CN113950246A - Stable formulations of dithiocarbamates - Google Patents

Abstract

The present invention relates to stable dithiocarbamate formulations, in particular stable formulations of active ingredients such as propineb, maneb and mancozeb, containing a dithiocarbamate group as a functional group.

Description

Stable formulations of dithiocarbamates

The present invention relates to stable formulations of dithiocarbamates, in particular of active ingredients containing a dithiocarbamate group as functional group, such as propineb (propineb), maneb (maneb) and mancozeb (mancozeb).

In particular, the invention relates to formulations comprising dithiocarbamate active ingredients which, when formulated and diluted, contain a particularly low content of the corresponding oxidative rearrangement products, both on and after dilution.

The invention also relates to methods for producing said preparations, to methods for controlling phytopathogenic fungi in crop protection, and to the use thereof as crop protection products.

Furthermore, the invention relates to formulations of dithiocarbamates containing specific antioxidants, in particular formulations containing vitamin C (ascorbic acid) and/or sodium sulfite, in particular formulations of agrochemical active ingredients having dithiocarbamate groups, and to the use of specific antioxidants, in particular vitamin C (ascorbic acid) and sodium sulfite, for stabilizing dithiocarbamate compounds, in particular agrochemical active ingredients having dithiocarbamate groups.

Finally, the invention relates to formulations comprising the above antioxidants as separately added active ingredients, either directly or in the form of a kit of parts, in the formulation. The greatest advantages of the kit are, for example, that the antioxidant can already deoxygenate the water before addition of the active ingredient/formulation, that no changes to the formulation are required, that the desired antioxidant is easy to administer, and that the kit does not adversely affect the storage stability or chemical stability of the finished stable formulation.

Furthermore, the present invention relates to the use of antioxidants, in particular vitamin C (ascorbic acid) and/or sodium sulfite, for stabilizing agrochemical active ingredients having a dithiocarbamate group, in particular propineb and mancozeb, in agrochemical formulations.

Dithiocarbamate active ingredients such as propineb (The Pesticide Manual, 15 th edition, 2009, 954-955 pages, and GB Patent 935,981, CAS number 12071-83-9), maneb (manganese ethylene-1, 2-bisdithiocarbamate/CAS number 12427-38-2) and mancozeb (manganese ethylene bis (dithiocarbamate)/CAS number 8018-01-7) have long been recognized as crop protection products for fungal diseases.

For example, they are used in the control of mildew and scab in the cultivation of fruits, vegetables and grapes, and of late blight and brown rot in potatoes and tomatoes.

For example, propineb, an active fungicidal ingredient with a wide range of applications, is used for plant protection on a global scale. The main fields of application are rice planting, potato planting, tomato, viticulture and many other secondary crops. The main administration forms are preparations such as Antrocol WP70 and WG70(BAYER), but mixtures with, for example, iprovalicarb and trifloxystrobin are also available on the market.

For the application of the active ingredient, the product formulation is formulated with water and different amounts of water are sprayed at different application rates per hectare of agricultural area.

However, due to atmospheric oxygen (c (O) dissolved in water₂Saturated) @20 ℃ ═ 9mg/l), some active ingredients containing dithiocarbamate groups may be degraded.

This is shown by the following example of propineb (scheme 1).

The chemical reaction which is possible in conventional spray liquids and which proceeds until the dissolved atmospheric oxygen present is completely consumed firstly in some cases reduces the efficacy of the active ingredient and secondly in some cases produces oxidation products, in this case methyldihydroimidazolethione (IUPAC nomenclature: 6-methyl-5, 6-dihydroimidazo (2,1-c) (1,2,4) dithiazol-3-thione), hereinafter DIDT.

Due to the stoichiometry of the reaction-1 molecule of oxygen O₂(32mg/mmol) theoretically formed 2 molecules of oxidation product (190mg/mmol x2) -thus theoretically 10.7g of oxidation product could be formed per 100l of sprayed liquid. It should be noted here that as the dilution of the active ingredient in the spray liquid increases, the loss of active ingredient through this reaction increases, as more oxygen is dissolved in a greater amount of water.

As mentioned above, the oxidation product DIDT may be associated with approval and registration, in addition to loss of active ingredients.

It is therefore very important to prevent this chemical reaction in the sprayed liquid from the beginning by removing dissolved atmospheric oxygen. However, since a large amount of water is required (in m)³Within range), degassing the water prior to addition of the formulation concentrate is not feasible here.

In this way, not only is the loss of active ingredient prevented, but the formation of oxidation products is also prevented. In addition, sodium sulfite and ascorbic acid are standard food additives (E221 and E300), which do not constitute a hindrance in toxicology and registration.

There is therefore a need for stable formulations of active ingredients containing dithiocarbamate groups which do not show any degradation of the active ingredient upon contact with oxygen, even in water-soluble form, and the stabilizers/antioxidants should be harmless or have no approval barrier in agrochemical use.

It is therefore an object of the present invention to provide new and improved formulations of active ingredients containing dithiocarbamate groups which have a high oxidative stability both during storage and during the formulation of spray liquids, and to provide the use of specific antioxidants for stabilizing formulations of active ingredients containing dithiocarbamate groups.

It is a further object of the present invention to provide stabilizers and/or stabilizer systems for formulations of active ingredients containing dithiocarbamate groups, which can be used in agrochemical formulations and are highly active even in small amounts.

It is a further object of the present invention to provide a process for preparing formulations of active ingredients containing dithiocarbamate groups and spray liquids resulting therefrom, wherein the antioxidant is already present in the finished formulation before dilution or is added as a tank mix (kit of parts).

Surprisingly, it has been found that even at low concentrations antioxidants such as sodium sulfite (Na) are added₂SO₃/E221), ascorbic acid (vitamin C/E300) or sodium metabisulfite (Na)₂S₂O₅) Oxidation of the dithiocarbamate, and thus the formation of oxidation products, may also be significantly reduced.

The invention therefore relates to formulations having an active ingredient containing a dithiocarbamate group, comprising

a) At least one active ingredient containing a dithiocarbamate group, and

b) at least one antioxidant, preferably selected from sodium sulfite (Na)₂SO₃E221), ascorbic acid (vitamin C/E300) and sodium metabisulfite (Na)₂S₂O₅/E223)。

The active ingredient a) is preferably selected from propineb, maneb and mancozeb, and mixtures thereof.

Further preferably, the antioxidant is selected from sodium sulfite and ascorbic acid, and mixtures thereof.

In a preferred embodiment, the active ingredient a) is propineb and the antioxidant is selected from sodium sulfite and ascorbic acid.

The active ingredient a) is preferably present in the formulations of the invention in an amount of from 10 to 99.5% by weight, further preferably from 25 to 99% by weight, even further preferably from 40 to 90% by weight, further preferably from 50 to 97% by weight and preferably from 40 to 95% by weight, further preferably from 50 to 90% by weight, even further preferably from 65 to 90% by weight and particularly preferably from 70 to 86% by weight, in each case based on the total weight of the formulation.

The antioxidants b) are preferably present in the formulations of the invention in an amount of from 0.5 to 90% by weight, further preferably from 1.0 to 75% by weight, even further preferably from 2.0 to 60% by weight and particularly preferably from 3.0 to 50% by weight, in each case based on the total weight of the formulation.

In an alternative embodiment, the formulation of the invention is in the form of a kit of parts. In this embodiment, the antioxidant b) is not present in the finished formulation, but is part of a separately packaged formulation, for example in tablet form or as a water soluble pouch or a split pouch or in another suitable package. In this case, the antioxidant is added to the water before the formulation is stirred.

Surprisingly, it has been found that adding an oxidizing agent to water even immediately prior to stirring the active ingredient provides sufficient protection against oxidative degradation of the active ingredient.

In the case of a kit of parts, the antioxidant is administered in such a way that it is preferably added in an amount of 0.1g to 15g/l water/spray liquid, further preferably 0.5g to 12g/l water and more preferably 2g to 8g/l water, wherein these ranges also apply to the spray liquid produced by diluting the formulation.

In an alternative embodiment, the antioxidant is administered in the case of a kit or for a spray liquid produced by dilution, such that it is preferably present in an amount of 0.3g to 10g/l spray liquid/water.

In any case, however, the antioxidant is used in a stoichiometric excess of preferably 1.1 to 50 equivalents, further preferably 1.5 to 25 equivalents, even further preferably 1.8 to 15 equivalents and particularly preferably 2 to 12 equivalents, based on the oxygen dissolved in the water, to ensure rapid removal of the dissolved atmospheric oxygen (reaction kinetics).

In this case, the person skilled in the art is familiar with the manner in which the amount of dissolved oxygen should be determined on the basis of temperature and other factors or by simple rapid testing.

The formulation is preferably an agrochemical formulation.

Furthermore, the formulations of the invention as described above may comprise further ingredients, further agrochemical active ingredients other than a).

The invention therefore also relates to formulations having an active ingredient containing a dithiocarbamate group, which comprise

a) At least one dithiocarbamate group-containing active ingredient,

b) at least one selected from sodium sulfite (Na)₂SO₃E221), ascorbic acid (vitamin C/E300) and sodium metabisulfite (Na)₂S₂O₅The antioxidants of the compounds of the formula/E223),

c) optionally other conventional formulation auxiliaries, and

d) other agrochemical active ingredients.

In a preferred embodiment, the active ingredient a) is propineb and the antioxidant is selected from sodium sulfite and ascorbic acid.

The formulation of the invention is preferably selected from WP and WG.

Further preferably, the pH of the formulation and the resulting spray liquid is in the weak acid range to the neutral range, i.e. pH 3-7.

To this end, a pH adjusting substance may be added to the formulation and kit. These also include buffer systems known to those skilled in the art.

More preferably, the buffer consists of ascorbic acid and sodium sulfite.

Furthermore, within the scope of the preferences stated in the present invention, different preference levels are to be understood such that they can be combined with one another in an aligned manner, but in any case the same preference levels and in particular the most preferred embodiments/preference levels should be combined with one another in each case and are actually disclosed as such combinations.

Compositions as described above which consist only of essential components (not optional components) are likewise to be regarded as disclosed.

Percentages-unless otherwise stated-shall be regarded as weight percentages, wherein the weight percentages of the composition add up to 100.

Formulations or use forms comprising formulation auxiliaries c) such as extenders, solvents, spontaneous accelerators, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and/or further auxiliaries, such as adjuvants, are preferred. In this case, the adjuvant is a component that enhances the biological effect of the formulation, and the component itself does not have any biological effect. Examples of adjuvants are agents that promote retention, spreading, attachment to the leaf surface or penetration.

The active ingredients specified herein by their common names are known and described, for example, in "Pesticide Manual" (16 th edition, British Crop Protection Council) or retrievable on the Internet (e.g.: http:// www.alanwood.net/pesticides).

In the context of the present invention, the further agrochemical active ingredients d) are active fungicidal, insecticidal or herbicidal ingredients. In an alternative embodiment, the formulation of the invention comprises one or more further active insecticidal or fungicidal ingredient d), more preferably one or more active fungicidal ingredient d). The active ingredients used are preferably water-insoluble.

The Pesticide Manual (The Pesticide Manual) provides an overview of typical crop protection agents.

Preferred insecticidal components d) are, for example, imidacloprid (imidacloprid), nitenpyram (nitenpyram), acetamiprid (acetamiprid), thiacloprid (thiacloprid), thiamethoxam (thiamethoxam), clothianidin (clothianidin), cyantraniliprole (cyantraniliprole), chlorantraniliprole (chlorantraniliprole), flubendiamide (fluendiamide), flucyanamide (tetraniloproprile), cyclic bromamide (cyclaniliprole), spirodiclofen (spirodiclofen), spirodiclofen (spiromesifen), spirotetramat (spirotetramat), abamectin (abamectin), fluthrin (acrilin), chlorfenapyr (chlorfenapyr), fluazuron (pyrazone), flufenozide (pyradifenozide), flufenozide (flufenozide), flufenoxafen (flufenoxaprop-ethyl), flufenoxazide), flufenoxaprop (pyrazide), flufenozide (flufenozide), flufenoxazide (flufenoxaprop-ethyl), flufenoxazide), flufenoxaprop-ethyl (flufenozide), flufenozide (flufenoxaprop-ne (flufenozide), flufenoxaprop-ethyl (flufenoxaprop-ne (flufenoxaprop-l), flufenoxaprop-ethyl), flufenozide), flufenoxaprop-ethyl (flufenoxaprop-ne (flufenoxaprop-ethyl), flufenoxaprop-ethyl (flufenoxaprop-ethyl), flufenozide), flufenoxaprop-ethyl (flufenoxaprop-ethyl), flufenoxaprop-p-ethyl), flufenoxaprop-ethyl (flufenozide), flufenoxaprop-ethyl), flufenoxaprop-p (flufenozide), flufenoxaprop-ethyl (flufenoxaprop-ethyl), flufenoxaprop-ethyl (flufenoxaprop-ethyl), flufenozide), flufenoxaprop-n (flufenoxaprop-ethyl (flufenozide), fluben-ne (fluben-ethyl), fluben-ethyl (fluben-ethyl), fluben-ethyl (fluben-ethyl), fluben (fluben-ethyl), fluben-ethyl (fluben-ethyl), fluben-ethyl, fluben (fluben-ethyl), fluben (flubencarb-ethyl), fluben (fluben-ethyl), fluben-ethyl), fluben (fluben-ethyl), fluben-ethyl, fluben (fluben, Pesticidal ureas (triflumuron), the compounds from WO 2006/089633 as examples I-1-a-4, the compounds disclosed as examples I-1-a-4 in WO 2008/067911, the compounds disclosed as examples Ib-14 in WO 2013/092350, the compounds disclosed as examples Ik-84 in WO 2010/51926.

Preferred fungicidal components d) are cited below by way of example.

All compounds mentioned in classes (1) to (15) can form salts with suitable bases or acids, if appropriate on the basis of their functional groups. All fungicidal compounds mentioned in classes (1) to (15) may include tautomeric forms, as the case may be.

1) Ergosterol biosynthesis inhibitors, such as (1.001) cyproconazole (cyproconazole), (1.002) difenoconazole (difenoconazole), (1.003) epoxiconazole (epoxyconazole), (1.004) fenhexamid (fenhexamid), (1.005) fenpropidin (fenpropidin), (1.006) fenpropimorph (fenpropimorph), (1.007) fenpyrazamide (fenpyrazamine), (1.008) fluquinconazole (fluquinconazole), (1.009) flutriafol, (1.010) imazalil (imazalil), (1.011) imazalil sulfate (imazalil), (1.012) ipconazole, (1.013) metconazole (metconazole), (1.014) fenpropiconazole (1.022), (1.022) propiconazole (fenpyrazalil), (1.0221.017) propiconazole (fenpyrazalil), (1.017) propiconazole (1.022), (1.017) propiconazole (propiconazole), (1.015) propiconazole (propiconazole), (1.022) propiconazole (propiconazole) (1.024) tridemorph (tridemorph), (1.025) triticonazole (triticonazole), (1.026) (1R,2S,5S) -5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2, 4-triazol-1-ylmethyl) cyclopentanol, (1.027) (1S,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- [ (1R) -2, 2-dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.029) (2R) -2- (1-chlorocyclopropyl) -4- [ (1S) -2, 2-dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.030) (2R) -2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl ] -1- (1H-1,2, 4-triazol-1-yl) propan-2-ol, (1.031) (2S) -2- (1-chlorocyclopropyl) -4- [ (1R) -2, 2-dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.032) (2S) -2- (1-chlorocyclopropyl) -4- [ (1S) -2, 2-dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.033) (2S) -2- [4- (4-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) -1, 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)1- ({ (2R,4S) -2- [ 2-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-chloro-4- (4-chlorophenoxy) phenyl ] -4-methyl-1, 3-dioxolan-2-yl } methyl) -1H-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)1- { [ rel (2R,3R) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazol-5-yl thiocyanate, (1.041)1- { [ 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-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazol-3-thione, (1.043)2- [ (2R,4R,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.044)2- [ (2R,4S,5R) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.045)2- [ (2R,4S,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.046)2- [ (2S,4R,5R) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.047)2- [ (2S,4R,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.048)2- [ (2S,4S,5R) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.049)2- [ (2S,4S,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.050)2- [1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.051)2- [ 2-chloro-4- (2, 4-dichlorophenoxy) phenyl ] -1- (1H-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) butan-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-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-triazole-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-triazole-3-thione, (1.058)2- { [ rel (2R,3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -2, 4-dihydro-3H-1, 2, 4-triazole-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-1,2, 4-triazole, (1.061)5- (allylsulfanyl) -1- { [ rel (2R,3R) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazole, (1.062)5- (allylsulfanyl) -1- { [ rel (2R,3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazole, (1.063) N ' - (2, 5-dimethyl-4- { [3- (1,1,2, 2-tetrafluoroethoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidocarboxamide, (1.064) N ' - (2, 5-dimethyl-4- { [3- (2,2, 2-trifluoroethoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidocarboxamide, (1.065) N ' - (2, 5-dimethyl-4- { [3- (2,2,3, 3-tetrafluoropropoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidocarb-oxamide Benzamide, (1.066) N '- (2, 5-dimethyl-4- { [3- (pentafluoroethoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidazolyliminamide, (1.067) N' - (2, 5-dimethyl-4- {3- [ (1,1,2, 2-tetrafluoroethyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methylimidazolyliminamide, (1.068) N '- (2, 5-dimethyl-4- {3- [ (2,2, 2-trifluoroethyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methylimidazolyliminamide, (1.069) N' - (2, 5-dimethyl-4- {3- [ (2,2,3, 3-tetrafluoropropyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methyloxyiminocarboxamide, (1.070) N '- (2, 5-dimethyl-4- {3- [ (pentafluoroethyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methyloxyiminocarboxamide, (1.071) N' - (2, 5-dimethyl-4-phenoxyphenyl) -N-ethyl-N-methyloxyiminocarboxamide, (1.072) N '- (4- { [3- (difluoromethoxy) phenyl ] sulfanyl } -2, 5-dimethylphenyl) -N-ethyl-N-methyloxyiminocarboxamide, (1.073) N' - (4- {3- [ (difluoromethyl) sulfanyl ] phenoxy } -2, 5-dimethylphenyl) -N-ethyl-N-methyloxyiminocarboxamide, (1.074) N ' - [ 5-bromo-6- (2, 3-dihydro-1H-inden-2-yloxy) -2-methylpyridin-3-yl ] -N-ethyl-N-methyloxyiminocarboxamide, (1.075) N ' - {4- [ (4, 5-dichloro-1, 3-thiazol-2-yl) oxy ] -2, 5-dimethylphenyl } -N-ethyl-N-methyloxyiminocarboxamide, (1.076) N ' - { 5-bromo-6- [ (1R) -1- (3, 5-difluorophenyl) ethoxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide, (1.077) N ' - { 5-bromo-6- [ (1S) -1- (3, 5-difluorophenyl) ethoxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide, (1.078) N ' - { 5-bromo-6- [ (cis-4-isopropylcyclohexyl) oxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide, (1.079) N ' - { 5-bromo-6- [ (trans-4-isopropylcyclohexyl) oxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide -methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide, (1.080) N' - { 5-bromo-6- [1- (3, 5-difluorophenyl) ethoxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide, (1.081) chlorofluoromethoxyfen-azole (mefenthiflunazole), (1.082) ipfenthiflunazole and (1.083)2- [6- (4-bromophenoxy) -2- (trifluoromethyl) -3-pyridyl ] -1- (1,2, 4-triazol-1-yl) propan-2-ol.

2) Respiratory chain inhibitors acting on complexes I or II, for example (2.001) benzovindiflupyr (benzovindiflupyr), (2.002) bixafen (bixafen), (2.003) boscalid (boscald), (2.004) carboxin (carboxin), (2.005) fluopyram (fluopyram), (2.006) flutolanil (flutolanil), (2.007) fluxapyroxad, (2.008) furametpyr), (2.009) isothiavalicarb (isoflutamide), (2.010) isopyrazam (isopyrazam) (trans-epimer 1R,4S,9S), (2.011) isopyram (trans-epimer 1S,4R,9R), (2.012) isopyram (trans-epimer 1R,4S,9S), (2.011) isopyram (trans-epimer 1S,4R,9 RS-racemic mixture of SR-4 RS, SR-epimer, and (SR-epimer) 4 RS, 9 RS-racemic mixture of SR-isopyram (SR-4 RS, 9, S, SR-epimer, 2.011), (2.014) isopyrazam (cis epimer 1R,4S,9R), (2.015) isopyrazam (cis epimer 1S,4R,9S), (2.016) isopyrazam (cis epimer 1RS,4SR,9RS), (2.017) penflufen (penflufen), (2.018) penthiopyrad (penthiopyrad), (2.019) pyrazoylhydroxylamine (pydiflumetofen), (2.020) pyraziflumumid, (2.021) sedaxane, (2.022)1, 3-dimethyl-N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) -1H-pyrazole-4-carboxamide, (2.023)1, 3-dimethyl-N- [ (3R) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-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 ] -1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6- (trifluoromethyl) -N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) benzamide, and pharmaceutically acceptable salts thereof, (2.027)3- (difluoromethyl) -1-methyl-N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) -1H-pyrazole-4-carboxamide, (2.028)3- (difluoromethyl) -1-methyl-N- [ (3R) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-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-1, 1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1-methyl-1H-pyrazole-4-carboxamide, (2.032)3- (difluoromethyl) -N- [ (3S) -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-methylbenzyl -1H-pyrazole-4-carboxamide, (2.036) N- (2-tert-butylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N- (5-chloro-2-ethylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-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- [ (1R,4S) -9- (dichloromethylene) -1,2,3, 4-tetrahydro-1, 4-methanonaphthalen-5-yl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.040) N- [ (1S,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-methoxypropan-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- (trifluoromethyl) benzyl ] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide -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) -1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropyl-5-methylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (5-fluoro-2-isopropylbenzyl) -1-methyl-1H-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-carboxamide, (2.054) N-cyclopropyl-N- (2-cyclopropyl-5-fluorobenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl- 1H-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) pyrapropofol, (2.058) isoflurypramim.

3) Respiratory chain inhibitors acting on complex III, such as (3.001) ametoctradin (ametoctradin), (3.002) ametoctradin (amisulbactam), (3.003) azoxystrobin (azoxystrobin), (3.004) tolutrobin (coumethoxyxystrobin), (3.005) coumoxystrobin (coumoxystrobin), (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enestrobin (enoxytrobin), (3.009) famoxadone (famoxadon), (3.010) fenamidone (fenaminozone), (3.011) flufenamido (flufenoxystrobin), (3.012) fluoxystrobin (fluoxystrobin), (3.013) kresoxim-metystrobin (kresoxim-methyl-014) flufenamido (fluoxystrobin), (3.014) fluoxystrobin (fluoxystrobin) (3.2-362) (fluoxystrobin) (3.11) fluoxystrobin (fluoxystrobin), (3.014) fluoxystrobin (fluoxystrobin) (3.11) fluoxystrobin (fluoxystrobin) (3.11) (fluoxystrobin) (flutrobin) (3.11) -2-phenylethenyl ] oxy } phenyl) ethylidene ] amino } oxy) methyl ] phenyl } -2- (methoxyimino) -N-methylacetamide, (3.022) (2E,3Z) -5- { [1- (4-chlorophenyl) -1H-pyrazol-3-yl ] oxy } -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, methyl-2- (methoxyimino) -N-methylacetamide, methyl-2-methoxy-N-methylacetamide, methyl-2-amino-methyl-2- (methoxyimino) -2-3-enamide, methyl-2-methoxy-N-methylacetamide, methyl-2-methyl-2-phenyl-2-methyl-acetamide, 3., (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-dioxononan-7-yl 2-methylpropionate, (3.026)2- {2- [ (2, 5-dimethylphenoxy) methyl ] phenyl } -2-methoxy-N-methylacetamide, (3.027) N- (3-ethyl-3, 5, 5-trimethylcyclohexyl) -3-carboxamido-2-hydroxybenzamide, (3.028) (2E,3Z) -5- { [1- (4-chloro-2-fluorophenyl) -1-yl H-pyrazol-3-yl ] oxy } -2- (methoxyimino) -N, 3-dimethylpent-3-enamide, methyl (3.029) {5- [3- (2, 4-dimethylphenyl) -1H-pyrazol-1-yl ] -2-methylbenzyl } carbamate, (3.030) metytetraprole, (3.031) florylpicoxamide.

4) Mitotic and cell-division inhibitors, for example (4.001) carbendazim (carbendazim), (4.002) diethofencarb (diethofencarb), (4.003) ethaboxam (ethaboxam), (4.004) fluopicolide (fluopicolid), (4.005) pencycuron (pencycuron), (4.006) thiabendazole (thiabendazole), (4.007) thiophanate-methyl (thiophanate-methyl), (4.008) zoxamide (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-chloropyridin-3-yl) -6-methyl-4- (2,4, 6-trifluorophenyl) pyridazine, (4.012)4- (2-bromo-4-fluorophenyl) -N- (2, 6-difluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (4.013)4- (2-bromo-4-fluorophenyl) -N- (2-bromo-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (4.014)4- (2-bromo-4-fluorophenyl) -N- (2-bromophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (4.015)4- (2-bromo-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (4.016)4- (2-bromo-4-fluorophenyl) -N- (2-chlorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (4.017)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-1H-pyrazol-5-amine, (4.019)4- (2-chloro-4-fluorophenyl) -N- (2-chloro-6-fluoro-phenyl) -N- (2-chloro-6-fluoro-5-amine Phenyl) -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-1H-pyrazol-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-chloro-2, 6-difluorophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine.

5) Compounds having multi-site activity, for example (5.001) Bordeaux mix (Bordeaux mix), (5.002) captafol, (5.003) captan (captan), (5.004) chlorothalonil (chlorothalonil), (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper sulfate (2+), (5.010) dithianon (dithianon), (5.011) dodin, (5.012) folpet, (5.013) mancozeb (mancozeb), (5.014) maneb), (5.015) metiram, (5.016) zineb (zineb), (5.017) copper hydroxyquinoline (cohexoxide), (5.018) propineb (propineb) (28) and (36020) zinc disulfide (5.4936) formulations including bisthiozine (365.7) bisthionate (5.493) and (thiobisthiobisthiozine (3623-366), 7-dioxo-6, 7-dihydro-5H-pyrrolo [3 ', 4': 5,6] [1,4] dithiino [2,3-c ] [1,2] thiazole-3-carbonitrile.

6) Compounds capable of triggering host defenses, such as (6.001) benzothiadiazole (acibenzolar-S-methyl), (6.002) isotianil (isotianil), (6.003) probenazole (probenazole), (6.004) tiadinil (tiadinil).

7) Inhibitors of amino acid and/or protein biosynthesis, for example (7.001) cyprodinil (cyprodinil), (7.002) kasugamycin (kasugamycin), (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline (oxytetracycline), (7.005) pyrimethanil, (7.006)3- (5-fluoro-3, 3,4, 4-tetramethyl-3, 4-dihydroisoquinolin-1-yl) quinoline.

8) Inhibitors of ATP production, for example (8.001) silthiofam (silthiofam).

9) Cell wall synthesis inhibitors, for example (9.001) benthiavalicarb (benthiavalicarb), (9.002) dimethomorph, (9.003) flumorph (flumorph), (9.004) iprovalicarb, (9.005) mandipropamid (maninparamide), (9.006) pyrimorph (pyrimorph), (9.007) pyrimethanil (valifenate), (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) Lipid and membrane synthesis inhibitors, for example (10.001) propamocarb (propamocarb), (10.002) propamocarb hydrochloride (propamocarb hydrochloride), (10.003) tolclofos-methyl.

11) Melanin biosynthesis inhibitors such as (11.001) tricyclazole, (11.002)2,2, 2-trifluoroethyl { 3-methyl-1- [ (4-methylbenzoyl) amino ] but-2-yl } carbamate.

12) Nucleic acid synthesis inhibitors, for example (12.001) benalaxyl (benalaxyl), (12.002) benalaxyl-M) (kiralaxyl), (12.003) metalaxyl (metalaxyl), (12.004) metalaxyl-M (mefenoxam).

13) Signal transduction inhibitors, for example (13.001) fludioxonil (fludioxonil), (13.002) iprodione (iprodione), (13.003) procymidone (procymidone), (13.004) proquinazid (proquinazid), (13.005) quinoxyfen (quinoxyfen), (13.006) vinclozolin (vinclozolin).

14) Compounds useful as uncouplers, for example (14.001) fluazinam, (14.002) meptyldinocap.

15) Other compounds, such as (15.001) abscisic acid (abscisic acid), (15.002) thiocyanobenzothioide (benthiazole), (15.003) betaxazine, (15.004) carbapenem (capsomycin), (15.005) carvone (carvone), (15.006) chlorfenapyr (chinomethionat), (15.007) thiabendazole (cufraneb), (15.008) cyflufenamid, (15.009) cyromazine (cyflufenamid), (15.010) cyclopropanesulfonamide (cysulfofamide), (15.011) fluvalinil, (15.012) fosetyl-aluminum (fosetyl-aliminium), (15.013) calcium fosetyl-calcium (fosetyl-calceium), (15.014) sodium fosetyl-sodium (fosetyl-sodium), (15.015) methyl isothiocyanate (cyazomycin 15.016), nickel (foscamycin), (368) thiocyanine (369) fluoroxyfenamate (369), (369) thiocyanine (foscamycin (369) and (thiocyanine (369) thiflufenamate (369), (15.023) oxyphenanthin, (15.024) pentachlorophenol and its salts, (15.025) phosphonic acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone (chlazafenone), (15.028) isobutoxyquinoline (tebufloquin), (15.029) cumylphthalide (tecloftalam), (15.030) sulffluanid (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) -1H-pyrazol-1-yl ] ethanone, (15.032)1- (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-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] ethanone, (15.033)2- (6-benzylpyridin-2-yl) quinazoline, (15.034)2, 6-dimethyl-1H, 5H- [1,4] dithiino [2,3-c:5,6-c' ] dipyrrole-1, 3,5,7(2H,6H) -tetraone, (15.035)2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- {5- [2- [2, 5 ] -1H-pyrazol-1-yl ] -1- [4 { [5- [2, 2] methyl-1H-yl ] quinazoline -prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.036)2- [3, 5-bis (difluoromethyl) -1H-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-thiazol-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- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } -3-chlorophenyl methanesulfonate, (15.040)2- { (5S) -3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 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, and mixtures thereof, (15.042)2- { 2-fluoro-6- [ (8-fluoro-2-methylquinolin-3-yl) oxy ] phenyl } propan-2-ol, (15.043)2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } -3-chlorophenyl methanesulfonate, (15.044)2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } phenylmethanesulfonate, (15.045) 2-phenylphenol and 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, and salts thereof, (15.046) 4- (4,4, 5-trifluoro-3, 4-dihydroisoquinolin-1-yl) quinoline, (15.050) 5-amino-1, 3, 4-thiadiazole-2-thiol, (15.051) 5-chloro-N '-phenyl-N' - (prop-2-yn-1-yl) thiophene 2-sulfonylhydrazide, (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-benzoazepine, (15.055) but-3-yn-1-yl {6- [ ({ [ (Z) - (1-methyl-1H-tetrazole- 5-yl) (phenyl) methylene amino } oxy) methyl ] pyridin-2-yl } carbamate, (15.056) (2Z) -ethyl 3-amino-2-cyano-3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4, 5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) {6- [ ({ [ (1-methyl-1H-tetrazol-5-yl) (phenyl) methylene ] amino } oxy) methyl ] pyridin-2-yl } carbamic acid tert-butyl ester, (15.062) 5-fluoro-4-imino-3-methyl-1- [ (4-methylphenyl) sulfonyl ] -3, 4-dihydropyrimidin-2 (1H) -one, (15.063) aminopyrifen, (15.064) (N '- [ 2-chloro-4- (2-fluorophenoxy) -5-methylphenyl ] -N-ethyl-N-methyliminocarboxamide), (15.065) (N' - (2-chloro-5-methyl-4-phenoxyphenyl) -N-ethyl-N-methyliminocarboxamide), (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-1H-benzimidazol-1-yl) -4, 4-difluoro-3, 3-dimethyl-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) ({4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl } carbamic acid methyl ester), (15.075) (N- {4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzyl } cyclopropanecarboxamide) ], and pharmaceutical compositions containing the compounds, (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-yl ] benzamide, (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-yl ] benzamide, (15.081)2, 2-difluoro-N-methyl-2- [4- [5- (trifluoromethyl) -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-carbonylimino ] -4- (5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide, (15.084) N- [ (Z) -N-methoxy-C-methyl-carbonylimino ] -4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide, (15.085) N-allyl-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propanamide, (15.086)4, 4-dimethyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] pyrrolidin-2-one, (15.087) N-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] thiophenylamide, (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-oxadiazol-3-yl ] phenyl ] methyl ] -3,3, 3-trifluoropropanamide, (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, and mixtures thereof, (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 ] urea, (15.095) N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl) cyclopropanecarboxamide, and pharmaceutically acceptable salts thereof, (15.096) N, 2-dimethoxy-N- [ [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-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, (15.100) 3-ethyl-1-methoxy-1- [ [4- [5- (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 ] isoxazolin-3-one, (15.103)5, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] isoxazolin-3-one, (15.104)3, 3-dimethyl-1- [ [4- [5- (trifluoromethyl) -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 ] isoxazolin-3-one and (15.107)5, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] isoxazolin-3-one.

Further preferred fungicidal components d) are, for example, bixafen, fenamidone (fenamidone), fenhexamid, fluopicolide (fluopicolide), fluopyram, fluoxastrobin, iprovalicarb, isotianil, isophtendamide, isopyrazam, pencycuron, penflufen, propineb, tebuconazole, trifloxystrobin, ametoctradin, amistar, azoxystrobin, benthiavalicarb-isoproyl, benzovindiflupyr, boscalid, carbendazim, chlorothiononil, cyazofamid, cyflufenamid, cymoxanil, cyflufenamidol, difenoconazole, ethaboxam, epoxiconazole, famoxadone (famoxadone), fluazinam, fluquinconazole, flusilazole (pyflusilazole), fluthianil, flufenamidone, pyrazopyram, naphthylamine, tophthromophenaphenanthren, zinc, servalix, pyraclostrobin, metoclopramide (fenpyraclostrobin), metoclopramide, flufenacetrin, flufenapyr, metoclopramide, meto, Picoxystrobin (picoxystrobin), probenazole (probenazole), propoxymidine (proquinazid), pyraclostrobin (pydiflumetofen), pyraclostrobin (pyraclosabin), sedaxane (sedaxane), spiroxamine (spiroxamine), isoethoxyquinoline (tebuflozin), tetraconazole (tetrazozole), valifenalate, zoxamide (zoxamide), ziram (ziram), N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, 2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } phenyl methanesulfonate, 2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } -3-chlorophenyl methanesulfonate, 2-Methylpropionic acid (3S,6S,7R,8R) -8-benzyl-3- [ ({3- [ (isobutyryloxy) methoxy ] -4-methoxypyridin-2-yl } carbonyl) amino ] -6-methyl-4, 9-dioxo-1, 5-dioxononan-7-yl ester (lysophenvalpyr), isoflurypram.

Particularly preferred fungicidal compounds are, for example: cymoxanil, tebuconazole, spiroxamine, bixafen, fluoxastrobin, trifloxystrobin, n- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, 2-methylpropanoic acid (3S,6S,7R,8R) -8-benzyl-3- [ ({3- [ (isobutyryloxy) methoxy ] -4-methoxypyridin-2-yl } carbonyl) amino ] -6-methyl-4, 9-dioxo-1, 5-dioxononan-7-yl ester (lyserpenvalpyr), iprovalicarb, fluxapripin, fluopicolide and fluopyram.

Very particular preference is given to mixtures with one or more compounds selected from the compounds d):

a) + d) tebuconazole;

a) + d) trifloxystrobin;

a) + d) fluoxastrobin;

a) + d) cymoxanil;

a) + d) iprovalicarb;

a)+d)fluoxapiproline；

a) + d) fluopicolide;

a) + d) bixafen;

a) + d) fluopyram;

a) + d) spiroxamine;

a)+d)isoflucypram；

a) + d) fluoxastrobin + trifloxystrobin;

a) + d) trifloxystrobin + spiroxamine;

a) + d) bixafen + tebuconazole;

a) + d) bixafen + fluoxastrobin;

a) + d) bixafen + trifloxystrobin;

a) + d) bixafen + spiroxamine;

a) + d) bixafen + fluopyram;

a) + d) tebuconazole + spiroxamine;

a) + d) tebuconazole + fluopyram;

a) + d) N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide;

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-1-methyl-1H-pyrazole-4-carboxamide + fluopyram (flupyram);

a) + d) Bixafen + 2-methylpropanoic acid (3S,6S,7R,8R) -8-benzyl-3- [ ({3- [ (isobutyryloxy) methoxy ] -4-methoxypyridin-2-yl } carbonyl) amino ] -6-methyl-4, 9-dioxo-1, 5-dioxononan-7-yl ester (lysophenavpyr).

The proportion of component d) in the formulations according to the invention is preferably from 1 to 40% by weight, particularly preferably from 3 to 35% by weight.

These formulations are prepared in a known manner, for example by mixing a compound of formula (I) with auxiliaries, for example extenders, solvents and/or solid carriers and/or further auxiliaries, for example surfactants. The formulations are prepared in suitable equipment or prior to or during administration.

Administration of

Examples of administration forms which can be used include all known methods which are generally used by the person skilled in the art: spraying, dipping, fogging and some specific methods for direct treatment of whole plants or parts (seeds, roots, stolons, stems, leaves) underground or above ground, such as stem injection in the case of trees or stem bandages in the case of perennial plants, and some specific indirect application methods.

The respective area-based and/or object-based application rates of a plurality of different formulation types of crop protection compositions for controlling harmful organisms vary widely. In general, the application media known to the person skilled in the art, which are generally used in the respective fields of use, are used in conventional amounts for this purpose, for example from several hundred liters of water per hectare in the case of standard spraying methods, via several liters of oil per hectare in the case of "ultra-low volume" aircraft applications, up to several milliliters of physiological solution in the case of injection methods. The concentration of the crop protection compositions of the invention in the particular application medium therefore varies within wide limits and depends on the respective field of use. In general, the concentrations usually used in the respective fields of use are known to the person skilled in the art. Preferred concentrations are from 0.01 to 99 wt.%, more preferably from 0.1 to 90 wt.%.

The agrochemical formulation of the present invention can be used, for example, as it is in the form of a formulation generally used for liquid formulations or after being diluted with water in advance, that is, for example, as an emulsion, a suspension or a solution. Application is carried out by conventional methods, i.e. for example by spraying, pouring or injection.

Depending on the nature of the active ingredients which may be present in addition to propineb, the formulations of the invention can be used for controlling a large number of pests and can be used both for treating plant crops and for treating inanimate substances and in the household.

"pests" or "harmful organisms" are understood here to mean all kinds of pests which can be controlled or maintained under control with organic crop protection active ingredients, i.e. crop protection agents, in particular fungicides and mixtures of fungicides with other crop protection agents. The term "pests" therefore includes organisms which are harmful to plants, in particular harmful fungi and their spores, and also harmful insects (insects), arachnids, nematodes and harmful plants. The term "control" includes both a therapeutic treatment, i.e. the treatment of the infected plants with the preparations according to the invention, and a protective treatment, i.e. the treatment of the plants to protect them from infestation by pests.

The present invention therefore also relates to the use of the formulations described herein for controlling pests, in particular plant pests, and to a method for controlling harmful organisms, in particular organisms harmful to plants, which comprises contacting the harmful organisms, their habitat, their host, such as plants and seeds and the soil, area and environment in which they are growing or may grow, and the materials, plants, seeds, soils, surfaces or spaces to be protected from attack or infestation by the organisms harmful to plants, with an effective amount of a formulation according to the invention.

Another aspect of the present invention relates to the use of the formulations described herein for protecting plants, including seeds, in particular useful plants, from infestation by harmful organisms, especially harmful fungi. The invention therefore also relates to the use of the formulations for controlling organisms harmful to plants, such as harmful fungi, insects, arachnids, nematodes and harmful plants, in particular for controlling harmful fungi.

The formulations of the invention can be used in crop protection in a manner known per se for controlling phytopathogenic fungi, in particular as foliar, seed-dressing and soil fungicides.

Plants that can be treated with the formulations of the present invention include the following: cotton, flax, grapevine, water fruit trees, vegetables, such as the Rosaceae (Rosaceae sp.) (e.g., pome fruits such as apples and pears, and stone fruits such as apricots, cherries, almonds and peaches, and berries such as strawberries), scirpus (ribeoidae sp.), Juglandaceae (juglaceae sp.), Betulaceae (Betulaceae sp.), Anacardiaceae (Anacardiaceae sp.), Fagaceae (Fagaceae sp.), Moraceae (Moraceae sp.), meliaceae), rhinoceraceae (Oleaceae sp.), actinidia (actinidiaceae sp.), Lauraceae (Lauraceae sp.), Lauraceae (avenae sp.) and plantations, herbaceae (Rubiaceae), Theaceae (caffeae sp.), Rosaceae (camellia sp.), Rosaceae) and grapevines (citraceae); solanaceae (Solanaceae sp.) (e.g., tomato), Liliaceae (Liliaceae sp.), Asteraceae (Asteraceae sp.) (e.g., lettuce), Umbelliferae (Umbelliferae sp.), Cruciferae (Cruciferae sp.), Chenopodiaceae (Chenopodiaceae sp.), Cucurbitaceae (Cucurbitaceae sp.) (e.g., cucumber), Alliaceae (Alliaceae sp.) (e.g., leek, onion), pteritaceae (papliliaceae sp.) (e.g., pea); primarily useful plants, such as, for example, the Gramineae (Gramineae sp.) (e.g. maize, turfgrass (turfgrass)), cereals such as wheat, rye, rice, barley, oats, millet and triticale), the compositae (Asteraceae sp.) (e.g. sunflower), the Brassicaceae (Brassicaceae sp.) (e.g. white cabbage, red cabbage, broccoli, cauliflower, brussel sprouts, bok choy, kohlrabi, radish and oilseed rape, mustard, horseradish and cress), the fabaceae (fabaceae sp.) (e.g. soybean, peanut), the pteraceae (palionoceae (papiioaceae sp.) (e.g. soybean), the Solanaceae (Solanaceae sp.) (e.g. potato), the Chenopodiaceae (nopodiaceae sp.) (e.g. sugar beet, fodder beet, swiss chard lettuce, red beet); sugar cane, poppy, olives, coconut, cocoa, tobacco, and useful and ornamental plants in parks and forest areas; as well as genetically modified varieties of each of these plants, and seeds of these plants.

The formulations of the invention are preferably used for the treatment of wheat, barley, rye, soybean, onion, corn and peanuts.

More particularly, the prothioconazole formulations of the invention can be used in principle to control all harmful fungal diseases which can also be controlled with known prothioconazole formulations. Depending on the particular compound present in each case, the plant diseases are, for example, the following plant diseases:

alternaria species in vegetables, rape, beet, soybean, cereals, cotton, water fruit trees and rice (e.g. Alternaria alternata (a. solani) or Alternaria (a. alternata) in potatoes and other plants), ascomyces species in beet and vegetables (Aphanomyces species), Ascochyta species in cotton and rice (Ascochyta sp.), helminthosporium species in maize, cereals, rice and turf grasses (Bipolaris) and helminthosporium species in maize, cereals, rice and turf grasses (e.g. intraumbilicaria umbilicalis (teres) in barley, d.tritci-reis in wheat), aleuromyces tritici (Blumeria graminis) (powdery mildew) in wheat, flowers in strawberry, vegetables, Botrytis (Botrytis nervosa) (boidinaria in bovines), Botrytis species in lettuce, rhizopus species (Bremia) in lettuce, asparagus (brevicia sp), Botrytis (Bremia sp.) species in lettuce, rice, asparagus (brassica), Ascochyta species in beet, asparagus, lettuce, rice, etc. (asparagus). The genera Cochliobolus (Cochliobolus species) in corn, cereal, rice (e.g. Cochliobolus graminis (Cochliobolus sativus) in cereals, Cochliobolus miyabenus (Cochliobolus miyabenus) in rice), corynebacterium (corynebacterium) in soybean, cotton and other plants, Colletotrichum (Colletotrichum species) in soybean, cotton and other plants (Colletotrichum species) (e.g. Colletotrichum (c.acutatum) in various plants), Curvularia (Curvularia sp.) in cereals and rice, Diplodia (diprosoma sp.) in cereals and rice, eurospora (septoria) in maize (Exserohilum species), Diplodia (erysipelomyces) in cucumber (eudiplodiella (septoria) and trichothecospora (trichothecium sp.) in maize (trichoderma) and trichoderma (trichoderma sp.) in rice). Grain staining complex in rice (maize complex), Helminthosporium species in corn and rice (e.g. h. graminicola), ascosphaera species in soybean and cotton (macrophospora sp.), phylloclavopus species (Michrodochium sp.) such as rhizoctonia solani (m.nivale) in cereals), coelomyces species in cereals, bananas and peanuts (mycosphaera species) (Mycosphaerella graminicola (m.graminicola) in wheat, Mycosphaerella globosa (m.fijiensis) in bananas), myceliophthora species (phaeoylspora sp) in soybeans, phakopsora sp) such as phakopsora (p.papyrizii) and phaeophyromyces phaeophysa (p.manillensis), Phomopsis sp.) such as Phomopsis solani (p.p.pazophyllum) in soybeans, Phomopsis sp., and Phomopsis sp. solani (p.solani) in grapevine, Phomopsis sp.), plasmopara viticola (Plasmopara viticola) in grapevine, Penicillium sp in soybean and cotton, Podosphaera leucotricha (Podosphaera leucotricha) in apple, Pseudoperonospora graminis (P.cubensis) in millet, Puccinia (P.tritici) in cereals, maize and asparagus, Puccinia (P.tritici) in wheat and Puccinia striiformis (P.tritici) in asparagus, Puccinia (P.tritici) in cereals, maize and asparagus, Puccinia (P.tritici) in wheat, Puccinia stipityrifera and Puccinia striiformis (P.striatellosis) in asparagus, Puccinia (P.asagrica) in Asparagus, Pyrenopsis (P.crassima) in asparagus, Pyrenophora (Pyrococcus oryzae) in cereals, Pyricularia (Pyricularia viridis) in rice, Pyricularia oryzae (P.oryzae), Rhizoctonia solani (P.oryzae) in rice, Rhizoctonia solani (Rhizoctonia solani) in cereals, Rhizoctonia solani, Rhizoctonia stoloni, Rhizoctonia solani, Rhizoctonia stoloni, Rhizoctonia solani, Rhizoctonia stoloni, Rhizoctonia solani, Rhizoctonia, Rhizoctoni, Pythium sp in sugar beet, vegetables and other plants, Rhizoctonia species (e.g.Rhizoctonia solani) in cotton, rice, potato, turf grass, corn, oilseed rape, potato, sugar beet, vegetables and other plants (e.g.Rhizoctonia solani), Rhizoctonia species (e.g.Rhizoctonia solani) in rice and cereals, Sclerotia species (e.g.Sclerotium) in rape, sunflower and other plants, Septoria tritici (e.g.Sclerotiorum) in wheat, Septoria cerealis (Septoria tritici) and Stagonospora nodorum (Stagonospora nodorum), Uncaria species (e.g.Rhizoctonia) in grapevine, Rhizoctonia species (e.Uysia), Rhizoctonia species (e.sp.) in maize and turf grass, Rhizoctonia species (e.s) in wheat, Rhizoctonia species (Setaria), Rhizoctonia species (Setaria species) in maize and maize), Rhizoctonia species (Setaria) in wheat and Ustilaginacea), Rhizoctonia) in corn and Ustilaginacea) in corn and maize, Ustilaginacea), Rhizoctonia (maize), and Venturia species (scab) in apples and pears (e.g. apple scab in apples (v. inaequalis).

The formulations of the present invention are typically diluted with at least one part water, preferably with 10 parts water and more preferably with at least 100 parts water, for example with 1 to 10000 parts, preferably 10 to 5000 parts and more preferably with 50 to 24000 parts water, based on one part formulation.

Dilution is achieved by pouring the formulation of the invention into water. For rapid mixing of the formulation with water, agitation, e.g. stirring, is generally used. However, agitation is generally not necessary. Although the temperature used for the dilution operation is not critical, the dilution is usually carried out at a temperature of from 0 ℃ to 50 ℃, in particular from 10 ℃ to 30 ℃ or at ambient temperature.

The water used for dilution is typically tap or well water or water from other local sources. However, the water may already contain water-soluble or finely divided compounds used in crop protection, such as nutrients, fertilizers or pesticides.

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 emulsions according to the invention in the form of premixes or, if appropriate, until shortly before use (tank mix). These compositions may be added to the formulations of the present invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10: 1.

The user will typically apply the formulation of the invention from a pre-measuring instrument, a backpack sprayer, a spray tank, a spray plane or an irrigation system; the formulations of the present invention are typically diluted with water, buffer and/or other adjuvants to the desired application concentration, which provides ready-to-use spray liquids or agrochemical compositions of the present invention. Typically, 20 to 2000 litres, preferably 50 to 400 litres, of ready-to-use spray liquor are used per hectare of agriculturally useful area.

The desired application rate of the pure active ingredient without formulation auxiliaries depends on the intensity of the pest infestation, the developmental stage of the plant, the climatic conditions of the place of use and the application method. In general, the application rate is from 0.001 to 10kg, preferably from 0.005 to 8kg, more preferably from 0.01 to 5kg and most preferably from 0.01 to 4kg of active ingredient per hectare, by active ingredient here is meant propineb plus possibly further active ingredients.

The normally diluted formulations of the present invention are applied primarily by spraying, especially onto the leaves. Application can be carried out by spraying techniques known to those skilled in the art, by using water as carrier and the amount of spraying liquid is about 50 to 2000 liters per hectare, for example 100 to 1000 liters per hectare.

The new propineb-containing formulation has advantageous properties in plant treatment; more particularly, they are characterized by good use properties, high stability and high fungicidal activity.

The present invention is illustrated in more detail by examples, but is not limited thereto.

Examples

General preparation of Wettable Powders (WP)

The solid components were first added at room temperature. All components were distributed homogeneously under vigorous mixing. The entire mixture is optionally comminuted in a dry environment, for example using a jet mill. The final product is WP (e.g. wettable powder WP 70).

Alternative methods for preparing WGs are known to those skilled in the art and are equally applicable.

General preparation of Water dispersible granules (WG)

First, water is added at room temperature. All components of the formulation, including the antioxidant, were added with stirring according to the recipe, while stirring. The aqueous suspension is sent to wet comminution if desired. Finally, the aqueous suspension is converted into the solid particulate form by granulation methods such as spray drying, fluidized bed spray granulation, pan granulation. The final product is WG (e.g. water dispersible granule WG 70).

Alternative methods for preparing WGs are known to those skilled in the art and are equally applicable.

DIDT measurement in agitated spray liquids

The DIDTs, in some cases formed in a sprayed liquid from atmospheric oxygen dissolved in water, were separated using an eluent gradient on a reverse phase column. Quantitative evaluation is performed by UV or MS/MS detection by comparing the peak area with the peak area of a reference object using an external or optionally isotopically stable labelled internal standard (in case of determination by LC-MS/MS).

High pressure liquid chromatograph Agilent 1290

Sample injection Agilent 1290 or CTC PAL

UV detector Agilent 1290DAD

Mass spectrometer Sciex API6500+

Integration and evaluation Agilent ChemStation Open Lab or Sciex

/Multiquant

Experiment 1: degradation of propineb

The results of the two measurement series are summarized:

monheim drinking water; 1 liter each time, no antioxidant was contained, and antioxidant and potassium permanganate oxidant were used as positive samples.

It is clear from the table that the degradation of the active ingredient (propineb) is significantly reduced even with the addition of small amounts of antioxidant.

Experiment 2:

kinetics study of spray liquids without and with antioxidants

In kinetic studies, it was shown that unwanted DIDT formation was significantly reduced by the addition of antioxidants. In particular, ascorbic acid (propineb WG70+ 10% ascorbic acid) shows very positive effects at concentrations > 5% by mass and above.

The measurements were carried out in a solution of 3g Antrocol WG70 per litre, corresponding to an active ingredient concentration of 2.1 g/l.

Figure 1 shows the increase in DIDT concentration in mg per liter in an aqueous spray liquid over time, depending on the type and amount of antioxidant, using the Antracol WG70 (active ingredient: propineb) formulation as the basis.

In experiments, it was found that weakly acidic pH (pH 3-4; caused by ascorbic acid) and buffer systems (pH 6-7; caused by a mixture of ascorbic acid and sodium sulfite) had a positive effect on the degradation.

The determination of the DIDT content is similar to the determination of DIDT in drinking water according to the calibration standards for DIDT.

Experiment 3:

greenhouse experiments on tomatoes with/without antioxidant treatment sprayed liquid water

It can also be shown in tomato greenhouse experiments (applied with 3kg/ha Antrocol WP70, 800-. The analysis of the residue on tomato samples was performed similarly to experiments 1 and 2 by LC-MS/MS according to calibration standards for DIDT and additional isotopically labeled internal standard for DIDT.

Figure 2 herein shows a significant decrease in DIDT concentration at 0 hours after application, with an increase in DIDT concentration within the first 24 hours after application.

Claims (17)

1. Formulation comprising

a) An active ingredient containing a dithiocarbamate group, and

b) at least one selected from sodium sulfite (Na)₂SO₃E221), ascorbic acid (vitamin C/E300) and sodium metabisulfite (Na)₂S₂O₅E223).

2. Formulation according to claim 1, characterized in that the antioxidant is selected from sodium sulfite and ascorbic acid, and mixtures thereof.

3. Formulation according to claim 1, characterized in that it is an aqueous formulation with ascorbic acid as antioxidant.

4. Formulation according to any one of the preceding claims, characterized in that the active ingredient a) is selected from propineb, maneb and mancozeb, and mixtures thereof.

5. Formulation according to any one of the preceding claims, characterized in that the active ingredient a) is propineb.

6. Formulation according to any one of the preceding claims, characterized in that the proportion of component a) is from 10% to 99.5% by weight.

7. Formulation according to any one of the preceding claims, characterized in that the proportion of component b) is between 0.5% and 90% by weight.

8. Formulation according to any one of the preceding claims, characterized in that the formulation according to the invention is in the form of a kit of parts, the antioxidant and the active ingredient formulation being in separate components.

9. Preparation according to any one of the preceding claims, characterized in that it comprises 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 other than a).

10. Formulation according to claim 9, characterized in that the agrochemical active ingredient d) is one or more active insecticidal or fungicidal ingredient.

11. A process for preparing a formulation according to any one of the preceding claims by mixing components a) and b) with any further additives and active ingredients.

12. Method for producing a spray liquid, characterized in that in a first step component b) of a kit is dissolved in a suitable amount of water and in a second step component a) or a preparation of component a) is added to component b) dissolved in water together with the other components c) and d).

13. A method for controlling harmful organisms, which comprises contacting the harmful organisms, their habitat, their host, such as plants and seeds, and the soil, area and environment in which they are growing or may grow, and the materials, plants, seeds, soils, surfaces or spaces to be protected from attack or infestation by organisms harmful to plants, with an effective amount of a formulation according to claim 1.

14. Use of a formulation according to any of the preceding claims for protecting plants, including seeds, in particular useful plants, from infestation by harmful organisms.

15. Use of the formulation according to any of the preceding claims for controlling organisms harmful to plants, such as phytopathogenic fungi, insects, arachnids, nematodes and harmful plants.

16. Adjuvant for stabilizing a formulation of an active ingredient containing a dithiocarbamate group in water, characterized in that said adjuvant is an antioxidant, preferably selected from sodium sulfite (Na)₂SO₃E221), ascorbic acid (vitamin C/E300) and sodium metabisulfite (Na)₂S₂O₅/E223)。

17. Use of an antioxidant for stabilizing a formulation of an active ingredient containing a dithiocarbamate group in water, characterized in that the adjuvant is selected from sodium sulfite (Na)₂SO₃E221), ascorbic acid (vitamin C/E300) and pyrosulfurous acidSodium acid (Na)₂S₂O₅E223).

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