WO2020254230A1 - Formulations stabilisées de dithiocarbamates - Google Patents

Formulations stabilisées de dithiocarbamates 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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Prior art keywords
methyl
formulations
formulation
plants
active ingredient
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PCT/EP2020/066443
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German (de)
English (en)
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 EP20733398.0A priority Critical patent/EP3982732A1/fr
Priority to JP2021573934A priority patent/JP2022537710A/ja
Priority to BR112021025246A priority patent/BR112021025246A2/pt
Priority to CN202080043590.XA priority patent/CN113950246A/zh
Publication of WO2020254230A1 publication Critical patent/WO2020254230A1/fr
Priority to CONC2021/0016879A priority patent/CO2021016879A2/es

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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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  • Pest Control & Pesticides (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne des formulations stabilisées de dithiocarbamates, en particulier de principes actifs contenant des dithiocarbamates comme groupes fonctionnels, tels que le propinèbe, le manèbe et le mancozèbe.
PCT/EP2020/066443 2019-06-15 2020-06-15 Formulations stabilisées de dithiocarbamates WO2020254230A1 (fr)

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EP20733398.0A EP3982732A1 (fr) 2019-06-15 2020-06-15 Formulations stabilisées de dithiocarbamates
JP2021573934A JP2022537710A (ja) 2019-06-15 2020-06-15 安定化ジチオカルバメート製剤
BR112021025246A BR112021025246A2 (pt) 2019-06-15 2020-06-15 Formulações estabilizadas de ditiocarbamatos
CN202080043590.XA CN113950246A (zh) 2019-06-15 2020-06-15 二硫代氨基甲酸盐的稳定制剂
CONC2021/0016879A CO2021016879A2 (es) 2019-06-15 2021-12-13 Formulaciones estabilizadas de ditiocarbamatos

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB935981A (en) 1960-12-28 1963-09-04 Bayer Ag Fungicidal carbamic acid salts
EP1140152A1 (fr) * 1998-12-21 2001-10-10 Akzo Nobel N.V. Methode de production de vaccins inactives associes a une emulsion eau dans huile adjuvante
WO2006089633A2 (fr) 2005-02-22 2006-08-31 Bayer Cropscience Ag Cetoenols cycliques substitues par spirocetal
WO2008067911A1 (fr) 2006-12-04 2008-06-12 Bayer Cropscience Ag Cétoénols spirocycliques substitués par le biphényle
WO2010051926A2 (fr) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft Nouveaux composés substitués par halogène
US20100240774A1 (en) * 2007-09-13 2010-09-23 Basf Se Use of hydrophobin polypeptides as penetration enhancers
WO2013092350A1 (fr) 2011-12-21 2013-06-27 Bayer Cropscience Ag Dérivés de sulfure de trifluoréthyle n-substitué d'arylamidine en tant qu'acaricide et insecticide
US20170112124A1 (en) * 2004-04-26 2017-04-27 Basf Se Aqueous fungicidal composition and use thereof for combating harmful micro organisms
DE102016210164A1 (de) * 2016-06-08 2017-12-14 Clariant International Ltd Verwendung von N-substituierten Pyrrolidonen zur Förderung der Penetration von agrochemischen Wirkstoffen

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1545878A (zh) * 2003-12-17 2004-11-17 许惠朝 代森锰锌水分散性粒剂及其制造方法
CN105777314A (zh) * 2014-12-24 2016-07-20 姜汉军 一种马铃薯拌种剂及其制备方法
CN105284869A (zh) * 2015-11-26 2016-02-03 利民化工股份有限公司 一种代森锰锌与三乙膦酸铝复配的可湿性粉剂及其制备方法
CN106613953A (zh) * 2016-11-03 2017-05-10 明光市大全甜叶菊专业合作社 一种甜叶菊组培方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB935981A (en) 1960-12-28 1963-09-04 Bayer Ag Fungicidal carbamic acid salts
EP1140152A1 (fr) * 1998-12-21 2001-10-10 Akzo Nobel N.V. Methode de production de vaccins inactives associes a une emulsion eau dans huile adjuvante
US20170112124A1 (en) * 2004-04-26 2017-04-27 Basf Se Aqueous fungicidal composition and use thereof for combating harmful micro organisms
WO2006089633A2 (fr) 2005-02-22 2006-08-31 Bayer Cropscience Ag Cetoenols cycliques substitues par spirocetal
WO2008067911A1 (fr) 2006-12-04 2008-06-12 Bayer Cropscience Ag Cétoénols spirocycliques substitués par le biphényle
US20100240774A1 (en) * 2007-09-13 2010-09-23 Basf Se Use of hydrophobin polypeptides as penetration enhancers
WO2010051926A2 (fr) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft Nouveaux composés substitués par halogène
WO2013092350A1 (fr) 2011-12-21 2013-06-27 Bayer Cropscience Ag Dérivés de sulfure de trifluoréthyle n-substitué d'arylamidine en tant qu'acaricide et insecticide
DE102016210164A1 (de) * 2016-06-08 2017-12-14 Clariant International Ltd Verwendung von N-substituierten Pyrrolidonen zur Förderung der Penetration von agrochemischen Wirkstoffen

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"The Pesticide Manual", 2009, pages: 954 - 955
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 12427-38-2

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CO2021016879A2 (es) 2022-01-17

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