J. ORG. CHEM., vol. 45, 1980, pages 3916
LETTERS IN ORGANIC CHEMISTRY, vol. 4, 2007, pages 20

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10130095B2 (en) 2014-02-19 2018-11-20 BASF Agro B.V. Fungicidal compositions of pyrazolecarboxylic acid alkoxyamides
WO2017121810A1 (en) * 2016-01-13 2017-07-20 Bayer Cropscience Aktiengesellschaft Use of active substances for controlling virus infection in plants
CN108601354A (en) * 2016-01-13 2018-09-28 拜耳作物科学股份公司 Active material is used to prevent the purposes of plant virus infection
US10440952B2 (en) 2016-01-13 2019-10-15 Bayer Corp Science Aktiengesellschaft Use of active substances for controlling virus infection in plants
EA034908B1 (en) * 2016-01-13 2020-04-06 Байер Кропсайенс Акциенгезельшафт Use of active substances for controlling virus infection in plants
CN111518702A (en) * 2020-04-17 2020-08-11 南京农业大学 Helminthosporium umbilicalis strain, screening and identifying method and application thereof
CN111518702B (en) * 2020-04-17 2022-04-12 南京农业大学 Helminthosporium umbilicalis strain, screening and identifying method and application thereof

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