Compositions containing four-membered ring carboxamide compounds
A stable emulsifiable concentrate formulation of cyclobutylcarboxamide compounds, using a solvent system with specific Hansen parameters and emulsifying surfactants, addresses the stability issues of aqueous formulations, ensuring long-term stability and uniform application.
Patent Information
- Application Number
- JP2025538403
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2022-12-30
- Filing Date
- 2023-12-19
- Publication Date
- 2025-12-22
AI Technical Summary
Existing aqueous formulations of cyclobutylcarboxamide compounds, such as cyclobutrifluram, face issues with rapid crystallization and increased crystal size growth during storage and dilution, affecting filterability and spray applicability, necessitating the development of stable emulsifiable concentrate (EC) formulations that maintain stability under various conditions.
A stable single-phase emulsifiable composition comprising cyclobutylcarboxamide compounds and a solvent system with specific Hansen polarity and hydrogen bonding parameters, combined with an emulsifying surfactant, forming an oil-in-water emulsion upon dilution, ensuring storage and dilution stability.
The composition provides long-term stability, improved wettability, and uniform application, preventing crystallization and nozzle blockage, while maintaining the active ingredient's quality and bioavailability.
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Abstract
Description
[Technical Field]
[0001] The present invention relates to emulsifiable concentrate (EC) formulations of four-membered ring carboxamide-containing compounds, particularly agrochemically active cyclobutylcarboxamide compounds, utilizing an improved solvent system comprising a primary solvent in combination with one or more co-solvents. [Background technology]
[0002] Four-membered ring carboxamide compounds have recently found increasing interest as pesticides due to their broad-spectrum activity against nematodes and important fungal diseases. In particular, cyclobutylcarboxamide compounds and their close analogues containing a four-membered ring in the core structure, as well as methods for their preparation, have been disclosed, for example, in WO 2013 / 143811, WO 2015 / 003951, WO 2015 / 022265, and WO 2019 / 158476.
[0003] A particularly effective cyclobutylcarboxamide compound, having the ISO name "cyclobutrifluram," is currently being pursued as a potent nematicide. The chemical structure of cyclobutrifluram is shown in formula (I): [ka] It is expressed according to
[0004] Cyclobutrifluram, its salts or N-oxides, and its close analogues have been reported to have some activity against root-knot nematodes such as Meloidogyne and cyst-forming nematodes such as Heterodera, as well as some fungicidal activity.
[0005] Most formulations of cyclobutylcarboxamide compounds proposed today are aqueous, such as emulsions or dispersions. While this provides a highly efficient, safe, and environmentally friendly method for applying these compositions, there are several characteristics that may limit their industrial applicability. For example, aqueous formulations containing cyclobutylcarboxamide compounds may exhibit a tendency for rapid crystallization and / or increased crystal size growth depending on storage and dilution conditions. While this may be useful for certain applications, industrial applicability often requires that the active ingredient be provided in a ready-to-use form or within a few days after dilution with water prior to actual application, such as field or greenhouse spraying. The active ingredient emulsion or dispersion must exhibit sufficiently high phase separation stability to maintain this stability for a suitable long period of time to allow application, not just immediately after dilution with water. In this case, the presence of crystals above a certain size may affect filterability and / or spray applicability, and as a result, blockage of pumps, lines, and spray nozzles may make effective and uniform application difficult.
[0006] It may also be desirable to exhibit a certain level of crystallization when wetting of the target substrate is desired and ultimately when (bio)availability in the field or greenhouse or elsewhere such as on the leaves, in the furrow, on the soil surface or in subsurface soil and in surface or groundwater reservoirs is desired.
[0007] Therefore, there remains a need to provide emulsifiable concentrate (EC) formulations that are substantially storage-stable and dilution-stable. Furthermore, it may be useful to provide such compositions in a form that can be used only for dilution with water prior to actual application, such as for field or greenhouse spraying. Ideally, such compositions should also be storage-stable under a wide range of conditions without chemically or physically affecting the quality of the active ingredient and without inducing crystallization.
[0008] Given the wide variety of conditions and special circumstances under which pesticides are stored, transported, and used throughout the world, there remains a need for EC premix formulations of pesticides that offer stability advantages under at least some of those conditions and circumstances.
[0009] There is a further need for EC premix formulations that can be easily prepared from components of commercially available aqueous pesticides, compositions that are preferably storage stable under temperature conditions ranging from -10°C to +54°C for at least several weeks, preferably at least one year. Summary of the Invention [Means for solving the problem]
[0010] Accordingly, in a first aspect of the present invention, there is provided a stable single-phase emulsifiable or dispersible composition comprising: (a) one or more compounds selected from the following: N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (1, cyclobutrifluram), and the following closely related analogs: N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide (2); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide (3); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (3); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (4); N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (5); N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl)pyrazine-2-carboxamide N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyridine-3-carboxamide (6); N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (7); N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl)benzamide (8); N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyridine N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide (10); N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (11); N-[(2,3cis)-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)benzamide (12);N-[(2,3cis)-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)-pyridine-3-carboxamide (13); N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (14); N-[(1,2cis)-2-(2-chloro-4-fluorophenyl)cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide (15); N-[(1,2cis)-2-(2-chloro-4-fluorophenyl)cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide Butyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (16); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (17); N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (18); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)-benzamide (19); N-[( 1,2cis)-2-[4-fluoro-2-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide (20); N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide (21); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-4-(trifluoromethyl)-thiazole-5-carboxamide (22); N-[(1,2cis)-2-(4-chloro-2-fluoro N-[(1,2-cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)-pyrazine-2-carboxamide (23); N-[(1,2-cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)-benzamide (24); and N-[(1,2-cis)-2-(2,4-difluorophenyl)cyclobutyl]-4-(trifluoromethyl)thiazole-5-carboxamide (25); N-[(1,2-cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (26);N-[(1,2 cis )-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide ( 27 ); N-[(1,2 cis )-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (28); N-[(1,2 cis )-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (29); N-[(2,3 cis )-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)benzamide ( 30 ); N-[(2,3 cis)-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)pyridine-3-carboxamide (31); N-[(1,2 cis)-2-(2-chloro-4-fluorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (32); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (33); N-[(1,2 cis )-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (34); N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (35); and N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (36), their stereoisomers, tautomers, salts, or N-oxides, and (b) a solvent system, (i) at least one non-aqueous polar solvent classified by an Hp (Hansen polarity) value in the range of 5 to 15 and an Hh (Hansen H-bond) parameter in the range of 5 to 15; (ii) a solvent system comprising at least one water-immiscible non-polar solvent; (c) an emulsifying surfactant system that enables the emulsifiable concentrate to form an oil-in-water emulsion when added to water, thereby forming an emulsifiable concentrate (EC).
[0011] In a further aspect of the present invention, there is provided a process for the preparation of a composition according to the present invention, comprising contacting one or more aliquots of compounds 1-25 with at least one of solvents (i) and / or (ii), and optionally at least a portion of an emulsifying surfactant system, to form the composition as a preformed concentrate composition capable of forming an emulsion / microemulsion upon dilution with water.
[0012] In a still further aspect the present invention provides a process for the preparation of an aqueous emulsion or dispersion, which process comprises contacting a composition according to the present invention with an aqueous liquid carrier under conditions to induce the formation of an emulsion or dispersion.
[0013] In a further aspect of the present invention there is provided an emulsion-in-water formulation obtainable according to the process, comprising a composition of active ingredients diluted in water in the form of an agrochemical concentrated aqueous formulation.
[0014] In yet a further aspect, the present invention provides a method for preventing or controlling pathogens in crops of useful plants, which method comprises treating the plant, plant part, plant propagation material or its habitat with an agrochemically effective amount of a water-diluted spray composition or an oil-in-water emulsion formed when a composition according to the present invention is added to an aqueous liquid carrier.
[0015] In a still further aspect of the invention, there is provided the use of the composition for the storage and delivery of one or more of compounds 1-36.
[0016] In a still further aspect of the present invention there is provided the use of the composition for preparing an oil-in-water emulsion.
[0017] In yet a further aspect of the present invention, there is provided the use of the composition for controlling unwanted plant pathogens, particularly nematodes and / or fungi. Also provided is a method for controlling unwanted plant pathogens, particularly nematodes and / or fungi, which comprises dispersing the formulation of the present invention in an aqueous solution and contacting the resulting mixture with a plant, plant propagation material or the habitat of said plant. DETAILED DESCRIPTION OF THE INVENTION
[0018] Throughout the description and claims of this specification, the words "comprise" and "contain," and variations thereof, mean "including but not limited to," and are not intended to exclude (and do not exclude) other moieties, additives, components, integers, or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context dictates otherwise. In particular, where the indefinite article is used, the specification is understood to contemplate the plural as well as the singular, unless the context dictates otherwise.
[0019] It is understood that any feature, integer, property, compound, chemical moiety, or group described in connection with a particular aspect, embodiment, or example of the invention is also applicable, to the extent compatible therewith, to other aspects, embodiments, or examples described herein. All of the features disclosed in this specification (including the accompanying claims, abstract, and drawings) and / or all of the steps of any method or process so disclosed may be combined in any combination, except for combinations in which at least some of such features and / or steps are mutually exclusive.
[0020] The invention is not limited to the details of the above embodiments, and extends to any novel one or any novel combination of features disclosed in this specification (including the accompanying claims, abstract and drawings), or any novel one or any novel combination of steps of any method or process so disclosed.
[0021] "Stereoisomers" in this invention refer to compounds composed of the same atoms joined by the same bond sequence, but having different three-dimensional structures that are not interchangeable.
[0022] As used herein, the term "about" specifically includes ±10% from the indicated value within the range. In addition, the endpoints of all ranges directed to the same component or property herein are inclusive and independently combinable, and include all intermediate endpoints and ranges.
[0023] It will be understood that when a range of a parameter is given, all integers and "some tenths thereof" numbers within that range are also contemplated by the present invention as if the integers and "some tenths thereof" numbers were expressly written herein. For example, "75-99 w / w%" includes 70.0 w / w%, 70.1 w / w%, 70.2 w / w%, 70.3 w / w%, etc., up to 99.0 w / w%.
[0024] "Active ingredient" herein refers primarily to the cyclobutylcarboxamide compounds of the present invention, and secondarily to any additional pest control agents, including, but not limited to, herbicides, insecticides, fungicides, nematicides, miticides, biocides, etc. Non-limiting examples of suitable active pesticides are listed below. Table 1 lists compounds 1-36 that exhibit selected nematicidal and fungicidal effects.
[0025] [Table 1-1]
[0026] [Table 1-2]
[0027] [Table 1-3]
[0028] The preparation of the compounds in Table 1, including cyclobutrifluram, is described in any of WO 2013 / 143811, WO 2015 / 003951, WO 2015 / 022265, and WO 2019 / 158476, all in the name of SYNGENTA PARTICIPATIONS AG, all of which are incorporated herein by reference.
[0029] Preferably, compound (a) comprises one or more stereoisomers of N-[(1,2 cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (cyclobutrifluram).
[0030] Cyclobutrifluram as disclosed above represents a cis racemate: the phenyl ring on the left and the pyridyl-C(=O)-NH group on the right correspond to compounds of formula (Ia) and (Ib) [ka] They are cis to each other on the cyclobutyl ring, as exemplified for
[0031] A racemic compound of cyclobutrifluram is a 1:1 mixture of compounds of formula (Ia) and (Ib). The wedged bonds shown in compounds of formula (Ia) and (Ib) represent absolute stereochemistry, while the bold, straight bonds as shown in compounds of formula (I) represent relative stereochemistry in the racemic compound. It has also surprisingly been found that one of the enantiomers of cyclobutrifluram is particularly useful in methods for controlling or preventing plant infestation by phytopathogenic microorganisms of the genus Aspergillus.
[0032] Thus, preferably, cyclobutrifluram is the (1S,2S) stereoisomer (Ia) [ka] There is provided a method according to the invention in the form of:
[0033] Those skilled in the art will recognize that, according to the methods of the present invention, cyclobutrifluram is generally applied as part of a pesticidal composition, whereby the compound of formula (I) is known to be particularly useful for controlling nematodes. Accordingly, there is provided a method for controlling or preventing plant infestation by nematode plant pests, comprising applying a pesticidal composition comprising cyclobutrifluram and one or more formulation adjuvants to a plant crop, its habitat, or its propagation material. In the methods according to the present invention, for beneficial compositions comprising both the (1S,2S) stereoisomer and the (1R,2R) stereoisomer of cyclobutrifluram, the ratio of the (1S,2S) stereoisomer to its enantiomer (1R,2R) is preferably greater than 1:1. More preferably, the ratio of (1S,2S) to (1S,2S) is greater than 1.5:1, more preferably greater than 2.5:1, especially greater than 4:1, advantageously greater than 9:1, desirably greater than 20:1, especially greater than 35:1.
[0034] It is understood that mixtures containing not more than 50%, preferably not more than 40%, more preferably not more than 30%, in particular not more than 20%, advantageously not more than 10%, desirably not more than 5%, in particular not more than 3% of the trans stereoisomer of the compound of formula (I) (i.e., in which the phenyl and pyridyl-C(=O)-NH groups are trans relative to each other) are also part of the present invention. Preferably, the ratio of cis to trans isomers is greater than 1.5:1, more preferably greater than 2.5:1, in particular greater than 4:1, advantageously greater than 9:1, desirably greater than 20:1, in particular greater than 35:1.
[0035] Preferably, the one or more compounds (a) are present in the composition in an amount of 0.01 to 15% by weight.
[0036] Preferably, the composition comprises water in an amount of 2% or less by weight of the composition.
[0037] "Emulsifiable concentrate" The present invention relates to pesticidal emulsifiable concentrates, their preparation, and methods for using such compositions to control pests in crops of useful plants. Emulsifiable concentrate (EC) formulations are advantageous liquid delivery systems for agriculturally active compounds. As a rule, conventional ECs contain at least one active ingredient, one or more surfactants that act as emulsifiers when the EC is diluted with water, and a water-immiscible solvent that has low water solubility and can dissolve a wide range of active ingredients. Typical ECs contain little or no water because high levels of water can cause phase inversion and creaming. Emulsifiable concentrates can be formulated into aqueous emulsions (EW), concentrated suspensions (SC), and other types of formulations for use in agriculture and to control all types of parasites.
[0038] Due to the presence of solvents, many pesticides formulated as ECs have advantages such as greater systemicity and higher overall activity compared to the same pesticides formulated as water-dispersible granules (WG) or as oil-in-water emulsions (EW).
[0039] In some cases, it may be desirable to combine different pesticides to provide a single formulation that takes advantage of the additive properties of each separate pesticide to optimize biological performance. Also, as opposed to tank-mixing separate pesticide products and adjuvants by the end user, transportation and storage costs can be minimized by preparing an EC in which the pesticide concentration is as high as practical and any desired adjuvants are "built into" the formulation. However, combining pesticide products with significantly different physical, chemical, or biological properties—for example, one pesticide is a water-insoluble solid and the other is a water-soluble salt—available as an aqueous SL formulation increases the likelihood that the stability of the resulting EC premix formulation will be disrupted or that one or more components will separate from the EC. This is particularly true when significant amounts of water are present in the form of the individual pesticide components used to make the EC premix.
[0040] The formulations are characterized by a long half-life ("storage stability"), a long crystallization time after the formulation is dissolved in water, improved wettability and excellent emulsion stability.
[0041] "solvent-based"; Hansen Solubility Parameter It has been surprisingly found that a combination of solvents within a specific region of the Hansen Solubility Parameters can be used as a solvent for the emulsifiable concentrate composition of the present invention, allowing for the formulation of a safe aqueous emulsion or dispersion while maintaining the availability of the active ingredient. Thus, the present invention utilizes a combination of solvents.
[0042] The Hansen Solubility Parameter comprises a mathematical method for characterizing the ability of a solvent to dissolve a compound. The Hansen Solubility Parameter differs from other solubility parameters in that the Hansen Parameter calculates the non-polar, polar, and hydrogen bonding components of the total solubility parameter separately, thereby allowing formulators to select a solvent based on four parameters rather than just one. The components of the Hansen Solubility Parameter of a solvent are (1) the non-polar index, (2) the polar index, and (3) the hydrogen bonding index. The solubility parameters referred to herein are those disclosed in "Hansen Solubility Parameters: A User's Handbook.--2nd ed. / edited by Charles Hansen, 2000, ISBN 0-8493-7248-8."
[0043] It is empirically known that the hydrogen bonding index is an approximate measure of the water solubility of a solvent and can be used to predict which solvents can form stable emulsions. Without wishing to be bound by any particular theory, it is assumed that when solvents are combined into a mixture, the Hansen solubility parameter of the mixture is approximately equal to the weighted average of the Hansen solubility parameters of the individual solvents, based on the molar volume of each solvent.
[0044] Useful Solvents In general, solvents or solvent blends with a high polarity index greater than 5.0 and up to 15.0, and a high hydrogen bonding index greater than 5.0 and up to 15.0, have been found to be effective solvents for the compositions of the present invention. Preferably, the solvents of the compositions of the present invention have a flash point greater than 50°C, more preferably greater than 90°C, because these solvents are generally safer to use and act as latent solvents in emulsions or dispersions, thereby reducing the tendency to crystallize the active ingredient in the organic phase. The active ingredient of the composition must be soluble in the solvent composition. The solvent system includes two components: (i) and (ii).
[0045] Any suitable solvent or solvent mixture that meets the required Hansen parameters can be used, optionally with the addition of one or more ionic or nonionic surfactants or emulsifiers. The solvent component (i) preferably also meets the requirements for use as an agrochemical composition. Suitable solvents exhibit many or all of the following properties: excellent solvency for pesticides or other organic molecules; being made from renewable plant or animal resources; low skin irritation; low biotoxicity, e.g., to daphnia; low volatile organic content; and high flash point. The compositions of the present invention each exhibit all or many of these properties, particularly excellent solvency, so that compounds can be effectively used as solvents. Table 2 shows the Hansen parameters of some useful solvents.
[0046] [Table 2-1]
[0047] [Table 2-2]
[0048] Therefore, useful solvents (i) having the required Hp and Hh values (i.e., dP and dH values in the tables hereinabove) include acetone, n-amyl alcohol, benzyl alcohol, benzyl benzoate, 2-butanol, t-butyl alcohol, butyl benzoate, butyl glycol acetate, n-butyl propionate, ε-caprolactone, m-cresol, cyclohexanone, diacetone alcohol, dimethyl sulfoxide (DMSO), 1,3-dioxolane, dipropylene glycol, methyl ether, dipropylene glycol mono-n-butyl ether, ethyl acetate, ethyl lactate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monomethyl ... ethyl ether, iso-pentyl alcohol, isophorone methyl acetate, methyl carbitol, methyl cellosolve, methyl ethyl ketone (MEK), N-methyl-2-pyrrolidone (NMP), methylene chloride, N,N-dimethylacetamide, N,N-dimethylformamide (DMF), 1-nitropropane, 2-phenoxyethanol, n-propyl propionate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol phenyl ether, sulfolane (tetramethylene sulfone), tetrahydrofuran (THF), and / or tetrahydrofurfuryl alcohol.
[0049] Other examples of suitable non-aqueous polar solvents (i) include acetone, amyl acetate, butanol, benzyl alcohol, cetyl alcohol, dimethyl ether, dipropylene glycol, diethylene glycol monomethyl ether, octanol, Hallcomid M-8-10, hexylene glycol, cyclohexanol, ethyl lactate, ethyl alcohol, 2-ethylhexanol, glycerol monoacetate, glycerol diacetate, glycerol triacetate, 3-hexanol, n-hexyl alcohol, isopropyl myristate, lactic acid, lactic acid 2-ethylhexyl ester, lactic acid n-propyl ester, methyl alcohol, methyl n-amyl ketone, methyl isobutyl ketone, oleyl alcohol, propanol, tetrahydrofurfuryl alcohol, butyrolactone, chlorobenzene, diacetone alcohol, n-decanol, N,N-dimethyldecanamide, N,N-dimethyloctanamide, dimethyl lactamide, n-decyl alcohol, dipropyl alcohol, Examples of suitable olefin copolymers include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, isobutyl alcohol, mesityl oxide, methyl ethyl ketone, 2-methyl-2,4-pentanediol, N-octylpyrrolidone, N-methylpyrrolidone, n-octyl alcohol, oxo-decyl acetate, oxo-heptyl acetate, oxo-hexyl acetate, oxo-nonyl acetate, oxo-octyl acetate, oxo-tridecyl acetate, propylene glycol monomethyl ether, triethylene glycol, triethyl phosphate, n-butyl lactic acid ester, ethyl lactic acid ester, dodecylpyrrolidone, N,N-dimethylacetamide, propylene carbonate, and mixtures thereof.
[0050] Preferred solvents are non-hydroxyl group-containing solvents, especially gamma-caprolactone, also known as gamma-hexyl lactone; ethyl butyrolactone; gamma-ethyl-n-butyrolactone; hexanolide-1,4; 4-hydroxyhexanoic acid gamma-lactone or tonkalide), 6-hexylactone, gamma-butyrolactone, etc. Gamma-hexylactone, Synperonic NCA 830, and dimethyl sulfoxide are used in some embodiments of the present invention.
[0051] Within other embodiments, solvents such as N,N-dimethyl-m-toluamide, eucalyptol, dimethyl isosorbide, diisopropyl adipate, and / or 1-methoxy-2-propyl acetate may be advantageously utilized in combination with gamma-hexylactone to comprise carrier solvent component (i).
[0052] Particularly preferred solvents (i) include N-methyl-2-pyrrolidone (NMP), γ-caprolactone, N-butylpyrrolidone, tetrahydrofurfuryl alcohol, dipropylene glycol monomethyl ether, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, and / or mixtures thereof. These solvents are high-boiling, polar, aprotic, low-density liquids that are miscible with water in the required temperature range while providing particularly good solubility for the active ingredient according to the present invention. These solvents also provide chemical and thermal stability and low toxicity. Particularly preferred solvents include N-methylpyrrolidone and γ-caprolactone.
[0053] The solvent system further comprises an essentially water-immiscible solvent component (ii). In a preferred embodiment, the solvent component (ii) is selected from the group consisting of aromatic hydrocarbons such as SOLVESSO solvents, paraffinic hydrocarbons such as EXXSOL solvents, cyclic hydrocarbons such as cyclohexanone and isophorone, methyl ester solvents (fatty acid-based methyl esters) such as methyl oleate, methyl palmitate, and methyl laurate, and canola oil or soybean oil methyl esters (methylated seed and vegetable oils), and propylene glycol methyl ether, C8-C 16 Dibasic esters (usually methyl esters) of long-chain diacids ranging in carbon units; amides such as long-chain primary amides, as well as C8-C 12 disubstituted amides such as dimethylamides, for example, N,N-dimethyldecanamide, N,N-dimethyllactamide, N,N-dimethyl-9-decenamide, and N,N-dimethyloctanamide; glycerol esters such as capric / caprylic triglyceride ester; ethoxylated phosphate esters such as nonylphenol POE-10 phosphate ester; acetates such as 2-ethylhexyl acetate, isopropyl acetate, and isobornyl acetate; alcohols such as 2-ethylhexanol, octanol, and benzyl alcohol; lactates such as 2-ethylhexyl lactate and butyl lactate; carbonates such as propylene carbonate, diphenyl carbonate, and polypropylene carbonate; citrates such as acetyl tributyl citrate, triethyl citrate, and n-butylyl tri-n-hexyl citrate; and other solvents such as dimethyl sulfoxide, dimethylformamide, and dimethyl isosorbide can also be utilized as needed for any reason.
[0054] These solvents or solvent blends (ii) comprising one or more of aromatic hydrocarbons or higher acetates such as isobornyl acetate are particularly suitable due to their high boiling and flash points. Preferably, the solvent component (i) is selected from the group consisting of monomethyl ether of propylene glycol, N-butylpyrrolidone, γ-caprolactone, N-methylpyrrolidone, ethyl lactate, tetrahydrofurfuryl alcohol, dipropylene glycol monomethyl ether, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, and / or mixtures thereof.
[0055] Preferably, the solvent component (ii) is selected from the group consisting of aromatic hydrocarbons, paraffinic hydrocarbons, cyclic hydrocarbons, fatty acids, seed and vegetable oil methyl esters, propylene glycol methyl ether, dibasic esters of long chain diacids ranging from C8 to C16 carbon atoms; long chain primary amides, and C8 to C16 carbon atoms. 12 They are selected from disubstituted amides such as dimethylamides, glycerol esters, ethoxylated phosphate esters, acetates, long chain aliphatic or aromatic alcohols, lactates, carbonates, citrates, dimethyl sulfoxide, dimethyl formamide, and dimethyl isosorbide.
[0056] The ratio of solvent components (i) to (ii) can be any suitable ratio that allows the active ingredient to be maintained in solution, even when an emulsifier component is included. Preferably, the weight ratio of solvent (i) to solvent (ii) is 10:1 to 1:10.
[0057] "Emulsifier system" (c): The emulsifiers herein are generally used in an amount of 0 to 25% by weight, preferably 0.01 to 15% by weight, of one or more emulsifiers. The emulsifier may be any suitable compound of a mixture of compounds. Ionic and non-ionic emulsifiers may be used.
[0058] Suitable ionic and / or anionic emulsifiers are phosphate esters and sulfate esters, such as polyethoxylated phosphate esters, ethoxylated tridecyl alcohol phosphate esters, ethoxylated fatty alcohol phosphate esters, and sulfate esters of polyethoxylated arylphenols.
[0059] Inorganic salts of alkylbenzene sulfonates are another example group of anionic emulsifiers, such as sodium dodecylbenzene and triethanolamine dodecylbenzene sulfonate.
[0060] Examples of nonionic emulsifiers may also generally be polyethoxylated chemicals such as ethoxylated alkylphenols, ethoxylated ethanolamides, amine ethoxylates, polyethoxylated castor oil, alcohol ethoxylates, ethoxylated fatty alcohols, ethoxylated castor oil, tridecyl alcohol polyglycol ethers, and ethoxylated tristyrylphenols, etc. Ethoxylated chemicals may be substituted for or combined with propoxylated versions.
[0061] Other examples of emulsifiers include block copolymers, EO / PO block copolymers, butyl block copolymers, random copolymers, and star-shaped polymeric surfactants, which are also desirable in some embodiments. Polysorbates are another example of emulsifiers, and optionally include, for example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, sorbitan monopalmitate, and sorbitan monostearate. The optional antifoaming agent can be any suitable compound or mixture of compounds.
[0062] additives Useful additives can include rheological additives, stabilizers and many other ingredients.
[0063] The rheological active additives include thickeners.Preferred thickeners include gums such as xanthan gum, guar gum, locust bean gum, alginates, polyvinyl alcohol, polyacrylates, starch, clay derivatives such as amine-treated magnesium aluminum silicate, and cellulose derivatives such as hydroxypropyl ethyl cellulose.Most preferred thickeners are clay derivatives, cellulose derivatives, and xanthan gum.
[0064] The purpose of the surfactant is to promote the formation of a stable, homogeneous emulsion. Surfactants useful in the compositions of the present invention include nonionic, cationic, and anionic surfactants. Surfactants suitable for the compositions of the present invention preferably have an HLB value of about 5 to about 15. When a blend of surfactants is used, the blend preferably has an overall HLB value of about 5 to about 15. The specific HLB value required will depend on the organic solvent selected.
[0065] Surfactants that can be used to prepare the compositions of the present invention include polyoxyethylated fatty amines, polyoxyethylated ethers, polyoxyethylated sorbitan esters, polyoxyethylated sorbitol esters, dodecylbenzenesulfonates, polyalkylene oxide-modified methylpolysiloxanes, alkylphenol ethoxylates, polyoxyethylene sorbitan fatty acid esters, and sorbitan fatty acid esters.
[0066] Preferred surfactants for the compositions of the present invention include polyoxyethylene sorbitan monooleate and sorbitan monooleate.
[0067] Selection of a particular surfactant can be readily accomplished by the procedures described in Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 8, John Wiley & Sons, Inc. (1979), pp. 909-919, which are incorporated herein by reference, or by the procedures described in "HLB System, a time-saving guide to emulsifier selection," ICI United States Inc., Specialty Chemicals Division (1976).
[0068] Other additives useful in the composition of the present invention include abrasive particles such as aluminum oxide, silicon carbide, and pumice.The amount of organic solvent must be sufficient to ensure effective removal of coating from surface.The amount of thickener and the amount of surfactant must be sufficient to allow the composition to exist as a stable emulsion.The amount of water can vary, and is essentially the difference between the total amount of the composition and the amount of organic solvent component, thickener component, and surfactant component.
[0069] The concentration of water in the composition may range from about 0.01% to about 2% by weight, and the concentration of one or more organic solvents may range from about 10% to about 90% by weight. The concentration of one or more thickeners may range from about 1% to about 10% by weight. The concentration of one or more surfactants may range from about 0.1% to about 10% by weight. As noted above, the composition must contain at least 50% by weight of water. At these concentrations, the concentration of solvent in the composition's vapor is sufficiently low so that ignition of the vapor does not occur when exposed to the flame of, for example, a match, lighter, or electric spark.
[0070] When the EC is emulsified, the purpose of the water is to act as a carrier and inhibit evaporation of the organic solvent, allowing the composition to be applied to the surface of the plant, its propagation material, or the plant's habitat. Preferably, the amount of water in such an emulsion or dispersion should be selected to be sufficient to render the composition flammable when mixed and / or applied. As used herein, the term "flammable" means incapable of igniting when exposed to a flame, such as a lit match or lighter.
[0071] Once emulsified, the composition preferably contains at least 80% by weight water, more preferably at least 85% by weight water, and most preferably at least 90% by weight water.
[0072] The purpose of the added thickener is to stabilize the solvent / water emulsion and provide good flow control, i.e., the presence of the thickener allows the composition to be easily applied, level out, and have the ability to stick to a vertical surface long enough for the solvent to soften the coating on the surface. It is recommended that the thickener be water-soluble or water-swellable and be able to promote the formation of a stable emulsion of the composition of the present invention.
[0073] Compositions according to the present invention may employ combinations of cyclobutrifluram and / or a compound of Table 1, as well as combinations of cyclobutrifluram and / or one or more compounds of Table 1 with one or more other pesticides.
[0074] When emulsified in water, the compositions can have a strengthening effect in plants at certain application rates.Therefore, they are also suitable for mobilizing the plant's defense system against attacks by undesirable pests and microorganisms, such as bacteria and fungi.In this context, plant strengthening (resistance-inducing) substances are understood to mean substances or combinations of substances that can stimulate the plant's defense system so that the treated plants, when subsequently inoculated with undesirable microorganisms, exhibit a significant degree of resistance to these microorganisms.In this case, undesirable microorganisms should be understood to mean plant pathogenic fungi, bacteria and viruses.
[0075] The compounds and compositions described herein are advantageously applied to pests, pest habitats, preferably plants, or plants susceptible to pest attacks.For example, regarding mites, they can be Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp.
[0076] With regard to nematodes, these may be, for example, the sweet potato root-knot nematode (Meloidogyne incognita), the pine wood nematode (Bursaphelenchus lignicolus Mamiya et Kiyohara), the rice root nematode (Aphelenchoides besseyi), the soybean cyst nematode (Heterodera glycines), Pratylenchus spp.
[0077] Cyclobutrifluram and / or the compounds of Table 1 and compositions thereof can generally be used against susceptible and resistant species and against all or some stages of infestation, including, inter alia, species of the suborder Phthiraptera (Louse), such as Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., and Trichodectes spp.
[0078] The compositions of the present invention are also suitable for protecting plant propagation material, such as seeds, for example fruits, tubers or grains, or seedlings, against the above-mentioned types of pests. The propagation material can be treated with the compounds before planting, for example seeds can be treated before sowing. Alternatively, the compounds can be applied to the seed kernels (coating) by immersing the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the composition when planting the propagation material at the application site, for example in the seed furrow during row planting. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the present invention.
[0079] The method according to the invention can be used in particular to control, i.e. contain or destroy, pests of the above-mentioned types occurring on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even on plant organs that are formed at a later time and remain protected from these pests. Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beets, for example sugar or fodder beets; fruits, for example pome fruits, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; legumes, for example beans, lentils, peas or soybeans; oil crops, for example rape, mustard, poppy, olives, sunflower, coconut, castor bean, cocoa or ground nuts; gourds Plants of the Atractylodes family, such as pumpkin, cucumber, or melon; fiber plants, such as cotton, flax, hemp, or jute; citrus fruits, such as orange, lemon, grapefruit, or tangerine; vegetables, such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, or bell pepper; Lauraceae, such as avocado, Cinnamonium, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevine, hops, Plantaginaceae, and latex plants. The method of the present invention can also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broad-leaved trees, and evergreen trees.
[0080] The following non-limiting examples illustrate compositions according to the present invention. [Example]
[0081] [Table 3]
[0082] [Table 4]
[0083] [Table 5]
[0084] The compositions of Examples 1 through 3 were then subjected to low and high temperature storage stability testing, including two weeks at -10° C. and two weeks at 54° C. All exemplified compositions remained clear liquids.
[0085] The compositions of Examples 1 to 3 were also subjected to dilution testing, whereby oil-in-water emulsions were prepared by adding 3% v / v in both 50 and 500 ppm water, and stability was observed for at least 24 hours. All exemplified compositions remained stable emulsions.
Claims
1. A stable single-phase emulsifiable composition comprising: (a) N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (1, cyclobutrifluram) and its closely related analogs: N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide (2); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (3); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (4); N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (4); N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (5); N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (6); N-[(1,2cis)-2-[2-chloro-4-(trifluoromethyl)phenyl] N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (7); N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl)benzamide (8); N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (9); N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl) N-[(1,2cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (11); N-[(2,3cis)-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)benzamide (12); N-[(2,3cis)-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)pyridine-3-carboxamide (13);N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (14); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide (15); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (16); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (17); N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)-pyridine-2-carboxamide (18); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)-benzamide (19); N-[(1,2cis)-2-[4-fluoro-2-(trifluoromethyl)phenyl]cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)-pyridine-3-carboxamide (21); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-4-(trifluoromethyl)-thiazole-5-carboxamide (22); N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)-pyrazine-2-carboxamide (23); N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)-pyrazine-2-carboxamide (24). N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide (24); and N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-4-(trifluoromethyl)thiazole-5-carboxamide (25); N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (26); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide (27);N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (28); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (29); N-[(2,3cis)-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)benzamide (30); N-[(2,3cis)-2-(2,4-difluorophenyl)oxetan-3-yl]-2-(trifluoromethyl)pyridine-3-carboxamide (31); N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide N-[(1,2cis)-2-(2-chloro-4-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (32); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (33); N-[(1,2cis)-2-(2,4-difluorophenyl)cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (34); N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-3-(trifluoromethyl)pyridine-2-carboxamide (35); and N-[(1,2cis)-2-(4-chloro-2-fluoro-phenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (36), stereoisomers, tautomers, salts or N-oxides thereof; (b) (i) at least one non-aqueous polar solvent classified by an Hp (Hansen Polarity) value in the range of 5 to 15 and an Hh (Hansen H-Bond) parameter in the range of 5 to 15; (ii) a solvent system comprising at least one water-immiscible non-polar solvent; (c) an emulsifying surfactant system that enables the emulsifiable concentrate to form an oil-in-water emulsion when added to water, thereby forming an emulsifiable concentrate (EC).
2. 10. The composition of claim 1, wherein the one or more compounds (a) are present in an amount of 0.01 to 15% by weight.
3. 3. The composition of claim 1, comprising water in an amount of 2% or less by weight of the composition.
4. The composition of any one of claims 1 to 3, wherein compound (a) comprises one or more stereoisomers of N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide.
5. 5. The composition of any one of claims 1 to 4, wherein the solvent component (i) is selected from monomethyl ether of propylene glycol, N-butylpyrrolidone, γ-caprolactone, N-methylpyrrolidone, ethyl lactate, tetrahydrofurfuryl alcohol, dipropylene glycol monomethyl ether, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, and / or mixtures thereof.
6. The solvent component (ii) is selected from the group consisting of aromatic hydrocarbons, paraffinic hydrocarbons, cyclic hydrocarbons, fatty acids, seed and vegetable oil methyl esters, propylene glycol methyl ether, C 8 ~C 16 Dibasic esters of long chain diacids ranging from 0.1 to 1.5 carbon atoms; long chain primary amides, and C 8 ~C 12 6. The composition of any one of claims 1 to 5, wherein the hydroxybenzoate is selected from disubstituted amides such as dimethylamides, glycerol esters, ethoxylated phosphate esters, acetates, long chain aliphatic or aromatic alcohols, lactates, carbonates, citrates, dimethyl sulfoxide, dimethyl formamide, and dimethyl isosorbide.
7. 7. The composition of any one of claims 1 to 6, wherein the weight ratio of solvent (i) to solvent (ii) is from 10:1 to 1:
10.
8. 8. A process for preparing a composition according to any one of claims 1 to 7, comprising contacting one or more aliquots of compounds 1 to 36 with at least one of said solvents (i) and / or (ii), and optionally at least a portion of said emulsifying surfactant system, to form said composition as a preformed concentrate composition capable of forming an emulsion / microemulsion upon dilution with water.
9. 9. A process for preparing an aqueous emulsion or dispersion, comprising contacting a composition according to any one of claims 1 to 8 with an aqueous liquid carrier under conditions to induce the formation of an emulsion or dispersion.
10. 10. An emulsion-in-water formulation obtainable by the process of claim 9, comprising the composition of any one of claims 1 to 7 diluted with water to form a concentrated aqueous agrochemical formulation.
11. 10. A method for preventing or controlling pathogens in crops of useful plants, comprising treating said plants, plant parts, plant propagation material or their habitats with an agrochemically effective amount of a water-diluted spray composition or an oil-in-water emulsion formed when the composition of any one of claims 1 to 7 is added to an aqueous liquid carrier.
12. Use of the composition according to any one of claims 1 to 7 for the storage and transport of said one or more compounds 1 to 36.
13. Use of a composition according to any one of claims 1 to 7 for the preparation of an oil-in-water emulsion.
14. Use of a composition according to any one of claims 1 to 7 for controlling unwanted plant pathogens, in particular nematodes and / or fungi.