WO2016174042A1 - Pesticidal compositions - Google Patents

Pesticidal compositions Download PDF

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Publication number
WO2016174042A1
WO2016174042A1 PCT/EP2016/059309 EP2016059309W WO2016174042A1 WO 2016174042 A1 WO2016174042 A1 WO 2016174042A1 EP 2016059309 W EP2016059309 W EP 2016059309W WO 2016174042 A1 WO2016174042 A1 WO 2016174042A1
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WIPO (PCT)
Prior art keywords
compound
component
methyl
compositions
methoxy
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PCT/EP2016/059309
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French (fr)
Inventor
Markus Gewehr
Frederik Menges
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BASF Agro B.V.
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Publication of WO2016174042A1 publication Critical patent/WO2016174042A1/en

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Classifications

    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • compositions comprising,
  • component I a compound selected from the following compounds 1-1 to I-5:
  • compound 1-1 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol;
  • compound I-2 1 -[2-chloro-4-(4-chlorophenoxy)phenyl]-1-cyclopropyl-2-(1 ,2,4-triazol-1 - yl)ethanol;
  • compound I-3 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)propan-2- ol;
  • compound I-4 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1- yl)ethanol;
  • compound I-5 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1 ,2,4-triazol-1- yl)butan-2-ol;
  • component II a compound selected from the group of compounds 11-1 to II-25
  • compound II-2 [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 ,5- dioxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate, in particular [2- [[(3S,7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 ,5-dioxonan-3- yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate (ll-2a);
  • compound II-4 [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
  • compound II-6 [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
  • compound II-7 [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyri- dine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
  • compound II-9 N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl- pyrazole-4-carboxamide;
  • compound 11-12 methyl-N-[2-[(1 ,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N- methoxy-carbamate;
  • compound 11-13 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylidene-aminooxy-methyl)-phenyl)-2- methoxyimino-N methyl-acetamide;
  • compound 11-16 methyl (E)-2-[2-[[2-(2,4-dichloroanilino)-6-(trifluoromethyl)pyrimidin-4- yl]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (common name: Pyriminostrobin);
  • compound II-20 (Z)-N-allyloxy-1 -(2,4-dichlorophenyl)-2-imidazol-1 -yl-ethanimine (Chlor- phenomizole);
  • the invention furthermore relates to the use of the inventive compositions as pesticides in particular for controlling phytopathogenic fungi as detained herein and preparations or compositions comprising them.
  • the invention furthermore also relates to seed comprising the compositions.
  • the invention furthermore also relates to methods for controlling pests, in particular phytopathogenic fungi as detained herein, wherein the fungi or the materials, plants, the soil or seed to be protected from fungal attack are treated with an effective amount of a compositions according to the invention.
  • the invention furthermore also relates to processes for preparing the compositions according to the invention.
  • compositions which, at a reduced total amount of active compounds applied, show improved activity against important pests, in particular phythopathogenic fungi, in particular for certain indications. It was a further object to provide for compositions that are useful for the control of specific pathogens in specific important crops that are often susceptible to the attack of pathogens.
  • the compounds I (component I), its preparation and use in crop protection are described in WO 2013/007767 and WO 2013/010862, which also disclose certain compositions with other active compounds.
  • the compounds I (component I) can also be obtained by various routes in analogy to prior art processes known (cf. J. Agric. Food Chem. (2009) 57, 4854-4860; EP-A 0 275 955; DE-A 40 03 180; EP-A 0 1 13 640; EP-A 0 126 430).
  • the compounds 1-1 , I-2, I-3, I-4 and I-5 are capable of forming salts or adducts with inorganic or organic acids or with metal ions, in particular salts with inorganic acids.
  • Compounds 1-1 to I-5 used as component I in the inventive compositions are selected from the following fungicidal compounds:
  • compound 1-1 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol; compound I-2 1-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-cyclopropyl-2-(1 ,2,4-triazol-1- yl)ethanol;
  • Compounds 1-1 to I-5 comprise chiral centers and they are generally obtained in the form of racemates.
  • the R- and S-enantiomers of the compounds contained as component I in the compositions according to the invention can be separated and isolated in pure form with methods known by the skilled person, e.g. by using chiral HPLC. Suitable for use in the compositions are both the enantiomers and compositions thereof. Furthermore, said
  • components I can be present in different crystal modifications, which may differ in biological activity.
  • a racemic composition of the respective components I namely of compound 1-1 , I-2, I-3, I-4 or I-5, respectively, is present.
  • any other proportions of the (R)-enantiomer and the (S)-enantiomer of the respective compound 1-1 , I-2, I-3, I-4 or I-5, respectively, may be present according to the present invention.
  • the (R)- enantiomer of compound I-3 is (R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4- triazol-1 -yl)propan-2-ol;
  • the S-enantiomer of I-3 is (S)-2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol. This applies to the other compounds accordingly.
  • the respective compound 1-1 , I-2, I-3, I-4 or I-5, respectively is provided and used as (R)-enantiomer with 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%.
  • an enantiomeric excess e.e.
  • the respective compound 1-1 , I-2, I-3, I-4 or I-5, respectively is provided and used as (S)-enantiomer with 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%.
  • an enantiomeric excess e.e.
  • component I is compound 1-1 .
  • component I is compound I-2.
  • component I is compound I-3.
  • component I is compound I-4.
  • component I is compound I-5.
  • component I is selected from compounds 1-1 and I-2. According to a more particular embodiment of the present invention, component I is selected from compounds I-3, I-4 and I-5. According to still a further embodiment of the present invention, component I is selected from compounds I-3 and I-5.
  • Component II is preferably a compound selected from the group of compounds 11-1 to 11-10: compound 11-1 [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; compound 11-2 [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6- dioxo-1 ,5-dioxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate, in particular [2-[[(3S,7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 , 5- dioxonan-3-yl]carb
  • compound II-4 [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
  • compound II-7 [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4- methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; compound 11—8 N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-5-fluoro-1 ,3-dimethyl- pyrazole-4-carboxamide;
  • the compounds 11-1 to II-7 and their pesticidal action and possible uses thereof can be found in WO 2014/105842, WO 2015/005355, WO 2014/106259.
  • II-2 is described in WO 2014/105842 and WO 2014/106259.
  • the preparation, the pesticidal action and possible uses for compound II-8 can be found in WO 2012/143127, WO 2014/060502, WO 2014/060521 and WO
  • Compound -1 1 is known from CN-A 1456054.
  • Compound -12 is known from CN-A 103387541
  • Compound -13 is known from CN-A 1309897.
  • Compound -14 is known from CN-A 1907024.
  • Compound -15 is known from WO 95/07693.
  • Compound -16 is known from WO 2010/139271
  • Compound -17 is known from CN-A 1907024.
  • Coumpound II-20 is known from CN-A 1465562 and CN-A 1308294.
  • Compound -21 is known from WO 06/98128.
  • Compound -22 is known from WO 07/129454 and WO 2012/16551 1.
  • component II is selected from compounds 11-1 , II-2, II-3, II-4, II-5, II-6 and II-7.
  • component II is compound 11-1.
  • component II is compound II-2, in particular ll-2a
  • component II is compound ll-2a.
  • component is compound -3. According to sti II a further particular inventive embodiment, component is compound -4. According to sti II a further particular inventive embodiment, component is compound -5. According to sti II a further particular inventive embodiment, component is compound -6. According to sti II a further particular inventive embodiment, component is compound -7.
  • component II is compound 11—8.
  • component II is selected from compounds II-9 and 11-10.
  • component II is compound II-9.
  • component II is compound 11-10.
  • Compounds II-9 and 11-10 comprise chiral centers and they are generally obtained in the form of racemates.
  • the R- and S-enantiomers of the compounds contained as component II in the compositions according to the invention can be separated and isolated in pure form with methods known by the skilled person, e.g. by using chiral HPLC. Suitable for use in the compositions are both the enantiomers and compositions thereof. Furthermore, said
  • components II can be present in different crystal modifications, which may differ in biological activity.
  • a racemic composition of the respective components II namely of compound II-9 or 11-10, respectively, is present.
  • any other proportions of the (R)- enantiomer and the (S)-enantiomer of the respective compound II-9 or 11-10, respectively, may be present according to the present invention.
  • the respective compound II-9 or 11-10 is provided and used as (R)-enantiomer with 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%.
  • the respective compound II-9 or 11-10, respectively is provided and used as (S)-enantiomer with 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%.
  • inorganic acids examples include hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, carbonic acid, sulfuric acid, phosphoric acid and nitric acid.
  • Suitable organic acids are, for example, formic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid and other arylcarboxylic acids, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naph
  • Suitable metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminum, tin and lead, and also of the elements of transition groups one to eight, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, and others. Particular preference is given to the metal ions of the elements of transition groups of the fourth period.
  • the metals can be present in the various valencies that they can assume.
  • compositions and their preferred uses are further described.
  • the use of the composition for controlling a particular phytopathogenic fungus is also meant to encompass the respective method for controlling the particular phytopathogenic fungi, wherein the fungi or the materials, plants, the soil or seed to be protected from fungal attack are treated with an effective amount of a composition as defined in that particular context.
  • the present invention relates to two-component compositions, i.e. compositions comprising component I, i.e in particular a compound selected from compounds
  • I- 1 , I-2, I-3, I-4 and I-5 or any group of compounds I detailled above, and component II selected from compounds 11-1 , II-2 (in particular I l-2a), II-3, II-4, II-5, II-6, II-7, II-8, II-9, 11-10, 11-1 1 , 11-12,
  • compositions may, of course, contain any kind of additive or the like as detailled below in order to provide a formulation suitable for use in agriculture.
  • the weight ratio of component I to component II in the inventive compositions is preferably from 1000:1 to 1 :1000, more specifically 500:1 to 1 :500, particularly 100:1 to 1 :100.
  • the weight ratio of component I to component II generally depends from the properties of the active substances used and is usually in the range of from 1 :100 to 100:1 , frequently in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , particularly preferably in the range of from 1 :10 to 10:1 , in particular in the range of from 1 :3 to 3:1 . It may also be preferable for the weight ratio to be in the range of from 1 :2 to 2:1.
  • two-component compositions according to the invention may preferably have weight ratios of compound I versus compound II in the range of from 1000:1 to 1 :1 , often in the range of from 100:1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1 .
  • two-component compositions according to the invention may preferably have weight ratios of compound I versus compound II usually is in the range of from 1 :1 to 1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
  • compositions of the invention are compiled in Tables B1 , B2 and B3, wherein each row corresponds to one embodiment of the compositions according to the invention, i.e. one specific individualized composition. According to one specific aspect, these are binary compositions which each only contain these two components as active compounds. Furthermore, also every combination of the compositions individualized in this table represent embodiments of the present invention.
  • Table B1 Two-component compositions B1-1 to B1-35 comprising one component I and one component II selected from compounds 11-1 to II-7, in particular binary compositions containing the respective component I and II as only active ingredients:
  • composition II component II selected from compounds 11-1 to II-7 Composition I II Composition I II Composition I II
  • One embodiment of the invention relates to any one of compositions B1-1 to B1-40 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 100:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
  • One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
  • Table B2 Two-component compositions B2-1 to B5-5 comprising one component I and one component II being compound 11 8 , in particular binary compositions containing the respective component I and II as only active ingredients:
  • One embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 100:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
  • One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
  • Table B3 Two-component compositions B3-1 to B3-10 comprising one component I and one component II selected from compounds II-9 and 11-10, in particular binary compositions containing the respective component I and II as only active ingredients:
  • One embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 100:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
  • One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
  • Table B4 Two-component compositions B4-1 to B4-75 comprising one component I and one component II selected from compounds 11-1 1 to II-25, in particular binary compositions containing the respective component I and II as only active ingredients:
  • component II component II selected from compounds 11-1 1 to II-25
  • composition I II Composition I II Composition I II
  • One embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 100:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
  • One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
  • the present invention relates to pesticidal compositions comprising, 1 ) as component I a compound selected from the compounds 1-1 to I-5 and the N- oxides and the agriculturally acceptable salts of each of the compounds, as defined above; and 2) as component II a compound selected from compounds 11-1 to II-25 and the N-oxides and the agriculturally acceptable salts of each of the compounds, as defined above; and 3) as component III a further pesticidal compound.
  • mixtures and compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the
  • Zygomycetes Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the mixtures and compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • cereals e. g. wheat, rye, barley, triticale, oats or rice
  • beet e. g. sugar beet or fodder beet
  • fruits such as pomes, stone fruits or soft fruits, e. g.
  • inventive mixtures and compositions are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • treatment of plant propagation materials with the inventive combination of component I and component II and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g.
  • HPPD hydroxyphenyl- pyruvate dioxygenase
  • ALS acetolactate synthase
  • EP-A 242 236, EP-A 242 246) or oxynil herbicides see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
  • Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydro- xysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Cor- poration, Belgium (corn cultivars producing the Cryl F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amyivora).
  • PR proteins pathogenesis-related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato cultiv
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • inventive mixtures and compositions are particularly suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A brassicola or brassicae), sugar beets (A tenuis), fruits, rice, soybeans, potatoes (e. g. A solan/ or A.
  • Albugo spp. white rust
  • vegetables e. g. A. Candida
  • sunflowers e. g. A tragopogonis
  • Alternaria spp. Alternaria leaf spot
  • rape A brassicola or brassicae
  • sugar beets A tenuis
  • fruits rice, soybeans, potatoes (e. g. A solan/ or A.
  • alternata tomatoes (e. g. A so/an/ or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; AscocAyte spp. on cereals and vegetables, e. g. A tritici (anthracnose) on wheat and A horde/ on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (£>. maydis) or Northern leaf blight (.5. zeicoia) on corn, e. g. spot blotch (£?. sorokiniana) on cereals and e. g. z5.
  • Cochliobolus spp. e. g. Southern leaf blight (£>. maydis) or Northern leaf blight (.5. zeicoia) on corn, e. g. spot blotch (£?
  • Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. bet/cola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus
  • anamorph Helminthosporium of Bipolaris
  • spp. leaf spots
  • corn C. carbonum
  • cereals e. g. C. sativus, anamorph: B. sorokiniana
  • rice e. g. C. miyabeanus, anamorph: H.
  • gossyp/ ⁇ corn (e. g. C. gram/n/co/a: Anthracnose stalk rot), soft fruits, potatoes (e. g. C.
  • coccodes black dot
  • beans e. g. C. lindemuthianum
  • soybeans e. g. C. truncatum or C. gloeosporioides
  • Corticium spp. e. g. C. sasakii (sheath blight) on rice
  • Corynespora cassiicoia leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectr/a spp.
  • C liriodendri, teleomorph Neonectria liriodendri. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans;
  • Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Form/t/por/a (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum),
  • Phaeoacremonium aleophilum and/or Botryosphaeria obtusa Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampe/ina: anthracnose); Enty/oma oryzae (leaf smut) on rice; Ep/coccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pis/), such as cucurbits (e. g. E. E.
  • spp. wilt, root or stem rot
  • various plants such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. so/an/ ( sp. glycines now syn. F. virguliforme ) and F. tucumaniae and F.
  • Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. /ara, fructicola and fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco ⁇ P. tabacina) and soybeans (e. g. P. manshurica);
  • Monilinia spp. e. g. /ara, fructi
  • Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum);
  • Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsicl), soybeans (e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. ha/stediion sunflowers
  • Podosphaera spp. powdery mildew
  • hum/lion hop Pseudopezicu/a tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. horde/ (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P.
  • Puccinia spp. rusts
  • P. triticina brown or leaf rust
  • P. striiformis stripe or yellow rust
  • P. horde/ dwarf rust
  • P. graminis
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. teres net blotch
  • Pyricularia spp. e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals
  • Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R.
  • collo-cygni Roso-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. bet/cola on sugar beets; Rh/zocton/a spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. so/ani (root and stem rot) on soybeans, R. so/ani (sheath blight) on rice or R.
  • Rhizoctonia spring blight on wheat or barley
  • Rhizopus sto/onifer b ⁇ ack mold, soft rot
  • strawberries a plant rot
  • cabbage a plant rot
  • tomatoes a plant rot
  • Rhynchosporium seca/is scald
  • Sarocladium oryzae and S. attenuatum sheath rot
  • Sclerotinia spp. stem rot or white mold
  • vegetables and field crops such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. ro/fsiior S.
  • Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucker!) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp.
  • smut on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora pp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph:
  • Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina pp., e. g. 7! deformans (leaf curl disease) on peaches and 7! /?/z//7/(plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp.
  • mixtures and compositions of the invention are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • protection of materials is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Hum/cola spp., Petriella spp., Trichurus spp:, Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Hum/cola spp., Petriella spp., Trichurus spp:, Basidiomycetes such as Coniophora spp
  • Candida spp. and Saccharomyces cerevisae Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucorspp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • the mixtures and compositions according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms.
  • the term "stored products” is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired.
  • Stored products of crop plant origin such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment.
  • Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Stored products of animal origin are hides, leather, furs, hairs and the like. The combinations according the present invention can prevent
  • stored products is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • compositions of the invention may also be suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
  • the mixtures and compositions of the invention may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of the inventive compositions or the components thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • compositions and mixtures containing the same are likewise subject matter of the present invention.
  • inventive compositions are employed as such or in form of agrochemical compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with the mixtures and compositions of the invention prophylactically either at or before planting or transplanting.
  • the invention also relates to agrochemical compositions comprising an auxiliary and one component I and a component II according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a component I and a component II.
  • effective amount denotes an amount of the composition or of the components I and II, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific component I and II used.
  • compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical
  • compositions are prepared in a known manner, such as described by Mollet and
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,
  • tetrahydronaphthalene alkylated naphthalenes
  • alcohols e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol
  • glycols DMSO; ketones, e. g. cyclohexanone; esters, e. g.
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates;
  • amines e. g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e. g. cellulose, star
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the component I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e. g. iron oxide, titan oxide, iron
  • organic colorants e. g. alizarin-, azo- and phthalocyanine colorants.
  • Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • active substances denote component I and component II:
  • active substances 10-60 wt% active substances and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e. g. alcohols) ad 100 wt%.
  • wetting agent e. g. alcohol alkoxylates
  • a water-soluble solvent e. g. alcohols
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e. g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water-insoluble organic solvent e. g. aromatic hydrocarbon
  • This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • active substances are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1 -2 wt% thickener (e. g. xanthan gum) and ad water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • 0.1 -2 wt% thickener e. g. xanthan gum
  • ad water ad 100 wt%
  • active substances are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • active substances are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e. g. sodium lignosulfonate), 1 -3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • wetting agents e. g. alcohol ethoxylate
  • solid carrier e. g. silica gel
  • active substances are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1 -5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • 1 -5 wt% thickener e. g. carboxymethyl cellulose
  • 5-20 wt% active substances are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 wt%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e. g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e. g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% active substances, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of active substances, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate monomer (e. g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol).
  • a polyamine e. g.
  • hexamethylenediamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1 -10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • active substances are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%.
  • solid carrier e. g. finely divided kaolin
  • active substances are ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%.
  • solid carrier e. g. silicate
  • Granulation is achieved by extrusion, spray-drying or fluidized bed.
  • organic solvent e. g. aromatic hydrocarbon
  • compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
  • auxiliaries such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substances.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations.
  • Methods for applying or treating component I and component II and compositions thereof, respectively, onto plant propagation material, especially seeds include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods.
  • component I and component II or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e. g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • a predosage device usually from a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • the compound ratios are advantageously chosen so as to produce a synergistic effect.
  • the term “synergistic effect” is understood to refer in particular to that defined by Colby's formula (Colby, S. R., “Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, pp. 20-22, 1967).
  • the term “synergistic effect” is also understood to refer to that defined by application of the Tammes method,
  • the weight ratio of component I and component II generally depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1 .
  • the weight ratio of component I versus component II usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100:1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1 .
  • the weight ratio of component I versus component II usually is in the range of from 1 :1 to 1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
  • the compound ratios are advantageously chosen so as to produce a synergistic effect.
  • the active compounds are prepared as a stock solution comprising 25 mg of active compound which is made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Uniperol ® EL (wetting agent having an emulsifying and dispersing action based on ethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of 99:1 .
  • the mixture is then made up to 100 ml with water.
  • This stock solution is diluted with the solvent/emulsifier/water mixture described to give the concentration of active compound stated below.
  • a corresponds to the fungicidal infection of the treated plants in %
  • ⁇ corresponds to the fungicidal infection of the untreated (control) plants in %
  • An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
  • y efficacy expressed in % of the untreated control, when using the active compound B at the concentration b.
  • Trials No. 1 to No. 4 were conducted under field conditions. Wheat was planted and grown under standard conditions with adequate supply of water and nutrients. At crop growth stage BBCH 32-37, an application of the test compounds was made. No other compounds were applied for pathogen control. The disease incidences for Septoria //#/ic/(SEPTTR) were evaluated on the specific leaf level 43-57 days after the fungicide treatment. Disease levels were converted into efficacies. An efficacy of 0 means that the level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants had no disease at all. The expected efficacies of active compound mixtures were determined using Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.

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Abstract

The present invention relates to compositions comprising, 1) as component I a compound selected from the following compounds I-1 to I-5, and 2) as component II a compound selected from the group of compounds II-1 to II-25. The invention furthermore relates to the use of the inventive compositions as pesticides in particular for controlling phytopathogenic fungi as detailled herein and preparations or compositions comprising them. The invention furthermore also relates to seed comprising the compositions. The invention furthermore also relates to methods for controlling pests, in particular phytopathogenic fungi as detailled herein, wherein the fungi or the materials, plants, the soil or seed to be protected from fungal attack are treated with an effective amount of a compositions according to the invention. The invention furthermore also relates to processes for preparing the compositions according to the invention.

Description

Pesticidal compositions
Description
The present invention relates to compositions comprising,
1 ) as component I a compound selected from the following compounds 1-1 to I-5:
compound 1-1 : 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol;
compound I-2: 1 -[2-chloro-4-(4-chlorophenoxy)phenyl]-1-cyclopropyl-2-(1 ,2,4-triazol-1 - yl)ethanol;
compound I-3: 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)propan-2- ol;
compound I-4: 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1- yl)ethanol; and
compound I-5: 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1 ,2,4-triazol-1- yl)butan-2-ol;
or the N-oxides or agriculturally acceptable salts of each of the compounds; and
2) as component II a compound selected from the group of compounds 11-1 to II-25
compound 11-1 : [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-2: [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 ,5- dioxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate, in particular [2- [[(3S,7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 ,5-dioxonan-3- yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate (ll-2a);
compound 11—3 : [(6S,7R,8R)-8-benzyl-3-[[4-methoxy-3-(propanoyloxymethoxy)-pyridine-2- carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-4: [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-5: [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-6: [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-7: [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyri- dine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound 11—8 : N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-5-fluoro-1 ,3-dimethyl- pyrazole-4-carboxamide;
compound II-9: N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl- pyrazole-4-carboxamide;
compound 11-10: 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6- trichlorophenyl)ethyl]pyrazole-4-carboxamide; compound 11-1 1 : methyl (E)-2-[2-[(2,5-dimethylphenoxy)methyl]phenyl]-3-methoxy-prop-2- enoate;
compound 11-12: methyl-N-[2-[(1 ,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N- methoxy-carbamate;
compound 11-13: 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylidene-aminooxy-methyl)-phenyl)-2- methoxyimino-N methyl-acetamide;
compound 11-14: methyl (E)-3-(fluoromethoxy)-2-[2-[(3,5,6-trichloro-2- pyridyl)oxymethyl]phenyl]prop-2-enoate;
compound 11-15: Mandestrobin;
compound 11-16: methyl (E)-2-[2-[[2-(2,4-dichloroanilino)-6-(trifluoromethyl)pyrimidin-4- yl]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (common name: Pyriminostrobin);
compound 11-17: methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2- enoate;
compound 11-18: Pyraziflumid;
compound 11-19: Methyldinocap;
compound II-20: (Z)-N-allyloxy-1 -(2,4-dichlorophenyl)-2-imidazol-1 -yl-ethanimine (Chlor- phenomizole);
compound 11-21 : 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide;
compound II-22: 3-[(3,4-dichloroisothiazol-5-yl)methoxy]-1 ,2-benzothiazole-1 ,1 -dioxide;
compound II-23: Diclocymet;
compound II-24: Fenitropan; and
compound II-25: Harpin.
The invention furthermore relates to the use of the inventive compositions as pesticides in particular for controlling phytopathogenic fungi as detained herein and preparations or compositions comprising them. The invention furthermore also relates to seed comprising the compositions. The invention furthermore also relates to methods for controlling pests, in particular phytopathogenic fungi as detained herein, wherein the fungi or the materials, plants, the soil or seed to be protected from fungal attack are treated with an effective amount of a compositions according to the invention. The invention furthermore also relates to processes for preparing the compositions according to the invention.
With a view to reducing the application rates and broadening the activity spectrum of the known compounds, it was an object of the present invention to provide compositions which, at a reduced total amount of active compounds applied, show improved activity against important pests, in particular phythopathogenic fungi, in particular for certain indications. It was a further object to provide for compositions that are useful for the control of specific pathogens in specific important crops that are often susceptible to the attack of pathogens.
Accordingly we have found the compositions and uses defined at the outset and in the following description. The compounds I (component I), its preparation and use in crop protection are described in WO 2013/007767 and WO 2013/010862, which also disclose certain compositions with other active compounds. The compounds I (component I) can also be obtained by various routes in analogy to prior art processes known (cf. J. Agric. Food Chem. (2009) 57, 4854-4860; EP-A 0 275 955; DE-A 40 03 180; EP-A 0 1 13 640; EP-A 0 126 430). Owing to the basic character of their nitrogen atoms, the compounds 1-1 , I-2, I-3, I-4 and I-5 are capable of forming salts or adducts with inorganic or organic acids or with metal ions, in particular salts with inorganic acids.
Compounds 1-1 to I-5 used as component I in the inventive compositions are selected from the following fungicidal compounds:
compound 1-1 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol; compound I-2 1-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-cyclopropyl-2-(1 ,2,4-triazol-1- yl)ethanol;
compound I-3 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1-yl)propan- 2-ol;
compound I-4 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-cyclopropyl-2-(1 ,2,4- triazol-1 -yl)ethanol; and
compound I-5 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1 ,2,4-triazol-1 - yl)butan-2-ol.
The structures are as follows:
1- -[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol
Figure imgf000004_0001
- -[2-chloro-4-(4-chlorophenoxy)phenyl]-1-cyclopropyl-2-(1 ,2,4-triazol-1-yl)ethanol
Figure imgf000004_0002
I-3: 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)propan-2-ol
Figure imgf000004_0003
I-4: 1-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1- yl)ethanol
Figure imgf000004_0004
I-5: 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1 ,2,4-triazol-1 -yl)butan-2-ol
Figure imgf000005_0001
In each case, the respective N-oxide and the agriculturally acceptable salts of the compounds as further defined below are encompassed.
Compounds 1-1 to I-5 comprise chiral centers and they are generally obtained in the form of racemates. The R- and S-enantiomers of the compounds contained as component I in the compositions according to the invention can be separated and isolated in pure form with methods known by the skilled person, e.g. by using chiral HPLC. Suitable for use in the compositions are both the enantiomers and compositions thereof. Furthermore, said
components I can be present in different crystal modifications, which may differ in biological activity.
In particular, in each case, a racemic composition of the respective components I, namely of compound 1-1 , I-2, I-3, I-4 or I-5, respectively, is present. Furthermore, any other proportions of the (R)-enantiomer and the (S)-enantiomer of the respective compound 1-1 , I-2, I-3, I-4 or I-5, respectively, may be present according to the present invention. For example, the (R)- enantiomer of compound I-3 is (R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4- triazol-1 -yl)propan-2-ol; the S-enantiomer of I-3 is (S)-2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol. This applies to the other compounds accordingly. According to one specific embodiment, the respective compound 1-1 , I-2, I-3, I-4 or I-5, respectively, is provided and used as (R)-enantiomer with 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%. According to a further specific embodiment, the respective compound 1-1 , I-2, I-3, I-4 or I-5, respectively, is provided and used as (S)-enantiomer with 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%. This applies to every composition detained herein.
According to one embodiment of the invention, component I is compound 1-1 .
According to a further embodiment of the invention, component I is compound I-2.
According to a further embodiment of the invention, component I is compound I-3.
According to still a further embodiment of the invention, component I is compound I-4.
According to still a further embodiment of the invention, component I is compound I-5.
According to one further embodiment of the present invention, component I is selected from compounds 1-1 and I-2. According to a more particular embodiment of the present invention, component I is selected from compounds I-3, I-4 and I-5. According to still a further embodiment of the present invention, component I is selected from compounds I-3 and I-5.
Component II is preferably a compound selected from the group of compounds 11-1 to 11-10: compound 11-1 [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; compound 11-2 [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6- dioxo-1 ,5-dioxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate, in particular [2-[[(3S,7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 , 5- dioxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate (ll-2a);
compound 11—3 [(6S,7R,8R)-8-benzyl-3-[[4-methoxy-3-(propanoyloxymethoxy)- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-4 [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound 11-5 [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-6 [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy- pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate;
compound II-7 [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4- methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; compound 11—8 N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-5-fluoro-1 ,3-dimethyl- pyrazole-4-carboxamide;
compound II-9 N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 - methyl-pyrazole-4-carboxamide; and
compound 11-10 3-(difluoromethyl)-N-methoxy-1 -methyl-N-[1 -methyl-2-(2,4,6- trichlorophenyl)ethyl]pyrazole-4-carboxamide; or the N-oxides or agriculturally acceptable salts of each of the compounds.
The structures are as follows:
11-1 : [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9- dioxo-1 5-dioxonan-7- l 2-meth l ro anoate
Figure imgf000006_0001
II-2: [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 ,5-dioxonan-3- yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate, in particular [2- [[(3S,7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-dioxo-1 ,5-dioxonan-3- yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate (ll-2a), namely
Figure imgf000007_0001
11—3 : [(6S,7R,8R)-8-benzyl-3-[[4-methoxy-3-(propanoyloxymethoxy)pyridine-2-carbonyl]amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]-2-methylpropanoate
Figure imgf000007_0002
II-4: [(3S,6S7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9- dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
Figure imgf000008_0001
11-5: [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl] methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
Figure imgf000008_0002
II-6: [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine- -carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
Figure imgf000008_0003
II-7: [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-car- bonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
Figure imgf000009_0001
11-8: N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-5-fluoro-1 ,3-dimethyl-pyrazole-4- carboxamide
Figure imgf000009_0002
II-9: N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl- 4-carboxamide
Figure imgf000009_0003
11-10: 3-(difluoromethyl)-N-methoxy-1 -methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethy p razole-4-carboxamide
Figure imgf000009_0004
The compounds 11-1 to II-7 and their pesticidal action and possible uses thereof can be found in WO 2014/105842, WO 2015/005355, WO 2014/106259. II-2 is described in WO 2014/105842 and WO 2014/106259. The preparation, the pesticidal action and possible uses for compound II-8 can be found in WO 2012/143127, WO 2014/060502, WO 2014/060521 and WO
2014/076007. The preparation, the pesticidal action and possible uses for compounds II-9 and 11-10 can be found in WO 2014/206855, WO 2014/023628, WO 2014/016279, WO 2013/127764 and WO 2010/063700.
Compound -1 1 is known from CN-A 1456054.
Compound -12 is known from CN-A 103387541
Compound -13 is known from CN-A 1309897.
Compound -14 is known from CN-A 1907024.
Compound -15 is known from WO 95/07693.
Compound -16 is known from WO 2010/139271
Compound -17 is known from CN-A 1907024.
Compound -18 is known from WO 2007/072999
Coumpound II-20 is known from CN-A 1465562 and CN-A 1308294.
Compound -21 is known from WO 06/98128.
Compound -22 is known from WO 07/129454 and WO 2012/16551 1.
Compounds 11-19, II-23, II-24 and II-25 and their pesticidal activity are known and can be found for example in the e-Pesticide Manual V5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ) and other publications.
According to one embodiment of the invention, component II is selected from compounds 11-1 , II-2, II-3, II-4, II-5, II-6 and II-7.
According to one particular embodiment of the invention, component II is compound 11-1.
According to a further particular embodiment of the invention, component II is compound II-2, in particular ll-2a
According to a further particular embodiment of the invention, component II is compound ll-2a.
According to sti II a further particular inventive embodiment, component is compound -3. According to sti II a further particular inventive embodiment, component is compound -4. According to sti II a further particular inventive embodiment, component is compound -5. According to sti II a further particular inventive embodiment, component is compound -6. According to sti II a further particular inventive embodiment, component is compound -7.
According to a further embodiment of the invention, component II is compound 11—8.
According to still a further embodiment of the invention, component II is selected from compounds II-9 and 11-10.
According to one particular embodiment of the invention, component II is compound II-9.
According to a further particular embodiment of the invention, component II is compound 11-10. Compounds II-9 and 11-10 comprise chiral centers and they are generally obtained in the form of racemates. The R- and S-enantiomers of the compounds contained as component II in the compositions according to the invention can be separated and isolated in pure form with methods known by the skilled person, e.g. by using chiral HPLC. Suitable for use in the compositions are both the enantiomers and compositions thereof. Furthermore, said
components II can be present in different crystal modifications, which may differ in biological activity.
In particular, in each case, a racemic composition of the respective components II, namely of compound II-9 or 11-10, respectively, is present. Furthermore, any other proportions of the (R)- enantiomer and the (S)-enantiomer of the respective compound II-9 or 11-10, respectively, may be present according to the present invention.
According to one specific embodiment, the respective compound II-9 or 11-10, respectively, is provided and used as (R)-enantiomer with 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%. According to a further specific embodiment, the respective compound II-9 or 11-10, respectively, is provided and used as (S)-enantiomer with 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%.
This applies to every of the respective compositions detained herein.
Examples of inorganic acids are hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, carbonic acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid and other arylcarboxylic acids, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two phosphoric acid radicals), where the alkyl or aryl radicals may carry further substituents, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc. Suitable metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminum, tin and lead, and also of the elements of transition groups one to eight, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, and others. Particular preference is given to the metal ions of the elements of transition groups of the fourth period. The metals can be present in the various valencies that they can assume.
In the following, the inventive compositions and their preferred uses are further described. In each case, according to the present invention, the use of the composition for controlling a particular phytopathogenic fungus is also meant to encompass the respective method for controlling the particular phytopathogenic fungi, wherein the fungi or the materials, plants, the soil or seed to be protected from fungal attack are treated with an effective amount of a composition as defined in that particular context.
According to one aspect, the present invention relates to two-component compositions, i.e. compositions comprising component I, i.e in particular a compound selected from compounds
I- 1 , I-2, I-3, I-4 and I-5, or any group of compounds I detailled above, and component II selected from compounds 11-1 , II-2 (in particular I l-2a), II-3, II-4, II-5, II-6, II-7, II-8, II-9, 11-10, 11-1 1 , 11-12,
II- 13, 11-14, 11-15, 11-16, 11-17, 11-18, 11-19, II-20, 11-21 , II-22, II-23, II-24 and II-25. According to a specific embodiment thereof, only two active compounds as defined are present in these binary compositions. The composition may, of course, contain any kind of additive or the like as detailled below in order to provide a formulation suitable for use in agriculture.
The weight ratio of component I to component II in the inventive compositions is preferably from 1000:1 to 1 :1000, more specifically 500:1 to 1 :500, particularly 100:1 to 1 :100. The weight ratio of component I to component II generally depends from the properties of the active substances used and is usually in the range of from 1 :100 to 100:1 , frequently in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , particularly preferably in the range of from 1 :10 to 10:1 , in particular in the range of from 1 :3 to 3:1 . It may also be preferable for the weight ratio to be in the range of from 1 :2 to 2:1.
According to one embodiment, two-component compositions according to the invention may preferably have weight ratios of compound I versus compound II in the range of from 1000:1 to 1 :1 , often in the range of from 100:1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1 .
According to one embodiment, two-component compositions according to the invention may preferably have weight ratios of compound I versus compound II usually is in the range of from 1 :1 to 1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
Consequently, the two-component compositions of the invention are compiled in Tables B1 , B2 and B3, wherein each row corresponds to one embodiment of the compositions according to the invention, i.e. one specific individualized composition. According to one specific aspect, these are binary compositions which each only contain these two components as active compounds. Furthermore, also every combination of the compositions individualized in this table represent embodiments of the present invention.
Table B1 : Two-component compositions B1-1 to B1-35 comprising one component I and one component II selected from compounds 11-1 to II-7, in particular binary compositions containing the respective component I and II as only active ingredients:
I = component I selected from compounds 1-1 to I-5
II = component II selected from compounds 11-1 to II-7 Composition I II Composition I II Composition I II
B1-1 1-1 11-1 B1-15 I-5 II-3 B1 -29 I-4 II-6
B1-2 I-2 11-1 B1-16 1-1 II-4 B1 -30 I-5 II-6
B1-3 I-3 11-1 B1-17 I-2 II-4 B1 -31 1-1 II-7
B1-4 I-4 11-1 B1-18 I-3 II-4 B1 -32 I-2 II-7
B1-5 I-5 11-1 B1-19 I-4 II-4 B1 -33 I-3 II-7
B1-6 1-1 II-2 B1-20 I-5 II-4 B1 -34 I-4 II-7
B1-7 I-2 II-2 B1-21 1-1 II-5 B1 -35 I-5 II-7
B1-8 I-3 II-2 B1-22 I-2 II-5 B1 -36 1-1 ll-2a
B1-9 I-4 II-2 B1-23 I-3 II-5 B1 -37 I-2 ll-2a
B1 -10 I-5 II-2 B1-24 I-4 II-5 B1 -38 I-3 ll-2a
B1 -1 1 1-1 II-3 B1-25 I-5 II-5 B1 -39 I-4 ll-2a
B1 -12 I-2 II-3 B1-26 1-1 II-6 B1 -40 I-5 ll-2a
B1 -13 I-3 II-3 B1-27 I-2 II-6
B1 -14 I-4 II-3 B1-28 I-3 II-6
One embodiment of the invention relates to any one of compositions B1-1 to B1-40 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 100:1 to 1 :1. One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
One further embodiment of the invention relates to any one of compositions B1 -1 to B1-40 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
Table B2: Two-component compositions B2-1 to B5-5 comprising one component I and one component II being compound 11 8 , in particular binary compositions containing the respective component I and II as only active ingredients:
I = component I selected from compounds 1-1 to I-5
II = component II being compound 11—8
Figure imgf000014_0003
Figure imgf000014_0001
Figure imgf000014_0002
One embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 100:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20. One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
One further embodiment of the invention relates to any one of compositions B2-1 to B2-5 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
Table B3: Two-component compositions B3-1 to B3-10 comprising one component I and one component II selected from compounds II-9 and 11-10, in particular binary compositions containing the respective component I and II as only active ingredients:
I = component I selected from compounds 1-1 to I-5
II = component II selected from compounds II-9 and 11-10
Figure imgf000016_0003
Figure imgf000016_0001
Figure imgf000016_0002
One embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 . One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 100:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
One further embodiment of the invention relates to any one of compositions B3-1 to B3-10 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
Table B4: Two-component compositions B4-1 to B4-75 comprising one component I and one component II selected from compounds 11-1 1 to II-25, in particular binary compositions containing the respective component I and II as only active ingredients:
I = component I selected from compounds 1-1 to I-5
II = component II selected from compounds 11-1 1 to II-25
Composition I II Composition I II Composition I II
B4-1 1-1 11-1 1 B4-7 I-2 11-12 B4-13 I-3 11-13
B4-2 I-2 11-1 1 B4-8 I-3 11-12 B4-14 I-4 11-13
B4-3 I-3 11-1 1 B4-9 I-4 11-12 B4-15 I-5 11-13
B4-4 I-4 11-1 1 B4-10 I-5 11-12 B4-16 1-1 11-14
B4-5 I-5 11-1 1 B4-1 1 1-1 11-13 B4-17 I-2 11-14
B4-6 1-1 11-12 B4-12 I-2 11-13 B4-18 I-3 11-14 Composition I II Composition I II Composition I II
B4-19 I-4 11-14 B4-38 I-3 11-18 B4-57 I-2 II-22
B4-20 I-5 11-14 B4-39 I-4 11-18 B4-58 I-3 II-22
B4-21 1-1 11-15 B4-40 I-5 11-18 B4-59 I-4 II-22
B4-22 I-2 11-15 B4-41 1-1 11-19 B4-60 I-5 II-22
B4-23 I-3 11-15 B4-42 I-2 11-19 B4-61 1-1 II-23
B4-24 I-4 11-15 B4-43 I-3 11-19 B4-62 I-2 II-23
B4-25 I-5 11-15 B4-44 I-4 11-19 B4-63 I-3 II-23
B4-26 1-1 11-16 B4-45 I-5 11-19 B4-64 I-4 II-23
B4-27 I-2 11-16 B4-46 1-1 II-20 B4-65 I-5 II-23
B4-28 I-3 11-16 B4-47 I-2 II-20 B4-66 1-1 II-24
B4-29 I-4 11-16 B4-48 I-3 II-20 B4-67 I-2 II-24
B4-30 I-5 11-16 B4-49 I-4 II-20 B4-68 I-3 II-24
B4-31 1-1 11-17 B4-50 I-5 II-20 B4-69 I-4 II-24
B4-32 I-2 11-17 B4-51 1-1 11-21 B4-70 I-5 II-24
B4-33 I-3 11-17 B4-52 I-2 11-21 B4-71 1-1 II-25
B4-34 I-4 11-17 B4-53 I-3 11-21 B4-72 I-2 II-25
B4-35 I-5 11-17 B4-54 I-4 11-21 B4-73 I-3 II-25
B4-36 1-1 11-18 B4-55 I-5 11-21 B4-74 I-4 II-25
B4-37 I-2 11-18 B4-56 1-1 II-22 B4-75 I-5 II-25
One embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component 11 is from 1000: 1 to 1 : 1000.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 500:1 to 1 :500.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 100:1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :100 to 100:1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :50 to 50:1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :20 to 20:1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :10 to 10:1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :3 to 3:1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :2 to 2:1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1000:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 100:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 50:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 20:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 10:1 to 1 :1 .
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 4:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 2:1 to 1 :1.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1000.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :100.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :50.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :20.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :10.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :4.
One further embodiment of the invention relates to any one of compositions B4-1 to B4-75 wherein the weight ratio of component I to component II is from 1 :1 to 1 :2.
According to a further embodiment, the present invention relates to pesticidal compositions comprising, 1 ) as component I a compound selected from the compounds 1-1 to I-5 and the N- oxides and the agriculturally acceptable salts of each of the compounds, as defined above; and 2) as component II a compound selected from compounds 11-1 to II-25 and the N-oxides and the agriculturally acceptable salts of each of the compounds, as defined above; and 3) as component III a further pesticidal compound.
The mixtures and compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the
Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes,
Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The mixtures and compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably the inventive mixtures and compositions are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with the inventive combination of component I and component II and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as hydroxyphenyl- pyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfo- nyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A 242 236, EP-A 242 246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.) and LibertyLink® (glufosinate- tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydro- xysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stil- bene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphinothricin- V-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the CrylAc toxin), Bollgard® I (cotton cultivars producing the Cry1 Ac toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Cor- poration, Belgium (corn cultivars producing the Cryl F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amyivora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
The inventive mixtures and compositions are particularly suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A brassicola or brassicae), sugar beets (A tenuis), fruits, rice, soybeans, potatoes (e. g. A solan/ or A.
alternata), tomatoes (e. g. A so/an/ or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; AscocAyte spp. on cereals and vegetables, e. g. A tritici (anthracnose) on wheat and A horde/ on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (£>. maydis) or Northern leaf blight (.5. zeicoia) on corn, e. g. spot blotch (£?. sorokiniana) on cereals and e. g. z5. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana. grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms;
Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. bet/cola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus
(anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H.
oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C.
gossyp/ή, corn (e. g. C. gram/n/co/a: Anthracnose stalk rot), soft fruits, potatoes (e. g. C.
coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicoia (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectr/a spp.) on fruit trees, vines (e. g. C liriodendri, teleomorph: Neonectria liriodendri. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans;
Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Form/t/por/a (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum),
Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampe/ina: anthracnose); Enty/oma oryzae (leaf smut) on rice; Ep/coccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pis/), such as cucurbits (e. g. E.
c/choracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium
(teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. so/an/ ( sp. glycines now syn. F. virguliforme ) and F. tucumaniae and F.
brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G fujikuror'. Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypiion cotton; Grainstaining complex on rice; Guignardia bidwellii '(black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochiioboius) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. /ara, fructicola and fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco {P. tabacina) and soybeans (e. g. P. manshurica);
Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum);
Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsicl), soybeans (e. g. P.
megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad- leaved trees (e. g. P. ramorurrr. sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. ha/stediion sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat {P. graminis) and sugar beets {P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapes/a yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. hum/lion hop; Pseudopezicu/a tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. horde/ (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagio asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. bet/cola on sugar beets; Rh/zocton/a spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. so/ani (root and stem rot) on soybeans, R. so/ani (sheath blight) on rice or R. cerea/is (Rhizoctonia spring blight) on wheat or barley; Rhizopus sto/onifer (b\ack mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium seca/is (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. ro/fsiior S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucker!) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora pp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph:
Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina pp., e. g. 7! deformans (leaf curl disease) on peaches and 7! /?/z//7/(plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp.
(common bunt or stinking smut) on cereals, such as e. g. T. tritici {s n. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis. corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae o strawberries, rape, potatoes and tomatoes.
The mixtures and compositions of the invention are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Hum/cola spp., Petriella spp., Trichurus spp:, Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucorspp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The mixtures and compositions according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms. According to the present invention, the term "stored products" is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired. Stored products of crop plant origin, such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and the like. The combinations according the present invention can prevent
disadvantageous effects such as decay, discoloration or mold. Preferably "stored products" is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
Compositions of the invention may also be suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
The mixtures and compositions of the invention may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of the inventive compositions or the components thereof, respectively.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The compounds of the inventive compositions or mixtures can be present in different crystal modifications whose biological activity may differ. Compositions and mixtures containing the same are likewise subject matter of the present invention.
The inventive compositions are employed as such or in form of agrochemical compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
Plant propagation materials may be treated with the mixtures and compositions of the invention prophylactically either at or before planting or transplanting.
The invention also relates to agrochemical compositions comprising an auxiliary and one component I and a component II according to the invention.
An agrochemical composition comprises a fungicidally effective amount of a component I and a component II. The term "effective amount" denotes an amount of the composition or of the components I and II, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific component I and II used.
The components I and components II, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical
Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and
Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New
developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g.
lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates;
amines; amides, e. g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid
alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the component I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e. g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e. g. iron oxide, titan oxide, iron
hexacyanoferrate) and organic colorants (e. g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types and their preparation are (wherein active substances denote component I and component II):
i) Water-soluble concentrates (SL, LS)
10-60 wt% active substances and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e. g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% active substances and 1 -10 wt% dispersant (e. g. polyvinyl pyrrolidone) are dissolved in organic solvent (e. g. cyclohexanone) ad 100 wt%. Dilution with water gives a dispersion. iii) Emulsifiable concentrates (EC)
15-70 wt% active substances and 5-10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% active substances and 1 -10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e. g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% active substances are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1 -2 wt% thickener (e. g. xanthan gum) and ad water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% active substances are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% active substances are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e. g. sodium lignosulfonate), 1 -3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% active substances are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1 -5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% active substances are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 wt%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% active substances, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of active substances, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate monomer (e. g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). The addition of a polyamine (e. g.
hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1-10 wt% active substances are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%.
xii) Granules (GR, FG)
0.5-30 wt% active substances are ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% active substances are dissolved in organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substances. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations.
Application can be carried out before or during sowing. Methods for applying or treating component I and component II and compositions thereof, respectively, onto plant propagation material, especially seeds include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, component I and component II or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the
agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
In the mixtures and compositions, the compound ratios are advantageously chosen so as to produce a synergistic effect. The term "synergistic effect" is understood to refer in particular to that defined by Colby's formula (Colby, S. R., "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, pp. 20-22, 1967). The term "synergistic effect" is also understood to refer to that defined by application of the Tammes method,
(Tammes, P. M. L, "Isoboles, a graphic representation of synergism in pesticides", Netherl. J. Plant Pathol. 70, 1964). In the mixtures and compositions according to the invention, the weight ratio of component I and component II generally depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1 .
According to further embodiments of the mixtures and compositions according to the invention, the weight ratio of component I versus component II usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100:1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1 .
According to further embodiments of the mixtures and compositions according to the invention, the weight ratio of component I versus component II usually is in the range of from 1 :1 to 1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
In the mixtures and compositions, the compound ratios are advantageously chosen so as to produce a synergistic effect.
The active compounds, separately or jointly, are prepared as a stock solution comprising 25 mg of active compound which is made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent having an emulsifying and dispersing action based on ethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of 99:1 . The mixture is then made up to 100 ml with water. This stock solution is diluted with the solvent/emulsifier/water mixture described to give the concentration of active compound stated below.
The visually determined percentages of infected leaf areas are converted into efficacies in % of the untreated control. The efficacy (E) is calculated as follows using Abbot's formula:
E = (1 - α/β) ■ 100
a corresponds to the fungicidal infection of the treated plants in % and
β corresponds to the fungicidal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
The expected efficacies of active compound combinations were determined using Colby's formula (Colby, S.R. "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 1J5, pp. 20-22, 1967) and compared with the observed efficacies.
Colby's formula: E = x + y - x »y/100
E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b
x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a
y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b.
The invention is further illustrated, but not limited by the following practical examples:
Trials No. 1 to No. 4 were conducted under field conditions. Wheat was planted and grown under standard conditions with adequate supply of water and nutrients. At crop growth stage BBCH 32-37, an application of the test compounds was made. No other compounds were applied for pathogen control. The disease incidences for Septoria //#/ic/(SEPTTR) were evaluated on the specific leaf level 43-57 days after the fungicide treatment. Disease levels were converted into efficacies. An efficacy of 0 means that the level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants had no disease at all. The expected efficacies of active compound mixtures were determined using Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
The dosages used and the obtained results are shown below:
Trial No. 1 Trial No. 2 Trial No. 3 Trial No. 4
Timing of 37 37 32 32 treatment
(crop
growth
stage
BBCH)
Evaluated flag leaf 3rd leaf flag leaf 2nd leaf flag leaf flag leaf 3rd leaf leaf level
Timing of 43 43 43 47 57 51 51 assessment (days
after
treatment)
Untreated 86 89 29 94 94 41 98 % severity
of attack
% efficacy 32 13 26 79 32 83 63 Compound
I-3 (75 g
(a.i.)/ha) Trial No. 1 Trial No. 2 Trial No. 3 Trial No. 4
% efficacy 4 6 4 1 1 2 28 8 Compound
ll-2a (97 g
(a.i.)/ha)
% efficacy 68 52 77 91 72 92 82 1-3 + ll-2a
(75+97 g
(a.i.)/ha)
calculated 35 18 29 81 34 88 66 efficacy
according
to Colby
synergism 33 35 48 1 1 39 4 16 (%)

Claims

Claims
1. Compositions comprising,
1 ) as component I a compound selected from the following compounds 1-1 to I-5:
compound 1-1 2- [2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1-yl)pent-
3- yn-2-ol;
compound I-2 1- [2-chloro-4-(4-chlorophenoxy)phenyl]-1-cyclopropyl-2-(1 ,2,4- triazol-1 -yl)ethanol;
compound I-3 2- [4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol- 1 -yl)propan-2-ol;
compound I-4 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-cyclopropyl-2- (1 ,2,4-triazol-1 -yl)ethanol; and
compound I-5 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 - (1 ,2,4-triazol-1-yl)butan-2-ol;
or the N-oxides or agriculturally acceptable salts of each of the compounds;
and
2) as component II a compound selected from the group of compounds 11-1 to II-25 compound 11-1 [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2- methylpropanoate;
compound II-2 [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6- dioxo-1 ,5-dioxonan-3-yl]carbamoyl]-4-methoxy-3- pyridyl]oxymethyl 2-methylpropanoate;
compound ll-2a [2-[[(3S,7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)- 2,6-dioxo-1 ,5-dioxonan-3-yl]carbamoyl]-4-methoxy-3- pyridyl]oxymethyl 2-methylpropanoate;
compound 11— 3 [(6S,7R,8R)-8-benzyl-3-[[4-methoxy-3-(propanoyloxymethoxy)- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2-methylpropanoate;
compound II-4 [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2-methylpropanoate; compound 11-5 [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2-methylpropanoate;
compound 11-6 [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy- pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2- methylpropanoate;
compound 11-7 [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4- methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5- dioxonan-7-yl] 2-methylpropanoate;
compound 11-8 N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-5-fluoro- 1 ,3-dimethyl-pyrazole-4-carboxamide;
compound 11-9 N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methyl-ethyl]-3- (difluoromethyl)-1-methyl-pyrazole-4-carboxamide;
compound 11-10 3- (difluoromethyl)-N-methoxy-1 -methyl-N-[1 -methyl-2-(2,4,6- trichlorophenyl)ethyl]pyrazole-4-carboxamide;
compound 11-1 1 methyl (E)-2-[2-[(2,5-dimethylphenoxy)methyl]phenyl]-3-methoxy- prop-2-enoate;
compound 11-12 methyl-N-[2-[(1 ,4-dimethyl-5-phenyl-pyrazol-3- yl)oxylmethyl]phenyl]-N-methoxy-carbamate;
compound 11-13 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylidene-aminooxy-methyl)- phenyl)-2-methoxyimino-N methyl-acetamide;
compound 11-14 methyl (E)-3-(fluoromethoxy)-2-[2-[(3,5,6-trichloro-2- pyridyl)oxymethyl]phenyl]prop-2-enoate;
compound 11-15 Mandestrobin;
compound 11-16 methyl (E)-2-[2-[[2-(2,4-dichloroanilino)-6- (trifluoromethyl)pyrimidin-4-yl]oxymethyl]phenyl]-3-methoxy-prop- 2-enoate (common name: Pyriminostrobin);
compound 11-17 methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3- methoxy-prop-2-enoate;
compound 11-18 Pyraziflumid;
compound 11-19 Methyldinocap:
compound II-20 (Z)-N-allyloxy-1-(2,4-dichlorophenyl)-2-imidazol-1 -yl-ethanimine
(Chlor-phenomizole);
compound 11-21 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide; compound 11-22 3-[(3,4-dichloroisothiazol-5-yl)methoxy]-1 ,2-benzothiazole-1 ,1- dioxide;
compound II-23 Diclocymet;
compound II-24 Fenitropan; and
compound II-25 Harpin;
or the N-oxides or agriculturally acceptable salts of each of the compounds.
2. The compositions according to claim 1 , wherein component II is selected from compounds 11-1 , II-2, ll-2a, II-3, II-4, II-5, II-6 and II-7.
3. The compositions according to claim 1 , wherein component II is compound II-2.
4. The compositions of anyone of claims 1 to 3, wherein component II is compound ll-2a.
5. The compositions according to claim 1 , wherein component II is compound 11—8.
6. The compositions according to claim 1 , wherein component II is selected from compounds II-9 and 11-10.
7. The compositions according to any one of claims 1 to 6, wherein the weight ratio of
component I to component II is from 1000:1 to 1 :1000.
8. The compositions according to any one of claims 1 to 7, wherein component I is
compound 1-1.
9. The compositions according to any one of claims 1 to 7, wherein component I is
compound I-2.
10. The compositions according to any one of claims 1 to 7, wherein component I is
compound I-3.
1 1. The compositions according to any one of claims 1 to 7, wherein component I is
compound I-4.
12. The compositions according to any one of claims 1 to 7, wherein component I is
compound I-5.
13. The compositions according to any one of claims 1 to 12, further comprising an comprising a solvent and/or at least one agrochemical auxiliary.
14. A use of a composition as defined in any one of claims 1 to 13 for combating
phytopathogenic fungi.
15. A method for combating phytopathogenic harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of a composition as defined in any of the claims 1 to 13.
16. Seed, coated with the components I and II of the compositions as defined in any one of claims 1 to 13, in an amount of from 0.1 to 10 kg active substances per 100 kg of seed.
17. Plant propagation material, coated with the components I and II of the compositions as defined in any one of claims 1 to 13.
PCT/EP2016/059309 2015-04-27 2016-04-26 Pesticidal compositions WO2016174042A1 (en)

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