Solvent-free formulations of low-melting active ingredients

Abstract

The present invention relates to solvent-free aqueous suspension concentrates and solvent-free solid, water-dispersible formulations containing one or more low-melting active substances and to a process for their preparation. The formulations according to the invention are suitable for use in the field of plant protection.

Description

[0001] This application is a divisional application of Chinese patent application No. 201780021831.9 entitled "Solvent-free formulation of low-melting-point active ingredient", which was filed on February 22, 2017, under the PCT international application PCT / EP2017 / 053987 and entered the Chinese national phase on September 29, 2018.

[0002] This invention relates to solvent-free aqueous suspension concentrates and solvent-free solid aqueous dispersions containing one or more low-melting-point active ingredients, and to methods for their preparation. Formulations according to the invention are applicable to the field of plant protection.

[0003] In principle, active ingredients can be formulated in many different ways, and the characteristics of the active ingredient and the properties of the formulation may present problems in terms of manufacturability, stability, usability, and efficacy. Furthermore, some formulations are more advantageous than others for economic and environmental reasons.

[0004] The advantage of water-based formulations is that they generally require a smaller proportion of organic solvents, if any.

[0005] On the other hand, high concentrations of active ingredient formulations are generally required because higher concentrations offer numerous advantages. For example, high-concentration formulations require less packaging than low-concentration formulations. Expenses in production, transportation, and storage are also correspondingly reduced. Furthermore, for example, the preparation of sprays for agricultural applications is simplified by using smaller quantities of crop protection compositions, which, for instance, must be handled in operations such as dispersion and mixing. Moreover, water-based concentrates generally not only have higher concentrations than formulations containing organic solvents but are also more environmentally friendly because they are solvent-free. A similar high-concentration formulation is a water-dispersible granule (WG). Therefore, from both economic and environmental perspectives, water-dispersible granules and suspension concentrates (SC) are preferred.

[0006] However, some substances, such as herbicide safeners, cannot be added directly to water due to their low and wide melting point range and amorphous structure. Therefore, they must first be dissolved in or formulated in an organic solvent. In this case, they are formulated as, for example, organic dispersants, aqueous emulsions, suspensions, capsule suspensions, or emulsion concentrates, where the low-melting-point active ingredient is in dissolved or emulsified form. The disadvantage here is that it is impossible to obtain aqueous dispersants by adding organic solvents; or, the resulting aqueous emulsions or suspensions are more unstable during storage and generally have lower concentrations compared to pure aqueous dispersants. When processing the parent drug to obtain water-dispersible granules, in the case of mineral oils (e.g., Solvesso from ExxonMobil) commonly used as solvents... ®200 ND), up to 20% by weight is retained in the final product.

[0007] For commercially available water-dispersible granules, quality impairment may occur. These include: insufficient dispersibility / suspension, unacceptable residue on sieves, insufficient free flowability / compaction of lumps, clogging of filters and nozzles, or persistent contamination of spraying equipment.

[0008] In summary, liquid formulations containing pyrazosulfuron or quinalazine as herbicide safeners, as known in the prior art, are emulsion concentrates or oil dispersants. Pure aqueous dispersants or granules of these herbicide safeners are, to date, unknown.

[0009] Specifically, herbicide safeners (such as pyrazosulfuron or quinalazine) are typically in the form of esterified acids, which can be obtained as solidified melts with a melting point range in industrial-grade quality. Only powders obtained through controlled crystallization purification are permitted to be added directly to the aqueous phase. However, such purification is not only technically complex and expensive; the particles are also unstable during grinding and therefore tend to adhere.

[0010] The prior art discloses high-concentration aqueous suspension concentrates, such as sulfur (EP-A-0220655) and metamitron (EP-A-0620971), or mixtures of formaldehyde condensation products, preferably lignin sulfonates and wetting agents.

[0011] WO-A 91 / 07874 discloses formulations containing pyrazole herbicides. However, the aqueous dispersion concentrate described therein contains 77% by weight of an organic solvent, and is therefore a suspension emulsion.

[0012] US-P 5,785,976 and WO-A 03 / 034822 describe melt dispersants, but the substances here are in a nanoscale amorphous state. Here, the pre-concentrate is cooled in a shock-like manner, thus a controlled, uniform crystalline dispersion is not possible. Furthermore, grinding with other dispersed active ingredients is impossible because the particles adhere to each other.

[0013] The disadvantage of formulations known by existing technology (whether in the form of suspension concentrates or water-dispersible granules) is that large amounts of organic solvents, which are undesirable to the environment and users, must be used to dissolve the safety agent.

[0014] Therefore, there remains a need for new formulations in the form of water-based dispersants that contain low-melting-point herbicidal safe agents with a melting point range and are produced without the need for organic solvents, as well as solid water-dispersible granules that can be prepared therefrom. Furthermore, these water-dispersible granules should not agglomerate or adhere.

[0015] Therefore, the object of the present invention is to provide solvent-free aqueous formulations (SC) and solid water-dispersible formulations (WG) based on low-melting-point herbicidal safe agents having a low melting point range.

[0016] The present invention provides a method for preparing a solvent-free aqueous formulation, characterized in that, in the first step, at least one active agricultural chemical component a) having a melting point range of 50°C to 80°C is first melted, and then the melt is added to water under stirring, wherein the water contains at least one ionic and / or nonionic dispersant b), and in the second step, the mixture is cooled to below the melting point of the active component.

[0017] In the method according to the invention, the water temperature is preferably from 0°C to 40°C, more preferably from 5°C to 20°C.

[0018] Preferably, in the second step of the method according to the invention, the mixture is stirred during cooling for at least 5 minutes, preferably 5 minutes to 24 hours, more preferably 10 minutes to 15 hours, under the condition that at least 90% by weight of pyrazole-propargyl crystals can be detected under a microscope, based on the pyrazole-propargyl used. In this case, the crystalline active ingredient should no longer have any amorphous structure.

[0019] In a preferred embodiment (I) of the method of the present invention, in the first step, component a) is added to an aqueous solution containing an ionic dispersant b1), a carrier material c1), and a filler c2). Preferably, for this embodiment (I), in the third step, the crystallized product is ground so that at least 50% of the particles have a size of 1 to 5 µm (d50, volumetric particle size). The resulting formulation is the parent drug (TC).

[0020] Similarly, nonionic dispersant b2) and ionic dispersant b1) can be added to the method according to the invention.

[0021] The present invention also provides a parent drug (TC) obtained by the method of the present invention.

[0022] Preferably, water is removed from the TC after the third step of the method (I) according to the invention. More preferably, water is removed by means of a fluidized bed method. The product thus obtained is a water-dispersible granule (WG). Therefore, the present invention also provides a water-dispersible granule (WG) obtained by the method of the present invention.

[0023] The fluidized bed method is the standard method for producing water-dispersible granules (WG). The principle involves injecting a portion of the concentrate into a fluidized bed chamber. This causes the aqueous components present within to dry and separate at high temperatures. This is accomplished by injecting a hot gas, such as hot nitrogen. The dissolved or dispersed material eventually agglomerates into solid granules.

[0024] In another preferred embodiment (II) of the method of the present invention, in the first step, component a) is added to an aqueous solution containing ionic dispersant b1), nonionic dispersant b2) and carrier material c1). Preferably, for this embodiment (II), in the third step, the crystallized product is milled so that at least 50% of the particles have a size of 1 to 5 µm (d50, volumetric particle size), and an organic thickener d1) is added after milling. The formulation obtained by embodiment (II) is a water-dispersible suspension concentrate (SC).

[0025] The present invention also provides a water-dispersible suspension concentrate (SC) obtained by the method of the present invention.

[0026] Grinding can be performed by methods known in the art, such as by wet grinding of the components in a ball mill (e.g., a discontinuous ball mill or a continuous ball mill) or a colloid mill (e.g., a toothed colloid mill).

[0027] In the formulations according to the invention, the proportion of water can typically be from 25% to 98% by weight, preferably from 35% to 85% by weight. Unless otherwise defined, the unit "% by weight" (weight percentage) herein and throughout the specification refers to the relative weight of a specific component based on the total weight of the formulation or a portion of the concentrate. The formulation may typically contain residues of organic solvents from 0% to 5% of the additive. In the context of the invention, "solvent-free" means that component a) is added in a solvent-free liquid form and, in the finished dispersant, forms undissolved crystals (dispersant) rather than dissolved.

[0028] Suitable active ingredients a) are all active agricultural chemicals with a melting point range of 50°C to 80°C in the solid state.

[0029] Examples of active ingredients a) with melting points ranging from 50°C to 80°C include: Anilofos, acephate, benfluralin, bifenthrin, bupirimate, butralin, chloroaceticacid, cyfluthrin, cypermethrin, demeton-S-methylsulphone, dimethametryn, dimethoate, dioxabenzofos, diphenylamine, dithiopyr, dodemorph Acetate, esfenvalerate, etalfluralin, ethofumesate, fenazaquin, finitropan, fenoxycarb, fenuron-TCA, fenvalerate, fluoroglycofen-ethyl, flupyradifuron, flurazole, flurochloridone, fluroxypyr-meptyl, flusilazole, furalaxyl, haloxyfop-etotyl, haloxyfop-methyl, imazalil, ioxynil octanoate, isoprothiolane, metalaxyl, methomyl, methomyl, monocrotophos, nitrapyrin, nitrothal-isopropyl, penconazole, pendimethalin, permethrin, propamocarb hydrochloride, propaquizafop, pyrazophos, quizalofop-P-tefuryl, resmethrin, trichloroacetic acidacid), tetramethrin, thiofanox, triflumizole, pyridaphenthion, 2-phenylphenol, dimethylvinphos, beta-cypermethrin, famur, clodinafop-propargyl, cloquintocet-mexyl, triazamate, tebufenpyrad, pyrimidifen, aldrin, bromophos, dialifos, pyriminobac-methyl, mefenpyr-diethyl, benzoylprop, benzoylprop-ethyl, binapacryl, camphechlor, chlorfenethol, chlorfenprop, chlorfenprop, chlorfenprop. lorfenprop-methyl, chlorphoxim, crufomate, cyometrinil, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, dimetilan, dinobuton, fenson, fenthiaprop, fenthiaprop-ethyl, fluenetil, glyodine, 2-isovalerylindane-1,3-dione, methoxyphenone, 2-methoxyethylmercury Herbicides including chloride, nitrofen, indanofan, acequinocyl, ipsdienol and (S)-cis-verbenol, fenoxanil, pyraclostrobin, trifloxystrobin, and cyflufenamid.Gamma-cyhalothrin, proquinazid, 2,6-diisopropylnaphthalene, and isothiazine.

[0030] The preferred active ingredient a) is a compound in ester form and has a melting point range. Active ingredients selected from herbicide safeners are particularly preferred. Pyrazosulfuron or quinalazine are very particularly preferred, and pyrazosulfuron is especially preferred. These formulations are preferably used on cereal crops.

[0031] In the formulation according to the invention, the proportion of the active ingredient (component a) is from 0.5% to 40% by weight, preferably from 0.5% to 30% by weight, more preferably from 0.5% to 15% by weight, and most preferably from 1% to 8% by weight.

[0032] Suitable anionic dispersants (b1) such as emulsifiers, surface wetting agents, and dispersants are, for example, alkali metal salts, alkaline earth metal salts, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof, such as alkyl sulfonates or alkyl phosphates and alkyl aryl sulfonates or alkyl aryl phosphates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecylbenzene and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates, or sulfosuccinamides. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, or sulfates of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol ethoxylates or alkylphenol ethoxylates. Also suitable are this group of anionic emulsifiers: alkali metal salts, alkaline earth metal salts, and ammonium salts of polystyrene sulfonic acid; salts of polyvinyl sulfonic acid; salts of alkylnaphthalene sulfonic acid; salts of alkylnaphthalene sulfonic acid-formaldehyde condensation products; salts of naphthalene sulfonic acid condensation products; phenol sulfonic acid; and formaldehyde. An example is calcium dodecylbenzenesulfonate, such as Rhodocal. ® 70 / B (Solvay), Phenylsulfonat CA100 (Clariant), or isopropylamine dodecylbenzenesulfonate, such as Atlox ® 3300B (Croda).

[0033] Other typical examples include Phenylsulfonat CA (calcium dodecylbenzenesulfonate) and Soprophor. ® Products (optional esterified derivatives of triphenylphenylphenol ethoxylate), Emulsogen ®3510 (alkylated EO / PO copolymer), Emulsogen ® EL 400 (ethoxylated castor oil), Tween ® Product (fatty acylated sorbitol ethoxylate), Calsogen ® AR 100 (calcium dodecylbenzenesulfonate). Preferably alkylated aromatic sulfonates (such as calcium phenylsulfonate and / or Calsogen). ® AR 100) with alkylated copolymers of ethylene oxide and propylene oxide (such as Emulsogen) ® Compositions of 3510. Particularly preferred are dodecylbenzene sulfonate (Calsogen). ® AR 100) with alkylated copolymers of ethylene oxide and propylene oxide (such as Emulsogen) ® The composition of 3510).

[0034] Other examples of anionic emulsifiers of naphthalene sulfonate (b1) include Galoryl ® MT 800 (Sodium dibutylnaphthalenesulfonate), Morwet ® IP (sodium diisopropylnaphthalenesulfonate) and Nekal ® BX (alkyl naphthalene sulfonate). An example of anionic surfactant derived from the condensation of naphthalene sulfonate and formaldehyde is Galoryl. ® DT 201 (a hydroxy polymer of naphthalenesulfonic acid with formaldehyde and sodium methylphenol), Galoryl ® DT 250 (a condensate of phenol sulfonate and naphthalene sulfonate), Reserve ® C (a condensate of phenol sulfonate and naphthalene sulfonate) or Morwet ® D-425, Tersperse ® 2020. Preferred are 1,2-dibutyl-substituted naphthalene sulfonates or 1,2-diisobutyl-substituted naphthalene sulfonates, such as products like Galoryl. ® MT 800 (CFPI-Nufarm) and Nekal ® BX (BASF). Other typical surfactants include Soprophor. ® 3D33, Soprophor ® 4D384, Soprophor ® BSU, Soprophor ® CY / 8 (Solvay) and Hoe ® S3474, and Sapogenat ®Products in T form (Clariant), such as Sapogenat ® T 100.

[0035] Useful nonionic dispersants (b2) include emulsifiers, wetting agents, surfactants, and dispersants, including standard surfactants present in active agrochemical formulations. Examples include ethoxylated nonylphenol, reaction products of straight-chain or branched alcohols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, alkoxylated straight-chain and branched saturated and unsaturated alcohols (e.g., butoxylated polyethylene glycol-polypropylene glycol), reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycol and polypropylene glycol, as well as fatty acid esters, fatty acid polyethylene glycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols, such as tristyrylphenol ethoxylates having an average of 16 ethylene oxide units per molecule, and ethoxylated and propoxylated arylalkylphenols, and sulfated and phosphorylated arylalkylphenol ethoxylates or ethoxylates and propoxylates. Tristyrylphenol alkoxylates and fatty acid polyethylene glycol ether esters are particularly preferred. Tristyrylphenol ethoxylate, tristyrylphenol ethoxypropoxylate, and castor oil polyethylene glycol ether ester are particularly preferred, used alone or in combination in each case. Also useful are additives, such as surfactants or fatty acid esters, which contribute to improved bioavailability. Suitable nonionic emulsifiers (b2) are, for example, Soprophor. ® 796 / P, Lucramul ® CO30, Lucramul ® HOT, Lucramul ® PSI 100 or Synperonic ® T304.

[0036] Suitable nonionic dispersants (b2) can also be selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymers of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymers of vinyl chloride and vinyl acetate, and partially hydrolyzed vinyl acetate, phenolic resins, and modified cellulose types, such as Luviskol. ® (Polyvinylpyrrolidone), Mowiol ® (Polyvinyl alcohol) or modified cellulose. Polyvinylpyrrolidone type is preferred, especially low molecular weight types such as Luviskol. ® K30 or Sokalan ® K30.

[0037] Other useful nonionic emulsifiers (b2) from diblock and triblock copolymers of epoxides are, for example, compounds based on ethylene oxide and propylene oxide, with an average molecular weight of 200 to 10,000, preferably 1,000 to 4,000 g / mol, wherein the mass proportion of polyethoxylated blocks varies from 10 to 80%, such as Synperonic. ® PE series (Uniqema), Pluronic ® PE series (BASF), VOP ® 32 or Genapol ® PF series (Clariant).

[0038] In the parent drug according to the invention, the required proportion of the anionic dispersing agent (b1) is 2% to 35% by weight, preferably 3% to 30% by weight, preferably 5% to 25% by weight, and most preferably 10% to 20% by weight.

[0039] In the suspension concentrate according to the invention, the required proportion of the anionic dispersant b1) is 0.1% to 10% by weight, preferably 0.2% to 7% by weight, and most preferably 0.3% to 4% by weight.

[0040] In the suspension concentrate according to the invention, the required proportion of nonionic dispersant b2) is 1% to 15% by weight, preferably 2% to 10% by weight and most preferably 2.5% to 8% by weight.

[0041] The present invention also provides a solvent-free, water-dispersible technical material (TC) comprising... - One or more active ingredients a) Its melting point ranges from 50 to 80°C. - One or more anionic emulsifiers (b1). - One or more nonionic emulsifiers (b2). - At least one or more carrier materials (c1) and - At least one filler (c2).

[0042] The present invention also provides a solvent-free water-dispersible suspension concentrate (SC) comprising... - One or more active ingredients a) Its melting point ranges from 50 to 80°C. - One or more anionic emulsifiers (b1). - One or more nonionic emulsifiers (b2). - Carrier material c1) and - At least one or more thickeners (d).

[0043] Suitable carrier material c1) is selected from highly absorbent carriers with an absorption capacity of at least 200 g dibutyl phthalate per 100 g carrier material.

[0044] The preferred high-absorbency carrier (c1) is silica, such as Sipernat. ® Products (synthesized highly absorbent precipitated silica) and fumed silica (Aerosil) ® (Product). Preferred precipitated silica.

[0045] According to the present invention, the proportion of filler (c1) required in TC is 0.1% to 10% by weight, preferably 0.3% to 8% by weight and more preferably 1% to 7% by weight.

[0046] According to the present invention, the proportion of filler c1) required in SC is 0.05% to 10% by weight, preferably 0.1% to 8% by weight, preferably 0.3% to 5% by weight and more preferably 0.5% to 3% by weight.

[0047] According to the present invention, the filler c2) in WG or TC is selected from: minerals; carbonates, sulfates, and phosphates of alkaline earth metals and alkali metals, such as calcium carbonate; polymeric carbohydrates; framework silicates, such as precipitated silica with low absorbency, and natural framework silicates, such as kaolin. A typical representative of suitable filler c2) is, for example, Agsorb. ® LVM ® -GA (Green Slope Stone), Harborlite ® 300 (pearlite), Collys ® HV (modified starch), Omya ® -Kreide (calcium carbonate), kaolin ® Tec 1 (kaolin, hydrated aluminum silicate), Steamic ® OOS (talc, magnesium silicate). For c2), natural framework silicates and calcium carbonate products such as Omya are preferred in this paper. ® Chalk (calcium carbonate), kaolin Tec 1 ® (Kaolin) and Harborlite ® 300 (pearlite), with a preference for naturally sourced framework silicates such as kaolin. ® Tec ® 1 (kaolin, hydrated aluminum silicate) and Harborlite ® 300 (pearlite). For c2), kaolin and calcium carbonate are particularly preferred.

[0048] According to the present invention, the proportion of filler (c2) required in TC or WG is 2% to 35% by weight, preferably 3% to 30% by weight, preferably 5% to 25% by weight and more preferably 10% to 20% by weight.

[0049] Useful thickeners (d) include organic thickeners (d1) and inorganic thickeners (d2).

[0050] Useful organic thickeners (d1) include organic natural or biotechnologically modified or organically synthesized thickeners. A common synthetic thickener is Rheostrux. ® (Croda) or Thixin ® Or Thixatrol ® Elementis series. These are typically based on acrylates. Typical organic thickeners are based on xanthan gum or cellulose (e.g., hydroxyethyl or carboxymethyl cellulose) or combinations thereof. Other typical representatives are based on lignin (e.g., lignin sulfonates, Borresperse). ® NA, REAX ® 88 or Kraftsperse 25 S). A xanthan gum-based, naturally modified thickener is preferred. A typical example is, for instance, Rhodopol. ® (Solvay) and Kelzan ® (Kelco Corp.), and Satiaxane ® (Cargill).

[0051] According to the present invention, the proportion of organic thickener d1 in SC 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.

[0052] Suitable inorganic thickeners (d2) are, for example, modified natural silicates such as chemically modified bentonite, lithium montmorillonite, palygorskite, montmorillonite, 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).

[0053] According to the present invention, the proportion of inorganic thickener d2 in SC 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.

[0054] A mixture of thickeners d1) and d2) is preferred. The use of only organic thickener d1) is particularly preferred. Those thickeners d1) based on xanthan gum (such as Rhodopol from Solvay) are very particularly preferred. ® G).

[0055] In addition to component a), the optional and suitable active agricultural chemical components (component e) may be herbicides, fungicides, insecticides, plant growth regulators, safeners, etc.

[0056] The active antifungal ingredients include, for example, 1) ergosterol biosynthesis inhibitors, such as (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) Ipconazole (1.013), Metconazole (1.014), Myclobutanil (1.015), Paclobutrazol (1.016), Prochloraz (1.017), Proiconazole (1.018), Prothioconazole (1.019), Pyrisoxazole (1.020), Spiroxamine (1.021), Tebuconazole (1.022), Tetraconazole (1.023), Triadimenol (1.024), Tridemorph (1.025) Triticonazole, (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol (1.029) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol, (1.031) (2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolane-2-yl}methyl)-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolane-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethyleneoxy-2-yl]methyl}-1H-1,2,4-triazole-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethyleneoxy-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethyleneoxy-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)but-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethyleneoxy-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxy-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethylene oxide-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazol-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylthioalkyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethylene oxide-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylthioalkyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethyleneoxy-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylthioalkyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)ethyleneoxy-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methyliminocarbamate, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]thioalkyl}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)thioalkyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyliminocarboxamide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]thioalkyl}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarbamate, (1.073) N'-(4-{3-[(difluoromethyl)thioalkyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarboxamide, (1.074) N'-[5-bromo-6-(2,3-dihydro-1H-indene-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methyliminocarboxamide, (1.075) N'-{4-[(4,5-dichloro-1,3-thiazolyl-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methyliminocarboxamide, (1.076) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.081) mefentrifluconazole, (1.082) ipfentrifluconazole.

[0057] 2) Inhibitors of respiratory chain complex I or II, such as (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furamettapyr, (2.009) isofetamid, (2.010) isopyrazam (trans epimeric enantiomers 1R, 4S, 9S), (2.011) Pyrazothiamethoxam (trans-episode enantiomers 1S, 4R, 9R), (2.012) Pyrazothiamethoxam (trans-episode racemic mixtures 1RS, 4SR, 9SR), (2.013) Pyrazothiamethoxam (a mixture of cis-episode racemic mixtures 1RS, 4SR, 9RS and trans-episode racemic mixtures 1RS, 4SR, 9SR), (2.014) Pyrazothiamethoxam (cis-episode enantiomers 1R, 4S, 9R), (2.015) Pyrazothiamethoxam (cis-episode enantiomers 1S, 4R, 9S), (2.016) Pyrazothiamethoxam (cis-episode racemic mixtures 1RS, 4SR, 9RS), (2.017) Penflufen, (2.018) Penthiophanate-methyl (2.019), Pydiflumetofen (2.020), Pyraziflumid (2.021), Sedaxane (2.022), 1,3-Dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl)-1H-pyrazole-4-carboxamide (2.023), 1,3-Dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1H-pyrazole-4-carboxamide (2.024) 1,3-Dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-Methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)diphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-Fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl)-1H-pyrazole-4-carboxamide, (2.028) 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1H-pyrazole-4-carboxamide, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1H-pyrazole-4-carboxamide, (2.030) 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indene-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-Difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methylenenaphthalene-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methylenenaphthyl-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxypropyl-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041)042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-thiocarboxamide, (2.049) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-Cyclopropyl-N-(2-Cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-Cyclopropyl-N-(2-Cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-Cyclopropyl-N-(2-Cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide.

[0058] 3) Inhibitors of respiratory chain complex III, such as (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) Fluoxastrobin (3.013), Kresoxim-methyl (3.014), Metominostrobin (3.015), Orysastrobin (3.016), Picoxystrobin (3.017), Pyraclostrobin (3.018), Pyrametostrobin (3.019), Pyraoxystrobin (3.020), Trifloxystrobin (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylene]amino]oxy}methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonon-7-yl 2-methylpropionate, (3.026) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-carbamoyl-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) methyl 5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate.

[0059] 4) Mitosis and cell division inhibitors, such as (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-Chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.016) 4-(2-Bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.017) 4-(2-Bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.022)024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine.

[0060] 5) Compounds with multi-site activity, such as (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper sulfate (2+), (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) mancozeb, (5.015) Metiram, (5.016) Zinc metiram, (5.017) Copperoxine, (5.018) Propineb, (5.019) Sulfur and sulfur preparations including calcium polysulfides, (5.020) Thiram, (5.021) Zinc zineb, (5.022) Ziram, (5.023) 6-Ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrole[3',4':5,6][1,4]disulfide[2,3-c][1,2]thiazolyl-3-carboxynitrile.

[0061] 6) Compounds that can trigger host defense, such as (6.001) acibenzolar-S-methyl, (6.002) isothiazine, (6.003) probenazole, and (6.004) tiadinil.

[0062] 7) Inhibitors of amino acid and / or protein biosynthesis, such as (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, and (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinoline-1-yl)quinoline.

[0063] (8) ATP production inhibitors, such as (8.001) silthiofam.

[0064] 9) Cell wall synthesis inhibitors, such as (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl) Prop-2-en-1-one.

[0065] 10) Inhibitors of lipid and membrane synthesis, such as (10.001) propamocarb, (10.002) propamocarb hydrochloride, and (10.003) tolclofos-methyl.

[0066] 11) Inhibitors of melanin biosynthesis, such as (11.001) tricyclazole, (11.002) 2,2,2-trifluoroethyl{3-methyl-1-[(4-methylbenzoyl)amino]but-2-yl}carbamate.

[0067] 12) Nucleic acid synthesis inhibitors, such as (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, and (12.004) metalaxyl-M.

[0068] 13) Signal transduction inhibitors, such as (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, and (13.006) vinclozolin.

[0069] 14) Compounds that can act as uncoupling agents, such as (14.001) fluazinam and (14.002) meptyldinocap.

[0070] 15) Other compounds, such as (15.001) abscisic acid, (15.002) bethoxazin, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.011) flutianil, (15.012) fosetyl-aluminium, (15.013) Fosetyl-calcium (15.014), Fosetyl-sodium (15.015), Methyl isothiocyanate (15.016), Metrafenone (15.017), Mildiomycin (15.018), Natamycin (15.019), Nickeldimethyldithiocarbamate (15.020), Nitrothal-isopropyl (15.021), Oxamocarb (15.022), Oxatispiprolin (15.023), Oxyfenthiin (15.024), Pentachlorophenol and its salts (15.025) Phosphate and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone (chlazafenone) (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazo-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl] acetone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazolyl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetone, (15.033) 2-(6-benzylpyridin-2-yl)quinazolin, (15.034) 2,6-dimethyl-1H,5H-[1,4]disulfide[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]acetone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]acetone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazolyl)piperidin-1-yl]acetone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazolin, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazolyl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethane sulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazolyl-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethane sulfonate, (15.041) 2-{2-[(7,8-difluoro-2-methylquinoline-3-yl)oxy]-6-fluorophenyl}prop-2-ol, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinoline-3-yl)oxy]phenyl}prop-2-ol, (15.043) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazolyl-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethane sulfonate, (15).044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazolyl-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenylmethane sulfonate, (15.045) 2-Phenylenol and its salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1-yl)quinoline, (15.047) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1-yl)quinoline, (15.048) 4-Amino-5-fluoropyrimidin-2-ol (tautomer form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butyric acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene 2-sulfonylhydrazine, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-Fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazopentenylene, (15.055) But-3-yn-1-yl{6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino]oxy}methyl]pyridin-2-yl}carbamate, (15.056) (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.057) Phenolicazine-1-carboxylic acid, (15.058) Propyl 3,4,5-trihydroxybenzoate, (15.059) Quinolin-8-ol, (15.060) Quinolin-8-ol sulfate (2:1), (15.061) {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino]oxy}methyl]pyridin-2-yl}tert-butyl carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one. The active insecticidal ingredient is, for example: . (1) Acetylcholinesterase (AChE) inhibitors, such as carbamates, including alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, and furathiocarb. ), isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb; or organophosphates, such as acephate, azamethiphos, and ethyl glutathione. Phosphorus (azinphos-ethyl), azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dichlorvos Crotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, O-(methoxyaminothio-phosphoryl)salicylic acid isopropyl ester,Oxazoline (isoxathion), malathion, mecarbam, methamidophos, methidathion, mevinphos, monocotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim Oxim), pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion.

[0071] (2) GABA-controlled chlorine channel antagonists, such as cyclodiene organochlorines, such as chlordane and endosulphan, or fiproles, such as ethiprole and fipronil.

[0072] (3) Sodium channel modulators / voltage-dependent sodium channel blockers, such as pyrethroids, including acridine, allethrin, d-cis-trans allethrin, and d-trans allethrin. Allethrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin Cyphenothrin (1R-trans isomers), deltamethrin, empenthrin (EZ-1R isomers), esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin (1R-trans isomers). [isomer], d-propargylpyrene (prallethrin), pyrethrins (pyrethrum), resmethrinSilafluofen, tefluthrin, tetramethrin, tetramethrin[(1R) isomers], tralomethrin, and transfluthrin, or DDT or methoxychlor.

[0073] (4) Nicotinic acetylcholine receptor (nAChR) agonists, such as neonicotinoids, such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulphoxaflor or flupyradifurone.

[0074] (5) Nicotinic acetylcholine receptor (nAChR) allosteric activators, such as spinosomycin, such as spintoram and spinosad.

[0075] (6) Chlorine channel activators, such as avermectins / milbemycins, such as abamectin, emamectin-benzoate, lepimectin, and milbemycin.

[0076] (7) Juvenile hormone analogues, such as hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxifen.

[0077] (8) Active ingredients with unknown or non-specific mechanisms of action, such as alkyl halides like methyl bromide and other alkyl halides; or chloropicrin or thiocyanate or borax or tartaric acid.

[0078] (9) Selective antifeedants, such as pymetrozine or flonicamid.

[0079] (10) Mite growth inhibitors, such as clofentezine, hexythiazox, diflovidazin, or etoxazole.

[0080] (11) Microbial disruptors of insect intestinal membranes, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and BT crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1.

[0081] (12) Inhibitors of oxidative phosphorylation, ATP interfering agents, such as diafenthiuron, or organic compounds such as azocyclotin, cyhexatin and fenbutatin oxide; or propargite or tetradifon.

[0082] (13) Oxidative phosphorylation uncoupling agents that interrupt the H proton gradient, such as chlorfenapyr, 4,6-dinitro-o-cresol (DNOC) and sulphluramid.

[0083] (14) Nicotinic acetylcholine receptor antagonists, such as bensultap, cartap hydrochloride, thiocyclam and thiosultap-sodium.

[0084] (15) Chitin biosynthesis inhibitors, type 0, such as bistrifluron, chlofluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron.

[0085] (16) Chitin biosynthesis inhibitors, type 1, such as buprofezin.

[0086] (17) Ecliptic disruptors for Diptera, such as cyromazine.

[0087] (18) Ecdysone receptor agonists, such as chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0088] (19) Octopus amine receptor agonists, such as amitraz.

[0089] (20) Complex III electron transfer inhibitors, such as hydramethylnon, acequinocyl, or fluacrypyrim.

[0090] (21) Complex I electron transfer inhibitors, such as METI acaricides, such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, and tebufenpyrad, as well as tolfenpyrad or rotenone (Derris).

[0091] (22) Voltage-gated sodium channel blockers, such as indoxacarb or metaflumizone.

[0092] (23) Acetyl-CoA carboxylase inhibitors, such as tetronic acid derivatives and tetramic acid derivatives, such as spirobudiclofen, spirodiclofen, spiromesifen and spirotetramat. (24) Complex IV electron transfer inhibitors, such as phosphine, such as aluminum phosphide, calcium phosphide, phosphine and zinc phosphide or zinc cyanide.

[0093] (25) Complex II electron transfer inhibitors, such as cyenopyrafen and cyflumetofen.

[0094] (28) Ryanodine receptor effectors, such as diamides, such as chlorantraniliprole, cyantraniliprole, flubendiamide and tetrachloroantraniliprole.

[0095] Other active insecticides with unknown or unclear mechanisms of action include afidopyropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, cyclaniliprole, cycloxaprid, and cyhalodiamide. ), dicloromezotiaz, dicofol, diflovidazin, fometoquin, fluazaindolizine, fluensulfone, flufenerim, flufenoxystrobin, flufiprole, fluhexafon, fluopyram, fluralaner, fluxametamide, fufenozide, guadipyr Heptafluthrin, imidaclothiz, iprodione, lotilaner, meperfluthrin, paichongding, pyflubumide, pyridalyl, pyrifluquinazon, pyriminostrobin, sarolaner, tetramethylfluthrin, tetraliprole, tetrachlorantraniliprole, tioxazafen, thiofluoximate, triflumezopyrim, and iodomethane; and additionally based on Bacillus thuringiensis. The formulation of firmus (I-1582, BioNeem, Votivo), and the following known active compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-Triazol-5-amine (known in WO2006 / 043635), {1'-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indol-3,4'-piperidin]-1(2H)-yl}(2-chloropyridin-4-yl)methyl ketone (known in WO2003 / 106457), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known in WO2006 / 003494), 3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4. 5] Dec-3-en-2-one (known in WO2009 / 049851), 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known in WO2009 / 049851), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known in WO2004 / 099160), 4-(but-2-yn-1-yloxy)-6-(3-chlorophenyl)pyrimidine (known in WO2003 / 076415), PF1364 (CAS Registry No. 1204776-60-2) 2-[2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-chloro-3-methylbenzoyl]-2-methylhydrazine carboxylate (known in WO2005 / 085216), 2-[2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-ethylhydrazine carboxylate (known in WO2005 / 085216), 2-[2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl] 2-Methylhydrazine carboxylate (known in WO2005 / 085216), 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-yl]carbonyl}amino)benzoyl]-2-ethylhydrazine carboxylate (known in WO2005 / 085216), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (known in CN102057925), 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-Oxazol-3-yl]-2-methyl-N-(1-Oxythiobutyron-3-yl)benzamide (known in WO2009 / 080250), N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (known in WO2012 / 029672), 1-[(2-chloro-1,3-thiazolyl-5-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-yl-2-ol (1-[(2-chloro-1,3-thiazolyl-5-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-yl-2-ol) (Known in WO2009 / 099929), 1-[(6-chloropyridin-3-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-yl-2-ol (1-[(6-chloropyridin-3-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-yl-2-ol) (Known in WO2009 / 099929), 4-(3-{2,6-dichloro-4-[(3,3-dichloroprop-2-en-1-yl)oxy]phenoxy}propoxy) )-2-methoxy-6-(trifluoromethyl)pyrimidine (known in CN101337940), N-[2-(tert-butylcarbamoyl)-4-chloro-6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known in WO2008 / 134969), [2-(2,4-dichlorophenyl)-3-oxo-4-oxaspiro[4,5]dec-1-en-1-yl]butyl carbonate (known in CN102060818), (3E)-3-[1- [(6-chloro-3-pyridinyl)methyl]-2-pyridinyl]-1,1,1-trifluoroprop-2-one (known in WO2013 / 144213), N-(methanesulfonyl)-6-[2-(pyridin-3-yl)-1,3-thiazolyl-5-yl]pyridin-2-carboxamide (known in WO2012 / 000896), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known in WO2010 / 051926), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known in CN103232431), tioxazafen, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxo-3-thionylbutane)benzamide, 4-[5-(3,5-dichlorophenyl)-4,[5-Dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxo-3-thionecyclobutyl)benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxo-3-thionecyclobutyl)benzamide (known in WO 2013050317) A1), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propionamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propionamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propionamide (known in WO 2013162715 A2, WO2013162716 A2, US 20140213448) A1), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carboxylonitrile (known in CN 101337937A), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (Liudaibenjiaxuanan, known in CN 103109816 A); N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known in WO 2012034403) A1), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known in WO 2011085575 A1), 4-[3-[2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)pyrimidine (known in CN101337940 A); (2E)- and (2Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazine carboxamide (known in CN 101715774) A); 3-(2,2-dichlorovinyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenylcyclopropane carboxylate (known in CN 103524422 A); (4aS)-7-chloro-2,5-Dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-formate (known in CN 102391261 A).

[0096] Examples of herbicide mixing partners include: Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicabazone, amidochlor, pyrimisulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrol, ammonium sulfamate sulphamate, ailofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benzolin, benzolin-ethyl, benzfluralin, benzuresate, benzsulfuron-methyl, benzulide, benzylphosphonate Tazone), benzobicyclon, benzofenap, bicyclopyron, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil butyrate, bromoxynil-potassium, bromoxynil-heptanoate, and bromoxynil-octanoate, busoxinoneButachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, and more. chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, cinitroxone don), indole-ethyl, cinidon, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, cromazine, comeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, ammonia Cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-dimethylammonium2,4-D-diolamin, 2,4-D-ethyl ester, 2,4-D-2-ethylhexyl ester, 2,4-D-isobutyl ester, 2,4-D-isooctyl ester, 2,4-D-isopropylammonium, 2,4-D- Potassium (2,4-D-potassium), 2,4-D-triisopropanolammonium, 2,4-D-trolamine, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isooctyl ester, 2,4-DB-potassium and 2,4-DB-sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosylpyrazolate (DTP), dicamba, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, pyrfluthrin, flupyridine Hydrazone (diflufenzopyr), diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquatDiquat-dibromid, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen-ethyl, ethoxysulfuron ron), ethoxybenzanid, F-9600, F-5231 (i.e., N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazole-1-yl]-phenyl]ethanesulfonamide), F-7967 (i.e., 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidin-2,4(1H,3H)-dione), fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-ethyl xaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, floraulam, fluazifop, fluazifop-P, fluazifop-butyl tyl), fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentylFlumioxazin, fluometuron, flurenol, flurenol-butyl, flurenol-dimethylammonium, flurenol-methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, and fluroxypyr-m eptyl), flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate (glufosinate-ammonium), glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, glyphosate-isopropylammonium Glyphosate-isopropylammonium, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-potassium, glyphosate-sodium, and glyphosate-trimesium; H-9201 (O-(2,4-dimethyl-6-nitrophenyl)-O-ethylisopropylphosphatidylthioate); halauxifen, halosafen, halosulfuron, halosulfuron-methyl, and haloxyfop.Haloxyfop-P, Haloxyfop-ethoxyethyl, Haloxyfop-P-ethoxyethyl, Haloxyfop-methyl, Haloxyfop-P-methyl, Hexazinone, HW-02 (2,4-Dichlorophenoxy)acetic acid 1-(dimethoxyphosphoryl)ethyl ester), imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-aimmonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl -sodium, iodobenzonitrile, iodobenzonitrile-octanoate, iodobenzonitrile-potassium, and iodobenzonitrile-sodium Sodium), ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043 (i.e., 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole), ketospiradox, lactoferrin, lenacil, linuron, MCPA, MCPA-butotyl, MCPA-dimethylammoniumMCPA-2-ethylhexyl, MCPA-isopropylammonium, MCPA-potassium and MCPA-sodium, MCPB, MCPB-methyl, MCPB-ethyl and MCPB-sodium, mecopropionic acid, mecoprop-sodium and mecoprop-butotyl, mecoprop-P, mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl and mecoprop-potassium -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrisulfuron, methiozolin methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinat, monolinuron, monosulfuron-ester, MT-5950 (i.e., N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methylpentanamide), NGGC-011,Napropamide, NC-310 (i.e., 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzylbenzyloxypyrazole), neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquatdichloride, pebulate, pendimethalin, penoxsulam, pentachlorophenol, penoxazone, pethoxamid, petroleum oils), phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron (primisulfuron-methyl), prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizaf The following are listed as potential drug names: op, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (pyraflufen-ethyl), and pyrasulfotole.Pyrazolynate (pyrazolate), pyrazosulfuron (pyrazosulfuron-ethyl), pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol Pyridate, pyriftalid, pyriminobac (pyriminobac-methyl), pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinchlorac, quinmerac, quinoclamine, quizalofop (quizalofop-ethyl), quizalofop-P Quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249 (i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300 (i.e., 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioimidazoline-4,5-dione), 2,3,6-TBA, TCA (trifluoroacetic acid), sodium trichloroacetate, tebuthiuron, tefuryltrione, tembotrione)Tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, toramezone, tralkoxydim, triafamone, triallate, triasulfuron, triazine-flufenoxam. (triaziflam), tribenuron, tribenuron-methyl, trilopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron-methyl, trimeturon, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862 (i.e., 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline), and the following compounds: Examples of plant growth regulators that can be used as mixed components include: Benzothiadiazole (acibenzolar), S-methyl-benzothiadiazole (acibenzolar-S-methyl), 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, brassinolide, catechol, chlormequat chloride, cloprop, cyclanilide, 3-(chloroprop-1-enyl)propionic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, endothal-disodium, and mono(N,N-dimethylalkylammonium), ethephon. Flumetralin, flurenol (flurenol-butyl), flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid (IAA), 4-indole-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic acid methyl ester, maleic hydrazine Hydrazide, mepiquat chloride, 1-methylcyclopropene, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthoxyacetic acid, nitrophenol mixture, 4-oxo-4-[(2-phenylethyl)amino]butyric acid, paclobutrazol, N-phenylphthalic acid, cyclohexanoic acid, calcium cyclohexanoate, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, tsitodef, uniconazole, uniconazole-P.

[0097] Examples of useful safety agents include compounds from the following group: S1) Compounds selected from heterocyclic hydroxy acid derivatives: S1 a Dichlorophenylpyrazoline-3-carboxylic acid compounds (S1) a Preferred compounds include 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid (S1-1) ("pyrazoline ester"), and related compounds, as described in WO-A-91 / 07874; S1 b Derivatives of dichlorophenylpyrazole carboxylic acid (S1) b Preferred compounds include ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4), and related compounds, such as those described in EP-A-333131 and EP-A-269 806; S1 c )1,5-Diphenylpyrazole-3-carboxylic acid derivatives (S1 c Preferred compounds include ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6), and related compounds, such as those described in EP-A-268554. S1 d Triazole carboxylic acid compounds (S1) d Preferred compounds include fenchlorazole (ethylester) , namely ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate (S1-7), and related compounds, such as those described in EP-A-174 562 and EP-A-346 620; S1 e 5-Benzyl-2-isooxazoline-3-carboxylic acid or 5-phenyl-2-isooxazoline-3-carboxylic acid or 5,5-diphenyl-2-isooxazoline-3-carboxylic acid compounds (S1) ePreferred compounds include ethyl 5-(2,4-dichlorobenzyl)-2-isooxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isooxazoline-3-carboxylate (S1-9) and related compounds, as described in WO-A-91 / 08202; or 5,5-diphenyl-2-isooxazolinecarboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isooxazoline-3-carboxylate (S1-11) (“ethyl bis(phenyloxazoline)”) or n-propyl 5,5-diphenyl-2-isooxazoline-3-carboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isooxazoline-3-carboxylate (S1-13), as described in patent application WO-A-95 / 07897.

[0098] S2) is selected from compounds of 8-quinolinyloxy derivatives (S2): S2 a )8-Quinolinoxyacetic acid compounds (S2) a ), preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate (“cloquintocet-mexyl”) (S2-1), 1,3-dimethylbut-1-yl(5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl(5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxypropyl-2-yl(5-chloro-8-quinolinoxy)acetate (S2-4), ethyl acetate (5-chloro-8-quinolinoxy) (S2-5), methyl 5-chloro-8-quinolinoxyacetate (S2-6), allyl acetate (5-chloro-8-quinolinoxy)acetate (S2-7), 2-(2-propyleneiminooxy)-1-ethyl(5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxopropyl-1-yl(5-chloro-8-quinolinoxy)acetate (S2-9), and related compounds such as EP-A-86 750, EP-A-94 349, and EP-A-191 As described in 736 or EP-A-0 492 366, and (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrate and its salts, such as its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in WO-A-2002 / 34048; S2 b (5-Chloro-8-quinolinoxy)malonic acid compounds (S2) b Preferred compounds include diethyl (5-chloro-8-quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8-quinolinoxy)malonate, and related compounds, as described in EP-A-0 582 198.

[0099] S3) Dichloroacetamide active ingredient (S3), commonly used as a pre-emergence safener (soil action safener), for example "Dichloropropyleneamide" (N,N-diallyl-2,2-dichloroacetamide) (S3-1) "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) (S3-2) from Stauffer "R-28725" (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) (S3-3) from Stauffer "benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4) PPG-1292 (N-allyl-N-[(1,3-dioxolane-2-yl)methyl]dichloroacetamide) (S3-5) from PPG Industries "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) (S3-6) from Sagro-Chem "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azaspiro[4.5]decane) (S3-7) from Nitrokemia or Monsanto. "TI-35" (1-dichloroacetylazetane) (S3-8) from TRI-Chemical RT "Diclonon" or "BAS145138" or "LAB145138" (S3-9) ((RS)-1-dichloroacetyl-3,3,8a-trimethyl-perhydropyrrolo[1,2-a]pyrimidin-6-one from BASF) "furilazole" or "MON 13900" ((RS)-3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine) (S3-10), and its (R)-isomer (S3-11).

[0100] S4) Acylsulfonamide compounds (S4): S4 a ) formula (S4 a N-acylsulfonamides and their salts, as described in WO-A-97 / 45016, in R A 1 It is (C1-C6)alkyl, (C3-C6)cycloalkyl, cycloalkyl, wherein the last two groups are selected from halogen, (C1-C4)alkoxy, (C1-C6)haloalkoxy and (C1-C4) alkylthio. A Substituents are substituted, and in the case of cyclic groups, they are also substituted by (C1-C4)alkyl and (C1-C4)haloalkyl groups; R A 2 It is a halogen, (C1-C4)alkyl, (C1-C4)alkoxy, or CF3; m A It can be 1 or 2; v A It can be 0, 1, 2, or 3; S4 b ) formula (S4 b 4-(benzoylaminosulfonyl)benzamides and their salts, as described in WO-A-99 / 16744, in R B 1 R B 2 Each can be independently classified as hydrogen, (C1-C6)alkyl, (C3-C6)cycloalkyl, (C3-C6)alkenyl, or (C3-C6)ynyl. R B 3 It is hydrogen, (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C4)alkoxy and m B It is 1 or 2. For example, these compounds, among which, R B 1 =Cyclopropyl, R B 2 =hydrogen and (R) B 3 ) = 2-OMe (“cyprosulfamide”, S4-1), R B 1 =Cyclopropyl, R B 2 =hydrogen and (R) B 3 ) = 5-Cl-2-OMe (S4-2), R B 1=Ethyl, R B 2 =hydrogen and (R) B 3 ) = 2-OMe (S4-3), R B 1 =Isopropyl, R B 2 =hydrogen and (R) B 3 ) = 5-Cl-2-OMe (S4-4) and R B 1 =Isopropyl, R B 2 =hydrogen and (R) B 3 ) = 2-OMe (S4-5); S4 c ) formula (S4 c Benzylaminosulfonylphenylurea compounds, such as those described in EP-A-365484, in R C 1 R C 2 Individually, it can be hydrogen, (C1-C8)alkyl, (C3-C8)cycloalkyl, (C3-C6)alkenyl, or (C3-C6)ynyl. R C 3 Halogen, (C1-C4)alkyl, (C1-C4)alkoxy, CF3 and m C It can be 1 or 2; For example 1-[4-(N-2-methoxybenzoylaminosulfonyl)phenyl]-3-methylurea, 1-[4-(N-2-methoxybenzoylaminosulfonyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoylaminosulfonyl)phenyl]-3-methylurea; S4 d ) formula (S4 d N-phenylsulfonyl terephthalamide compounds and their salts, as known for example from CN101838227, in R D 4It is a halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, or CF3; m D It can be 1 or 2; R D 5 It can be hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-ynyl or (C5-C6)-cycloalkenyl.

[0101] S5) Hydroxy aromatic compounds and aromatic-aliphatic carboxylic acid derivatives of active ingredients (S5), such as ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004 / 084631, WO-A-2005 / 015994, and WO-A-2005 / 016001.

[0102] S6) 1,2-Dihydroquinoxalin-2-one active ingredients, such as 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005 / 112630.

[0103] S7) Diphenylmethoxyacetic acid derivatives (S7), such as methyl diphenylmethoxyacetate (CAS Registry No. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid, as described in WO-A-98 / 38856.

[0104] Compounds of formula (S8), such as those described in WO-A-98 / 27049, The symbols and subscripts are defined as follows: R D 1 It is a halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, or (C1-C4)haloalkoxy. R D 2 It is hydrogen or (C1-C4) alkyl. R D 3It is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, or aryl, wherein each of the above carbon-containing groups is unsubstituted or substituted by one or more, preferably up to three identical or different groups selected from halogens and alkoxy groups; or a salt thereof. n D It is an integer between 0 and 2.

[0105] S9) 3-(5-tetrazolylcarbonyl)-2-quinolone active ingredients, such as 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Registry No.: 219479-18-2) and 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Registry No. 95855-00-8), as described in WO-A-1999 / 000020.

[0106] S10) formula (S10) a ) or (S10 b ) compounds As recorded in WO-A-2007 / 023719 and WO-A-2007 / 023764 in R E 1 Halogen, (C1-C4)alkyl, methoxy, nitro, cyano, CF3, OCF3 Y E Z E Independently O or S, n E Integers from 0 to 4 R E 2 For (C1-C 16 alkyl, (C2-C6)alkenyl, (C3-C6)cycloalkyl, aryl; benzyl, halobenzyl, R E 3 It is hydrogen or (C1-C6) alkyl.

[0107] S11) is an active ingredient of the oxy-imino compound class, known as a seed dressing agent, for example... "Oxabetrinil" ((Z)-1,3-dioxolane-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1) is known as a seed treatment safer for protecting millet / sorghum from isopropyl chlorine damage. Fluxofenim (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethylone O-(1,3-dioxolane-2-ylmethyl)oxime) (S11-2) is known as a seed treatment safener for millet / sorghum to protect it from metolachlor damage, and “Cyometrinil” or “CGA-43089” ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3) is known as a seed treatment safer for protecting millet / sorghum from isopropyl acetochlor damage.

[0108] S12) Isothiochromanone active ingredients, such as [(3-oxo-1H-2-benzothiaran-4(3H)-ylidene)methoxy]methyl acetate (CAS Registry No. 205121-04-6) (S12-1) and related compounds in WO-A-1998 / 13361.

[0109] S13) One or more compounds selected from group (S13): "Naphthalenedicarboxylic anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1) is known as a seed treatment safener for protecting maize from damage caused by thiocarbamate herbicides. Fenclorim (4,6-dichloro-2-phenylpyrimidine) (S13-2) is known to be used as a safener for pretilachlor in sown rice. Flurazole (2-chloro-4-trifluoromethyl-1,3-thiazolyl-5-carboxylate) (S13-3) is known as a seed treatment safener for millet / sorghum to protect it from damage by alachlor and metolachlor. “CL 304415” (CAS Registration No. 31541-57-8) (4-Carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4), purchased from American Cyanamid, is known as a safer agent for protecting corn from imidazolinone damage. "MG 191" (CAS Registry No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5), purchased from Nitrokemia, is known as a safer for use in maize. “MG 838” (CAS Registration No. 133993-74-5) (1-oxa-4-azaspiro[4.5]decane-4-dithiocarbonate 2-propene ester) (S13-6) purchased from Nitrokemia. "Disulfoton" (S-2-ethylthioethyl dithiophosphate O,O-diethyl ester) (S13-7) “dietholate” (O-phenyl thiophosphate O,O-diethyl ester) (S13-8) “mephenate” (4-chlorophenyl methylcarbamate) (S13-9).

[0110] S14) In addition to its herbicidal activity against weeds, it also contains active ingredients that are safe for crops such as rice, for example... "Dimepiperate" or "MY-93" (S-1-methyl-1-phenylethylpiperidine-1-thiocarbamate) is known as a safe agent for protecting rice from the herbicide molinate. Daimuron, or SK 23 (1-(1-methyl-1-phenylethyl)-3-p-toluene), is known as a safe agent for protecting rice from the herbicide imazosulphuron. "Cumyluron" = "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087254), is known as a safener for protecting rice from certain herbicides. "Methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone) is known as a safener for protecting rice from certain herbicides. "CSB" (1-bromo-4-(chloromethylsulfonyl)benzene), purchased from Kumiai (CAS Registry No. 54091-06-4), is known to be used in rice as a safe agent against damage from certain herbicides.

[0111] Compounds of formula (S15) or their tautomers As described in WO-A-2008 / 131861 and WO-A-2008 / 131860, in R H 1 (C1-C6)-haloalkyl and R H 2Hydrogen or halogen and R H 3 R H 4 Independently, they are hydrogen, (C1-C) 16 )-alkyl, (C2-C 16 )-Alkenyl or (C2C 16 )- Acynyl group, The last three groups are each unsubstituted or substituted by one or more groups selected from the following: halogen, hydroxyl, cyano, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]-amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclic groups. Alternatively, (C3-C6)-cycloalkyl, (C4-C6)-cycloalkenyl, (C3-C6)-cycloalkyl fused to a 4- to 6-membered saturated or unsaturated carbon ring on one side of the ring, or (C4-C6)-cycloalkenyl fused to a 4- to 6-membered saturated or unsaturated carbon ring on one side of the ring. Each of the last four groups is either unsubstituted or substituted with one or more groups selected from the following: halogen, hydroxyl, cyano, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C1-C4)alkylthio, (C1-C4)alkylamino, di[(C1-C4)alkyl]amino, [(C1-C4)alkoxy]carbonyl, [(C1-C4)haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclic groups. or R H 3 It is (C1-C4)-alkoxy, (C2-C4)-enoxy, (C2-C6)-alkynoxy, or (C2-C4)-haloalkoxy and R H 4 It is hydrogen or (C1-C4)-alkyl or R H 3 and R H 4Together with the directly bonded N atom, it forms a 4- to 8-membered heterocycle. In addition to the N atom, the heterocycle may also contain other heterocyclic atoms, preferably up to two other heterocyclic atoms selected from N, O, and S, and the heterocycle is unsubstituted or substituted by one or more groups selected from: halogen, cyano, nitro, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, and (C1-C4) alkylthio.

[0112] S16) is an active ingredient primarily used as a herbicide and also acting as a safener for crops, for example... (2,4-Dichlorophenoxy)acetic acid (2,4-D), (4-Chlorophenoxy)acetic acid, (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (chloropropionic acid), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-Chloro-o-tolyloxy)acetic acid (MCPA), 4-(4-chloro-o-tolyloxy)butyric acid, 4-(4-Chlorophenoxy)butyric acid, 3,6-Dichloro-2-methoxybenzoic acid (dicamba), 3,6-Dichloro-2-methoxybenzoic acid 1-(ethoxycarbonyl)ethyl ester (dichloroethyl lactate).

[0113] More preferably, the solvent-free water-dispersible parent drug (TC) contains -0.5% to 40% by weight, preferably 0.5% to 30% by weight, and more preferably 0.5% to 15% by weight of component a), -2% to 35% by weight, preferably 3% to 30% by weight, more preferably 5% to 25% by weight and even more preferably 10% to 20% by weight of component b1). -0.1% to 10% by weight, preferably 0.3% to 8% by weight, and most preferably 1% to 7% by weight of component c1), -2% to 35% by weight, preferably 3% to 30% by weight, preferably 5% to 25% by weight, and most preferably 10% to 20% by weight of component c2).

[0114] Most preferably, they are combined with active ingredient e) and other active ingredients, said active ingredient e) being selected from herbicides, preferably sulfonylureas, such as mesosulfuron-methyl (0.5 wt%-5 wt%), sodium salt or acid of mesosulfuron-methyl (0.05 wt%-10 wt%), amidosulfuron (0.5 wt%-5 wt%), and HPPD (4-hydroxyphenylpyruvate dioxygenase) inhibitors, said other active ingredients being selected from ALS (acetyllactate synthase) inhibitors, such as thiencarbazone-methyl (0.2 wt%) and / or typical pigment bleaching agents, such as diflufenican (2 wt%-20 wt%). Active ingredients based on iodosulfuron, amidosulfuron, and mesosulfuron are preferred.

[0115] It is highly preferred to use a combination of kaolin or calcium carbonate and silica as c2). It is highly preferred to use precipitated silica as c1), and it is highly preferred to use calcium carbonate as c2 in combination with precipitated silica.

[0116] More preferably, the solvent-free aqueous dispersible suspension concentrate contains -0.5% to 40% by weight, preferably 0.5% to 30% by weight, and more preferably 0.5% to 15% by weight of component a), -0.1% to 10% by weight, preferably 0.2% to 7% by weight, and most preferably 0.3% to 4% by weight of component b1), -1% to 15% by weight, preferably 2% to 10% by weight, and most preferably 2.5% to 8% by weight of component b2), -0.05% to 10% by weight, preferably 0.1% to 8% by weight, more preferably 0.3% to 5% by weight, and most preferably 0.5% to 3% by weight of component c1), -0.01 wt% to 1.0 wt%, more preferably 0.01 wt% to 0.6 wt%, even more preferably 0.05 wt% to 0.5 wt%, and even more preferably 0.1 wt% to 0.3 wt% of component d1).

[0117] Most preferably, they are combined with active ingredient e), which is selected from herbicides, preferably from auxins, such as halauxifen-methyl (0.05 wt%-5 wt%), and / or from pigment synthesis inhibitors (pigment bleaching agents), such as pyrifluquinazon (5-30%), and from DOXP synthase inhibitors, such as isochordazone and preferably isoxazolidinone, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl- (CAS No. 81777-95-9) and / or from VLCFA inhibitors ("very long-chain fatty acids", which inhibit cell division by targeting fatty acid production) fluthiamethoxam (5%-30 wt%). Halauxifen-methyl and / or pyrifluquinazon are preferred.

[0118] Furthermore, according to the present invention, SC, TC, or WG may optionally include the following substances as additional component f): Wetting agents, pH adjusters, defoamers, biocides, disintegrants, adhesion promoters, antifreeze agents, preservatives, dyes or fertilizers, and surfactants other than component b).

[0119] Suitable defoamers are surface-active silicone-based or silane-based compounds, such as Tegopren. ® Products (Goldschmidt), SE ® Products (Wacker), and Bevaloid ® (Kemira), Rhodorsil ® (Solvay) and Silcolapse ® Products (Blustar Silicones), SE preferred ® (Wacker), Rhodorsil ® and Silcolapse ® Products, especially preferred, such as Silcolapse. ® 5020.

[0120] Suitable antifreeze agents are those derived from urea, glycols, and polyols, such as ethylene glycol and propylene glycol, and glycerin, preferably propylene glycol or glycerin.

[0121] 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).

[0122] Suitable wetting agents are selected from naphthalenesulfonic acid and sulfosuccinic acid derivatives and their salts, primarily including monoesters and diesters of sulfosuccinic acid and their salts (sulfosuccinates), and secondarily including alkylated naphthalenesulfonic acid and its salts, such as Aerosol. ® OTB (Dioctyl Sulfosuccinate), Morwet ® EFW (alkylated naphthalene sulfonate), Nekal ® BX (alkylated naphthalene sulfonate), Galoryl ® MT 804 (alkylated naphthalene sulfonate).

[0123] Preferred wetting agents in this paper are salts of alkyl naphthalene sulfonic acid and salts of dioctyl sulfosuccinic acid, more preferably sodium salts of alkyl naphthalene sulfonic acid, such as Morwet. ® EFW, and sodium salts of dioctyl sulfosuccinic acid, such as Aerosol ® OTB.

[0124] Suitable adhesion promoters can be selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymers of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymers of vinyl chloride and vinyl acetate, sodium salts of copolymers of propenesultanic acid and partially hydrolyzed vinyl acetate, sodium caseinate, phenolic resins, and modified cellulose types, such as Luviskol. ® (Polyvinylpyrrolidone), Mowiol ® (Polyvinyl alcohol), modified cellulose.

[0125] Preferred types are polyvinylpyrrolidone, with low molecular weight types such as Luviskol being particularly preferred. ® K30.

[0126] Suitable disintegrants can be self-modified carbohydrates, such as microcrystalline cellulose, and cross-linked polyvinylpyrrolidone, such as Avicel. ® PH 101 (microcrystalline cellulose), Agrimer ® XLF (crosslinked polyvinylpyrrolidone), Disintex ® 200 (cross-linked polyvinylpyrrolidone). Cross-linked polyvinylpyrrolidone, such as Agrimer, is preferred. ® XLF.

[0127] Suitable defoamers can be selected from esters of phosphoric acid and lower alcohols; C6-C10 alcohols; silicone surfactants (suspending agents for hydrophobic silica particles in aqueous emulsion concentrates based on liquid silicone surfactants), such as polydimethylsiloxane; and absorbents on solid carrier materials, such as Rhodorsil. ® 432 (silicone surfactant), butyl phosphate, isobutyl phosphate, n-octanol, Wacker ASP15 (polydimethylsiloxane, adsorbed on a solid support), Antifoam ® SE (polydimethylsiloxane). Preferably, it is a suspending agent for hydrophobic silica particles in aqueous emulsion concentrates based on liquid silicone surfactants, such as Antifoam. ® SE (polydimethylsiloxane), and solid defoamers such as Wacker ASP 15 (polydimethylsiloxane).

[0128] Suitable emulsifiers, wetting agents, and dispersants include, for example, nonionic emulsifiers and nonionic dispersants, such as: - A polyalkoxylated, preferably polyethoxylated saturated and unsaturated aliphatic alcohol having 8 to 24 carbon atoms in an alkyl group, derived from the corresponding fatty acid or from petrochemical products, and wherein the aliphatic alcohol has 1 to 100, preferably 2 to 50 ethylene oxide units (EO), wherein the free hydroxyl group is optionally alkoxylated, for example, Genapor ® X and Genapor ® O series (Clariant), Crovol ® M series (Croda) or Lutensol ® BASF series; - Polyalkoxylated, preferably polyethoxylated, hydroxy fatty acids or glycerides containing hydroxy fatty acids (e.g., ricin or castor oil), having an ethoxylation level of 10 to 80, preferably 25 to 40, such as Emulsogen. ® EL series (Clariant) or Agnique ® CSO series (BASF); - Polyalkoxylated, preferably polyethoxylated, dehydrated sorbitol esters, such as Atplus ® 309 F (Croda) or Alkamuls ® The Solvay series.

[0129] Preferred nonionic emulsifiers and nonionic dispersants are, for example, polyethoxylated alcohols and polyethoxylated triglycerides containing hydroxy fatty acids.

[0130] Ionic emulsifiers and ionic dispersants are equally suitable, for example: - Polyalkoxylated, preferably polyethoxylated, emulsifiers / dispersants, which are ionically modified, for example, by converting the terminal free hydroxyl functional groups of the polyethylene oxide blocks into sulfate or phosphate esters (e.g., alkali metal and alkaline earth metal salts), such as Genapole. ® LRO or Dispergiermittel 3618 (Clariant), Emulphor ® (BASF) or Crafol ® AP (BASF); - Alkali metal and alkaline earth metal salts of alkyl aryl sulfonic acids having straight or branched alkyl chains, such as Phenylsulfonat CA or Phenylsulfonat CAL (Clariant), Atlox ® 3377BM (Croda), Empiphos ® TM series (Huntsman); - Polyelectrolytes, such as polystyrene sulfonates or sulfonated unsaturated polymers or aromatic polymers (polystyrene, polybutadiene or polyterpenes).

[0131] According to the invention, any other conventional auxiliaries and additives (f) added to the dispersant may be in the proportion of up to 20% by weight, preferably up to 15% by weight.

[0132] According to the present invention, the proportion of water in the dispersant is 20% to 70% by weight, preferably 20% to 60% by weight, more preferably 30% to 55% by weight, and most preferably 25% to 45% by weight.

[0133] The present invention also relates to herbicidal compositions that can be produced by diluting the SC, TC or WG according to the present invention with a liquid, preferably water.

[0134] Advantageously, other active ingredients, preferably active agrochemicals (e.g., tank-mixed components in suitable formulations) and / or conventionally used adjuvants and additives, such as self-emulsifying oils like vegetable oils or paraffin oils and / or fertilizers, are added to the resulting herbicidal compositions. Therefore, the present invention also provides such compositions, preferably herbicidal compositions, based on the formulations of the present invention.

[0135] One particular embodiment of the invention relates to the use of a herbicidal composition (hereinafter referred to as "herbicidal composition") that can be obtained from the SC, TC or WG according to the invention for the control of unwanted plant growth.

[0136] This herbicidal composition exhibits excellent herbicidal efficacy against a broad spectrum of economically important monocot and dicot weeds. It also provides good control over difficult-to-control perennial weeds that produce shoots from rhizomes, rhizomes, or other permanent organs. The herbicidal composition can be applied, for example, before sowing, before emergence, or after emergence. Some representative examples of monocot and dicot weed populations that can be controlled by this herbicidal composition are listed below, but this is not intended to limit the application to any particular species.

[0137] Examples of weed species that are effectively controlled include monocotyledonous weeds, annuals such as Apera spicaventi, *Avena* spp., *Alopecurus* spp., *Brachiaria* spp., *Digitaria* spp., *Lolium* spp., *Echinochloa* spp., *Panicum* spp., *Phalaris* spp., *Poa* spp., *Setaria* spp., and *Bromus* spp., such as *Bromus catharticus*, *Bromus secalinus*, *Bromus erectus*, *Bromus tectorum*, and *Bromus*. The genera *japonicus* and *Cyperus*; as well as perennial plants, including *Agropyron*, *Cynodon*, *Imperata*, and *Sorghum*, and perennial *Cyperus* species. In the case of dicotyledonous weed species, the spectrum of action extends to species such as annuals of the genera *Abutilon*, *Amaranthus*, *Chenopodium*, *Chrysanthemum*, *Galium* such as *Galium aparine*, *Ipomoea*, *Kochia*, *Lamium*, *Matricaria*, *Pharbitis*, *Polygonum*, *Sida*, *Sinapis*, *Solanum*, *Stellaria*, *Veronica*, and *Viola*. spp.), Xanthium spp., and in the case of perennial weeds, Convolvulus, Cirsium, Rumex and Artemisia.

[0138] The herbicide composition also provides excellent control of weeds that arise under specific growing conditions in rice, such as those in the genera *Echinochloa*, *Sagittaria*, *Alisma*, *Eleocharis*, *Scirpus*, and *Cyperus*. If applied to the soil surface before germination, the herbicide composition can completely prevent weed seedlings from appearing or from growing to the cotyledon stage, after which growth ceases and the weeds eventually die completely within three to four weeks.

[0139] If the herbicidal composition is applied to the green parts of the plant after emergence, growth also stops abruptly within a very short time after treatment, and the weeds remain in the growth stage at the time of application, or they die completely after a certain period of time, thus eliminating the competition of harmful weeds for the crop plant as early as possible and in a lasting manner.

[0140] The herbicidal composition is characterized by rapid onset of action and long-lasting weed control. Rain resistance of the active ingredient in the herbicidal composition is generally advantageous. A particular advantage is that the effective dosage of the herbicidal compound used in the herbicidal composition can be adjusted to such a low level that its soil action is minimal. Therefore, it can be used not only in sensitive crops but also, in effect, to prevent groundwater contamination. The active ingredient composition of the present invention significantly reduces the required application rate of the active ingredient.

[0141] The properties and advantages described herein are beneficial for practical weed control, keeping crops away from unwanted competing plants, thereby ensuring and / or increasing yields in both quality and quantity. These novel weed control compositions significantly improve the technical standards regarding these properties.

[0142] Although the herbicidal composition exhibits excellent herbicidal activity against both monocot and dicot weeds, it causes only negligible, if any, damage to economically important crops, such as dicot crops like soybeans, cotton, rapeseed, and sugar beets, or gramineous crops like wheat, barley, rye, oats, millet / sorghum, rice, or corn. For these reasons, the herbicidal composition of the present invention is highly suitable for the selective control of unwanted plant growth in agriculturally useful or ornamental plants.

[0143] Furthermore, depending on the crop, the corresponding herbicidal compositions possess excellent growth-regulating properties. They intervene in the plant's own metabolism through regulatory effects, and thus can be used to control the effects of plant components and promote harvest, for example, by triggering dehydration and dwarfing growth. In addition, they are suitable for the general control and suppression of unwanted vegetative growth without killing the plant in the process. Suppressing vegetative growth plays an important role in many monocot and dicot crops because it can, for example, reduce or completely prevent lodging.

[0144] Due to their weed-controlling and plant growth-regulating properties, herbicidal compositions—as already mentioned—can also be used to control weeds in known or yet-to-be-developed genetically modified plant crops. Generally, transgenic plants are characterized by particularly advantageous properties, such as resistance to certain pesticides, especially certain herbicides, and resistance to plant diseases or pathogens, such as certain insects or microorganisms like fungi, bacteria, or viruses. Other special properties relate to, for example, the quantity, quality, storability, composition, and specific components of the harvest. For instance, transgenic plants are known to have increased starch content or altered starch quality, or transgenic plants with different fatty acid compositions in their harvests.

[0145] The herbicidal composition is preferably used in genetically modified crops of economically important useful and ornamental plants, such as gramineous crops like wheat, barley, rye, oats, millet / sorghum, rice, and corn, or crops like sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas, and other vegetables. The herbicidal composition may also be preferably used in useful plant crops that are tolerant to the phytotoxic effects of herbicides, or that have already developed resistance to the phytotoxic effects of herbicides through recombinant methods.

[0146] When herbicidal compositions are used on genetically modified crops, they are effective not only against harmful plants observed in other crops, but also generally against those specifically applied to particular genetically modified crops, such as altering or particularly broadening the spectrum of controllable weeds, changing the application rate available for application, preferably having good compatibility with other active herbicidal ingredients tolerable by genetically modified crops, and influencing the growth and yield of genetically modified crop plants.

[0147] Therefore, the present invention also provides a preferred method for controlling unwanted plant growth in crop plants, said crop plants being such as cereals (e.g., wheat, barley, rye, oats, rice, corn, millet / sorghum), sugar beets, sugarcane, rapeseed, cotton, and soybeans, more preferably monocotyledonous crops such as cereals like wheat, barley, rye, and oats, and their hybrids such as triticale, rice, corn, and millet / sorghum, characterized in that the herbicidal composition according to the invention is applied to weeds, plant parts, plant seeds, or areas where plants grow, such as cultivated areas. The crop plants may also be genetically modified or obtained through mutational selection, and are preferably resistant to acetyllactate synthase (ALS) inhibitors.

[0148] By using the WG and SC according to the invention, better biological effects can be achieved at the same application rate. Advantageously, the SC, TC or WG according to the invention exhibit excellent plant compatibility, such as a tendency to reduce phytotoxic damage.

[0149] Furthermore, the SC, TC, or WG according to the invention, in the form of a combination of specific active ingredients (synonyms: mixed formulation, co-formulation), has other advantages, such as lower packaging expenditures than when using a single active ingredient, thereby reducing costs and inconveniences associated with production, transportation, and storage, and making the preparation of sprays for agricultural use easier to control, for example, through small and effective ratios already set in the measurement and mixing operations.

[0150] Surprisingly, after further dilution with water, preferably liquid, the SC, TC, or WG according to the invention exhibits additionally excellent dispersibility and stability.

[0151] In addition, SC, TC, or WG give the formulation extended storage stability and impeccable suitability.

[0152] Another preferred embodiment is to use SC, TC, or WG according to the invention as growth regulators (phytotonics). Preferably, these combinations are used to improve the "greening" of plants.

[0153] Plant growth regulators can produce a variety of effects on plants. The effects of these substances depend primarily on the timing of application relative to the plant's developmental stage, the amount of active ingredient applied to the plant or its environment, and the method of application. In each case, the growth regulator should produce a specific, desired effect on the crop.

[0154] Growth regulation effects include earlier budding, better seedling emergence, more developed root systems and / or improved root growth, increased tillering capacity, more productive tillers, earlier flowering, increased plant height and / or biomass, stem shortening, branch growth, grain / ear count, and ear / m 2Improved number of stolons and / or flowers, increased harvest index, larger leaves, less basal leaf death, improved phyllotaxis, earlier maturity / earlier fruit formation, uniform maturity, increased grain filling time, better fruit formation, larger fruit / vegetable size, improved germination resistance and reduced lodging.

[0155] Increased or improved yield refers to total biomass per hectare, yield per hectare, grain / fruit weight, seed size and / or weight per hectoliter, and improved product quality, including the following: Improved processability related to the following aspects: size distribution (grains, fruits, etc.), uniform maturity, grain moisture, better milling, better wine processing, better brewing, increased juice yield, improved harvestability, improved digestibility, improved sedimentation value, improved falling number, improved pod stability, improved storage stability, improved fiber length / strength / uniformity, improved milk and / or meat quality of silage animals, and adaptability to cooking and frying. It also includes better marketability related to the following aspects: improved fruit / grain quality, size distribution (grains, fruits, etc.), improved shelf life, firmness / softness, taste (aroma, texture, etc.), grade (berry size, shape, quantity, etc.), number of berries / fruits per bunch, crispness, freshness, wax coverage, frequency of physiological disorders, color, etc. It also includes the increase of desired components, such as protein content, fatty acids, oil content, oil quality, amino acid composition, sugar content, acid content (pH), sugar / acid value (Brix), polyphenols, starch content, nutritional value, gluten content / index, energy content, taste, etc. It also includes reductions in undesirable components, such as fewer mycotoxins, fewer aflatoxins, less geosmin, less phenolic aroma, lactase, polyphenol oxidase and peroxidase, or less nitrate.

[0156] Plant growth regulators can be used, for example, to slow down the vegetative growth of plants. This growth inhibition has economic benefits, for example, in the case of grasses, because it reduces the frequency of mowing in ornamental gardens, parks and sports facilities, roadsides, airports, or fruit crops. It is also important to inhibit the growth of herbaceous and woody plants along roadsides, near pipes or overhead cables, or in areas where vigorous plant growth is not typically desired.

[0157] Importantly, plant growth regulators are used to suppress longitudinal growth in grains. This reduces or completely eliminates the risk of lodging before harvest. Furthermore, growth regulators strengthen the stalks of grains, which also helps resist lodging. Using growth regulators to shorten and strengthen stalks allows for the application of larger amounts of fertilizer to increase yields, without any risk of lodging in grain crops.

[0158] In the case of many crops, the suppression of vegetative growth allows for denser planting and thus a higher number of plants per unit area of ​​the soil surface. Another advantage of the smaller plants obtained in this way is that the crops are easier to cultivate and harvest.

[0159] A reduction in vegetative growth in plants can also lead to increased or improved yields because nutrients and absorbates are more beneficial to the formation of flowers and fruits than to the vegetative parts of the plant.

[0160] Alternatively, growth regulators can be used to promote vegetative growth. This is highly advantageous when harvesting vegetative plant parts. However, promoting vegetative growth can also promote reproductive growth, by forming more absorbent material, thus producing more or larger fruits.

[0161] In addition, beneficial effects on growth or yield can be achieved through: improved nutrient utilization, especially nitrogen (N) utilization, phosphorus (P) utilization, and water utilization; increased transpiration rate, respiration rate, and / or CO2 absorption rate; better growth; and improved Ca- metabolism, etc.

[0162] Similarly, plant growth regulators can be used to alter the composition of plants, which in turn can lead to increased yield quality. Under the influence of plant growth regulators, parthenocarpic fruits can form. Furthermore, they can affect the sex of flowers. They can also produce sterile pollen, which is of great significance in the breeding and production of hybrid seeds.

[0163] Plant growth regulators can be used to control branching in plants. On the one hand, by disrupting apical dominance, they can promote the development of lateral branches, which may be particularly needed in the cultivation of ornamental plants, and also in the simultaneous suppression of growth. However, on the other hand, they can also suppress the growth of lateral branches. This effect is particularly beneficial, for example, in the cultivation of tobacco or tomatoes.

[0164] Under the influence of plant growth regulators, the number of leaves in a plant can be controlled, allowing the plant to shed its leaves at the desired time. This leaf drop plays a major role in the mechanical harvesting of cotton and is also beneficial for promoting harvesting in other crops, such as grape cultivation. Leaf drop can also be used to reduce transpiration before transplanting.

[0165] In addition, growth regulators can regulate plant senescence, which can lead to a longer duration of green leaf area, a longer grain-filling stage, and improved yield and quality.

[0166] Plant growth regulators can also be used to regulate fruit cracking. On the one hand, they can prevent premature fruit cracking. On the other hand, they can promote fruit cracking or even promote flower abortion to achieve the desired quality ("thinning"). In addition, to allow for mechanical harvesting or promote manual harvesting, plant growth regulators can be used at harvest to reduce the force required to detach the fruit.

[0167] Growth regulators can also be used to achieve faster or delayed ripening of harvested material before or after harvest. This is particularly advantageous because it allows for optimal adjustment based on market demand. Furthermore, in some cases, growth regulators can improve fruit color. Additionally, growth regulators can be used to synchronize ripening over a period of time. This establishes the prerequisite for fully mechanized or manual harvesting in a single operation, as in the cases of tobacco, tomatoes, or coffee.

[0168] By using growth regulators, the dormancy of plant seeds or buds can be further influenced, causing plants (such as pineapples or ornamental plants in nurseries) to germinate, sprout, or flower when they would not normally tend to do so. In areas at risk of frost, delaying seed germination or sprouting with the assistance of growth regulators to avoid damage from later frosts is desirable.

[0169] Finally, growth regulators can induce plant tolerance to frost, drought, or high soil salinity. This enables the cultivation of plants in areas that are not normally suitable for this purpose.

[0170] The formulations according to the invention also exhibit effective fortifying effects in plants. Therefore, they can be used to mobilize plant defenses against unwanted microbial invasion. In the context of this invention, plant fortifying (resistance-inducing) substances are those substances that can stimulate the plant's defense system in such a manner that, upon subsequent inoculation with unwanted microorganisms, the treated plants develop high resistance to those microorganisms.

[0171] Furthermore, in the context of this invention, plant physiological effects include the following: Abiotic stress tolerance includes tolerance to high or low temperatures, drought tolerance and recovery after drought stress, water use efficiency (related to reduced water consumption), flood tolerance, ozone stress and UV tolerance, and tolerance to chemicals (such as heavy metals, salts, pesticides, etc.).

[0172] Biological stress tolerance includes enhanced fungal resistance and enhanced resistance to nematodes, viruses, and bacteria. In the context of this invention, biological stress tolerance preferably includes enhanced fungal resistance and enhanced resistance to nematodes.

[0173] Enhanced plant vitality, including plant health / plant quality and seed vigor, reduced lodging, improved appearance, enhanced recovery ability after stress, improved pigmentation (e.g., chlorophyll content, green retention, etc.) and improved photosynthetic efficiency.

[0174] Therefore, the present invention provides the use of SC, TC or WG according to the invention for enhancing plant resistance to abiotic stresses, preferably resistance to drought stress, and particularly for enhancing plant growth and / or for increasing plant yield.

[0175] The various other benefits to plants mentioned above can be combined with each other in known ways and are generally described using applicable terminology. These terms include, for example, the following names: plant strengthening effect, resistance to stress factors, less plant stress, plant health, healthy plant, plant fitness, good plant condition, plant concept, vitality effect, stress protection, protective shield, crop health, crop health characteristics, crop health products, crop health management, crop health therapy, plant health, plant health characteristics, plant health products, plant health management, plant health therapy, greening effect or regreening effect, freshness, or other terms fully familiar to those skilled in the art.

[0176] The present invention also includes a method for processing seeds.

[0177] In the following text, SC, TC or WG according to the invention are collectively referred to as formulations according to the invention.

[0178] Another aspect of the invention relates particularly to seeds (dormant, budding, pre-germinating, or even seeds with exposed roots and leaves) treated with the formulation according to the invention. The seeds of the invention are used in methods for protecting seeds and germinating plants from plant pathogenic fungi. In these methods, seeds treated with the formulation according to the invention are used.

[0179] The formulations according to the invention are also suitable for the treatment of seeds and young seedlings. Most damage to crop plants caused by pests is due to infection of seeds before sowing or after germination. This stage is particularly critical because the roots and buds of growing plants are especially sensitive, and even minor damage can lead to plant death. Therefore, there is great interest in protecting seeds and germinating plants through the use of suitable compositions.

[0180] It is also desirable to optimize the amount of active ingredients used to provide the best possible protection for seeds, germinating plants, and seedlings against plant pathogenic fungi, without harming the plants themselves. In particular, the method of seed treatment should also take into account the intrinsic phenotype of transgenic plants in order to achieve optimal protection for seeds and germinating plants using the minimum amount of crop protection composition.

[0181] Therefore, the present invention also relates to a method for protecting seeds, germinating plants, and seedlings from animal pests and / or plant pathogenic microorganisms by treating seeds with the formulation according to the invention. The present invention also relates to the use of the formulation according to the invention for treating seeds to protect seeds, germinating plants, and seedlings against animal pests and / or plant pathogenic microorganisms. The present invention further relates to seeds treated with the formulation according to the invention for protecting seeds from animal pests and / or plant pathogenic microorganisms.

[0182] One advantage of this invention is that treating seeds with these formulations protects not only the seeds themselves but also the resulting plants from animal pests and / or plant pathogenic microorganisms after emergence. In this way, the crop is treated at or shortly after sowing to protect both the plants and the seeds treated before sowing. It is also considered advantageous that the formulations according to the invention can be used particularly for transgenic seeds, in which case the plants grown from these seeds express proteins that are resistant to pests, weed damage, or abiotic stresses. Treating these seeds with formulations according to the invention, such as insecticidal proteins, can control certain pests. Surprisingly, further synergistic effects can be observed in this case, which additionally increases the effectiveness against pests, microorganisms, weeds, or abiotic stresses.

[0183] The formulation according to the invention is suitable for protecting the seeds of any plant variety used in agriculture, greenhouses, forestry, or horticulture. More particularly, the seeds are cereals (e.g., wheat, barley, rye, millet / sorghum, and oats), oilseed rape, corn, cotton, soybeans, rice, potatoes, sunflowers, legumes, coffee, sugar beets (e.g., sugar beets and forage beets), peanuts, vegetables (e.g., tomatoes, cucumbers, onions, and lettuce), lawns, and ornamental plants. It is particularly important to treat the seeds of wheat, soybeans, oilseed rape, corn, and rice. Wheat is especially preferred.

[0184] As described below, treating transgenic seeds with the formulation according to the invention is of particular importance. This refers to seeds of plants containing at least one heterologous gene that allows the expression of, for example, polypeptides or proteins with insecticidal properties. These heterologous genes in the transgenic seeds can, for example, originate from microorganisms of the genera *Bacillus*, *Rhizobium*, *Pseudomonas*, *Serratia*, *Trichoderma*, *Clavibacter*, *Glomus*, or *Gliocladium*. These heterologous genes are preferably derived from *Bacillus*, in which case the gene product is effective against the European corn borer and / or the western corn rootworm. Particularly preferably, the heterologous gene is derived from *Bacillus thuringiensis*.

[0185] In the context of this invention, the formulation according to the invention is applied to seeds alone or in a suitable formulation form. Preferably, the seeds are treated in a sufficiently stable state so that no damage occurs during treatment. Generally, the seeds can be treated at any time between harvest and sowing. Seeds that have been separated from the plant and from which the rachis, husk, stem, epidermis, pubescence, or pulp of the fruit are usually used. For example, seeds that have been harvested, cleaned, and dried to a moisture content of less than 15% by weight can be used. Alternatively, seeds that have been treated with, for example, water and dried again after drying, or newly germinated seeds, or seeds stored under pre-germination conditions, or seeds sown on seedling trays, seedling tapes, or seedling paper can also be used.

[0186] The formulations according to the invention can be used directly or after pre-diluting with water to treat various kinds of seeds. For example, the concentrates or formulations obtained by dilution with water can be used to treat seeds of cereals such as wheat, barley, rye, oats, and triticale, as well as seeds of corn, soybeans, rice, rapeseed, peas, broad beans, cotton, sunflowers, and sugar beets, or various kinds of vegetable seeds. The formulations according to the invention or diluted formulations thereof can also be used for seeds of genetically modified plants. In this case, additional synergistic effects may also occur in the interaction with substances formed through expression.

[0187] For treating seeds with the formulation according to the invention or a formulation prepared therefrom by adding water, all mixing units generally available for seed dressing are applicable. Specifically, the seed dressing operation involves placing the seeds in a mixer, adding the desired amount of the formulation (as is or after pre-diluting with water), and mixing everything until the applied formulation is evenly distributed on the seeds. If suitable, a drying operation is then performed.

[0188] The application rate of the formulation according to the invention can vary over a relatively wide range. It is guided by the specific content of the active ingredient in the formulation and the seed. The application rate of each individual active ingredient is typically from 0.001 g to 15 g per kilogram of seed, preferably from 0.01 g to 5 g per kilogram of seed.

[0189] A further preferred embodiment is the use of the formulation according to the invention for seed treatment.

[0190] The present invention will be described in detail through examples, but is not limited thereto.

[0191] Example: Raw materials used: The terms used in the following embodiments have the following meanings: Pyrazole herbicide ( RS Diethyl 1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylic acid (Bayer CropScience AG), melting point range 50-55℃ Fluthiamethoxam 4'-fluoro-N-isopropyl-2-(5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy)acetanilide (Bayer CropScience AG) Iodosulfuron-methyl ({[5-iodo-2-(methoxycarbonyl)phenyl]sulfonyl}carbamoyl)(4-methoxy-6-methyl-1,3,5-triazin-2-yl)imine salt (azanide) (Bayer CropScience AG) Methyl disulfuron-2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)aminosulfonyl]-α-(methanesulfonylamino)-p-toluene (Bayer CropScience AG) Pyrfluthrin 2',4'-difluoro-2-(α,α,α-trifluoro-m-tolyloxy)nicotinamide (BayerCropScience AG) Detoxifying Quinine ( RS 1-Methylhexyl(5-chloroquinoline-8-yloxy)acetate, melting point range 60-70℃ 4-Amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl) methyl pyridine-2-carboxylate (CAS No.: 943831-98-9) Morwet ® D-425 Naphthalenesulfonic acid / formaldehyde condensate, sodium salt (Akzo Nobel) Morwet ®IP diisopropylnaphthalenesulfonate, sodium salt (Akzo Nobel) Pluronic ® PE 10500 propylene oxide-ethylene oxide (PO-EO) block polymer (BASF) Citric acid polyacid Rhodopol ® 23. Xanthan Gum Derivatives (Solvay) Silcolapse ® 411 Silicone Defoamer (Solvay) Silfoam ® SE 2 Silicone Defoamer (Wacker) Glycerin antifreeze Proxel ® GXL preservative (biocide, Proxel) Kaolin TEC1 hydrated aluminum silicate Sipernat ® 22S precipitated silica Sokalan ® K30 Polyvinylpyrrolidone, nonionic dispersant Solvesso 200 ND Mineral Oil, ExxonMobil, Naphthalene-Free Calsogen ® Calcium dodecylbenzenesulfonate (approximately 40%) in 48142-ethylhexanol, Clariant Emulsogen ® 3510 Nonionic Surfactant, n-Butyl-PO-EO Block Alkoxylate, Clariant Testing and storage methods: All tests were conducted using the CIPAC method commonly used in crop protection (CIPAC = Collaborative International Pesticides Analytical Council; www.cipac.org). Long-term storage was performed according to CIPAC MT 46.3, at 40°C for 8 weeks. The terms used below have the following meanings: unless otherwise stated, tests were conducted at 23°C with a 1% solution in water (CIPAC D, water hardness 342 ppm).

[0192] -0TW = Stores test results after 0 days; -8W40 = The result of an accelerated storage test (8 weeks at 40°C) conducted to test the long-term stability of the formulation product; - Suspension density = Distribution of active ingredient in a 1% aqueous solution (100% = completely uniform distribution, 0% = complete precipitation); a value <100% results in uneven distribution of the product during application; according to international standards, the value for formulated products must be >60%; -Suspension degree 8W40 = Value after 8 weeks of storage at 40℃; -D90 = Active ingredient particle size (laser scattering, 90% of all volumetric particles); -D90 8W40 = Particle size of the active ingredient after storage test (8 weeks at 40°C); an increase in the value indicates crystal growth, and an increase of 2 times is generally still acceptable; an increase of more than 4 times is unacceptable. A value of -precipitate => 10% indicates the formation of significant precipitate.

[0193] - Sediment that can be shaken is acceptable; therefore, it is not suitable for pharmaceutical products because the active ingredient can no longer be converted into a spray. -Wet sieving = Measures the potential for filter clogging during spray application; values ​​> 0.1% on a 150 µm sieve and > 0.2% on a 45 µm sieve (based on the amount of formulation used, respectively) are unacceptable.

[0194] Preparation of aqueous suspension concentrate B: To prepare the products of the examples listed in Table 1, water is first added at room temperature. Then, while stirring, a) (and any other active ingredient e) and other components b), c), and f) (in no particular order) are added. a) is added warm (65°C in the case of pyrazosulfuron-methyl or 80°C in the case of quinalazine), and the mixture is stirred for 2 to 24 hours until crystals form. The mixture is then wet-milled, for example, in a ball mill. Finally, an organic thickener (component d1) is added.

[0195] In the alternative, water at 5°C is used instead of water at room temperature. The container is also cooled to 5°C. Initial pulverization is performed using a colloid mill. This allows crystallization to occur within half an hour. Wet grinding, such as by a ball mill, is then carried out.

[0196] Table 1: The numbers are in percentage of weight, weight % Comparative Example: When comparing C3 with 1 and C4 with 3, c1 is missing. Amorphous pyrazosulfuron is formed in the formulation and cannot be further processed. The formulation is not storage stable and must be discarded. Similarly, in C5, which does not contain the organic thickener d1, the result is a storage unstable product, which must also be discarded.

[0197] Stability of water-containing dispersants: The dispersants of the present invention in the examples exhibit excellent storage stability. They are stable without any significant changes for at least 2 years at room temperature and at least 3 months at 40°C.

[0198] Table 2: Storage stability and other formulation properties of suspension concentrates 1-3: All formulations according to the present invention exhibit very good storage stability. No amorphous active ingredients were identified under a microscope.

[0199] Preparation of the present invention - Concentrate A) To prepare Examples 4-6 and C2 listed in Table 2, water was first added at room temperature. While stirring, active ingredient e was added (in the case of iodosulfuron, the reaction was carried out with NaOH (32%) to pH 8). B1), B2), C1), C2), and F) were added. Component a) was added warmly (65°C in the case of pyrazosulfuron), and the mixture was stirred for 2 to 24 h until crystals formed. Then, wet milling was performed, for example, using a ball mill.

[0200] Preparation of a portion-concentrate not of this invention To prepare the product of Example C1 listed in Table 2, water was first added at room temperature. While stirring, active ingredient e) was added (in the case of iosulfuron, the reaction was carried out with NaOH (32%) to pH 8). b1), b2), c1), c2), and f) were added. Then component a) was dissolved in Solvesso. ® It is added as a solution in 200 ND. Then, wet milling is performed, for example, by ball milling. This forms a suspension consisting of dispersed solids (e) and emulsified solids (a).

[0201] The TC slurries according to the invention obtained from Examples 1 to 3 and non-Example C1 were further processed to obtain WG. Fluidized bed drying was performed according to prior art. Examples 1-3 were free of organic solvents; C1 still contained 16% by weight of Solvesso. ® 200 ND.

[0202] Table 3: Mother drug:(The numbers are in weight percentage, weight %) WG's stability: The water-dispersible granules (4WG-6WG and C1 WG) of the embodiments of the present invention, prepared from parent drugs 4-6 and C1, exhibit excellent storage stability. They are stable without any significant changes for at least 2 years at room temperature and at least 3 months at 40°C. The comparative example C1 WG contains undesirable Solvesso. ® 200 ND.

[0203] Table 4: Storage stability and other formulation properties

Claims

1. A method for preparing an aqueous formulation without organic solvents, characterized in that: In the first step, at least one active agricultural chemical component a) with a melting point in the range of 50°C to 80°C is first melted, and then the melt is added to water containing at least one ionic and / or nonionic dispersant b) under stirring. In the second step, the mixture is cooled to below the melting point of the active component. Characterized by the fact that the active ingredient a) is pyrazolyl glufosinate, and wherein... In the first step, component a) is added to an aqueous solution comprising an ionic dispersant b1), a carrier material c1), and a filler c2), wherein the temperature of the water is 0°C to 40°C, and wherein, in the second step, the mixture is stirred for 5 minutes to 24 hours during cooling, and wherein at least 90% by weight of pyrazole-propargyl crystals are detectable under a microscope, based on the pyrazole-propargyl used, and the crystalline active ingredient no longer has an amorphous structure. And c1) is selected from a highly absorbent carrier with an absorption capacity of at least 200 g dibutyl phthalate / 100 g carrier material, wherein the highly absorbent carrier is selected from silica.

2. The method according to claim 1, characterized in that, In the third step, the crystallized product is ground so that at least 50% of the particles have a size of 1 to 5 µm (d50, volumetric particle size).

3. The parent drug (TC) obtainable by the method according to claim 2.

4. The water-dispersible granules (WG) obtainable by the method according to claim 1, characterized in that, After the third step, the water is removed, and particles are prepared using a fluidized bed method.

5. Solvent-free, water-dispersible technical material (TC), containing - Active ingredient a), having a melting point range of 50 to 80°C, wherein active ingredient a) is pyrazolium bromide. - One or more anionic emulsifiers (b1). - One or more nonionic emulsifiers (b2). - At least one or more carrier materials (c1) and - At least one filler (c2).

6. The solvent-free, water-dispersible parent drug (TC) according to claim 5, characterized in that, It contains active ingredient e), which is selected from sulfonylureas, HPPD (4-hydroxyphenylpyruvate dioxygenase) inhibitors, ALS (acetyllactate synthase) inhibitors and / or conventional pigment bleaching agents.

7. The solvent-free, water-dispersible parent drug (TC) according to claim 6, characterized in that, The active ingredient e) is selected from mesosulfuron-methyl, sodium salt of mesosulfuron-methyl or β-acid, pyrimisulfuron-methyl, thiamethoxam or pyrfluthrin.

8. Solvent-free water-dispersible suspension concentrate (SC), containing - Active ingredient a), having a melting point range of 50 to 80°C, wherein active ingredient a) is pyrazolium bromide. - One or more anionic emulsifiers (b1). - One or more nonionic emulsifiers (b2). - Carrier material c1), and - At least one or more thickeners (d).

9. The solvent-free aqueous dispersible suspension concentrate (SC) according to claim 8, characterized in that, It contains active ingredient e), which is selected from auxin, pigment synthesis inhibitor, DOXP synthase inhibitor and / or VLCFA inhibitor.

10. The solvent-free aqueous dispersible suspension concentrate (SC) according to claim 9, characterized in that, The active ingredient e) is selected from fluroxypyridine ester, pyrfluthrin, isochoryl ketone, isoxazolidinone, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-(CAS No. 81777-95-9) or fluthiamethoxam.

11. The herbicidal composition obtainable by diluting the formulation prepared according to the method of claim 1 with water.

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