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WO2013011010A1 - Mélanges fongicides - Google Patents

Mélanges fongicides 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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WIPO (PCT)
Prior art keywords
compound
methyl
chlorophenyl
isoxazole
formula
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PCT/EP2012/063968
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English (en)
Inventor
Camilla Corsi
Carla Bobbio
Peter Schneiter
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Syngenta Participations AG
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Syngenta Participations AG
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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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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
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Abstract

La présente invention concerne une composition convenant à la lutte contre des maladies provoquées par des phytopathogènes. Cette composition comprend un composé (A) représenté par la formule (I), ou l'un de ses sels ou N-oxydes. Dans cette formule (I), les substituants sont conformes aux définitions qui en sont données dans la Revendication 1. La composition comprend également un composé (B) choisi dans le groupe de composés connus pour leur activité fongicide. La composition comprend enfin un dernier composé (C) choisi dans le groupe des composés (B), mais à condition que lesdits composés soient tous différents. L'invention concerne également un procédé de lutte contre des maladies affectant des plantes utiles.
PCT/EP2012/063968 2011-07-19 2012-07-17 Mélanges fongicides Ceased WO2013011010A1 (fr)

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WO2017121810A1 (fr) * 2016-01-13 2017-07-20 Bayer Cropscience Aktiengesellschaft Utilisation de principes actifs pour lutter contre une infection virale dans des plantes
US10130095B2 (en) 2014-02-19 2018-11-20 BASF Agro B.V. Fungicidal compositions of pyrazolecarboxylic acid alkoxyamides
CN111518702A (zh) * 2020-04-17 2020-08-11 南京农业大学 一种山田平脐蠕孢菌菌株、其筛选和鉴定方法及其用途
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