Branched amino acid surfactants for agricultural products

Abstract

Agricultural products, such as pesticides, plant growth regulators, fungicides, herbicides, and insecticides, can be formulated to include one or more branched surfactants from one or more surfactant classes, such as derivatives of amino acids having surface-active properties.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to provisional application number 63 / 051,197, filed on July 13, 2020, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to branched-chain surfactants for use in agricultural products. Such branched-chain surfactants may include derivatives of amino acids, wherein the derivatives have surface-active properties. Background of the Invention

[0005] Surfactants (molecules with surface-active properties) are widely used in commercial agricultural formulations. These formulations can include a variety of agricultural surfactants, such as pesticides, plant growth regulators, fungicides, herbicides, and insecticides. Many of these agricultural surfactants exhibit limited water solubility or may crystallize easily. Precipitation of agricultural surfactants can lead to a loss of efficacy. If the surfactant is concentrated in a precipitate, it can hinder uniform distribution of the surfactant when sprayed onto the field. Therefore, surfactants can be included in formulations to improve the solubility, wetting, and spreadability of the surfactant.

[0006] Surfactants can be uncharged, amphoteric, cationic, or anionic. Although in principle any class of surfactant (e.g., cationic, anionic, nonionic, amphoteric) is suitable, formulations may include combinations of two or more surfactants from two or more surfactant classes.

[0007] Typically, surfactants are amphiphilic molecules with a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can adsorb at interfaces, such as between two liquids, a liquid and a gas, or a liquid and a solid. In systems containing relatively polar and relatively nonpolar components, the hydrophobic tail preferentially interacts with one or more of the relatively nonpolar components, while the hydrophilic head preferentially interacts with one or more of the relatively polar components. In the case of a water-oil interface, the hydrophilic head group preferentially extends into the water, while the hydrophobic tail preferentially extends into the oil. When added to a water-gas interface, the hydrophilic head group preferentially extends into the water, while the hydrophobic tail preferentially extends into the gas. The presence of surfactants disrupts at least some of the intermolecular interactions between water molecules, replacing at least some of the interactions between water molecules with the typically weaker interactions between the surfactant and at least some of the water molecules. This results in a reduction in surface tension and can also be used to stabilize the interface.

[0008] At sufficiently high concentrations, surfactants can form aggregates that confine the hydrophobic tails to polar solvents. One such aggregate is a micelle. In a typical micelle, molecules are arranged in a spherical shape, with the hydrophobic tails of one or more surfactants preferentially located inside the sphere, while the hydrophilic heads of one or more surfactants preferentially located outside the micelle, where the heads preferentially interact with the more polar solvent. The effect of a given compound on surface tension and the concentration at which it forms micelles can be considered defining characteristics of a surfactant. Summary of the Invention

[0009] This disclosure provides formulations of agricultural products, such as pesticides, plant growth regulators, fungicides, herbicides, and insecticides. These products can be formulated to include one or more surfactants from one or more of the surfactant classes disclosed herein. Surfactants can be used as emulsifiers, wetting agents, dispersants, and / or agents that improve spreadability. Furthermore, surfactants can be used as adjuvants and agents for controlling spray drift.

[0010] This disclosure provides surfactants for agricultural products in the form of amino acid derivatives with surface-active properties. The amino acids can be naturally occurring or synthetic, or they can be obtained via ring-opening reactions of molecules such as lactams (e.g., caprolactam). Amino acids can be functionalized with different types of groups to form compounds with surface-active properties. Characteristically, these compounds may have a low critical micelle concentration (CMC) and / or the ability to reduce the surface tension of liquids.

[0011] This disclosure provides formulations for use in pesticides or plant growth regulators, comprising at least one surfactant of formula I:

[0012] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups; a pesticide or plant growth regulator; and a water-insoluble solvent.

[0013] This disclosure further provides formulations for fungicides comprising at least one surfactant of formula I:

[0014]

[0015] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups; optionally, a co-surfactant and optionally, a carrier, such as a solvent or solid carrier.

[0016] This disclosure also provides formulations for herbicides comprising at least one surfactant of formula I:

[0017]

[0018] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5The compound is selected from hydrogen, oxygen, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; and optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide, and 4-methylbenzenesulfonate groups; one or more herbicides, a water-insoluble solvent, and water.

[0019] This disclosure further provides formulations for insecticides comprising at least one surfactant of formula I:

[0020]

[0021] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups; an insecticide, optionally an antifoaming agent, optionally an antifreeze agent and water.

[0022] The above and other features of this disclosure, and the ways in which they are implemented, will become more apparent and will be better understood by referring to the following description of the embodiments in conjunction with the accompanying drawings. Attached Figure Description

[0023] Figure 1 The graph shows the surface tension versus concentration measured at pH = 7 as described in Example 1B, where the Y-axis depicts the surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts the concentration (c) in millimoles (mM).

[0024] Figure 2A The graph shows the surface tension versus concentration measured at pH = 7 as described in Example 2B, where the Y-axis depicts the surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts the concentration (c) in millimoles (mM).

[0025] Figure 2BA graph showing the dynamic surface tension as a function of time, as described in Example 2C, is displayed, where the Y-axis depicts the surface tension in millinewtons per meter (mN / m) and the X-axis depicts the surface age in milliseconds (ms).

[0026] Figure 3 The graph shows the surface tension versus concentration measured at pH = 7 as described in Example 3B, where the Y-axis depicts the surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts the concentration (c) in millimoles (mM).

[0027] Figure 4A The graph shows the surface tension versus concentration measured at pH = 7 as described in Example 4B, where the Y-axis depicts the surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts the concentration (c) in millimoles (mM).

[0028] Figure 4B A graph showing the dynamic surface tension as a function of time, as described in Example 4C, is displayed, where the Y-axis depicts the surface tension in millinewtons per meter (mN / m) and the X-axis depicts the surface lifetime in milliseconds (ms).

[0029] Figure 5A The graph shows the surface tension versus concentration measured at pH = 7 as described in Example 5B, where the Y-axis depicts the surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts the concentration (c) in millimoles (mM).

[0030] Figure 5B A graph showing the dynamic surface tension as a function of time, as described in Example 5C, is displayed, where the Y-axis depicts the surface tension in millinewtons per meter (mN / m) and the X-axis depicts the surface lifetime in milliseconds (ms).

[0031] Figure 6A The graph shows the surface tension versus concentration measured at pH = 7 as described in Example 6B, where the Y-axis depicts the surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts the concentration (c) in millimoles (mM).

[0032] Figure 6B A graph showing the dynamic surface tension as a function of time, as described in Example 6C, is displayed, where the Y-axis depicts the surface tension in millinewtons per meter (mN / m) and the X-axis depicts the surface lifetime in milliseconds (ms).

[0033] Figure 7A The graph shows the surface tension versus concentration measured at pH = 7 as described in Example 7B, where the Y-axis depicts the surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts the concentration (c) in millimoles (mM).

[0034] Figure 7B A graph showing the dynamic surface tension as a function of time, as described in Example 7C, is displayed, where the Y-axis depicts the surface tension in millinewtons per meter (mN / m) and the X-axis depicts the surface lifetime in milliseconds (ms). Detailed Implementation

[0035] I. Definition

[0036] The phrase “within any range using these endpoints” as used in this article literally means any range of values ​​that can be selected from any two values ​​listed before this phrase, regardless of whether those values ​​are in the lower or higher parts of the list. For example, a pair of values ​​can be selected from two lower values, two higher values, or one lower value and one higher value.

[0037] The term "alkyl" as used in this article refers to any saturated carbon chain, which can be straight or branched.

[0038] As used herein, the phrase "surfactant" refers to the ability of a compound to reduce the surface tension of the medium in which it is at least partially dissolved, and / or the interfacial tension with other phases, and thus to be at least partially adsorbed at liquid / vapor and / or other interfaces. The term "surfactant" can be applied to such compounds.

[0039] Regarding imprecise terminology, the terms "approximately" and "roughly" are used interchangeably to refer to a measurement that includes the stated measurement and any measurement that is reasonably close to it. As understood and readily determined by one of ordinary skill in the art, a measurement that is reasonably close to the stated measurement deviates from it by a reasonably small amount. For example, such deviations may be attributed to measurement errors or minor adjustments made to optimize performance. In cases where the value of such a reasonably small difference is not readily determined by one of ordinary skill in the art, the terms "approximately" and "roughly" may be understood to mean the value plus or minus 10%.

[0040] This disclosure provides formulations of agricultural products, such as pesticides, plant growth regulators, fungicides, insecticides, and herbicides. II. Pesticide and plant growth regulator formulations

[0041] Agricultural active agents (such as pesticides) are routinely provided to end users in various concentrated forms so that they can be diluted by the end user in water or other suitable media into diluted, ready-to-use formulations. These concentrated forms include solid formulations (e.g., powders) and liquid formulations. In many applications, liquid formulations are preferred because they avoid the problems of dusting toxic powders and slow dissolution in diluents.

[0042] Liquid concentrates include so-called emulsion concentrates and soluble liquid concentrates. Emulsion concentrates contain pesticides, water-insoluble solvents, and emulsifiers, and when added to water, they spontaneously or after mixing form an oil-in-water emulsion, with the agricultural active ingredient primarily present in the emulsion droplets. This type of concentrate is particularly suitable for water-insoluble / low-water-soluble agricultural active ingredients, and where the recommended concentration in ready-to-use formulations exceeds the solubility of the agricultural active ingredient.

[0043] This disclosure provides pesticide or plant growth regulator formulations with high concentrations of agronomic active agents, suitable for long-term storage and delivery to end users who will ultimately treat plants by contacting the agronomic formulation prepared from the concentrated pesticide formulation described herein.

[0044] The pesticide formulations disclosed herein may include agricultural active agents (pesticides or plant growth regulators), one or more surfactants or co-surfactants selected from one or more surfactant classes, and water-insoluble solvents.

[0045] 1. Pesticides

[0046] The term "pesticide" as used herein is well-known in the art and is described at least by the Environmental Protection Agency (EPA) in the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA), in the Insecticides and Environmental Pesticide Control Subchapter (7U.SC §136(u)), in the Code of Federal Regulations (CFR) relating to "environmental protection," and in EPA regulations in 40 CFR §152.3. Pesticides are generally understood in the art to be substances used to prevent, eliminate, repel, regulate, and / or mitigate any harmful organism. A harmful organism is an organism that is harmful to humans or the environment but does not include any internal parasite of a living human or other living animal, or any fungus, bacteria, virus, or other microorganism in or on the body of a living human or other living animal. In other words, the term "harmful organism" generally does not include any organism that causes infection or disease in humans or animals. Furthermore, the term "pesticide" as used herein generally does not include any human or animal drug or medicine, any product that is a "new animal drug" as defined in the art, any liquid sterilizing agent applied to equipment used in the human body, and / or any product intended to combat fungi, bacteria, viruses, or other microorganisms in or on a living human or animal. Additionally, the pesticides disclosed herein generally do not include drugs or medicines used to prevent or treat diseases in humans or animals (such as livestock and pets).

[0047] As used in this article, the term "plant growth regulator" refers to a compound that, through physiological action, accelerates or slows the growth rate or maturation rate of an ornamental or crop plant or its products, or otherwise alters its behavior.

[0048] In particular, it is envisioned that the pesticides and plant growth regulators used in this invention are organic compounds, preferably synthetic organic compounds. Suitable pesticides and plant growth regulators include triazoles, strobilurins, alkylene bis(dithiocarbamate) compounds, benzimidazoles, phenoxycarboxylic acids, benzoic acids, ureas, sulfonylureas, triazines, pyridinecarboxylic acids, neonicotinoids, amidines, organophosphates, and pyrethroids. The pesticides may have a water solubility of 1 g / L or less.

[0049] In the concentrated formulations disclosed herein, the pesticide or plant growth regulator may be present in amounts of about 5% by weight or more, about 10% by weight or more, about 15% by weight or more, about 20% by weight or more, or about 25% by weight or less, about 30% by weight or less, about 35% by weight or less, about 40% by weight or less, or in any range of these endpoints, based on the weight of the composition.

[0050] 2. Surfactants

[0051] The pesticide formulations disclosed herein comprise one or more surfactants, also referred to as surfactant systems. Surfactant systems are included to emulsify compositions and / or act as adjuvants. Surfactant systems comprise at least one surfactant, which may be an amphoteric surfactant, amphoteric surfactant, cationic surfactant, nonionic surfactant, and optionally at least one other surfactant, said at least one surfactant being an amphoteric surfactant, amphoteric surfactant, cationic surfactant, nonionic surfactant, or a combination thereof. Such surfactants should be physically and chemically compatible with the basic components described herein, or should not otherwise unduly impair the stability, appearance, or performance of the product.

[0052] Suitable surfactants for use in pesticide formulations disclosed herein include one or more surfactants of formula I and / or co-surfactants:

[0053]

[0054] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, counterions may associate with the compound, and if present, counterions may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups.

[0055] In particular, suitable surfactants or co-surfactants may include any one or more of the surfactants 1-7 described herein.

[0056] The concentration range of the surfactant system in the pesticide formulation can be about 20% by weight or more, about 30% by weight or more, about 40% by weight or more, or about 50% by weight or less, about 60% by weight or less, about 70% by weight or less, or about 80% by weight or less, or any range using these endpoints.

[0057] 3. Water-insoluble solvents

[0058] The pesticide formulations disclosed herein may include water-insoluble solvents. A solvent is considered to be water-insoluble if its water solubility at 20°C is about 10 g / L or less, about 5 g / L or less, about 1 g / L or less, or about 0.1 g / L or less.

[0059] Suitable water-insoluble solvents may include aromatic solvents, such as those sold under the trade name Solvesso, and water-insoluble alcohols, such as linear or branched, aliphatic or aromatic, saturated or unsaturated alcohols having at least 6 carbon atoms.

[0060] 4. Other additives

[0061] Pesticide formulations may include other additives such as additional surfactants, water, thickeners, sedimentation enhancers, drift control agents, salts, stabilizers, penetrants, spreaders, wetting agents, building agents, extenders, emulsifiers, dispersants, suspending agents, plant penetrants, translocators, oils, activators, foliar nutrients, compatibilizers, drift inhibitors, foam inhibitors, buffers, conversion agents, soil penetrants, stabilizers, UV filters, feeding stimulants, detergents, settling agents, binders, liquid carriers, and drying carriers such as palygorskite, kaolinite, vermiculite, starch polymers, corn cobs, and combinations thereof. Pesticide formulations may also contain other chemical compounds that are not pesticides, such as activators, antifeedants, antifouling agents, attractants, chemical sterilizers, disinfectants, fumigants, pheromones, repellents, defoliants, desiccants, insect growth regulators, plant growth regulators, synergists, adjuvants, and combinations thereof.

[0062] These additives may be present independently in pesticide formulations in amounts of about 0% by weight or more, about 5% by weight or more, about 10% by weight or more, about 15% by weight or more, or about 20% by weight or less, about 25% by weight or less, about 30% by weight or less, or in any range using these endpoints.

[0063] Additional surfactants (such as additional anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants) may be present in the concentrated composition at a concentration of about 5% by weight or more, about 10% by weight or more, about 15% by weight or more, about 20% by weight or more, or about 25% by weight or less, about 30% by weight or less, about 35% by weight or less, about 40% by weight or less, or in any range of these endpoints, based on the weight of the composition.

[0064] Water may be present in the concentrated composition at a concentration of about 0% by weight or more, about 5% by weight or more, about 10% by weight or more, about 20% by weight or more, about 30% by weight or more, or about 35% by weight or less, about 45% by weight or less, about 55% by weight or less, about 65% by weight or less, or in any range of these endpoints, based on the weight of the composition.

[0065] Polymers can be included in concentrated compositions as thickeners, deposition enhancers, or drift control agents. Suitable polymers may include polysaccharide ethers and synthetic polymers.

[0066] Water-soluble organic solvents (such as glycol ethers (such as diethylene glycol butyl ether), N-formylmorpholine, shorter aliphatic alcohols, propylene carbonate, etc.) may be present in pesticide formulations in a weight ratio of up to 1:2 of water-soluble organic solvent to water-insoluble organic solvent.

[0067] 5. Manufacturing method

[0068] The method includes the step of combining a surfactant system, a pesticide, and optionally a solvent. This step may also include the addition of any of the aforementioned additives. The aforementioned components and compounds may be added to one or more of each other in any order, and may be added in any amount, and may be added in one or more separate steps, such as all or part of the addition.

[0069] 6. How to use

[0070] The concentrated pesticide formulation disclosed herein can be in liquid form at room temperature and atmospheric pressure, wherein the agricultural active ingredient is dissolved.

[0071] Before final use, the concentrated pesticide formulation should be mixed with an aqueous medium (usually tap water). The concentrated composition should be added to the tank before, simultaneously with, or after adding the aqueous medium (water). The concentrated pesticide composition is then diluted to the appropriate concentration of the agricultural active ingredient.

[0072] The water content in the diluted pesticide formulation of this disclosure may be about 75% by weight or more, about 90% by weight or more, about 99% by weight or more, or about 99.9% by weight or more, based on the total weight of the diluted composition, and will ultimately depend on the amount of water required to dilute the agronomic active ingredient in the concentrated pesticide formulation of this disclosure to the desired concentration in the ready-to-use composition.

[0073] When mixed with and diluted in an aqueous medium, the agricultural active ingredient is uniformly distributed in the aqueous medium in the form of a solution or fine emulsion, and can be diluted without any crystal growth.

[0074] Plants can be treated with diluted, ready-to-use pesticide formulations by contacting the plants to be treated with the diluted composition in any conventional manner. As used herein, the term "plant" refers not only to the stems, leaves, and fruits of plants visible on the ground, but also to roots and seeds. The amount of active ingredient that comes into contact with the plant is preferably sufficient to allow the active ingredient to exert its pesticide or plant growth-regulating activity, i.e., an effective amount.

[0075] III. Fungicidal preparations

[0076] This disclosure provides formulations of fungicides. The fungicide formulations may be in solid or liquid form. Fungi that can be combated using this formulation include: Basidiomycetes, Ascomycetes, Adalomycetes, or Deuteromycetes, especially *Heifers*, *oidia*, eyespot, *fusarioses*, *Fusarium roseum*, *Fusarium nivale*, net blotch, leaf spot, *Septoria spot*, and *sinRhizoctonia*. These harmful fungi can cause disease in most vegetables and plants, but are particularly prevalent in cereals such as wheat, barley, rye, oats, or their hybrids, as well as rice and maize.

[0077] A fungicide formulation may include a fungicide, an emulsifier component such as one or more surfactants or co-surfactants selected from one or more surfactant classes, an optional co-emulsifier, and an optional carrier such as a solvent or solid carrier.

[0078] 1. Fungicides

[0079] Fungicides include fungicides. Suitable fungicides include, but are not limited to: azoxystrobin, benalaxyl, carbendazim, chlorothalonil, cupfer, cymoxanil, cyproconazol, diphenoconazol, diinocap, epioxyconazol, fluazinam, flusilazol, flutriafol, folpel, and fosetyl-aluminum. Alumnium, kresoximmethyl, hexaconazol, mancozeb, metalaxyl, metconazol, myclobutanil, ofuronamide, phentinhydroxide, prochloraz, pyremethanil, soufre, tebuconazol, and tetraconazol, and mixtures thereof. Suitable herbicides include, but are not limited to: alachlor, acloniphen, acetochlor, amidosulfuron, aminotriazol, atrazin, bentazon, biphenox, and bromoxynil.octanoate, bromoxynil, clethodim, chlodinafop-propargyl, chloridazon, chlorsulfuron, chlortoluron, clonazon, cycloxydim, desmedipham, dicamba, dicyclofop-methyl, diuron ea), difluphenicanil, dimitenamid, ethofumesat, fluazifop, fluazifop-p-butyl, fluorochloridon, fluroxypyr, glufosinat, glyphosate, galoxyfop-R, ioxynil octanoate, isoproturon, isoxaben, metamitron, metazachlor, metolachlor, metsulfuron-methyl, nicosulfuron, notflurazon, oryzalin, oxadiazon, oxyfluorphen, paraquat, pendimethalin, sweet... Phenmedipham, phenoxyprop-p-ethyl, propaquizafop, prosulfocarb, quizalofop, sulcotrion, sulphosat, terbutylazin, triasulfuron, trichlorpyr, triflualin, and triflusulforon-methyl can be used alone or in combination with each other.

[0080] The amount of fungicide can be approximately 1% or more, approximately 5% or more, approximately 10% or more, approximately 20% or more, approximately 30% or more, approximately 40% or more, or approximately 50% or less, approximately 60% or less, or approximately 70% or less, approximately 80% or less, approximately 90% or less, or any combination of these ranges based on the total weight of the liquid fungicide.

[0081] 2. Surfactants

[0082] The fungicidal formulation of the present invention comprises one or more surfactants, also referred to as a surfactant system. The surfactant system can be used as a dispersant or wetting agent. When prepared for agricultural applications, the surfactant system can also be used as an emulsifier component to form a stable emulsion of the liquid fungicidal formulation. The emulsifier component can also be used to form a stable emulsifiable concentrate. The surfactant system comprises at least one surfactant, which can be an amphoteric surfactant, an amphoteric surfactant, a cationic surfactant, a nonionic surfactant, and optionally at least one other surfactant, said other surfactant being an amphoteric surfactant, an amphoteric surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof.

[0083] Suitable surfactants for use in the fungicidal formulations of this disclosure include one or more surfactants of formula I and / or co-surfactants:

[0084]

[0085] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, counterions may associate with the compound, and if present, counterions may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups.

[0086] In particular, suitable surfactants or co-surfactants may include any one or more of the surfactants 1-7 described herein.

[0087] The total amount of one or more surfactants in a fungicidal preparation may be about 1% or more by weight, about 5% or more by weight, about 10% or more by weight, or about 15% or less by weight, about 20% or less by weight, about 25% or less by weight, about 30% or less by weight, about 35% or less by weight, or in any range using these endpoints.

[0088] 3. Co-emulsifiers or co-surfactants

[0089] The fungicidal composition may include optional co-emulsifiers or co-surfactants. Optional co-surfactants may be anionic and / or nonionic surfactants, and may include those surfactants disclosed herein, as well as others. For example, anionic surfactants include surfactants disclosed herein or any surfactant known in the art, and may include alkali metal salts, alkaline earth metal salts, or ammonium salts of fatty acids, such as potassium stearate, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates or isoalkyl sulfonates, alkyl naphthalene sulfonates, alkyl methyl ester sulfonates, acyl glutamates, alkyl sulfosuccinates, sarcosinates such as sodium lauroyl sarcosinate or taurine, and combinations thereof. Anionic surfactants may be present in the emulsifier component in any amount.

[0090] Nonionic emulsifiers may include those surfactants disclosed herein or any surfactants known in the art, such as alkoxylated animal or vegetable fats and oils, such as corn oil ethoxylates, soybean oil ethoxylates, castor oil ethoxylates, tallow ethoxylates, glycerides such as glyceryl monostearate, fatty alcohol alkoxylates and carbonyl synthetic alcohol alkoxylates, fatty acid alkoxylates such as oleic acid ethoxylates, alkylphenol alkoxylates such as isononylphenol ethoxylates, fatty amine alkoxylates, fatty acid amide alkoxylates, sugar surfactants such as sorbitol fatty acid esters (e.g., sorbitol monooleate and sorbitol tristearate), polyoxyethylene sorbitol fatty acid esters, alkyl polyglycosides, N-alkyl glucosamides, alkyl methyl sulfoxides, alkyl dimethyl phosphine oxides such as tetradecyl dimethyl phosphine oxide, and combinations thereof.

[0091] 4. Carrier agent

[0092] The fungicidal formulations disclosed herein may include carriers. As used herein, the term "carrier" refers to a material, in natural or synthetic, organic or inorganic form, that, when combined with an active ingredient, facilitates the application of that active ingredient to plants, seeds, or soil. Therefore, such carriers are generally inert but must also be agriculturally acceptable, especially for the plants to be treated. Carriers may be solid (clay, natural or synthetic silicates, silica, resins, waxes, or solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum grades, aromatics or alkanes, chlorinated hydrocarbons, liquefied gases, etc.).

[0093] 5. Other additives

[0094] Fungicidal formulations may contain other additives such as stabilizers, penetrants, spreaders, wetting agents, building blocks, extenders, emulsifiers, dispersants, suspending agents, plant penetrants, translocators, oils, activators, foliar nutrients, compatibilizers, drift inhibitors, foam inhibitors, buffers, conversion agents, soil penetrants, stabilizers, UV filters, feeding stimulants, detergents, settling agents, binders, liquid carriers, and drying carriers such as palygorskite, kaolinite, vermiculite, starch polymers, corn cobs, and combinations thereof. Pesticide formulations may also contain other chemical compounds that are not pesticides, such as activators, antifeedants, antifouling agents, attractants, chemical sterilizers, disinfectants, fumigants, pheromones, repellents, defoliants, desiccants, insect growth regulators, plant growth regulators, synergists, adjuvants, and combinations thereof.

[0095] These additives may be present independently in pesticide formulations in amounts of about 0% by weight or more, about 5% by weight or more, about 10% by weight or more, about 15% by weight or more, or about 20% by weight or less, about 25% by weight or less, about 30% by weight or less, or in any range using these endpoints.

[0096] 6. Antifungal emulsion

[0097] Liquid fungicides can be added to water or another solvent at the time of sale and / or use to form agricultural emulsions. Typically, a fully formed agricultural emulsion is milky white in color, spontaneously blooms (i.e., forms), and has sufficient stability for effective application. However, the fungicides disclosed herein are not limited to these parameters and may have other properties indicating successful emulsion formation.

[0098] This disclosure provides an aqueous fungicide formulation comprising the above-described fungicide and water. The liquid fungicide formulation can be combined with water in a spray can or a separate container before being added to a spray can. For example, the liquid fungicide formulation can be added together with water or separately from water to a separate container and / or spray can. The term "diluted" describes an agricultural liquid fungicide formulation comprising water.

[0099] The diluted fungicide may be present in an amount of about 5% by weight or more, about 10% by weight or more, about 20% by weight or more, about 30% by weight or more, about 40% by weight or more, about 50% by weight or more, or about 60% by weight or less, about 70% by weight or less, about 80% by weight or less, about 90% by weight or less, about 99% by weight or less, about 99.5% by weight or less, or in any range using these endpoints.

[0100] The fungicide may be present in the diluted fungicide in amounts of about 0.00001% by weight or more, about 0.0001% by weight or more, about 0.001% by weight or more, about 0.01% by weight or more, about 0.1% by weight or more, about 1% by weight or more, or about 2% by weight or less, about 4% by weight or less, about 6% by weight or less, about 8% by weight or less, about 10% by weight or less, or in any range using these endpoints.

[0101] The fungicide may be present in amounts of about 100 g / ha or greater, about 200 g / ha or greater, about 300 g / ha or greater, about 400 g / ha or greater, about 500 g / ha or greater, or about 600 g / ha or less, about 700 g / ha or less, about 800 g / ha or less, about 900 g / ha or less, about 1000 g / ha or less, or in any range of these endpoints (or in amounts equivalent to these).

[0102] 7. Emulsifiable concentrate

[0103] This disclosure provides antifungal emulsions that can be formed using emulsifiable concentrates (also referred to in the art as "EC"). The aforementioned liquid antifungal compositions may be further described as EC or may not be EC. The emulsifiable concentrate can be a liquid having a viscosity of about 1 cps or greater, 20 cps or greater, 40 cps or greater, 60 cps or greater, 80 cps or greater, 100 cps or greater, or 120 cps or less, 140 cps or less, 160 cps or less, 180 cps or less, 200 cps or less, or, within any range using these endpoints, up to 200, 50 to 200, 100 to 200, or less than or equal to about 200 cps at 25°C. Not intended to be bound by any particular theory, it is believed that a viscosity of less than or equal to about 200 cps at 25°C promotes effective formation of creams and emulsions when using emulsifiable concentrates.

[0104] The emulsifiable concentrate itself may be anhydrous, i.e., free of water. Alternatively, the emulsifiable concentrate may include water. The emulsifiable concentrate may include water in amounts of 5% by weight or less, 2.5% by weight or less, 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less. The emulsifiable concentrate may include less than 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 part by weight of water per 100 parts by weight of the emulsifiable concentrate. The emulsifiable concentrate is a single oily (e.g., hydrophobic) phase that does not contain water. When added to water or another solvent, the emulsifiable concentrate can form a milky white agricultural emulsion that is frosty and has little to no phase separation, as described in more detail below.

[0105] Emulsifiable concentrates may comprise a single phase. In other words, an emulsifiable concentrate may not include a distinct nonpolar phase and a distinct polar phase, but rather comprise a single phase consisting of an active ingredient (fungicide), a surfactant system, optional co-surfactants, and / or optional water-insoluble solvents. It should be understood that a single phase may include partial phase separation, but generally does not include complete phase separation. Phase separation may occur at low temperatures. An emulsifiable concentrate may be described as comprising, or comprising, the aforementioned surfactant system and fungicide (e.g., without optional solvents and / or without optional co-surfactants).

[0106] 8. Solid dosage forms

[0107] For compositions in solid form, powders or dispersions suitable for spraying may be mentioned, particularly extruded, extruded, or extruded granular compositions. Solid formulations can be formed by impregnating carrier powder with an active agent or by powder granulation.

[0108] The amount of activator in these particulate compositions may be about 1% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, about 40% or less by weight, about 50% or less by weight, about 60% or less by weight, about 70% or less by weight, about 80% or less by weight, or in any range using these endpoints.

[0109] Wettable powder formulations (or spray powders) may include an active agent in amounts of about 20% or more, about 30% or more, about 40% or more, or about 50% or more, about 60% or less, about 70% or less, about 80% or less, about 90% or less, about 95% or less, or in any range using these endpoints.

[0110] Wettable powder formulations may include wetting agents, such as surfactants, in amounts of about 0% or more, about 1% or more, about 2% or more, or about 3% or less, about 4% or less, about 5% or less, or in any range using these endpoints. These may include those surfactants disclosed herein.

[0111] Wettable powder formulations may include dispersants, such as surfactants, in amounts of about 3% or more, about 4% or more, about 5% or more, about 6% or more, or about 7% or less, about 8% or less, about 9% or less, or about 10% or less, or in any range using these endpoints.

[0112] Wettable powder formulations may include a solid carrier in amounts of about 0% or more, about 1% or more, about 2% or more, about 3% or more, about 4% or more, about 5% or more, or about 6% or less, about 7% or less, about 8% or less, about 9% or less, about 10% or less, or in any range using these endpoints. The solid carrier may include any solid carrier known in the art.

[0113] Wettable powder formulations may contain one or more stabilizers and / or other additives, such as pigments, colorants, penetrants, adhesion promoters or anti-caking agents.

[0114] To produce these wettable powder formulations or sprayable powders, one or more active agents are tightly mixed with other components in a suitable mixing apparatus, and the resulting mixture is ground using a mill or other suitable grinding equipment. This yields sprayable powders with wettability and suspension properties. Consequently, they can be suspended in water at any concentration, and in particular, these suspensions are especially suitable for seed treatment.

[0115] In addition to wettable powder formulations, pastes can also be produced. The conditions and methods for preparing and using pastes are similar to those for wettable powders or spray powders.

[0116] Dispersible particulate compositions can be prepared by agglomeration in a suitable granulation system to provide powder compositions similar to wettable powder formulations.

[0117] IV. Herbicide Formulations

[0118] This disclosure further provides formulations of herbicides. These formulations can be applied to plants in a herbicidal amount and can effectively control one or more plant species from one or more of the following genera, but are not limited to: Abutilon, Amaranthus, Artemisia, Asclepias, Avena, Axonopus, Borrelia, Brachiaria, Brassica, Bromus, Chenopodium, Cirsium, Commelina, Convolvulus, Cynodon, Cyperus, Digitaria, Echinochloa, Eleusine, Elymus, Equisetum, and Geraniaceae. The genera *Helianthus*, *Imperata*, *Ipomoea*, *Kochia*, *Lolium*, *Malva*, *Oryza*, *Ottochloa*, *Panicum*, *Paspalum*, *Phalaris*, *Phragmites*, and *Polygonum* are all genera in Chinese. m), Portulaca, Pteridium, Pueraria, Rubus, Salsola, Setaria, Sida, Sinapis, Sorghum, Triticum, Typha, Ulex, Xanthium, and Zea.

[0119] The herbicidal formulation disclosed herein may include a herbicide and an optional second herbicide, one or more surfactants selected from one or more surfactant classes, a water-insoluble solvent, and water.

[0120] 1. Herbicides

[0121] The herbicide formulations disclosed herein may include herbicides or their water-soluble salts. Suitable herbicides may include 2,4-D (2,4-dichlorophenoxyacetic acid), 2,4-DB (4-(2,4-dichlorophenoxy)butyric acid), aminocyclopyrachlor, aminopyralid, clopyralid, dicamba, glyphosate, MCPA, MCPB, picloram, triclopyr, or mixtures thereof.

[0122] The water-soluble salts of herbicides may include salts containing one or more cations selected from the organic ammonium cation class, wherein the organic ammonium cations may have 1 to about 12 carbon atoms, such as isopropylammonium, diethylene glycolammonium (2-(2-aminoethoxy)ethanolammonium), dimethylammonium, diethylammonium, triethylammonium, monoethanolammonium, dimethylethanolammonium, diethanolammonium, triethanolammonium, triisopropanolammonium, tetramethylammonium, tetraethylammonium, N,N,N-trimethylethanolammonium (choline) and N,N-bis(3-aminopropyl)methylammonium (BAPMA).

[0123] In addition, the water-soluble salts of herbicides may include salts containing one or more cations selected from inorganic cations (such as sodium and / or potassium).

[0124] In the case of acidic herbicides (such as auxin herbicides), the herbicide may be present in the herbicide formulation in amounts of about 100 g acid equivalent per liter (g ae / L) or more, about 200 g ae / L or more, about 300 g ae / L or more, or about 400 g ae / L or less, about 500 g ae / L or less, about 600 g ae / L or less, about 625 g ae / L or less, or in any range of these endpoints.

[0125] Some of the herbicidal actives described herein do not contain acidic functional groups, and for these active ingredients, the terms "acid equivalent" and "acid equivalent base" do not accurately describe the amount of the secondary herbicide present. Generally, in such cases, the terms "active ingredient" or "active ingredient base" are used to describe the amount of the secondary herbicide active ingredient present. For example, when the active ingredient does not have an acid equivalent, grams of active ingredient per liter (gai / L) can be used instead of grams of acid equivalent per liter (gae / L), or grams of active ingredient per kilogram (gai / kg) can be used instead of grams of acid equivalent per kilogram (gae / kg).

[0126] 2. Optional second herbicide

[0127] Suitable secondary herbicides may be selected from, but are not limited to, esters of 4-CPA, 4-CPB, 4-CPP, 2,4-D, 3,4-DA, 2,4-DB, 3,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DP, 2,4,5-T, 2,4,5-TB and 2,3,6-TBA, allidochlor, acetochlor, acifluorfen, aclonifen, alachlor, alloxydim, alarac, ametridone, ametryn, amibuzin, amicabazone, amidosulfuron, aminocyclopyr esters, and aminopyralid. esters), amiprofos-methyl, amitrole, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benzolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, be... The following herbicides are listed: ntazone, benzadox, benzfendizone, benzzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicylopyrone, bifenox, bilanafos, bispyribac, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, and brompyrazon.Butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cafenstrole, cambendichlor, carbasulam, and styrax. (carbetamide), carboxazole, chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenp-oat ester rop), chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinitrofop-methyl don-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, cromazine, comeprop, comeprop, cloprop, cloproxydim, clopyralidesters, cloransulam, CPMFCPPC, credazine, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba esters), dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethachlor ethenamid), dimethenamid-P, dimexano, dimidazon, diinitramine, diinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, EBEP, eglinazine, endothal, epronaz, epronaz, EPTC, erbon.esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etnipromid, etobenzanid, EXD, fenasulfuron LAM), fenasulam, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, flamprop, flamprop-M, flazasulfuron, and florasulam. Fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipr Optimum, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, tetrafluoropropanate, flupyrsulfuron, fluridone, fluorochloridoneNon-liquid fluoroxypyr esters, fluoroxypyr-meptyl, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glyphosate, halauxfen, halauxfen-methyl, halosafen, ha losafen), halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indazon-fluorine (in...) daziflam), iodobonil, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocillin, isomethiozin, isooruron, isopolinate, isopropalin, isoproturon, isouron, isoxalon Soxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MCPA ester, MCPA-thioethyl, MCPA-EHE, MCPB ester, mecoprop, mecoprop-P, medinoterbMefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, mesoproplatin alpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, methoxyfenozide metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monolinuron, monuron, morfamquat, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitrali n), nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfenParafluoron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, penoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham-ethyl, phenobenzuron, and picloram esters), picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxy Carbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, piraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalidPyriminobac, pyrimisulfan, pyrithiobac, pyrosulfotole, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, sulcot rione), sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulglycapin, swep, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, non-liquid triclopyralid triclopyr esters), thidiazimin, thidiazuron, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, toramezone, tralkoxydim, tri-allateTriasulfuron, triaziflam, tribenuron, tricamba, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, xylachlor, and their mixtures and derivatives.

[0128] If used, the second herbicide is present in amounts of about 0 g ae / L or greater, 0.1 g ae / L or greater, 10 g ae / L or greater, 50 g ae / L or greater, 100 g ae / L or greater, or 200 g ae / L or less, about 300 g ae / L or less, about 400 g ae / L or less, or in any range of these endpoints.

[0129] Some of the secondary herbicidal actives described herein do not contain acidic functional groups, and for these active ingredients, the terms "acid equivalent" and "acid equivalent base" do not accurately describe the amount of secondary herbicide present. Generally, in such cases, the terms "active ingredient" or "active ingredient base" are used to describe the amount of secondary herbicide active ingredient present. For example, when the active ingredient does not have an acid equivalent, grams of active ingredient per liter (gai / L) can be used instead of grams of acid equivalent per liter (ge / L), or grams of active ingredient per kilogram (gai / kg) can be used instead of grams of acid equivalent per kilogram (ge / kg).

[0130] 3. Surfactants

[0131] Suitable surfactants for use in the herbicide formulations of this disclosure include one or more surfactants of formula I and / or co-surfactants:

[0132]

[0133] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, counterions may associate with the compound, and if present, counterions may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups.

[0134] In particular, suitable surfactants or co-surfactants may include any one or more of the surfactants 1-7 described herein.

[0135] Herbicides may include one or more surfactants in amounts of about 0% or more by weight, about 2% or more by weight, about 4% or more by weight, about 6% or more by weight, about 8% or more by weight, or about 10% or less by weight, about 12% or less by weight, about 14% or less by weight, about 16% or less by weight, or in any range using these endpoints.

[0136] 4. Water-insoluble solvents

[0137] Suitable water-insoluble and immiscible organic solvents include those derived from or prepared from natural non-petroleum sources (such as plants and animals), and include vegetable oils, seed oils, animal oils, etc., such as N,N-dimethyloctylamide, N,N-dimethyldecylamide, and mixtures thereof, which can be used as... AMD 810 and AMD 10 was purchased from BASF (Florham Park, NJ) as... 4166、 4231 and 4296 was commercially available from Clariant (Charlotte, NC), from Stepan (Northfield, Ill.) as Hallcomid M-8-10 and Hallcomid M-10, and from AkzoNobel (Chicago, Ill.) as Amid DM10 and DM810. Other examples of naturally derived organic solvents include morpholinamides of caprylic / capric fatty acids (C8 / C10), which can be used as... The AG-1730 solvent was commercially available from Huntsman International LLC (The Woodlands, Tex.).

[0138] Other suitable water-insoluble solvents may include aromatic hydrocarbons, mixed naphthalene and alkylnaphthalene fractions, aromatic solvents, especially alkyl-substituted benzenes, such as xylene or propylbenzene fractions; C1-C6 esters of fatty acids derived from vegetable oils, seed oils, or animal oils, such as methyl hexanoate, methyl octanoate, methyl decanoate, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenic acid, etc.; ketones, such as isophorone and trimethylcyclohexanone (dihydroisophorone); acetate esters, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, or heptyl acetate, etc.; and cyclic alkyl carbonate esters, such as propylene carbonate and butyl carbonate, which can be used as... Alkyl carbonates are obtained from Huntsman (The Woodlands, Tex.), and dibutyl carbonate, also obtained from Huntsman, as well as any mixtures of water-immiscible organic solvents described herein.

[0139] Water-insoluble solvents may be present in the herbicide formulation in amounts of about 0% by weight or more, about 10% by weight or more, about 20% by weight or more, or about 30% by weight or less, about 40% by weight or less, about 50% by weight or less, or in any range using these endpoints.

[0140] 5. Water

[0141] Water may be present in the herbicidal formulations of this disclosure to serve as an aqueous solvent and a carrier for the components in the composition.

[0142] The herbicides disclosed herein may include water in amounts of about 200 g / L or more, about 300 g / L or more, about 400 g / L or more, or about 500 g / L or less, about 600 g / L or less, about 700 g / L or less, about 800 g / L or less, or in any range using these endpoints.

[0143] 6. Other additives

[0144] Herbicides may contain one or more additional compatible ingredients. These additional ingredients may include, for example, one or more pesticides or other ingredients that can be dissolved or dispersed in the composition, and may include acaricides, algaecides, predatory antagonists, bird killers, bactericides, bird repellents, chemical sterilizers, defoliants, desiccants, disinfectants, fungicides, herbicide safeners, herbicides, insect attractants, insecticides, insect repellents, mammal repellents, mating disruptors, molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, chemical pheromones, synergists, and virucides. Furthermore, any other additional ingredients that provide functional utility, such as defoamers, antimicrobial agents, buffers, corrosion inhibitors, dispersants, dyes, fragrances, freezing point inhibitors, neutralizers, odorants, penetration enhancers, multivalent chelating agents, spray drift control agents, spreading agents, stabilizers, adhesives, viscosity modifiers, water-soluble solvents, etc., may be included in these compositions.

[0145] When the herbicides are used in combination with additional active ingredients (such as herbicide active ingredients), the compositions described herein may be formulated as a premixed concentrate with one or more other active ingredients, barrel-mixed in water with one or more other active ingredients for spray application, or applied sequentially in separate spray applications with one or more other active ingredients.

[0146] 7. Manufacturing method

[0147] The herbicide formulation disclosed herein may be prepared by the following steps: 1) preparing a solution of one or more second herbicides in an organic solvent and a surfactant; 2) adding the solution prepared in step 1) to a concentrated solution of a water-soluble salt of the herbicide in water, and mixing thoroughly to form a clear solution; and 3) optionally, adding any other compatible active or inert ingredient.

[0148] Alternatively, the herbicide formulation of this disclosure may be prepared by the following steps: 1) providing a second herbicide as a liquid, and optionally mixing it with an organic solvent and a surfactant; 2) adding the composition prepared in step 1) to a concentrated solution of the water-soluble salt of the herbicide in water, mixing thoroughly to form a clear solution; and 3) optionally adding any other compatible active or inert ingredient.

[0149] Suitable water-compatible ingredients that can be added to herbicide formulations include, but are not limited to, water-soluble or water-insoluble dispersing surfactants (such as the surfactants disclosed herein), water-insoluble active ingredients, and optional other inert ingredients such as pH buffers, wetting agents, antifreeze agents, defoamers, and biocides.

[0150] 8. How to use

[0151] The aqueous herbicides described herein may optionally be diluted in aqueous spray mixtures for agricultural applications, such as for weed control in crop fields or turf. Such herbicides are typically diluted with an inert carrier, such as water, before application. Diluted herbicides typically applied to, for example, weeds, the location of weeds, or the area where weeds may eventually appear, may contain an agricultural active agent (herbicide) in amounts of about 0.0001% by weight or more, about 0.001% by weight or more, about 0.01% by weight or more, about 0.1% by weight or more, about 1% by weight or more, or about 2% by weight or less, about 3% by weight or less, about 4% by weight or less, or about 5% by weight or less, or in any range using these endpoints. The herbicide formulations disclosed herein can be applied to, for example, weeds or their location, by using conventional ground or air sprayers, by adding to irrigation water, and by other conventional methods known to those skilled in the art.

[0152] The herbicide formulations disclosed herein can be used to control undesirable vegetation in crops that have single, multiple, or superimposed genomic characteristics that confer tolerance to one or more herbicide chemicals and / or inhibitors with single or multiple modes of action.

[0153] V. Insecticide formulations

[0154] This disclosure also provides formulations of insecticides. Such formulations may be in liquid or solid form, such as emulsifiable concentrates, oil-in-water (O / W) emulsions, suspension concentrates, and wettable powders.

[0155] Insecticide formulations may include insecticides, one or more surfactants selected from one or more surfactant classes, optional defoamers, optional antifreeze agents, and water.

[0156] 1. Insecticides

[0157] Suitable insecticides may include one or more of the following: pyrethroids, such as synthetic pyrethroids; organophosphate compounds, such as chlorpyrifos-ethyl, chlorpyrifos-methyl, pirimiphos-methyl, and fenitrothion; phenyl ethers, such as pyriproxyfen; benzoylurea, such as flufenoxuron; carbamates, such as fenoxycarb and carbosulfan; neonicotinoids, such as acetamiprid; pyridinecarboxamides, such as flonicamid; and / or others. Pyrethrins can be selected from one or more of bifenthrin, zeta-cypermethrin, alpha-cypermethrin, tetra-methrin, lambda-cyhalothrin, fenvalerate, cyfluthrin, bio-resmethrin, permethrin, and delta-methrin.

[0158] Insecticides may be present in insecticide formulations in amounts of approximately 1% or more, approximately 5% or more, approximately 10% or more, or approximately 15% or less, approximately 20% or less, or in any range using these endpoints, measured by weight / volume.

[0159] 2. Surfactants

[0160] Insecticide formulations may include one or more surfactants selected from one or more surfactant classes, collectively referred to as surfactant systems.

[0161] Suitable surfactants for use in the insecticide formulations of this disclosure include one or more surfactants of formula I and / or co-surfactants:

[0162]

[0163] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, counterions may associate with the compound, and if present, counterions may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups.

[0164] In particular, suitable surfactants or co-surfactants may include any one or more of the surfactants 1-7 described herein.

[0165] The surfactant system may be present in the insecticide formulation in amounts measured by weight / volume of approximately 1% or more, approximately 5% or more, approximately 10% or more, approximately 15% or more, or approximately 20% or less, approximately 25% or less, approximately 30% or less, approximately 35% or less, approximately 40% or less, or in any range using these endpoints.

[0166] 3. Optional defoamer

[0167] Optional defoamers in insecticide formulations may include silicone emulsions and / or surfactants, such as those disclosed herein.

[0168] The defoamer may be present in the insecticide formulation in amounts of about 0.0% or more, about 0.1% or more, about 0.2% or more, about 0.3% or more, about 0.4% or more, about 0.5% or more, or about 0.6% or less, about 0.7% or less, about 0.8% or less, about 0.9% or less, about 1.0% or less, or in any range using these endpoints, as measured by weight / volume.

[0169] 4. Optional antifreeze

[0170] Insecticide formulations may include optional antifreeze agents. Suitable antifreeze agents may include glycols, such as alkyl glycols or dialkyl glycols.

[0171] Insecticide formulations may include antifreeze in amounts measured by weight / volume of about 0% or more, about 1% or more, about 2% or more, about 3% or more, about 4% or more, about 5% or more, or about 6% or less, about 7% or less, about 8% or less, about 9% or less, about 10% or less, or in any range using these endpoints.

[0172] 5. Water

[0173] Insecticide formulations may include water in amounts measured by weight / volume of approximately 25% or greater, approximately 30% or greater, approximately 35% or greater, approximately 40% or greater, approximately 45% or greater, approximately 50% or greater, approximately 55% or greater, or approximately 60% or less, approximately 65% ​​or less, approximately 70% or less, approximately 75% or less, approximately 80% or less, approximately 85% or less, approximately 90% or less, approximately 95% or less, approximately 98% or less, or in any range using these endpoints.

[0174] 6. Other additives

[0175] The insecticide formulations disclosed herein may include viscosity modifiers. Such viscosity modifiers may include thickeners, such as cellulose derivatives, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and natural gums.

[0176] Viscosity modifiers can be present in insecticides in any amount suitable for changing the viscosity to the desired level.

[0177] The insecticide formulations disclosed herein may also include preservatives. Suitable preservatives include methylparaben.

[0178] Preservatives may be present in insecticide formulations in amounts of 0.0% or more, 0.1% or more, or 0.2% or less, by weight / volume, or in any range using these endpoints.

[0179] VI. Adjuvants

[0180] In addition to the uses described above, the surfactants disclosed herein can be used as adjuvants in agricultural active agent formulations (such as pesticides, plant growth regulators, herbicides, fungicides, and insecticides). Adjuvant compounds can be used to improve one or more properties of agricultural active agent formulations, such as storage stability, handleability, and pesticide efficacy against target organisms.

[0181] VII. Spray drift reducer

[0182] Spray drift refers to the unintentional spread of pesticides and other agrochemicals, including off-target contamination. This can lead to harm to human health, environmental pollution, and property damage. The surfactants disclosed herein can be used to reduce the amount of driftable particles in agrochemical formulations applied by air and ground spraying.

[0183] The surfactants and mixtures thereof disclosed herein can be incorporated into aqueous spray mixtures, for example by direct mixing with diluted formulations of agricultural active agents (such as pesticides, plant growth regulators, fungicides, herbicides, or insecticides).

[0184] The optimal spray droplet size depends on the application to which the composition is used. If the droplets are too large, the spray coverage will be smaller; for example, large droplets will fall in some areas while areas in between will receive little or no spray coverage. The maximum acceptable droplet size can depend on the amount of composition applied per unit area and the need for uniform spray coverage. Smaller droplets provide more uniform coverage but are more prone to drift during spraying. Therefore, application parameters such as uniform spray coverage must be balanced with the tendency for smaller droplets to drift. For example, if there is particularly strong wind during spraying, larger droplets may be needed to reduce drift, while smaller droplets may be acceptable on calmer days. In addition to the specific physical properties of the aqueous composition, the spray droplet size can also depend on the spraying device, such as nozzle size and construction.

[0185] The reduction in spray drift can be caused by a variety of factors, including a reduction in the generation of fine spray droplets (<150 μm minimum diameter) and an increase in the volumetric median diameter (VMD) of the spray droplets. In any case, for a given spray apparatus, application, and conditions, and based on the surfactant used, the median diameter of multiple spray droplets generated using the surfactants described herein increases to a higher level than the median diameter of spray compositions excluding the surfactants disclosed herein.

[0186] VIII. Surfactants

[0187] This disclosure provides surfactants for agricultural products in the form of amino acid derivatives. The amino acids may be naturally occurring or synthetic, or they may be derived from the ring-opening reaction of lactams, such as caprolactam. The compounds of this disclosure have shown to possess surface-active properties and can be used, for example, as surfactants and wetting agents. In particular, this disclosure provides compounds of formula I:

[0188]

[0189] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; and optionally, counterions may associate with the compound, and if present, counterions may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups.

[0190] A specific compound (surfactant 1) disclosed herein is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide, having the following formula:

[0191]

[0192] The second specific compound (surfactant 2) provided in this disclosure is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula:

[0193]

[0194] The third specific compound (surfactant 3) disclosed herein is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride, having the following formula:

[0195]

[0196] The fourth specific compound (surfactant 4) disclosed herein is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula:

[0197]

[0198] The fifth specific compound (surfactant 5) disclosed herein is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide, which has the following formula:

[0199]

[0200] The sixth specific compound (surfactant 6) disclosed herein is 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, having the following formula:

[0201]

[0202] The seventh specific compound (surfactant 7) disclosed herein is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, having the following formula:

[0203]

[0204] These surfactants can be synthesized by various methods. One such method involves opening a lactam to produce an amino acid having an N-terminus and a C-terminus. The N-terminus can react with one or more alkylating agents and / or acids to produce a quaternary ammonium salt. Alternatively, the N-terminus can react with an oxidizing agent to produce an amine N-oxide. The C-terminus can react with an alcohol in the presence of an acid to produce an ester.

[0205] Amino acids can be naturally occurring or synthetic, or they can be derived from ring-opening reactions of lactams (such as caprolactam). Ring-opening reactions can be acid- or base-catalyzed, and an example of an acid-catalyzed reaction is shown in Scheme 1 below.

[0206] Option 1

[0207]

[0208] Amino acids may have as few as one or as many as 12 carbons between the N-terminus and C-terminus. The alkyl chain may be branched or straight. The alkyl chain may be interrupted by nitrogen, oxygen, or sulfur. The alkyl chain may be further substituted by one or more substituents selected from hydroxyl, amino, amide, sulfonyl, sulfonate, carboxyl, and carboxylate groups. The N-terminal nitrogen may be acylated or alkylated by one or more alkyl groups. For example, the amino acid may be 6-(dimethylamino)hexanoic acid or 6-aminohexanoic acid.

[0209] Surfactant 1 can be synthesized as shown in Scheme 2 below. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is alkylated with iodomethane in the presence of sodium carbonate.

[0210] Option 2

[0211]

[0212] Surfactant 2 can be synthesized as shown in Scheme 3 below. As shown, the C-terminus of 6-(dimethylamino)hexanoic acid is treated with 2-butyloctyl alcohol in toluene in the presence of p-toluenesulfonic acid (PTSA) to obtain the corresponding ester as 4-methylbenzenesulfonate, 2-butyloctyl 6-(dimethylamino)hexanoic acid.

[0213] Option 3

[0214]

[0215] Surfactant 3 can be synthesized as shown in Scheme 4 below. As shown, 2-butyloctyl 6-(dimethylamino)hexanoate is treated with an equivalent amount of hydrochloric acid to obtain 2-butyloctyl 6-(dimethylamino)hexanoate as a chloride salt.

[0216] Option 4

[0217]

[0218] Surfactant 4 can be synthesized as shown in Scheme 5 below. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is treated with 1,4-butanesulfonyl lactone in refluxed ethyl acetate to produce the desired sulfonate.

[0219] Option 5

[0220]

[0221] Surfactant 5 can be synthesized as shown in Scheme 6 below. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is treated with hydrogen peroxide in water to provide the desired N-oxide.

[0222] Option 6

[0223]

[0224] Surfactant 6 can be synthesized as shown in Scheme 7 below. As shown, the N-terminus of 2-butyloctyl 6-aminohexanoate is treated with an equivalent amount of hydrochloric acid to provide the corresponding chloride salt.

[0225] Option 7

[0226]

[0227] Surfactant 7 can be synthesized as shown in Scheme 8 below. As shown, 6-aminohexanoic acid is treated in benzene with 2-butyloctyl alcohol and p-toluenesulfonic acid (PTSA) to provide the corresponding 4-methylbenzenesulfonate.

[0228] Option 8

[0229]

[0230] The compounds disclosed herein exhibit surface-active properties. These properties can be measured and described by various methods. One way to describe surfactants is by the critical micelle concentration (CMC) of the molecule. The CMC can be defined as the concentration of the surfactant at which micelles form, and above this concentration, all other surfactants are incorporated into the micelles.

[0231] As surfactant concentration increases, surface tension decreases. Once the surface is completely covered by surfactant molecules, micelles begin to form. This point represents the center of gravity (CMC) and the minimum surface tension. Further addition of surfactant will not further affect the surface tension. Therefore, the CMC can be measured by observing the change in surface tension as a function of surfactant concentration. One such method for measuring this value is the Wilhelmy plate method. The Wilhelmy plate is typically a thin iridium-platinum plate, which is attached to a balance by a wire and placed perpendicular to the air-liquid interface. The balance is used to measure the force applied to the plate by wetting. The surface tension (γ) is then calculated using this value according to Equation 1:

[0232] Equation 1: γ=F / l cosθ

[0233] Where l equals the wetted perimeter (2w+2d, where w and d are the thickness and width of the plate, respectively), and cosθ is the contact angle between the liquid and the plate, which is assumed to be 0 in the absence of existing literature values.

[0234] Another parameter used to evaluate surfactant performance is dynamic surface tension. Dynamic surface tension is the surface tension value over a specific surface or interface lifetime. In the case of liquids with added surfactants, this can differ from the equilibrium value. Immediately after surface formation, the surface tension is equal to that of the pure liquid. As mentioned above, surfactants reduce surface tension; therefore, the surface tension decreases until an equilibrium value is reached. The time required to reach equilibrium depends on the surfactant's diffusion and adsorption rates.

[0235] One method for measuring dynamic surface tension relies on a bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble forming in a liquid via a capillary. The measured value corresponds to the surface tension at a given surface lifetime (the time from the start of bubble formation to the attainment of the maximum pressure). The dependence of surface tension on surface lifetime can be measured by varying the rate of bubble formation.

[0236] Surfactant compounds can also be evaluated by their wetting ability on solid substrates (e.g., measured by contact angle). When a droplet comes into contact with a solid surface in a third medium (such as air), a three-phase line is formed between the liquid, gas, and solid. The angle between the unit vector of surface tension acting on the three-phase line and tangent to the droplet and the surface is described as the contact angle. The contact angle (also known as the wetting angle) is a measure of the wettability of a liquid on a solid. In the case of complete wetting, the liquid spreads completely over the solid, and the contact angle is 0°. The wetting properties of a given compound are typically measured at concentrations of 1–10 × CMC; however, it is not a concentration-dependent property, and therefore, wetting properties can be measured at higher or lower concentrations.

[0237] In one method, an optical contact angle goniometer can be used to measure the contact angle. This device uses a digital camera and software to obtain the contact angle by analyzing the profile shape of a droplet attached to a surface.

[0238] Potential applications of the surfactant compounds disclosed herein include formulations for use in shampoos, conditioners, detergents, spot-free rinses, floor and carpet cleaners, graffiti removers, wetting agents for crop protection, adjuvants for crop protection, and wetting agents for aerosol spraying.

[0239] Those skilled in the art will understand that small differences between compounds can lead to significantly different surfactant properties, allowing different compounds to be used with different substrates in different applications.

[0240] The following non-limiting embodiments are provided to demonstrate the different properties of various surfactants. In Table 1 below, the abbreviations of surfactants are associated with their corresponding chemical structures.

[0241] Table 1

[0242]

[0243]

[0244] Each of the seven compounds is effective as a surfactant, especially as a wetting or foaming agent, dispersant, emulsifier, and detergent.

[0245] Surfactants 1, 2, 3, 6, and 7 are cationic. These surfactants can be used in the applications described above, as well as in some other specialized applications such as surface treatments, personal hair care products, and can also be used to create waterproof surfaces.

[0246] Surfactant 4 is amphoteric. These surfactants can be used as co-surfactants in all the applications described above.

[0247] Surfactant 5 is nonionic and can be used in shampoos, detergents, hard surface cleaners and a variety of other surface cleaning formulations.

[0248] Example

[0249] Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500MHz spectrometer. The critical micelle concentration (CMC) was determined at 23°C using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate via the Wilhelmy pendant method. Dynamic surface tension was determined at 23°C using a bubble pressure tensiometer (Krüss BP100, Krüss GmbH). The contact angle was determined using an optical contact angle goniometer (OCA 15Pro, DataPhysics GmbH) equipped with a digital camera.

[0250] Example 1a:

[0251] Synthesis of 6-((2-Butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide

[0252] 2-Butyloctyl 6-(dimethylamino)hexanoate (2.04 mmol, 700 mg) was dissolved in acetonitrile (10 mL). Sodium carbonate (2.44 mmol, 259 mg) was added, and the mixture was stirred at room temperature for 10 min. Iodomethane (6.12 mmol, 0.38 mL) was added, and the mixture was heated to 40 °C for 24 h, followed by cooling to room temperature. The mixture was filtered, and the solvent was removed under vacuum to give 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide as a yellow solid in 90% yield. 1 H NMR(500MHz,DMSO)δ3.93(d,J=5.7Hz,2H),3.29–3.22(m,2H),3.04(s,9H),2. 34(t,J=7.4Hz,2H),1.73-1.53(m,5H),1.33-1.25(m,18H),0.88-0.85(m,6H).

[0253] Example 1b:

[0254] Determining the critical micelle concentration (CMC)

[0255] The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide from Example 1a was tested. Figure 1 As shown in the graph, the CMC value cannot be clearly determined at concentrations up to 10 mg / mL, where the surface tension asymptotically approaches a value of approximately 27 mN / m. Figure 1 These are graphs of the results, showing the effect of surface tension on concentration. From the graphs, the surface tension at CMC is equal to or less than approximately 27 mN / m.

[0256] Example 2a:

[0257] Synthesis of 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate

[0258] 6-(dimethylamino)hexanoic acid was treated in benzene at 120 °C with 2-butyloct-1-ol and p-toluenesulfonic acid for 12 hours. 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate was isolated as a white waxy solid and recrystallized from acetone in 49% yield. 1 H NMR (500MHz, DMSO) δ7.48(dd,J=8.4,0.6Hz,2H),7.12(dd,J=8.4,0.6Hz,1H),3.93(d,J=5.7Hz,2H),3.02–3.00(m, 2H), 2.76 (d, J = 5.0Hz, 6H), 2.37–2.25 (m, 6H), 1.59–1.53 (m, 5H), 1.25–1.29 (m, 18H), 0.87 (td, J = 6.8, 2.7Hz, 6H).

[0259] Example 2b:

[0260] Determining the critical micelle concentration (CMC)

[0261] The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate from Example 2a was tested. Based on the change in surface tension with concentration in water, the CMC was determined to be approximately 0.97 mmol. The minimum surface tension plateau value achievable by this surfactant is approximately 27 mN / m, i.e., 27 mN / m ± 3 mN / m. Figure 2A These are graphs of the results, showing the effect of surface tension on concentration. From the graphs, the surface tension at CMC is equal to or less than approximately 30 mN / m.

[0262] Example 2c:

[0263] Determine dynamic surface tension

[0264] The dynamic surface tension of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate from Example 2a was determined using a bubble pressure tensiometer that measures the change in surface tension at the newly formed air-water interface over time. Figure 2BA graph of surface tension versus time is shown, indicating that the surface tension decreases rapidly from approximately 46 mN / m to approximately 30 mN / m in the time interval from 10 ms to 100 ms. In the time interval from 100 ms to 8,000 ms, the surface tension decreases slowly from 30 mN / m to approximately 27 mN / m, asymptotically approaching the saturation value of surface tension at the CMC.

[0265] Example 2d:

[0266] Determine wetting properties

[0267] In addition to surface tension and surface dynamics, the wetting properties of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate from Example 2a were tested on various surfaces. For example, hydrophobic substrates (such as polyethylene-HD) exhibited surface wetting with a contact angle of 24.3°. On oleophobic and hydrophobic substrates (such as Teflon), the measured contact angle was much smaller than the water contact angle of 119°, at 48.2° (Table 2).

[0268] Table 2

[0269]

[0270]

[0271] Example 3a:

[0272] Synthesis of 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride

[0273] Treat 2-butyloctyl 6-(dimethylamino)hexanoate with one equivalent of hydrochloric acid to provide 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride.

[0274] Example 3b:

[0275] Determining the critical micelle concentration (CMC)

[0276] The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride from Example 3a was tested. Based on the change in surface tension with concentration in water, the CMC was determined to be approximately 27.47 mmol. The minimum achievable surface tension of this surfactant is approximately 29 mN / m, i.e., 29 mN / m ± 3 mN / m. Figure 3 The graph shows the surface tension versus concentration. From the graph, the CMC value cannot be clearly determined at concentrations up to 27.4 mmol, where the surface tension asymptotically approaches a value of approximately 29 mN / m.

[0277] Example 4a:

[0278] Synthesis of 4-((6-((2-Butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate

[0279] 2-Butyloctyl 6-(dimethylamino)hexanoate (2.04 mmol, 700 mg) was dissolved in ethyl acetate (30 mL). 1,4-Butanesulfonyl lactone (3.06 mmol, 0.31 mL) was added. The mixture was heated to reflux for 12 hours, followed by solvent evaporation. The resulting white waxy solid was washed with acetone to give 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate in 89% yield. 1 H NMR(500MHz,DMSO)δ3.93(d,J=5.7Hz,2H),3.30-3.28(m,4H),2.97(s,3H),2.49–2.43( m,2H),2.34(t,J=7.4Hz,2H),1.96–1.76(m,9H),1.27-1.25(m,18H),0.88–0.85(m,6H).

[0280] Example 4b:

[0281] Determining the critical micelle concentration (CMC)

[0282] The critical micelle concentration (CMC) of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate from Example 4a was tested. Based on the change in surface tension with concentration in water, the CMC was determined to be approximately 0.54 mmol. The minimum surface tension plateau value achievable by this surfactant is approximately 32 mN / m, i.e., 32 mN / m ± 3 mN / m. Figure 4A These are graphs of the results, showing the effect of surface tension on concentration. From the graphs, the surface tension at CMC is equal to or less than approximately 32 mN / m.

[0283] Example 4c:

[0284] Determine dynamic surface tension

[0285] The dynamic surface tension of 4-((6-((2-Butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate from Example 4a was determined using a bubble pressure tensiometer that measures the change in surface tension at the newly formed air-water interface over time. Figure 4BA graph of surface tension versus time is shown, indicating that the surface tension decreases rapidly from approximately 66 mN / m to approximately 36 mN / m in the time interval from 10 ms to 100 ms. In the time interval from 100 ms to 8,000 ms, the surface tension decreases slowly from 36 mN / m to approximately 32 mN / m, asymptotically approaching the saturation value of surface tension at the CMC.

[0286] Example 4d:

[0287] Determine wetting properties

[0288] In addition to surface tension and surface dynamics, the wetting properties of 4-((6-(((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate from Example 4a were tested on various surfaces. For example, hydrophobic substrates (such as polyethylene-HD) exhibited surface wetting with a contact angle of 44.4°. On oleophobic and hydrophobic substrates (such as Teflon), the measured contact angle was much smaller than the water contact angle of 119°, at 62.2° (Table 3).

[0289] Table 3

[0290]

[0291] Example 5a:

[0292] Synthesis of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide

[0293] 6-(dimethylamino)hexanoic acid 2-butyloctyl ester was treated with hydrogen peroxide in water at 70°C for 24 hours to obtain 6-(dimethylamino)hexanoic acid 2-butyloctyl ester N-oxide as an oil, with a yield of 90%. 1 H NMR(500MHz,DMSO)δ3.93(d,J=5.7Hz,2H),3.30-3.28(m,4H),2.97(s,3H),2.49–2.43( m,2H),2.34(t,J=7.4Hz,2H),1.96–1.76(m,9H),1.27-1.25(m,18H),0.88–0.85(m,6H).

[0294] Example 5b:

[0295] Determining the critical micelle concentration (CMC)

[0296] The critical micelle concentration (CMC) of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was tested. Based on the change in surface tension with concentration in water, the CMC was determined to be approximately 0.29 mmol. The minimum surface tension plateau value achievable by this surfactant is approximately 28 mN / m, i.e., 28 mN / m ± 3 mN / m. Figure 5A These are graphs of the results, showing the effect of surface tension on concentration. From the graphs, the surface tension at CMC is equal to or less than approximately 28 mN / m.

[0297] Example 5c:

[0298] Determine dynamic surface tension

[0299] The dynamic surface tension of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was determined using a bubble pressure tensiometer that measures the change in surface tension at the newly formed air-water interface over time. Figure 5B A graph of surface tension versus time is shown, indicating that the surface tension decreases rapidly from approximately 60 mN / m to approximately 30 mN / m in the time interval from 10 ms to 1,000 ms. In the time interval from 1,000 ms to 8,000 ms, the surface tension decreases slowly from 30 mN / m to approximately 28 mN / m, asymptotically approaching the saturation value of surface tension at the CMC.

[0300] Example 5d:

[0301] Determine wetting properties

[0302] In addition to surface tension and surface dynamics, the wetting properties of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a were tested on various surfaces. For example, hydrophobic substrates (such as polyethylene-HD) exhibited surface wetting with a contact angle of 31.6°. On oleophobic and hydrophobic substrates (such as Teflon), the measured contact angle was much smaller than the water contact angle of 119°, at 41.5° (Table 4).

[0303] Table 4

[0304]

[0305] Example 6a:

[0306] Synthesis of 6-((2-Butyloctyl)oxy)-6-oxohexane-1-amineonium chloride

[0307] Treat 2-butyloctyl 6-(dimethylamino)hexanoate with 1 equivalent of hydrochloric acid to provide 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride.

[0308] Example 6b:

[0309] Determining the critical micelle concentration (CMC)

[0310] The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride from Example 6a was tested. Based on the change in surface tension with concentration in water, the CMC was determined to be approximately 0.15 mmol. The minimum surface tension plateau value achievable by this surfactant is approximately 27 mN / m, i.e., 27 mN / m ± 3 mN / m. Figure 6A These are graphs of the results, showing the effect of surface tension on concentration. From the graphs, the surface tension at CMC is equal to or less than approximately 30 mN / m.

[0311] Example 6c:

[0312] Determine dynamic surface tension

[0313] The dynamic surface tension of 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride from Example 6a was determined using a bubble pressure tensiometer that measures the change in surface tension at the newly formed air-water interface over time. Figure 6B A graph of surface tension versus time is shown, showing that the surface tension slowly decreases from about 69 mN / m to about 29 mN / m in the time interval from 10 ms to 8,000 ms, with a slight plateau of about 49 mN / m at the surface lifetime of 1,000 ms, close to the saturation value of surface tension at CMC.

[0314] Example 6d:

[0315] Determine wetting properties

[0316] In addition to surface tension and surface dynamics, the wetting properties of the 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride from Example 6a were tested on various surfaces. For example, hydrophobic substrates (such as polyethylene-HD) exhibited surface wetting with a contact angle of 25.8°. On oleophobic and hydrophobic substrates (such as Teflon), the measured contact angle was much smaller than the water contact angle of 119°, at 48.7° (Table 5).

[0317] Table 5

[0318]

[0319] Example 7a:

[0320] Synthesis of 6-((2-Butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate

[0321] 6-Aminohexanoic acid (38.11 mmol, 5 g) was dissolved in benzene (50 mL) in a 100 mL round-bottom flask fitted with a Dean-Stark collector. p-Toluenesulfonic acid monohydrate (38.11 mmol, 7.25 g) and 2-butyloctyl alcohol (38.11 mmol, 7.1 g, 8.5 mL) were added, and the mixture was heated to reflux for one week until no more water separated in the Dean-Stark collector. The solvent was removed under vacuum, and the product was crystallized from acetone at -20 °C to remove any remaining unreacted alcohol. The resulting white waxy solid was filtered to give 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate in 82% yield. 1 H NMR (500MHz, DMSO) δ7.49(d,J=8.0Hz,2H),7.12(dd,J=8.4,0.6Hz,2H),3.93(d,J=5.7Hz,2H),2 .79–2.73(m,2H),2.31–2.28(m,5H),1.55-1.50(m,5H),1.31–1.25(m,18H),0.88–0.85(m,6H).

[0322] Example 7b:

[0323] Determining the critical micelle concentration (CMC)

[0324] The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate from Example 7a was tested. Based on the change in surface tension with concentration in water, the CMC was determined to be approximately 2.12 mmol. The minimum surface tension plateau value achievable by this surfactant is approximately 27 mN / m, i.e., 27 mN / m ± 3 mN / m. Figure 7A The graph shows the results, illustrating the surface tension pairs. From the graph, the surface tension at CMC is equal to or less than approximately 30 mN / m, and at concentrations of approximately 1.0 mmol or greater, the surface tension is equal to or less than approximately 28.5 mN / m.

[0325] Example 7c:

[0326] Determine dynamic surface tension

[0327] The dynamic surface tension of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate from Example 7a was determined using a bubble pressure tensiometer that measures the change in surface tension at the newly formed air-water interface over time. Figure 7BA graph of surface tension versus time is shown, indicating that the surface tension decreases rapidly from approximately 46 mN / m to approximately 30 mN / m in the time interval from 10 ms to 100 ms. In the time interval from 100 ms to 8,000 ms, the surface tension decreases slowly from 30 mN / m to approximately 27 mN / m, asymptotically approaching the saturation value of surface tension at the CMC.

[0328] Example 7d:

[0329] Determine wetting properties

[0330] In addition to surface tension and surface dynamics, the wetting properties of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate from Example 7a were tested on various surfaces. For example, hydrophobic substrates (such as polyethylene-HD) exhibited surface wetting with a contact angle of 14.6°. On oleophobic and hydrophobic substrates (such as Teflon), the measured contact angle was much smaller than the water contact angle of 119°, at 49.4° (Table 6).

[0331] Table 6

[0332]

[0333] Example 8:

[0334] Formulations used in pesticides

[0335] In this example, a concentrated formulation is provided for use as a pesticide. The components of the formulation are shown in Table 7 below. The formulation may also include additional surfactants, water, thickeners, sedimentation enhancers, drift control agents, and salts.

[0336] Table 7

[0337] Components Function weight% pesticide Agricultural surfactants 5-40 surfactants emulsifier 20-80 Water-insoluble solvents solvent 0.1-50

[0338] Example 9:

[0339] Formulations for use in liquid antifungal compositions

[0340] In this example, a formulation is provided for use as a liquid antifungal composition. This formulation is shown in Table 8 below.

[0341] Table 8

[0342] Components Function weight% fungicides Agricultural surfactants 1-90 surfactants emulsifier 1-30 Co-surfactants co-emulsifier 0-20 Water-insoluble solvents solvent 0-90

[0343] Example 10:

[0344] Formulations for use as herbicides

[0345] In this example, a formulation is provided for use as a herbicide. This formulation is shown in Table 9 below.

[0346] Table 9

[0347] Components Function weight% Herbicide salt Agricultural surfactants 5-70 Second herbicide Agricultural surfactants 0.1-40 surfactants emulsifier 0-15 Water-insoluble solvents solvent 0-50 water 20-80

[0348] Example 11:

[0349] Formulations for use as insecticides

[0350] In this example, a formulation is provided for use as an insecticide. This formulation is shown in Table 10 below.

[0351] Table 10

[0352] Components Function weight% Insecticide Agricultural surfactants 5-70 surfactants 0.1-40 surfactants Defoamer 0-15 Thickener Viscosity modifier 0-50 water 20-80

[0353] aspect

[0354] Aspect 1 is a formulation for use in pesticides, comprising: at least one surfactant of the following formula:

[0355]

[0356] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups; and pesticides.

[0357] Aspect 2 is a formulation of aspect 1, which further comprises a water-insoluble solvent.

[0358] Aspect 3 is a formulation based on aspect 1 or aspect 2, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide, having the following formula:

[0359]

[0360] Aspect 4 is a formulation based on aspect 1 or aspect 2, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula:

[0361]

[0362] Aspect 5 is a formulation based on aspect 1 or aspect 2, wherein the surfactant is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride, which has the following formula:

[0363]

[0364] Aspect 6 is a formulation based on aspect 1 or aspect 2, wherein the surfactant is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula:

[0365]

[0366] Aspect 7 is a formulation based on aspect 1 or aspect 2, wherein the surfactant is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide, which has the following formula:

[0367]

[0368] Aspect 8 is a formulation based on aspect 1 or aspect 2, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, which has the following formula:

[0369]

[0370] Aspect 9 is a formulation based on aspect 1 or aspect 2, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula:

[0371]

[0372] Aspect 10 is a formulation for use as a fungicide, comprising: at least one surfactant of the following formula:

[0373]

[0374] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups; and a fungicide.

[0375] Aspect 11 is a formulation of aspect 10, which further contains a co-surfactant.

[0376] Aspect 12 is a formulation of either aspect 10 or aspect 11, further comprising a carrier agent.

[0377] Aspect 13 is a formulation according to any one of Aspects 10-12, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide having the following formula:

[0378]

[0379] Aspect 14 is a formulation according to any one of Aspects 10-12, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium-4-methylbenzenesulfonate, having the following formula:

[0380]

[0381] Aspect 15 is a formulation according to any one of Aspects 10-12, wherein the surfactant is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride, having the following formula:

[0382]

[0383] Aspect 16 is a formulation according to any one of Aspects 10-12, wherein the surfactant is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula:

[0384]

[0385] Aspect 17 is a formulation according to any one of Aspects 10-12, wherein the surfactant is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide, having the following formula:

[0386]

[0387] Aspect 18 is a formulation according to any one of Aspects 10-12, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, having the following formula:

[0388]

[0389] Aspect 19 is a formulation according to any one of Aspects 10-12, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium-4-methylbenzenesulfonate, having the following formula:

[0390]

[0391] Aspect 20 is a formulation for use as a herbicide, comprising: at least one surfactant of the following formula:

[0392]

[0393] Where R 1 and R 2 Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups; and a herbicide.

[0394] Aspect 21 is a formulation of aspect 20, which further contains a second herbicide.

[0395] Aspect 22 is a formulation of aspect 20 or aspect 21, which further comprises a water-insoluble solvent.

[0396] Aspect 23 is a formulation of any one of aspects 20-22, which further comprises water.

[0397] Aspect 24 is a formulation according to any one of Aspects 20-23, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide having the following formula:

[0398]

[0399] Aspect 25 is a formulation according to any one of Aspects 20-23, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium-4-methylbenzenesulfonate, having the following formula:

[0400]

[0401] Aspect 26 is a formulation according to any one of Aspects 20-23, wherein the surfactant is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride, having the following formula:

[0402]

[0403] Aspect 27 is a formulation according to any one of Aspects 20-23, wherein the surfactant is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula:

[0404]

[0405] Aspect 28 is a formulation according to any one of Aspects 20-23, wherein the surfactant is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide, having the following formula:

[0406]

[0407] Aspect 29 is a formulation according to any one of Aspects 20-23, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, having the following formula:

[0408]

[0409] Aspect 30 is a formulation according to any one of Aspects 20-23, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium-4-methylbenzenesulfonate, having the following formula:

[0410]

[0411] Aspect 31 is a formulation for use as an insecticide, comprising: at least one surfactant of the following formula:

[0412]

[0413] Where R 1 and R 2Independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate groups; n is an integer from 2 to 5 (inclusive); R 3 It is C5-C 12 Alkyl; R 4 It is C3-C 10 Alkyl; terminal nitrogen optionally further converted to R 5 Replace, where R 5 The compound is selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate groups; optionally, a counterion may associate with the compound, and if present, the counterion may be selected from chloride, bromide, iodide and 4-methylbenzenesulfonate groups; and an insecticide.

[0414] Aspect 32 is a formulation of aspect 31, which further includes an antifoaming agent.

[0415] Aspect 33 is a formulation of either aspect 31 or aspect 32, further comprising an antifreeze agent.

[0416] Aspect 34 is a formulation of any one of aspects 31-33, further comprising water.

[0417] Aspect 35 is a formulation according to any one of Aspects 31-34, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide having the following formula:

[0418]

[0419] Aspect 36 is a formulation according to any one of aspects 31-34, wherein the surfactant is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, having the following formula:

[0420]

[0421] Aspect 37 is a formulation according to any one of Aspects 31-34, wherein the surfactant is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-amineonium chloride, having the following formula:

[0422]

[0423] Aspect 38 is a formulation according to any one of aspects 31-34, wherein the surfactant is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula:

[0424]

[0425] Aspect 39 is a formulation according to any one of aspects 31-34, wherein the surfactant is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide, having the following formula:

[0426]

[0427] Aspect 40 is a formulation according to any one of Aspects 31-34, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, having the following formula:

[0428]

[0429] Aspect 41 is a formulation according to any one of aspects 31-34, wherein the surfactant is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, having the following formula:

[0430]

Claims

1. A pesticide formulation comprising: At least one surfactant of the following formula: Where R 1 and R 2 The components are independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxyl groups, hydroxyl groups, sulfonyl groups, or sulfonate groups; n is an integer from 2 to 5; R 3 It is C5-C 12 alkyl; R 4 It is C3-C 10 alkyl; The terminal nitrogen is optionally further converted to R 5 Replace, where R 5 Selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl group may be substituted with a carboxyl group, a hydroxyl group, a sulfonyl group or a sulfonate group; Optional counterions may associate with the compound, and if present, said counterions may be selected from chloride ions, bromide ions, iodide ions, and 4-methylbenzenesulfonate ions; and pesticide, The surfactant comprises at least one of the following: 6-((2-Butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide, having the following formula: 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 4-((6-((2-Butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula: ； 2-Butyloctyl 6-(dimethylamino)hexanoate N-oxide has the following formula: 6-((2-Butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, which has the following formula: and 6-((2-Butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 。 2. The formulation of claim 1, further comprising a water-insoluble solvent.

3. A fungicide formulation comprising: At least one surfactant of the following formula: Where R 1 and R 2 The components are independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxyl groups, hydroxyl groups, sulfonyl groups, or sulfonate groups; n is an integer from 2 to 5; R 3 It is C5-C 12 alkyl; R 4 It is C3-C 10 alkyl; The terminal nitrogen is optionally further converted to R 5 Replace, where R 5 Selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl group may be substituted with a carboxyl group, a hydroxyl group, a sulfonyl group or a sulfonate group; Optional counterions may associate with the compound, and if present, said counterions may be selected from chloride ions, bromide ions, iodide ions, and 4-methylbenzenesulfonate ions; and fungicides The surfactant comprises at least one of the following: 6-((2-Butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide, having the following formula: 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 4-((6-((2-Butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula: ； 2-Butyloctyl 6-(dimethylamino)hexanoate N-oxide has the following formula: 6-((2-Butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, which has the following formula: and 6-((2-Butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 。 4. The formulation of claim 3, further comprising a co-surfactant and / or a carrier agent.

5. A herbicide formulation comprising: At least one surfactant of the following formula: Where R 1 and R 2 The components are independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxyl groups, hydroxyl groups, sulfonyl groups, or sulfonate groups; n is an integer from 2 to 5; R 3 It is C5-C 12 alkyl; R 4 It is C3-C 10 alkyl; The terminal nitrogen is optionally further converted to R 5 Replace, where R 5 Selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl group may be substituted with a carboxyl group, a hydroxyl group, a sulfonyl group or a sulfonate group; Optional counterions may associate with the compound, and if present, said counterions may be selected from chloride ions, bromide ions, iodide ions, and 4-methylbenzenesulfonate ions; and herbicide, The surfactant comprises at least one of the following: 6-((2-Butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide, having the following formula: 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 4-((6-((2-Butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula: ； 2-Butyloctyl 6-(dimethylamino)hexanoate N-oxide has the following formula: 6-((2-Butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, which has the following formula: and 6-((2-Butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 。 6. The formulation of claim 5, further comprising a second herbicide.

7. The formulation of claim 5, further comprising a water-insoluble solvent or water.

8. An insecticide formulation comprising: At least one surfactant of the following formula: Where R 1 and R 2 The components are independently selected from hydrogen, oxygen atoms, and C1-C6 alkyl groups, wherein the C1-C6 alkyl groups may be substituted with carboxyl groups, hydroxyl groups, sulfonyl groups, or sulfonate groups; n is an integer from 2 to 5; R 3 It is C5-C 12 alkyl; R 4 It is C3-C 10 alkyl; The terminal nitrogen is optionally further converted to R 5 Replace, where R 5 Selected from hydrogen, oxygen atoms and C1-C6 alkyl groups, wherein the C1-C6 alkyl group may be substituted with a carboxyl group, a hydroxyl group, a sulfonyl group or a sulfonate group; Optional counterions may associate with the compound, and if present, said counterions may be selected from chloride ions, bromide ions, iodide ions, and 4-methylbenzenesulfonate ions; and Insecticide, The surfactant comprises at least one of the following: 6-((2-Butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-amineonium iodide, having the following formula: 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 4-((6-((2-Butyloctyl)oxy)-6-oxohexyl)dimethylammonium)butane-1-sulfonate, having the following formula: ； 2-Butyloctyl 6-(dimethylamino)hexanoate N-oxide has the following formula: 6-((2-Butyloctyl)oxy)-6-oxohexane-1-amineonium chloride, which has the following formula: and 6-((2-Butyloctyl)oxy)-6-oxohexane-1-aminoonium 4-methylbenzenesulfonate, which has the following formula: 。 9. The formulation of claim 8, further comprising an antifoaming agent.

10. The formulation of claim 8 or claim 9, further comprising an antifreeze agent.

11. The formulation according to any one of claims 8 to 10, further comprising water.

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