Sulfoxides for agrochemical applications
Specific sulfoxides, as described by formula (I), provide a cost-effective and non-phytotoxic solution for agrochemical applications, offering improved solubility and stability for agrochemical formulations, thereby overcoming the limitations of traditional solvents.
Patent Information
- Application Number
- PCT/EP2024/087459
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-12-20
- Filing Date
- 2024-12-19
- Publication Date
- 2025-06-26
AI Technical Summary
Current agrochemical solvents, such as DMSO and fatty acid dialkyl amides, face challenges including high toxicity, phytotoxicity, and high costs, necessitating the development of alternative solvents that are cost-effective, have low phytotoxicity, and provide good solubilization properties.
The use of specific sulfoxides, as defined by formula (I), which serve as solvents or dispersants for agrochemical actives, offering improved solubility, non-phytotoxicity, and cost-effectiveness compared to traditional solvents.
The sulfoxides demonstrate excellent solvency for various agrochemical actives, are non-phytotoxic, and can be readily formulated, addressing the limitations of existing solvents and enhancing the stability of agrochemical formulations.
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Figure EP2024087459_26062025_PF_FP_ABST
Abstract
Description
[0001] SULFOXIDES FOR AGROCHEMICAL APPLICATIONS
[0002] FIELD OF THE INVENTION
[0003] The invention relates to a composition, comprising a. at least one specific sulfoxide according to formula (I); and b. at least one agrochemical active. Furthermore, the invention relates to the use of such a sulfoxide according to formula (I) as a solvent or dispersant for at least one agrochemical active or to the use thereof as a solvent in an agrochemical formulation.
[0004] BACKGROUND OF THE INVENTION
[0005] In agricultural applications a wide variety of agents are used, for example for crop protection, fertilization and plant stimulation. Many of the agrochemical compositions used are in liquid form and are provided as solutions or dispersions, for example suspensions or emulsions, of an active in a liquid phase. Accordingly, there is widespread use of solvent-based formulations in agrochemical applications. While many different solvents are used, in many cases the solvent mixture needs to be tailored to the intended use and the active. Further, many known and suitable solvents have drawbacks with respect to toxicity and sustainability.
[0006] One type of solvent widely used in agrochemical applications are fatty acid dialkyl amides. However, while they have many advantageous properties, they are mostly made from palm oil, are cost-intensive and exhibit phytotoxicity on certain plants.
[0007] Dimethylsulfoxide (DMSO) is another well-known solvent used in agrochemical applications. However, it has a high melting point (Tm = 18 °C) and can penetrate the skin of the applicant.
[0008] In view of the above, there is thus an ongoing need for alternative solvents which are preferably costefficient, have low phytotoxicity, while providing for good solubilization properties.
[0009] The present invention meets this need. Surprisingly, the inventors have been found that specific sulfoxides meet these requirements and may serve as a replacement of other known solvents, such as DMSO and fatty acid dialkyl amides, especially in agrochemical applications and compositions.
[0010] These sulfoxide have good availability and good solvency for various agrochemical actives, are non- phytotoxic and can be readily formulated.
[0011] SUMMARY OF THE INVENTION
[0012] Therefore, in a first aspect, the invention relates to a composition comprising a. at least one sulfoxide according to formula (I)
[0013] R1-O-R2-S(=O)-R3-O-R4(I) wherein
[0014] R1and R4are, independently of each other, H, C1-C8 alkyl or C(=O)(C1-C12 alkyl); and
[0015] R2and R3are, independently of each other, linear or branched C1-C10 alkylene groups; and b. at least one agrochemical active.
[0016] In various embodiments, the at least one agrochemical active is not a sulfoxide according to formula (I).
[0017] In various embodiments, at least one of R1and R4is not H, optionally both of R1and R4are not H.
[0018] It is preferred that
[0019] (1) at least one of R1and R4is C(=O)(C1-C12 alkyl), preferably C(=O)(C1-C8 alkyl), more preferably C(=O)(C1-C4 alkyl), such as C(=O)(CH3), C(=O)(CH2-CH3) or C(=O)(CH2-CH2-CH3); and / or
[0020] (2) at least one of R1and R4is C1-C8 alkyl, preferably Ci-Ce alkyl, more preferably C1-C4 alkyl, such as methyl, ethyl, propyl, or butyl, most preferably methyl or n-butyl.
[0021] In various embodiments, R1and R4are, independently of each other, C1-C8 alkyl, preferably Ci-Ce alkyl, more preferably C1-C4 alkyl, such as methyl, ethyl, propyl, or butyl, most preferably methyl or n-butyl.
[0022] Furthermore, it is preferred that R2and R3are, independently of each other, (CR52)m, wherein m is an integer of 1 to 8, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and each R5is independently selected from H and a C1-C4 alkyl group.
[0023] In various embodiments, R2and R3are, independently of each other, CH2-CH2, CH2-CH2-CH2, CH2-CH(R5) or CH(R5)-CH2, with R5optionally being methyl or ethyl.
[0024] Preferably, R2and R3are, independently of each other, CH2-CH2, CH2-CH2-CH2, CH2-CH(CH3) or CH(CH3)- CH2; and R1and R4are, independently of each other, C1-C4 alkyl, such as methyl, ethyl, propyl, or butyl, preferably methyl or n-butyl.
[0025] In various embodiments, it is preferred that R2and R3are identical, and / or R1and R4are identical.
[0026] In preferred embodiments, R2and R3are identical, preferably CH2-CH2; and R1and R4are identical C1-C4 alkyl, preferably methyl, ethyl, propyl, or butyl, more preferably methyl or n-butyl.
[0027] In particular, the sulfoxide according to formula (I) is
[0028] In various embodiments, the at least one agrochemical active is selected from the group consisting of pesticides, fungicides, insecticides, nematicides, herbicides, safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides and / or growth regulators. Also encompassed are mixtures of any one or more of the afore-mentioned. In various embodiments, the at least one agrochemical active is selected from the group consisting of azoxystrobin, tebuconazole, oxyfluorfen, trifloxystrobin, cyproconazole, prothioconazole, flufenacetate, imidacloprid, difenoconazole, pyraclostrobin, and mixtures thereof, more preferably azoxystrobin, pyraclostrobin, flufenacetate, prothioconazole, oxyfluorfen, difenoconazole, tebuconazole, and mixtures thereof.
[0029] In various embodiments, the composition comprises at least one further compound selected from the group consisting of co-solvents, dispersants, adjuvants, surfactants, thickeners, humectants, antioxidants, colorants, fragrances, defoamers, anti-caking agents, emulsifiers, and mixtures thereof.
[0030] It is preferred that
[0031] - the at least one co-solvent is selected from fatty acid methyl esters, aromatic hydrocarbons, 2- ethylhexanol esters, dimethyl amides, fatty alcohols, glycols, alkyl esters, lactate esters, alkyl pyrrolidones, paraffinic mineral oils, vegetable oils, lactones, carbonates, carbamates, sulfoxides different from the sulfoxides of formula (I), alkyl amides, ketones, phosphate esters, aldehydes, ethers, acetals and mixtures thereof, preferably dimethyl fatty acid amides, dimethyl alkyl acid amides, or dimethyl alkyl hydroxy acid amides and mixtures thereof; and / or
[0032] - the emulsifier is selected from non-ionic or anionic surfactants, and mixtures thereof, optionally, castor oil ethoxylates, fatty acid alkoxylates, alcohol alkoxylates, alkyl amine alkoxylates, polyether copolymers, sorbitan ethoxylate esters, aromatic alcohol alkoxylates, alkylbenzene sulfonates or (di-octyl) sulfosuccinates.
[0033] In preferred embodiments, the composition comprises a. at least one sulfoxide according to formula (I) in an amount of 1 to 99 wt.-%, preferably 5 to 90 wt.-%, more preferably 10 to 70 wt.-%, such as about 45 wt.-%, about 50 wt.-%, about 55 wt.-%, about 60 wt.-%, or about 63 wt.-%; b. at least one agrochemical active in an amount of 1 to 50 wt.-%, preferably 10 to 40 wt.-%, more preferably 15 to 30 wt.-%, such as about 20 wt.-% or about 25 wt.-%; and, optionally, c. at least one further compound, preferably selected from co-solvents, surfactants, adjuvants and / or emulsifiers in amounts of 0 to 90 wt.-%, preferably 0.1 to 70 wt.-%, more preferably such as 1 to 50 wt.-%; and / or d. water, preferably ad 100 wt.-%; each based on the total weight of the composition.
[0034] In preferred embodiments, the composition according to the invention is an agrochemical composition.
[0035] In a further aspect, the invention relates to the use of a sulfoxide according to formula (I) as a solvent or dispersant for at least one agrochemical active.
[0036] In a still further aspect, the invention relates to the use of a sulfoxide according to formula (I) as a solvent in an agrochemical formulation, such as a concentrate, including an emulsion concentrate, a suspension concentrate and a dispersion concentrate. In preferred embodiments, the sulfoxide is able to maintain or improve the emulsion / suspension / dispersion stability of an emulsion / suspension / dispersion concentrate or emulsion / suspension / dispersion formulation, preferably in comparison to other solvents, such as N,N- dimethyl decanamide, alkyl esters, such as 2-ethyl hexyl acetate, and aromatic solvent naphtha (available under the tradename Solvesso™).
[0037] The use of the compositions disclosed herein for controlling pests in plants, comprising applying the compositions of the invention to said plants, to the soil in which they are growing or to their seeds, also forms part of the present invention.
[0038] Also encompassed by the present invention are methods of using the sulfoxides disclosed herein as solvents for agrochemical actives as well as the methods of using the compositions described herein for controlling pests in plants, comprising applying the compositions of the invention to said plants, to the soil in which they are growing or to their seeds.
[0039] These and other aspects, embodiments, features, and advantages of the invention become apparent to the person skilled in the art from the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, the examples contained herein are intended to describe and illustrate the invention, but not to restrict it. In particular, the invention is not limited to these examples.
[0040] BRIEF DESCRIPTION OF THE DRAWINGS
[0041] Figure 1 shows the results of an active ingredient solvency study with bis(2-methoxyethyl)sulfoxide. Bis(2- methoxyethyl)sulfoxide has a similar solvency to dimethyl lactamide, and improved solubility in comparison to propylene carbonate and propylene glycol.
[0042] Figure 2 shows the results of an active ingredient solvency study with bis(2-butoxyethyl)sulfoxide.
[0043] DETAILED DESCRIPTION OF THE INVENTION
[0044] All technical and scientific terms used herein have, unless explicitly stated otherwise, the meanings as commonly understood in the art.
[0045] The singular forms of "a" and "an" also include the respective plurals unless the context clearly dictates otherwise.
[0046] “At least one” as used herein, means one or more, i.e., 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more of the referenced species. Similarly, “one or more”, as used herein, relates to at least one and comprises 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with a given species, the term does not relate to the total number of molecules, but rather to the type of species. “At least one sulfoxide”, for example, thus means that one type of sulfoxide or two or more different types of sulfoxide may be present. In connection with amounts, the term relates to the total amount of the referenced species. Numeric values specified without decimal places here refer to the full value specified with one decimal place, i.e., for example, 99 % means 99.0 %, unless otherwise defined.
[0047] All percentages given herein in relation to compositions or formulations relate to weight % (wt.-%) relative to the total weight of the respective composition or formula, if not explicitly stated otherwise. Numeric ranges specified in the format “from x to y” include the specified values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges created by combining the different endpoints are also included.
[0048] The terms “about”, “approximately” or “approx.”, in connection with a numerical value, refer to a variance of ± 20 %, preferably ± 15 %, more preferably ± 10 %, and even more preferably ± 5 %, with respect to the given numerical value.
[0049] It is to be understood that the term "comprising" is not limiting. For the purposes of the present invention the term "consisting of is considered to be a preferred embodiment of the term "comprising of. If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only.
[0050] Furthermore, the terms "first", "second", "third" or "a.", "b.", "c.", "d.", “(1)”, “(2)”, etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "a.", "b.", "c.", "d.", “(1)”, “(2)”, etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
[0051] It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention that will be limited only by the appended claims.
[0052] In a first aspect, the invention relates to a composition comprising a. at least one sulfoxide according to formula (I)
[0053] R1-O-R2-S(=O)-R3-O-R4(I) wherein
[0054] R1and R4are, independently of each other, H, C1-C8 alkyl or C(=O)(C1-C12 alkyl); and
[0055] R2and R3are, independently of each other, linear or branched C1-C10 alkylene groups; and b. at least one agrochemical active. Sulfoxides (a.) according to the present invention are sulfoxides of formula (I). The preparation of such sulfoxides is well known in the state of the art. The sulfoxides of formula (I) may be used as solvents herein and thus also termed “sulfoxide solvents” or “sulfoxide-based solvents”, without limiting the compounds to this utility.
[0056] “Solvent”, as used herein in relation to the compositions of the invention, refers to compounds that are liquid under standard conditions (20°C, 1013 mbar) and are suitable to dissolve at least one active, as described herein. Accordingly, it may be preferred that the solubility of the at least one active, as described herein below, in the solvent is at least 1 g / 100mL, preferably 1 g / 10 mL, (at 20°C).
[0057] The term “liquid”, as used herein, relates to compounds and compositions that are liquid under standard conditions (20°C, 1013 mbar).
[0058] In various embodiments, at least one of R1and R4is not H, optionally the compound is non-symmetrically and R1and R4are non-identical, preferably, wherein R1or R4is H and the other residue is C(=O)(C1-C12 alkyl) or C1-C8 alkyl. In various embodiments, R1and R4are not H.
[0059] It is preferred that at least one of R1and R4is
[0060] (1) C(=O)(C1-C12 alkyl), preferably C(=O)(C1-C8 alkyl), more preferably C(=O)(C1-C4 alkyl), such as C(=O)(CH3), C(=O)(CH2-CH3), C(=O)(CH2-CH2-CH3), C(=O)(CH2-CH2-CH2-CH3), or C(=O)(CH2-CH2- (CH3)2; and / or
[0061] (2) C1-C8 alkyl, preferably C1-C6 alkyl, more preferably C1-C4 alkyl, more preferably methyl, ethyl, propyl, isopropyl, tert-butyl, 2-butyl or n-butyl, more preferably methyl, ethyl or n-butyl, most preferably methyl or n-butyl.
[0062] In various embodiments, R1and R4are, independently of each other, C1-C8 alkyl, preferably Ci-Ce alkyl, more preferably C1-C4 alkyl, more preferably methyl, ethyl, propyl or butyl, most preferably methyl or n- butyl.
[0063] Furthermore, it is preferred that R2and R3are, independently of each other, (CR52)m, wherein m is an integer of 1 to 8, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and each R5is independently selected from H and a C1-C4 alkyl group, such as methyl or ethyl, in particular methyl. In various embodiments at least one R5on each C atom is H. In various embodiments, where m is >1 only 1 or 2, preferably only one C atom carries an R5substituent that is not H. In various embodiments, all R5are H.
[0064] In various embodiments, R2and R3are, independently of each other, CH2-CH2, CH2-CH2-CH2, CH2-CH(R5) or CH(R5)-CH2, with R5optionally being methyl or ethyl.
[0065] Preferably, R2and R3are, independently of each other, CH2-CH2, CH2-CH2-CH2, CH2-CH(CH3) or CH(CH3)- CH2; and R1and R4are, independently of each other, C1-C4 alkyl, preferably methyl, ethyl, propyl, or butyl, with propyl including isopropyl and n-propyl, and butyl including tert-butyl, 2-butyl and n-butyl, more preferably methyl or n-butyl. In various embodiments, it is preferred that R2and R3are identical, and / or R1and R4are identical.
[0066] In preferred embodiments, R2and R3are identical, preferably CH2-CH2; and R1and R4are identical C1-C4 alkyl, preferably methyl, ethyl, propyl, or butyl, more preferably methyl or n-butyl.
[0067] In particular, the sulfoxide according to formula (I) is the water-soluble compound of formula y y sulfoxide.
[0068] In various embodiments, the sulfoxide is water-soluble, however, water-soluble and water insoluble sulfoxides can be used. In other embodiments, the sulfoxide is hydrophobic / lipophilic and not water-soluble.
[0069] All sulfoxides disclosed herein can be produced by synthesis methods well-known to those skilled in the art.
[0070] The above solvent may be especially suitable for emulsion formulations or emulsion concentrates.
[0071] An emulsion (formulation) as used in the context of the invention is preferably a finely dispersed or distributed mixture of non-mixable liquids. The emulsions may be o / w or w / o emulsions. Emulsions and their preparations are well-known to the person skilled in the art.
[0072] In this context, “emulsion concentrate” relates to a concentrated emulsion formulation / composition, which can be diluted by the end user to prepare ready-to-use compositions (emulsions) for spraying plants. Similarly, the terms “suspension concentrate” and the more general term “dispersion concentrate” relate to the respective suspension and dispersion formulations and compositions, respectively.
[0073] The composition of the invention further contains one or more agrochemical actives (b.).
[0074] The agrochemical active is typically different from the sulfoxide (a.), in particular is not a sulfoxide according to formula (I). This means that the agrochemical active and the sulfoxide used as a solvent are chemically different compounds, particular to the extent that the agrochemical active does not qualify as a sulfoxide according to formula (I). In various embodiments, the agrochemical active is no sulfoxide at all.
[0075] The term “agrochemical active” refers to a substance that confers a desirable biological activity to the composition. Typically, the agrochemical active is a pesticide. Agrochemical actives are typically selected from fungicides, insecticides, nematicides, herbicides, safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides and / or growth regulators. In one embodiment, the agrochemical active is an insecticide. In another embodiment, the agrochemical active is a herbicide. In a further embodiment, the agrochemical active is a fungicide.
[0076] A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term “pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
[0077] The following lists of pesticides that are suitable for use in compositions of the invention, is intended to illustrate the possible combinations but does not limit them:
[0078] A) Respiration inhibitors inhibitors of complex III at Qosite: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin / flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, pyribencarb, triclopyricarb / chlorodincarb, famoxadone, fenamidone, pyriminostrobin, bifujunzhi, metyltetraprole; inhibitors of complex III at Qi site: cyazofamid, amisulbrom, fenpicoxamid, florylpicoxamid, metarylpicoxamid; inhibitors of complex II: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, pydiflumetofen, pyraziflumid, sedaxane, tecloftalam, thifluzamide, inpyrfluxam, pyrapropoyne, fluindapyr, isoflucypram, cyclobutrifluram; other respiration inhibitors: diflumetorim; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, meptyldinocap; ferimzone; organometal compounds: fentin salts, e.g. fentin-acetate, fentin chloride or fentin hydroxide; silthiofam; quinone outside inhibitor stigmatellin binding type: ametoctradin.
[0079] B) Sterol biosynthesis inhibitors (SBI fungicides)
[0080] C14 demethylase inhibitors: triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole , fluoxytioconazole, ipfentrifluconazole, mefentrifluconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines, piperazines: fenarimol, pyrifenox, triforine;
[0081] Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
[0082] Inhibitors of 3-keto reductase: fenhexamid, fenpyrazamine; other Sterol biosynthesis inhibitors: chlorphenomizole.
[0083] C) Nucleic acid synthesis inhibitors
[0084] RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, oxadixy I; other nucleic acid synthesis inhibitors: hymexazole, octhilinone, oxolinic acid, bupirimate, 5- fluorocytosine, ipflufenoquin, quinofumelin.
[0085] D) Inhibitors of cell division and cytoskeleton
[0086] - tubulin polymerization inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate- methyl, pyridachlometyl; other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, phenamacril, fluopimomide.
[0087] E) Inhibitors of amino acid and protein synthesis methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil; protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracycline.
[0088] F) Signal transduction inhibitors
[0089] MAP I histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fludioxonil; mechanism unknown: quinoxyfen, proquinazid.
[0090] G) Lipid and membrane synthesis inhibitors
[0091] Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; compounds affecting cell membrane permeability and fatty acids: propamocarb; inhibitors of oxysterol binding protein: oxathiapiprolin, fluoxapiprolin.
[0092] H) Inhibitors with Multi Site Action inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
[0093] - thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid; guanidines and others: guanidine, dodine, dodine free bas, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, fluoroimide, methasulfocarb, chinomethionat.
[0094] I) Cell wall synthesis inhibitors inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, tolprocarb; cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate.
[0095] J) Plant defense inducers acibenzolar-S-methyl, probenazol, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts, calcium phosphonate, potassium phosphonate, potassium or sodium bicarbonate, dichlobentiazox.
[0096] K) Unknown mode of action bronopol, cyflufenamid, cymoxanil, dazomet, debacarb, diclocymet, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenitropan, fenpyrazamine, flumetover, flumetylsulforim, flusulfamide, flutianil, harpin, nitrapyrin, nitrothal-isopropyl, oxin-copper, seboctylamine, tebufloquin, tecloftalam, triazoxide, pyrisoxazole, , benziothiazolinone, bromothalonil, aminopyrifen, flufenoxadiazam.
[0097] L) Biopesticides
[0098] L1) Microbial pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain).
[0099] L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract.
[0100] L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and / or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus, Cryptophlebia leucotreta granulovirus, Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus, Helicoverpa zea nucleopolyhedrovirus, Helicoverpa zea single capsid nucleopolyhedrovirus, Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus, Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus.
[0101] L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and / or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,11 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)- 2,13-octadecadien-1-ol acetate, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, pentatermanone, (E,Z,Z)-3,8,11 -tetradecatrienyl 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, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract.
[0102] L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and / or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropic!, Sinorhizobium meliloti.
[0103] O) Insecticides from classes 0.1 to 0.31
[0104] 0.1 Acetylcholine esterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, Phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion.
[0105] 0.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole.
[0106] 0.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin; DDT, methoxychlor.
[0107] 0.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin.
[0108] 0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram.
[0109] 0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin.
[0110] 0.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen.
[0111] 0.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic.
[0112] 0.9 Chordotonal organ TRPV channel modulators: afidopyropen, pymetrozine, pyrifluquinazon.
[0113] 0.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole.
[0114] 0.1 1 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, B. sphaericus and the insecticidal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1.
[0115] 0.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon.
[0116] 0.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid.
[0117] 0.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium. 0.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron.
[0118] 0.16 Inhibitors of the chitin biosynthesis type 1 : buprofezin.
[0119] 0.17 Moulting disruptors: cyromazine.
[0120] 0.18 Ecdyson receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide.
[0121] 0.19 Octopamin receptor agonists: amitraz.
[0122] 0.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate.
[0123] 0.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone.
[0124] 0.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone.
[0125] 0.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, spidoxamat.
[0126] 0.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide.
[0127] 0.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide.
[0128] 0.26 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlodiniliprole; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; cyhalodiamide.
[0129] 0.27 Chordotonal organ modulators: flonicamid.
[0130] 0.28 GABA-gated chloride channel allosteric modulators: broflanilide, fluxametamide, isocycloseram.
[0131] 0.29 Calcium-activated potassium channel modulators: acynonapyr.
[0132] 0.30 Mitochondrial complex III electron transport inhibitors at Qi site: flometoquin.
[0133] 0.31 Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, benzoximate, bromopropylate, chinomethionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, actives on basis of Bacillus firmus (Votivo); fluazaindolizine; tyclopyrazoflor; sarolaner, lotilaner; benzpyrimoxan; tigolaner; oxazosulfyl; cyproflanilide, nicofluprole; indazapyroxamet; flupentiofenox; cyclobutrifluram.
[0134] P) Herbicides from the classes P1 to P15
[0135] P1) lipid biosynthesis inhibitors:
[0136] - ACC-herbicides: alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim;
[0137] - non ACC herbicides: benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate.
[0138] P2) ALS inhibitors:
[0139] - sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron- ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl- sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron- methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron;
[0140] - imidazolinones: imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr;
[0141] - triazolopyrimidine herbicides and sulfonanilides: cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam;
[0142] - pyrimidinylbenzoates: bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium;
[0143] - sulfonylaminocarbonyl-triazolinone herbicides: flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl;
[0144] - and triafamone.
[0145] P3) photosynthesis inhibitors: amicarbazone, inhibitors of the photosystem II, triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uraciles such as bromacil, lenacil and terbacil, and bentazon and bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-dimetilsulfate.
[0146] P4) protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, epyrifenacil.
[0147] P5) bleacher herbicides:
[0148] - PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, rimisoxafen;
[0149] - HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxopyritrione;
[0150] - bleacher, unknown target: aclonifen, amitrole flumeturon, bixlozone.
[0151] P6) EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate).
[0152] P7) glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium.
[0153] P8) DHP synthase inhibitors: asulam.
[0154] P9) mitosis inhibitors:
[0155] - group K1 : dinitroanilines: benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin; phosphoramidates: amiprophos, amiprophos-methyl, and butamiphos; benzoic acid herbicides: chlorthal, chlorthal-dimethyl; pyridines: dithiopyr and thiazopyr; benzamides: propyzamide and tebutam;
[0156] - group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M- isopropyl, flamprop-M-methyl and propham. P10) VLCFA inhibitors:
[0157] - chloroacetamides: acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor,
[0158] - oxyacetanilides: flufenacet and mefenacet;
[0159] - acetanilides: diphenamid, naproanilide, napropamide and napropamide-M;
[0160] - tetrazolinones: fentrazamide;
[0161] - other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, dimesulfazet and isooxazoline.
[0162] P11) cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam.
[0163] P12) decoupler herbicides: dinoseb, dinoterb and DNOC and its salts.
[0164] P13) auxinic herbicides:
[0165] 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-ethyl, 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, dichlorprop-P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P 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, florpyrauxifen-benzyl and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 / 7- indol-6-yl)picolinic acid.
[0166] P14) auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium.
[0167] P15) other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tetflupyrolimet, tridiphane.
[0168] Q) Safeners
[0169] (quinolin-8-oxy)acetic acids, 1-phenyl-5-haloalkyl-1 H-1 ,2,4-triazol-3-carboxylic acids, 1-phenyl-4,5- dihydro-5-alkyl-1 H-pyrazol-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2- phenylpyrimidines, A / -[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1 ,8-naphthalic anhydride, 2- halo-4-(haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.
[0170] In preferred embodiments, the composition comprises at least one agrochemical active selected from the group consisting of herbicides, fungicides, and insecticides, and / or at least one plant growth regulator or a combination of any two or more of the afore-mentioned.
[0171] In various embodiments, used in accordance with the present invention are agrochemical actives selected from the group consisting of (tri)azoles, oxyfluorfen, strobilurins, flufenacetate, neonicotinoids or mixtures thereof.
[0172] In various embodiments, the at least one agrochemical active is selected from the group consisting of azoxystrobin, tebuconazole, oxyfluorfen, trifloxystrobin, cyproconazole, prothioconazole, flufenacetate, imidacloprid, difenoconazole, pyraclostrobin, and mixtures thereof, preferably azoxystrobin, prothioconazole, oxyfluorfen, difenoconazole, tebuconazole, and mixtures thereof.
[0173] The composition may comprise at least one further compound selected from the group consisting of cosolvents, dispersants, adjuvants, surfactants, thickeners, humectants, antioxidants, colorants, fragrances, defoamers, anti-caking agents, emulsifiers, and mixtures thereof.
[0174] Preferably, the at least one co-solvent is selected from fatty acid methyl esters, aromatic hydrocarbons, 2- ethylhexanol esters, dimethyl fatty amides, dimethyl alkyl amides, fatty alcohols, glycols, alkyl esters, lactate esters, aromatic esters, alkyl pyrrolidones, paraffinic mineral oils, vegetable oils, lactones, carbonates, carbamates, alkyl amides, ketones, phosphate esters, aldehydes, ethers, acetals, and mixtures thereof.
[0175] In various embodiments, the at least one co-solvent is selected from C12-C18 fatty acid methyl esters, aromatic hydrocarbons, or mixtures thereof.
[0176] In various embodiments, the at least one further compound is an emulsifier and / or surfactant. Suitable compounds include non-ionic and anionic surfactants and their mixtures. Non-ionic surfactants include for example:
[0177] - products of the addition of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto linear C8-22 fatty alcohols, onto C12-22 fatty acids and onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group;
[0178] - C12 / 18 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol;
[0179] - glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof;
[0180] - addition products of 15 to 60 mol ethylene oxide onto castor oil and / or hydrogenated castor oil;
[0181] - polyol esters and, in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isostearate. Mixtures of compounds from several of these classes are also suitable; - addition products of 2 to 15 mol ethylene oxide onto castor oil and / or hydrogenated castor oil;
[0182] - 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);
[0183] - mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and salts thereof;
[0184] - wool wax alcohols;
[0185] - polysiloxane / polyalkyl polyether copolymers and corresponding derivatives;
[0186] - mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of C6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol;
[0187] - polyalkylene glycols.
[0188] The addition products of ethylene oxide and / or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known commercially available products. They are homologue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C12 / 18 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations. The preferred emulsifiers are described in more detail as follows:
[0189] In various embodiments, the emulsifier or surfactant can be a partial glyceride. Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30, and preferably 5 to 10, mol ethylene oxide onto the partial glycerides mentioned are also suitable.
[0190] In various embodiments, the emulsifier or surfactant can be a sorbitan ester. Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesqui isostea rate, sorbitan diisostearate, sorbitan tri isostea rate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30, and preferably 5 to 10, mol ethylene oxide onto the sorbitan esters mentioned are also suitable. In various embodiments, the emulsifier or surfactant can be an alk(en)yl oligoglycoside. The alkyl or alkenyl oligoglycosides representing also preferred emulsifiers may be derived from aldoses or ketoses containing 5 or 6 carbon atoms, preferably glucose. Accordingly, the preferred alkyl and / or alkenyl oligoglycosides are alkyl or alkenyl oligoglucosides. These materials are also known generically as "alkyl polyglycosides" (APG). The alk(en)yl oligoglycosides according to the invention correspond to formula (II):
[0191] RaO[G]P(II) wherein Rais an alkyl or alkenyl radical having from 6 to 22 carbon atoms, G is a sugar unit having 5 or 6 carbon atoms and p is a number from 1 to 10. The index p in general formula (III) indicates the degree of oligomerisation (DP degree), i.e. the distribution of mono- and oligoglycosides, and is a number of 1 to 10. Whereas p in a given compound must always be an integer and, above all, may assume a value of 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined calculated quantity which is mostly a broken number. Alk(en)yl oligoglycosides having an average degree of oligomerisation p of 1 .1 to 3.0 are preferably used. Alk(en)yl oligoglycosides having a degree of oligomerisation below 1.7 and, more particularly, between 1 .2 and 1 .4 are preferred from the applicational point of view. The alkyl or alkenyl radical Ramay be derived from primary alcohols containing 4 to 22 and preferably 8 to 16 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof such as are formed, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen’s oxo synthesis. Alkyl oligoglucosides based on hydrogenated Ca-Ci6 coconut oil alcohol having a DP of 1 to 3 are preferred. Also suitable are alkoxylation products of alkyl oligoglucosides, for example adducts of 1 to 10 moles ethylene oxide and / or 1 to 5 moles propylene oxide to Ca-Cio or C12-C18 alkyl oligoglucoside having a DP between 1 .2 and 1 .4.
[0192] In various embodiments, the emulsifier or surfactant is an alkoxylated vegetable oil. Suitable emulsifiers are castor oil, rape seed oil, soy bean oil ethoxylated with 3 to 80 moles ethylene oxide (Agnique CSO 35, Agnique SBO 10, Agnique SBO 60)).
[0193] In various embodiments, the emulsifier or surfactant is an alkoxylated copolymer. Typical copolymers are ethoxylated and propoxylated block and / or random polymers of C2-22 linear or branched alcohols.
[0194] In various embodiments, the emulsifier can be a miscellaneous emulsifier. Typical anionic emulsifiers are for example alkylbenzene sulfonates like dodecylbenzene sulfonate salts (e.g. Agnique® ABS 70 C or65C), di-octyl sulfosuccinates or anionic polymers like polyacrylates. Other suitable emulsifiers are zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3- carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a Cs / 18 alkyl or acyl group, contain at least one free amino group and at least one -COOH- or -SO3H- group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N- alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C12 / 18 acyl sarcosine.
[0195] In preferred embodiments, the emulsifier or surfactant is selected from non-ionic or anionic surfactants, and mixtures thereof, optionally, castor oil ethoxylates, fatty acid alkoxylates, alcohol alkoxylates, alkyl amine alkoxylates, polyether copolymers, sorbitan ethoxylate esters, aromatic alcohol alkoxylates, alkylbenzene sulfonates or (di-octyl) sulfosuccinates, or mixtures thereof.
[0196] In various embodiments, the at least one emulsifier or surfactant is a castor oil ethoxylate or an alkylbenzene sulfonate or a mixture thereof.
[0197] In addition to these essential components, the formulation / mixture may further comprise adjuvants conventionally used for agrochemical formulations, the choice of the adjuvants depending on the specific use form, the type of formulation or the active substance. Examples of suitable adjuvants are surface-active substances (such as solubilizers, protective colloids, wetters and tackifiers), retention agents, wetting agents, spreaders, uptake enhancers, penetration agents, spray drift controllers, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, optionally colorants and adhesives (for example for the treatment of seed) or conventional adjuvants for bait formulations (for example attractants, feedants, bittering substances).
[0198] In various embodiments, the composition comprises the at least one sulfoxide according to formula (I) in an amount of 1 to 99 wt.-%, preferably 5 to 90 wt.-%, more preferably 10 to 70 wt.-%, even more preferably 20 to 70 wt.-% or 30 to 70 wt.-%, such as 35 to 65 wt.-%. In various embodiments, the amount may be about 45 wt.-%, about 48 wt.-%, about 50 wt.-%, about 55 wt.-%, about 60 wt.-%, or about 63 wt.-%, relative to the total weight of the composition.
[0199] In various embodiments, the composition comprises the at least one agrochemical active in an amount of 1 to 50 wt.-%, preferably 5 to 45 wt.-%, more preferably 10 to 40 wt.-% or 15 to 35 wt.-%,for example in an amount of about 15, about 18, about 20, about 22, about 25, about 28, about 30 or about 32 wt.-%, relative to the total weight of the composition.
[0200] In various embodiments, the composition comprises a. at least one sulfoxide according to formula (I) in an amount of 1 to 99 wt.-%, preferably 5 to 90 wt.-%, more preferably 10 to 70 wt.-%, even more preferably 20 to 70 wt.-% or 30 to 70 wt.-%, such as 35 to 65 wt.-%. In various embodiments, the amount may be about 45 wt.-%, about 48 wt.-%, about 50 wt.-%, about 55 wt.-%, about 60 wt.-%, or about 63 wt.-%; b. at least one agrochemical active in an amount of 1 to 50 wt.-%, preferably 5 to 45 wt.-%, more preferably 10 to 40 wt.-% or 15 to 35 wt.-%,for example in an amount of about 15, about 18, about 20, about 22, about 25, about 28, about 30 or about 32 wt.-%; and, optionally, c. at least one further compound, preferably selected from co-solvents, surfactants, adjuvants and / or emulsifiers and / or surfactants and / or adjuvants in amounts of 0 to 90 wt.-%, preferably 0.1 to 70 wt.-%, more preferably such as 1 to 50 wt.-%, for example 1 to 40 wt.-% or 1 to 30 wt.-%; and / or, optionally, d. water, preferably ad 100 wt.-%; each based on the total weight of the composition.
[0201] The wording “ad 100 wt.-%” means, in the context of the present invention, that the composition can be filled up with water to reach a total volume of 100 wt.-%.
[0202] It is preferred that the composition according to the invention is an agrochemical composition.
[0203] “Agrochemical” or “agrochemical composition”, in the context of the present invention, preferably refers to a chemical product used in industrial agriculture.
[0204] In a second aspect, the invention relates to the use of sulfoxides according to formula (I) as a solvent or dispersant for at least one active, preferably an agrochemical active in agrochemicals.
[0205] Preferably, the sulfoxides are sulfoxides according to formula (I) as described above. It is preferred that the sulfoxides are non-protic solvents.
[0206] The invention also pertains to the use of sulfoxides according to formula (I) as a solvent in an agrochemical formulation, such as concentrate, for example an emulsion concentrate, a suspension concentrate or a dispersion concentrate, in particular an emulsion concentrate.
[0207] In various embodiments, the sulfoxide maintains or improves the stability of a concentrate or formulation, such as an emulsion concentrate or emulsion formulation, preferably in comparison to other solvents, such as alkyl esters including 2-ethylhexylacetate, which are not according to the invention. In various embodiments, the sulfoxide according to the invention is either bis(2-methoxyethyl) sulfoxide or bis(2- butoxyethyl) sulfoxide.
[0208] The compositions disclosed herein are generally used for controlling pests, for example harmful fungi or insects, in plants. Such uses typically comprise applying the compositions of the invention to at least part of said plants, to the soil in which they are growing or to their seeds. The application may be by any suitable and generally known means, such as for example by spraying.
[0209] The corresponding method of using the compositions described herein for controlling pests, for example harmful fungi or insects, in plants is also intended to be encompassed by the present invention. Such methods comprise applying the composition of the invention to said plants, to the soil in which they are growing or to their seeds, for example by spraying.
[0210] In case the composition of the invention is a concentrate, said use or method may also include (the step of) diluting the concentrate to the desired concentration with a suitable liquid medium, for example water. The concentrate may be, without limitation, an emulsion concentrate, a suspension concentrate, or a dispersion concentrate.
[0211] The term "plant", as used herein, is preferably to be understood as a plant of economic importance and / or men-grown plant. In certain embodiments, the term may also be understood as plants which have no or no significant economic importance. The plant is preferably selected from agricultural, silvicultural, and horticultural (including ornamental) plants. The term also relates to genetically modified plants.
[0212] The term "plant" as used herein further includes all parts of a plant such as germinating seeds, emerging seedlings, plant propagules, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.
[0213] In one embodiment, the plant is an agricultural plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oilseed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants.
[0214] In a further embodiment, the plant is a horticultural plant. The term "horticultural plants" are to be understood as plants which are commonly used in horticulture, e.g. the cultivation of ornamentals, vegetables and / or fruits. Examples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas, and lettuce and more preferably from tomatoes, onions, peas, and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots, and blueberries. In a further embodiment, the plant is an ornamental plant. "Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
[0215] In another embodiment of the present invention, the plant is a silvicultural plant. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec., fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec., poplar (cottonwood), in particular Populus spec., beech, in particular Fagus spec., birch, oil palm, and oak.
[0216] The term "genetically modified plants" is to be understood as plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that under natural circumstances it cannot readily be obtained by cross breeding, mutations, or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post- translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
[0217] Plants that have been modified by breeding, mutagenesis or genetic engineering, e.g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4- D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i.e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering, are also covered. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e.g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets, and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above.
[0218] Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral, or fungal pathogens. Examples of such proteins are the so-called “pathogenesis-related proteins” (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanurri) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above.
[0219] Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. biomass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial, or viral pathogens of those plants.
[0220] Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
[0221] Moreover, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
[0222] In a still further embodiment the present invention is directed to the compound bis(2-methoxyethyl) sulfoxide and / or bis(2-butoxyethyl) sulfoxide. The structures of these two compounds are also shown herein above.
[0223] All embodiments and examples described herein for the composition also apply to the uses and methods disclosed herein and vice versa.
[0224] The present invention is further illustrated by the following examples.
[0225] EXAMPLES
[0226] Determination of maximum pesticide solubility
[0227] The maximum solubility of pesticides in various solvents were determined at 21 °C. Herein, small amounts of active ingredients were added to the 10 g of solvent in a 25 mL beaker under stirring with a magnetic stirrer bar. Active ingredient doses were added to the solvent until dissolution was no longer achieved, with a maximum 2 h stirring time conducted to achieve dissolution between dosing. The solubility was calculated according to the following equation: 100
[0228] Determination of Solvent Water solubility:
[0229] The water solubility of the solvent was determined according to a method based on CIPAC MT157.1 and OECD 105 via the assessment of undissolved solvent in water after vigorous mixing and standing. Herein, various amounts of solvent and water were mixed with vigorous shaking in a glass-stoppered graduated cylinder or separating funnel, followed by standing for at least 30 min to enable separation. For example, if undissolved solvent was observed after thorough mixing of 0.1 g solvent in 100 mL of water, the solvent had a water-solubility equal to or below 0.1 % (< 1 g / L). This method can be repeated with various amounts of solvent and water to enable the determination of the water-solubility of the solvent.
[0230] CIPAC D water: Made in the lab using a standard recipe published by CIPAC “MT 18.1.4”: Standard Waters. The water has a hardness of 342 ppm, with a 4:1 mixture of Ca:Mg ions at pH 6-7.
[0231] Example 1 : Water solubility
[0232] Water solubilities were determined for various solvents using the methods as described above. The results are shown in Table 1 .
[0233] Table 1 : Comparison of water-soluble sulfoxide properties with other solvents
[0234] Emulsion stability at 5 % at room temperature (21 °C)
[0235] The emulsion was tested for its dispersibility by the effect known as blooming.
[0236] The emulsions were assessed according to their spontaneous emulsification when the concentrate is added to water (known in the art as "blooming") with a visual assessment given on a scale of 1 to 5, whereby 1). Excellent, “cloud of emulsion”, does not sink to bottom of cylinder. 2). Good, “cloud of emulsion”, but sinks to bottom of cylinder 3). Okay, “poor emulsion cloud”, larger droplets 4). Poor, “no emulsion cloud”, small “particles” observed 5). Very poor, no emulsion, oil and water phases immediately separate" Emulsifiable concentrates were prepared in the following examples and the resulting 5% w / w emulsions in various water hardness at 21 °C after 1 , 2, and 4 hours were assessed. Emulsion stability was determined as a function of time, with the amount of either cream or sediment measured.
[0237] To measure emulsion stability, 5.0 mL of the emulsifiable concentrate was diluted in 95.0 mL CIPAC D water in a 100 mL measuring cylinder. The resulting oil-in-water emulsion stability was assessed after 1 , 2, and 4 hours. A highly stable emulsion does not form cream or sediment or has less than 1 .5 mL cream or sediment after 4 hours. Emulsification was achieved by gently inverting the emulsion 10 times. In the following tables Y (i.e. yes) indicates that at most 1.5 mL cream or sediment is observed after 4 hours, whilst N (i.e. no) indicates that more than 1 .5 mL cream or sediment is observed after 4 hours.
[0238] Emulsion (concentrates) shown in Table 2 were formed as described above and evaluated. The results are shown in the Table 3 below.
[0239] Table 2: Emulsion compositions
[0240] Table 3: Emulsion stability
[0241] The emulsions are tested at 5 wt.-% in water. “Good stability” means that the cream / sediment level after
[0242] 4h is <1 .5 mL (S = sediment, C= cream).
[0243] Example 2: Active ingredient solubility
[0244] Active ingredient solubilities were determined for various actives using the methods as described above.
[0245] The results are shown in Table 4. Table 4: Active ingredient solubility in w / w %
[0246] From the active ingredient solvency study (results are shown in Fig. 1 and Fig. 2), it can be seen that bis(2- methoxyethyl)sulfoxide has similar solution properties to dimethyl lactamide. For difenoconazole and prothioconazole, the solubility is similar or increased for bis(2-methoxyethyl)sulfoxide in comparison to DMSO. It can also be seen that bis(2-butoxyethyl)sulfoxide has better solution properties than a solvent naphtha (Solvesso 150 ND) and C8 fatty acid methyl ester for the pesticides tebuconazole, pyraclostrobin, difenoconazole, prothioconazole, and flufenacetate, with the difference being particularly pronounced for tebuconazole and prothioconazole.
Claims
AMENDED CLAIMS received by the International Bureau on 16 May 2025 (16.05.2025)1 . Composition comprising a. at least one sulfoxide according to formula (I)R1-O-R2-S(=O)-R3-O-R4(I) whereinR1and R4are, independently of each other, H, C1-C8alkyl or C(=O)(C1-C12alkyl); and R2and R3are, independently of each other, linear or branched C1-C10 alkylene groups; and b. at least one agrochemical active.
2. The composition according to claim 1 , wherein at least one of R1and R4is not H, optionally both of R1and R4are not H.
3. The composition according to claim 1 or 2, wherein,(1) at least one of R1and R4is C(=O)(C1-C12alkyl), preferably C(=O)(C1-C8alkyl), more preferably C(=O)(C1-C4alkyl), such as C(=O)(CH3), C(=O)(CH2-CH3) or C(=O)(CH2-CH2-CH3); and / or(2) at least one of R1and R4is C1-C8alkyl, preferably C1-C6alkyl, more preferably C1-C4alkyl, more preferably methyl, ethyl or butyl, most preferably methyl or n-butyl.
4. The composition according to any one of claims 1 to 3, wherein R1and R4are, independently of each other, C1-C8alkyl, preferably C1-C6alkyl, more preferably C1-C4alkyl, even more preferably methyl, ethyl or butyl, most preferably methyl or n-butyl.
5. The composition according to any one of claims 1 to 4, wherein(1) R2and R3are, independently of each other, (CR52)m, wherein m is an integer of 1 to 8, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and each R5is independently selected from H and a C1-C4alkyl group; or(2) R2and R3are, independently of each other, CH2- CH2, CH2-CH2-CH2, CH2-CH(R5) or CH(R5)-CH2, with R5optionally being methyl or ethyl; or(3) R2and R3are, independently of each other, CH2-CH2, CH2-CH2-CH2, CH2-CH(CH3) or CH(CH3)-CH2; and R1and R4are, independently of each other, C1-C4alkyl, preferably methyl, ethyl or butyl, more preferably methyl or n-butyl.
6. The composition according to any one of claims 1 to 5, wherein R2and R3are identical, and / or R1and R4are identical.
7. The composition according to any one of claims 1 to 6, whereinR2and R3are identical, preferably CH2-CH2; and R1and R4are identical C1-C4alkyl, preferably methyl, ethyl or butyl, more preferably methyl or n-butyl.
8. The composition according to any one of claims 1 to 7, wherein the sulfoxide according to formula (I) is9. The composition according to any one of claims 1 to 8, wherein the at least one agrochemical active is selected from the group consisting of herbicides, fungicides, insecticides, plant stimulators and combinations thereof.
10. The composition according to any one of claims 1 to 9, wherein the at least one agrochemical active is selected from the group consisting of azoxystrobin, tebuconazole, oxyfluorfen, trifloxystrobin, cyproconazole, prothioconazole, flufenacetate, imidacloprid, difenoconazole, pyraclostrobin, and combinations thereof, preferably pyraclostrobin, flufenacetate, azoxystrobin, prothioconazole, oxyfluorfen, difenoconazole, tebuconazole, and combinations thereof.
11. The composition according to any one of claims 1 to 10, wherein the composition comprises at least one further compound selected from the group consisting of co-solvents, dispersants, adjuvants, surfactants, thickeners, humectants, antioxidants, colorants, fragrances, defoamers, anti-caking agents, emulsifiers, and mixtures thereof.
12. The composition according to claim 1 1 , wherein- the at least one co-solvent is selected from fatty acid methyl esters, aromatic hydrocarbons, 2- ethylhexanol esters, dimethyl amides, fatty alcohols, glycols, alkyl esters, lactate esters, alkyl pyrrolidones, paraffinic mineral oils, vegetable oils, lactones, carbonates, carbamates, alkyl amides, ketones, phosphate esters, aldehydes, ethers, acetals and mixtures thereof; preferably dimethyl fatty acid amides, dimethyl alkyl acid amides, or dimethyl alkyl hydroxy acid amides and mixtures thereof; and / or- the emulsifier is selected from non-ionic or anionic surfactants, and mixtures thereof, optionally, castor oil ethoxylates, fatty acid alkoxylates, alcohol alkoxylates, alkyl amine alkoxylates, polyether copolymers, sorbitan ethoxylate esters, aromatic alcohol alkoxylates, alkylbenzene sulfonates or (di-octyl) sulfosuccinates.
13. The composition according to any one of claims 1 to 12, wherein the composition comprises a. at least one sulfoxide according to formula (I) in an amount of 1 to 99 wt.-%, preferably 5 to 90 wt.-%, more preferably 10 to 70 wt.-%, such as about 45 wt.-%, about 50 wt.-%, about 55 wt.-%, about 60 wt.-%, or about 63 wt.-%; b. at least one agrochemical active in an amount of 1 to 50 wt.-%, preferably 10 to 40 wt.-%, more preferably 15 to 30 wt.-%, such as about 20 wt.-% or about 25 wt.-%; and, optionally, c. at least one further compound, preferably selected from co-solvents, surfactants, adjuvants and / or emulsifiers in amounts of 0 to 90 wt.-%, preferably 0.1 to 70 wt.-%, more preferably such as 1 to 50 wt.-%; and / or d. water, preferably ad 100 wt.-%;each based on the total weight of the composition.
14. The composition according to any one of claims 1 to 13, wherein the composition is an agrochemical composition.
515. Use of a sulfoxide according to formula (I)R1-O-R2-S(=O)-R3-O-R4(I)10 whereinR1and R4are, independently of each other, H, C1-C8alkyl or C(=O)(C1-C12alkyl); and R2and R3are, independently of each other, linear or branched C1-C10alkylene groups, as(1) a solvent or dispersant for at least one agrochemical active; or(2) as a solvent in an agrochemical formulation, preferably to improve stability compared to other15 solvents.
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