CA3195732A1 - 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

Stabilization of thioketones on surfaces The present invention relates to a method of stabilizing thioketones (thiones) on surfaces, in particular active ingredients containing thione building blocks, especially triazolinethiones, as functional groups, and to the use of decenamide and tocopherols (vitamin E) for stabilization of thione compounds.
The present invention relates in particular to the stabilization of thiones on surfaces, in particular cotton or else leaf surfaces.
The present invention further relates to a method of stabilizing thiones on surfaces, in particular leaf surfaces or cotton fabrics, by decenamide and/or tocopherols (vitamin E).
In addition, the present invention relates to a method of stabilizing thiones on surfaces, in particular cotton or else leaf surfaces, by applying a formulation comprising decenamide and/or tocopherols (vitamin E).
It is already known that, for example, prothioconazole can be used in standard formulations for control of fungi (WO-A 96/16 048). This active ingredient is 242-(1-chlorocyclopropy1)-3-(2-chloropheny1)-2-hydroxypropyll-2,4-dihydro-3H-1,2,4-triazole-3-thione. Prothioconazole-containing formulations are generally liquid formulations and are supplied on the market, for example, in the form of emulsion concentrates.
Furthermore, it is known that the active ingredient prothioconazoles can be degraded under particular conditions to give the compound 2-(1-chlorocyclopropy1)-1-(2-chloropheny1)-3-(1H-1,2,4-triazol-1-y0propan-2-ol (PSM-Zulassungsbericht [Crop Protection Agent Registration Report], Tilmor, 2010.08.30, serial no. 21, German Federal Office of Consumer Protection and Food Safety).
Therefore, prothioconazole (hereinbelow referred to as PTZ)-containing formulations, as early as in the course of production, may contain a certain amount of 2-(1-chlorocyclopropy1)-1-(2-chloropheny1)-3-(1H-1,2,4-triazol-1-y0propan-2-ol. In the case of storage under severe conditions, such as elevated temperatures, incidence of light and intensive oxygen contact, it is likewise possible for degradation of prothioconazoles to take place to give 2-(1-chlorocyclopropy1)-1 -(2-chloropheny1)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol, as a result of which the proportion of active ingredient in the formulations is correspondingly reduced. Since the compound 2-(1-chlorocyclopropy1)-1-(2-chloropheny1)-3-(1H-1,2,4-triazol-1-y1)propan-2-ol (hereinbelow referred to as desthio) is a relevant impurity, the content thereof in prothioconazole-containing formulations is subject to regulatory limitation.
This also applies analogously to other thione-containing compounds such as 4-46-(2-(2,4-difluoropheny1)-1,1-difluoro-2-hydroxy-3-(5-mercapto-1H-1,2,4-triazol-1-yl)propyl)pyridin-3-y0oxy)benzonitriles.
Here, the maximum permissible amount of desthio in PTZ formulations depends on the amount of PTZ in the formulation in g/l. The maximum permissible amount of desthio is given in ppm, with the permissible Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 2 -proportion of desthio in ppm being half of the value of the PTZ load in g/l.
Thus, the maximum permissible desthio content in a formulation with 100 g/1 PTZ is 50 ppm (= 0.005% by weight).
WO-A 2012/033590 discloses aqueous dispersions of prothioconazoles containing a sulfur compound, for example L-cysteine, for stabilization.
WO 2017/097882 and W02018/228885 describe stabilized PTZ-containing formulations which can be considered to be the closest prior art. What is described therein are emulsion concentrates and suspension concentrates comprising PTZ dissolved in a solvent. It was possible to stabilize the formulation by addition of compounds of the formula (I) N/
- - n (0 in which n represents 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15 or 18 and to achieve a reduction of the desthio content.
Compounds of the formula (I) are known from WO-A 2012/061094 and can be prepared by the process of metathesis. These are, for example, products from Stepan ((N,N-dimethyl 9-decenamide, CAS number:
1356964-77-6, Hallcomid 1025 or Steposol MET-10U).
These compounds have the disadvantage that they require very large amounts of up to 30% of stabilizer to achieve a desired effect, which represents a mayor modification of the formulation. Also, these are novel additives which, in some cases, still require approval for use in crop protection formulations.
While the prior art describes the stabilization of thiones in spray liquors and concentrated storable formulations, there is no pointer in the prior art as to how thiones can be stabilized even after deployment on surfaces, since the degradation products are undesirable here too.
There was therefore a need for a method of stabilizing PTZ-comprising formulations after application thereof to surfaces, where they are exposed, for example, to oxygen, high temperatures or the action of light, which effectively accelerate the degradation of the thiones, in particular the triazolinethiones and especially of PTZ to the corresponding desthio products, e.g. 2-(1-chlorocyclopropy1)-1-(2-chloropheny1)-

3-(1H-1,2,4-triazol-1-y0propan-2-ol (compound III).
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08 It was thus an object of the invention to provide a method of stabilizing thiones on surfaces after application thereof, in particular of stabilization of prothioconazoles, in order to counteract degradation to 2-(1-chlorocyclopropy1)-1-(2-chloropheny1)-3-(1H-1,2,4-triazol-1-y0propan-2-ol.
Furthermore, it was found that the degradation of thiones to desthio products is easily triggered by light, inter alia of certain wavelengths. Surprisingly, it was however found that, here, conventional UV blockers or UV absorbers are only insufficiently effective.
In addition, it was found that even various commercial antioxidants do not provide effective protection against degradation of the thiones but, rather, even promote degradation.
Surprisingly, it has been found that even very small amounts of certain antioxidants and free-radical scavengers such as decenamide and tocopherols (vitamin E) extremely effectively prevent the degradation of thiones, in particular of prothioconazole, to desthio products on surfaces, in particular at a high concentration of active ingredient.
The present invention therefore provides for the use of decenamide and tocopherols for stabilization of thiones on surfaces, in particular after the application of said thiones as fungicidal spray compositions.
The tocopherols here are preferably selected from the group consisting of tocotrienols, tocopherols (e.g.
(+)-delta-tocopherol, (+/-)-alpha-tocopherol), and mixtures of these compounds.
The present invention therefore further provides the use of formulations comprising tocopherol or decenamide for stabilization of the thiones on surfaces following application and drying.
The formulations to be stabilized after application are preferably agrochemical formulations.
In a further preferred embodiment, the active ingredient a) having a thione group is selected from the group comprising prothioconazole and 4-46-(2-(2,4-difluoropheny1)-1,1-difluoro-2-hydroxy-3-(5-mercapto-1H-1,2,4-triazol-1-y1)propyl)pyridin-3-y0oxy)benzonitrile , particularly preferably only prothioconazole.
Furthermore, the active ingredient is preferably present in an amount of from 1% by weight to 50% by weight, more preferably from 4% by weight to 30% by weight, and particularly preferably from 5% by weight to 28% by weight, based on the total weight of the formulation.
The antioxidant b) is more preferably from the group comprising decenamide, N,N-dimethy1-9-decenamide unless stated otherwise within the context of the present invention, and tocopherols and tocotrienols (preferably (+)-delta-tocopherol, (+/-)-alpha-tocopherol, (+)-alpha-tocopherol and vitamin E
and mixtures of tocopherols).
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 4 -Vitamin E is a collective term for fat-soluble substances having antioxidative action, with tocopherols and tocotrienols being the most frequently encountered forms. Hereinbelow, the term vitamin E is meant to comprise alpha-tocopherol (RRR-a-tocopherol or D-a-TO), beta-tocopherol, gamma-tocopherol, delta-tocopherol, alpha-tocotrienol, beta-tocotrienol, gamma-tocotrienol, delta-tocotrienol, and also their derivatives such as, for example, acetates.
Independently of the formulation type, the antioxidants are preferably present in an amount of from 0.01%
by weight to 15.00% by weight, more preferred from 0.03% by weight to 5.00% by weight, and particularly preferably from 0.2% by weight to 4% by weight, based on the total weight of the formulation.
Depending of the formulation, e.g. water- or oil-based, preference is given to using water- or oil-soluble antioxidants, preferably in the following amounts:
SC formulations:
In SCs, the antioxidants are preferably present in an amount of from 0.01% by weight to 10.00% by weight, more preferably from 0.03% by weight to 5% by weight, even more preferably from 0.03% by weight to 1.00% by weight and particularly preferably from 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 present in an amount of from 0.10% by weight to 5.00% by weight, more preferably from 0.2% by weight to 4.00% by weight, and particularly preferably from 0.2% by weight to 3% by weight, based on the total weight of the formulation.
In ECs, the antioxidants are preferably present in an amount of from 0.50% by weight to 15.00% by weight, more preferred from 1% by weight to 10.00% by weight, and particularly preferably from 3% by weight to 10% by weight, based on the total weight of the formulation.
Prothioconazoles (with the chemical name 2-{2-( 1 -chlorocy clopropy1)-3-(2-chloropheny1)-2-hydroxypropy11-1,2-dihydro-3H-1,2,4-triazole-3-thione) (CAS number 178928-70-6) take the form of a racemate. Suitable processes for preparation thereof are described in DE-A
195280. Prothioconazoles may be present in the thiono form of the general formula (II) Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 5 -CI OH
CH2 ________________________________ C V CI

1 (II) ,N, S

or in the tautomeric mercapto form of the general formula (Ha).
CI OH
CH2 ________________________________ C V CI

1 (11a) ,N SH
N , N
The use of the term "prothioconazoles" hereinafter always covers the isomers shown here and further possible tautomers.
2-(1-Chlorocyclopropy1)-1-(2-chloropheny1)-3-(1H-1,2,4-triazol-1-y0propan-2-ol is also present as a racemate and has the general formula (III), where in turn all tautomeric forms are to be embraced by this representation.
CI OH
CH2 ________________________________ C V CI

1 (III) ,NI
_____________________________________ 11 N
Furthermore, the formulations according to the present invention, as described above, may each comprise further ingredients, such as:
a) cl: non-ionic dispersant/emulsifier, c2: ionic dispersant/emulsifier b) other active agrochemical ingredients different from a) c) solvents including OD carriers d) carriers (WGs, and also Aerosils for SC/TC/WG) e) gl: organic thickeners g2: inorganic thickeners Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 6 -0 further additives and auxiliaries.
Formulation types are defined by the FAO and are found at www.fao.org/ag/agp/agpp/pesticid. In the March 2016 edition, the customary formulation types are described on pages 66-231. The formulation according to the invention is a customary formulation type described by the FAO. Examples which may be mentioned here are suspension concentrates (SC), and also colorant-containing concentrates 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).
Preferred are EC, SC, FS, SE, OD and WG formulation types, very particular preference being given to formulations where at least one active ingredient is not dissolved. Very particular preference is given to FS, SC, SE, OD and WG formulations, most preferably SC, FS and WG
formulations.
The present invention further provides for the use of the formulations of the invention for treatment of plants and corresponding methods.
Nonionic emulsifiers and dispersants cl) Useful nonionic emulsifiers and dispersants cl), such as emulsifiers, wetting agents, surfactants and dispersers, include standard surface-active substances present in formulations of active agrochemical ingredients. 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 group-capped and non-end group-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g. butoxy polyethylenepropylene glycols), reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, and also fatty acid esters, fatty acid polyglycol ether esters, alkylsulfonates, alkylsulfates, arylsulfates, ethoxylated arylalkylphenols, for example tristyrylphenol ethoxylate having an average of 16 ethylene oxide units per molecule, and also ethoxylated and propoxylated arylalkylphenols, and also sulfated or phosphated arylalkylphenol ethoxylates or ethoxy- and propoxylates. Particular preference is given to tristyrylphenol alkoxylates and fatty acid polyglycol ether esters. Very particular preference is given to tristyrylphenol ethoxylates, tristyrylphenol ethoxy propoxylates and castor oil polyglycol ether esters, in each case individually or in mixtures. Additives may additionally be useful, such as surfactants or esters of fatty acids, which contribute to improvement in biological efficacy.
Suitable nonionic emulsifiers and dispersants cl) are, for example, Soprophor 796/P, Lucramul C030, Lucramul HOT, Lucramul PSI 100 or Synperonic T304.
Suitable nonionic dispersers c 1) may likewise be selected from the group comprising 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, for example Luviskol (polyvinylpyrrolidone), Mowiol Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 7 -(polyvinyl alcohol) or modified cellulose. Preference is given to polyvinylpyrrolidone types, particular preference to types of low molecular weight such as Luviskol K30 or Sokalan K30.
Useful further nonionic emulsifiers and dispersants cl) from the group of the di- and triblock copolymers of alkylene oxides are, for example, compounds based on ethylene oxide and propylene oxide, having mean molar masses between 200 and 10 000 and preferably 1000 to 4000 g/mol, where the proportion by mass of the polyethoxylated block varies between 10 and 80%, for example the Synperonic PE series (Uniqema), the Pluronic PE series (BASF), the VOP 32 or Genapol PF series (Clariant).
The proportion of nonionic emulsifiers and dispersants c 1) required 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 b1), such as emulsifiers, surfactants, wetting agents and dispersers, are, for example, alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof, for example the salts of alkylsulfonic acids or alkylphosphoric acids and alkylarylsulfonic or alkylarylphosphoric acids, diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols or of fatty acid esters. Examples of phosphates are phosphate esters.
Examples of carboxylates are alkyl carboxylates and carboxylated alcohol ethoxylates or alkylphenol ethoxylates. Likewise suitable is the group of anionic emulsifiers of the alkali metal, alkaline earth metal and ammonium salts of the polystyrenesulfonic acids, salts of the polyvinylsulfonic acids, salts of the alkylnaphthalenesulfonic acids, salts of alkylnaphthalenesulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde. Examples are calcium dodecylbenzenesulfonate such as Rhodocal 70/B (Solvay), Phenylsulfonat CA100 (Clariant) or isopropylammonium dodecylbenzenesulfonates such as Atlox 3300B (Croda).
Further typical representatives include Phenylsulfonat CA (calcium dodecylbenzenesulfonate), Soprophor products (optionally esterified derivatives of tristyrylphenol ethoxylates), Emulsogen 3510 (alkylated EO/PO copolymer), Emulsogen EL 400 (ethoxylated castor oil), Tween products (fatty acylated sorbitan ethoxylates), Calsogen AR 100 (calcium dodecylbenzenesulfonate). Preference is given to combinations of salts of alkylated aromatic sulfonic acids, such as calcium phenylsulfonate and/or Calsogen AR 100, with alkylated copolymers of ethylene oxide and propylene oxide, such as Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 8 -Emulsogen 3510. Particular preference is given to combinations of salts of dodecylbenzenesulfonic acid, such as Calsogen AR 100, with alkylated copolymer of ethylene oxide and propylene oxide, such as Emulsogen 3510.
Examples of further anionic emulsifiers and dispersants c2) from the group of the naphthalenesulfonates are Galoryl MT 800 (sodium dibutylnaphthalenesulfonate), Morwet IP (sodium diisopropylnaphthalenesulfonate) and Nekal BX (alkylnaphthalenesulfonate).
Examples of anionic surfactants from the group of the condensates of naphthalenesulfonates with formaldehyde are Galoryl DT 201 (naphthalenesulfonic acid hydroxy polymer with formaldehyde and methylphenol sodium salt), Galoryl DT 250 (condensate of phenol- and naphthalenesulfonates), Reserve C
(condensate of phenol-and naphthalenesulfonates) or Morwet D-425, Tersperse 2020. Preference is given to 1,2-dibutyl- or -diisobutyl-substituted naphthalenesulfonates, for example products such as Galoryl MT 800 (CFPI-Nufann) and Nekal BX (BASF). Further 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) required 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% to 20% by weight.
The proportion of anionic emulsifiers and dispersants c2) required 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.
Further active agrochemical ingredients different from PTZ d):
Further active agrochemical ingredients d) in the context of the present invention 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 ingredients d), more preferably one or more active fungicidal ingredients d). The active ingredients used are preferably water-insoluble.
The Pesticide Manual provides a review of typical crop protection agents.
Preferred insecticidal components d) are, for example, imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole, spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron, the compound from WO-A 2006/089633 as Example I-1-a-4, the compound disclosed in Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 9 -as Example I-1-a-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, ametoctradin, amisulbrom, azoxystrobin, benthiavalicarb-isopropyl, benzovindiflupyr, boscalid, carbendazim, chlorothanonil, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, difenoconazole, ethaboxam, epoxiconazole, famoxadone, fluazinam, fluquinconazole, flusilazole, flutianil, fluxapyroxad, isopyrazam, kresoxim-methyl, lyserphenvalpyr, mancozeb, mandipropamid, metconazol, pyriofenone, folpet, metaminostrobin, oxathiapiprolin, penthiopyrad, picoxystrobin, probenazole, proquinazid, pydiflumetofen, pyraclostrobin, sedaxane, spiroxamin, tebufloquin, tetraconazole, valiphenalate, zoxamide, ziram, N45-chloro-2-isopropylbenzy1)-N-cyclopropyl-34difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, N-(5-chloro-2-isopropylbenzy1)-N-cyclopropy1-34difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, 2- {34241- {{3,5-bis(difluoromethyl)-1H-pyrazol-1-yll acetyl}
piperidin-4-y1)-1,3-thiazol-4-y11-4,5-dihydro-1,2-oxazol-5-yll phenyl methane sulfonate, 2- {34241- { [3,5-bi s(difluoromethyl)-1H-pyrazol-1 -yll acetyl} piperidin-4-y1)-1,3-thiazol-4-y11-4,5-dihydro-1,2-oxazol-5-y11-3-chlorophenylmethane-sulfonate, (3 S,6S,7R,8R)-8-benzy1-34( {34(isobutyryloxy)methoxy1-4-methoxypyridin-2-yllcarbonyl)amino1-6-methy1-4,9-dioxo-1,5-dioxonan-7-y1 2-methy 1propanoate (lyserphenvalpyr).
Particularly preferred fungicidal mixing partners d) for prothioconazole are, for example: tebuconazole, spiroxamin, bixafen, fluoxastrobin, trifloxystrobin, N45-chloro-2-isopropylbenzy1)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-1H-pyrazole-4-carboxamide, (35,65,7R,8R)-8-benzy1-34( {3-Risobutyryloxy)methoxy1-4-methoxypyridin-2-yll carbonyl)amino1-6-methy1-4,9-dioxo-1,5-dioxonan-7-y1 2-methylpropanoate (lyserphenvalpyr) and fluopyram.
Very particular preference is given to the mixtures of a) (prothioconazole) with one or more compounds selected from the group of the 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) spiroxamine;
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 10 -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-isopropylbenzy1)-N-cyclopropy1-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide a) + d) N-(5-chloro-2-isopropylbenzy1)-N-cyclopropy1-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide + tebuconazole a) + d) N-(5-chloro-2-isopropylbenzy1)-N-cyclopropy1-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide + flupyram a) + d) bixafen + (35,65,7R,8R)-8-benzy1-34({3-Risobutyryloxy)methoxy1-4-methoxypyridin-2-yll carbonyl)amino1-6-methy1-4,9-dioxo-1,5-dioxonan-7-y1 2-methylpropanoate (lyserphenvalpyr) The proportion of component d) in the formulations of the invention is preferably 1% by weight to 40%
by weight, particularly preferably 3% by weight to 35% by weight.
Solvents e):
The formulations may comprise solvents e), for example in the case of EC, OD
or SE formulations.
= aromatic hydrocarbon mixtures (preferably naphaline reduced), for example Solvesso ;
= aromatic hydrocarbons, for example white spirit, petroleum, alkylbenzenes and spindle oil, xylene, toluene or alkylnaphthalenes;
= aliphatic/cycloaliphatic hydrocarbons, for example mineral oils, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, decalin or white oil;
= chlorinated aromatic or aliphatic hydrocarbons, for example chlorobenzene, chloroethylene, or methylene chloride, chloroform or tetrachloromethanes;
= alcohols, for example methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol or benzyl alcohol;
= ethers, for example tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydropyran, 1,4-dioxanes, diethyl ether, methyl tert-butyl ether, dihexyl ether, dioctyl ether, didecyl ether, dibenzyl ether, dimethylisosorbide, diphenyl ether, ethyl phenyl ether, phenyl benzyl ether or anisole;
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 11 -= monoesters/diesters/glycerol esters, for example 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, for example rapeseed oil, sunflower oil, soya oil, castor oil or corn oil;
= lactones, for example butyrolactone, alpha-methyl-gamma-butyrolactone, gamma-valerolactone or delta-valerolactone;
= polyethylene/propylene oxides, for example 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 the longer ethylene glycol homologs thereof;
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 the longer propylene homologs thereof; monoethylene glycol monomethyl ether acetate, monoethylene glycol diacetate, and the longer ethylene glycol homologs thereof;
monopropylene glycol monomethyl ether acetate, monopropylene glycol acetate, and the longer polypropylene glycol homologs thereof;
= simple and substituted amines, for example diethylamines, triethylamines, diisopropylamines, diisopropylethylamines, monoethanolamines, diethanolamines, triethanolamines and more highly alkoxylated amines, anilines or dimethylanilines;
= amides/ureas, for example N-formylmorpholine, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylbenzamide, N,N-dimethyloctanamide, N,N-dimethyldecanamide, N,N-dimethyldec-9-en-1-amide, N,N-dimethyldodedecanamide, N,N-dimethyllactamide, N,N-decylmethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propy1-2-pyrrolidone, N-butyl-2-pyrrolidone, N-penty1-2-pyrrolidone, N-hexy1-2-pyrrolidone, N-hepty1-2-pyrrolidone, N-octy1-2-pyrrolidone, N-nony1-2-pyrrolidone, N-decy1-2-pyrrolidone, N-undeceny1-2-pyrrolidone, N-dodecy1-2-pyrrolidone, N-methyl-2-piperidone, N-Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 12 -methylc aprolactam, N-octylcaprolactam, tetramethylurea, tetraethylurea, 1,3-dimethy1-2-imidazolidinone, 1,3,4-trimethy1-2-imidazolidinone, 1,3-dimethy1-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, 1-hepty1-3-methyl-2-imidazolidinone, 1-hepty1-1,3-dihydro-3-methy1-2H-imidazol-2-one;
= ketones, for example 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-tetramethy1-3-pentanone, cyclopentanone, cyclohexanone. cycloheptanone, cyclooctanone, 2,4,6-cycloheptatrien- 1 -one, acetophenone, propiophenone, 1-(4-methylphenypethanone, 1-(4-ethylphenyl)ethanone, 2-methyl-1-pheny1-1-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, for example acetonitrile, propanenitrile, 2-methylpropanenitrile, butanenitrile, 3-methylbutanenitrile, pentanenitrile, 4-methylpentanenitrile, hexanenitrile, heptanenitrile, octanenitrile, nonanenitrile, decanenitrile, benzonnitrile, benzeneacetonitrile, pentanedinitrile, 2-methylpentanedinitrile, hexanedinitrile, heptanedinitrile, octanedinitrile or nonanedinitrile;
= acetals, for example 1,1-dimethoxymethane; 1,1-dimethoxyethane; 1,1-[methylenebis(oxy)bisethane; 1,1-diethoxyethane;
1,114methylenebis(oxy)bispropane; 2,4,6,8-tetraoxanonane, 1,114methylenebis(oxy)bisbutane, 2-methy1-14(2-methylpropoxy)methoxylpropane, 2,4,6,8,10-pentaoxaundecane, 2,5,7,10-tetraoxaundecane, 1,3-dioxolane, 1,3-dioxane or 4-methy1-1,3-dioxane; orthoesters, for example 1,1,1-trimethoxymethane, 1,1,1-trimethoxyethane, 1,1,1-trimethoxypropane, 2-methoxy-1,3-dioxolane, 2-methoxy-2-methy1-1,3-dioxolane, 2-methoxy-2-methy1-1,3-dioxolane, 2-ethoxy-1,3-dioxolane, 2-ethoxy-2-methy1-1,3-dioxolane, 2-ethy1-2-methoxy-1,3-dioxolane, 2-methoxy-1,3-dioxane, 2-methoxy -2-methy1-1,3-dioxane or 2-ethoxy-1,3-dioxane;
= carbonates, for example 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, for example 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, for example dimethyl sulfoxide, diethyl sulfoxide, 1,1-dioxotetrahydrothiophene, 1,1-dioxotetrahy dro-3-methylthiophene or 1,1-dioxotetrahydro-2,4-dimethylthiophene.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 13 -In addition, the formulations of the invention may optionally comprise liquid fillers e), for example vegetable or mineral oils or esters of vegetable or mineral oils. Suitable vegetable oils e) are all oils which can typically 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 soya oil.
Possible esters are, for example, ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate, ethylhexyl caprylate, isopropyl myristate, isopropyl palmitate, methyl oleate, methyl palmitate, ethyl oleate.
Preference is given to rapeseed oil methyl ester and ethylhexyl palmitate.
Possible mineral oils are Exxsol D100 and white oils.
Table 1: Illustrative trade names and CAS numbers of preferred compounds e) Trade name Company General description CAS No.
Sunflower oil Triglycerides of different 8001-21-6 C14-C18 fatty acids, predominantly unsaturated Rapeseed oil Triglycerides of different 8002-13-9 C14-C18 fatty acids, predominantly unsaturated Corn oil Triglycerides of different 8001-30-7 C14-C18 fatty acids, predominantly unsaturated Soya oil Triglycerides of different 8001-22-7 C14-C18 fatty acids, predominantly unsaturated Rice oil Triglycerides of different 68553-81-1 C14-C18 fatty acids, predominantly unsaturated Radia 7129 Oleon NV, BE Ethylhexyl palmitate 29806-73-3 Crodamol OP Croda, UK
Radia 7331 Oleon NV, BE Ethylhexyl oleate 26399-02-0 Radia 7128 Oleon NV, BE C12/C14 ethylhexyl 29806-75-5 myristate/laurate Radia 7127 Oleon NV, BE Ethylhexyl laurate 20292-08-4 Radia 7126 Oleon NV, BE C8/10 ethylhexyl 63321-70-0 caprylate/caprate Estol 1514 Croda Isopropyl myristate 110-27-0 Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 14 -Rade 7104 Oleon NV, BE Caprylic and capric acid 73398-61-triglycerides, neutral 5. 65381-vegetable oil 09-1 Radia 7732 Oleon NV, BE Isopropyl palmitate 142-91-6 Crodamol Croda, UK
IPM
Radia 7060 Oleon NV, BE Methyl oleate 112-62-9 Radia 7120 Oleon NV, BE Methyl palmitate 112-39-0 Crodamol EO Croda Ethyl oleate 111-62-6 AGNIQUE Clariant rapeseed oil methyl ester 67762-38-ME 18 RD-F, 3. 85586-Edenor BASF 25-0 MESU
Exxsol D100 Exxon Mobil Hydrotreating low boilers 64742-47-8 (petroleum) Solvesso ExxonMobil Solvent naphtha 64742-94-5 200ND (petroleum), heavy aromatic, naphthalene-depleted Kristor M14 Carless White mineral oil 8042-47-5 Marcol 82 ExxonMobil (petroleum), C14-C30 Ondina 917 Shell branched and linear Exxsol D130 ExxonMobil White mineral oil 64742-46-7 Banole 50 Total (petroleum) Genera -12 Total White mineral oil 72623-86-0 (petroleum) Genera -9 Total White mineral oil 97862-82-3 (petroleum) Carrier materials f) for WGs.
Fillers and carrier materials f) in the formulations according to the invention are selected from the group comprising minerals, carbonates, sulfates and phosphates of alkaline earth metals and alkali metals, such as calcium carbonate, polymeric carbohydrates, framework silicates, such as precipitated silicas having low absorption, and natural framework silicates, such as kaolin. Typical representatives of suitable fillers f) are, for example, Agsorb LVM -GA (attapulgite), Harborlite 300 (pearlite), Collys HV (modified Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 15 -starch), Omya chalk (calcium carbonate), Kaolin Tec 1 (kaolin, aluminum hydrosilicate), Steamic 00S (talc, magnesium silicate). For c2), preference is given here to natural framework silicates and calcium carbonate products such as Omya chalk (calcium carbonate), Kaolin Tec 1 (kaolin) and Harborlite 300 (pearlite), particular preference to natural framework silicates such as Kaolin , Tec 1 (kaolin, aluminum hydrosilicate) and Harborlite 300 (pearlite). For WG
formulations, very particular preference is given to using kaolin and calcium carbonate. Further suitable carrier materials or fillers 0 are selected from the group of the highly absorptive carriers having an absorption capacity of at least 200 g of dibutyl phthalate per 100 g of carrier material. Preferred highly absorptive carriers 0 are silicas, for example Sipemat products (synthetic precipitated silica of high absorptivity) and fumed silica (Aerosil products). Preference is given to precipitated silica. The proportion of the fillers f) in the TCs according to the invention is preferably 0.1% to 10% by weight, particularly preferably 0.3% to 8% by weight and very particularly preferably 1% to 7% by weight.
Thickeners 2) Useful thickeners g) include organic thickeners gl) and inorganic thickeners g2).
Useful organic thickeners gl) include organic natural or biotechnologically modified or organic synthetic thickeners. Typical synthetic thickeners are Rheostrux (Croda) or the Thixin or Thixatrol series (Elementis). These are typically based on acrylates. Typical organic thickeners are based on xanthan or cellulose (for instance hydroxyethyl or carboxymethyl cellulose) or a combination thereof. Further typical representatives are based on lignin (such as lignosulfonates, BorresperseNA, REAX 88 or Kraftsperse .. 25 S). Preference is given to using natural modified thickeners based on xanthan. Typical representatives are, for example, Rhodopol (Solvay) and Kelzan (Kelco Corp.), and also Satiaxane (Cargill).
The proportion of the organic thickeners gl) in the SCs according to the invention B) is not more than 5%
by weight, preferably 0.01% to 1.0% by weight, more preferably 0.01% to 0.6%
by weight, even more preferably 0.05% to 0.5% by weight and even more preferably 0.1% to 0.3% by weight.
Suitable inorganic thickeners g2) are, for example, 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 (R.T. Vanderbilt).
The proportion of inorganic thickeners g2) in the formulations according to the invention is 0% to 5% by weight, preferably 0.1% to 3% by weight, more preferably 0.2% to 1.5% by weight, even more preferably 0.3% to 1.5% by weight and even more preferably 0.4% to 1.3% by weight.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 16 -Preference is given to using a mixture of thickener gl) and g2). In the case of Scs, particular preference is given to using exclusively organic thickeners dl). Very particular preference is given to those thickeners gl) based on xanthan (such as Rhodopol G from Solvay).
Further components h) In addition, the SCs or TCs or WGs according to the invention may optionally also comprise, as further components h):
wetting agents, pH adjusters, defoamers, biocides, disintegrants, adhesion promoters, antifreezes, preservatives, dyes or fertilizers, and surfactants other than component c).
Suitable defoamers are surface-active silicone- or silane-based compounds such as the Tegopren products (Goldschmidt), the SE products (Wacker), and the Bevaloid (Kemira), Rhodorsil (Solvay) and Silcolapse products (Blustar Silicones), preference being given to SE
(Wacker), Rhodorsil and Silcolapse products, particular preference, for example, to products such as Silcolapse 5020.
Suitable antifreezes are those from the group of the 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, for instance Proxel GXL (BIT), Acticide SPX (MIT, CIT).
Suitable adhesion promoters may 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 propenesultanic acid and partially hydrolyzed vinyl acetate, sodium caseinate, phenol resins, modified cellulose types, for example Luviskol (polyvinylpyrrolidone), Mowiol (polyvinyl alcohol), modified cellulose.
Suitable anti-foaming agents may be selected from the group of the esters of phosphoric acid with lower alcohols, C6-C10 alcohols, silicone surfactants (suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants), such as polydimethylsiloxane, and the absorbates thereof onto solid carrier material, for example Rhodorsil 432 (silicone surfactant), butyl phosphate, isobutyl phosphate, n-octanol, Wacker ASP15 (polydimethylsiloxane, absorbed on solid carrier), Antifoam SE (polydimethylsiloxane). Preference is given to suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants, such as Antifoam SE (polydimethylsiloxane), and solid antifoams, such as Wacker ASP 15 (polydimethylsiloxane).
Further additives h) which may be present in the formulations of the invention are penetrants, wetting agents, spreading agents and/or retention agents. Suitable substances are all of those which can typically be used for this purpose in agrochemicals.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 17 -Suitable additives h) are, for example, = ethoxylated branched alcohols (e.g. Genapol X type) with 2-20 EO units;
= ethoxylated branched alcohols with terminal methyl (e.g. Genapol XM
type) with 2-20 EO units;
= ethoxylated coconut alcohols (e.g. Genapol C types) with 2-20 EO units;
= ethoxylated C12/15 alcohols (e.g. Synperonic A types) with 2-20 EO
units;
= propoxy-ethoxylated alcohols, branched or linear, e.g. Antarox B/848, Atlas G5000, Lucramul HOT 5902;
= propoxy-ethoxylated fatty acids with terminal methyl, e.g. Leofat 000503M;
= organomodified polysiloxanes, e.g. BreakThru 0E444, BreakThru S240, Silwett L77, Silwett 408;
= mono- and di esters of sulfosuccinate sodium salts with branched or linear alcohols having 1-10 carbon atoms;
= ethoxylated diacetylenediols (e.g. Surfyno18).
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 18 -Table 2: Illustrative trade names and CAS numbers of preferred compounds h) Trade name Company General description CAS No.
Lucramul HOT Levaco Alcohol ethoxylate-propoxylate 64366-70-7 5902 (C8-P08/E06) Genapol X060 Clariant Alcohol ethoxylate (iso-C13- 9043-30-5 E06) Genapol XM Clariant Alcohol ethoxylate (iso-C13- 345642-79-7 060 E06/with Me end group) Triton GR 7 ME Dow Dioctylsulfosuccinate, sodium 577-11-7 salt BreakThru OE Evonik Siloxanes and silicones, cetyl- 191044-49-2 444 Industries Me, di-Me BreakThru S240 Evonik Poly ether-modified trisiloxane 134180-76-0 Industries Silwett L77 Momentive Poly alkylene oxide-modified 67674-67-3 heptamethyltrisiloxane Silwett 408 Momentive Poly alkylene oxide-modified 67674-67-3 heptamethyltrisiloxane Antarox B/848 Solvay Oxirane, methyl-, polymer with 9038-95-3 oxirane, monobutyl ether Atlas G5000 Croda Oxirane, methyl-, polymer with 9038-95-3 oxirane, monobutyl ether Leofat OC- Lion Oxirane, methyl-, polymer with 181141-31-1 0503M Chemical, JP oxirane, mono-(9Z)-9-octadecenoate, methyl ether, block Surfynol 440 Air Products 2,4,7,9-tetramethyldec-5-yne- 9014-85-1 4,7-diol, ethoxylated Suitable defoamers h are all substances which can typically be used for this purpose in agrochemicals.
Preference is given to silicone oils, silicone oil formulations, magnesium stearate, phosphinic acids and phosphonic acids. Examples are Silcolapse 482 from Bluestar Silicones, Silfoam SC1132 from Wacker [dimethylsiloxanes and -silicones, CAS No. 63148-62-91, SAG 1538 or SAG 1572 from Momentive [dimethylsiloxanes and -silicones, CAS-No. 63148-62-91 or Fluowet PL 80.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 19 -Possible preservatives h are all substances which can typically be used for this purpose in agrochemicals.
Suitable preservatives are, for example, formulations comprising 5-chloro-2-methyl-4-isothiazolin-3-one [CIT; CAS No. 26172-55-41, 2-methyl-4-isothiazolin-3-one [MIT, CAS No. 2682-20-41 or 1,2-benzisothiazol-3(2H)-one [BIT, CAS No. 2634-33-51. Examples include Preventol D7 (Lanxess), Kathon CG/ICP (Rohm & Haas), Acticide SPX (Thor GmbH) and Proxel GXL (Arch Chemicals).
Suitable antioxidants h are all substances which can typically be used for this purpose in agrochemicals.
Preference is given to butylhydroxytoluene [3,5-di-tert-butyl-4-hydroxytoluene, CAS No. 128-37-01 and citric acid.
Possible colorants h are all substances which can typically 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 typically be used for this purpose in agrochemicals and which do not function as thickeners. Preference is given to inorganic particles such as carbonates, silicates and oxides, and also organic substances such as urea-formaldehyde condensates. Examples include kaolin, rutile, silicon dioxide ("finely divided silica"), silica gel and natural and synthetic silicates, and additionally talc.
The present invention further provides water-dispersible technical concentrates (TCs) based on the compositions described above, comprising - one or more anionic emulsifiers c2, - one or more nonionic emulsifiers cl), - at least one or more than one carrier material f.
The present invention likewise provides suspension concentrates (SCs) comprising - one or more anionic emulsifiers c2, - one or more nonionic emulsifiers cl, - at least one or more than one thickener g).
The present invention likewise provides ECs comprising - one or more nonionic emulsifiers cl, - at least one solvent e) Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 20 -The present invention likewise provides ECs comprising - one or more nonionic emulsifiers cl, - at least one further active agrochemical ingredient, preferably a fungicide.
The present invention likewise provides ODs comprising - one or more nonionic emulsifiers cl, - one or more anionic emulsifiers c2, - at least one solvent e) - at least one thickener g) Application .. Examples of administration forms which can be used include all the processes known as commonly used to the person skilled in the art: spraying, dipping, misting and a number of specific processes for direct treatment below or above ground of whole plants or parts (seed, root, stolons, stem, trunk, leaf), for example trunk injection in the case of trees or stem bandages in the case of perennial plants, and a number of specific indirect application processes.
The respective area- and/or object-based application rate of the crop protection compositions of a wide variety of different formulation types for control of the harmful organisms varies very greatly. In general, the application media known to the person skilled in the art to be commonly used for the respective field of use are used in the conventional amounts for this purpose, for example from several hundred litres of water per hectare in the case of standard spraying processes through a few litres of oil per hectare in the case of 'ultra low volume aircraft application down to a few millilitres of a physiological solution in the case of injection processes. The concentrations of the inventive crop protection compositions in the particular application media therefore vary within a wide range and are dependent on the respective field of use. In general, concentrations known to the person skilled in the art to be commonly used for the respective field of use are used. Preferred concentrations are from 0.01% by weight to 99% by weight, .. more preferably from 0.1% by weight to 90% by weight.
The agrochemical formulations of the invention can be deployed, for example, in the formulation forms customary for liquid preparations, either as such or after prior dilution with water, i.e., for example, as emulsions, suspensions or solutions. Application is effected by customary methods, i.e., for example by spraying, pouring or injecting.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 21 -Depending on the nature of the active ingredient possibly present in addition to prothioconazole, the formulations of the invention are useful for controlling a large number of pests and can be used either for treatment of plant crops or else for that of inanimate material and in the household.
"Pests" or "harmful organisms" are understood here to mean all kinds of pests which can be controlled or kept under control with organic crop protection active ingredients, i.e. crop protection agents, especially fungicides and mixtures of fungicides with other crop protection agents. The term "pest" therefore encompasses organisms that are harmful to plants, especially harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants. The term "control"
encompasses both curative treatment, i.e. the treatment of affected plants with a formulation of the invention, and protective treatment, i.e. the treatment of plants for protection from pest infestation.
The present invention thus also relates to the use of the formulations described herein for the control of pests, especially plant pests, and to a method of controlling harmful organisms, especially plant-damaging organisms, comprising the contacting of the harmful organisms, their habitat, their hosts, such as plants and seed, and the soil, the area and the environment in which they grow or could grow, but also of materials, plants, seeds, soil, surfaces or spaces which are to be protected from attack or infestation by organisms that are harmful to plants, with an effective amount of the formulations of the invention.
A further aspect of the invention relates to the use of the formulations described herein for protection of plants including seed, especially useful plants, from infestation by harmful organisms, especially harmful fungi. The present invention thus also relates to the use of the formulations for control of plant-damaging organisms, for example harmful fungi, insects, arachnids, nematodes and harmful plants, especially for control of harmful fungi.
The formulations of the invention can be used in crop protection, particularly as foliar, seed-dressing and soil fungicides, in a manner known per se for control of phytopathogenic fungi.
Plants which can be treated with the formulations of the invention include the following: cotton, flax, grapevine, 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 soft fruits 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), Rub iaceae sp. (for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example lemons, oranges and grapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumber), Alliaceae sp. (for example leek, onion), Papilionaceae sp. (for example peas); major crop plants, such as Gramineae sp. (for example corn, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example white cabbage, red Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 22 -cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress), Fabacae sp. (for example bean, peanuts), Papilionaceae sp. (for example soybean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, swiss chard, beetroot); sugar cane, poppy, olive, coconut, cacao, tobacco and useful plants and ornamental plants in garden and forest; and genetically modified varieties of each of these plants, and also the seeds of these plants.
Preference is given to using the formulations of the invention for treatment of wheat, barley, rye, soya, onions, corn and peanuts.
More particularly, it is possible in principle to use the formulations of prothioconazole of the invention to control all harmful fungi diseases which can also be controlled with the known formulations of prothioconazole. Depending on the particular mixing partner present in each case, the plant diseases are, for example, the following plant diseases:
Alternaria species on vegetables, oilseed rape, sugar beet, soybean, cereals, cotton, fruit and rice (e.g. A.
solani or A. alternata on potato and other plants), Aphanomyces species on sugar beet and vegetables, Ascochyta sp. on cotton and rice, Bipolaris and Drechslera species on corn, cereals, rice and lawn (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 grapevines, Botryodiplodia sp. on cotton, Bremia lactucae on lettuce, Cerospora species on corn, soybeans, rice and sugar beet (e.g. C. beticula on sugar beet), Cochliobolus species on corn, 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, Exserohdum species on corn, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumber species, Fusarium and Verticillium species (e.g. V.
dahliae) on various plants (e.g.
F. gram inearum 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 soybean and cotton, Michrodochium sp. (e.g. M
nivale on cereals), Mycosphaerella species on cereals, bananas and peanuts (M
gram inicola on wheat, M
fijiesis on banana), Phaeoisaripsis sp. on soybeans, Phakopsara sp. (e.g. P.
pachyrhizi and P. meibomiae on soybeans), Phoma sp. on soybeans, Phomopsis species on soybeans, sunflowers and grapevines (P.
viticola on grapevines, P. helianthii on sunflowers), Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grapevines, Penecilium sp. on soybeans and cotton, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on cereals, Pseudoperonospora species on hops and cucumber species (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 species on cereals, Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae on rice, Pyricularia grisea on lawn and cereals, Pythium spp. on lawn, rice, corn, cotton, oilseed rape, sunflowers, Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 23 -sugar beet, vegetables and other plants, Rhizoctonia species (e.g. R. solani) on cotton, rice, potatoes, lawn, corn, oilseed rape, potatoes, sugar beet, vegetables and other 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. Uncinula necator) on grapevines, Setosphaeria species on corn and lawn, Sphacelotheca reilinia on corn, Thievaliopsis species on soybeans and cotton, Tilletia species on cereals, Ustilago species on cereals, corn and sugar beet, and Venturia species (scab) on apple and pear (e.g. V. inaequalis on apple).
The formulations of the invention can be applied in undiluted form or diluted with water. In general, they are 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 10 000, preferably 10 to 5000 and more preferably with 50 to 24 000 parts water, based on one part of the formulation.
The present invention likewise provides an emulsion obtainable by mixing water with the liquid formulation of the invention. The mixing ratio of water to emulsion concentrate may 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 of the invention into the water. For rapid mixing of the concentrate with water, it is customary to use agitation, for example stirring. However, agitation is generally unnecessary. Even though the temperature for the dilution operation is an uncritical factor, dilutions are typically conducted at temperatures in the range from 0 C to 50 C, in particular at 10 C to 30 C or at ambient temperature.
The water used for dilution is generally tap water. The water may, however, already contain water-soluble or finely dispersed compounds which are used in crop protection, for instance nutrients, fertilizers or pesticides.
It is possible to add various kinds of oils, wetting agents, adjuvants, fertilizers or micronutrients and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) to the emulsion of the invention in the form of a premix or, if appropriate, not until shortly before use (tank-mix). These compositions may be added to the formulations of the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
The user will apply the formulation of to the invention typically from a pre-dosing system, a backpack sprayer, a spraying tank, a spraying aircraft or an irrigation system. The formulation of the invention is typically diluted to the desired application concentration with water, buffer and/or further auxiliaries, which affords the ready-to-use spray liquor or agrochemical composition of the invention. Typically, 20 to 2000 litres, preferably 50 to 400 litres, of the ready-to-use spray liquor are deployed per hectare of useful agricultural area.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 24 -The required application rates of the pure active ingredients without formulation aids depend on the intensity of pest infestation, on the development phase of the plants, on the climatic conditions of the site of use and on 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, more preferably from 0.01 to 1 kg and most preferably from 50 to 500 g of active ingredient per hectare, active ingredient here meaning prothioconazoles plus possible further active ingredients.
The generally diluted formulations of the invention are applied mainly by spraying, especially spraying of the leaves. The application can be conducted by spraying techniques known to those skilled in the art, for example using water as carrier and amounts of spray liquors of about 50 to 1000 liters per hectare, for example from 100 to 00 liters per hectare.
The novel prothioconazole-containing formulations have advantageous properties in respect of the treatment of plants; more particularly, they feature good use properties, high stability and high fungicidal activity.
The invention is illustrated in detail by the examples but is not restricted thereto.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 25 -Examples Feedstocks used:
The terms used in the examples below have the following meanings:
prothioconazole PTZ (Bayer AG) Atlox Metasperse 500 Croda, acrylate-based copolymer Vitamin E Sigma-Aldrich, alpha-tocopherol Pluronic PE 10500 propylene oxide/ethylene oxide (PO-E0) block polymer (BASF) Rhodopol 23 xanthan derivative (Solvay) Silcolapse 426 silicone defoamer (Solvay) Proxel GXL preservative (biozide, Proxel) Lucramult C030 non-ionic emulsifier, ethoxylated castor oil, Levaco Chemicals, DE
5AG1572 aqueous emulsion of polydimethylsiloxane Momentivet Genagent 4296 dimethyldecanamide (DAA), Clariant Hallcomidt 1025 N,N-dimethyl 9-decenamide, CAS number: 1356964-77-6 General preparation of an aqueous suspension concentrate (SC):
First of all, water is initially charged at room temperature. The active ingredients and the other components are added (in no particular order) with stirring. The mixture is pre-comminuted in a colloid mill, followed by wet grinding using, for example, a bead mill. Finally, the organic thickener is added.
General preparation of an emulsion concentrate (EC) The organic solvent is initially charged. All other components are then added (in no particular order) with stirring. Stirring is continued until a clear solution is formed.
Determination of 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(111-1,2,4-triazol-l-Apropan-2-ol (compound III) in formulations The cotton samples were extracted with acetonitrile (containing 20 mg/1 cysteine hydrochloride) and deep-frozen before the analysis.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 26 -2-(1-Chlorocyclopropy1)-1-(2-chloropheny1)-3-(1H-1,2,4-triazol-1-y0propan-2-ol is separated from the formulation constituents on a reverse phase column using an isocratic eluent.
After MS/MS detection, the quantitative evaluation is conducted 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 In each case, the samples are, unless indicated otherwise, exposed to light and stored for 4 weeks.
Example 1: Recipe 1 comparison Component % by weight % by % by weight weight Prothioconazoles 12.75 12.75 12.75 Tebuconazoles 12.75 12.75 12.75 Lucramul CO 30 7.5 7.5 7.5 5AG1572 0.1 0.1 0.1 Genagen 4296 59.38 49.38 54.38 Hallcomid 1025 10.0 alpha-Tocopherol 5.0 (according to the invention) Three dilutions of each formulation containing 62.5 g/l, 2 g/1 and 0.2 g/1 PTZ
were produced. The actual PTZ concentration in the concentrated formulations is 125 g/l.
Each of the 3 dilutions was sprayed onto 10 cotton squares stretched out on cardboard, with spraying of only 6 cotton squares as control.
After the spraying, the pieces of cardboard with the cotton squares were placed under a sunlamp. 5 each of the cotton squares were analysed 1 h and 6 h after the spraying, with analysis of the cotton samples by the method described above. The analytes (PTZ and desthio) were determined via HPLC-MS.
Date recue/Date received 2023-03-17 BCS203070 Foreign Countries Sr/Ho 2023-03-08

- 27 -The result of the evaluation is shown in Figure 1 (Prosare = Ex. 1 comparison).
As the result shows, for all formulations and all dilutions, the degradation of PTZ to desthio is time-dependent. The conversion rates on the cotton samples increased from 1 h after spraying to 6 h after spraying. The conversion rate is likewise dependent on the PTZ concentration, with lower concentrations having a higher conversion rate. The lowest PTZ degradation was detected in the solution with 62.5 g/1 PTZ, while the 0.2 g/1 dilution showed the highest degradation.
Particularly good stabilization of PTZ on the surfaces was shown by vitamin E
(tocopherol).
Date recue/Date received 2023-03-17

Claims (6)

Claims

1. Use of decenamide and/or tocopherols for stabilization of 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 of the preceding claims, characterized in that thiones from agrochemical formulations are stabilized on surfaces.

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

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