WO2022058522A1 - Stabilization of thioketones on surfaces - Google Patents

Abstract

The present invention relates to a method for stabilizing thioketones (thiones) on surface, in particular of active substances containing thione structural elements, especially triazoline thiones, as functional groups, and to the use of decenamide and tocopherols (vitamin E) in order to stabilize thione compounds.

Description

of thioketones on surfaces

The present invention relates to a method for stabilizing thioketones (thiones) on surfaces, in particular active substances which contain thione building blocks, in particular triazolinthiones, as functional groups, and the use of decenamide and tocopherols (vitamin E) for stabilizing thione compounds .

In particular, the present invention is aimed at stabilizing thiones on surfaces, in particular cotton or also leaf surfaces.

Furthermore, the present invention is directed to a method for stabilizing thiones on surfaces, in particular leaf surfaces or cotton fabrics, using decenamide and/or tocopherols (vitamin E).

In addition, the present invention is directed to a method for stabilizing thiones on surfaces, in particular cotton or else leaf surfaces, by applying a formulation containing decenamide and/or tocopherols (vitamin E).

It is already known that, for example, prothioconazole can be used in customary formulations for controlling fungi (WO-A 96/16 048). This active ingredient is 2-[2-(l-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-3H-l,2, 4-triazole-3-thione.

Prothioconazole-containing formulations are generally liquid formulations and are available on the market, for example, as emulsion concentrates.

It is also known that the active ingredient prothioconazole converts under certain conditions to the compound 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propane -2-ol can degrade (PSM approval report, Tilmor, 08/30/2010, Serial No. 21, Federal Office for Consumer Protection and Food Safety).

Therefore, formulations containing prothioconazole (hereinafter referred to as PTZ) can contain a certain amount of 2-(l-chlorocyclopropyl)-l-(2-chlorophenyl)-3-(lH-l,2,4-triazole-l - yl)propan-2-ol included. When stored under drastic conditions, such as elevated temperatures, exposure to light and intensive contact with oxygen, prothioconazole can also degrade to 2-( 1 -chlorocyclopropyl)- 1 -(2-chlorophenyl)-3-( 1H- 1 ,2, 4-triazol-1-yl)propan-2-ol take place, which reduces the proportion of active ingredient in the formulations accordingly. Since the compound 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (hereinafter called desthio) is a relevant impurity, its content is in Prothioconazole-containing formulations limited by regulation. The same applies here analogously to other thione-containing compounds, such as 4-((6-(2-(2,4-difluorophenyl)-1,I-difluoro-2-hydroxy-3-(5-mercapio-I HI, 2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitriles.

The maximum permissible amount of Desthio in PTZ formulations depends on the amount of PTZ in the formulation in g/L. The maximum allowable amount of desthio is given in ppm, where the allowable amount of desthio in ppm is given as half the value of the PTZ loading in g/L. The maximum permissible Desthio content in a formulation with 100 g/L PTZ is therefore 50 ppm (=0.005 wt%).

WO-A 2012/033590 discloses aqueous dispersions of prothioconazole which contain a sulfur-containing compound, such as L-cysteine, for stabilization.

Stabilized PTZ-containing formulations are described in WO 2017/097882 and WO2018/228885, which can be regarded as the closest prior art. These describe emulsion concentrates and suspension concentrates with PTZ dissolved in a solvent. The formulation could be improved by adding compounds of formula (I)

in which n is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15 or 18 and a reduction in the desthio content can be achieved.

Compounds of the formula (I) are known from WO-A 2012/061094 and can be prepared via the metathesis process. These are, for example, products from the Stepan company ((N,N-dimethyl 9-decenamide, CAS number: 1356964-77-6, Hallcomid® 1025 or Steposol® MET-10U).

A disadvantage of these compounds is that very large amounts of up to 30% of the stabilizer are necessary to achieve a desired effect and thus represent a major intervention in the formulation. These are also novel additives, which in some cases first have to be approved for crop protection formulations. While the prior art describes the stabilization of thiones in spray liquors and concentrated storable formulations, the prior art gives no indication of how thiones can also be stabilized after they have been applied to surfaces, since the degradation products are also undesirable here.

There was therefore a need for a method for stabilizing PTZ-containing formulations after they have been applied to surfaces where they are exposed, for example, to oxygen contact, high temperatures or exposure to light, for example the degradation of the thiones, in particular the triazoline thiones and especially PTZ to the corresponding desthio products 2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (Compound III), effectively accelerate.

The object of the present invention was therefore to provide a method for stabilizing thiones on surfaces after they have been applied, in particular for stabilizing prothioconazole, in order to prevent degradation to 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-( to counteract lH-l,2,4-triazol-l-yl)propan-2-ol.

It has also been shown that the degradation of thiones to desthio products is strongly triggered by light, including certain wavelengths. Surprisingly, however, conventional UV blockers or UV absorbers show only an inadequate effect here.

In addition, it turned out that various commercially available antioxidants did not offer any effective protection against degradation of the thiones, but rather even promoted it.

Surprisingly, it has been found that certain antioxidants and free-radical scavengers such as decenamide and tocopherols (vitamin E), even in very small amounts, are extremely effective in preventing the degradation of thiones to desthio products on surfaces, especially prothioconazole, especially at high concentrations of active ingredient.

The subject matter of the present invention is therefore the use of decenamide and tocopherols for stabilizing thiones on surfaces, in particular after these thiones have been applied as a fungicidal spray. The tocopherols are preferably selected from the group consisting of tocotrienols, tocopherols (e.g. (+)-delta-tocopherol, (+/-)-alpha-tocopherol), and mixtures of these compounds.

A further object of the present invention is therefore the use of tocopherol- or decenamide-containing formulations for stabilizing the thiones on surfaces after application and drying.

Preferably, the formulations to be stabilized after application are agrochemical formulations. In a further preferred embodiment, the active ingredient a) with a thione group is selected from the group consisting of prothioconazole and 4-((6-(2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3- (5-mercapio-IH,2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitrile, particularly preferably only prothioconazole.

Furthermore, the active ingredient is preferably present in an amount of from 1% to 50% by weight, more preferably from 4% to 30% by weight, and particularly preferably from 5% to 28% by weight to the total weight of the formulation.

The antioxidant b) is more preferably from the group that includes decenamide, unless otherwise specified for the purposes of the present invention, N,N-dimethyl-9-decenamide, and tocopherols and tocotrienols (preferably (+)-delta-tocopherol, (+/ -)-alpha-tocopherol, (+)-alpha-tocopherol as well as vitamin E and mixtures of tocopherols).

Vitamin E is a collective term for fat-soluble substances with antioxidant effects, the most common forms being tocopherols and tocotrienols. In the following, the term vitamin E should include alpha-tocopherol (RRR-a-tocopherol or Da-T0), beta-tocopherol, gamma-tocopherol, delta-tocopherol, alpha-tocotrienol, beta-tocotrienol, gamma-tocotrienol, delta-tocotrienol, and derivatives thereof such as acetates.

Regardless of the type of formulation, the antioxidants are preferably present in an amount of from 0.01% to 15.00% by weight, more preferably from 0.03% to 5.00% by weight, and most preferably 0 .2% by weight to 4% by weight based on the total weight of the formulation.

Depending on the formulation, e.g. water- or oil-based, water- or oil-soluble antioxidants are preferably used in the following amounts:

SC formulations:

In SCs, the antioxidants are preferably at a level of from 0.01% to 10.00% by weight, more preferably from 0.03% to 5% by weight, even more preferably from 0.03% % by weight to 1.00% by weight, and more preferably 0.05% by weight to 0.5% by weight, based on the total weight of the formulation.

OD and EC formulations:

In ODs, the antioxidants are preferably in an amount of from 0.10% to 5.00% by weight, more preferably from 0.2% to 4.00% by weight, and particularly preferably 0. 2% by weight to 3% by weight based on the total weight of the formulation. In ECs, the antioxidants are preferably at a level of from 0.50% to 15.00% by weight, more preferably from 1% to 10.00% by weight, and most preferably 3% by weight. % to 10% by weight based on the total weight of the formulation.

Prothioconazole (with the chemical name 2-[2-(l-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-l,2-dihydro-3H-l,2,4-triazole-3-thione) (CAS number 178928-70-6) exists as a racemate. Suitable processes for its production are described in DE-A 195280. Prothioconazole can be in the thiono form of general formula (II)

or in the tautomeric mercapto form of general formula (Ila)

present. When the term prothioconazole is used below, the isomers shown here and other possible tautomers are always covered.

2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol also exists as a racemate and has the general formula (III ), again all tautomeric forms are intended to be included within this representation.

Furthermore, the formulations according to the present invention, as described above, can each contain further ingredients, such as: a) cl: nonionic dispersant/emulsifier, c2: ionic dispersant/emulsifier b) other agrochemical active ingredients different from a). c) solvents including OD carriers d) carriers (WGs, as well as aerosils for SC/TKWG) e) gl: organic thickener g2: inorganic thickener f) other additives and auxiliaries

Formulation types are defined by the FAO and can be found at www.fao.org/ag/agp/agDD/pesticid. In the March 2016 issue, the usual formulation types are described on pages 66-231. The formulation according to the invention is one of the usual types of formulation described by the FAO. Examples include suspension concentrates (SC) and concentrates containing dye for seed treatment (FS), emulsion concentrates (EC), water-dispersible concentrates (WG), oil dispersions (OD), suspoemulsions (SE), aqueous emulsions (EW), microemulsions (ME) and liquid formulations (SL) mentioned here. These are preferably EC, SC, FS, SE, OD and WG formulation types, very particularly preferably formulations in which at least one active ingredient is not present in dissolved form. Very particularly preferably, these are FS, SC, SE, OD and WG formulations, very particularly preferably SC, FS and WG formulations.

Further objects of the present invention are the use of the formulations according to the invention for the treatment of plants and corresponding methods. Nonionic emulsifiers and dispersants cl)

Suitable nonionic emulsifying and dispersing agents cl), such as emulsifiers, wetting agents, surfactants and dispersants, are customary surface-active substances present in formulations of agrochemically active compounds. Examples include ethoxylated nonylphenols, reaction products of linear or branched alcohols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, end-capped and uncapped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g. butoxypolyethylene-propylene glycols), reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, furthermore fatty acid esters, fatty acid polyglycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols, such as tristyryl-phenol ethoxylate with an average of 16 ethylene oxide units per molecule, also ethoxylated and propoxylated Arylalkylphenols and sulfated or phosphated arylalkylphenol ethoxylates or ethoxylates and propoxylates. Tristryl-phenol alkoxylates and fatty acid polyglycol ether esters are particularly preferred. Tristyryl phenol ethoxylates, tristyryl phenol ethoxy propoxylates and castor oil polyglycol ether esters, each individually or in mixtures, are very particularly preferred. There may also be additives, such as surfactants or esters of fatty acids, which contribute to improving the biological effectiveness. Examples of suitable nonionic emulsifiers and dispersants cl) are Soprophor® 796/P, Lucramul® CO30, Lucramul® HOT, Lucramul® PSI 100 or Synperonic® T304.

Suitable nonionic dispersants cl) can also be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymer of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymer of vinyl chloride and vinyl acetate, and partially hydrolyzed vinyl acetate, phenolic resins, modified cellulose Types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol) or modified cellulose. Polyvinylpyrrolidone grades are preferred, and low molecular weight grades such as Luviskol® K30 or Sokalan® K30 are particularly preferred.

Other suitable nonionic emulsifiers and dispersants cl) from the group of di- and tri-block copolymers of alkylene oxides are, for example, compounds which are based on ethylene and propylene oxide and have average molecular weights of between 200 and 10,000, preferably 1000 to 4000 g/mol, the mass fraction of the polyethoxylated block varying between 10 and 80%, such as Synperonic® PE series (Uniqema), Pluronic® PE series (BASF), VOP® 32 or Genapol® PF series (Clariant).

The proportion of the nonionic emulsifiers and dispersants c1) in the suspension concentrates according to the invention is preferably 1 to 15% by weight, more preferably 2 to 10% by weight and particularly preferably 2.5 to 8% by weight. Anionic emulsifiers and dispersants c2)

Suitable anionic emulsifiers and dispersants bl) such as emulsifiers, surfactants, wetting agents and dispersants are, for example, alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof such as the salts of alkyl sulfonic acids or alkyl phosphoric acids and alkylaryl sulfonic or alkylaryl phosphoric acids, Diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkyl phenols, sulfonates of alkoxylated aryl phenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecyl benzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkyl phenols, of alcohols, of ethoxylated alcohols or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkyl phenol ethoxylates. Also suitable is the group of anionic emulsifiers of the alkali metal, alkaline earth metal and ammonium salts of polystyrene sulfonic acids, salts of polyvinyl sulfonic acids, salts of alkyl naphthalene sulfonic acids, salts of alkyl naphthalene sulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalene sulfonic acid, phenol sulfonic acid and formaldehyde. Examples are calcium dodecyl benzene sulfonate such as Rhodocal® 70/B (Solvay), phenyl sulfonate CAI 00 (Clariant) or isopropylammonium dodecyl benzene sulfonate such as Atlox® 3300B (Croda).

Other typical representatives include phenylsulfonate CA (Ca-dodecylbenzenesulfonate), Soprophor® types (optionally esterified derivatives of tristyrylphenoi ethoxylates), Emmulsogen® 3510 (alkylated EO/PO copolymer), Emulsogen® EL 400 (ethoxylated castor oil), Tween® types (fatty-acylated sorbitan ethoxylates), Calsogen® AR 100 (Ca-dodecylbenzenesulfonate). Combinations of salts of alkylated aromatic sulfonic acids, such as phenylsulfonate Ca and/or Calsogen® AR 100, with alkylated copolymers of ethylene and propylene oxide, such as Emulsogen® 3510, are preferred. Combinations of salts of dodecylbenzenesulfonic acid, such as Calsogen® AR 100 with alkylated copolymer of ethylene and propylene oxide, such as Emulsogen® 3510.

Examples of further anionic emulsifiers and dispersants c2) from the group of naphthalene sulfonates are Galoryl® MT 800 (sodium dibutylnaphthalene sulfonic acid), Morwet® IP (sodium diisopropylnaphthalene sulfonate) and Nekal® BX (alkyl naphthalene sulfonate). Examples of anionic surfactants from the group of condensation products of naphthalene sulfonates with formaldehyde are Galoryl® DT 201 (naphthalene sulfonic acid hydroxy polymer with formaldehyde and methylphenol sodium salt), Galoryl® DT 250 (condensation product of phenol and naphthalene sulfonates), Reserve® C (condensation product of phenol and Naphthalene sulfonates) or Morwet® D-425, Tersperse® 2020. Preferred are 1,2-dibutyl or diisobutyl-substituted naphthalene sulfonates, such as products such as Galoryl® MT 800 (CFPI-Nufarm) and Nekal® BX (BASF ). Other typical surfactants are Soprophor® 3D33, Soprophor® 4D384, Soprophor® BSU, Soprophor® CY/8 (Solvay) and Hoe® S3474 and in the form of the Sapogenat® T products (Clariant), for example Sapogenat® T 100.

The proportion of anionic emulsifiers and dispersants c2) in the technical concentrates according to the invention is preferably 2 to 35% by weight, more preferably 3 to 30% by weight, even more preferably 5 to 25% by weight, and particularly preferably 10 up to 20% by weight.

The proportion of the anionic emulsifiers and dispersants c2) in the suspension concentrates according to the invention is preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight and particularly preferably 0.3 to 4% by weight. .

Agrochemical other active ingredients other than PTZ d):

Further agrochemical active ingredients d) for the purposes of the present invention are fungicidal, insecticidal or herbicidal active ingredients. In an alternative embodiment, the formulation according to the invention contains one or more other insecticidal or fungicidal active ingredients d), particularly preferably one or more fungicidal active ingredients d). The active ingredients used are preferably water-insoluble.

An overview of typical crop protection agents can be found in the Pesticide manual.

Examples of preferred insecticidal components d) are imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole, spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flunicamid , indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron, the compound from WO-A 2006/089633 as example Ila-4, the compound disclosed in WO-A 2008/067911 as example Ila- 4, the compound disclosed in WO 2013/092350 as example Ib-14, the compound disclosed in WO 2010/51926 as example Ik-84.

Preferred fungicidal components d) are, for example, bixafen, bixlozone, fenamidone, fenhexamid, fluopicolide, fluopyram, fluoxastrobin, isoflucypram, iprovalicarb, isotianil, isopyrazam, pencycuron, penflufen, propineb, tebuconazole, trifloxystrobin, ametoctradine, amisulbrom, azoxystrobin, benthiavalicarb-isopyr, benzovindiflupropyl , Boscalid, Carbendazim, Chlorothanonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Difenoconazole, Ethaboxam, Epoxiconazole, Famoxadone, Fluazinam, Fluquinconazole, Flusilazole, Flutianil, Fluxapyroxad, Isopyrazam, Kresoxim- methyl, Lyserphenvalpyr, Mancozeb, Mandipropamid, Metconazole, Fol , Metaminostrobin, Oxathiapiproline, Penthiopyrad, Picoxystrobin, Probenazole, Proquinazid, Pydiflumetofen, Pyraclostrobin, Sedaxane, Spiroxamine, Tebufloquine, Tetraconazole, Valiphenalate, Zoxamide, Ziram, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-( difluoromethyl)-5-fluoro-l-methyl- lH-pyrazole-4-carboxamide, N-(5-chloro-2-isopropylbenzyl)- N-cyclopropyl-3-(difluoromethyl)-5- fluoro- 1 -methyl- lH-pyrazole-4-carboxamide, 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidine-4- yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(l-{[3,5- bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}- 3-chlorophenylmethane-sulfonate, (3S,6S,7R,8R)-8-benzyl-3-[({3-

[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate (lyserphenvalpyr).

Examples of particularly preferred fungicidal mixing partners d) of prothioconazole are: tebuconazole, spiroxamine, bixafen, fluoxastrobin, 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-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate (lyserphenvalpyr) and fluopyram.

The mixtures of a) (prothioconazole) with one or more compounds selected from the group of compounds d): a) + d) tebuconazole; a) + d) trifloxystrobin; a) + d) fluoxastrobin; a) + d) bixafen; a) + d) bixlozone a) + d) isoflucypram; a) + d) fluopyram; a) + d) spiroxamines; 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-l-methyl-lH-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 + flupyram a) +d) bixafen + (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9- dioxo-1,5-dioxonan-7-yl 2-methylpropanoate

(Lyserphenvalpyr)

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.

solvent e):

The formulations can contain solvents e), for example in the case of EC, OD or SE formulations. ® Aromatic hydrocarbon mixtures (preferably reduced naphalin) such as Solvesso®;

® Aromatic hydrocarbons such as white spirit, petroleum, alkyl benzenes and spindle oil, xylene, toluene or alkyl naphthalenes;

® Aliphatic/Cyclaliphatic hydrocarbons such as mineral oils, hexane, heptane, donean, nonane, decane, cyclopentane, cyclohexane, decalin or white oil;

® Chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene, or methylene chloride, chloroform or tetrachloromethane;

® alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol or benzyl alcohol;

® Ethers such as tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydropyran, 1,4-dioxanes, diethyl ether, methyl tert-butyl ether, dihexyl ether, dioctyl ether, didecyl ether, dibenzyl ether, dimethyl isosorbide, diphenyl ether, ethyl phenyl ether, phenyl benzyl ether or anisole;

® monoester/diester/glycerol ester such as ethyl acetate, butyl propionate, pentyl propionate, benzyl acetate, benzyl benzoate, butyl benzoate, Rhodiasolv® Polarclean, Rhodiasolv® RPDE, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethylhexyl lactate, ethyl 3-ethoxypropionate (UCAR® ester EEP, Dow Chemical Company), dimethyl succinate, diethyl succinate, dipropyl succinate, dimethyl adipate, diethyl adipate, dipropyl adipate, dimethyl glutarate, diethyl glutarate, dipropyl glutarate, bis(2-ethylhexyl) adipate, diisopropyl adipate, dimethyl-2-methylglutarate, dioctyl maleate, glycerol monoacetate, glycerol diacetate, glycerol triacetate, vegetable oils such as rapeseed oil, sunflower oil, soybean oil, castor oil or corn oil;

® Lactones such as butyrolactone, alpha-methyl-gamma-butyrolactone, gamma-valerolactone or delta-valerolactone;

® Polyethylene/propylene oxides such as monoethylene glycol, monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monobutyl ether, monoethylene glycol monopentyl ether, monoethylene glycol monohexyl ether, monoethylene glycol monophenyl ether, monoethylene glycol dimethyl ether, monoethylene glycol diethyl ether, monoethylene glycol dipropyl ether, monoethylene glycol dibutyl ether, monoethylene glycol dipentyl ether, monoethylene glycol dihexyl ether, monoethylene glycol diphenyl ether, and their longer ethylene glycol homologues; Monopropylene Glycol, Monopropylene Glycol Monomethyl Ether, Monopropylene Glycol Monoethyl Ether,

monopropylene glycol monopropyl ether, monopropylene glycol monobutyl ether,

monopropylene glycol monopentyl ether, monopropylene glycol monohexyl ether,

monopropylene glycol monophenyl ether, monopropylene glycol dimethyl ether,

monopropylene glycol diethyl ether, monopropylene glycol dipropyl ether, monopropylene glycol dibutyl ether, monopropylene glycol dipentyl ether, monopropylene glycol dihexyl ether, monopropylene glycol diphenyl ether, and their longer propylene homologues; Monoethylene glycol monomethyl ether acetate, monoethylene glycol diacetates and their longer ethylene glycol homologues; monopropylene glycol monomethyl ether acetate,

monopropylene glycol diacetate and their longer polypropylene glycol homologues;

Simple and substituted amines such as diethylamine, triethylamine, diisopropylamine, diisopropylethylamine, monoethanolamine, diethanolamine, triethanolamine and higher alkoxylated amines, anilines or dimethylanilines;

Amides/ureas such as N-formylmorpholine, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylbenzamide, N,N-dimethyloctanamide, NN-dimethyldecanamide, N,N-dimethyl-dec-9-en-1 -amide, N,N-dimethyldodedecanamide, N,N-dimethyllactamide, N,N-decylmethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2 -pyrrolidone, N-pentyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-nonyl-2-pyrrolidone, N-decyl-2-pyrrolidone , N-undecenyl-2-pyrrolidone, N-dodecyl-2-pyrrolidone, N-methyl-2-piperidone, N-methyl-caprolactam, N-octyl-caprolactam, tetramethylurea, tetraethylurea, l,3-dimethyl-2-imidazolidinone , l,3,4-Trimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidinone, l-heptyl-3 -methyl -2-imidazolidinone, 1- heptyl-1,3-dihydro-3-methyl-2H-imidazol-2-one;

Ketones such as acetone, diacetone alcohol, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone , methyl isopropyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, ethyl isopropyl ketone, ethyl isobutyl ketone, ethyl isopentyl ketone, propyl isopropyl ketone, propyl isobutyl ketone, propyl isopentyl ketone, 3,3-dimethyl-2-butanone, 2,4-dimethyl -3-pentanone, 4,4-dimethyl -2-pentanone, 2,6-dimethyl-4-heptanone, 2,2,4,4-tetramethyl-3-pentanone, cyclopentanone, cyclohexanone. Cycloheptanone, Cyclooctanone, 2,4,6-cycloheptatrien-l-one, acetophenone, propiophenone, l-(4-methylphenyl)-ethanone, l-(4-ethylphenyl)-ethanone, 2-methyl-l -phenyl- 1- propanone, 1-(3-ethylphenyl)-ethanone, 4-phenyl-2-butanone, 1-phenyl-2-propanone, 1-phenyl-2-butanone, 2-phenyl-3-butanone, butyrophenone or valerophenone. • Nitriles such as acetonitrile, propanenitrile, 2-methyl-propanenitrile, butanenitrile, 3-methyl-butanenitrile, pentanenitrile, 4-methyl-pentanenitrile, hexanenitrile, heptanenitrile, octanenitrile, nonanenitrile, decanenitrile, benzonitrile, benzene-acetonitrile, pentane-dinitrile, 2-methylpentanedinitrile, hexanedinitrile, heptanedinitrile, octanedinitrile or nonanedinitrile;

® acetals such as 1,1-dimethoxymethane; 1,1-dimethoxyethane; 1,1'-[methylenebis(oxy)]bis-ethane; 1,1-diethoxyethane; 1,1'-[methylenebis(oxy)]bispropane; 2,4,6,8-Tetraoxanonane, 1,1'-[Methylenebis(oxy)]bis-butane, 2-Methyl-1-[(2-methylpropoxy)methoxy]-propane, 2, 4, 6, 8, 10-

pentaoxaundecane, 2,5,7,10-tetraoxaundecane, 1,3-dioxolane, 1,3-dioxane or 4-methyl-1,3-dioxane; orthoesters such as 1,1,1-trimethoxymethane, 1,1,1 -trimethoxyethane, 1,1,1-trimethoxypropane, 2-methoxy-1,3-dioxolane, 2-methoxy-2-methyl-1,3-dioxolane, 2-methoxy-2-methyl-1,3-dioxolane, 2 -Ethoxy-1,3-dioxolane, 2-ethoxy-2-methyl-1,3-dioxolane, 2-ethyl-2-methoxy-1,3-dioxolane, 2-methoxy-1,3-dioxane, 2-methoxy -2-methyl-1,3-dioxane or 2-ethoxy-1,3-dioxane;

® Carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, didecyl carbonate, ethylene carbonate, 4-methyl-1,3-dioxolan-2-one, 4-(methoxymethyl)- 1,3-dioxolan-2-one, glycerol carbonate, butylene carbonate, 4,6-dimethyl-3-dioxan-2-one or dibenzyl carbonate;

® phosphates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-butoxyethyl) phosphate or triphenyl phosphate;

® Sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, 1,1-dioxide-tetrahydro-thiophene, 1,1-dioxide-tetrahydro-3-methyl-thiophene or 1,1-dioxide-tetrahydro-2,4-dimethyl-thiophene.

Furthermore, the formulations according to the invention can optionally contain liquid fillers e), such as vegetable or mineral oils or esters of vegetable or mineral oils. Suitable vegetable oils e) are all oils which can usually be used in agrochemicals and can be obtained from plants. Examples include sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, corn oil, cottonseed oil, walnut oil, coconut oil and soybean oil. Examples of possible esters are ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate, ethylhexyl caprylate, isopropyl myristate, isopropyl palmitate, methyl oleate, methyl palmitate, ethyl oleate. Rapeseed oil methyl ester and ethylhexyl palmitate are preferred. Possible mineral oils are Exxsol® D100 and white oils.

Table 1: Exemplary trade names and CAS numbers of preferred compounds e)

Carrier materials f) for shared apartments.

Fillers and carrier materials f) in the formulations according to the invention are selected from the group containing minerals, carbonates, sulfates and phosphates of alkaline earth metals and earth metals such as calcium carbonate, polymeric carbohydrates, tectosilicates such as precipitated silicas with low absorbency and natural tectosilicates such as kaolin. Typical representatives of suitable fillers f) are, for example, Agsorb® LVM®-GA (attapulgite), Harborlite® 300 (perlite), Collys® HV (modified starch), Omya® chalk (calcium carbonate), Kaolin® Tec 1 (kaolin, aluminum hydrosilicate) , Steamic® OOS (talc, magnesium silicate). Natural tectosilicates and types of calcium carbonate such as Omya® chalk (calcium carbonate), Kaolin Tec 1® (kaolin) and Harborlite® 300 (perlite) are preferred for c2) here, natural tectosilicates such as Kaolin®, Tec® 1 (kaolin, aluminum hydrosilicate) and Harborlite® 300 (perlite). Kaolin and calcium carbonate are very particularly preferably used for WG formulations. Other suitable carrier materials or fillers f) are selected from the group of highly absorbent carriers with an absorption capacity of at least 200 g dibutyl phthalate per 100 g carrier material. Preferred highly absorbent carriers f) are silicic acids such as, for example, Sipemat® types (synthetic precipitated silicic acid of high absorptivity) and pyrogenic silicic acid (Aerosil® types). Precipitated silica is preferred. the The proportion of fillers f) in the TKs according to the invention is preferably 0.1 to 10% by weight, more preferably 0.3 to 8% by weight and very particularly preferably 1 to 7% by weight.

thickener g)

Suitable thickeners g) are organic thickeners g1) and inorganic thickeners g2).

Organic thickeners g1) are suitable as organically natural or biotechnologically modified or organically synthetic thickeners. Typical synthetic thickeners are Rheostrux® (Croda), Thixin® or Thixatrol® series (Elementis). These are typically based on acrylates. Typical organic thickeners are based on xanthan or cellulose (such as hydroxyethyl or carboxymethyl cellulose) or a combination thereof. Other typical representatives are based on lignin (such as lignin sulfonates, Borresperse®NA, REAX® 88 or Kraftsperse 25 S). Natural modified thickeners based on xanthan are preferably used. Typical representatives are, for example, Rhodopol® (Solvay) and Kelzan® (Kelco Corp.) and Satiaxane® (Cargill).

The proportion of the organic thickeners g1) in the SCs B) according to the invention is less than or equal to 5% by weight, preferably from 0.01 to 1.0% by weight, particularly preferably from 0.01 to 0.6% by weight, in total more preferably 0.05 to 0.5% by weight and most preferably 0.1 to 0.3% by weight.

Examples of suitable inorganic thickeners g2) are modified natural silicates, such as chemically modified bentonites, hectorites, attapulgites, montmorillonites, smectites or other silicate minerals, such as Bentone® (Elementis), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo Nobel) or the Van Gel series (RT Vanderbilt).

The proportion of inorganic thickeners g2) in the formulations according to the invention is up to 0 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.2 to 1.5% by weight, very particularly preferably 0. 3 to 1.5% by weight and most preferably 0.4 to 1.3% by weight.

A mixture of thickeners g1) and g2) is preferably used. In the case of SCs, particular preference is given to using exclusively organic thickeners d1). Very particular preference is given to thickeners g1) based on xanthan gum (such as Rhodopol® G from Solvay).

Other components h)

In addition, the SC's or TC's or WG's according to the invention can optionally also contain as further components h):

Wetting agents, pH adjusters, defoamers, biocides, disintegration agents, adhesion promoters, antifreeze agents, preservatives, dyes or fertilizers, and surfactants different from component c). Suitable defoamers are surface-active compounds based on silicone or silane, such as the Tegopren® products (Goldschmidt), the SE® products (Wacker), and the Bevaloid® (Kemira), Rhodorsil® (Solvay) and Silcolapse® products (Blustar Silicones) SE® (Wacker), Rhodorsil® and Silcolapse® products are preferred, and products such as Silcolapse® 5020 are particularly preferred.

Suitable antifreeze agents are those from the group of ureas, diols and polyols, such as ethylene glycol and propylene glycol, glycerol, preferably propylene glycol or glycerol.

Suitable preservatives are, for example, products such as Acticide® MBS (Biozid, Thor Chemie), CIT, MIT or BIT such as Proxel® GXL (BIT), Acticide® SPX (MIT, CIT).

Suitable adhesion promoters can be selected from the group of polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymer of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymer of vinyl chloride and vinyl acetate, sodium salt of the copolymer of propene sultanic acid and partially hydrolyzed vinyl acetate, sodium caseinate, Phenolic resins, modified cellulose types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol), modified cellulose

Suitable antifoam agents can be selected from the group of esters of phosphoric acid with lower alcohols, Cg-Cio alcohols, silicone surfactants (suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants), such as polydimethylsiloxane, and their absorbates on solid carrier material such as Rhodorsil® 432 (silicone surfactant), butyl phosphate, isobutyl phosphate, n-octanol, Wacker ASP 15 (polydimethylsiloxane, absorbed on a solid carrier), Antifoam Agent®SE (polydimethylsiloxane). Preference is given to suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants, such as Antischaum-mittel® SE (polydimethylsiloxane), and solid antifoams, such as Wacker ASP 15 (polydimethylsiloxane).

Other additives h) optionally contained in the formulations according to the invention are penetration enhancers, wetting agents, spreading agents and/or retention aids. All substances which can usually be used in agrochemicals for this purpose are suitable.

Examples of suitable additives h) are:

• ethoxylated branched alcohols (e.g. Genapol® type X) with 2-20 EO units;

® ethoxylated methyl-terminated branched alcohols (e.g. Genapol® type XM) with 2-20 EO units;

® ethoxylated coconut alcohols (e.g. Genapol® C types) with 2-20 EO units;

® ethoxylated CI 2/ 15 alcohols (e.g. Synperonic® A types) with 2-20 EO units;

® propoxy-ethoxylated alcohols, branched or linear, eg Antarox® B/848, Atlas® G5000, Lucramul® HOT 5902; ® propoxy-ethoxylated methyl-terminated fatty acids, eg Leofat® OC0503M;

® organomodified polysiloxanes, e.g., BreakThru® OE444, BreakThru® S240, Silwet® L77, Silwet® 408;

® mono- and diesters of sodium sulfosuccinate salts with branched or linear alcohols having 1-10 carbon atoms;

® ethoxylated diacetylene diols (e.g. Surfynol®).

Table 2: Exemplary trade names and CAS numbers of preferred compounds h)

Suitable defoamers h are all substances which can usually be used for this purpose in agrochemicals. Silicone oils, silicone oil preparations, magnesium stearate, phosphinic and phosphonic acids are preferred. Examples are Silcolapse® 482 from Bluestar Silicones, Silfoam® SCI 132 from Wacker [dimethylsiloxanes and silicones, CAS no. 63148-62-9], SAG 1538 or SAG 1572 from Momentive [dimethyl siloxanes and silicones, CAS no. 63148-62-9] or Fluowet® PL 80.

Possible preservatives h are all substances that can usually be used in agrochemicals for this purpose. Examples of suitable preservatives are preparations containing 5-chloro-2-methyl-4-isothiazolin-3-one [CIT; CAS no. 26172-55-4], 2-methyl-4-isothiazolin-3-one [MIT, CAS no. 2682-20-4] or 1.2-benzisothiazol-3(2H)-one [BIT, CAS no. 2634-33-5], Examples include Preventol® D7 (Lanxess), Kathon® CG/ICP (Rohm & Haas), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).

All substances which can usually be used in agrochemicals for this purpose are suitable as antioxidants h. Butylhydroxytoluene [3,5-di-tert-butyl-4-hydroxytoluene, CAS no. 128-37-0] and citric acid.

Possible dyes h are all substances which can usually be used for this purpose in agrochemicals. Examples include titanium dioxide, carbon black, zinc oxide, blue pigments, red pigments and Permanent Red FGR.

Suitable inert fillers h) are all substances which can usually be used for this purpose in agrochemicals and which do not function as thickeners. Inorganic particles, such as carbonates, silicates and oxides, and also organic substances, such as urea-formaldehyde condensates, are preferred. Examples include kaolin, rutile, silicon dioxide (“highly dispersed silicic acid”), silica gel and natural and synthetic silicates, as well as talc.

The present invention also relates to water-dispersible technical concentrates (TK's) based on the compositions described above, containing one or more anionic emulsifiers c2, one or more nonionic emulsifiers c1), at least one or more carrier materials f,

Also subject of the present invention are suspension concentrates (SC's) containing one or more anionic emulsifiers c2, one or more nonionic emulsifiers cl, at least one or more thickeners g).

Also subject of the present invention are EC's containing one or more nonionic emulsifiers cl, at least one solvent e)

The present invention also relates to EC's containing one or more nonionic emulsifiers cl, at least one other agrochemical active substance, this preferably being a fungicide.

The present invention also relates to ODs containing one or more nonionic emulsifiers c1, one or more anionic emulsifiers c2, at least one solvent e) at least one thickener g)

All methods known to those skilled in the art as customary can be used as application forms; Examples include: spraying, dipping, misting and a number of special methods for direct underground or above-ground treatment of entire plants or parts (seeds, roots, stolons, stalks, stems, leaves), such as trunk injections for trees or stalk bandages for perennial plants , and a number of special indirect application methods.

The respective area and/or object-related application rate of the crop protection agents of the most varied of formulation types for combating the harmful organisms mentioned varies greatly. In general, the application media known to the person skilled in the art as customary for the respective area of use are used in the customary quantities for this purpose; such as from several hundred liters of water per hectare with standard spraying methods to a few liters of oil per hectare with 'ultra low volume' aircraft application to a few milliliters of a physiological solution with injection methods. The concentrations of the crop protection agents according to the invention in the corresponding application media therefore vary within a wide range and depend on the respective Application dependent. In general, concentrations are used which are known to the person skilled in the art as customary for the respective area of use. Concentrations of 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 be applied, for example, in the preparation forms customary for liquid preparations, either as such or after prior dilution with water, ie, for example, as emulsions, suspensions or solutions. The application is carried out according to the usual methods, e.g. by spraying, pouring or injecting.

Depending on the type of active ingredient that may be present in addition to prothioconazole, the formulations according to the invention are useful for controlling a large number of pests and can be used not only for the treatment of plant cultures, but also for inanimate matter and in the home.

"Pests" or "harmful organisms" are understood here to mean all types of pests that can be combated or kept under control with organic plant protection agents, i.e. plant protection products, in particular fungicides and mixtures of fungicides with other plant protection products. The term pest therefore includes organisms that damage plants, in particular harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants. The term "control" includes both curative treatment, i.e. treating infested plants with a formulation according to the invention, and protective treatment, i.e. treating plants to protect them from pest infestation.

The present invention thus also relates to the use of formulations described herein for controlling pests, in particular plant pests; and a method for controlling noxious organisms, particularly plant-damaging organisms, comprising contacting the noxious organisms, their habitat, their hosts such as plants and seeds, and the soil, area and environment in which they grow or may grow , But also of materials, plants, seeds, soil, surfaces or rooms that are to be protected from attack or infestation by plant-damaging organisms, with an effective amount of the formulations according to the invention.

A further aspect of the invention relates to the use of the formulations described herein for protecting plants, including seeds, in particular for protecting useful plants from infestation by harmful organisms, in particular harmful fungi. The present invention thus also relates to the use of the formulations for controlling plant-damaging organisms such as, for example, 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, especially as foliar, dressing and soil fungicides, in a manner known per se for controlling phytopathogenic fungi.

The following may be mentioned as plants which can be treated with the formulations according to the invention: cotton, flax, grapevines, fruit, vegetables such as Rosaceae sp. (For example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches and berries such as strawberries), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp. (for example banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (e.g. lemons, organs and grapefruit); Solanaceae sp. (e.g. tomatoes), Liliaceae sp., Asteraceae sp. (e.g. lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (e.g. cucumber), Alliaceae sp. (e.g. leeks, onions), Papilionaceae sp. (e.g. peas); Major crops such as Gramineae sp. (e.g. corn, 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. (e.g. sugar beet, fodder beet, chard, beetroot); sugarcane, poppy, olive, coconut, cocoa, tobacco and useful and ornamental plants in garden and forest; and in each case genetically modified species of these plants, and the seeds of these plants.

The formulations according to the invention are preferably used for the treatment of wheat, barley, rye, soya, onions, corn and peanuts.

In particular, the formulations of prothioconazole according to the invention can in principle be used to combat all harmful fungal diseases which can also be combated with the known formulations of prothioconazole. Depending on the respective mixing partner, if any, these are, for example, the following plant diseases:

Alternaria species on vegetables, oilseed rape, sugar beets, soybeans, cereals, cotton, fruit and rice (e.g. A. solani or A. alternata on potatoes and other plants), Aphanomyces species on sugar beets and vegetables, Ascochyta sp. on cotton and rice, bipalaris and turner species on maize, cereals, rice and turf (e.g. teres on barley, D. tritci-repentis on wheat), Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, Vegetables, flowers and vines, Botryodiplodia sp. on cotton, Bremia lactucae on lettuce, Cerospora species on maize, soybeans, rice and sugar beets (e.g. C. beticula on sugar beets), Cochliobolus species on maize, cereals, rice (e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice), Corynespora sp . on soybeans, cotton and other plants, Colletotrichum species on soybeans, cotton and other plants (e.g. C. acutatum on various plants), Curvularia sp. on cereals and rice, Diplodia sp. on cereals and rice, Exserohilum species on maize, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumber plants, Fusarium and Verticillium species (e.g. V. dahliae) on various plants (e.g. F. graminearum on wheat), Gaeumanomyces graminis on cereals, Gibberella species on cereals and rice (e.g. Gibberella fujikuroi on rice), grainstaining complex on rice, Helminthosporium species (e.g. H. graminicola) on corn and rice, Macrophomina sp. on soya and cotton, Michrodochium sp. (eg M. nivale on cereals), Mycosphaerella species on cereals, bananas and peanuts (M. graminicola on wheat, M. fijiesis on banana), Phaeoisaripsis sp. on soybeans, Phakopsara sp. (eg P. pachyrhizi and P. meibomiae on soybeans), Phoma sp. on soybeans, Phomopsis species on soybeans, sunflowers and vines (P. viticola on vines, P. helianthii on sunflowers), Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Penecilium sp. on soya and cotton, Podosphaera leucotricha on apple, Pseudocercosporella herpotrichoides on cereals, Pseudoperonospora species on hops and cucumbers (e.g. P. cubenis on cucumber), Puccinia species on cereals, corn and asparagus (P. triticina and P. striformis on wheat, P .asparagi on asparagus), Pyrenophora spp. on cereals, Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae on rice, Pyricularia grisea on turf and cereals, Pythium spp. on turf, rice, corn, cotton, rape, sunflower, sugar beet, vegetables and other plants, Rhizoctonia axes (e.g. R. solani) on cotton, rice, potato, turf, corn, rape, potato, sugar beet, vegetables and others plants, Rynchosporium sp. (e.g. R. secalis) on rice and cereals, Sclerotinia species (e.g. S. sclerotiorum) on oilseed rape, sunflowers and other plants, Septoria tritici and Stagonospora nodorum on wheat, Erysiphe (syn. Uncinulanecator) on grapevines, Setospaeria species on maize and turf , Sphacelotheca reilinia on corn, Thievaliopsis spp. on soybeans and cotton, Tilletia spp. on corn, Ustilago spp. on corn, corn and sugar beet, and Venturia spp. (scab) on apple and pear (eg V. inaequalis on apple).

The formulations according to the invention can be applied undiluted or diluted with water. As a rule, they are mixed 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 with 50 to 24,000 parts of water based on one part of the formulation diluted.

The subject of the present invention is also an emulsion obtainable by mixing water with the liquid formulation according to the invention. The mixing ratio of water to emulsion concentrate can be in the range from 1000:1 to 1:1, preferably 400:1 to 10:1.

The dilution is achieved by pouring the emulsion concentrates according to the invention to the water. Agitation, such as stirring. However, agitation is usually not necessary. Although temperature is not a critical factor in the dilution process, dilutions are usually carried out at temperatures in the range 0°C to 50°C, more preferably 10°C to 30°C, or at ambient temperature.

The water used for dilution is usually tap water. However, the water can already contain water-soluble or finely dispersed compounds that are used in plant 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 emulsion according to the invention as a premix or, if appropriate, only shortly before use (tank mix). These agents can be added to the formulations according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user usually applies the formulation according to the invention from a pre-dosing device, a knapsack sprayer, a spray tank, a spray plane or an irrigation system; the formulation according to the invention is usually diluted to the desired application concentration with water, buffer and/or other auxiliary substances, as a result of which the ready-to-use spray liquid or Agrochemical composition of the invention. Usually, 20 to 2000 liters, preferably 50 to 400 liters, 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 at the place of use and the application method. In general, the application rate is in the range from 0.001 to 3 kg, preferably from 0.005 to 2 kg, particularly preferably from 0.01 to 1 kg and very particularly preferably from 50 to 500 g of active ingredient per hectare, the active ingredient here being prothioconazole plus possible other active ingredients means.

The generally diluted formulations of the invention are applied primarily by spraying, especially foliar spraying. The application can be carried out using spraying techniques known to those skilled in the art, for example using water as the carrier and amounts of spray mixture of about 50 to 1000 liters per hectare, for example from 100 to 00 liters per hectare.

The new formulations containing prothioconazole have advantageous properties for the treatment of plants, in particular they are distinguished by good application properties, high stability and high fungicidal activity. The invention is explained in more detail by the examples without being restricted thereto.

examples

Materials used:

The terms used in the following examples have the following meanings:

Prothioconazole PTZ (Bayer AG)

Atlox Metasperse 500 Croda, acrylate based co-polymer

Vitamin E Sigma-Aldrich, alpha-tocopherol

Pluronic PE 10500 propylene oxide ethylene oxide (PO-EO) block polymer (BASF)

Rhodopol® 23 Xanthan Derivative (Solvay)

Silcolapse® 426 Silicone Defoamer (Solvay)

Proxel® GXL Preservative (Biocide, Proxel)

Lucramul® CO30 Nonionic Emulsifier, Castor Oil Ethoxylated, Levaco Chemicals, DE

SAG 1572 Aqueous emulsion of polydimethylsiloxane Momentive®

Genagen® 4296 dimethyl decanamide (DAA), Clariant

Hallcomid® 1025 N,N-dimethyl 9-decenamide, CAS number: 1356964-77-6

General Preparation of an Aqueous Suspension Concentrate (SC):

Water at room temperature is initially introduced. The active ingredients and the other components are added while stirring (in no particular order). Pre-comminution takes place using a colloid mill, followed by wet grinding, for example using a bead mill. Finally, the organic thickener is added.

General Preparation of an Emulsion Concentrate (EC)

The organic solvent is presented. All components are then added while stirring (in no particular order). It is stirred until a clear solution is formed.

-2-01

The cotton samples were extracted with acetonitrile (containing 20 mg/L cysteine hydrochloride) and deep-frozen prior to analysis.

2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol is separated from the formulating ingredients on a reverse phase column using an isocratic eluent Cut. After the MS/MS detection, the quantitative evaluation is performed by comparing the peak areas with those of the reference object using an external standard.

High Pressure Liquid Chromatograph : HP 1090

Sample injection : HP 1090 Autoinjector

Mass spectrometer : Quattro I, Fisons

Integration and evaluation MassLynx from Micromass

Unless otherwise stated, the samples are exposed to light and stored for 4 weeks.

Example 1: Recipe 1

Three dilutions of each formulation containing 62.5 g/L, 2 g/L and 0.2 g/L PTZ were prepared.

The actual PTZ concentration in the concentrated formulations is 125 g/L.

Each of the three dilutions was sprayed onto 10 cotton squares mounted on cardboard, with only 6 cotton squares being sprayed as a control.

After spraying, the cartons of cotton squares were placed under a daylight lamp. 5 each of the cotton squares were analyzed 1 hour and 6 hours after spraying, with the Cotton samples were analyzed using the method described above. The analytes (PTZ and Desthio) were determined via HPLC-MS.

The result of the evaluation is shown in FIG. 1 (Prosare=example 1 comparison).

As the result shows, the degradation of PTZ to Desthio is time-dependent for all formulations and all dilutions. The conversion rates on the cotton samples increase from 1 hour after spraying to 6 hours after spraying. The conversion rate is also dependent on the PTZ concentration, with lower concentrations exhibiting a higher conversion rate. The lowest PTZ degradation was observed in the 62.5 g/L PTZ solution, while the 0.2 g/L dilution showed the highest degradation.

Vitamin E (tocopherol) showed a particularly good stabilization of PTZ on the surfaces.

Claims

- 29 -Claims

1. Use of decenamide and/or tocopherols to stabilize thiones on surfaces.

2. Use according to claim 1, characterized in that tocopherol is used.

3. Use according to claim 1 or 2, characterized in that the thione is prothioconazole.

4. Use according to any one of the preceding claims, characterized in that thiones from agrochemical formulations are stabilized on surfaces.

5. Use according to any one of the preceding claims, characterized in that the surface is a leaf surface.

6. Use according to any one of the preceding claims, characterized in that the surface is a cotton fabric.