WO2020254230A1 - Stabilized dithiocarbamate formulations - Google Patents

Stabilized dithiocarbamate formulations Download PDF

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Publication number
WO2020254230A1
WO2020254230A1 PCT/EP2020/066443 EP2020066443W WO2020254230A1 WO 2020254230 A1 WO2020254230 A1 WO 2020254230A1 EP 2020066443 W EP2020066443 W EP 2020066443W WO 2020254230 A1 WO2020254230 A1 WO 2020254230A1
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WIPO (PCT)
Prior art keywords
methyl
formulations
formulation
plants
active ingredient
Prior art date
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PCT/EP2020/066443
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German (de)
French (fr)
Inventor
Sven STUKE
Helmut WIRKNER
Markus SAFFERLING
Nuran GÖRGÜLÜ
Christian ZUPANC
Kathrin ERTZ
Martin Steinbeck
Karl-Josef Haack
Julia JASAK
Regine DIOT
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Bayer Aktiengesellschaft
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Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to BR112021025246A priority Critical patent/BR112021025246A2/en
Priority to CN202080043590.XA priority patent/CN113950246A/en
Priority to EP20733398.0A priority patent/EP3982732A1/en
Priority to JP2021573934A priority patent/JP2022537710A/en
Publication of WO2020254230A1 publication Critical patent/WO2020254230A1/en
Priority to CONC2021/0016879A priority patent/CO2021016879A2/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof

Definitions

  • the present invention relates to stabilized formulations of dithiocarbamates, in particular of active ingredients which contain dithiocarbamates as functional groups, such as, for example, propineb, maneb and mancozeb.
  • the present invention is directed to formulations with dithiocarbamate active ingredients which contain a particularly low content of the corresponding oxidation rearrangement products during and after formulation and ready-to-use dilution.
  • the present invention is also directed to a process for producing the above-mentioned formulations, a process for combating phytopathogenic fungi in crop protection, and their use as crop protection agents.
  • the present invention is directed to certain antioxidant-containing formulations, in particular vitamin C (ascorbic acid) and / or formulations containing sodium sulfite, of dithiocarbamates, in particular of agrochemical active ingredients with dithiocarbamate groups, and the use of certain antioxidants, in particular vitamin C. (Ascorbic acid) and sodium sulfite to stabilize dithiocarbamate compounds, in particular agrochemical active ingredients with dithiocarbamate groups.
  • vitamin C ascorbic acid
  • sodium sulfite to stabilize dithiocarbamate compounds, in particular agrochemical active ingredients with dithiocarbamate groups.
  • the present invention is directed to formulations which contain the above-mentioned antioxidants in the formulation directly or also as a “kit of parts” as an active ingredient to be added individually.
  • a kit of parts are, for example, that the antioxidants deoxygenate the water before the active ingredient / formulation is added, there is no need to change the formulation, the required antioxidants can be easily added and the kit of parts does not have a negative effect on stability or chemical stability of finished stable formulations.
  • the present invention is directed to the use of antioxidants, in particular vitamin C (ascorbic acid) and / or sodium sulfite, for stabilizing agrochemical active ingredients with dithiocarbamate groups, in particular propineb and mancozeb, in agrochemical formulations.
  • antioxidants in particular vitamin C (ascorbic acid) and / or sodium sulfite
  • Dithiocarbamate active ingredients such as propineb (The Pesticide Manual, 15 th Edition 2009, pages 954-955 and GB Patent 935.981, Cas no. 12071-83-9) maneb (manganese ethylene-l, 2-bis-dithiocarbamate / Cas no. 12427- 38-2) and Mancozeb (Manganese-Zinc-Ethylenebis (dithiocarbamate) / Cas No. 8018-01-7) have long been known as plant protection agents for fungal diseases. For example, they are used in the cultivation of fruit, vegetables and wine to combat powdery mildew and scab as well as late blight and brown rot in potatoes and tomatoes.
  • the broad-spectrum fungicidal active ingredient Propineb for example, is used worldwide in crop protection.
  • the main areas of application are rice cultivation, potato cultivation, tomatoes, viticulture and many other secondary crops.
  • the main dosage forms are the formulations such as Antracol WP70 and WG70 (BAYER), but also mixtures with e.g. Iprovalicarb and trifloxystrobin have been placed on the market.
  • the product formulation is mixed with water and sprayed on in various amounts and amounts of water per hectare of agricultural area.
  • DIDT methyl-dihydro-imidazo-dithiazole -thion
  • the oxidation product DIDT may be relevant for approval and registration.
  • sodium sulfite and ascorbic acid are common food additives (E221 and E300) that do not represent any hurdles in terms of toxicology and registration.
  • the object of the present invention was thus to provide new, improved dithiocarbamate-containing active ingredient formulations which have a high level of oxidation stability, both during storage, but in particular when the spray liquors are mixed, and the use of specific antioxidants to stabilize dithiocarbamate containing active ingredient formulations.
  • a further object of the present invention was to provide stabilizers and / or stabilizer systems for dithiocarbamate-containing active ingredient formulations which can be used in agrochemical formulations and are highly effective even in small amounts.
  • antioxidants such as sodium sulfite (NaaSCF / E221), ascorbic acid (vitamin C / E300) or sodium disulfite (Na S, often even in low concentrations, the oxidation of the dithiocarbamates and thus the formation of the oxidation product can be significantly reduced.
  • the present invention thus relates to formulations with dithiocarbamate-containing active ingredients, containing: a) at least one dithiocarbamate-containing active ingredient, and b) at least one antioxidant, preferably selected from the group consisting of sodium sulfite (Na SO ', / E221), ascorbic acid (vitamin C / E300) and sodium disulfite (Na SO ⁇ / E223).
  • the active ingredient a) is preferably selected from the group comprising Propineb, Maneb and Mancozeb and mixtures thereof.
  • the antioxidant is more preferably selected from the group comprising sodium sulfite and ascorbic acid and mixtures thereof.
  • the active ingredient a) is propineb and the antioxidant is selected from the group comprising sodium sulfite and ascorbic acid.
  • the active ingredient a) is preferably present in the formulations according to the invention in an amount of 10-99.5% by weight, more preferably 25-99% by weight, even more preferably 40-98% by weight, more preferably 50% - 97% by weight, and preferably from 40-95% by weight, more preferably in an amount of 50-90% by weight, even more preferably in an amount of 65-90% by weight, and particularly preferred in an amount of 70-86% by weight, based in each case on the total weight of the formulation.
  • the antioxidant b) is preferably present in the formulations according to the invention in an amount of 0.5-90% by weight, more preferably in an amount of 1.0-75% by weight, even more preferably in an amount of 2.0 - 60 wt .-%, and particularly preferably in an amount of 3.0-50 wt .-%, each based on the total weight of the formulation.
  • the formulation according to the invention is available as a “kit of parts”, in the following construction kit.
  • the antioxidant b) is not contained in the finished formulation, but rather as an accessory pack, for example in tablet form or as a water-soluble bag or tear-open pouch or in another suitable packaging component of the formulation. In this case, the antioxidant is added to the water before the formulation is mixed.
  • the antioxidant is dosed in such a way that it is preferably in an amount of 0.1 g - 15 g / L water / spray liquid, more preferably 0.5 g - 12 g / L water and particularly preferably 2 g - 8 g / L water is added, these ranges also applying to the spray liquor produced by diluting the formulation.
  • the antioxidant in the case of a modular system or for the spray liquor produced by dilution, is dosed in such a way that it is preferably present in an amount of 0.3 g-10 g / L spray liquor / water. In any case, however, the antioxidant is used in a stoichiometric excess of preferably 1.1 to 50 equivalents, more preferably 1.5 to 25 equivalents, even more preferably 1.8 to 15 equivalents and particularly preferably 2-12 equivalents the dissolved oxygen in the water is used to ensure rapid removal of the dissolved oxygen in the air (reaction kinetics)
  • the formulations are agrochemical formulations.
  • formulations according to the present invention can also contain other ingredients other than a) agrochemical active ingredients.
  • the present invention thus further relates to formulations with dithiocarbamate-containing active ingredients, containing: a) at least one dithiocarbamate-containing active ingredient, b) at least one antioxidant selected from the group consisting of sodium sulfite (NaaSCE / E221), ascorbic acid (vitamin CI E300) and sodium disulfite (Na S CE / E223) comprises c) optionally customary further formulation auxiliaries, and d) further agrochemical active ingredients.
  • the active ingredient a) is propineb and the antioxidant is selected from the group comprising sodium sulfite and ascorbic acid.
  • the formulation according to the invention is preferably selected from the group comprising WP and WG.
  • pH-adjusting substances can be added to the formulations and “kit of parts”. This also includes buffer systems known to the person skilled in the art.
  • the buffer particularly preferably consists of ascorbic acid and sodium sulfite.
  • the preferred areas mentioned in the present invention are to be understood as meaning that they can be combined with one another in a permutating manner, but in any case the same preferred levels and in particular the most preferred embodiment / preferred level are to be combined with one another and also disclosed as such a combination.
  • compositions as described above are to be viewed as disclosed which consist only of the essential components (non-optional components).
  • percentages are to be understood as percentages by weight, the percentages by weight of the compositions adding up to 100.
  • formulations or application forms which contain formulation auxiliaries c) such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or other auxiliaries such as adjuvants.
  • formulation auxiliaries c) such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or other auxiliaries such as adjuvants.
  • An adjuvant in this context is a component that improves the biological effect of the formulation without the component itself having a biological effect.
  • adjuvants are agents that promote retention, spreading behavior, adhesion to the leaf surface or penetration.
  • agrochemical active ingredients d) for the purposes of the present invention are fungicidal, insecticidal or herbicidal active ingredients.
  • the formulation according to the invention contains one or more further insecticidal or fungicidal active ingredients d), particularly preferably one or more fungicidal active ingredients d).
  • the active ingredients used are preferably water-insoluble.
  • Preferred insecticidal components d) are, for example, Imidacloprid, Nitenpyram, Acetamiprid, Thiacloprid, Thiamethoxam, Clothianidin, Cyantraniliprole, Chlorantraniliprole, Flubendiamide, Tetraniliprole, Cyclaniliprole, Spirodiclorfen, Eminaphrinamid, Flincrinamido, Fyradiclofen, Flincrinatripone, Fyradyratripone, Fyradyratrifone, , Indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron, the compound from WO-A 2006/089633 as example Ila-4, the compound disclosed in WO-A 2008/067911 as example Ila- 4, the
  • All of the above-mentioned mixing partners of classes (1) to (15) can, if they are capable of doing so on the basis of their functional groups, form salts with suitable bases or acids. All of the named fungicidal mixture partners of classes (1) to (15) can optionally include tautomeric forms.
  • Inhibitors of ergosterol biosynthesis e.g. (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamide, (1.005) fenpropidine, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, ( 1.009) flutriafol, (1.010) imazalil, (L011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazole, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023)
  • Inhibitors of the respiratory chain at complex I or II for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr , (2.009) isofetamide, (2.010) isopyrazam (anti-epimeric enantiomer 1R, 4S, 9S), (2.011) isopyrazam (anti-epimeric enantiomer 1S, 4R, 9R), (2.012) isopyrazam (anti-epimeric racemate 1RS, 4SR , 9SR), (2.013) isopyrazam (mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti-epimeric racemate 1RS, 4SR, 9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1
  • Inhibitors of the respiratory chain at complex III for example (3.001) ametoctradin, (3.002)
  • Inhibitors of mitosis and cell division for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate methyl, (4.008) zoxamide ,, (4.009) 3-chloro-4- (2,6-difluorophenyl) -6-methyl-5-phenylpyridazine, (4.010) 3-chloro-5- (4-chlorophenyl) -4- (2,6-difluorophenyl ) -6-methylpyridazine, (4.011) 3-chloro-5- (6-chloropyridine-3- yl) -6-methyl-4- (2,4,6-trifluorophenyl) pyridazine, (4,012) 4- (2-bromo-4-fluorophenyl) -N- (2,6-di
  • Inhibitors of amino acid and / or protein biosynthesis for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3 - (5 -fluoro- 3, 3, 4,4-tetramethyl-3, 4-dihydroisoquinolin-1-yl) quinoline.
  • Inhibitors of ATP production for example (8.001) Silthiofam.
  • Inhibitors of cell wall synthesis e.g. (9.001) Benthiavalicarb, (9.002) Dimethomorph, (9.003) Flumorph, (9.004) Iprovabcarb, (9.005) Mandipropamid, (9.006) Pyrimorph, (9.007) Valifenalat, (9.008) (2E) -3 - (4-tert-Butylphenyl) -3 - (2-chloropyridin-4-yl) - 1 - (morpholin-4-yl) prop-2-en- 1 -one, (9.009) (2Z) -3 - (4-tert-Butylphenyl) -3 - (2-chloropyridin-4-yl) -1 - (morpholin-4-yl) prop-2-en-1 -one.
  • Inhibitors of lipid and membrane synthesis for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
  • Inhibitors of melanin biosynthesis for example (11,001) tricyclazole, (11,002) 2,2,2-trifluoroethyl- ⁇ 3 -methyl-1 - [(4-methylbenzoyl) amino] butan-2-yl ⁇ carbamate.
  • Inhibitors of nucleic acid synthesis for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
  • Inhibitors of signal transduction e.g. (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) procinazid, (13.005) quinoxyfen, (13.006) vinclozoline.
  • fungicidal components d) are, for example, bixafen, fenamidone, fenhexamid, fluopicolide, fluopyram, fluoxastrobin, iprovalicarb, isotianil, isopyrazam, pencycuron, penflufen, propineb, tebuconazole, trifloxystrobin, amhietoctrobin, benzifoxystrobin, benzhietoctrobin, benzifoxylabyrbine, azifoxylabyrbine, iscalidoxylabyrbine, iscalidoxystrobin, benzifoxylabyrbine, iscalidoxylabyrbine, bosifoxylabyrbine, iscalidoxylabyrbine, benzifoxylabyrbine, Carbendazim, Chlorothanonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Difenoconazole,
  • fungicidal mixture partners are, for example: cymoxanil, tebuconazole, spiroxamine, bixafen, fluoxastrobin, iprovalicarb, trifloxystrobin, N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl -lH-pyrazole-4-carboxamide, (3S, 6S, 7R, 8R) -8-Benzyl-3 - [( ⁇ 3 - [(isobutyryloxy) methoxy] -4-methoxypyridin-2-yl ⁇ carbonyl) amino] - 6-methyl-4,9-dioxol, 5-dioxonan-7-yl, 2-methylpropanoate (lyserphenvalpyr), isoflucypram, fluoxapiproline
  • the proportion of component d) in the formulations according to the invention is preferably 1% by weight to 40% by weight, more preferably 3% by weight to 35% by weight.
  • formulations are prepared in a known manner, e.g. B. by mixing the compounds of formula (I) with auxiliaries such as extenders, solvents and / or solid carriers and / or other auxiliaries such as surface-active substances.
  • auxiliaries such as extenders, solvents and / or solid carriers and / or other auxiliaries such as surface-active substances.
  • the formulations are produced either in suitable systems or before or during use.
  • customary methods can be used as application forms; Examples include: spraying, dipping, misting and a number of special methods for the direct underground or above-ground treatment of entire plants or parts (seeds, roots, stolons, stems, stems, leaves), such as stem injection for trees or stem bandages for perennial plants , and a number of special indirect application methods.
  • the respective area- and / or object-related application rate of the plant protection agents of the most varied of formulation types for combating the harmful organisms mentioned varies very widely.
  • the application media known to the person skilled in the art as being customary for the respective field of use are used in the customary amounts; For example, from several hundred liters of water per hectare in the case of standard spraying methods to a few liters of oil per hectare in the 'Ultra Low Volume' aircraft application to a few milliliters of a physiological solution in the case of injection methods.
  • concentrations of the crop protection agents according to the invention in the corresponding application media therefore vary within a wide range and are dependent on the particular area of use.
  • concentrations are used which are known to the person skilled in the art as customary for the respective field of application. Concentrations from 0.01% by weight to 99% by weight are preferred, particularly preferably from 0.1% by weight to 90% by weight.
  • the agrochemical formulations according to the invention can e.g. in the usual forms of preparation for liquid preparations either as such or after prior dilution with water, e.g. as emulsions, suspensions or solutions.
  • the application takes place according to the usual methods, e.g. by spraying, pouring or injecting.
  • the formulations according to the invention are useful and for controlling a large number of pests can be used both for the treatment of plant cultures, but also for inanimate matter and in the household.
  • Pests or “harmful organisms” are understood here to mean all types of pests which are associated with organic pesticides, i.e. Plant protection agents, in particular fungicides and mixtures of fungicides with other plant protection agents, can be controlled or kept under control.
  • the term pest therefore includes organisms that are harmful to plants, in particular harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants.
  • control includes both curative treatment, i. the treatment of infected plants with a formulation according to the invention, as well as the protective treatment, i.e. the treatment of plants to protect them from pest infestation.
  • the present invention thus also relates to the use of the formulations described herein for controlling pests, in particular plant pests; and a method for controlling harmful organisms, in particular plant-damaging organisms, comprising bringing the harmful organisms, their habitats, their hosts, such as plants and seeds, and the soil, the area and the environment in which they grow or could grow into contact , but also of materials, plants, seeds, soil, surfaces or rooms which are to be protected from attack or attack by organisms which are harmful to plants, with an effective amount of the formulations according to the invention.
  • Another aspect of the invention relates to the use of the formulations described herein for protecting plants, including seeds, in particular in order to protect useful plants from attack by harmful organisms, in particular harmful fungi.
  • the present invention thus also relates to the use of the formulations for combating organisms which are harmful to plants, such as, for example, harmful fungi, insects, arachnids, nematodes and harmful plants, in particular for combating harmful fungi.
  • the formulations of the invention can be used primarily as foliar, dressing and soil fungicides in a manner known per se for combating phytopathogenic fungi.
  • the following plants which can be treated with the formulations according to the invention may be mentioned: cotton, flax, grapevines, fruit, vegetables, such as Rosaceae sp. (for example pome fruits like apple and pear, but also stone fruits like apricots, cherries, almonds and peaches and berries like strawberries), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp.
  • Rosaceae sp. for example pome fruits like apple and pear, but also stone fruits like apricots, cherries, almonds and peaches and berries like strawberries
  • Rosaceae sp. for example pome fruits like apple and pear, but
  • Rubiaceae sp. e.g. coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. e.g. lemons, organs and grapefruit
  • Solanaceae sp. for example Tomatoes
  • Liliaceae sp. for example lettuce
  • Umbelliferae sp. for example lettuce
  • Alliaceae sp. for example leek, onion
  • Papilionaceae sp. e.g.
  • Main crops such as Gramineae sp. (for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (e.g. sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress), Fabacae sp. (e.g. beans, peanuts), Papilionaceae sp. (e.g. soybean), Solanaceae sp. (e.g. potatoes), Chenopodiaceae sp.
  • Gramineae sp. for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale
  • Asteraceae sp. e.g. sunflower
  • sugar beet for example sugar beet, fodder beet, Swiss chard, beetroot
  • Sugar cane poppy seeds, olives, coconut, cocoa, tobacco and useful plants and ornamental plants in gardens and forests; as well as genetically modified species of these plants and the seeds of these plants.
  • the formulations according to the invention are preferably used for treating wheat, barley, rye, soybeans, onions, corn and peanuts.
  • prothioconazole in principle all harmful fungal diseases can be combated which can also be combated with the known formulations of prothioconazole.
  • plant diseases it is for example the following plant diseases:
  • Altemaria species on vegetables, rape, sugar beet, soy, grain, cotton, fruit and rice e.g. A. solani or A. alternata on potatoes and other plants
  • Aphanomyces species on sugar beets and vegetables e.g. Ascochyta sp. on cotton and rice
  • Bipalaris and Drechslera species on maize, grain, rice and turf e.g. teres on barley, D. tritci-repentis on wheat
  • Blumeria graminis prowdery mildew
  • Botrytis cinerea gray mold
  • Vegetables, flowers and vines Botryodiplodia sp.
  • Rhizoctonia species e.g. R. solani
  • Rynchosporium sp. e.g. R. secalis
  • Sclerotinia species e.g. S. sclerotiorum
  • Septoria tritici and Stagonospora nodorum on wheat, Erysiphe (syn.
  • Uncinulanecator on grapevines, Setospaeria species on maize and lawn , Sphacelotheca reilinia on maize, Thievaliopsis species on soybeans and cotton, Tilletia species on grain, Ustilago species on grain, maize and sugar beet, and Venturia species (scab) on apple and pear (e.g. V inaequalis on apple).
  • the formulations according to the invention are generally with at least one part of water, preferably with 10 parts of water and particularly preferably with at least 100 parts of water, for example with 1 to 10,000, preferably 10 to 5,000 and very particularly preferably 50 to 24,000 parts of water per part the formulation diluted.
  • the dilution is achieved by pouring the formulations according to the invention into the water. Agitation, such as, for example, stirring, is usually used for rapid mixing of the formulation with water. However, agitation is usually not necessary. Although the temperature is not a critical factor for the dilution process, dilutions are usually carried out at temperatures in the range from 0 ° C. to 50 ° C., in particular at 10 ° C. to 30 ° C., or at ambient temperature.
  • the water used for dilution is usually tap water or well water or water from other local sources.
  • the water can already contain water-soluble or finely dispersed compounds that are used in crop protection, such as nutrients, fertilizers or pesticides.
  • oils, wetting agents, adjuvants, fertilizers or micronutrients and other pesticides can be added to the emulsion according to the invention as a premix or, if necessary, shortly before use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be added to the formulations according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
  • the user usually applies the formulation according to the invention from a pre-metering device, a knapsack sprayer, a spray tank, a spray aircraft or an irrigation system.
  • the formulation according to the invention is diluted to the desired concentration with water, buffer and / or other auxiliaries, whereby the ready-to-use spray liquid or agrochemical Composition of the invention obtained.
  • 20 to 2000 Fiter, preferably 50 to 400 Fiter, of the ready-to-use spray mixture are applied per hectare of agricultural land.
  • the required application rates of the pure active ingredients without formulation auxiliaries depend on the intensity of the pest infestation, the development phase of the plants, the climatic conditions of the place of use and the application method.
  • the application rate is in the range from 0.001 to 10 kg, preferably from 0.005 to 8 kg, particularly preferably from 0.01 to 5 kg and very particularly preferably from 0.1 to 4 active ingredient per hectare, with active ingredient here plus propineb means of possible further active ingredients.
  • the generally diluted formulations of the invention are applied mainly by spraying, in particular spraying the leaves.
  • the application can be carried out with spray techniques known to the person skilled in the art, for example using water as the carrier and spray liquor quantities of about 50 to 2,000 liters per hectare, for example from 100 to 1000 liters per hectare.
  • the new propineb-containing formulations have advantageous properties for the treatment of plants, in particular they are distinguished by good application properties, high stability and high fungicidal activity.
  • the solid components are presented at room temperature. All components are distributed homogeneously with intensive mixing. If necessary, comminution takes place in a dry environment, e.g. with an air jet mill, the entire mixture.
  • the final product is the WP (e.g. wettable powder WP70).
  • WG e.g. water dispersible granules WG70
  • the DIDT which may be formed in the spray liquor by the atmospheric oxygen dissolved in the water, is separated on a reversed-phase column using a solvent gradient.
  • the quantitative evaluation is carried out by comparing the peak areas with those of the reference object, using an external or, if necessary, stable isotope-labeled internal standard (when determined using LC-MS / MS).
  • Agilent 1290 high pressure liquid chromatograph Sample injection Agilent 1290 or CTC PAL
  • UV detector Agilent 1290 DAD
  • FIG. 1 shows the increase in the DIDT concentration in an aqueous spray liquor in mg per L over time, depending on the amount and type of antioxidant, an Antracol WG70 (active ingredient: Propineb) formulation serving as the basis.
  • the experiment showed that a weakly acidic pH value (pH 3-4; due to ascorbic acid) and buffered systems (pH 6-7; due to the mixture of ascorbic acid and sodium sulfite) have a positive influence on the degradation.
  • the DIDT content was determined analogously to the determination of DIDT in drinking water against calibration standards from DIDT
  • FIG. 2 shows the significantly lower DIDT concentration at the time 0 hours after the application and the increase in the DIDT concentration in the first 24 hours after the application.

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Abstract

The invention relates to stabilized dithiocarbamate formulations, in particular stabilized formulations of active ingredients that contain dithiocarbamates as functional groups, such as for example propineb, maneb and mancozeb.

Description

Stabilisierte Formulierungen von Dithiocarbamaten Stabilized formulations of dithiocarbamates
Die vorliegende Erfindung betrifft stabilisierte Formulierungen von Dithiocarbamaten, insbesondere von Wirkstoffen, die Dithiocarbamate als Funktionsgruppen enthalten, wie beispielsweise Propineb, Maneb und Mancozeb. The present invention relates to stabilized formulations of dithiocarbamates, in particular of active ingredients which contain dithiocarbamates as functional groups, such as, for example, propineb, maneb and mancozeb.
Im Besonderen ist die vorliegende Erfindung auf Formulierungen mit Dithiocarbamt-Wirkstoffen gerichtet, die bei und nach der Formulierung und anwendungsfertigen Verdünnung einen besonders niedrigem Gehalt der entsprechenden Oxidations-Umlagerungsprodukte enthalten. In particular, the present invention is directed to formulations with dithiocarbamate active ingredients which contain a particularly low content of the corresponding oxidation rearrangement products during and after formulation and ready-to-use dilution.
Ferner ist die vorliegende Erfindung auf ein Verfahren zur Herstellung der oben genannten Formulierungen, ein Verfahren zur Bekämpfung phytopathogener Pilze im Pflanzenschutz, sowie deren Verwendung als Pflanzenschutzmittel gerichtet. The present invention is also directed to a process for producing the above-mentioned formulations, a process for combating phytopathogenic fungi in crop protection, and their use as crop protection agents.
Darüber hinaus ist die vorliegende Erfindung auf bestimmte Antioxidantien enthaltende Formulierungen, insbesondere Vitamin C (Ascorbinsäure) und/oder Natriumsulfit-haltige Formulierungen, von Dithiocarbamaten gerichtet, insbesondere von agrochemischen Wirkstoffen mit Dithiocarbamat-Gruppen, gerichtet, sowie die Verwendung bestimmter Antioxidantien, inbesondere Vitamin C (Ascorbinsäure) und Natriumsulfit zur Stabilisierung von Dithiocarbamat-Verbindungen, insbesondere von agrochemischen Wirkstoffen mit Dithiocarbamat-Gruppen. In addition, the present invention is directed to certain antioxidant-containing formulations, in particular vitamin C (ascorbic acid) and / or formulations containing sodium sulfite, of dithiocarbamates, in particular of agrochemical active ingredients with dithiocarbamate groups, and the use of certain antioxidants, in particular vitamin C. (Ascorbic acid) and sodium sulfite to stabilize dithiocarbamate compounds, in particular agrochemical active ingredients with dithiocarbamate groups.
Schließlich ist die vorliegende Erfindung auf Formulierungen gerichtet, die die oben genannten Antioxidantien in der Formulierung direkt oder auch als "Kit of Parts" als einzeln zuzugebenden Wirkstoff enthalten. Die größten Vorteile eines Kit of Parts liegen beispielsweise darin, dass die Antioxidantien das Wasser bereits vor der Wirkstoff- / Formulierungszugabe entoxygnieren, keine Veränderung der Formulierung erfolgen muss, sich die erforderlichen Antioxidantien leicht zudosieren lassen und sich das Kit of Parts nicht negativ auf Fagerstabilität oder chemische Stabilität von fertigen stabilen Formulierungen auswirkt. Finally, the present invention is directed to formulations which contain the above-mentioned antioxidants in the formulation directly or also as a “kit of parts” as an active ingredient to be added individually. The greatest advantages of a kit of parts are, for example, that the antioxidants deoxygenate the water before the active ingredient / formulation is added, there is no need to change the formulation, the required antioxidants can be easily added and the kit of parts does not have a negative effect on stability or chemical stability of finished stable formulations.
Darüber hinaus ist die vorliegende Erfindung auf die Verwendung von Antioxidantien, insbesondere von Vitamin C (Ascorbinsäure) und/oder Natriumsulfit, zur Stabilisierung von agrochemischen Wirkstoffen mit Dithiocarbamat-Gruppen, insbesondere Propineb und Mancozeb, in agrochemischen Formulierungen gerichtet. In addition, the present invention is directed to the use of antioxidants, in particular vitamin C (ascorbic acid) and / or sodium sulfite, for stabilizing agrochemical active ingredients with dithiocarbamate groups, in particular propineb and mancozeb, in agrochemical formulations.
Dithiocarbamat-Wirkstoffe wie Propineb (The Pesticide Manual, 15th Edition 2009, Seiten 954-955 und GB Patent 935,981, Cas Nr. 12071-83-9) Maneb (Manganethylen-l,2-bis-dithiocarbamat / Cas Nr. 12427- 38-2) und Mancozeb (Mangan-Zink-Ethylenbis(dithiocarbamat) / Cas Nr. 8018-01-7) sind seit langem als Pflanzenschutzmittel bei Pilzerkrankungen bekannt. So werden sie beispielsweise beim Anbau von Obst, Gemüse und Wein zur Bekämpfüng von Mehltau und Schorf sowie Kraut- und Braunfäule bei Kartoffeln und Tomaten eingesetzt. Dithiocarbamate active ingredients such as propineb (The Pesticide Manual, 15 th Edition 2009, pages 954-955 and GB Patent 935.981, Cas no. 12071-83-9) maneb (manganese ethylene-l, 2-bis-dithiocarbamate / Cas no. 12427- 38-2) and Mancozeb (Manganese-Zinc-Ethylenebis (dithiocarbamate) / Cas No. 8018-01-7) have long been known as plant protection agents for fungal diseases. For example, they are used in the cultivation of fruit, vegetables and wine to combat powdery mildew and scab as well as late blight and brown rot in potatoes and tomatoes.
Der Breitbandfungizidwirkstoff Propineb wird zum Beispiel weltweit im Pflanzenschutz angewendet. Die Hauptanwendungsbereiche sind der Reisanbau, Kartoffelanbau, Tomaten, Weinbau und viele weitere Nebenkulturen. Die Hauptdarreichungsformen sind die Formulierungen wie Antracol WP70 und WG70 (BAYER), aber auch Mischungen mit z.B. Iprovalicarb und Trifloxystrobin sind im Markt platziert. The broad-spectrum fungicidal active ingredient Propineb, for example, is used worldwide in crop protection. The main areas of application are rice cultivation, potato cultivation, tomatoes, viticulture and many other secondary crops. The main dosage forms are the formulations such as Antracol WP70 and WG70 (BAYER), but also mixtures with e.g. Iprovalicarb and trifloxystrobin have been placed on the market.
Zur Applikation des Wirkstoffes wird die Produktformulierung in Wasser angerührt und in verschiedenen Aufwand- und Wassermengen pro Hektar landwirtschaftlicher Fläche ausgesprüht. To apply the active ingredient, the product formulation is mixed with water and sprayed on in various amounts and amounts of water per hectare of agricultural area.
Aufgrund des in Wasser gelösten Luftsauerstoffs (cfO gesättigt) @ 20°C = 9 mg/L) kann jedoch ein Teil des Dithiocarbamat-enthaltenden Wirkstoffes abgebaut werden. Due to the oxygen in the air (cfO saturated) @ 20 ° C = 9 mg / L) dissolved in water, part of the active ingredient containing dithiocarbamate can be broken down.
Im Nachfolgenden ist dieses Beispielhaft für Propineb gezeigt (Schema 1). This is shown below as an example for Propineb (Scheme 1).
Figure imgf000003_0001
Figure imgf000003_0001
(Schema 1) (Scheme 1)
Auf Grund dieser in üblichen Spritzbrühen möglichen und bis zum vollständigen Verbrauch des anwesenden gelösten Luftsauerstoffs ablaufenden chemischen Reaktion wird zum einen die Wirksamkeit des Wirkstoffes unter Umständen reduziert, zum anderen kann in manchen Fällen ein Oxidationsprodukt entstehen, in diesem Fall Methyl -dihydro-imidazo-dithiazol-thion (Iupac-Nomenklatur: 6-methyl-5,6- dihydro-imidazo(2, l-c)(l,2,4)dithiazole-3-thion), im folgenden DIDT. Due to this chemical reaction, which is possible in conventional spray liquors and which takes place until the dissolved atmospheric oxygen present is completely consumed, on the one hand the effectiveness of the active ingredient may be reduced, and on the other hand an oxidation product can arise in some cases, in this case methyl-dihydro-imidazo-dithiazole -thion (Iupac nomenclature: 6-methyl-5,6-dihydro-imidazo (2, lc) (l, 2,4) dithiazole-3-thione), hereinafter DIDT.
Bedingt durch die Stöchiometrie der oben gezeigten Umsetzung - ein Sauerstoffmolekül O2 (32 mg/mmol) bildet theoretisch zwei Oxidationsproduktmoleküle (190 mg/mmol x2) - können so pro 100 L Spritzbrühe theoretisch 10.7 g Oxidationsprodukt gebildet werden. Hierbei ist zu beachten, dass mit steigender Verdünnung des Wirkstoffs in der Spritzbrühe der Wirkstoffverlust durch diese Reaktion steigt, da in einer größeren Wassermenge mehr Sauerstoff gelöst werden kann. Due to the stoichiometry of the conversion shown above - one oxygen molecule O2 (32 mg / mmol) theoretically forms two oxidation product molecules (190 mg / mmol x2) - theoretically 10.7 g of oxidation product can be formed per 100 L spray mixture. It should be noted here that the greater the dilution of the active ingredient in the spray liquor, the greater the loss of active ingredient due to this reaction, since more oxygen can be dissolved in a larger amount of water.
Neben dem WirkstoffVerlust ist, wie oben erwähnt, das Oxidationsprodukt DIDT gegebenenfalls für Zulassung und Registrierung relevant. In addition to the loss of active ingredient, as mentioned above, the oxidation product DIDT may be relevant for approval and registration.
Demnach ist es ist von großer Bedeutung, diese chemische Reaktion in der Spritzbrühe von Anfang an durch Entfernen des gelösten Uuftsauerstoffs zu unterbinden. Aufgrund der großen erforderlichen Wassermengen (im m3 Bereich) ist hier jedoch eine Entgasung des Wassers vor Zugabe des Formulierungskonzentrats nicht praktikabel. It is therefore of great importance to prevent this chemical reaction in the spray mixture from the start by removing the dissolved oxygen. Because of the large required For water quantities (in the m 3 range), however, degassing the water before adding the formulation concentrate is not practicable.
Somit wird nicht nur der Verlust an Wirkstoff verhindert, sondern auch die Bildung eines Oxidationsproduktes. Darüber hinaus sind Natriumsulfit und Ascorbinsäure übliche Lebensmittelzusatzstoffe (E221 und E300), die hinsichtlich Toxikologie und Registrierung keine Hürden dar stellen. This not only prevents the loss of active ingredient, but also the formation of an oxidation product. In addition, sodium sulfite and ascorbic acid are common food additives (E221 and E300) that do not represent any hurdles in terms of toxicology and registration.
Es bestand somit Bedarf an stabilen Dithiocarbamat-haltigen Wirkstoff-Formulierungen, die beim Kontakt mit Sauerstoff, auch in wassergelöster Form, keinen Abbau der Wirkstoffe zeigen, wobei die Stabilisierungsmittel / Antioxidantien für den agrochemischen Einsatz unbedenklich oder ohne Zulassungshürden sein sollten. There was therefore a need for stable dithiocarbamate-containing active ingredient formulations which show no degradation of the active ingredients on contact with oxygen, even in water-dissolved form, and the stabilizing agents / antioxidants should be harmless for agrochemical use or without approval hurdles.
Die Aufgabe der vorliegenden Erfindung bestand somit in der Bereitstellung von neuen, verbesserten Dithiocarbamat-haltigen Wirkstoff-Formulierungen, die über eine hohe Oxidationsstabilität, sowohl bei Lagerung, insbesondere aber beim Anrühren der Spritzbrühen aufweisen, sowie die Verwendung von spezifischen Antioxidantien zur Stabilisierung von Dithiocarbamat-haltigen Wirkstoff-Formulierungen.. The object of the present invention was thus to provide new, improved dithiocarbamate-containing active ingredient formulations which have a high level of oxidation stability, both during storage, but in particular when the spray liquors are mixed, and the use of specific antioxidants to stabilize dithiocarbamate containing active ingredient formulations.
Ferner war es Aufgabe der vorliegenden Erfindung, Stabilisatoren und/oder Stabilisatorsysteme für Dithiocarbamat-haltigen Wirkstoff-Formulierungen bereitzustellen, die in agrochemischen Formulierungen einsetzbar und schon in geringer Menge hochwirksam sind. A further object of the present invention was to provide stabilizers and / or stabilizer systems for dithiocarbamate-containing active ingredient formulations which can be used in agrochemical formulations and are highly effective even in small amounts.
Darüber hinaus war es eine Aufgabe ein Verfahren zur Herstellung von Dithiocarbamat-haltigen Wirkstoff-Formulierungen sowie den daraus erzeugten Spritzbrühen zur Verfügung zu stellen, wobei die Antioxidantien entweder in der fertigen Formulierung bereits vor dem Verdünnen vorliegen oder als Tank- Mix zugesetzt werden (Kit of Parts). In addition, it was an object to provide a method for the production of dithiocarbamate-containing active ingredient formulations and the spray liquors produced therefrom, the antioxidants either being present in the finished formulation before dilution or being added as a tank mix (kit of Parts).
Überraschenderweise wurde gefunden, dass durch Zugabe von Antioxidantien wie Natriumsulfit (NaaSCF / E221), Ascorbinsäure (Vitamin C / E300) oder auch Natriumdisulfit (Na S Oft schon in geringer Konzentration die Oxidation der Dithiocarbamate und somit die Entstehung des Oxidationsproduktes signifikant verringert werden kann. Surprisingly, it was found that by adding antioxidants such as sodium sulfite (NaaSCF / E221), ascorbic acid (vitamin C / E300) or sodium disulfite (Na S, often even in low concentrations, the oxidation of the dithiocarbamates and thus the formation of the oxidation product can be significantly reduced.
Die vorliegende Erfindung betrifft somit Formulierungen mit Dithiocarbamat-haltigen Wirkstoffen, enthaltend: a) mindestens einen Dithiocarbamat-haltigen Wirkstoff, und b) mindestens ein Antioxidans, vorzugsweise ausgewählt aus der Gruppe, die Natriumsulfit (Na SO’, / E221), Ascorbinsäure (Vitamin C / E300) und Natriumdisulfit (Na S O^ / E223) umfasst. Vorzugsweise ist der Wirkstoff a) ausgewählt aus der Gruppe, die Propineb, Maneb und Mancozeb sowie deren Mischungen umfasst. The present invention thus relates to formulations with dithiocarbamate-containing active ingredients, containing: a) at least one dithiocarbamate-containing active ingredient, and b) at least one antioxidant, preferably selected from the group consisting of sodium sulfite (Na SO ', / E221), ascorbic acid (vitamin C / E300) and sodium disulfite (Na SO ^ / E223). The active ingredient a) is preferably selected from the group comprising Propineb, Maneb and Mancozeb and mixtures thereof.
Weiter bevorzugt ist das Antioxidans ausgewählt aus der Gruppe, die Natriumsulfit und Ascorbinsäure sowie deren Mischungen umfasst. The antioxidant is more preferably selected from the group comprising sodium sulfite and ascorbic acid and mixtures thereof.
In einer bevorzugten Ausführungsform ist der Wirkstoff a) Propineb und das Antioxidanz ausgewählt aus der Gruppe, die die Natriumsulfit und Ascorbinsäure umfasst. In a preferred embodiment, the active ingredient a) is propineb and the antioxidant is selected from the group comprising sodium sulfite and ascorbic acid.
Der Wirkstoff a) liegt vorzugsweise in den erfmdungsgemäßen Formulierungen in einer Menge von 10 - 99,5 Gew.-%, weiter bevorzugt von 25 - 99 Gew.%, noch weiter bevorzugt von 40 - 98 Gew.-%, weiter bevorzugt von 50 - 97 Gew.-%, sowie bevorzugt von 40 - 95 Gew.-%, weiter bevorzugt in einer Menge von 50 - 90 Gew.-%, noch weiter bevorzugt in einer Menge von 65 - 90 Gew.-%, und besonders bevorzugt in einer Menge von 70 - 86 Gew. -%, jeweils bezogen auf das Gesamtgewicht der Formulierung vor. The active ingredient a) is preferably present in the formulations according to the invention in an amount of 10-99.5% by weight, more preferably 25-99% by weight, even more preferably 40-98% by weight, more preferably 50% - 97% by weight, and preferably from 40-95% by weight, more preferably in an amount of 50-90% by weight, even more preferably in an amount of 65-90% by weight, and particularly preferred in an amount of 70-86% by weight, based in each case on the total weight of the formulation.
Das Antioxidans b) liegt vorzugsweise in den erfmdungsgemäßen Formulierungen in einer Menge von 0,5 - 90 Gew.-%, weiter bevorzugt in einer Menge von 1,0 - 75 Gew.-%, noch weiter bevorzugt in einer Menge von 2,0 - 60 Gew.-%, und besonders bevorzugt in einer Menge von 3,0 - 50 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Formulierung vor. The antioxidant b) is preferably present in the formulations according to the invention in an amount of 0.5-90% by weight, more preferably in an amount of 1.0-75% by weight, even more preferably in an amount of 2.0 - 60 wt .-%, and particularly preferably in an amount of 3.0-50 wt .-%, each based on the total weight of the formulation.
In einer alternativen Ausführungsform liegt die erfindungsgemäße Formulierung als "Kit of Parts", im folgenden Baukasten, vor. In dieser Ausführungsform ist das Antioxidans b) nicht in der fertigen Formulierung enthalten, sondern als Beipack beispielsweise in Tablettenform oder als wasserlöslicher Beutel oder Aufreißbeutel oder in einer anderen geeigneten Verpackung Bestandteil der Formulierung. Das Antioxidans wird in diesem Fall vor dem Anmischen der Formulierung in das Wasser gegeben. In an alternative embodiment, the formulation according to the invention is available as a “kit of parts”, in the following construction kit. In this embodiment, the antioxidant b) is not contained in the finished formulation, but rather as an accessory pack, for example in tablet form or as a water-soluble bag or tear-open pouch or in another suitable packaging component of the formulation. In this case, the antioxidant is added to the water before the formulation is mixed.
Überraschenderweise zeigte sich, dass auch eine unmittelbar vor dem Anmischen des Wirkstoffs erfolgende Zugabe des Antioxidans in das Wasser einen ausreichenden Schutz vor oxidativem Abbau des Wirkstoffs liefert. Surprisingly, it was found that adding the antioxidant to the water immediately prior to mixing the active ingredient also provides adequate protection against oxidative degradation of the active ingredient.
Im Falle eines Baukastens wird das Antioxidans so dosiert, dass es vorzugsweise in einer Menge von 0,1 g - 15 g / L Wasser/Spritzbrühe, weiter bevorzugt von 0,5 g - 12 g / L Wasser und besonders bevorzugt von 2 g - 8 g / L Wasser zugesetzt wird, wobei diese Bereiche auch für die durch Verdünnung der Formulierung hergestellten Spritzbrühe gelten. In the case of a modular system, the antioxidant is dosed in such a way that it is preferably in an amount of 0.1 g - 15 g / L water / spray liquid, more preferably 0.5 g - 12 g / L water and particularly preferably 2 g - 8 g / L water is added, these ranges also applying to the spray liquor produced by diluting the formulation.
In einer alternativen Ausführungsform wird im Falle eines Baukastens oder für die durch Verdünnung hergestellten Spritzbrühe das Antioxidans so dosiert, dass es vorzugsweise in einer Menge von 0,3 g - 10 g / L Spritzbrühe/Wasser vorliegt. In jedem Fall wird das Antioxidans aber in einem stöchiometrischen Überschuss von vorzugsweise 1,1 bis 50 Equivalenten, weiter bevorzugt von 1,5 bis 25 Equivalenten, noch weiter bevorzugt von 1,8 bis 15 Equivalenten und besonders bevorzugt von 2- 12 Equivalenten bezogen auf den im Wasser gelösten Sauerstoff eingesetzt, um eine schnelle Entfernung des gelösten Luftsauerstoffs zu gewährleisten (Reaktionskinetik) In an alternative embodiment, in the case of a modular system or for the spray liquor produced by dilution, the antioxidant is dosed in such a way that it is preferably present in an amount of 0.3 g-10 g / L spray liquor / water. In any case, however, the antioxidant is used in a stoichiometric excess of preferably 1.1 to 50 equivalents, more preferably 1.5 to 25 equivalents, even more preferably 1.8 to 15 equivalents and particularly preferably 2-12 equivalents the dissolved oxygen in the water is used to ensure rapid removal of the dissolved oxygen in the air (reaction kinetics)
Dem Fachmann ist hierbei geläufig, wie die Menge des gelösten Sauerstoff in Abhängigkeit von Temperatur und anderen Faktoren oder aber mit einfachen Schnelltests zu bestimmen ist. The person skilled in the art is familiar with how the amount of dissolved oxygen is to be determined as a function of temperature and other factors or with simple quick tests.
Vorzugsweise sind die Formulierungen agrochemische Formulierungen. Preferably the formulations are agrochemical formulations.
Weiterhin können die Formulierungen gemäß der vorliegenden Erfindung, wie sie vorangehend beschrieben worden sind, noch weitere Inhaltsstoffe andere von a) verschiedene agrochemische Wirkstoffe enthalten. Furthermore, the formulations according to the present invention, as they have been described above, can also contain other ingredients other than a) agrochemical active ingredients.
Die vorliegende Erfindung betrifft somit ferner Formulierungen mit Dithiocarbamat-haltigen Wirkstoffen, enthaltend: a) mindestens einen Dithiocarbamat-haltigen Wirkstoff, b) mindestens ein Antioxidans ausgewählt aus der Gruppe, die Natriumsulfit (NaaSCE / E221), Ascorbinsäure (Vitamin CI E300) und Natriumdisulfit (Na S CE / E223) umfaßt, c) optional übliche weitere Formulierungshilfsstoffe, und d) weitere agrochemische Wirkstoffe. The present invention thus further relates to formulations with dithiocarbamate-containing active ingredients, containing: a) at least one dithiocarbamate-containing active ingredient, b) at least one antioxidant selected from the group consisting of sodium sulfite (NaaSCE / E221), ascorbic acid (vitamin CI E300) and sodium disulfite (Na S CE / E223) comprises c) optionally customary further formulation auxiliaries, and d) further agrochemical active ingredients.
In einer bevorzugten Ausführungsform ist der Wirkstoff a) Propineb und das Antioxidanz ausgewählt aus der Gruppe, die die Natriumsulfit und Ascorbinsäure umfasst. In a preferred embodiment, the active ingredient a) is propineb and the antioxidant is selected from the group comprising sodium sulfite and ascorbic acid.
Vorzugsweise ist die erfmdungsgemäße Formulierung ausgewählt aus der Gruppe, die WP und WG umfaßt. The formulation according to the invention is preferably selected from the group comprising WP and WG.
Weiter bevorzugt ist der pH-Wert der Formulierung sowie der daraus resultierenden Spritzbrühen im schwach sauren Bereich bis neutralem Bereich, d.h. pH 3-7. Hierzu können den Formulierungen und„Kit of parts“ pH-adjustierende Stoffe zugegeben werden. Hierzu zählen auch Puffersysteme, die dem Fachmann bekannt sind. The pH of the formulation and of the spray liquors resulting therefrom in the weakly acidic to neutral range, i.e. pH 3-7. For this purpose, pH-adjusting substances can be added to the formulations and “kit of parts”. This also includes buffer systems known to the person skilled in the art.
Besonders bevorzugt besteht der Puffer aus Ascorbinsäure und Natriumsulfit. Ferner sind in der vorliegenden Erfindung genannten Vorzugsbereichen die verschiedenen Vorzugsebenen so zu verstehen, dass diese permutierend miteinander kombiniert werden können, in jedem Fall sind aber gleiche Vorzugsebenen und insbesondere die jeweils am meisten bevorzugte Ausführungsform / Vorzugsebene miteinander zu kombinieren und als solche Kombination auch offenbart. The buffer particularly preferably consists of ascorbic acid and sodium sulfite. Furthermore, the preferred areas mentioned in the present invention are to be understood as meaning that they can be combined with one another in a permutating manner, but in any case the same preferred levels and in particular the most preferred embodiment / preferred level are to be combined with one another and also disclosed as such a combination.
Ebenso sollen Zusammensetzungen wie oben beschrieben als offenbart angesehen werden, die nur aus den essentiellen Komponenten (nicht optionale Komponenten) bestehen. Likewise, compositions as described above are to be viewed as disclosed which consist only of the essential components (non-optional components).
Prozentzahlen sind - wenn nicht anders angegeben - als Gewichtsprozente zu verstehen, wobei sich die Gew-% der Zusammensetzungen zu 100 addieren. Unless stated otherwise, percentages are to be understood as percentages by weight, the percentages by weight of the compositions adding up to 100.
Vorzugsweise handelt es sich um Formulierungen oder Anwendungsformen, welche Formulierungshilfsstoffe c) wie beispielsweise Streckmittel, Lösemittel, Spontanitätsförderer, Trägerstoffe, Emulgiermittel, Dispergiermittel, Frostschutzmittel, Biozide, Verdicker und/oder weitere Hilfsstoffe wie beispielsweise Adjuvantien enthalten. Ein Adjuvant in diesem Kontext ist eine Komponente, die die biologische Wirkung der Formulierung verbessert, ohne dass die Komponente selbst eine biologische Wirkung hat. Beispiele für Adjuvantien sind Mittel, die die Retention, das Spreitverhalten, das Anhaften an der Blattoberfläche oder die Penetration fördern. These are preferably formulations or application forms which contain formulation auxiliaries c) such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or other auxiliaries such as adjuvants. An adjuvant in this context is a component that improves the biological effect of the formulation without the component itself having a biological effect. Examples of adjuvants are agents that promote retention, spreading behavior, adhesion to the leaf surface or penetration.
Die hier mit ihrem“Common Name” spezifizierten Wirkstoffe sind bekannt und beispielsweise im “Pesticide Manual” (16. Aufl. British Crop Protection Council) oder im Internet recherchierbar (beispielsweise: http://www.alanwood.net/Desticidesl beschrieben. The active ingredients specified here with their “Common Name” are known and are described, for example, in the “Pesticide Manual” (16th edition. British Crop Protection Council) or on the Internet (for example: http://www.alanwood.net/Desticidesl).
Weitere agrochemische Wirkstoffe d) im Sinne der vorliegenden Erfindung sind füngizide, insektizide oder herbizide Wirkstoffe. In einer alternativen Ausführungsform enthält die erfmdungsgemäße Formulierung ein oder mehrere weitere insektizide oder fungizide Wirkstoffe d), besonders bevorzugt ein oder mehrere füngizide Wirkstoffe d). Bevorzugt sind die eingesetzten Wirkstoffe wasserunlöslich. Further agrochemical active ingredients d) for the purposes of the present invention are fungicidal, insecticidal or herbicidal active ingredients. In an alternative embodiment, the formulation according to the invention contains one or more further insecticidal or fungicidal active ingredients d), particularly preferably one or more fungicidal active ingredients d). The active ingredients used are preferably water-insoluble.
Eine Übersicht typischer Pflanzenschutzwirkstoffe findet sich im Pesticide manual. An overview of typical crop protection agents can be found in the Pesticide manual.
Bevorzugte insektizide Komponenten d) sind beispielsweise Imidacloprid, Nitenpyram, Acetamiprid, Thiacloprid, Thiamethoxam, Clothianidin, Cyantraniliprole, Chlorantraniliprole, Flubendiamide, Tetraniliprole, Cyclaniliprole, Spirodiclofen, Spiromesifen, Spirotetramat, Abamectin, Acrinathrin, Chlorfenapyr, Emamectin, Ethiprole, Fipronil, Flonicamid, Flupyradifürone, Indoxacarb, Metaflumizone, Methoxyfenozid, Milbemycin, Pyridaben, Pyridalyl, Silafluofen, Spinosad, Sulfoxaflor, Triflumuron, die Verbindung aus WO-A 2006/089633 als Beispiel I-l-a-4, die Verbindung offenbart in WO-A 2008/067911 als Beispiel I-l-a-4, die Verbindung offenbart in WO 2013/092350 als Beispiel Ib- 14, die Verbindung offenbart in WO 2010/51926 als Beispiel Ik-84. Bevorzugte fungizide Komponenten d) sind beispielsweise im Folgenden genannt. Preferred insecticidal components d) are, for example, Imidacloprid, Nitenpyram, Acetamiprid, Thiacloprid, Thiamethoxam, Clothianidin, Cyantraniliprole, Chlorantraniliprole, Flubendiamide, Tetraniliprole, Cyclaniliprole, Spirodiclorfen, Eminaphrinamid, Flincrinamido, Fyradiclofen, Flincrinatripone, Fyradyratripone, Fyradyratrifone, , Indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron, the compound from WO-A 2006/089633 as example Ila-4, the compound disclosed in WO-A 2008/067911 as example Ila- 4, the compound disclosed in WO 2013/092350 as an example Ib-14, the compound disclosed in WO 2010/51926 as an example Ik-84. Preferred fungicidal components d) are mentioned below, for example.
Alle genannten Mischungspartner der Klassen (1) bis (15) können, wenn sie auf Grund ihrer funktionellen Gruppen dazu imstande sind, gegebenenfalls mit geeigneten Basen oder Säuren Salze bilden. Alle genannten fungiziden Mischungspartner der Klassen (1) bis (15) können gegebenenfalls tautomere Formen einschließen. All of the above-mentioned mixing partners of classes (1) to (15) can, if they are capable of doing so on the basis of their functional groups, form salts with suitable bases or acids. All of the named fungicidal mixture partners of classes (1) to (15) can optionally include tautomeric forms.
1) Inhibitoren der Ergosterol-Biosynthese, beispielsweise (1.001) Cyproconazol, (1.002) Difenoconazol, (1.003) Epoxiconazol, (1.004) Fenhexamid, (1.005) Fenpropidin, (1.006) Fenpropimorph, (1.007) Fenpyrazamin, (1.008) Fluquinconazol, (1.009) Flutriafol, (1.010) Imazalil, (L011) Imazalil Sulfat, (1.012) Ipconazol, (1.013) Metconazol, (1.014) Myclobutanil, (1.015) Paclobutrazol, (1.016) Prochloraz, (1.017) Propiconazol, (1.018) Prothioconazol, (1.019) Pyrisoxazol, (1.020) Spiroxamin, (1.021) Tebuconazol, (1.022) Tetraconazol, (1.023) Triadimenol, (1.024) Tridemorph, (1.025) Triticonazol, ( 1.026) ( 1 R,2S,5 S)-5 -(4-Chlorbenzyl)-2-(chlormethyl)-2-methyl- 1 -( 1H- 1 ,2,4-triazol- 1 - ylmethyl)cyclopentanol, (1.027) (1 S,2R,5R)-5-(4-Chlorbenzyl)-2-(chlormethyl)-2-methyl-l-(lH- 1,2,4- triazol- 1 -ylmethyl)cyclopentanol, ( 1.028) (2R)-2-( 1 -Chlorcyclopropyl)-4-[( 1 R)-2,2-dichlorcyclopropyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol ( 1.029) (2R)-2-( 1 -Chlorcyclopropyl)-4-[( 1 S)-2,2- dichlorcy clopropyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, (1.030) (2R)-2- [4-(4-Chlorphenoxy)-2-1) Inhibitors of ergosterol biosynthesis, e.g. (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamide, (1.005) fenpropidine, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, ( 1.009) flutriafol, (1.010) imazalil, (L011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazole, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) triticonazole, (1.026) (1 R, 2S, 5 S) -5 - (4-chlorobenzyl) -2- (chloromethyl) -2-methyl- 1 - (1H- 1, 2,4-triazol- 1-ylmethyl) cyclopentanol, (1.027) (1 S, 2R, 5R) -5- ( 4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2,4-triazol-1 -ylmethyl) cyclopentanol, (1.028) (2R) -2- (1 -chlorocyclopropyl) -4 - [(1 R) -2,2-dichlorocyclopropyl] - 1 - (1H- 1, 2,4-triazol- 1 -yl) butan-2-ol (1.029) (2R) -2- (1 -chlorocyclopropyl) -4 - [(1 S) -2,2- d chlorocyclopropyl] - 1 - (1H- 1, 2,4-triazol- 1 -yl) butan-2-ol, (1.030) (2R) -2- [4- (4-chlorophenoxy) -2-
(trifluormethyl)phenyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol, (1.031) (2S)-2-( 1 -Chlorcyclopropyl)-4-(trifluoromethyl) phenyl] - 1 - (1H- 1, 2,4-triazol- 1 -yl) propan-2-ol, (1.031) (2S) -2- (1 -chlorocyclopropyl) -4-
[( 1 R)-2,2-dichlorcyclopropyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, (1.032) (2S)-2-( 1 -Chlorcyclopropyl)- 4-[( 1 S)-2,2-dichlorcy clopropyl]- 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, (1.033) (2S)-2-[4-(4-[(1 R) -2,2-dichlorocyclopropyl] - 1 - (1H- 1, 2,4-triazol-1 -yl) butan-2-ol, (1.032) (2S) -2- (1 -chlorocyclopropyl) - 4 - [(1 S) -2,2-dichlorocyclopropyl] - 1 - (1H- 1, 2,4-triazol-1 -yl) butan-2-ol, (1.033) (2S) -2- [ 4- (4-
Chlorphenoxy)-2-(trifluormethyl)phenyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol, (1.034) (R)- [3 -(4-Chlor- 2-fluorphenyl)-5-(2,4-difluorphenyl)-l,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035) (S)-[3-(4-Chlor-2- fluorphenyl)-5 -(2,4-difluorphenyl)- 1 ,2-oxazol-4-yl] (pyridin-3 -yl)methanol, (1.036) [3 -(4-Chlor-2- fluorphenyl)-5 -(2,4-difluorphenyl)- 1 ,2-oxazol-4-yl] (pyridin-3 -yl)methanol, (1.037) l-({ (2R,4S)-2-[2-Chlorophenoxy) -2- (trifluoromethyl) phenyl] -1 - (1H-1, 2,4-triazol-1 -yl) propan-2-ol, (1.034) (R) - [3 - (4-chloro-2 -fluorophenyl) -5- (2,4-difluorophenyl) -l, 2-oxazol-4-yl] (pyridin-3-yl) methanol, (1.035) (S) - [3- (4-chloro-2- fluorophenyl) -5 - (2,4-difluorophenyl) - 1,2-oxazol-4-yl] (pyridin-3-yl) methanol, (1.036) [3 - (4-chloro-2-fluorophenyl) -5 - (2,4-difluorophenyl) - 1,2-oxazol-4-yl] (pyridin-3-yl) methanol, (1.037) l - ({(2R, 4S) -2- [2-
Chlor-4-(4-chlorphenoxy)phenyl] -4-methyl- 1 ,3 -dioxolan-2-yl }methyl)- 1H- 1 ,2,4-triazol, (1.038) 1 -Chloro-4- (4-chlorophenoxy) phenyl] -4-methyl-1, 3-dioxolan-2-yl} methyl) - 1H- 1, 2,4-triazole, (1.038) 1 -
({(2S,4S)-2-[2-Chlor-4-(4-chlorphenoxy)phenyl]-4-methyl-l,3-dioxolan-2-yl}methyl)-lH-l,2,4-triazol, (1.039) 1 -{ [3 -(2-Chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2-yl]methyl } - 1H- 1 ,2,4-triazol-5 -yl- thiocyanat, (1.040) l-{[rel(2R,3R)-3-(2-Chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2-yl]methyl}-lH- l,2,4-triazol-5-yl-thiocyanat, (1.041) l-{[rel(2R,3S)-3-(2-Chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2- yl]methyl } - 1H- 1 ,2,4-triazol-5 -yl-thiocyanat, ( 1.042) 2-[(2R,4R,5R)- 1 -(2,4-Dichlorphenyl)-5 -hydroxy- 2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazol-3-thion, (1.043) 2-[(2R,4R,5S)-l-(2,4-({(2S, 4S) -2- [2-chloro-4- (4-chlorophenoxy) phenyl] -4-methyl-1,3-dioxolan-2-yl} methyl) -lH-1,2,4- triazole, (1,039) 1 - {[3 - (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -1H-1, 2,4-triazol-5-yl-thiocyanate , (1,040) l - {[rel (2R, 3R) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -lH-1,2,4-triazole -5-yl-thiocyanate, (1.041) l - {[rel (2R, 3S) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -1H-1 , 2,4-triazol-5-yl-thiocyanate, (1,042) 2 - [(2R, 4R, 5R) -1 - (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptane-4 -yl] -2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.043) 2 - [(2R, 4R, 5S) -l- (2,4-
Dichlorphenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazol-3-thion, (1.044) 2- [(2R,4S,5R)-l-(2,4-Dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4- triazol-3-thion, (1.045) 2-[(2R,4S,5S)-l-(2,4-Dichlorphenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4- dihydro-3H-l,2,4-triazol-3-thion, (1.046) 2-[(2S,4R,5R)-l-(2,4-Dichlorphenyl)-5-hydroxy-2,6,6- trimethylheptan-4-yl]-2,4-dihydro-3H- 1 ,2,4-triazol-3 -thion, ( 1.047) 2- [(2S,4R,5 S)- 1 -(2,4-Dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl] -2,4-dihydro-3H-1,4-triazol-3-thione, (1.044) 2- [(2R, 4S , 5R) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl] -2,4-dihydro-3H-1,2,4-triazol-3-thione , (1.045) 2 - [(2R, 4S, 5S) -l- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl] -2,4-dihydro-3H- l, 2,4-triazol-3-thione, (1.046) 2 - [(2S, 4R, 5R) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptane-4- yl] -2,4-dihydro-3H-1, 2,4-triazol-3-thione, (1.047) 2- [(2S, 4R, 5 S) - 1 - (2,4-
Dichlorphenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazol-3-thion, (1.048) 2- [(2S,4S,5R)-l-(2,4-Dichlorphenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazol-Dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl] -2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.048) 2- [(2S, 4S, 5R) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl] -2,4-dihydro-3H-1,2,4- triazole
3-thion, (1.049) 2-[(2S,4S,5S)-l-(2,4-Dichlorphenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4- dihydro-3H-l,2,4-triazol-3-thion, (1.050) 2-[l-(2,4-Dichlorphenyl)-5-hydroxy-2,6,6-trimethylheptan-4- yl]-2,4-dihydro-3H-l,2,4-triazol-3-thion, (1.051) 2-[2-Chlor-4-(2,4-dichlorophenoxy)phenyl]-l-(lH-3-thione, (1.049) 2 - [(2S, 4S, 5S) -1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl] -2,4-dihydro -3H-l, 2,4-triazol-3-thione, (1.050) 2- [1- (2,4-dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl] -2, 4-dihydro-3H-l, 2,4-triazol-3-thione, (1.051) 2- [2-chloro-4- (2,4-dichlorophenoxy) phenyl] -l- (1H-
1.2.4-triazol- 1 -yl)propan-2-ol, (1.052) 2-[2-Chlor-4-(4-chlorphenoxy)phenyl] - 1 -( 1H- 1 ,2,4-triazol- 1 - yl)butan-2-ol, (1.053) 2-[4-(4-Chlorphenoxy)-2-(trifluormethyl)phenyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan- 2-ol, (1.054) 2-[4-(4-Chlorphenoxy)-2-(trifluormethyl)phenyl]- 1 -( 1H- 1 ,2,4-triazol- 1 -yl)pentan-2-ol,1.2.4-triazol-1 -yl) propan-2-ol, (1.052) 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -1 - (1H-1, 2,4-triazol-1 - yl) butan-2-ol, (1.053) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] - 1 - (1H- 1, 2,4-triazol- 1 -yl) butane 2-ol, (1.054) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] -1 - (1H-1, 2,4-triazol-1 -yl) pentan-2-ol,
(1.055) 2-[4-(4-Chlorphenoxy)-2-(trifluormethyl)phenyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol, (1.056) 2-{[3-(2-Chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-l,2,4-triazol-3-thion, (1.057) 2-{[rel(2R,3R)-3-(2-Chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-(1.055) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] - 1 - (1H- 1, 2,4-triazol-1 -yl) propan-2-ol, (1.056) 2- {[3- (2-Chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.057 ) 2 - {[rel (2R, 3R) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -2,4-dihydro-3H-
1.2.4-triazol-3 -thion, (1.058) 2- { [rel(2R,3 S)-3 -(2-Chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2- yl]methyl } -2,4-dihydro-3H- 1 ,2,4-triazol-3 -thion, (1.059) 5 -(4-Chlorbenzyl)-2-(chlormethyl)-2-methyl- 1 - ( 1H- 1 ,2,4-triazol- 1 -ylmethyl)cyclopentanol, (1.060) 5 -(Allylsulfanyl)- 1 - { [3-(2-chlorphenyl)-2-(2,4- difluorphenyl)oxiran-2-yl]methyl}-lH-l,2,4-triazol, (1.061) 5-(Allylsulfanyl)-l-{[rel(2R,3R)-3-(2- chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2-yl]methyl} - 1H- 1 ,2,4-triazol, ( 1.062) 5 -(Allylsulfanyl)- 1 -1.2.4-triazol-3-thione, (1.058) 2- {[rel (2R, 3 S) -3 - (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2- yl] methyl} -2,4-dihydro-3H-1, 2,4-triazol-3-thione, (1.059) 5 - (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1 - (1H-1, 2 , 4-triazol- 1 -ylmethyl) cyclopentanol, (1.060) 5 - (allylsulfanyl) - 1 - {[3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} - 1H-l, 2,4-triazole, (1.061) 5- (allylsulfanyl) -1 - {[rel (2R, 3R) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxirane-2 -yl] methyl} - 1H- 1, 2,4-triazole, (1.062) 5 - (Allylsulfanyl) - 1 -
{ [rel(2R,3 S)-3 -(2-chlorphenyl)-2-(2,4-difluorphenyl)oxiran-2-yl]methyl } - 1H- 1 ,2,4-triazol, (1.063) N'- (2,5-Dimethyl-4-{[3-(l,l,2,2-tetrafluorethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N- methylimidoformamid, ( 1.064) N'-(2,5-Dimethyl-4-{[3-(2,2,2-trifluorethoxy)phenyl]sulfanyl}phenyl)- N-ethyl-N-methylimidoformamid, (1.065) N'-(2,5-Dimethyl-4-{[3-(2, 2,3,3- tetrafluorpropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidofonnamid, (1.066) N'-(2,5-Dimethyl-{[rel (2R, 3 S) -3 - (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl} -1H-1, 2,4-triazole, (1.063) N '- (2,5-Dimethyl-4 - {[3- (l, l, 2,2-tetrafluoroethoxy) phenyl] sulfanyl} phenyl) -N-ethyl-N-methylimidoformamide, (1.064) N' - (2, 5-dimethyl-4 - {[3- (2,2,2-trifluoroethoxy) phenyl] sulfanyl} phenyl) - N-ethyl-N-methylimidoformamide, (1.065) N '- (2,5-dimethyl-4- { [3- (2, 2,3,3-tetrafluoropropoxy) phenyl] sulfanyl} phenyl) -N-ethyl-N-methylimidofonamide, (1.066) N '- (2,5-dimethyl-
4-{[3-(pentafluorethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidofonnamid, (1.067) N'-(2,5-4 - {[3- (pentafluoroethoxy) phenyl] sulfanyl} phenyl) -N-ethyl-N-methylimidofonnamide, (1.067) N '- (2,5-
Dimethyl-4-{3-[(l, l,2,2-tetrafluorethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidofonnamid, (1.068) N'-(2,5-Dimethyl-4-{3-[(2,2,2-trifluorethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N- methylimidofonnamid, (1.069) N'-(2,5-Dimethyl-4-{3-[(2, 2,3,3- tetrafluorpropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamid, (1.070) N'-(2,5-Dimethyl- 4-{3-[(pentafluorethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamid, (1.071) N'-(2,5-Dimethyl-4- {3 - [(l, l, 2,2-tetrafluoroethyl) sulfanyl] phenoxy} phenyl) -N-ethyl-N-methylimidoformamide, (1.068) N '- (2,5-dimethyl-4- { 3 - [(2,2,2-trifluoroethyl) sulfanyl] phenoxy} phenyl) -N-ethyl-N-methylimidoformamide, (1,069) N '- (2,5-dimethyl-4- {3 - [(2, 2 , 3,3-tetrafluoropropyl) sulfanyl] phenoxy} phenyl) -N-ethyl-N-methylimidoformamide, (1,070) N '- (2,5-dimethyl- 4- {3 - [(pentafluoroethyl) sulfanyl] phenoxy} phenyl) -N-ethyl-N-methylimidoformamide, (1.071) N '- (2.5-
Dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidofonnamid, ( 1.072) N'-(4-{ [3-Dimethyl-4-phenoxyphenyl) -N-ethyl-N-methylimidofonnamide, (1.072) N '- (4- {[3-
(Difluonnethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidofonnamid, (1.073) N'- (4-{3-[(Difluonnethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidofonnamid, (1.074) N'-[5-Brom-6-(2,3-dihydro-lH-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N- methylimidofonnamid, (1.075) N'-{4-[(4,5-Dichlor-l,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl- N-methylimidoformamid, (1.076) N'-{5-Brom-6-[(lR)-l-(3,5-difluorophenyl)ethoxy]-2-methylpyridin- 3 -yl } -N -ethy 1-N -methylimidoformamid, (1.077) N'-{5-Brom-6-[(lS)-l-(3,5 -difluorphenyl)ethoxy] -2- methylpyridin-3-yl}-N-ethyl-N-methylimidofonnamid, (1.078) N'-{5-Brom-6-[(cis-4- isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidofonnamid, (1.079) N'-{5-(Difluonnethoxy) phenyl] sulfanyl} -2,5-dimethylphenyl) -N-ethyl-N-methylimidofonnamid, (1.073) N'- (4- {3 - [(Difluonnethyl) sulfanyl] phenoxy} -2,5-dimethylphenyl) -N-ethyl-N-methylimidoform-amide, (1.074) N '- [5-bromo-6- (2,3-dihydro-1H-inden-2-yloxy) -2-methylpyridin-3-yl] -N -ethyl -N- methylimidofonnamid, (1.075) N '- {4 - [(4,5-dichloro-1,3-thiazol-2-yl) oxy] -2,5-dimethylphenyl} -N-ethyl-N-methylimidoformamide, (1.076) N '- {5-Bromo-6 - [(IR) -1- (3,5-difluorophenyl) ethoxy] -2-methylpyridin-3 -yl} -N -ethyl 1-N -methylimidoformamide, (1.077 ) N '- {5-Bromo-6 - [(lS) -l- (3,5-difluorophenyl) ethoxy] -2-methylpyridin-3-yl} -N-ethyl-N-methylimidofonnamid, (1.078) N' - {5-Bromo-6 - [(cis -4-isopropylcyclohexyl) oxy] -2-methylpyridin-3-yl} -N-ethyl-N-methylimidofonnamide, (1.079) N '- {5-
Brom-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidofonnamid, (1.080) N'-{5-Bromo-6-[l-(3,5-difluorphenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N- methylimidoformamid, (1.081) Mefentrifluconazole, (1.082) Ipfentrifluconazole und (1.082) 2-[6-(4- Bromphenoxy)-2-(trifluormethyl)-3 -pyridyl] - 1 -( 1 ,2,4-triazol- 1 -yl)propan-2-ol . Bromo-6 - [(trans -4-isopropylcyclohexyl) oxy] -2-methylpyridin-3-yl} -N-ethyl-N-methylimidofonamide, (1,080) N '- {5-bromo-6- [1- (3rd , 5-difluorophenyl) ethoxy] -2-methylpyridin-3-yl} -N-ethyl-N- methylimidoformamide, (1.081) mefentrifluconazole, (1.082) Ipfentrifluconazole and (1.082) 2- [6- (4-bromophenoxy) -2- (trifluoromethyl) -3 -pyridyl] - 1 - (1, 2,4-triazole- 1 - yl) propan-2-ol.
2) Inhibitoren der Atmungskette am Komplex I oder II beispielsweise (2.001) Benzovindiflupyr, (2.002) Bixafen, (2.003) Boscalid, (2.004) Carboxin, (2.005) Fluopyram, (2.006) Flutolanil, (2.007) Fluxapyroxad, (2.008) Furametpyr, (2.009) Isofetamid, (2.010) Isopyrazam (anti-epimeres Enantiomer 1R,4S,9S), (2.011) Isopyrazam (anti-epimeres Enantiomer 1S,4R,9R), (2.012) Isopyrazam (anti-epimeres Racemat 1RS,4SR,9SR), (2.013) Isopyrazam (Mischung des syn-epimeren Razemates 1RS,4SR,9RS und des anti-epimeren Razemates 1RS,4SR,9SR), (2.014) Isopyrazam (syn-epimeres Enantiomer 1R,4S,9R), (2.015) Isopyrazam (syn-epimeres Enantiomer 1S,4R,9S), (2.016) Isopyrazam (syn-epimeres Racemat 1RS,4SR,9RS), (2.017) Penflufen, (2.018) Penthiopyrad, (2.019) Pydiflumetofen, (2.020) Pyraziflumid, (2.021) Sedaxane, (2.022) l,3-Dimethyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazol-4- carboxamid, (2.023) l,3-Dimethyl-N-[(3R)-l, l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-lH-pyrazol-4- carboxamid, (2.024) l,3-Dimethyl-N-[(3S)-l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-lH-pyrazol-4- carboxamid, (2.025) l-Methyl-3-(trifluormethyl)-N-[2'-(trifluormethyl)biphenyl-2-yl]-lH-pyrazol-4- carboxamid, (2.026) 2-Fluor-6-(trifluoromethyl)-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4- yl)benzamid, (2.027) 3-(Difluormethyl)-l-methyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH- pyrazol-4-carboxamid, (2.028) 3-(Difluormcthyl)- 1 -methyl-N-|(3R)- 1. 1 3-trimcthyl-2.3-dihydro- 1 H- inden-4-yl]-lH-pyrazol-4-carboxamid, (2.029) 3-(Difluormethyl)-l-methyl-N-[(3S)-l, l,3-trimethyl-2,3- dihydro- lH-inden-4-yl] - lH-pyrazol-4-carboxamid, (2.030) 3 -(Difluormethyl)-N-(7 -fluor- 1,1,3- trimethyl-2,3-dihydro-lH-inden-4-yl)-l-methyl-lH-pyrazol-4-carboxamid, (2.031) 3 -(Difluormethyl) -N- [(3R)-7-fluor-l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-l-methyl-lH-pyrazol-4-carboxamid, (2.032) 3 -(Difluoromethyl)-N- [(3 S)-7 -fluor- 1 , 1 ,3 -trimethyl-2,3 -dihydro- lH-inden-4-yl] - 1 -methyl- lH-pyrazol- 4-carboxamid, (2.033) 5,8-Difluor-N-[2-(2-fluor-4-{[4-(trifluormethyl)pyridin-2- yl]oxy}phenyl)ethyl]quinazolin-4-amin, (2.034) N-(2-Cyclopentyl-5-fluorbenzyl)-N-cyclopropyl-3- (difluormethyl)-5-fluor-l-methyl-lH-pyrazol-4-carboxamid, (2.035) N-(2-tert-Butyl-5-methylbenzyl)-N- cyclopropyl-3-(difluormethyl)-5-fluor-l-methyl-lH-pyrazol-4-carboxamid, (2.036) N-(2-tert- Butylbenzyl)-N-cyclopropyl-3-(difluormethyl)-5-fluor-l -methyl- lH-pyrazol-4-carboxamid, (2.037) N- (5-Chlor-2-ethylbenzyl)-N-cyclopropyl-3-(difluormethyl)-5-fluor-l-methyl-lH-pyrazol-4-carboxamid, (2.038) N-(5-Chlor-2-isopropylbenzyl)-N-cyclopropyl-3-(difluormethyl)-5-fluor-l-methyl-lH-pyrazol- 4-carboxamid, (2.039) N-[(lR,4S)-9-(Dichlormethylen)-l,2,3,4-tetrahydro-l,4-methanonaphthalen-5- yl]-3-(difluormethyl)-l-methyl-lH-pyrazol-4-carboxamid, (2.040) N-[(lS,4R)-9-(Dichlormethylen)- 1 ,2,3 ,4-tetrahydro- 1 ,4-methanonaphthalen-5 -yl] -3 -(difluormethyl)- 1 -methyl- lH-pyrazol-4-carboxamid, (2.041 ) N-[ 1 -(2,4-Dichlorphenyl)- 1 -methoxypropan-2-yl] -3 -(difluormethyl)- 1 -methyl- lH-pyrazol-4- carboxamid, (2.042) N-[2-Chlor-6-(trifluormethyl)benzyl]-N-cyclopropyl-3-(difluormethyl)-5-fluor-l- methyl- lH-pyrazol-4-carboxamid, (2.043) N-[3-Chlor-2-fluor-6-(trifluormethyl)benzyl]-N-cyclopropyl- 3-(difluormethyl)-5-fluor-l-methyl-lH-pyrazol-4-carboxamid, (2.044) N-[5-Chlor-2-2) Inhibitors of the respiratory chain at complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr , (2.009) isofetamide, (2.010) isopyrazam (anti-epimeric enantiomer 1R, 4S, 9S), (2.011) isopyrazam (anti-epimeric enantiomer 1S, 4R, 9R), (2.012) isopyrazam (anti-epimeric racemate 1RS, 4SR , 9SR), (2.013) isopyrazam (mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti-epimeric racemate 1RS, 4SR, 9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1R, 4S, 9R), ( 2.015) isopyrazam (syn-epimeric enantiomer 1S, 4R, 9S), (2.016) isopyrazam (syn-epimeric racemate 1RS, 4SR, 9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) pyraziflumide , (2.021) Sedaxane, (2.022) l, 3-dimethyl-N- (l, l, 3-trimethyl-2,3-dihydro-lH-inden-4-yl) -lH-pyrazole-4-carboxamide, ( 2.023) l, 3-Dimethyl-N - [(3R) -l, l, 3-trimethyl-2,3-dihydro-lH-inden-4-yl] -lH-pyrazole-4-carboxamide, (2.024) 1,3-Dimethyl- N - [(3S) -1, 1,3-trimethyl-2,3-dihydro-1H-inden-4-yl] -1H -pyrazole-4-carboxamide, (2.025) 1-methyl -3- (trifluoromethyl) -N- [2 '- (trifluoromethyl) biphenyl-2-yl] -1 H -pyrazole-4-carboxamide, (2.026) 2-fluoro-6- (trifluoromethyl) -N- (l, l , 3-trimethyl-2,3-dihydro-1H-inden-4-yl) benzamide, (2.027) 3- (difluoromethyl) -l-methyl-N- (1,3-trimethyl-2,3-dihydro -lH-inden-4-yl) -lH-pyrazole-4-carboxamide, (2.028) 3- (difluoromethyl) -1-methyl-N- | (3R) -1.1 3-trimethyl-2,3-dihydro-1 H-inden-4-yl] -1 H -pyrazole-4-carboxamide, (2.029) 3- (difluoromethyl) -1-methyl- N - [(3S) -1, 1,3-trimethyl-2,3-dihydro - 1H-inden-4-yl] - 1H-pyrazole-4-carboxamide, (2.030) 3 - (difluoromethyl) -N- (7 -fluoro-1,1,3-trimethyl-2,3-dihydro-1H- inden-4-yl) -1-methyl-1H-pyrazole-4-carboxamide, (2.031) 3 - (difluoromethyl) -N- [(3R) -7-fluoro-l, l, 3-trimethyl-2,3 -dihydro-1H-inden-4-yl] -l-methyl-1H-pyrazole-4-carboxamide, (2.032) 3- (difluoromethyl) -N- [(3 S) -7 -fluoro-1, 1, 3 -trimethyl-2,3-dihydro- 1H-inden-4-yl] -1 -methyl- 1H-pyrazole-4-carboxamide, (2 .033) 5,8-Difluoro-N- [2- (2-fluoro-4 - {[4- (trifluoromethyl) pyridin-2-yl] oxy} phenyl) ethyl] quinazolin-4-amine, (2.034) N - (2-Cyclopentyl-5-fluorobenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N- (2-tert-butyl-5 -methylbenzyl) -N- cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N- (2-tert-butylbenzyl) -N-cyclopropyl-3- ( difluoromethyl) -5-fluoro-l -methyl- lH-pyrazole-4-carboxamide, (2.037) N- (5-chloro-2-ethylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-l- methyl-1H-pyrazole-4-carboxamide, (2.038) N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide , (2.039) N - [(lR, 4S) -9- (dichloromethylene) -l, 2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -3- (difluoromethyl) -l-methyl- lH-pyrazole-4-carboxamide, (2.040) N - [(lS, 4R) -9- (dichloromethylene) - 1, 2,3, 4-tetrahydro-1, 4-methanonaphthalen-5 -yl] -3 - ( difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.041) N- [1 - (2,4-dichlorophenyl) -1-methoxyp ropan-2-yl] -3 - (difluoromethyl) -1-methyl- 1H-pyrazole-4-carboxamide, (2.042) N- [2-chloro-6- (trifluoromethyl) benzyl] -N-cyclopropyl-3- ( difluoromethyl) -5-fluoro-1-methyl- 1H-pyrazole-4-carboxamide, (2.043) N- [3-chloro-2-fluoro-6- (trifluoromethyl) benzyl] -N-cyclopropyl- 3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N- [5-chloro-2-
(trifluormethyl)benzyl]-N-cyclopropyl-3-(difluormethyl)-5-fluor-l-methyl-lH-pyrazol-4-carboxamid, (2.045) N-Cyclopropyl-3-(difluormethyl)-5-fluor-l-methyl-N-[5-methyl-2-(trifluormethyl)benzyl]-lH- pyrazol-4-carboxamid, (2.046) N-Cyclopropyl-3-(difluormethyl)-5-fluor-N-(2-fluor-6-isopropylbenzyl)- l-methyl-lH-pyrazol-4-carboxamid, (2.047) N-Cyclopropyl-3-(difluormethyl)-5-fluor-N-(2-isopropyl-5- methylbenzyl)-l-methyl-lH-pyrazol-4-carboxamid, (2.048) N-Cyclopropyl-3-(difluormethyl)-5-fluor-N- (2-isopropylbenzyl)-l-methyl-lH-pyrazol-4-carbothioamid, (2.049) N-Cyclopropyl-3-(difluoromethyl)- 5-fluor-N-(2-isopropylbenzyl)-l-methyl-lH-pyrazol-4-carboxamid, (2.050) N-Cyclopropyl-3- (difluormethyl)-5-fluor-N-(5-fluor-2-isopropylbenzyl)-l-methyl-lH-pyrazol-4-carboxamid, (2.051) N- Cyclopropyl-3-(difluormethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluor-l-methyl-lH-pyrazol-4- carboxamid, (2.052) N-Cyclopropyl-3-(difluormethyl)-N-(2-ethyl-5-fluorbenzyl)-5-fluor-l-methyl-lH- pyrazol-4-carboxamid, (2.053) N-Cyclopropyl-3-(difluormethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluor-l- methyl- lH-pyrazole-4-carboxamid, (2.054) N-Cyclopropyl-N-(2-cyclopropyl-5-fluorbenzyl)-3- (difluormethyl)-5-fluor-l-methyl-lH-pyrazole-4-carboxamid, (2.055) N-Cyclopropyl-N-(2-cyclopropyl- 5-methylbenzyl)-3-(difluormethyl)-5-fluor-l-methyl-lH-pyrazole-4-carboxamid, (2.056) N- Cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluormethyl)-5-fluor-l-methyl-lH-pyrazole-4-carboxamid, (2.057) Pyrapropoyne, Isoflucypram (2.058). (trifluoromethyl) benzyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-Cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-N- [5-methyl-2- (trifluoromethyl) benzyl] -1H-pyrazole-4-carboxamide, (2.046) N-Cyclopropyl -3- (difluoromethyl) -5-fluoro-N- (2-fluoro-6-isopropylbenzyl) - l-methyl-lH-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3- (difluoromethyl) -5- fluoro-N- (2-isopropyl-5-methylbenzyl) -l-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropylbenzyl) -l-methyl-lH-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropylbenzyl) -l-methyl-lH-pyrazole-4-carboxamide, (2.050) N-Cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (5-fluoro-2-isopropylbenzyl) -l-methyl-lH-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3- (Difluoromethyl) -N- (2-ethyl-4,5-dimethylbenzyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-Cyclopropyl-3- (difluoromethyl) -N- ( 2-ethyl-5-fluorobenzyl) -5-fluoro-1-methyl-1H- pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3- (difluoromethyl) -N- (2-ethyl-5-methylbenzyl) - 5-fluoro-1-methyl-1H-pyrazole-4-c arboxamid, (2.054) N-Cyclopropyl-N- (2-cyclopropyl-5-fluorobenzyl) -3- (difluoromethyl) -5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.055) N-Cyclopropyl- N- (2-cyclopropyl-5-methylbenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N- (2-cyclopropylbenzyl) -3 - (Difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoyne, isoflucypram (2.058).
3) Inhibitoren der Atmungskette am Komplex III, beispielsweise (3.001) Ametoctradin, (3.002)3) Inhibitors of the respiratory chain at complex III, for example (3.001) ametoctradin, (3.002)
Amisulbrom, (3.003) Azoxystrobin, (3.004) Coumethoxystrobin, (3.005) Coumoxystrobin, (3.006) Cyazofamid, (3.007) Dimoxystrobin, (3.008) Enoxastrobin, (3.009) Famoxadon, (3.010) Fenamidon, (3.011) Flufenoxystrobin, (3.012) Fluoxastrobin, (3.013) Kresoxim-Methyl, (3.014) Metominostrobin, (3.015) Orysastrobin, (3.016) Picoxystrobin, (3.017) Pyraclostrobin, (3.018) Pyrametostrobin, (3.019) Pyraoxystrobin, (3.020) Trifloxystrobin (3.021) (2E)-2-{2-[({ [(lE)-l-(3-{[(E)-l-Fluor-2- phenylvinyl]oxy}phenyl)ethyliden]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamid,Amisulbrom, (3.003) Azoxystrobin, (3.004) Coumethoxystrobin, (3.005) Coumoxystrobin, (3.006) Cyazofamid, (3.007) Dimoxystrobin, (3.008) Enoxastrobin, (3.009) Famoxadrobin, (3.010) Fenamidon (3.0ox12 )11) Fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin (3.021) 2- {2 - [({[(lE) -l- (3 - {[(E) -l-fluoro-2- phenylvinyl] oxy} phenyl) ethylidene] amino} oxy) methyl] phenyl} -2- ( methoxyimino) -N-methylacetamide,
(3.022) (2E,3Z)-5 - { [ 1 -(4-Chlorphenyl)- lH-pyrazol-3 -yljoxy } -2-(methoxyimino)-N,3 -dimethylpent-3 - enamid, (3.023) (2R)-2-{2-[(2,5-Dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamid, (3.024) (2S)-2-{2-[(2,5-Dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamid, (3.025) (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6- methyl-4,9-dioxo- 1 ,5 -dioxonan-7 -yl-2-methylpropanoat, (3.026) 2- {2-[(2,5 -(3.022) (2E, 3Z) -5 - {[1 - (4-chlorophenyl) - lH-pyrazol-3-yyoxy} -2- (methoxyimino) -N, 3 -dimethylpent-3-enamide, (3.023) ( 2R) -2- {2 - [(2,5-Dimethylphenoxy) methyl] phenyl} -2-methoxy-N-methylacetamide, (3.024) (2S) -2- {2 - [(2,5-dimethylphenoxy) methyl ] phenyl} -2-methoxy-N-methylacetamide, (3.025) (3S, 6S, 7R, 8R) -8-benzyl-3 - [({3 - [(isobutyryloxy) methoxy] -4-methoxypyridin-2-yl } carbonyl) amino] -6-methyl-4,9-dioxo-1,5-dioxonane-7-yl-2-methylpropanoate, (3.026) 2- {2 - [(2.5 -
Dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamid, (3.027) N-(3-Ethyl-3,5,5- trimethylcyclohexyl)-3-formamido-2-hydroxybenzamid, (3.028) (2E,3Z)-5-{[l-(4-Chlor-2-fluorphenyl)- lH-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamid, (3.029) Methyl {5-[3-(2,4- dimethylphenyl)-lH-pyrazol-l-yl]-2-methylbenzyl}carbamate, (3.030) Metyltetraprole, (3.031) Florylpicoxamid. Dimethylphenoxy) methyl] phenyl} -2-methoxy-N-methylacetamide, (3.027) N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3-formamido-2-hydroxybenzamide, (3.028) (2E, 3Z) -5 - {[1- (4-Chloro-2-fluorophenyl) -1H -pyrazol-3-yl] oxy} -2- (methoxyimino) -N, 3-dimethylpent-3-enamide, (3,029) methyl {5 - [3- (2,4-dimethylphenyl) -1H -pyrazol-1-yl] -2-methylbenzyl} carbamate, (3,030) methyltetraprole, (3,031) florylpicoxamide.
4) Inhibitoren der Mitose und Zellteilung, beispielsweise (4.001) Carbendazim, (4.002) Diethofencarb, (4.003) Ethaboxam, (4.004) Fluopicolid, (4.005) Pencycuron, (4.006) Thiabendazol, (4.007) Thiophanat- Methyl, (4.008) Zoxamid, , (4.009) 3-Chlor-4-(2,6-difluorphenyl)-6-methyl-5-phenylpyridazin, (4.010) 3- Chlor-5-(4-chlorphenyl)-4-(2,6-difluorphenyl)-6-methylpyridazin, (4.011) 3-Chlor-5-(6-chlorpyridin-3- yl)-6-methyl-4-(2,4,6-trifluorphenyl)pyridazin, (4.012) 4-(2-Brom-4-fluorphenyl)-N-(2,6-difluorphenyl)- l,3-dimethyl-lH-pyrazol-5-amin, (4.013) 4-(2-Brom-4-fluorphenyl)-N-(2-brom-6-fluorphenyl)-l,3- dimethyl-lH-pyrazol-5-amin, (4.014) 4-(2-Brom-4-fluorphenyl)-N-(2-bromphenyl)-l,3-dimethyl-lFl- pyrazol-5-amin, (4.015) 4-(2-Brom-4-fluorphenyl)-N-(2-chlor-6-fluorphenyl)-l,3-dimethyl-lH-pyrazol- 5-amin, (4.016) 4-(2-Brom-4-fluorphenyl)-N-(2-chlorphenyl)-l,3-dimethyl-lH-pyrazol-5-amin, (4.017)4) Inhibitors of mitosis and cell division, for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate methyl, (4.008) zoxamide ,, (4.009) 3-chloro-4- (2,6-difluorophenyl) -6-methyl-5-phenylpyridazine, (4.010) 3-chloro-5- (4-chlorophenyl) -4- (2,6-difluorophenyl ) -6-methylpyridazine, (4.011) 3-chloro-5- (6-chloropyridine-3- yl) -6-methyl-4- (2,4,6-trifluorophenyl) pyridazine, (4,012) 4- (2-bromo-4-fluorophenyl) -N- (2,6-difluorophenyl) -1, 3-dimethyl -lH-pyrazol-5-amine, (4.013) 4- (2-bromo-4-fluorophenyl) -N- (2-bromo-6-fluorophenyl) -l, 3- dimethyl-lH-pyrazol-5-amine, (4.014) 4- (2-Bromo-4-fluorophenyl) -N- (2-bromophenyl) -1, 3-dimethyl-1Fl-pyrazol-5-amine, (4.015) 4- (2-bromo-4-fluorophenyl ) -N- (2-chloro-6-fluorophenyl) -l, 3-dimethyl-lH-pyrazol- 5-amine, (4.016) 4- (2-bromo-4-fluorophenyl) -N- (2-chlorophenyl) -l, 3-dimethyl-lH-pyrazol-5-amine, (4.017)
4-(2-Brom-4-fluorphenyl)-N-(2-fluorphenyl)-l,3-dimethyl-lH-pyrazol-5-amin, (4.018) 4-(2-Chlor-4- fluorphenyl)-N-(2,6-difluorphenyl)-l,3-dimethyl-lH-pyrazol-5-amin, (4.019) 4-(2-Chlor-4-fluorphenyl)- N-(2-chlor-6-fluorphenyl)-l,3-dimethyl-lH-pyrazol-5-amin, (4.020) 4-(2-Chlor-4-fluorphenyl)-N-(2- chlorphenyl)- 1 ,3 -dimethyl- lH-pyrazol-5 -amin, (4.021 ) 4-(2-Chlor-4-fluorphenyl)-N-(2-fluorphenyl)- 1 ,3 -dimethyl- lH-pyrazol-5 -amin, (4.022) 4-(4-Chlorphenyl)-5 -(2,6-difluorphenyl)-3 ,6- dimethylpyridazin, (4.023) N-(2-Brom-6-fluorphenyl)-4-(2-chlor-4-fluorphenyl)-l,3-dimethyl-lH- pyrazol-5-amin, (4.024) N-(2-Bromphenyl)-4-(2-chlor-4-fluorphenyl)-l,3-dimethyl-lH-pyrazol-5-amin, (4.025) N-(4-Chlor-2,6-difluorphenyl)-4-(2-chlor-4-fluorphenyl)-l,3-dimethyl-lH-pyrazol-5-amin. 4- (2-Bromo-4-fluorophenyl) -N- (2-fluorophenyl) -1, 3-dimethyl-1H -pyrazol-5-amine, (4.018) 4- (2-chloro-4-fluorophenyl) -N - (2,6-difluorophenyl) -1, 3-dimethyl-lH-pyrazol-5-amine, (4.019) 4- (2-chloro-4-fluorophenyl) - N- (2-chloro-6-fluorophenyl) - 1,3-dimethyl-1H-pyrazol-5-amine, (4,020) 4- (2-chloro-4-fluorophenyl) -N- (2-chlorophenyl) -1, 3-dimethyl-1H-pyrazol-5 -amine , (4.021) 4- (2-Chloro-4-fluorophenyl) -N- (2-fluorophenyl) -1, 3 -dimethyl-1 H -pyrazole-5-amine, (4.022) 4- (4-chlorophenyl) -5 - (2,6-difluorophenyl) -3, 6- dimethylpyridazine, (4.023) N- (2-bromo-6-fluorophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H- pyrazol-5-amine, (4.024) N- (2-bromophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (4.025) N- (4 -Chlor-2,6-difluorophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine.
5) Verbindungen mit Befähigung zu Multisite-Aktivität, beispielsweise (5.001) Bordeauxmischung, (5.002) Captafol, (5.003) Captan, (5.004) Chlorthalonil, (5.005) Kupferhydroxid, (5.006) Kupfemaphthenat, (5.007) Kupferoxid, (5.008) Kupferoxychlorid, (5.009) Kupfer(2+)-sulfat, (5.010) Dithianon, (5.011) Dodin, (5.012) Folpet, (5.013) Mancozeb, (5.014) Maneb, (5.015) Metiram, (5.016) Zinkmetiram, (5.017) Kupfer-Oxin, (5.018) Propineb, (5.019) Schwefel und Schwefelzubereitungen einschließlich Calciumpolysulfid, (5.020) Thiram, (5.021) Zineb, (5.022) Ziram, (5.023) 6-Ethyl-5,7- dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][l,4]dithiino[2,3-c][l,2]thiazole-3-carbonitrile. 5) Compounds capable of multisite activity, e.g. (5.001) Bordeaux mixture, (5.002) Captafol, (5.003) Captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride , (5.009) copper (2+) sulfate, (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) zinc metiram, (5.017) Copper oxine, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulphide, (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7- dihydro-5H-pyrrolo [3 ', 4': 5.6] [1,4] dithiino [2,3-c] [1,2] thiazole-3-carbonitriles.
6) Verbindungen, die zum Auslösen einer Wirtsabwehr befähigt sind, beispielsweise (6.001) Acibenzolar-6) Compounds capable of triggering host defenses, for example (6.001) acibenzolar
5-Methyl, (6.002) Isotianil, (6.003) Probenazol, (6.004) Tiadinil. 5-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) tiadinil.
7) Inhibitoren der Aminosäure- und/oder Protein-Biosynthese, beispielsweise (7.001) Cyprodinil, (7.002) Kasugamycin, (7.003) Kasugamycinhydrochlorid-hydrat, (7.004) Oxytetracyclin (7.005) Pyrimethanil, (7.006) 3 -(5 -Fluor-3 ,3 ,4,4-tetramethyl-3 ,4-dihydroisochinolin- 1 -yl)chinolin. 7) Inhibitors of amino acid and / or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3 - (5 -fluoro- 3, 3, 4,4-tetramethyl-3, 4-dihydroisoquinolin-1-yl) quinoline.
(8) Inhibitoren der ATP -Produktion, beispielsweise (8.001) Silthiofam. (8) Inhibitors of ATP production, for example (8.001) Silthiofam.
9) Inhibitoren der Zellwandsynthese, beispielsweise (9.001) Benthiavalicarb, (9.002) Dimethomorph, (9.003) Flumorph, (9.004) Iprovabcarb, (9.005) Mandipropamid, (9.006) Pyrimorph, (9.007) Valifenalat, (9.008) (2E)-3 -(4-tert.-Butylphenyl)-3 -(2-chlorpyridin-4-yl)- 1 -(morpholin-4-yl)prop-2-en- 1 -on, (9.009) (2Z)-3 -(4-tert. -Butylphenyl)-3 -(2-chlorpyridin-4-yl)- 1 -(morpholin-4-yl)prop-2-en- 1 -on. 9) Inhibitors of cell wall synthesis, e.g. (9.001) Benthiavalicarb, (9.002) Dimethomorph, (9.003) Flumorph, (9.004) Iprovabcarb, (9.005) Mandipropamid, (9.006) Pyrimorph, (9.007) Valifenalat, (9.008) (2E) -3 - (4-tert-Butylphenyl) -3 - (2-chloropyridin-4-yl) - 1 - (morpholin-4-yl) prop-2-en- 1 -one, (9.009) (2Z) -3 - (4-tert-Butylphenyl) -3 - (2-chloropyridin-4-yl) -1 - (morpholin-4-yl) prop-2-en-1 -one.
10) Inhibitoren der Lipid- und Membran-Synthese, beispielsweise (10.001) Propamocarb, (10.002) Propamocarbhydrochlorid, (10.003) Tolclofos-Methyl. 11) Inhibitoren der Melanin-Biosynthese, beispielsweise (11.001) Tricyclazol, (11.002) 2,2,2- Trifluorethyl- { 3 -methyl- 1 -[(4-methylbenzoyl)amino]butan-2-yl } carbamat. 10) Inhibitors of lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl. 11) Inhibitors of melanin biosynthesis, for example (11,001) tricyclazole, (11,002) 2,2,2-trifluoroethyl- {3 -methyl-1 - [(4-methylbenzoyl) amino] butan-2-yl} carbamate.
12) Inhibitoren der Nukleinsäuresynthese, beispielsweise (12.001) Benalaxyl, (12.002) Benalaxyl-M (Kiralaxyl), (12.003) Metalaxyl, (12.004) Metalaxyl-M (Mefenoxam). 12) Inhibitors of nucleic acid synthesis, for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
13) Inhibitoren der Signaltransduktion, beispielsweise (13.001) Fludioxonil, (13.002) Iprodion, (13.003) Procymidon, (13.004) Proquinazid, (13.005) Quinoxyfen, (13.006) Vinclozolin. 13) Inhibitors of signal transduction, e.g. (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) procinazid, (13.005) quinoxyfen, (13.006) vinclozoline.
14) Verbindungen, die als Entkoppler wirken können, beispielsweise (14.001) Fluazinam, (14.002) Meptyldinocap. 14) Compounds that can act as decouplers, for example (14.001) fluazinam, (14.002) meptyldinocap.
15) Weitere Verbindungen, beispielsweise (15.001) Abscisinsäure, (15.002) Benthiazol, (15.003)15) Other compounds, for example (15.001) abscisic acid, (15.002) benthiazole, (15.003)
Bethoxazin, (15.004) Capsimycin, (15.005) Carvon, (15.006) Chinomethionat, (15.007) Cufraneb, (15.008) Cyflufenamid, (15.009) Cymoxanil, (15.010) Cyprosulfamid, (15.011) Flutianil, (15.012) Fosetyl-Aluminium, (15.013) Fosetyl-Calcium, (15.014) Fosetyl-Natrium, (15.015) Methylisothiocyanat, (15.016) Metrafenon, (15.017) Mildiomycin, (15.018) Natamycin, (15.019) Nickel- Dimethyldithiocarbamat, (15.020) Nitrothal-Isopropyl, (15.021) Oxamocarb, (15.022) Oxathiapiprolin, (15.023) Oxyfenthiin, (15.024) Pentachlorphenol und Salze, (15.025) Phosphonsäure und deren Salze, (15.026) Propamocarb-fosetylat, (15.027) Pyriofenone (Chlazafenone) (15.028) Tebufloquin, (15.029) Tecloftalam, (15.030) Tolnifanide, (15.031) l-(4-{4-[(5R)-5-(2,6-Difluorphenyl)-4,5-dihydro-l,2- oxazol-3 -yl] - 1 ,3 -thiazol-2-yl}piperidin- 1 -yl)-2- [5 -methyl-3 -(trifluormethyl)- lFl-pyrazol- 1 -yl]ethanon, (15.032) l-(4-{4-[(5S)-5-(2,6-Difluorphenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l- yl)-2-[5-methyl-3-(trifluormethyl)-lH-pyrazol-l-yl]ethanon, (15.033) 2-(6-Benzylpyridin-2- yl)quinazolin, (15.034) 2,6-Dimethyl-lH,5H-[l,4]dithiino[2,3-c:5,6-c']dipyrrol-l,3,5,7(2H,6H)-tetron, (15.035) 2-[3,5-Bis(difluormethyl)-lH-pyrazol-l-yl]-l-[4-(4-{5-[2-(prop-2-in-l-yloxy)phenyl]-4,5- dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanon, (15.036) 2-[3,5-Bis(difluormethyl)- IH-pyrazol- 1 -yl] - 1 - [4-(4- { 5 -[2-chlor-6-(prop-2-in- 1 -yloxy)phenyl] -4,5 -dihydro- 1 ,2-oxazol-3 -yl } - 1 ,3 - thiazol-2-yl)piperidin- 1 -yl]ethanon, (15.037) 2-[3 ,5 -Bis(difluormethyl)- lH-pyrazol- 1 -yl] - 1 - [4-(4- { 5 -[2- fluor-6-(prop-2-in- 1 -yloxy)phenyl] -4,5 -dihydro- 1 ,2-oxazol-3 -yl} - 1 ,3 -thiazol-2-yl)piperidin- 1 - yl]ethanon, (15.038) 2-[6-(3-Fluor-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazolin, (15.039) 2- {(5R)-3-[2-(l-{[3,5-Bis(difluormethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5- dihydro-l,2-oxazol-5-yl}-3-chlorphenyl methanesulfonat, (15.040) 2-{(5S)-3-[2-(l-{[3,5-Bethoxazine, (15.004) capsimycin, (15.005) carvone, (15.006) quinomethionate, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.011) flutianil, (15.012) fosetyl aluminum, 15.013) fosetyl calcium, (15.014) fosetyl sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal isopropyl, Oxamocarb, (15.022) oxathiapiproline, (15.023) oxyfenthiine, (15.024) pentachlorophenol and salts, (15.025) phosphonic acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone (chlazafenone) (15.029 ).028) tebufooft , (15.030) tolnifanide, (15.031) 1- (4- {4 - [(5R) -5- (2,6-difluorophenyl) -4,5-dihydro-1,2-oxazol-3 -yl] - 1 , 3 -thiazol-2-yl} piperidin-1-yl) -2- [5 -methyl-3 - (trifluoromethyl) - lFl-pyrazol-1 -yl] ethanone, (15.032) l- (4- {4- [(5S) -5- (2,6-Difluorophenyl) -4,5-dihydro-1,2-oxazol-3-yl] -1, 3-thiazol-2-yl} piperidin-1-yl) -2 - [5-methy l-3- (trifluoromethyl) -lH-pyrazol-l-yl] ethanone, (15.033) 2- (6-benzylpyridin-2-yl) quinazoline, (15.034) 2,6-dimethyl-lH, 5H- [l, 4] dithiino [2,3-c: 5,6-c '] dipyrrole-1,3,5,7 (2H, 6H) -tetron, (15,035) 2- [3,5-bis (difluoromethyl) -lH -pyrazol-l-yl] -l- [4- (4- {5- [2- (prop-2-yn-l-yloxy) phenyl] -4,5-dihydro-1,2-oxazole-3- yl} -l, 3-thiazol-2-yl) piperidin-1-yl] ethanone, (15.036) 2- [3,5-bis (difluoromethyl) - IH-pyrazol-1-yl] - 1 - [4- (4- {5 - [2-chloro-6- (prop-2-yn-1-yloxy) phenyl] -4,5-dihydro-1, 2-oxazol-3-yl} - 1, 3-thiazole- 2-yl) piperidin-1-yl] ethanone, (15.037) 2- [3, 5 -Bis (difluoromethyl) -1H-pyrazol-1-yl] -1 - [4- (4- {5 - [2- fluoro-6- (prop-2-yn-1-yloxy) phenyl] -4,5-dihydro-1, 2-oxazol-3-yl} -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.038) 2- [6- (3-fluoro-4-methoxyphenyl) -5-methylpyridin-2-yl] quinazoline, (15.039) 2- {(5R) -3- [2- (l- { [3,5-bis (difluoromethyl) -lH-pyrazol-l-yl] acetyl} piperidin-4-yl) -l, 3-thiazol-4-yl] -4,5-dihydro-1,2-oxazole- 5-yl} -3-chlorophenyl methanesulfonate, (15,040) 2 - {(5S) -3- [2nd - (l - {[3.5-
Bis(difluormethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5- yl}-3-chlorphenyl methanesulfonat, (15.041) 2-{2-[(7,8-Difluor-2-methylchinolin-3-yl)oxy]-6- fluorphenyl}propan-2-ol, (15.042) 2-{2-Fluor-6-[(8-fluor-2-methylchinolin-3-yl)oxy]phenyl}propan-2- ol, (15.043) 2-{3-[2-(l-{[3,5-Bis(difluormethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4- yl] -4,5 -dihydro- 1 ,2-oxazol-5 -yl} -3 -chlorphenyl-methansulfonat, (15.044) 2- {3 - [2-( 1 - { [3 ,5 -Bis (difluoromethyl) -lH-pyrazol-l-yl] acetyl} piperidin-4-yl) -l, 3-thiazol-4-yl] -4,5-dihydro-1,2-oxazol-5-yl} - 3-chlorophenyl methanesulfonate, (15.041) 2- {2 - [(7,8-Difluoro-2-methylquinolin-3-yl) oxy] -6-fluorophenyl} propan-2-ol, (15.042) 2- {2- Fluoro-6 - [(8-fluoro-2-methylquinolin-3-yl) oxy] phenyl} propan-2-ol, (15,043) 2- {3- [2- (l - {[3,5-bis ( difluoromethyl) -lH-pyrazol-l-yl] acetyl} piperidin-4-yl) -l, 3-thiazol-4-yl] -4,5-dihydro-1,2-oxazol-5-yl} -3 - chlorophenyl methanesulfonate, (15.044) 2- {3 - [2- (1 - {[3, 5 -
Bis(difluormethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5- yl}phenyl methanesulfonat, (15.045) 2-Phenylphenol und deren Salze, (15.046) 3-(4,4,5-Trifluor-3,3- dimethyl-3 ,4-dihydroisochinolin- 1 -yl)chinolin, ( 15.047) 3 -(4,4-Difluor-3 ,3 -dimethyl-3 ,4- dihydroisochinolin-l-yl)chinolin, (15.048) 4-Amino-5-fluorpyrimidin-2-ol (Tautomere Form: 4-Amino- 5-fluorpyrimidin-2(lH)-on), (15.049) 4-Oxo-4-[(2-phenylethyl)amino]buttersäure, (15.050) 5-Amino-Bis (difluoromethyl) -lH-pyrazol-l-yl] acetyl} piperidin-4-yl) -l, 3-thiazol-4-yl] -4,5-dihydro-1,2-oxazol-5- yl} phenyl methanesulfonate, (15.045) 2-phenylphenol and its salts, (15.046) 3- (4,4,5-trifluoro-3,3-dimethyl-3, 4-dihydroisoquinolin-1-yl) quinoline, (15.047) 3 - (4,4-Difluoro-3, 3-dimethyl-3, 4- dihydroisoquinolin-1-yl) quinoline, (15,048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5 -fluoropyrimidin-2 (1H) -one), (15.049) 4-Oxo-4 - [(2-phenylethyl) amino] butyric acid, (15.050) 5-amino-
1.3.4-thiadiazol-2-thiol, (15.051) 5 -Chlor-N'-phenyl-N'-(prop-2-yn- 1 -yl)thiophen-2-sulfonohydrazid,1.3.4-thiadiazol-2-thiol, (15.051) 5-chloro-N'-phenyl-N '- (prop-2-yn-1 -yl) thiophene-2-sulfonohydrazide,
(15.052) 5-Fluor-2-[(4-fluorbenzyl)oxy]pyrimidin-4-amin, (15.053) 5-Fluor-2-[(4- methylbenzyl)oxy]pyrimidin-4-amin, (15.054) 9-Fluor-2,2-dimethyl-5-(chinolin-3-yl)-2,3-dihydro-l,4- benzoxazepin, (15.055) But-3-yn-l-yl {6-[({[(Z)-(l-methyl-lH-tetrazol-5- yl)(phenyl)methylen]amino}oxy)methyl]pyridin-2-yl}carbamat, (15.056) Ethyl (2Z)-3-amino-2-cyano-(15.052) 5-Fluoro-2 - [(4-fluorobenzyl) oxy] pyrimidin-4-amine, (15.053) 5-Fluoro-2 - [(4-methylbenzyl) oxy] pyrimidin-4-amine, (15.054) 9 -Fluoro-2,2-dimethyl-5- (quinolin-3-yl) -2,3-dihydro-1,4-benzoxazepine, (15,055) but-3-yn-1-yl {6 - [({[ (Z) - (l-methyl-lH-tetrazol-5-yl) (phenyl) methylene] amino} oxy) methyl] pyridin-2-yl} carbamate, (15.056) ethyl (2Z) -3-amino-2- cyano-
3-phenylacrylat, (15.057) Phenazin- 1 -carbonsäure, (15.058) Propyl 3,4,5-trihydroxybenzoat, (15.059)3-phenyl acrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059)
Chinolin-8-ol, (15.060) Chinolin-8-ol sulfat (2: 1), (15.061) tert-Butyl {6-[({[(l-methyl-lH-tetrazol-5- yl)(phenyl)methylene]amino } oxy)methyl]pyridin-2-yl } carbamat, (15.062) 5 -Fluor-4-imino-3 -methyl- 1 - [(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(lH)-one(15.063) Aminopyrifen, (15.064) (N'-[2- Chlor-4-(2-fluorphenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamid), (15.065) (N'-(2-Chlor-5- methyl-4-phenoxyphenyl)-N-ethyl-N-methybmidoformamid), (15.066) (2-{2-[(7,8-Difluor-2- methylchinolin-3-yl)oxy]-6-fluorphenyl}propan-2-ol), (15.067) (5-Brom-l-(5,6-dimethylpyridin-3-yl)- 3 ,3 -dimethyl-3 ,4-dihydroisochinolin), (15.068) (3 -(4,4-Difluor-5 ,5 -dimethyl-4,5 -dihydrothieno [2,3 - c]pyridin-7-yl)chinolin), (15.069) (1 -(4,5 -Dimethyl- lH-benzimidazol- 1 -yl)-4,4-difluor-3 ,3 -dimethyl-Quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2: 1), (15.061) tert-butyl {6 - [({[(l-methyl-1H-tetrazol-5-yl) (phenyl) methylene] amino} oxy) methyl] pyridin-2-yl} carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1 - [(4-methylphenyl) sulfonyl] -3,4-dihydropyrimidine-2 ( lH) -one (15.063) aminopyrifen, (15.064) (N '- [2-chloro-4- (2-fluorophenoxy) -5-methylphenyl] -N-ethyl-N-methylimidoformamide), (15.065) (N'- (2-Chloro-5-methyl-4-phenoxyphenyl) -N-ethyl-N-methybmidoformamide), (15.066) (2- {2 - [(7,8-Difluoro-2-methylquinolin-3-yl) oxy] -6-fluorophenyl} propan-2-ol), (15.067) (5-bromo-1- (5,6-dimethylpyridin-3-yl) -3, 3-dimethyl-3, 4-dihydroisoquinoline), (15.068) (3 - (4,4-Difluoro-5, 5 -dimethyl-4,5-dihydrothieno [2,3 - c] pyridin-7-yl) quinoline), (15.069) (1 - (4,5 -dimethyl- lH-benzimidazol- 1 -yl) -4,4-difluoro-3, 3 -dimethyl-
3.4-dihydroisochinolin), ( 15.070) 8-Fluor-3 -(5 -Fluor-3 ,3 -dimethyl-3 ,4-dihydroisochinolin- 1 -yl)chinolon, (15.071) 8-Fluor-3 -(5 -fluor-3 ,3 ,4, 4-tetramethyl-3 ,4-dihydroisochinolin- 1 -yl)chinolon, ( 15.072) 3 -(4,4- Difluor-3,3-dimethyl-3,4-dihydroisochinolin-l-yl)-8-fluorchinolin, (15.073) (N-Methyl-N-phenyl-4-[5- (trifluormethyl)-l,2,4-oxadiazol-3-yl]benzamid), (15.074) (Methyl{4-[5-(trifluormethyl)-l,2,4- oxadiazol-3-yl]phenyl} carbamat), (15.075) (N-{4-[5-(Trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzyl}- cyclopropancarboxamid), (15.076) N-Methyl-4-(5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]benzamid, (15.077) N- [(E)-Methoxyiminomethyl] -4-[5 -(trifluormethyl)- 1 ,2,4-oxadiazol-3 -yljbenzamid, (15.078) N-[(Z)-Methoxyiminomethyl]-4-[5-(trifluormethyl)-l,2,4-oxadiazol-3-yl]benzamid, (15.079) N-[4-[5- (Trifluormethyl)-l,2,4-oxadiazol-3-yl]phenyl]cyclopropancarboxamid, (15.080) N-(2-Fluorphenyl)-4-[5- (trifluormethyl)-l, 2, 4-oxadiazol-3 -yljbenzamid, (15.081) 2,2-Difluor-N-methyl-2-[4-[5-(trifluormethyl)-3,4-dihydroisoquinoline), (15,070) 8-fluoro-3 - (5-fluoro-3, 3 -dimethyl-3, 4-dihydroisoquinolin-1 -yl) quinolone, (15,071) 8-fluoro-3 - (5 -fluoro -3, 3, 4, 4-tetramethyl-3, 4-dihydroisoquinolin-1-yl) quinolone, (15,072) 3 - (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl ) -8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] benzamide), (15.074) (methyl {4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] phenyl} carbamate), (15.075) (N- {4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3- yl] benzyl} - cyclopropanecarboxamide), (15.076) N-methyl-4- (5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] benzamide, (15.077) N- [(E) -methoxyiminomethyl] -4- [5 - (trifluoromethyl) -1, 2,4-oxadiazol-3-ylbenzamide, (15.078) N - [(Z) -Methoxyiminomethyl] -4- [5- (trifluoromethyl) -1, 2,4- oxadiazol-3-yl] benzamide, (15.079) N- [4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] phenyl] cyclopropanecarboxamide, (15.080) N- (2-fluorophenyl) - 4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-ylbenzamide, (15,081) 2,2-difluoro-N-methyl -2- [4- [5- (trifluoromethyl) -
1.2.4-oxadiazol-3-yl]phenyl]acetamid, (15.082) N-allyl-N-[[4-[5-(Trifluormethyl)-l,2,4-oxadiazol-3- yl)phenyl]methyl]acetamid, (15.083) N-[(E)-N-Methoxy-C-methyl-carbonimidoyl]-4-(5-1.2.4-oxadiazol-3-yl] phenyl] acetamide, (15.082) N-allyl-N - [[4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl) phenyl] methyl] acetamide, (15.083) N - [(E) -N-methoxy-C-methyl-carbonimidoyl] -4- (5-
(trifluormethyl)-l, 2, 4-oxadiazol-3 -yljbenzamid, (15.084) N-[(Z)-N-Methoxy-C-methyl-carbonimidoylJ-(trifluoromethyl) -1, 2, 4-oxadiazol-3-ylbenzamide, (15.084) N - [(Z) -N-methoxy-C-methyl-carbonimidoylJ-
4-[5-(trifluormethyl)-l,2,4-oxadiazol-3-yl]benzamide, (15.085) N-allyl-N-[[4-[5-(Trifluormethyl)- 1,2,4- oxadiazol-3 -yljphenyljmethyljpropanamid, (15.086) 4,4-Dimethyl- 1 - [[4-[5 -(Trifluormethyl)- 1,2,4- oxadiazol-3-yl]phenyl]methyl]pyrrobdin-2-on, (15.087) N-Methyl-4-[5-(trifluormethyl)-l,2,4-oxadiazol- 3-yl]benzolcarbothioamid, (15.088) 5-Methyl-l-[[4-[5-(trifluormethyl)-l,2,4-oxadiazol-3- yl]phenyl]methyl]pyrrolidin-2-on, (15.089) N-((2,3-Difluor-4-[5-(trifluormethyl)-l,2,4-oxadiazol-3- yl]phenyl]methyl]-3,3,3 -trifluor-propanamid, (15.090) 1 -Methoxy- 1 -methyl-3-[[4-[5-(trifluormetyhl} - 1.2.4-oxadiazol-3 -yl]phenyl]methyl]hamstoff, (15.091) 1,1 -Diethyl-3 -[[4-[5 -(trifluormethyl } - 1 ,2,4- oxadiazol-3-yl]phenyl]methyl]hamstoff, (15.092) N-[[4-[5- (Trifluormethyl)- 1, 2, 4-oxadiazol-3- yl]phenyl)methyl)propanamid, (15.093) N-Methoxy-N-[[4-[5-(trifluormethyl)-l,2,4-oxadiazol-3- yl]phenyl]methyl]cy clopropancarboxamid, (15.094) 1 -Methoxy-3 -methyl- 1 -[ [4-[5 -(trifluormethyl)-4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] benzamides, (15,085) N -allyl- N - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazole -3 -yl-phenyl-methyl-propanamide, (15.086) 4,4-dimethyl-1 - [[4- [5 - (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] pyrrobdin-2-one, ( 15,087) N-methyl-4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] benzenecarbothioamide, (15,088) 5-methyl-1 - [[4- [5- (trifluoromethyl) -1 , 2,4-oxadiazol-3-yl] phenyl] methyl] pyrrolidin-2-one, (15,089) N - ((2,3-difluoro-4- [5- (trifluoromethyl) -1, 2,4-oxadiazole -3-yl] phenyl] methyl] -3,3,3-trifluoro-propanamide, (15,090) 1-methoxy-1-methyl-3 - [[4- [5- (trifluoromethyl} - 1.2.4-oxadiazol-3-yl] phenyl] methyl] urea, (15.091) 1,1-diethyl-3 - [[4- [5 - (trifluoromethyl} - 1,2,4-oxadiazol-3-yl]) phenyl] methyl] urea, (15.092) N - [[4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl) methyl) propanamide, (15.093) N-methoxy-N- [ [4- [5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] phenyl] methyl] cyclopropanecarboxamide, (15.094) 1-methoxy-3-methyl-1 - [[4- [5 - ( trifluoromethyl) -
1.2.4-oxadiazol-3-yl]phenyl]methyl]hamstoff, (15.095) N-Methoxy-N-[[4-[5-(trifluormethyl)-l,2,4- oxadiazol-3-yl]phenyl]methly)cyclopropancarboxamid, (15.096) N,2-Dimethoxy-N-[[4-[5-1.2.4-oxadiazol-3-yl] phenyl] methyl] urea, (15.095) N-methoxy-N - [[4- [5- (trifluoromethyl) -l, 2,4-oxadiazol-3-yl] phenyl] methly) cyclopropanecarboxamide, (15.096) N, 2-dimethoxy-N - [[4- [5-
(trifluormethyl}-l,2,4-oxadiazol-3-yl]phenyl]methyl]propanamid, (15.097) N-Ethyl-2-methyl-N-[[4-[5- (trifluormethyl)- 1 ,2,4-oxadiazol-3-yl)phenyl]melhyl]propanamid, (15.098) 1 -Methoxy-3 -methyl- 1-[[4- [5 -(trifluormethyl)- 1, 2, 4-oxadiazol-3-yl]phenyl]methyl]hamstoff, (15.099) l,3-Dimethoxy-l-[[4-[5-(trifluoromethyl} -1, 2,4-oxadiazol-3-yl] phenyl] methyl] propanamide, (15.097) N-ethyl-2-methyl-N - [[4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl) phenyl] methyl] propanamide, (15.098) 1-methoxy-3-methyl-1 - [[4- [5 - (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] urea, (15.099) 1,3-dimethoxy-l - [[4- [5-
(trifluormethyl)- 1 ,2,4-oxadiazol-3 -yl]phenyl]methyl]hamstoff, (15.100) 3 -Ethyl- 1 -methoxy- 1 - [[4-[5 -(trifluoromethyl) -1, 2,4-oxadiazol-3 -yl] phenyl] methyl] urea, (15,100) 3-ethyl-1-methoxy-1 - [[4- [5 -
(trifluormethyl)- 1 ,2,4-oxadiazol-3 -yl]phenyl]methyl]hamstoff, (15.101) 1 - [[4-[5 -(Trifluormethyl)- 1,2,4- oxadiazol-3-yl]phenyl]methyl]piperidin-2-on, (15.102) 4,4-Dimethyl-2-[[4-(5-(trifluormethyl)-l,2,4- oxadiazol-3-yl]phenyl]methyl]isooxazolidin-3-on, (15.103) 5,5-Dimethyl-2-[[4-[5-(Trifluormethyl)-(trifluoromethyl) -1, 2,4-oxadiazol-3-yl] phenyl] methyl] urea, (15.101) 1 - [[4- [5 - (trifluoromethyl) - 1,2,4-oxadiazol-3-yl] phenyl] methyl] piperidin-2-one, (15.102) 4,4-dimethyl-2 - [[4- (5- (trifluoromethyl) -1, 2,4-oxadiazol-3-yl] phenyl] methyl] isooxazolidine- 3-one, (15.103) 5,5-dimethyl-2 - [[4- [5- (trifluoromethyl) -
1.2.4-oxadiazol-3 -yl]phenyl]methyl]isoxazolidin-3 -on, (15.104) 3 ,3 -Dimethyl- 1 -[[4- [5 -(trifluormethyl)-1.2.4-oxadiazol-3 -yl] phenyl] methyl] isoxazolidin-3-one, (15.104) 3, 3-dimethyl-1 - [[4- [5 - (trifluoromethyl) -
1.2.4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-on, (15.105) 1 -[[3-Fluor-4-(5-(trifluormethyl)- 1 ,2,4- oxadiazol-3-yl]phenyl]methyl]azepan-2-on, (15.106) 4, 4-Dimethyl-2-[[4-(5 -(Trifluormethyl)- 1,2,4- oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-on und (15.107) 5,5-Dimethyl-2-[[4-[5-1.2.4-oxadiazol-3-yl] phenyl] methyl] piperidin-2-one, (15.105) 1 - [[3-fluoro-4- (5- (trifluoromethyl) - 1, 2,4-oxadiazol-3- yl] phenyl] methyl] azepan-2-one, (15.106) 4,4-dimethyl-2 - [[4- (5 - (trifluoromethyl) - 1,2,4-oxadiazol-3-yl] phenyl] methyl] isoxazolidin-3-one and (15.107) 5,5-dimethyl-2 - [[4- [5-
(Trifluormethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-on. (Trifluoromethyl) -1, 2,4-oxadiazol-3-yl] phenyl] methyl] isoxazolidin-3-one.
Weiter bevorzugte fungizide Komponenten d) sind beispielsweise Bixafen, Fenamidone, Fenhexamid, Fluopicolide, Fluopyram, Fluoxastrobin, Iprovalicarb, Isotianil, Isopyrazam, Pencycuron, Penflufen, Propineb, Tebuconazole, Trifloxystrobin, Ametoctradin, Amisulbrom, Azoxystrobin, Benthiavabcarb- isopropyl, Benzovindiflupyr, Boscalid, Carbendazim, Chlorothanonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Difenoconazole, Ethaboxam, Epoxiconazole, Famoxadone, Fluazinam, Fluquinconazole, Flusilazole, Flutianil, Fluxapyroxad, Isopyrazam, Kresoxim-methyl, Fyserphenvalpyr, Mancozeb, Mandipropamid, Metconazol, Pyriofenone, Folpet, Metaminostrobin, Oxathiapiprolin, Penthiopyrad, Picoxystrobin, Probenazole, Proquinazid, Pydiflumetofen, Pyraclostrobin, Sedaxane, Spiroxamin, Tebufloquin, Tetraconazole, Valiphenalate, Zoxamide, Ziram, N-(5-chloro-2- isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, N- (5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol- 4-yl]-4,5-dihydro-l,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH- pyrazol- 1 -yl]acetyl }piperidin-4-yl)- 1 ,3 -thiazol-4-yl] -4,5 -dihydro- 1 ,2-oxazol-5 -yl } -3 - chlorophenylmethane-sulfonate, (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4- methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-l,5-dioxonan-7-yl 2-methylpropanoatOther preferred fungicidal components d) are, for example, bixafen, fenamidone, fenhexamid, fluopicolide, fluopyram, fluoxastrobin, iprovalicarb, isotianil, isopyrazam, pencycuron, penflufen, propineb, tebuconazole, trifloxystrobin, amhietoctrobin, benzifoxystrobin, benzhietoctrobin, benzifoxylabyrbine, azifoxylabyrbine, iscalidoxylabyrbine, iscalidoxystrobin, benzifoxylabyrbine, iscalidoxylabyrbine, bosifoxylabyrbine, iscalidoxylabyrbine, benzifoxylabyrbine, Carbendazim, Chlorothanonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Difenoconazole, Ethaboxam, Epoxiconazole, Famoxadone, Fluazinam, Fluquinconazole, Flusilazole, Flutianil, Fluxapyroxofenad, Isiprobin, Metrobin, Manosto-zebofenad, Metrobin, Metrobin, pyrazol-pyramid, metrobin, pyrazoli, pyramido-pyramid, Manosol-pyramid, Metrobin, Man-sto-zeb-methyl Oxathiapiproline, Penthiopyrad, Picoxystrobin, probenazole, Proquinazid, Pydiflumetofen, Pyraclostrobin, Sedaxane, Spiroxamine, Tebufloquine, Tetraconazole, Valiphenalate, Zoxamide, Ziram, N- (5-chloro-2-isopropyl-3- - -cylolu-isopropyl-3-propylbenzyl) -N 5-fluoro-1-methyl-1H-pyrazole-4-carboxamides, N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (i.e. ifluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamides, 2- {3- [2- (1 - {[3,5-bis (difluoromethyl) -1H-pyrazol-1-yl] acetyl } piperidin-4-yl) -l, 3-thiazol-4-yl] -4,5-dihydro-1,2-oxazol-5-yl} phenyl methanesulfonate, 2- {3- [2- (l- { [3,5-bis (difluoromethyl) -lH-pyrazol-1-yl] acetyl} piperidin-4-yl) -1, 3 -thiazol-4-yl] -4,5-dihydro-1,2-oxazole- 5 -yl} -3 - chlorophenylmethanesulfonate, (3S, 6S, 7R, 8R) -8-Benzyl-3 - [({3 - [(isobutyryloxy) methoxy] -4-methoxypyridin-2-yl} carbonyl) amino ] -6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate
(Fyserphenvalpyr), Isoflucypram. Besonders bevorzugte fungizide Mischungspartner sind beispielsweise: Cymoxanil, Tebuconazol, Spiroxamin, Bixafen, Fluoxastrobin, Iprovalicarb, Trifloxystrobin, N-(5-chloro-2-isopropylbenzyl)-N- cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (3S,6S,7R,8R)-8- Benzyl-3 - [( { 3 -[(isobutyryloxy)methoxy] -4-methoxypyridin-2-yl } carbonyl)amino] -6-methyl-4,9-dioxo- l,5-dioxonan-7-yl 2-methylpropanoat (Lyserphenvalpyr), Isoflucypram, Fluoxapiprolin, Fluopicolide sowie Fluopyram. (Fyserphenvalpyr), isoflucypram. Particularly preferred fungicidal mixture partners are, for example: cymoxanil, tebuconazole, spiroxamine, bixafen, fluoxastrobin, iprovalicarb, trifloxystrobin, N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl -lH-pyrazole-4-carboxamide, (3S, 6S, 7R, 8R) -8-Benzyl-3 - [({3 - [(isobutyryloxy) methoxy] -4-methoxypyridin-2-yl} carbonyl) amino] - 6-methyl-4,9-dioxol, 5-dioxonan-7-yl, 2-methylpropanoate (lyserphenvalpyr), isoflucypram, fluoxapiproline, fluopicolide and fluopyram.
Ganz besonders bevorzugt sind die Mischungen mit ein oder mehreren Verbindungen ausgewählt aus der Gruppe der Verbindungen d): a) + d) Tebuconazole; The mixtures with one or more compounds selected from the group of compounds d): a) + d) tebuconazole;
a) + d) Trifloxystrobin; a) + d) trifloxystrobin;
a) + d) Fluoxastrobin; a) + d) fluoxastrobin;
a) + d) Cymoxanil; a) + d) cymoxanil;
a) + d) Iprovalicarb; a) + d) iprovalicarb;
a) + d) Fluoxapiproline; a) + d) fluoxapiproline;
a) + d) Fluopicolide; a) + d) fluopicolide;
a) + d) Bixafen; a) + d) bixafen;
a) + d) Fluopyram a) + d) fluopyram
a) + d) Spiroxamine; a) + d) spiroxamine;
b) a) + d) Isoflucypram b) a) + d) isoflucypram
a) + d) Fluoxastrobin + Trifloxystrobin; a) + d) fluoxastrobin + trifloxystrobin;
a) +d) Trifloxystrobin+Spiroxamin; a) + d) trifloxystrobin + spiroxamine;
a) + d) Bixafen + Tebuconazole; a) + d) bixafen + tebuconazole;
a) + d) Bixafen + Fluoxastrobin; a) + d) bixafen + fluoxastrobin;
a) + d) Bixafen + Trifloxystrobin; a) + d) bixafen + trifloxystrobin;
a) + d) Bixafen + Spiroxamin; a) + d) bixafen + spiroxamine;
a) + d) Bixafen + Fluopyram; a) + d) bixafen + fluopyram;
a) + d) Tebuconazole + Spiroxamin; a) + d) tebuconazole + spiroxamine;
a) + d) Tebuconazole + Fluopyram; a) + d) tebuconazole + fluopyram;
a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide a) + d) N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamides
a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide + Tebuconazole a) + d) N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide + tebuconazole
a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide + Flupyram a) +d) Bixafen + (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2- yl}carbonyl)amino]-6-methyl-4,9-dioxo-l,5-dioxonan-7-yl 2-methylpropanoata) + d) N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide + flupyram a) + d) Bixafen + (3S, 6S, 7R, 8R) -8-Benzyl-3 - [({3 - [(isobutyryloxy) methoxy] -4-methoxypyridin-2-yl} carbonyl) amino] -6- methyl 4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate
(Lyserphenvalpyr) (Lyserphenvalpyr)
Der Anteil der Komponente d) in den erfmdungsgemäßen Formulierungen beträgt vorzugsweise 1 Gew.- % bis 40 Gew.-%, weiter bevorzugt 3 Gew.-% bis 35 Gew.-%. The proportion of component d) in the formulations according to the invention is preferably 1% by weight to 40% by weight, more preferably 3% by weight to 35% by weight.
Diese Formulierungen werden in bekannter Weise hergestellt, z. B. durch Vermischen der Verbindungen der Formel (I) mit Hilfsstoffen wie beispielsweise Streckmitteln, Lösemitteln und/oder festen Trägerstoffen und/oder weiteren Hilfsstoffen wie beispielsweise oberflächenaktiven Stoffen. Die Herstellung der Formulierungen erfolgt entweder in geeigneten Anlagen oder auch vor oder während der Anwendung. These formulations are prepared in a known manner, e.g. B. by mixing the compounds of formula (I) with auxiliaries such as extenders, solvents and / or solid carriers and / or other auxiliaries such as surface-active substances. The formulations are produced either in suitable systems or before or during use.
Applikation application
Als Applikationsformen können alle, dem Fachmann als gebräuchlich bekannten Verfahren verwendet werden; beispielsweise genannt seien: Spritzen, Tauchen, Nebeln sowie eine Reihe spezieller Verfahren zur direkten unter- oder oberirdischen Behandlung von gesamten Pflanzen oder Teilen (Saatgut, Wurzel, Stolonen, Stängel, Stamm, Blatt), wie beispielsweise Stamminjektion bei Bäumen oder Stängelbandagen bei perennierenden Pflanzen, und eine Reihe spezieller indirekter Applikationsverfahren. All methods known to the person skilled in the art as customary methods can be used as application forms; Examples include: spraying, dipping, misting and a number of special methods for the direct underground or above-ground treatment of entire plants or parts (seeds, roots, stolons, stems, stems, leaves), such as stem injection for trees or stem bandages for perennial plants , and a number of special indirect application methods.
Die jeweilige flächen- und/oder objektbezogene Aufwandmenge der Pflanzenschutzmittel unterschiedlichster Formulierungstypen zur Bekämpfung der genannten Schadorganismen variiert sehr stark. Im Allgemeinen werden hierfür die, dem Fachmann als gebräuchlich für das jeweilige Einsatzgebiet bekannten Applikationsmedien in den gebräuchlichen Mengen eingesetzt; wie beispielsweise von mehreren hundert Liter Wasser pro Hektar bei Standard-Spritzverfahren über wenige Liter Öl pro Hektar bei der 'Ultra Low Volume'-Flugzeugapplikation bis hin zu wenigen Millilitern einer physiologischen Lösungen bei Injektionsverfahren. Die Konzentrationen der erfmdungsgemäßen Pflanzenschutzmittel in den entsprechenden Applikationsmedien variieren daher in einem weiten Bereich und sind vom jeweiligen Einsatzgebiet abhängig. Im Allgemeinen werden Konzentrationen verwendet, die dem Fachmann als gebräuchlich für das jeweilige Einsatzgebiet bekannt sind. Bevorzugt sind Konzentrationen von 0,01 Gew.% bis 99 Gew.%, besonders bevorzugt von 0,1 Gew.% bis 90 Gew.%. The respective area- and / or object-related application rate of the plant protection agents of the most varied of formulation types for combating the harmful organisms mentioned varies very widely. In general, the application media known to the person skilled in the art as being customary for the respective field of use are used in the customary amounts; For example, from several hundred liters of water per hectare in the case of standard spraying methods to a few liters of oil per hectare in the 'Ultra Low Volume' aircraft application to a few milliliters of a physiological solution in the case of injection methods. The concentrations of the crop protection agents according to the invention in the corresponding application media therefore vary within a wide range and are dependent on the particular area of use. In general, concentrations are used which are known to the person skilled in the art as customary for the respective field of application. Concentrations from 0.01% by weight to 99% by weight are preferred, particularly preferably from 0.1% by weight to 90% by weight.
Die erfmdungsgemäßen agrochemischen Formulierungen können z.B. in den für Flüssigpräparate üblichen Zubereitungsformen entweder als solche oder nach vorherigem Verdünnen mit Wasser ausgebracht werden, also z.B. als Emulsionen, Suspensionen oder Lösungen. Die Anwendung erfolgt dabei nach üblichen Methoden, also z.B. durch Verspritzen, Gießen oder Injizieren. The agrochemical formulations according to the invention can e.g. in the usual forms of preparation for liquid preparations either as such or after prior dilution with water, e.g. as emulsions, suspensions or solutions. The application takes place according to the usual methods, e.g. by spraying, pouring or injecting.
In Abhängigkeit von der Art des neben Propineb möglicherweise zusätzlich vorliegenden Wirkstoffs sind die erfmdungsgemäßen Formulierungen zur Bekämpfung einer großen Zahl von Schädlingen nützlich und können sowohl zur Behandlung von Pflanzenkulturen, aber auch von unbelebter Materie und im Haushalt eingesetzt werden. Depending on the type of active ingredient possibly additionally present in addition to Propineb, the formulations according to the invention are useful and for controlling a large number of pests can be used both for the treatment of plant cultures, but also for inanimate matter and in the household.
Unter "Schädlingen" oder "schädlichen Organismen" werden hier alle Arten von Schädlingen verstanden, die mit organischen Pflanzenschutzwirkstoffen, d.h. Pflanzenschutzmitteln, insbesondere Fungiziden und Mischungen von Fungiziden mit anderen Pflanzenschutzmitteln, bekämpft bzw. unter Kontrolle behalten werden können. Der Begriff Schädling umfasst daher pflanzenschädigende Organismen, insbesondere Schadpilze und deren Sporen, aber auch schädliche Insekten, Arachniden, Nematoden und Schadpflanzen. Der Begriff "Kontrolle" umfasst sowohl die kurative Behandlung, d.h. die Behandlung von befallenen Pflanzen mit einer erfindungsgemäßen Formulierung, als auch die protektive Behandlung, d.h. die Behandlung von Pflanzen zum Schutz vor einem Schädlingsbefall. "Pests" or "harmful organisms" are understood here to mean all types of pests which are associated with organic pesticides, i.e. Plant protection agents, in particular fungicides and mixtures of fungicides with other plant protection agents, can be controlled or kept under control. The term pest therefore includes organisms that are harmful to plants, in particular harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants. The term "control" includes both curative treatment, i. the treatment of infected plants with a formulation according to the invention, as well as the protective treatment, i.e. the treatment of plants to protect them from pest infestation.
Die vorliegende Erfindung betrifft somit auch die Verwendung von hierin beschriebenen Formulierungen zur Bekämpfung von Schädlingen, insbesondere Pflanzenschädlingen; und ein Verfahren zur Bekämpfung von schädlichen Organismen, insbesondere von pflanzenschädigenden Organismen, umfassend das in Kontakt Bringen der schädlichen Organismen, ihres Habitats, ihrer Wirte, wie Pflanzen und Saatgut, sowie des Erdreichs, des Gebiets und der Umgebung in denen sie wachsen oder wachsen könnten, aber auch von Materialien, Pflanzen, Saatgut, Erdreich, Oberflächen oder Räumen, die vor dem Angriff oder dem Befall durch pflanzenschädigende Organismen geschützt werden sollen, mit einer wirksamen Menge der erfindungsgemäßen Formulierungen. The present invention thus also relates to the use of the formulations described herein for controlling pests, in particular plant pests; and a method for controlling harmful organisms, in particular plant-damaging organisms, comprising bringing the harmful organisms, their habitats, their hosts, such as plants and seeds, and the soil, the area and the environment in which they grow or could grow into contact , but also of materials, plants, seeds, soil, surfaces or rooms which are to be protected from attack or attack by organisms which are harmful to plants, with an effective amount of the formulations according to the invention.
Ein weiterer Gesichtspunkt der Erfindung betrifft die Verwendung der hierin beschriebenen Formulierungen zum Schutz von Pflanzen einschließlich Saatgut, insbesondere um Nutzpflanzen vor dem Befall durch schädliche Organismen, insbesondere Schadpilzen, zu schützen. Die vorliegende Erfindung betrifft somit auch die Verwendung der Formulierungen zur Bekämpfung pflanzenschädlicher Organismen wie beispielsweise Schadpilzen, Insekten, Arachniden, Nematoden und Schadpflanzen, insbesondere zur Bekämpfung von Schadpilzen. Another aspect of the invention relates to the use of the formulations described herein for protecting plants, including seeds, in particular in order to protect useful plants from attack by harmful organisms, in particular harmful fungi. The present invention thus also relates to the use of the formulations for combating organisms which are harmful to plants, such as, for example, harmful fungi, insects, arachnids, nematodes and harmful plants, in particular for combating harmful fungi.
Die Formulierungen der Erfindung können im Pflanzenschutz vor allem als Blatt-, Beiz- und Bodenfungizide in an sich bekannter Weise zur Bekämpfung von pflanzenpathogenen Pilzen eingesetzt werden. In crop protection, the formulations of the invention can be used primarily as foliar, dressing and soil fungicides in a manner known per se for combating phytopathogenic fungi.
Als Pflanzen, welche mit den erfindungsgemäßen Formulierungen behandelt werden können, seien folgende erwähnt: Baumwolle, Flachs, Weinrebe, Obst, Gemüse, wie Rosaceae sp. (beispielsweise Kernfrüchte wie Apfel und Birne, aber auch Steinfrüchte wie Aprikosen, Kirschen, Mandeln und Pfirsiche und Beerenfrüchte wie Erdbeeren), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp. (beispielsweise Bananenbäume und -plantagen), Rubiaceae sp. (beispielsweise Kaffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (beispielsweise Zitronen, Organen und Grapefruit); Solanaceae sp. (beispielsweise Tomaten), Liliaceae sp., Asteraceae sp. (beispielsweise Salat), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (beispielsweise Gurke), Alliaceae sp. (beispielsweise Lauch, Zwiebel), Papilionaceae sp. (beispielsweise Erbsen); Hauptnutzpflanzen, wie Gramineae sp. (beispielsweise Mais, Rasen, Getreide wie Weizen, Roggen, Reis, Gerste, Hafer, Hirse und Triticale), Asteraceae sp. (beispielsweise Sonnenblume), Brassicaceae sp. (beispielsweise Weißkohl, Rotkohl, Brokkoli, Blumenkohl, Rosenkohl, Pak Choi, Kohlrabi, Radieschen sowie Raps, Senf, Meerrettich und Kresse), Fabacae sp. (beispielsweise Bohne, Erdnüsse), Papilionaceae sp. (beispielsweise Sojabohne), Solanaceae sp. (beispielsweise Kartoffeln), Chenopodiaceae sp. (beispielsweise Zuckerrübe, Futterrübe, Mangold, Rote Rübe); Zuckerrohr, Mohn, Olive, Kokosnuss, Kakao, Tabak und Nutzpflanzen und Zierpflanzen in Garten und Wald; sowie jeweils genetisch modifizierte Arten dieser Pflanzen, sowie die Samen dieser Pflanzen. The following plants which can be treated with the formulations according to the invention may be mentioned: cotton, flax, grapevines, fruit, vegetables, such as Rosaceae sp. (for example pome fruits like apple and pear, but also stone fruits like apricots, cherries, almonds and peaches and berries like strawberries), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (e.g. lemons, organs and grapefruit); Solanaceae sp. (for example Tomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (e.g. cucumber), Alliaceae sp. (for example leek, onion), Papilionaceae sp. (e.g. peas); Main crops such as Gramineae sp. (for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (e.g. sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress), Fabacae sp. (e.g. beans, peanuts), Papilionaceae sp. (e.g. soybean), Solanaceae sp. (e.g. potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, Swiss chard, beetroot); Sugar cane, poppy seeds, olives, coconut, cocoa, tobacco and useful plants and ornamental plants in gardens and forests; as well as genetically modified species of these plants and the seeds of these plants.
Bevorzugt werden die erfmdungsgemäßen Formulierungen zur Behandlung von Weizen, Gerste, Roggen, Soja, Zwiebeln, Mais und Erdnüssen eingesetzt. The formulations according to the invention are preferably used for treating wheat, barley, rye, soybeans, onions, corn and peanuts.
Insbesondere lassen sich mit den erfmdungsmäßigen Formulierungen des Prothioconazols grundsätzlich alle Schadpilzerkrankungen bekämpfen, die auch mit den bekannten Formulierungen des Prothioconazols bekämpft werden können. Abhängig von dem jeweiligen, gegebenenfalls vorliegenden Mischungspartner handelt es sich beispielsweise um die folgenden Pflanzenerkrankungen: In particular, with the formulations of prothioconazole according to the invention, in principle all harmful fungal diseases can be combated which can also be combated with the known formulations of prothioconazole. Depending on the particular mixing partner that may be present, it is for example the following plant diseases:
Altemaria Arten an Gemüse, Raps, Zuckerrüben, Soja, Getreide, Baumwolle, Obst und Reis (z.B. A. solani oder A. alternata an Kartoffel und anderen Pflanzen), Aphanomyces Arten an Zuckerrüben und Gemüse, Ascochyta sp. an Baumwolle und Reis, Bipalaris- und Drechslera Arten an Mais, Getreide, Reis und Rasen (z.B. teres an Gerste, D. tritci-repentis an Weizen), Blumeria graminis (Echter Mehltau) an Getreide, Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Blumen und Weinreben, Botryodiplodia sp. an Baumwolle, Bremia lactucae an Salat, Cerospora Arten an Mais, Sojabohnen, Reis und Zuckerrüben (z.B. C. beticula an Zuckerrüben), Cochliobolus Arten an Mais, Getreide, Reis (z.B. Cochliobolus sativus an Getreide, Cochliobolus miyabeanus an Reis), Corynespora sp. an Sojabohnen, Baumwolle und anderen Pflanzen, Colletotrichum Arten an Sojabohnen, Baumwolle und anderen Pflanzen (z.B. C. acutatum an verschiedenen Pflanzen), Curvularia sp. an Getreide und Reis, Diplodia sp. an Getreide und Reis, Exserohilum Arten an Mais, Erysiphe cichoracearum und Sphaerotheca fuliginea an Gurkengewächsen, Fusarium und Verticillium Arten (z.B. V dahliae) an verschiedenen Pflanzen (z.B. F. graminearum an Weizen), Gaeumanomyces graminis an Getreide, Gibberella Arten an Getreide und Reis (z.B. Gibberella fujikuroi an Reis), Grainstaining complex an Reis, Helminthosporium Arten (z.B. H. graminicola) an Mais und Reis, Macrophomina sp. an Soja und Baumwolle, Michrodochium sp. (z.B. M. nivale an Getreide), Mycosphaerella Arten an Getreide, Bananen und Erdnüssen (M graminicola an Weizen, M. fijiesis an Banane), Phaeoisaripsis sp. an Sojabohnen, Phakopsara sp. (z.B. P. pachyrhizi und P. meibomiae an Sojabohnen), Phoma sp. an Soja, Phomopsis Arten an Sojabohnen, Sonnenblumen und Weinreben (P. viticola an Weinreben, P. helianthii an Sonnenblumen), Phytophthora infestans an Kartoffeln und Tomaten, Plasmopara viticola an Weinreben, Penecilium sp. an Soja und Baumwolle, Podosphaera leucotricha an Apfel, Pseudocercosporella herpotrichoides an Getreide, Pseudoperonospora Arten an Hopfen und Gurkengewächsen (z.B. P. cuhenis an Gurke), Puccinia Arten an Getreide, Mais und Spargel (P. triticina und P. striformis an Weizen, P. asparagi an Spargel), Pyrenophora Arten an Getreide, Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae an Reis, Pyricularia grisea an Rasen und Getreide, Pythium spp. an Rasen, Reis, Mais, Baumwolle, Raps, Sonnenblumen, Zuckerrüben, Gemüse und anderen Pflanzen, Rhizoctonia- Arten (z.B. R. solani) an Baumwolle, Reis, Kartoffeln, Rasen, Mais, Raps, Kartoffeln, Zuckerrüben, Gemüse und anderen Pflanzen, Rynchosporium sp. (z.B. R. secalis) an Reis und Getreide, Sclerotinia Arten (z.B. S. sclerotiorum) an Raps, Sonnenblumen und anderen Pflanzen, Septoria tritici und Stagonospora nodorum an Weizen, Erysiphe (syn. Uncinulanecator) an Weinrebe, Setospaeria Arten an Mais und Rasen, Sphacelotheca reilinia an Mais, Thievaliopsis Arten an Sojabohnen und Baumwolle, Tilletia Arten an Getreide, Ustilago Arten an Getreide, Mais und Zuckerrübe, und Venturia Arten (Schorf) an Apfel und Birne (z.B. V inaequalis an Apfel). Altemaria species on vegetables, rape, sugar beet, soy, grain, cotton, fruit and rice (e.g. A. solani or A. alternata on potatoes and other plants), Aphanomyces species on sugar beets and vegetables, Ascochyta sp. on cotton and rice, Bipalaris and Drechslera species on maize, grain, rice and turf (e.g. teres on barley, D. tritci-repentis on wheat), Blumeria graminis (powdery mildew) on grain, Botrytis cinerea (gray mold) on strawberries, Vegetables, flowers and vines, Botryodiplodia sp. on cotton, Bremia lactucae on lettuce, Cerospora species on maize, soybeans, rice and sugar beet (e.g. C. beticula on sugar beet), Cochliobolus species on maize, grain, rice (e.g. Cochliobolus sativus on grain, Cochliobolus miyabeanus on rice), Corynespora sp . on soybeans, cotton and other plants, Colletotrichum species on soybeans, cotton and other plants (eg C. acutatum on various plants), Curvularia sp. on cereals and rice, Diplodia sp. on grain and rice, Exserohilum species on maize, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumber plants, Fusarium and Verticillium species (e.g. V dahliae) on various plants (e.g. F. graminearum on wheat), Gaeumanomyces graminis on grain, Gibberella species on grain and rice (eg Gibberella fujikuroi on rice), Grainstaining complex on rice, Helminthosporium species (e.g. H. graminicola) on maize and rice, Macrophomina sp. on soy and cotton, Michrodochium sp. (eg M. nivale on cereals), Mycosphaerella species on cereals, bananas and peanuts (M graminicola on wheat, M. fijiesis on banana), Phaeoisaripsis sp. on soybeans, Phakopsara sp. (e.g. P. pachyrhizi and P. meibomiae on soybeans), Phoma sp. on soybeans, Phomopsis species on soybeans, sunflowers and grapevines (P. viticola on grapevines, P. helianthii on Sunflowers), Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grapevines, Penecilium sp. on soy and cotton, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on cereals, Pseudoperonospora species on hops and cucumber plants (e.g. P. cuheis on cucumber), Puccinia species on cereals, maize and asparagus (P. triticina and P. striformis on wheat, P. asparagi on asparagus), Pyrenophora species on grain, Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae on rice, Pyricularia grisea on lawn and grain, Pythium spp. on lawn, rice, maize, cotton, rapeseed, sunflowers, sugar beet, vegetables and other plants, Rhizoctonia species (e.g. R. solani) on cotton, rice, potatoes, turf, maize, rape, potatoes, sugar beet, vegetables and other plants , Rynchosporium sp. (e.g. R. secalis) on rice and grain, Sclerotinia species (e.g. S. sclerotiorum) on oilseed rape, sunflowers and other plants, Septoria tritici and Stagonospora nodorum on wheat, Erysiphe (syn. Uncinulanecator) on grapevines, Setospaeria species on maize and lawn , Sphacelotheca reilinia on maize, Thievaliopsis species on soybeans and cotton, Tilletia species on grain, Ustilago species on grain, maize and sugar beet, and Venturia species (scab) on apple and pear (e.g. V inaequalis on apple).
Die erfmdungsgemäßen Formulierungen werden in der Regel mit wenigstens einem Teil Wasser, bevorzugt mit 10 Teilen Wasser und besonders bevorzugt mit wenigstens 100 Teilen Wasser, beispielsweise mit 1 bis 10.000, vorzugsweise 10 bis 5.000 und ganz besonders bevorzugt mit 50 bis 24000 Teilen Wasser bezüglich eines Teiles der Formulierung verdünnt. The formulations according to the invention are generally with at least one part of water, preferably with 10 parts of water and particularly preferably with at least 100 parts of water, for example with 1 to 10,000, preferably 10 to 5,000 and very particularly preferably 50 to 24,000 parts of water per part the formulation diluted.
Die Verdünnung wird erreicht, indem die erfmdungsgemäßen Formulierungen zu dem Wasser gegossen werden. Zur raschen Vermischung der Formulierung mit Wasser wird üblicherweise Agitation, wie beispielsweise Rühren, eingesetzt. Allerdings ist eine Agitation in der Regel nicht notwendig. Obwohl die Temperatur für den Verdünnungsvorgang ein unkritischer Faktor ist, werden Verdünnungen üblicherweise bei Temperaturen im Bereich von 0°C bis 50°C, insbesondere bei 10°C bis 30°C oder bei Umgebungstemperatur durchgeführt. The dilution is achieved by pouring the formulations according to the invention into the water. Agitation, such as, for example, stirring, is usually used for rapid mixing of the formulation with water. However, agitation is usually not necessary. Although the temperature is not a critical factor for the dilution process, dilutions are usually carried out at temperatures in the range from 0 ° C. to 50 ° C., in particular at 10 ° C. to 30 ° C., or at ambient temperature.
Das zum Verdünnen eingesetzte Wasser ist in der Regel Leitungswasser oder Brunnenwasser oder Wasser aus anderen lokalen Quellen. Das Wasser kann aber bereits wasserlösliche oder feindispergierte Verbindungen beinhalten, die im Pflanzenschutz verwendet werden, wie etwa Nährstoffe, Düngemittel oder Pestizide. The water used for dilution is usually tap water or well water or water from other local sources. However, the water can already contain water-soluble or finely dispersed compounds that are used in crop protection, such as nutrients, fertilizers or pesticides.
Zu der erfmdungsgemäßen Emulsion können als Vormischung oder gegebenenfalls erst kurz vor der Verwendung (Tank-Mix) verschiedene Arten von Ölen, Netzmitteln, Adjuvantien, Düngemitteln oder Mikronährstoffen sowie weitere Pestizide (z.B. Herbizide, Insektizide, Fungizide, Wachstumsregulatoren, Safener) hinzugefügt werden. Diese Mittel können den erfmdungsgemäßen Formulierungen im Gewichtsverhältnis 1 : 100 bis 100: 1, bevorzugt 1 : 10 bis 10: 1, zugemischt werden. Der Verwender appliziert die erfmdungsgemäße Formulierung üblicherweise aus einem Vordosierungsgerät, einer Rückenspritze, einem Spritztank, einem Spritzflugzeug oder einem Bewässerungssystem üblicherweise wird die erfmdungsgemäße Formulierung mit Wasser, Puffer und/oder weiteren Hilfsstoffen auf die gewünschte Ausbringungskonzentration verdünnt, wodurch man die gebrauchsfertige Spritzflüssigkeit bzw. agrochemische Zusammensetzung der Erfindung erhält. Üblicherweise werden pro Hektar landwirtschaftlicher Nutzfläche 20 bis 2000 Fiter, bevorzugt 50 bis 400 Fiter, der gebrauchsfertigen Spritzbrühe ausgebracht. Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the emulsion according to the invention as a premix or, if necessary, shortly before use (tank mix). These agents can be added to the formulations according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1. The user usually applies the formulation according to the invention from a pre-metering device, a knapsack sprayer, a spray tank, a spray aircraft or an irrigation system.Usually, the formulation according to the invention is diluted to the desired concentration with water, buffer and / or other auxiliaries, whereby the ready-to-use spray liquid or agrochemical Composition of the invention obtained. Usually 20 to 2000 Fiter, preferably 50 to 400 Fiter, of the ready-to-use spray mixture are applied per hectare of agricultural land.
Die erforderlichen Aufwandmengen der reinen Wirkstoffe ohne Formulierungshilfsstoffe hängen von der Intensität des Schädlingsbefalls, von der Entwicklungsphase der Pflanzen, von den klimatischen Bedingungen des Einsatzortes und dem Applikationsverfahren ab. Im Allgemeinen liegt die Aufwandmenge im Bereich von 0,001 bis 10 kg, bevorzugt von 0,005 bis 8 kg, besonders bevorzugt von 0,01 bis 5 kg und ganz besonders bevorzugt von 0, 0,1 bis 4 Wirkstoff pro Hektar, wobei Wirkstoff hier Propineb zuzüglich möglicher weiterer Wirkstoffe bedeutet. The required application rates of the pure active ingredients without formulation auxiliaries depend on the intensity of the pest infestation, the development phase of the plants, the climatic conditions of the place of use and the application method. In general, the application rate is in the range from 0.001 to 10 kg, preferably from 0.005 to 8 kg, particularly preferably from 0.01 to 5 kg and very particularly preferably from 0.1 to 4 active ingredient per hectare, with active ingredient here plus propineb means of possible further active ingredients.
Die in der Regel verdünnten Formulierungen der Erfindung werden hauptsächlich durch Besprühen, insbesondere Besprühen der Blätter, appliziert. Die Applikation kann mit dem Fachmann bekannten Sprühtechniken, beispielsweise unter Verwendung von Wasser als Träger und Spritzbrühenmengen von etwa 50 bis 2 000 Fitem pro Hektar, beispielsweise von 100 bis 1000 Fitem pro Hektar, durchgeführt werden. The generally diluted formulations of the invention are applied mainly by spraying, in particular spraying the leaves. The application can be carried out with spray techniques known to the person skilled in the art, for example using water as the carrier and spray liquor quantities of about 50 to 2,000 liters per hectare, for example from 100 to 1000 liters per hectare.
Die neuen Propineb-haltigen Formulierungen verfügen über vorteilhafte Eigenschaften für die Behandlung von Pflanzen, insbesondere zeichnen sie sich durch gute Anwendungseigenschaften, hohe Stabilität und hohe fungizide Aktivität aus. The new propineb-containing formulations have advantageous properties for the treatment of plants, in particular they are distinguished by good application properties, high stability and high fungicidal activity.
Die Erfindung wird durch die Beispiele näher erläutert ohne sie darauf zu beschränken. The invention is illustrated in more detail by the examples without being restricted thereto.
Beispiele Examples
Allgemeine Herstellung eines benetzbares Pulvers (wettable powder (WP)) General preparation of a wettable powder (WP)
Es werden die festen Bestandteile bei Raumtemperatur vorgelegt. Unter intensivem Mischen werden alle Bestandteile homogen verteilt. Gegebenenfalls erfolgt eine Zerkleinerung in trockener Umgebung, z.B. mit einer Uuftstrahlmühle, der gesamten Mischung. Als Endprodukt hegt das WP vor (z.B. wettable powder WP70). The solid components are presented at room temperature. All components are distributed homogeneously with intensive mixing. If necessary, comminution takes place in a dry environment, e.g. with an air jet mill, the entire mixture. The final product is the WP (e.g. wettable powder WP70).
Alternative Herstellverfahren eines WGs sind dem Fachmann bekannt und ebenso anwendbar. Alternative manufacturing processes for a WG are known to the person skilled in the art and can also be used.
Allgemeine Herstellung eines wasserdispergierbarben Granulates (water dispersible granules (WGD General production of water dispersible granules (WGD
Es wird zunächst Wasser bei Raumtemperatur vorgelegt. Unter Rühren werden alle Bestandteile der Formulierung entsprechend der Rezeptur, einschließlich den Antioxidantien eingerührt. Falls notwendig wird diese wässrige Suspension einer Nasszerkleinerung zugeführt. Abschließend wird die wässrige Suspension in einem Granulationsverfahren, wie z.B. Sprühtrocknung, Wirbelschichtsprühgranulation, Tellergranulation, in eine feste Granulatform überführt. Als Endprodukt liegt das WG vor (z.B. water dispersible granules WG70). First, water is initially introduced at room temperature. All ingredients of the formulation, including the antioxidants, are stirred in while stirring. If necessary, this aqueous suspension is fed to wet grinding. Finally, the aqueous suspension is subjected to a granulation process, e.g. Spray drying, fluidized bed spray granulation, plate granulation, converted into a solid granulate form. The final product is the WG (e.g. water dispersible granules WG70).
Alternative Herstellverfahren eines WGs sind dem Fachmann bekannt und ebenso anwendbar. Alternative manufacturing processes for a WG are known to the person skilled in the art and can also be used.
Bestimmung von DIDT in der angerührten Spritzbrühe Determination of DIDT in the mixed spray mixture
Das unter Umständen in der Spritzbrühe durch den im Wasser gelösten Luftsauerstoff gebildete DIDT wird auf einer Umkehrphasensäule unter Verwendung eines Fliessmittelgradienten getrennt. Nach der UV oder MS/MS Detektion, wird die quantitative Auswertung durch Vergleich der Peakflächen mit denen des Referenzgegenstandes, unter Verwendung eines externen oder ggf. stabil isotopenmarkierten internen Standards (bei Bestimmung mittels LC-MS/MS) durchgeführt. The DIDT, which may be formed in the spray liquor by the atmospheric oxygen dissolved in the water, is separated on a reversed-phase column using a solvent gradient. After the UV or MS / MS detection, the quantitative evaluation is carried out by comparing the peak areas with those of the reference object, using an external or, if necessary, stable isotope-labeled internal standard (when determined using LC-MS / MS).
Hochdruckflüssigkeitschromatograph Agilent 1290 Probeninj ektion : Agilent 1290 oder CTC PAL Agilent 1290 high pressure liquid chromatograph Sample injection: Agilent 1290 or CTC PAL
UV-Detektor: Agilent 1290 DAD UV detector: Agilent 1290 DAD
Massenspektrometer Sciex API6500+ Sciex API6500 + mass spectrometer
Integration und Auswertung: Agilent ChemStation Open Lab oder Sciex Integration and evaluation: Agilent ChemStation Open Lab or Sciex
Analyst®/Multiquant Versuch 1: Abbau von Propineb Analyst® / Multiquant Experiment 1: degradation of propineb
Ereebnisübersicht aus zwei Messreihen: Overview of results from two series of measurements:
Trinkwasser Monheim jeweils 1 Liter ohne Antioxidans, mit Antioxidantien und Oxidans Kalium permanganat als Positiv-Probe. Drinking water Monheim 1 liter each without antioxidant, with antioxidants and oxidant potassium permanganate as a positive sample.
Figure imgf000023_0001
Figure imgf000023_0001
Wie der Tabelle klar zu entnehmen ist, ist der Abbau des Wirkstoffs (Propineb) bei Zugabe schon geringer Mengen Antioxidantien deutlich verringert. As the table clearly shows, the breakdown of the active ingredient (propineb) is significantly reduced when even small amounts of antioxidants are added.
Versuch 2: Experiment 2:
Kinetische Untersuchung von Spritzbrühen ohne und mit Antioxidans Kinetic investigation of spray mixtures with and without antioxidants
In kinetischen Untersuchungen konnte gezeigt werden, dass die unerwünschte Bildung des DIDT durch Zugabe von Antioxidantien signifikant reduziert wird. Besonders Ascorbinsäure (propineb WG70 + 10% Ascorbinsäure) zeigt dabei ab einer Konzentration > 5% Massenanteile eine sehr positive Wirkung. Kinetic studies have shown that the undesired formation of DIDT is significantly reduced by adding antioxidants. Especially ascorbic acid (propineb WG70 + 10% ascorbic acid) shows a very positive effect from a concentration> 5% by mass.
Die Messung erfolgte in einer Lösung von 3 g Antracol WG 70 pro Liter, was einer Wirkstoffkonzentration von 2, 1 g/L entspricht. Figur 1 zeigt dabei den Anstieg der DIDT-Konzentration in einer wässrigen Spritzbrühe in mg pro L über die Zeit in Abhängigkeit von der Menge und Art des Antioxidans, wobei als Basis eine Antracol WG70 (Wirksstoff: Propineb) Formulierung diente. The measurement was carried out in a solution of 3 g Antracol WG 70 per liter, which corresponds to an active ingredient concentration of 2.1 g / L. FIG. 1 shows the increase in the DIDT concentration in an aqueous spray liquor in mg per L over time, depending on the amount and type of antioxidant, an Antracol WG70 (active ingredient: Propineb) formulation serving as the basis.
Im Versuch zeigte sich, dass ein schwach saurer pH-Wert (pH 3-4; bedingt durch Ascorbinsäure) und gepufferte Systeme (pH 6-7; bedingt durch Mischung von Ascorbinsäure und Natriumsulfit) einen positiven Einfluss auf den Abbau haben. Die Bestimmung des DIDT-Gehalts erfolgte analog zur Bestimmung des DIDT in Trinkwasser gegen Kalibrierstandards von DIDT The experiment showed that a weakly acidic pH value (pH 3-4; due to ascorbic acid) and buffered systems (pH 6-7; due to the mixture of ascorbic acid and sodium sulfite) have a positive influence on the degradation. The DIDT content was determined analogously to the determination of DIDT in drinking water against calibration standards from DIDT
Versuch 3: Experiment 3:
Gewächshausversuch an Tomaten mit/ohne Antioxidant- vorbehandeltem Spritzbrühenwasser Auch in einem Gewächshausversuch mit Tomaten (Applikation mit 3 kg/ha Antracol WP70, 800-1000 L Spritzbrühe + mit/ohne Zusatz von Antioxidantien) konnte gezeigt werden, dass direkt nach der Applikation und Trocknen der Spritzbrühe die Rückstände an DIDT signifikant niedriger waren (6 Einzelanalysen der Proben mit/ohne Natriumsulfit von Zeitpunkt 0), wenn dem verwendeten Wasser zuvor Natriumsulfit zugegeben worden war. Die Rückstandsanalytik der Tomatenproben erfolgte analog zu den Versuchen 1 und 2 mittels LC-MS/MS gegen Kalibrierstandards von DIDT und zusätzlich isotopenmarkierte interne Standards von DIDT. Greenhouse test on tomatoes with / without antioxidant-pretreated spray liquid water Also in a greenhouse test with tomatoes (application with 3 kg / ha Antracol WP70, 800-1000 L spray liquid + with / without addition of antioxidants) it could be shown that directly after application and drying the DIDT residues in the spray liquor were significantly lower (6 individual analyzes of the samples with / without sodium sulfite from time 0) if sodium sulfite had previously been added to the water used. The residue analysis of the tomato samples was carried out analogously to experiments 1 and 2 by means of LC-MS / MS against calibration standards from DIDT and additionally isotope-labeled internal standards from DIDT.
Figur 2 zeigt hierbei die signifikant niedrigere DIDT-Konzentration zum Zeitpunkt 0 Stunden nach der Applikation und den Anstieg der DIDT-Konzentration in den ersten 24 Stunden nach der Applikation. FIG. 2 shows the significantly lower DIDT concentration at the time 0 hours after the application and the increase in the DIDT concentration in the first 24 hours after the application.

Claims

Patentansprüche Claims
1. Formulierungen enthaltend a) Dithiocarbamat-haltigen Wirkstoff, und b) mindestens ein Antioxidans ausgewählt aus der Gruppe, die Natriumsulfit (NaaSCE / E221), Ascorbinsäure (Vitamin C / E300) und Natriumdisulfh (Na S CE / E223) umfasst. 1. Formulations containing a) dithiocarbamate-containing active ingredient, and b) at least one antioxidant selected from the group comprising sodium sulfite (NaaSCE / E221), ascorbic acid (vitamin C / E300) and sodium disulfide (Na S CE / E223).
2. Formulierungen gemäß Anspruch 1, dadurch gekennzeichnet, dass das Antioxidans ausgewählt ist aus der Gruppe, die Natriumsulfit und Ascorbinsäure sowie deren Mischungen umfasst. 2. Formulations according to claim 1, characterized in that the antioxidant is selected from the group comprising sodium sulfite and ascorbic acid and mixtures thereof.
3. Formulierungen gemäß Anspruch 1, dadurch gekennzeichnet, dass die Formulierung eine wässrige Formulierung mit Ascorbinsäure als Antioxidans ist. 3. Formulations according to claim 1, characterized in that the formulation is an aqueous formulation with ascorbic acid as the antioxidant.
4. Formulierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Wirkstoff a) ausgewählt ist aus der Gruppe, die Propineb, Maneb und Mancozeb sowie deren Mischungen umfasst. 4. Formulation according to one of the preceding claims, characterized in that the active ingredient a) is selected from the group comprising propineb, maneb and mancozeb and mixtures thereof.
5. Formulierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Wirkstoff a) Propineb ist. 5. Formulation according to one of the preceding claims, characterized in that the active ingredient a) is propineb.
6. Formulierungen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Anteil der Komponente a) 10 Gew.-% bis 99,5 Gew.-% beträgt. 6. Formulations according to one of the preceding claims, characterized in that the proportion of component a) is 10% by weight to 99.5% by weight.
7. Formulierungen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Anteil der Komponente b) 0,5 Gew.-% bis 90 Gew.-% beträgt. 7. Formulations according to one of the preceding claims, characterized in that the proportion of component b) is 0.5% by weight to 90% by weight.
8. Formulierungen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die erfindungsgemäße Formulierung als "Kit of Parts" mit dem Antioxidanz und der Wirkstofformulierung in getrennten Bausteinen vorliegt. 8. Formulations according to one of the preceding claims, characterized in that the formulation according to the invention is present as a "kit of parts" with the antioxidant and the active ingredient formulation in separate building blocks.
9. Formulierungen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass diese weiterhin mindestens eine der folgenden Komponenten enthalten: c) optional mindestens einen weiteren üblichen Formulierungshilfsstoff, und d) mindestens einen weiteren agrochemischen Wirkstoff verschieden von a). 9. Formulations according to one of the preceding claims, characterized in that they also contain at least one of the following components: c) optionally at least one further customary formulation auxiliary, and d) at least one further agrochemical active ingredient different from a).
10. Formulierungen gemäß Anspruch 9, dadurch gekennzeichnet, dass agrochemische Wirkstoffe d) ein oder mehrere insektizide oder fungizide Wirkstoffe sind. 10. Formulations according to claim 9, characterized in that agrochemical active ingredients d) are one or more insecticidal or fungicidal active ingredients.
11. Verfahren zur Herstellung der Formulierungen gemäß einem der vorhergehenden Ansprüche durch Mischen der Komponenten a) und b) sowie den gegebenenfalls weiteren Additiven und Wirkstoffen. 11. Process for the preparation of the formulations according to one of the preceding claims by mixing components a) and b) and any further additives and active ingredients.
12. Verfahren zur Herstellung einer Spritzbrühe dadurch gekennzeichnet, dass in einem ersten Schritt Komponente b) eines Kit of Parts in einer entsprechenden Menge Wasser gelöst wird und in einem zweiten Schritt die Komponente a ) oder eine Formulierung der Komponente a) mit weiteren Bestandteilen c) und d) zur im Wasser gelösten Komponente b) gegeben wird. 12. A method for preparing a spray mixture, characterized in that in a first step component b) of a kit of parts is dissolved in a corresponding amount of water and in a second step component a) or a formulation of component a) with further ingredients c) and d) is added to component b) dissolved in the water.
13. Verfahren zur Bekämpfung von schädlichen Organismen umfassend das in Kontaktbringen der schädlichen Organismen, ihres Habitats, ihrer Wirte, wie Pflanzen und Saatgut, sowie des Erdreichs, des Gebiets und der Umgebung in denen sie wachsen oder wachsen könnten, aber auch von Materialien, Pflanzen, Saatgut, Erdreich, Oberflächen oder Räumen, die vor dem Angriff oder dem Befall durch pflanzenschädigende Organismen geschützt werden sollen, mit einer wirksamen Menge der Formulierungen gemäß Anspruch 1. 13. Method for combating harmful organisms, including bringing into contact the harmful organisms, their habitat, their hosts, such as plants and seeds, as well as the soil, the area and the environment in which they grow or could grow, but also materials, plants , Seeds, soil, surfaces or rooms which are to be protected from attack or attack by organisms which are harmful to plants, with an effective amount of the formulations according to claim 1.
14. Verwendung der Formulierungen gemäß einem der vorhergehenden Ansprüche zum Schutz von Pflanzen einschließlich Saatgut, insbesondere um Nutzpflanzen vor dem Befall durch schädliche Organismen zu schützen. 14. Use of the formulations according to one of the preceding claims for protecting plants including seeds, in particular in order to protect useful plants from attack by harmful organisms.
15. Verwendung der Formulierungen gemäß einem der vorhergehenden Ansprüche zur Bekämpfung pflanzenschädlicher Organismen, wie beispielsweise phytopathogene Schadpilzen, Insekten, Arachniden, Nematoden und Schadpflanzen. 15. Use of the formulations according to one of the preceding claims for combating organisms which are harmful to plants, such as, for example, phytopathogenic harmful fungi, insects, arachnids, nematodes and harmful plants.
16. Adjuvant zur Stabilisierung von Dithiocarbamat-haltigen Wirkstoff-Formulierungen in Wasser, dadurch gekennzeichnet, dass das Adjuvant ein Antioxidans ist, vorzugsweise ausgewählt aus der Gruppe, die Natriumsulfit (Na2S03 / E221), Ascorbinsäure (Vitamin C / E300) und Natriumdisulfit (NaaSaOs / E223) umfasst. 16. Adjuvant for stabilizing dithiocarbamate-containing active ingredient formulations in water, characterized in that the adjuvant is an antioxidant, preferably selected from the group consisting of sodium sulfite (Na2S03 / E221), ascorbic acid (vitamin C / E300) and sodium disulfite (NaaSaOs / E223).
17. Verwendung eines Antioxidans zur Stabilisierung von Dithiocarbamat-haltigen Wirkstoff- Formulierungen in Wasser, dadurch gekennzeichnet, dass das Adjuvant ein Antioxidans ist, ausgewählt aus der Gruppe, die Natriumsulfit (Na2SÜ3 / E221), Ascorbinsäure (Vitamin C / E300) und Natriumdisulfit (Na2S20s / E223) umfasst. 17. Use of an antioxidant to stabilize dithiocarbamate-containing active ingredient formulations in water, characterized in that the adjuvant is an antioxidant selected from the group consisting of sodium sulfite (Na 2 SÜ 3 / E221), ascorbic acid (vitamin C / E300) and sodium disulfite (Na 2 S 2 Os / E223).
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