Emulsifiable concentrate with lactone-based solvent system

Abstract

An emulsifiable concentrate (EC) comprising one or more pesticidal agents, one or more emulsifiers, and certain lactone-derived solvents, an emulsion-in-water (EW) formulation formed from the emulsifiable concentrate (EC), and the use of certain lactone-derived solvents as solvents in agrochemical emulsifiable concentrates are disclosed.

Description

Technical Field

[0001] The present invention relates to an emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers and certain lactone-derived solvents, to an emulsion-in-water (EW) formulation formed from the emulsifiable concentrate (EC), and to the use of certain lactone-derived solvents as solvents in agrochemical emulsifiable concentrates. Background Art

[0002] When preparing agricultural chemical formulations, it is usually necessary to dissolve agricultural chemical active ingredients (for example, one or more pesticides) in a solvent, then dilute it in the water of a larger volume, so that it is applied in the form of a fine spray. Alternatively, it may be necessary to dilute the agricultural chemical active ingredients in solution and load it onto a seed or a solid carrier. Although some agricultural chemical active ingredients are salts and therefore highly water-soluble, thereby allowing simple dissolution, many other non-ionic agricultural chemical active ingredients are hydrophobic and fully water-insoluble.

[0003] In the case where the active ingredient is not soluble in water, it is generally necessary to dissolve the formulation in a water-immiscible solvent and add one or more surfactants so that when added to water, the solution will form an oil-in-water emulsion. Such formulations are known as emulsifiable concentrate (EC) formulations. Alternatively, the water-immiscible solution containing the active ingredient can be pre-emulsified in water in concentrated form. Such formulations are known as emulsion-in-water (EW) formulations.

[0004] Water-immiscible solvents commonly used in EC and EW formulations include, but are not limited to, aromatic hydrocarbons such as Series, chain alkanes such as Category, ester solvents such as The invention relates to solvents which are immiscible with water at high concentrations and which exhibit improved toxicity and reduced flammability properties. These solvents include dibasic ester solvents of long chain diacids having 8-16 carbon units (which are typically methyl ester derivatives) and fatty acid amide solvents (examples of which are C6-C 16 Dimethylamide and morpholineamide derivatives of fatty acids). Monoalkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate are also used as cosolvents.

[0005] Combinations of water-immiscible solvents with highly polar water-miscible co-solvents such as N-methylpyrrolidone (NMP), dimethyl sulfoxide, dimethyl isosorbide, monoethylene glycol, monopropylene glycol, and various glycol ethers have been used in the past to achieve physical stability in EC formulations, particularly if crystallization of the active ingredient occurs at subambient temperatures. However, the use of such solvent combinations often leads to problems with crystallization in diluted formulations.

[0006] In the pesticide industry, there is a strong desire to find alternatives to currently used solvents (such as fatty acid amides, isophorone, methyl butyl ketone (MBK), NMP, etc.), which may be expensive, difficult to obtain, and / or environmentally undesirable due to their inherent phytotoxicity, toxicity (e.g., teratogenicity), or regulatory status.

[0007] Fatty acid esters have been used in emulsifiable concentrates and are known to be less hazardous / lower odor than fatty acid amides; however, they typically achieve only moderate to low solubility in a wide range of commercially important pesticides.

[0008] Thus, there remains a need for solvents suitable for use in emulsifiable concentrate formulations and emulsion-in-water formulations that combine low phytotoxicity and generally non-hazardous (e.g., non-irritating) properties with high solubility for a range of commonly used agrochemical active ingredients. Summary of the Invention

[0009] The discovery of the present invention is that certain lactone-derived solvents combine low phytotoxicity and generally non-hazardous (eg, non-irritating) properties with high solubility for a range of agrochemical active ingredients.

[0010] In a first aspect, the present invention relates to an emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers and one or more solvents, wherein at least one of the one or more solvents has a structure according to formula (I):

[0011]

[0012] wherein X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-,

[0013] R is selected from linear and branched C1 to C 15 alkyl or alkenyl, and each instance of R' is independently selected from H, Me, and Et.

[0014] In a further aspect, the present invention relates to an emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is the emulsifiable concentrate (EC) of the first aspect.

[0015] In another aspect, the present invention relates to the use of a compound having a structure according to formula (I) as a solvent in an agrochemical emulsifiable concentrate, preferably an emulsifiable concentrate (EC) according to the first aspect:

[0016]

[0017] wherein X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-,

[0018] R is selected from linear and branched C1 to C 15 alkyl or alkenyl, and each instance of R' is independently selected from H, Me, and Et.

[0019] In a final aspect, the present invention relates to the use of the emulsion-in-water (EW) formulation according to the above further aspects for treating plants in order to maintain plant health without causing plant damage.

[0020] definition

[0021] Emulsifiable concentrates are typically optically clear, oily liquid formulations prepared by dissolving a certain amount of a pesticide in an organic solvent (such as benzene, toluene, xylene, and mineral spirits), and may also contain surfactants (i.e., emulsifiers) and other additives. These concentrates are suitable for dispersion in an aqueous phase to form an emulsion-in-water formulation. Emulsifiable concentrates must be single-phase, i.e., the pesticide and any emulsifier must be completely soluble in the organic solvent at the concentration used.

[0022] An emulsion is a mixture of two or more generally immiscible liquids in which one liquid forms the dispersed phase, suspended as tiny droplets within another liquid (called the continuous phase). Emulsions are typically referred to as oil-in-water (i.e., water is the continuous phase) or water-in-oil (i.e., oil is the continuous phase). In the context of agrochemical formulations, oil-in-water emulsions (called water-in-emulsion formulations) are often used to disperse hydrophobic pesticides in fields of crop plants.

[0023] The U.S. Environmental Protection Agency (EPA) defines a pesticide as "any substance or mixture of substances intended for use in preventing, destroying, repelling, or mitigating any harmful organism." A pesticide can be a chemical substance or biological agent (such as a virus or bacteria) used against harmful organisms, including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microorganisms that compete with humans for food, destroy property, spread disease, or are otherwise a nuisance. In the context of agrochemical formulations, pesticides are used to actively target harmful organisms (typically fungi, insects, and / or weedy plants) without unduly damaging crop plants.

[0024] Phytotoxicity describes any adverse effect on plant growth, physiology, or metabolism caused by a chemical or biological agent. In the context of agrochemical formulations, it is desirable to avoid phytotoxic properties so that the health of the crop plants is not affected.

[0025] In the context of the present invention, alkyl refers to both straight and branched alkyl chains, whereas aryl refers to any aromatic carbocyclic ring system, either a single ring (eg phenyl) or a fused ring system (eg naphthyl or anthracenyl).

[0026] Lactones are cyclic carboxylic acid esters, i.e., hydrocarbon rings containing a -(C=O)-O- moiety. Lactones are typically classified by their ring size. α-lactones (α-lactone / alpha-lactone) have a 3-membered ring, β-lactones (β-lactone / beta-lactone) have a 4-membered ring, γ-lactones (γ-lactone / gamma-lactone) have a 5-membered ring, δ-lactones (δ-lactone / delta-lactone) have a 6-membered ring, and ε-lactones (ε-lactone / epsilon-lactone) have a 7-membered ring. Of these lactones, γ-lactones and δ-lactones are the most stable and common. DETAILED DESCRIPTION

[0027] In a first aspect, the present invention relates to an emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers and one or more solvents, wherein at least one of the one or more solvents has a structure according to formula (I):

[0028]

[0029] wherein X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-,

[0030] R is selected from linear and branched C1 to C 15alkyl or alkenyl, and each instance of R' is independently selected from H, Me, and Et.

[0031] solvent

[0032] An essential component of an emulsifiable concentrate (EC) is one or more solvents.

[0033] At least one of the one or more solvents according to the present invention has a structure according to formula (I):

[0034]

[0035] wherein X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-,

[0036] R is selected from linear and branched C1 to C 15 alkyl or alkenyl, and each instance of R' is independently selected from H, Me, and Et.

[0037] In its broadest form, R is selected from linear and branched C1 to C 15 However, it is preferred that R is selected from linear and branched C1 to C 15 Alkyl, more preferably selected from C2 to C 12 Alkyl, more preferably selected from C3 to C 10 Alkyl, most preferably selected from C4 to C8 alkyl.

[0038] Particularly preferred examples of R include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, sec-pentyl, sec-hexyl, sec-heptyl, and sec-octyl, most particularly n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and sec-pentyl.

[0039] In its broadest form, X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-. In the above structures, the left-hand end of the X moiety is directly bonded to the carbonyl group, while the right-hand end of the X moiety is directly bonded to the CHR group. This means that in the case of X=-CR'=CR'CR'2-, the lactone is a stable α,β-unsaturated δ-lactone, rather than an unstable β,γ-unsaturated δ-lactone.

[0040] Within each definition of X, each instance of R' is independently selected from H, Me, and Et. Preferably, each instance of R' is independently selected from H and Me. In a particularly preferred embodiment, each instance of R' is H. In an alternative embodiment, one instance of R' is Me, and every other instance of R' is H. In yet another alternative embodiment, two instances of R' are Me, and every other instance of R' is H.

[0041] Particularly preferably, X is selected from -CH2CH2-, -CH(Me)CH2-, -CH2CH(Me)-, and -CH2CH2CH2-, more preferably selected from -CH2CH2-, -CH2CH(Me)-, and -CH2CH2CH2-.

[0042] For reasons explained above regarding which end of the X moiety is bonded to the carbonyl group, the structure with X = -CH(Me)CH2- represents an α-methylated γ-lactone, while the structure with X = -CH2CH(Me)- represents a β-methylated γ-lactone.

[0043] In a particularly preferred embodiment, the structure according to formula (I) is a γ-lactone.

[0044] In the γ-lactone according to formula (I), X is preferably selected from -CH2CH2-, -CH(Me)CH2-, and -CH2CH(Me)-, more preferably selected from -CH2CH2- and -CH2CH(Me)-.

[0045] Particularly preferred γ-lactones include γ-octalactone, γ-nonalactone, γ-decanolactone, γ-undecalactone, γ-dodecalactone, β-methyl-γ-octalactone, δ-methyl-γ-octalactone, and β,δ-dimethyl-γ-octalactone.

[0046] In an alternative particularly preferred embodiment, the structure according to formula (I) is a delta-lactone.

[0047] In the delta-lactone according to formula (I), X is preferably -CH2CH2CH2-.

[0048] Particularly preferred delta-lactones include delta-nonalactone, delta-decanolide, delta-dodecalactone, and delta-tridecalactone.

[0049] In a particularly preferred embodiment, the solvent having a structure according to formula (I) has 8 or more carbon atoms.

[0050] Another advantage of solvents having a structure according to formula (I) is that they have a pleasant odor. For example, γ-nonalactone has a coconut odor, γ-decalactone has a peach-like odor, and δ-decalactone has a creamy peach-like odor. These odors mean that the resulting emulsifiable concentrates (ECs) and emulsions prepared therefrom are more pleasant to use than many commercial amide-containing emulsifiable concentrate solvents, which typically have an unpleasant fishy odor.

[0051] Preferably, the solvent has low water solubility to ensure that an emulsion is formed rather than a solution.

[0052] Therefore, it is preferred that the solvent has a water solubility of less than 2.0% w / w, more preferably less than 1.0% w / w, most preferably less than 0.5% w / w.

[0053] It is also preferred that the solvent has low phytotoxicity, meaning that the presence of the solvent in the emulsifiable concentrate (EC) and any emulsion-in-water (EW) formulation formed therefrom does not cause plant damage, more particularly does not cause plant damage to soybean plants.

[0054] In particular, it is preferred that the solvent has low phytotoxicity, wherein low phytotoxicity is defined as when an emulsion containing 99.0% w / w water relative to the total weight of the emulsion and 1.0% w / w of a non-aqueous phase relative to the total weight of the emulsion (which contains 90% w / w of the solvent, 7.5% w / w of castor oil ethoxylate and 2.5% w / w of calcium dodecylbenzenesulfonate (each relative to the total weight of the non-aqueous phase)) does not cause more plant damage than an aqueous solution of 0.075% w / w castor oil ethoxylate and 0.025% w / w of calcium dodecylbenzenesulfonate (each relative to the total weight of the aqueous solution) when measured 14 days after application to soybean plants at an application rate of 200 L / hectare.

[0055] This is particularly important for agrochemical emulsifiable concentrates because it improves the specificity of the resulting in-water emulsion when applied to crop plants.Pesticides can actively target relevant pests (e.g., insects, fungi or weed plants) while the crop plants are not adversely affected.

[0056] The total content of solvents having a structure according to formula (I) is preferably in the range of 10% w / w to 85% w / w, more preferably 15% w / w to 75% w / w, most preferably 25% w / w to 60% w / w relative to the total weight of the emulsifiable concentrate (EC).

[0057] The one or more pesticides

[0058] Another essential component of the emulsifiable concentrate (EC) is one or more pesticides.

[0059] The one or more pesticides of the present invention are not limited.

[0060] A pesticide is generally a chemical or biological agent (such as a pesticidal active ingredient, compound, composition, virus, bacteria, antimicrobial agent, or disinfectant) that, through its effect, deters, disables, kills, or otherwise thwarts pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microorganisms that damage property, cause nuisances, spread disease, or are vectors of disease. The term "pesticide" also includes plant growth regulators that alter the desired growth, flowering, or reproductive rate of a plant; defoliants that cause leaves or other foliage to fall from a plant, typically to facilitate harvesting; desiccants that promote the drying of living tissue, such as unwanted aerial parts of a plant; plant activators that activate plant physiology to defend against certain pests; safeners that reduce the unwanted herbicidal effects of pesticides on crop plants; and plant growth promoters that affect plant physiology, for example, to enhance plant growth, biomass, yield, or any other quality parameter of harvestable items of a crop plant.

[0061] The following list of pesticides suitable for use in the emulsifiable concentrates of the present invention is intended to illustrate possible combinations but does not limit them:

[0062] A) Respiratory depressants

[0063] - Complex III inhibitors at the Qo site: azoxystrobin, cypermethrin, syringosterone, kypermethrin, enestrobin, enestrobin, fenoxystrobin (flufenoxystrobin), fluoxastrobin, kresoxim-methyl, mandestrobin, fenoxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, trifloxystrobin, pyraclostrobin, trifloxystrobin, pyraclostrobin, trifloxystrobin, triclopyricarb, chlorodincarb, oxadiazon, fenamid, pyrimidine, pyrimethanil, pyrifloxystrobin, tetracycline;

[0064] - Complex III inhibitors at the Qi site: cyazofamid, indazolesulfamide, fenpicoxamid, pyridoxamide, pyridoxamide;

[0065] - Complex II inhibitors: oxadixanil, benzovinflupyr, bixafen, boscalid, carboxin, furamide, fluopyram, flutolanil, fluopyram, furazolidone, isopyram, pyraclostrobin, mefenadil, oxycarboxin, fluopyram, penthiopyrad, fluopyram, bixafen, flutolanil, chlorothalonil, thiofuran, inpyrfluxam, pyrapropoyne, fluinoxam, isoflucypram, triflupyramide;

[0066] - Other respiratory inhibitors: diflumetorim; nitrophenyl derivatives: binapacryl, diflubenzuron, diclofenac, fluazinam, nitrostrobin; ferimzone; organometallic compounds: triphenyltin salts, for example, triphenyltin acetate, triphenyltin chloride or triphenyltin hydroxide; silthiopyrad;

[0067] - Quinone exo-inhibitor stigmatellin binding type: ametoctradin;

[0068] B) Sterol biosynthesis inhibitors (SBI fungicides)

[0069] -C14 demethylase inhibitors: triazoles: azaconazole, bifenthiazolin, oxadiazole, cyproconazole, difenoconazole, diniconazole, R-diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imipenem, picronil, metconazole, myclobutanil, oximidazole, paclobutrazol, penconazole, propiconazole, prothioconazole, silyclofazole, tebuconazole, fluconazole, triadimefon, triadimenol, triticonazole, uniconazole, fluopyram, ipfentrifluconazole, clofoconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines, piperazines: clofofenamide, pyrimidine oxime, triflumizol;

[0070] -δ14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, isotridemorph, fenpropidin, spiroxathiapiprolin, spiroxathiapiprolin;

[0071] -3-Ketoreductase inhibitors: fenacet, fenacet-3-pyraclostrobin;

[0072] -Other sterol biosynthesis inhibitors: clofentoxazole;

[0073] C) Nucleic acid synthesis inhibitors

[0074] - RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, furamide, oxadixyl;

[0075] - Other nucleic acid synthesis inhibitors: oxamexazole, octhiocarb, oxolinic acid, pyrimethanol sulfonate, 5-flucytosine, isoflurane, and flutolanil;

[0076] D) Inhibitors of cell division and cytoskeleton

[0077] - Tubulin polymerization inhibitors: benomyl, carbendazim, thiophanate-methyl, thiophanate-methyl, pyridachlometyl;

[0078] - Other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopyram, zoxamide, mefenacet, fenpyrad, cyproconazole, cyproconazole, fluopyram;

[0079] E) Amino acid and protein synthesis inhibitors

[0080] -Methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;

[0081] - Protein synthesis inhibitors: blasticidin, kasugamycin, kasugamycin hydrochloride hydrate, midonomycin, streptomycin, oxytetracycline;

[0082] F) Signal transduction inhibitors

[0083] -MAP / histidine kinase inhibitors: fluazifop, iprodione, procymidone, vinclozolin, fludioxonil;

[0084] -Mechanism unknown: fluphenoxyquin, propoxyiodoquin;

[0085] G) Lipid and membrane synthesis inhibitors

[0086] - Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyraclostrobin, isoprothiolane;

[0087] -Lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, and etridiazole;

[0088] -Compounds and fatty acids that affect cell membrane permeability: propamocarb;

[0089] - Oxysterol-binding protein inhibitors: fluoxapiprolin, fluoxapiprolin;

[0090] H) Inhibitors with multi-site action

[0091] - Inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

[0092] -Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;

[0093] -Organochlor compounds: difop-butyl, chlorothalonil, captol, captan, folpet, bacteriostatic, dichlorophen, hexachlorobenzene, pentachlorophenol and its salts, phthalide, tolylfluanid;

[0094] -Guanidine and others: guanidine, dodine, dodine free base, guazatine, guazatine acetate, guazatine octylamine, guazatine octylamine triacetate, guazatine trioctylbenzenesulfonate, dithianon, fluazifop, sulfamethoxazole, and chloranil;

[0095] I) Cell wall synthesis inhibitors

[0096] - Glucan synthesis inhibitors: validamycin, polyoxin B;

[0097] -Melanin synthesis inhibitors: pyroquilon, tricyclazole, cyproconazole, dicyclomet, pyraclostrobin, trifluomethiocarb;

[0098] - Cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benzathiapyr, valinomycin, and valosin;

[0099] J) Plant defense inducers

[0100] -Acibenzolar-S-methyl, probenazol, isothiocyanate, tiadinil, prohexadione-calcium; phosphonates: fosetyl acid, fosetyl-aluminum, phosphorous acid and its salts, calcium phosphonate, potassium phosphonate, potassium or sodium bicarbonate, dichlorobenzothiazole;

[0101] K) Unknown mode of action

[0102] - bronopol, cyfluanid, cymoxanil, dazomethanil, imidacloprid, dichlorocyanamide, pyraclostrobin, diflubenzuron, diflubenzuron methyl sulfate, diphenylamine, chloranil, flumetover, flumetylsulforim, sulfamethoxam, fluthiazolinone, hypersensitive protein, chlorpyrifos, phthalocyanine, copper quinoline, seboctylamine, isobutylethoxyquin, phthalocyanine, imidazolin, pyraclostrobin, thiabendazole, bromothionil, aminopyrifen, flufenoxadiazam;

[0103] L) Biopesticides

[0104] L1) Microbial pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: Parasiticidal spores, Aspergillus flavus, Aureobasidium brevis, Bacillus spp., Bacillus amyloliquefaciens, Bacillus amyloliquefaciens plantarum (also known as Bacillus velez), Bacillus megaterium, Bacillus mohaievii, Bacillus mycoides, Bacillus pumilus, Bacillus simplex, Bacillus haloterreus, Bacillus subtilis, Bacillus subtilis var. amyloliquefaciens, Bacillus velez, Candida oleifera, Candida saitoana, Clavibactermichiganensis (bacteriophage), Cleometheus spp., Cryptococcus parasiticus, Cryptococcus albus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea. catenulate (also known as Gliocladium catenulatum), pink Glioma, Antibiotic Lysobacter, Mycobacterium, Drupe Meiqi yeast, Microdochium dimerum, Sphaeroides, Muscodor albus, Bacillus alveoli, Paenibacillus epiphyticus, Paenibacillus polymyxa, Pantoea agglomerans, Penicillium bilaireae, Macrocortisone, Pseudomonas species, Pseudomonas viridis, Pseudo-zyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces glaucum, Streptomyces lydicus, Streptomyces violaceus, Streptomyces leucoderma, Trichoderma spp. asperelloides), Trichoderma acanthophorum, Trichoderma amurensis, Trichoderma apical, Trichoderma gaimsii, Trichoderma harmatum, Trichoderma harzianum, Trichoderma polysporum, Trichoderma stromaticum, Trichoderma virens, Trichoderma viride, Typhula phacorrhiza, Typhula serrata, Verticillium dahliae, and zucchini yellow mosaic virus (avirulent strain);

[0105] L2) biochemical pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: hypersensitive proteins, Knotweed extracts;

[0106] L3) Microbial pesticides with insecticidal, acaricidal, snail-killing and / or nematicidal activity: Agrobacterium radiobacterium, Bacillus cereus, Bacillus firmus, Bacillus thuringiensis, Bacillus thuringiensis subsp. ayuzawa, Bacillus thuringiensis subsp. israelensis, Bacillus thuringiensis subsp. wax moth, Bacillus thuringiensis subsp. kurstak, Bacillus thuringiensis subsp. pseudolobatus, Beauveria bassiana, Beauveria bassiana, Burkholderia species, Chromobacterium sub-tsugae, Codling moth granulovirus, Pseudocodling moth granulovirus, Flavobacterium species, Helicoverpa armigera nuclear polyhedrosis virus, Spodoptera zea nuclear polyhedrosis virus, Spodoptera zea single capsid nuclear polyhedrosis virus, Heterorhabditis elegans, Coryneformis fumosorum, Lecanicillium longisporum longisporum), L. muscarium, Metarhizium anisopliae, Metarhizium anisopliae microspore var., Metarhizium anisopliae locust var., Nomura leishmanii, Paecilomyces fumosoroseus, Paecilomyces lilacinus, Paenibacillus japonicus, Pasteurella species, Pasteurella szabalais, Pasteurella penetrantis, Pasteurella ramosa, Pasteurella listeri, Pasteurella usgae, Pseudomonas fluorescens, Spodoptera nuclei nuclear polyhedrosis virus, Steinberger nematode, Steinberger nematode, Sawfly nematode, Streptomyces luteus, Streptomyces tenuis;

[0107] L4) Biochemical pesticides with insecticidal, acaricidal, molluscicidal, pheromone and / or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-decadienoic acid ethyl ester (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavandulyl senecioate, cis-jasmone, 2-methyl-1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-acetic acid )-2,13-octadecadien-1-ol ester, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, termite pheromone (pentatermanone), (E,Z,Z) 3,8,11-tetradecadien-1-yl acetate, (Z,E) 9,12-tetradecadien-1-yl acetate, (Z) 7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, Chenopodium ambrosiodes extract, neem oil, Quillay extract;

[0108] L5) Microbial pesticides with plant stress-reducing, plant growth regulator, plant growth-promoting and / or yield-enhancing activity: Azospirillum agalactiae, Azospirillum brasiliensis, Azospirillum lipogenicum, Azospirillum iraqium, Azospirillum euryhaline, Bradyrhizobium sp., Bradyrhizobium elsdenii, Bradyrhizobium glycines, Bradyrhizobium liaoningensis, Bradyrhizobium lupini, Delftia acidovorans, arbuscular mycorrhizal fungi, Mesorhizobium sp., Rhizobium leguminosarum biotype bean, Rhizobium leguminosarum biotype trifolium, Rhizobium leguminosarum biotype faba bean, Rhizobium tropicalis, and Sinorhizobium meliloti;

[0109] O) Insecticides from categories O.1 to O.29

[0110] O.1 Acetylcholinesterase (AChE) inhibitors: aldicarb, cotton boll carb, benfuracarb, benfuracarb, butanone carb, butanone sulfone carb, carbaryl, carbofuran, butanfuracarb, ethiofencarb, fenbutacarb, fenthiocarb, furamicarb, isoprocarb, methiocarb, methomyl, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, long-lasting carb, mixed carb, XMC, methomyl, triazolam; acephate, methyl pyridinium, ethyl azinphos-methyl, azinphos-methyl, cadusofos, chlorpyrifos, chlorpyrifos, methyl chlorpyrifos, coumaphos, nitrobenzene, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, methyl chlorpyrifos, Ethiophos, EPN, ethion, propamiphos, fenamiphos, fenamiphos, fenitrothion, fenthion, thiathion, heptenophos, cyanimiphos, isopropylamidophos, O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, chlorpyrifos, methamidophos, methidathion, mevinphos, monocrotophos, dibromophos, omethoate, sulfone, parathion, methyl parathion, fenamiphos, phorate, phosalone, phosmet, phosphamidon, phoxim, methyl pirimiphos, profenofos, methoprene, profenofos, pyraclofos, pyridazinphos, quinalphos, chlorpyrifos, butyl pirimiphos, tebufos, terbufos, chlorpyrifos, methyl pirimiphos, triazophos, trichlorfon, aphidox;

[0111] O.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, butenefipronil, pyrafluprole, pyriprole;

[0112] O.3 Sodium channel modulators: flumethrin, allethrin, dextro-cis-trans allethrin, dextro-trans allethrin, bifenthrin, k-bifenthrin, bio-allethrin, bio-allethrin S-cyclopentenyl, bio-resmethrin, acetothrin, cypermethrin, β-cypermethrin, flucypermethrin, λ-cypermethrin, γ-cypermethrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, phenothrin, deltamethrin, Cypermethrin, esfenvalerate, etofenprox, cypermethrin, fenvalerate, flucythrin, flumethrin, fluvalinate, bromofluthrin, tefluthrin, iminothrin, chlorfluthrin, metofluthrin, methifluthrin, ε-metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), pyrethrum, silafluthrin, tefluthrin, kappa-tefluthrin, tetrafluthrin, tetramethrin, tralomethrin, transfluthrin; DDT, methoxychlor;

[0113] O.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloheximide, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyralid, trifluanid, bithiazol, flufenoxam;

[0114] O.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, ethyl spinosad;

[0115] O.6 Chloride channel activators: abamectin, avermectin benzoate, ivermectin, lepidomectin, and mitramectin;

[0116] O.7 Juvenile hormone simulants: methoprene, methoprene, methoprene; fenoxycarb, pyriproxyfen;

[0117] O.8 Various nonspecific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfonyl fluoride, borax, tartar emetic;

[0118] O.9 String organ TRPV channel modulators: diprofenoic acid, pymetrozine, and flubendiamide;

[0119] O.10 Mite growth inhibitors: clofentezine, hexythiazox, fluazifop; etoxazole;

[0120] O.11 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, Bacillus sphaericus, and insecticidal proteins produced by them: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis; Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1;

[0121] O.12 Mitochondrial ATP synthase inhibitors: diafenthiuron; azoxatin, cyhexatin, fenbutatin, propargite, and fenbutalin;

[0122] O.13 Oxidative phosphorylation decouplers via proton gradient interference: chlorfenapyr, DNOC, sulfluramid;

[0123] O.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: sulfamethoxazole, cartap, thiophanate-methyl, and dimethoate;

[0124] O.15 Chitin biosynthesis inhibitors type 0: bistrifluanuron, chlorfluazuron, diflubenzuron, flufenoxuron, flufenoxuron, hexaflumuron, lufenuron, flufenoxuron, perfluanidone, flubendiamide, fluazifop-urea;

[0125] O.16 Chitin biosynthesis inhibitor type 1: thiazolinone;

[0126] O.17 Molting disruptor: cyromazine;

[0127] O.18 Ecdysone receptor agonists: methoxyfenozide, tebufenozide, chlorfenozide, furofenozide, chlorfenozide;

[0128] O.19 Octopamine receptor agonist: amitraz;

[0129] O.20 Mitochondrial complex III electron transport inhibitors: hydrazone, acequinoxaline, pyrimidifen, bifenazate;

[0130] O.21 Mitochondrial complex I electron transport inhibitors: quinazofen, fenpyraclostrobin, pyrimidifen, pyridabenz, tebufenpyrad, tolfenpyrad; rotenone;

[0131] O.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone;

[0132] O.23 Acetyl-CoA carboxylase inhibitors: spirodiclofen, spiromesifen, spirotetramat, methoxyfenethyl, spirodiclofen, spidoxamat;

[0133] O.24 Mitochondrial complex IV electron transport inhibitors: aluminum phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;

[0134] O.25 Mitochondrial complex II electron transport inhibitors: cypermethrin, cyfluthrin, ethoxyfen, pyrazoanilide;

[0135] O.28 Rianodin receptor modulators: chlorantraniliprole, cyantraniliprole, cyclobromofenamic acid, flubendiamide, fluchlorfenapyr; tetrachlorfenapyr; tetrazolyl fenamic acid; thiofenamic acid; chlorantraniliprole;

[0136] O.29 String organ regulator: flonicamid;

[0137] O.30 GABA-gated chloride channel allosteric modulators: bromofenac, chlorfluanid, isoxathiapyr;

[0138] O.33 Calcium-activated potassium channel modulator: acynonapyr;

[0139] O.34 Mitochondrial complex III electron transport inhibitor at the Qi site: flometoquin;

[0140] O.UN Insecticide compounds with unknown or uncertain mode of action: afolan, azadirachtin, sulfamethoxam, benzyl methacrylate, bromopyralid, chlorpyrifos, cryolite, cyprodinil, dichlorothiazide, dicofol, methifenpyrad, flumethrin, flometoquin, flufenoxanil, fluopyram, fluopyram, flurelana, metaldehyde, oxazolidinone, piperonyl butoxide, trifluoromethylpyralid, thiophene, trifluoroacetic acid ester, umifoxolaner, based on Bacillus firmus firmus) (Votivo); trifluanidamide; chlorpyrifos; sarolana, lotirana; benzpyrimoxan; tigolaner; oxazolidinone; cyprodinil, nicofluprole; indole; flufenacet; cyclobutrifluram; trifluanidamide (cyclobutrifluram).

[0141] P) Herbicides from categories P1 to P15

[0142] P1) Lipid biosynthesis inhibitors:

[0143] -ACC-herbicides: fenpyroxene, fenpyroxene-sodium, fenpyroxene, clethodim, clodinafop-butyl, clodinafop-butyl, cyhalofop-butyl, cyhalofop-butyl acid, cyhalofop-butyl, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene;

[0144] - Non-ACC herbicides: benfuresate, butylate, cycloate, dalapon, pyraclostrobin, EPTC, pentocarb, ethoxyfuroxate, tetrafluoropropionic acid, molinate, orbencarb, pebulate, prosulfocarb, TCA, pyraclostrobin, pyraclostrobin, and vernolate;

[0145] P2) ALS inhibitors:

[0146] -Sulfonylureas: amidosulfuron-methyl, tetrazosulfuron-methyl, benzylsulfuron-methyl acid, benzylsulfuron-methyl, chlorimuron-methyl acid, chlorimuron-methyl ... , metazosulfuron, metsulfuron-methyl acid, metsulfuron-methyl, nicosulfuron-methyl, pyrimidinesulfuron-methyl, epoxysulfuron-methyl, primisulfuron-methyl acid, primisulfuron-methyl, promazinesulfuron-methyl, prosulfuron, pyrazosulfuron-methyl acid, pyrazosulfuron-methyl, sulfonesulfuron-methyl, sulfosulfuron-methyl acid, sulfosulfuron-methyl, thifensulfuron-methyl acid, thifensulfuron-methyl, ethersulfuron-methyl, tribenuron-methyl acid, tribenuron-methyl, trifloxysulfuron, trifloxysulfuron-methyl acid, trifloxysulfuron-methyl and trifloxysulfuron-methyl;

[0147] - Imidazolinones: imazamox, imazamox methyl, imazamox, imazamox-methyl, imazapyr, imazapyr, imazaquin and imazamox;

[0148] - triazolopyrimidine herbicides, and sulfonanilides: clofosulphonic acid, clofosulphonamide, diclofosulphonamide, fluazifop, fluazifop, penoxsulam, pyrimisulfan and pyrimisulfan;

[0149] - Pyrimidinyl benzoates: bispyribac-sodium, bispyribac-sodium, pyrimidoxifen, pyrimidoxifen-sodium, pyrimidoxifen acid, pyrimidoxifen-sodium, pyrimidoxifen-sodium;

[0150] -Sulfonylaminocarbonyl-triazolinone herbicides: flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiathionyl acid and thiathionyl;

[0151] - and fluazifop;

[0152] P3) Photosynthesis inhibitors:

[0153] Amicarbazone, inhibitors of photosystem II, triazine herbicides including chlorotriazines, triazinones, triazindiones, methylthiotriazines, and pyridazinones such as ametryn, atrazine, chlorpyrifos, cyanazine, dichlorvos, isopentanol, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazine, terbutryn and trietazin, aryl ureas such as chlorbromide, chlorotoluron, chloroxuron, oxazoluron, diuron, fluuron, isoproturon, isoproturon, oxazolidinone, linuron, metamitron, methylbenzimidazole, pyranuron, methoxuron, chlorothiazuron, thiocarb, lenauron, tebuthiocarb and thiadiazuron, phenylcarbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uracils such as bromophenoxim, lenauryl and ternacil, as well as bentazone and bentazone-sodium, pyridate, pyridafol, meclofenamide and propanil, and inhibitors of photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-bismethylsulfate;

[0154] P4) Protoporphyrinogen-IX oxidase inhibitors:

[0155] Acifluorfen, Acifluorfen sodium, Fenpyrazone, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron-butyl ...

[0156] P5) Bleach Herbicides:

[0157] -PDS inhibitors: fluazifop, flufenacet, flupyridone, flurochloridone, fluchloridone, norflurazon, flupyridone, rimisoxafen;

[0158] -HPPD inhibitors: benzobicyclon, benzofenap, flupyralid, isoxaflutole, fenquinone, isoxaflutole, mesotrione, oxotrione, pyrazolynate, pyrazoxyfen, sulfotrione, tefuryltrione, cyproconazole, pyraclostrobin, benzyltrione, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxypyrithione;

[0159] - bleaching agents, unknown target: aclonifen, chlorfenapyr, flumeturon, bixlozone;

[0160] P6) EPSP synthase inhibitors:

[0161] glyphosate, glyphosate-isopropylammonium, glyphosate-potassium, and glyphosate-trimethylsulfonate (glufosinate);

[0162] P7) Glutamine synthase inhibitors: bialaphos (bialaphos), bialaphos-sodium, glufosinate, glufosinate-sharpened, and glufosinate-ammonium;

[0163] P8) DHP synthase inhibitors: asulam;

[0164] P9) Mitosis inhibitors:

[0165] -K1 group: Dinitroanilines: fluazifop, butralin, dimethalin, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine, and trifluralin; Phosphamides: fenamiphos, fenamiphos-methyl, and butamiphos; Benzoic acid herbicides: chlorthal, chlorthal-methyl; Pyridines: dithiopyr and thiapyr; Benzamides: propyzamide and tebutam;

[0166] -K2 group: carbetamide, chlorpropamine, chlorpyrifos, chlorpyrifos-isopropyl, chlorpyrifos-methyl, chlorpyrifos-isopropyl, chlorpyrifos-methyl and chlorpyrifos;

[0167] P10) VLCFA inhibitors:

[0168] - Chloroacetamides: acetochlor, alachlor, acetamiprid, butachlor, dimethachlor, dimethenamid, dimethenamid-S, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propisochlor, propisochlor, and thenylchlor,

[0169] -Oxyacetanilides: flufenacet and mefenacet;

[0170] - Acetanilides: diphenamid, naproxen, naproxen, and dichlorvos;

[0171] - Tetrazolinones: fentrazamide;

[0172] - Other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, pyroxasulfone, pyroxasulfone, dimethoate and isoxazoline;

[0173] P11) Cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, fluazifop, indazine fluazifop, isoxaben, triazine fluazifop;

[0174] P12) Decoupling herbicides: dinoseb, dinoterb and DNOC and their salts;

[0175] P13) Auxin herbicides:

[0176] 2,4-D and its salts and esters, such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts, such as aminopyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, 2,4-dichlorprop and its salts and esters, flopyrauxifen ), fluroxypyr, fluroxyisopropyl butoxyisopropyl, fluroxyisooctyl isooctyl, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl ester, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-squared and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA(2,3,6) and its salts and esters, triclopyr and its salts and esters, florpyrauxifen, halauxifen ester and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid;

[0177] P14) Auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam, and naptalam-sodium;

[0178] P15) Other herbicides: bromobutyric acid chloranil, chloranil, chloranil, cyproconazole, benzylpyridinium, cyclopyrimorate and its salts and esters, dalapon, dazomethanil, diazepam, diazepam methyl sulfate, thiamethoxam, DSMA, cypermethrin, cypermethrin and its salts, ethoxybenzone, cypermethrin, cypermethrin butyl ester, furazolidone, cypermethrin, cypermethrin ammonium, indole, maleic hydrazide, fluazifop, methamphetamine, methacrylic acid sulfonate, methyl azide, methyl bromide, methyl-cypermethrin, methyl iodide, MSMA, oleic acid, oxazolidinone, nonanoic acid, chlorpyrifos, quinazolin, tetrafluanid, and cypermethrin.

[0179] Q) Safener

[0180] (Quinolin-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazole-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide, α-oximinophenylacetonitrile, acetophenone oxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzamide, 1,8-naphthalene dicarboxylic anhydride, 2-halo-4-(haloalkyl)-5-thiazolecarboxylic acid, thiophosphates and N-alkyl-O-phenylcarbamates and agriculturally acceptable salts thereof and agriculturally acceptable derivatives thereof, such as amides, esters and thioesters, provided that they have an acid group.

[0181] Each of the one or more pesticides can be any substance used to control pests, whether chemical or biological, such as insecticides, herbicides, fungicides, acaricides, rodenticides, nematicides, and miticides.

[0182] Suitable insecticides may preferably be selected from the group consisting of neonicotinoids, bisamides, benzoylureas and carbamates.

[0183] It is particularly preferred that each insecticide is selected from the group consisting of fenoxycarb, deltamethrin, piperonyl butoxide, imidacloprid, thiacloprid, acetamiprid, aldicarb, aldicarb sulfoxide, aldicarb sulfone, pirimicarb, chlorantraniliprole, terbufos, quinalphos, difenophos, phosmet, carbaryl, etoxazole, thiamethoxam, flonicamid, etofenprox, phorate, profenofos, parathion, methyl parathion, acephate, disulfoton, fenthion, fenvalerate, fipronil, propoxur, methomyl, metaflumizone, pymetrozine, oxamyl, fluvalinate, cypermethrin, flucythrin, bifenthrin, tetrathrin, prallethrin (mixture of isomers), permethrin (mixture of isomers), flumethrin (mixture of isomers), pyrethrins (mixture of isomers), spinetoram (J), abamectin (mixture of isomers), fenobucarb (BPMC), methiocarb, isoprocarb (MIPC), spirotetramat, spinosad, trichlorfon, fenamiphos sulfoxide, fenamiphos sulfone, 3-hydroxycarbofuran, aldrin, DDE(p-p'), DDD(op), DDD(p-p'), DDE(op), DDT(o-p'), dieldrin, endrin, endrin aldehyde, endrin ketone, isoaldrin, chlordecone, or mirex (dodecachlorooctahydro-1H-1,3,4-(epi-methanetriyl)cyclobuta[cd]pentadiene).

[0184] Suitable herbicides may preferably be selected from the group consisting of triazines and other photosystem 2 inhibitors, 2,6-dinitroanilines, ACCase inhibitors, PPO inhibitors, synthetic auxins, sulfonylureas, bipyrillium herbicides, chloroacetanilides, triazolopyrimidines, pyrazoles and herbicide safeners.

[0185] It is particularly preferred that each herbicide is selected from paclobutrazol, diuron, linuron, isoproturon, alachlor, pendimethalin, chlorpropham, 2,4,5-t-propionic acid, bentazone, isopropylamine, propazine, bromid, 2,4-DB, oxadiazine, fluazifop, pinoxaden, cypermethrin, cyanazine, simazine, atrazine, desethyl atrazine, or metribuzin.

[0186] Suitable fungicides may preferably be selected from the group consisting of pyrimidines, anilinopyrimidines, triazoles and other sterol demethylation inhibitors, triazolopyrimidines, MAP kinase inhibitors, strobilurins, adenosine deaminase inhibitors, pyrazoles and carboxamides.

[0187] It is particularly preferred that each fungicide is selected from the group consisting of triadimefon, boscalid, cyproconazole, cyproconazole, triadimefon, diniconazole, epoxiconazole, ethiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, myclobutanil, penconazole, propiconazole, prothioconazole, tebuconazole, tetrafluconazole, triadimefon, triadimenol, triticonazole, 2-aminobutane, 8-hydroxyquinoline sulfate, 2-phenylphenol (OPP), allethrin, clofonate, difop, azoxystrobin, bensulfuron, benomyl, benomyl, binapacryl, biphenyl, blasticidin, pyrimidine sulfonate, thiocyanate, calcium polysulfide, captol, captan, carbendazim, carboxin, cyproconazole, quinthiocarb, methylthiocarb ... , dimethoate, nitrochloroform, chlorothalonil, acetaminophen, thiophanate-methyl, thiophanate-methyl, cyazolin, cyazolin, cymoxanil, cyprodinil, bispyribac, dichlorophen, dichlorocyanamide, bacteriostatic, chloranil, chlornithine, ethofluanid, fluazifop, dimethomorph, diclofenac, diphenylamine, bispyribac, dimethomorph ... Amine, flutolanil, folpet, fosetyl-aluminum, tetrachlorophthalide, furalaxyl, seed dressing amine, biguanide salts, hexachlorobenzene, imazalil, biguanide octylamine, isothiocyanate (IBP), iprodione, valinomycin, blastifungin, kasugamycin, copper preparations (such as copper hydroxide, copper naphthaleneate, copper oxychloride, copper sulfate, copper oxide, quinoline copper and Bordeaux mixture), mancozeb, mancozeb, maneb, myrabendazole, kresoxim-methyl, mefenamic acid, metalaxyl, sulfamethoxam, furafur, mesamiprole, mefenamic acid, mefenamic acid, thiamethoxam, myclobutanil, nickel dimethyldithiocarbamate, phthalostrobin, chlorpyrifos, furamide, oxadixyl, oxamo carb, oxycarboxin, blastifogluconate, pencuron, chlorpyrifos, picoxystrobin, natamycin, piprolin, polyoxin, allylbenzazole, prochloraz, procymidone, propamocarb, propineb, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyrimethanil, pyrimethanil, pyrimethanil, pyroquilon, fluphenoxyquin, pentachloronitrobenzene (PCNB), silthiopyrad, spiroxam, sulfur and sulfur preparations, chlorpyrifos, tetrachloronitrobenzene, thiabendazole, thiabendazole, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, imidazobactam, salicystrobin, tricyclazole, isotride, trifloxystrobin, triflumizole, triflumuron, validamycin, vinclozolin, mancozeb, ziram, or zoxamide.

[0188] Suitable acaricides may preferably be selected from tebufenpyrad, aldicarb, azinphos-methyl, trithion, dimethoate, dicrotophos, triazophos, malathion, phosalone, methidathion, hexathiazox, propargyl, spirodiclofen, methamidophos, monocrotophos, fenthion, methylpirimiphos, epn, dichlorvos, ethion, fenitrothion, diazinon, chlorpyrifos, sulfamethoxam, pyridaben, cypermethrin, bifenazate, spiromesifen, fenpyroximate (mixture of isomers), acequinoxaline, or carbofuran.

[0189] One suitable rodenticide is coumaphos.

[0190] One suitable nematicide is ethoprophos.

[0191] A suitable acaricide is clofentezine.

[0192] In the context of agrochemical emulsifiable concentrates, the one or more pesticides are preferably selected from the group consisting of insecticides, herbicides, fungicides and combinations thereof, wherein examples of each class of pesticides may be as defined above and below.

[0193] Particularly preferably, at least one of the one or more pesticides is selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, difenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenacetate, epoxiconazole, flupyrad, fenbuconazole, tebuconazole, metaflumizone, pinoxaden, deltamethrin and pendimethalin.

[0194] The present invention has discovered that the solubility of each of these commercially important pesticides is generally improved in the solvents according to the present invention when compared to typical solvent systems used in agrochemical emulsifiable concentrates, such as fatty acid methyl esters and fatty acid dimethylamides.

[0195] Therefore, it is preferred that the total pesticide content in the emulsifiable concentrate (EC) is in the range of 5% w / w to 70% w / w, more preferably in the range of 10% w / w to 65% w / w, most preferably in the range of 15% w / w to 60% w / w relative to the total weight of the emulsifiable concentrate (EC).

[0196] In the context of agrochemical emulsifiable concentrates, it is also well known that more than one pesticide can be used, resulting in so-called combination formulations. Such combination formulations may have an improved effect because the individual pesticides act synergistically, or alternatively, the pesticides may be active against different pests, for example, one pesticide may be a herbicide and another may be an insecticide.

[0197] In one embodiment, the emulsifiable concentrate (EC) comprises two or more pesticides.

[0198] Many such combination formulations are commercially available and well known in the art.Therefore, there are no particular restrictions on the choice made in selecting the pesticide combination.

[0199] In a preferred embodiment, at least one, more preferably at least two, of the two or more pesticides are selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, difenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenamate ethyl, epoxiconazole, flupyrad, fenbuconazole, tebuconazole, metaflumizone, pinoxaden, deltamethrin and pendimethalin.

[0200] The one or more emulsifiers

[0201] Another essential component of the emulsifiable concentrate (EC) is one or more emulsifiers.

[0202] The one or more emulsifiers of the present invention are not particularly limited. In its broadest form, the one or more emulsifiers may be selected from any conventional emulsifier typically used in the field of agrochemical compositions and formulations.

[0203] For example, the one or more emulsifiers may be selected from:

[0204] - products of addition of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide to linear C8-22 fatty alcohols, C12-22 fatty acids and alkylphenols having 8 to 15 carbon atoms in the alkyl group;

[0205] - C12-18 fatty acid monoesters and diesters of addition products of 1 to 30 mol of ethylene oxide onto glycerol;

[0206] - glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof,

[0207] - addition products of 15 to 60 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0208] - polyol esters, and in particular polyglycerol esters, such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerisostearate;

[0209] - addition products of 2 to 15 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0210] - partial esters based on linear, branched, unsaturated or saturated C6-22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose);

[0211] - mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

[0212] - Wool wax alcohol;

[0213] - polysiloxane / polyalkyl polyether copolymers and corresponding derivatives;

[0214] - mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols and / or mixed esters of C6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol, and

[0215] -Polyalkylene glycol.

[0216] The one or more emulsifiers are preferably selected from the group consisting of nonionic emulsifiers, anionic emulsifiers and combinations thereof.

[0217] It is particularly preferred that at least one of the one or more emulsifiers is a nonionic emulsifier.

[0218] It is also preferred that at least one of the one or more emulsifiers is an anionic emulsifier.

[0219] In a particularly preferred embodiment, the one or more emulsifiers comprise, more preferably consist of, a nonionic emulsifier and an anionic emulsifier.

[0220] Suitable nonionic emulsifiers can be selected from the group consisting of copolymers containing ethylene oxide and propylene oxide monomers, alcohol alkoxylates, alkyl polyglucosides, amino polyols, polyalkylene glycols, alkoxylated animal or vegetable fats and oils such as corn oil ethoxylate, soybean oil ethoxylate, castor oil ethoxylate, tallow fat ethoxylate, glycerides such as glycerol monostearate, fatty alcohol alkoxylates and oxyalcohol alkoxylates, fatty acid alkoxylates such as oleic acid ethoxylate, alkylphenol alkoxylates such as isononylphenol ethoxylate, fatty amine alkoxylates, fatty acid amide alkoxylates, sugar surfactants such as sorbitan fatty acid esters (e.g., sorbitan monooleate and sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkyl glucamides, alkyl methyl sulfoxides, alkyldimethylphosphine oxides such as tetradecyldimethylphosphine oxide, or combinations thereof.

[0221] Preferably, at least one of the one or more emulsifiers is castor oil ethoxylate.

[0222] Suitable anionic emulsifiers include salts wherein the anion may be selected from the group consisting of fatty acids, fatty alcohol ether sulfates, fatty alcohol sulfates, alkylbenzenesulfonates, ether phosphates, alkyl sulfates, alkyl ether sulfates, alkylsulfonates or isoalkylsulfonates, alkylnaphthalenesulfonates, alkyl methyl estersulfonates, acylglutamates, alkylsulfosuccinates, sarcosinates, taurates, and combinations thereof, and the cation may be selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and combinations thereof.

[0223] Preferably, at least one of the one or more emulsifiers is an alkylbenzene sulfonate, more preferably a linear alkylbenzene sulfonate.

[0224] In a particularly preferred embodiment, the one or more emulsifiers comprise, more preferably consist of, castor oil ethoxylate and alkylbenzene sulfonate. In this particularly preferred embodiment, the alkylbenzene sulfonate is more preferably a linear alkylbenzene sulfonate.

[0225] The total content of the one or more emulsifiers in the emulsifiable concentrate (EC) is preferably in the range of 1% w / w to 30% w / w, more preferably in the range of 5% w / w to 20% w / w, most preferably in the range of 10% w / w to 15% w / w, relative to the total weight of the emulsifiable concentrate (EC).

[0226] Emulsifiable concentrates (EC)

[0227] As detailed above, the emulsifiable concentrates (EC) according to the invention comprise one or more pesticides, one or more emulsifiers and a solvent as described above.

[0228] Particularly preferred combinations of one or more pesticides, one or more emulsifiers and one or more solvents are given in Table A:

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] wherein P1 is azoxystrobin, P2 is prothioconazole, P3 is pyraclostrobin, P4 is oxyfluorfen, P5 is difenoconazole, P6 is trifloxystrobin, P7 is propiconazole, P8 is cyproconazole, P9 is flufenamic acid ethyl ester, P10 is flufenamic acid oxadiazole, P11 is flupyrosinamide, P12 is fenbuconazole and P13 is tebuconazole, S1 is γ-octalactone, S2 is γ-nonalactone, S3 is β-methyl-γ-octalactone, S4 is δ-methyl-γ-octalactone, S5 is γ-decalactone, S6 is γ-undecalactone, S7 is γ-dodecalactone, S8 is δ-decalactone, S9 is δ-dodecalactone, and E1 is any emulsifier, E2 is a block copolymer containing ethylene oxide and propylene oxide monomers, E3 is a sulfonate, and E4 is ethoxylated castor oil.

[0245] In addition to these essential components, the emulsifiable concentrates (EC) may further contain adjuvants customary for agrochemical formulations, the choice of which depends on the specific form of use, the type of formulation or the active substance. Examples of suitable adjuvants are surface-active substances (such as solubilizers, protective colloids, wetting agents and tackifiers), retention agents, wetting agents, spreading agents, absorption enhancers, penetrants, spray drift control agents, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, optionally colorants and binders (for example for seed treatment) or customary adjuvants for bait formulations (for example attractants, food attractants, bitter substances).

[0246] The emulsifiable concentrate (EC) according to the invention preferably comprises, more preferably consists of:

[0247] a) 5% w / w to 70% w / w, more preferably 10% w / w to 65% w / w, most preferably 15% w / w to 60% w / w of one or more pesticides relative to the total weight of the emulsifiable concentrate (EC);

[0248] b) 1% w / w to 30% w / w, more preferably 5% w / w to 20% w / w, most preferably 10% w / w to 15% w / w of one or more emulsifiers relative to the total weight of the emulsifiable concentrate (EC);

[0249] c) 10% w / w to 85% w / w, more preferably 15% w / w to 75% w / w, most preferably 25% w / w to 60% w / w of the one or more solvents having a structure according to formula (I), relative to the total weight of the emulsifiable concentrate (EC); and

[0250] d) optionally, from 1% w / w to 84% w / w, more preferably from 5% w / w to 60% w / w, most preferably from 10% w / w to 35% w / w of one or more adjuvants relative to the total weight of the emulsifiable concentrate (EC),

[0251] The total amount of components a), b), c), and d) does not exceed 100%.

[0252] As mentioned above, the discovery of the present invention is that many typical commercially important pesticides have improved solubility in the solvents according to the present invention when compared to typical solvent systems used for agrochemical emulsifiable concentrates.

[0253] In addition to this finding, it has further been found that the emulsifiable concentrates (EC) of the present invention form highly stable emulsions when mixed with water to form an emulsion, a so-called emulsion-in-water (EW) formulation.

[0254] The stability of an emulsion-in-water formulation can be assessed by determining how much sediment or cream is formed after homogenization (i.e., after emulsification). Both creaming and sedimentation represent deviations from idealized emulsion behavior, in which dispersed particles either rise to the surface (creaming) or sink to the bottom (sedimentation), depending on their density. When determining the degree of creaming or sedimentation, it is not critical whether the emulsion droplets remain intact or aggregate to form a new continuous phase - both are sufficient to determine that the emulsion has broken down.

[0255] The stability of a given emulsion depends on many factors, including the nature of the two immiscible phases, the relative amounts of each phase, and the emulsifier used to stabilize the emulsion. In the context of the present invention, for the purpose of quantifying emulsion stability, a stable emulsion is considered to form less than or equal to a given amount of cream and / or sedimentation 24 hours after homogenization.

[0256] The present invention has found that the emulsifiable concentrates (EC) of the present invention are suitable for forming a wide range of emulsion-in-water (EW) formulations when mixed with water and homogenized, which demonstrates unexpectedly beneficial emulsion stability.

[0257] To quantify this beneficial characteristic of emulsifiable concentrates (EC), a model emulsion system comprising 5.0 mL of emulsifiable concentrate (EC) and 95.0 mL of water can be used. In this case, a stable emulsion is defined as one that produces less than or equal to 1.5 mL of cream or sediment 24 hours after forming the emulsion.

[0258] Thus, it is preferred that the emulsifiable concentrate (EC) forms a stable emulsion when 5.0 mL of the emulsifiable concentrate (EC) is combined with 95.0 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having less than or equal to 1.5 mL of cream or sediment 24 hours after forming the emulsion.

[0259] More preferably, the emulsion forms less than or equal to 1.0 mL of cream or sediment 24 hours after forming the emulsion. Most preferably, the emulsion forms less than or equal to 0.5 mL of cream or sediment 24 hours after forming the emulsion.

[0260] If the emulsion does produce a measurable level of sediment or cream, it is further preferred that the emulsion can be re-homogenized, i.e., re-emulsified, to reform a stable emulsion, wherein a stable emulsion is as defined above, wherein less than or equal to 1.5 mL of cream or sediment is formed 30 minutes after re-homogenization, more preferably wherein less than or equal to 1.0 mL of cream or sediment is formed 30 minutes after re-homogenization, and most preferably wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after re-homogenization.

[0261] Methods for initial homogenization and re-homogenization are well known in the art, and the precise method used in such testing is not critical.

[0262] That is, preferably, homogenization is performed by gently inverting the emulsion 10 times, and re-homogenization is also performed by gently inverting the emulsion 10 times.

[0263] As will be appreciated by those skilled in the art, the threshold at which how much cream or sediment will indicate that the emulsion will be unstable depends on the amount of each phase present in the emulsion. Thus, for example, alternative tests can be envisaged.

[0264] A model emulsion system comprising 0.5 mL of emulsifiable concentrate (EC) and 99.5 mL of water can be used to assess stability, in which case a stable emulsion is defined as an emulsion that produces less than or equal to 0.5 mL of cream or sediment 24 hours after forming the emulsion. Therefore, it is further preferred that the emulsifiable concentrate (EC) forms a stable emulsion when 0.5 mL of the emulsifiable concentrate (EC) is combined with 99.5 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having less than or equal to 0.5 mL of cream or sediment 24 hours after forming the emulsion.

[0265] More preferably, the emulsion forms less than or equal to 0.2 mL of cream or sediment 24 hours after forming the emulsion.

[0266] If the emulsion does produce a measurable level of sediment or cream, it is further preferred that the emulsion can be re-homogenized, i.e., re-emulsified, to reform a stable emulsion, wherein a stable emulsion is as defined above, wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after re-homogenization, preferably wherein less than or equal to 0.2 mL of cream or sediment is formed 30 minutes after re-homogenization.

[0267] It is further preferred that the emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is the emulsifiable concentrate (EC), achieves improved penetration of the one or more pesticides into the plant relative to a comparable emulsion-in-water formulation using a different solvent and / or without a solvent. In particular, it is preferred that the emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is the emulsifiable concentrate (EC), achieves improved penetration of the one or more pesticides into the plant relative to a comparable emulsion-in-water formulation without a solvent.

[0268] The improved permeability can be 50% greater than a comparable emulsion-in-water formulation and can be measured by evaluating the permeability of the PS II inhibitor as measured by fluorescence index and other suitable measurements known to those skilled in the art.

[0269] Emulsion-in-water (EW) formulations

[0270] As mentioned above, the emulsifiable concentrates (EC) of the present invention are most suitable for forming highly stable emulsion-in-water (EW) formulations.

[0271] In a further aspect, the present invention relates to an emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is the emulsifiable concentrate (EC) of the first aspect.

[0272] The precise amounts of emulsifiable concentrate (EC) and water present in the emulsion-in-water (EW) formulation are not critical; however, it is preferred that the emulsifiable concentrate (EC) according to the first aspect is present in an amount in the range of 0.01% w / w to 80.0% w / w and water is present in an amount in the range of 20.0% w / w to 99.99% w / w, both amounts expressed relative to the total weight of the emulsion-in-water (EW) formulation, more preferably consists of.

[0273] It is further preferred that the emulsion-in-water (EW) formulation comprises, more preferably consists of, the emulsifiable concentrate (EC) according to the first aspect in an amount in the range of 0.1% w / w to 50.0% w / w and water in an amount in the range of 50.0% w / w to 99.9% w / w, both amounts expressed relative to the total weight of the emulsion-in-water (EW) formulation.

[0274] It is particularly preferred that the emulsion-in-water (EW) formulation comprises, more preferably consists of, the emulsifiable concentrate (EC) according to the first aspect in an amount in the range of 0.5% w / w to 5.0% w / w and water in an amount in the range of 95.0% w / w to 99.5% w / w, both amounts expressed relative to the total weight of the emulsion-in-water (EW) formulation.

[0275] In addition to the emulsifiable concentrate (EC) according to the first aspect and water, the emulsion-in-water (EW) formulation may further contain adjuvants customary for agrochemical formulations (so-called tank adjuvants), the choice of which depends on the specific form of use, the type of formulation or the active substance. Examples of suitable adjuvants are surface-active substances (such as solubilizers, protective colloids, wetting agents and tackifiers), retention agents, wetting agents, spreading agents, absorption enhancers, penetrants, spray drift control agents, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, optionally colorants and binders (for example for seed treatment) or customary adjuvants for bait formulations (for example attractants, food attractants, bitter substances).

[0276] It is further preferred that the emulsion-in-water (EW) formulation achieves improved penetration of the one or more pesticides into the plant relative to a comparable emulsion-in-water formulation using a different solvent and / or without a solvent. In particular, it is preferred that the emulsion-in-water (EW) formulation achieves improved penetration of the one or more pesticides into the plant relative to a comparable emulsion-in-water formulation without a solvent.

[0277] The improved permeability can be 50% greater than a comparable emulsion-in-water formulation and can be measured by evaluating the permeability of the PS II inhibitor as measured by fluorescence index and other suitable measurements known to those skilled in the art.

[0278] All preferred embodiments and alternatives relating to the emulsifiable concentrate (EC) of the first aspect apply mutatis mutandis to the emulsion-in-water (EW) formulation of this further aspect.

[0279] use

[0280] In yet another aspect, the present invention relates to the use of a compound having a structure according to formula (I) as a solvent in an agrochemical emulsifiable concentrate, preferably an emulsifiable concentrate (EC) according to the first aspect:

[0281]

[0282] wherein X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-,

[0283] R is selected from linear and branched C1 to C 15 alkyl or alkenyl, and each instance of R' is independently selected from H, Me, and Et.

[0284] All preferred embodiments and alternatives relating to the emulsifiable concentrate (EC) of the first aspect apply mutatis mutandis to the use of the compound having a structure according to formula (I) of the present aspect.

[0285] Likewise, all preferred embodiments and alternatives relating to the compound having a structure according to formula (I) given for the first aspect are applicable mutatis mutandis to the compound having a structure according to formula (I) as used in the present aspect.

[0286] In a final aspect, the present invention relates to the use of the emulsion-in-water (EW) formulation according to the above further aspects for treating plants in order to maintain plant health without causing plant damage.

[0287] Plant damage can be assessed relative to plants treated with an aqueous solution containing the same emulsifier simply without the solvent and pesticide. Avoidance of plant damage is often achieved by combining one or more pesticides known to have low phytotoxicity with a solvent having low phytotoxicity.

[0288] In particular, it is preferred that the solvent has low phytotoxicity, wherein low phytotoxicity is defined as when an emulsion containing 99.0% w / w water relative to the total weight of the emulsion and 1.0% w / w of a non-aqueous phase relative to the total weight of the emulsion (which contains 90% w / w of the solvent, 7.5% w / w of castor oil ethoxylate and 2.5% w / w of calcium dodecylbenzenesulfonate (each relative to the total weight of the non-aqueous phase)) does not cause more plant damage than an aqueous solution of 0.075% w / w castor oil ethoxylate and 0.025% w / w of calcium dodecylbenzenesulfonate (each relative to the total weight of the aqueous solution) when measured 14 days after application to soybean plants at an application rate of 200 L / hectare.

[0289] The phytotoxicity of various commonly used pesticides is within the common knowledge of those skilled in the art.

[0290] As will be understood by those skilled in the art, the use of an emulsion-in-water (EW) formulation will be for treating crop plants so as to maintain crop plant health without causing crop plant damage. In the event that an emulsion-in-water (EW) formulation contains an herbicide that damages weeds (i.e., non-crop plants), this would not be considered to cause "plant damage" since this term refers to the crop plants rather than the weeds.

[0291] All preferred embodiments and alternatives relating to the emulsion-in-water (EW) formulation of the further aspects described above apply mutatis mutandis to the use of the emulsion-in-water (EW) formulation of the final aspect for treating plants.

[0292] Experimental part

[0293] Materials used:

[0294] Solvents: β-methyl-γ-octalactone, β,δ-dimethyl-γ-octalactone, 2-ethylhexyl lactate, C8-C10 fatty acid methyl esters, and dimethyldecanamide were from BASF. All other lactones were from Sigma-Aldrich.

[0295] CIPAC D water: prepared in the laboratory using the standard recipe "MT 18.1.4" published by CIPAC: Standard Water. This water has a hardness of 342 ppm and a 4:1 mixture of Ca:Mg ions at a pH of 6-7.

[0296] Pesticides: Azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, difenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenamate ethyl, epoxiconazole, flupyrad, fenbuconazole, tebuconazole, metaflumizone, pinoxaden, deltamethrin, and pendimethalin were purchased from various commercial sources.

[0297] Emulsifiers: The emulsifiers used in the experiments are listed below.

[0298]

[0299] Example 1: Determination of water solubility

[0300] The water solubility of a solvent is determined by visually assessing the amount of undissolved solvent in water after vigorous mixing and standing according to a method based on CIPAC MT157.1 and OECD 105. Here, varying amounts of solvent and water are mixed in a glass-stoppered graduated cylinder or separatory funnel with vigorous shaking, then allowed to stand for at least 30 minutes to allow separation. For example, if undissolved solvent is observed after thoroughly mixing 0.1 g of solvent in 100 mL of water, the solvent has a water solubility of 0.1% or less (≤ 1 g / L). This method can be repeated with varying amounts of solvent and water to determine the water solubility of the solvent.

[0301] A number of different lactone-based solvents were evaluated, with the following structures and water solubilities:

[0302] Table 1: Solubility of lactones in water

[0303]

[0304]

[0305] Example 2: Determination of Maximum Pesticide Solubility

[0306] The maximum solubility of pesticides in various solvents was determined at 21°C. A small amount of the active ingredient was added to 10 g of solvent in a 25 mL beaker while stirring with a magnetic stir bar. The active ingredient was added to the solvent until no further dissolution was achieved, with a maximum stirring time of 2 hours between additions to allow for dissolution. The solubility was calculated according to the following equation:

[0307]

[0308] As can be seen from Table 2, the solubility of most pesticides is improved in lactone-based solvents relative to methyl ester solvents. In many cases, solubility is also improved compared to dimethylamides; however, even in cases where improved solubility is not observed, the use of lactone solvents is preferred due to their reduced odor and reduced health hazards (see Examples below).

[0309] Example 3: Stable pesticide emulsion using the lactone of the present invention as a solvent

[0310] Emulsions are tested for their dispersibility by an effect known as blooming.

[0311] The emulsions were evaluated based on their spontaneous emulsification (referred to in the art as "self-emulsification") when the concentrate was added to water using a visual assessment on a scale of 1 to 5, where 1). Excellent, "emulsion cloud", did not sink to the bottom of the graduated cylinder; 2). Good, "emulsion cloud", but sank to the bottom of the graduated cylinder; 3). Okay, "poor emulsion cloud", larger droplets; 4). Poor, "no emulsion cloud", small "grains" were observed; 5). Very poor, no emulsion, the oil and water phases separated immediately.

[0312] In the following examples, emulsifiable concentrates were prepared and the resulting 5% w / w emulsions were evaluated after 24 hours at various water hardnesses at 21° C. The emulsion stability was determined over time, where the amount of cream or sediment was measured.

[0313] To measure emulsion stability, 5.0 mL of the emulsifiable concentrate was diluted in 95.0 mL of CIPAC D water in a 100 mL graduated cylinder. The stability of the resulting oil-in-water emulsion was evaluated after 1, 2, 4, and 24 hours. Highly stable emulsions did not form a cream after 24 hours, or had less than 1.5 mL of cream, and could be easily re-emulsified without forming a cream after standing for 24 hours, wherein such re-emulsified emulsions were evaluated 30 minutes after re-emulsification. Both initial emulsification and re-emulsification were achieved by gently inverting the emulsion 10 times.

[0314]

[0315]

[0316]

[0317]

[0318]

[0319] Table 3.1.3 Low Temperature Recirculation Test of Pesticide Formulation Emulsions Using γ-Nonalactone

[0320] A low-temperature emulsion recirculation test was conducted to evaluate the stability of the emulsion under field application conditions. Here, a 5-liter temperature-controlled container maintained isothermally at 4°C was prepared containing 3 liters of a pesticide emulsion with a 0.5% w / w emulsifiable concentrate. The emulsion contained 3 liters of CIPAC D water and 15 g of emulsifiable concentrate, resulting in an emulsion concentration of 0.5% w / w. The resulting emulsion was pumped through a metal filter with a 140 μm pore size attached to the temperature-controlled container at a flow rate of 1 L / min at 4°C for 6 hours, with the pressure continuously monitored. The fully stable emulsion maintained a pressure of <1.0 bar throughout the 6-hour recirculation period, and after the 6-hour recirculation, the filter was removed and dried, with the total collected solid material measured to be <100 mg.

[0321] IE1 IE3 Vessel pressure after 6 hours of recirculation [bar] 0.3 0.3 Weight of dry filter material collected after 6 hours [mg] 59.9 1.6

[0322] No comparative examples could be evaluated because unstable emulsions would have blocked the equipment.

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329] As can be seen from IE1 to IE46 in Tables 3.1.1 to 3.4, a wide range of agrochemical active compounds (i.e., pesticides) can be provided as emulsifiable concentrates for application to crops. As can be seen from CE1 to CE11, many of the emulsifiable concentrates exemplified in the above tables, particularly those containing prothioconazole, are notoriously insoluble in typical EC solvents.

[0330] Example 4: Permeability measured by fluorescence index enhancement

[0331] Improved penetration of pesticidal active ingredients into plants is a key means of improving the biological efficacy of formulations. Certain adjuvants can achieve improved penetration efficiency of active ingredients, which can significantly improve the activity of the formulation, resulting in higher performance at elevated dosage rates or standard performance at lower dosage rates.

[0332] The effective rate of penetration enhancement of PS II inhibitors into plant leaves using selected adjuvants can be monitored using chlorophyll fluorescence methods. PS II inhibitors effectively block the chlorophyll photosynthesis pathway in the leaves, resulting in enhanced fluorescence from unabsorbed incident light. The resulting emitted light can be measured at selected time intervals, enabling the uptake rate of the PS II inhibitor and therefore the penetration effectiveness of the selected adjuvant to be determined.

[0333] The following experiments were conducted on the broadleaf weed Abutilon theophrasti (EPPO code ABUTH) at growth stage 13 to 14 of the Biologische Bundesanstalt, Bundessortenamt und Chemische Industrie (BBCH).

[0334] The penetration experiment was carried out by depositing two drops (5 μl) of the herbicide / emulsifier / lactone-based solvent formulation onto the leaf surface. These drops were allowed to rest for 1 h on the leaf surface, after which a fluorescence image of the exposed leaf surface was recorded using a PAM chlorophyll fluorescence imaging system (Imaging PAM, Heinz-Walz GmbH, Germany). The recorded fluorescence images were then quantified using image analysis software to analyze the resulting "total fluorescence" and "fluorescence area." This enabled the calculation of a "fluorescence index":

[0335] Fluorescence index = total fluorescence × fluorescence area

[0336] The "fluorescence index" is therefore a direct measure of the penetration of the active ingredient into the plant leaves and can therefore be used to measure the enhanced penetration by the use of selected adjuvants. The same experiment was performed on a further 7 leaves using the same formulation to account for biological variability and experimental error.

[0337] Table 4.1: Formulations for application to foliar surfaces

[0338]

[0339] The results of these tests are summarized in Table 4.2.

[0340] Table 4.2 Summary of the fluorescence index enhancement measured using various lactone-based solvents

[0341]

[0342]

[0343] *Na B = bentazone sodium, E = emulsifier, S = solvent

[0344] Fluorescence index is shown in Figure 5middle.

[0345] As shown in Table 4.2 / Figure 5 As can be seen from the data in Figure 2, the use of lactone-based solvents in the emulsions improved the penetration of bentazone sodium into the leaves in all cases. However, the effect was most pronounced for lactone solvents with at least 8 carbon atoms, peaking at 9 carbon atoms for γ-lactone. For δ-lactone, penetration continued to improve at least up to 12 carbon atoms. Therefore, lactone solvents with at least 8 carbon atoms represent a particularly preferred embodiment of the present invention.

[0346] Example 5: Phytotoxicity test on soybean:

[0347] Soybean plants grown under standard greenhouse conditions at growth stage 13 were treated with the aqueous emulsion in a spray chamber. The resulting plant spray dose represents an application rate of 200 L / ha of a 1% w / w emulsion, corresponding to an application of 2 L / ha of an emulsifiable concentrate. The emulsifiable concentrate contained 90% w / w solvent and 10% w / w emulsifier (an emulsifier mixture of 75% w / w castor oil ethoxylate and 25% w / w calcium dodecylbenzene sulfate). The experimental period lasted 14 days, during which time the soybean plants were given optimal watering, nutrients, and light.

[0348] Solvent phytotoxicity was assessed by visual inspection on a scale of 0% to 100% relative to plants treated with an aqueous solution of 0.075% w / w castor oil ethoxylate and 0.025% w / w calcium dodecylbenzenesulfonate (see Figure 1 Here, 0% indicates no plant damage, with no difference between treated and untreated plants. A phytotoxicity rating of 1% to 10% is the limit of plant damage acceptable to farmers. A phytotoxicity level of 11% to 30% indicates moderate damage, between 31% and 60% indicates high damage, over 61% indicates very high damage, and a rating of 100% indicates complete plant destruction.

[0349] Since 0% phytotoxicity was observed for the γ-nonalactone solvent of the present invention (see Figure 2 ), so it can be said that γ-nonalactone is completely selective and non-phytotoxic. On the other hand, the application of 2-ethylhexyl lactate and dimethyldecylamide, which are not solvents of the present invention, resulted in 30% and 50% phytotoxicity, respectively, after 14 days (see Figure 3 and Figure 4 ).

[0350] The solvents according to the invention have no or little phytotoxic effect and can therefore be used in agricultural formulations in order to reduce the phytotoxicity in such compositions.

Claims

1. An emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers and one or more solvents, wherein at least one of the one or more solvents has a structure according to formula (I): wherein X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-, R is selected from linear and branched C1 to C 15 alkyl or alkenyl, and each instance of R' is independently selected from H, Me and Et.

2. The emulsifiable concentrate (EC) according to claim 1, wherein X is selected from -CH2CH2-, -CH2CH(Me)-, and -CH2CH2CH2-.

3. The emulsifiable concentrate (EC) according to claim 1 or claim 2, wherein At least one of the one or more solvents having a structure according to formula (I) has 8 or more carbon atoms.

4. The emulsifiable concentrate (EC) according to any one of claims 1 to 3, wherein X is -CH2CH2- or -CH2CH(Me)-, preferably wherein at least one of the one or more solvents is selected from the group consisting of γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecalactone, γ-dodecalactone, β-methyl-γ-octanolactone, δ-methyl-γ-octanolactone, and β,δ-dimethyl-γ-octanolactone.

5. The emulsifiable concentrate (EC) according to any one of claims 1 to 3, wherein X is -CH2CH2CH2-, preferably wherein at least one of the one or more solvents is selected from the group consisting of: delta-nonalactone, delta-decanolide, delta-dodecalactone, and delta-tridecalactone.

6. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein At least one of the one or more pesticides is selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, difenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenamic acid ethyl, epoxiconazole, flupyrad, fenbuconazole, tebuconazole, metaflumizone, pinoxaden, deltamethrin and pendimethalin.

7. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein At least one of the one or more solvents having a structure according to formula (I) has a water solubility of less than 2.0% w / w, more preferably less than 1.0% w / w, most preferably less than 0.5% w / w.

8. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein The total pesticide content is in the range of 5% w / w to 70% w / w, more preferably in the range of 10% w / w to 65% w / w, most preferably in the range of 15% w / w to 60% w / w relative to the total weight of the emulsifiable concentrate (EC).

9. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein The total content of solvents having a structure according to formula (I) is preferably in the range of 10% w / w to 85% w / w, more preferably 15% w / w to 75% w / w, most preferably 25% w / w to 60% w / w relative to the total weight of the emulsifiable concentrate (EC).

10. Emulsifiable concentrate (EC) according to any of the preceding claims, containing one or more nonionic emulsifiers, preferably at least one of which is a castor oil ethoxylate, and optionally one or more anionic emulsifiers, preferably at least one of which is an alkylbenzene sulfonate.

11. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein The emulsifiable concentrate (EC) forms a stable emulsion when 5.0 mL of the emulsifiable concentrate (EC) is combined with 95.0 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having less than or equal to 1.5 mL of cream or sediment 24 hours after forming the emulsion.

12. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein Emulsion-in-water (EW) formulations comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is the emulsifiable concentrate (EC), achieve improved penetration of the one or more pesticides into plants relative to comparable emulsion-in-water formulations using different solvents and / or no solvent.

13. An emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is an emulsifiable concentrate (EC) according to any one of claims 1 to 12.

14. Use of a compound having a structure according to formula (I) as a solvent in an agrochemical emulsifiable concentrate, preferably an emulsifiable concentrate (EC) according to any one of claims 1 to 12 wherein X is selected from -CR'2CR'2-, -CR'=CR'-, -CR'2CR'2CR'2-, and -CR'=CR'CR'2-, R is selected from linear and branched C1 to C 15 alkyl or alkenyl, and each instance of R' is independently selected from H, Me and Et.

15. Use of the emulsion-in-water (EW) formulation according to claim 13 for treating plants to maintain plant health without causing plant damage.

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