Branched amino acid surfactants for agricultural products

Abstract

To provide formulations for agricultural products, such as pesticides, plant growth regulators, fungicides, herbicides and insecticides.SOLUTION: A formulation comprises at least one surfactant of the formula in the figure, and a pesticide. (R1 and R2 are independently selected from H, O and C1-C6 alkyl, where the C1-C6 alkyl may be substituted with carboxylates or the like; n is an integer from 2 to 5; R3 is C5-C12 alkyl; R4 is C3-C10 alkyl; the terminal nitrogen may be further substituted with R5; R5 is selected from among H, O and C1-C6 alkyl, where the C1-C6 alkyl may be substituted with carboxylates or the like; and an optional counterion may be associated with the compound.)SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Provisional Application No. 63 / 051,197, filed July 13, 2020, which is incorporated by reference in its entirety herein.

[0002] The present disclosure relates to branched surfactants for use on agricultural products. Such branched surfactants may include derivatives of amino acids, which derivatives have surface active properties. [Background technology]

[0003] Surfactants (molecules with surface active properties) are widely used in commercial agricultural formulations. These formulations may contain a wide variety of agricultural active agents, such as pesticides, plant growth regulators, fungicides, herbicides, and insecticides. Many such agricultural active agents may exhibit limited water solubility or may be prone to crystallization. Precipitation of the agricultural active agent may reduce efficiency. If the active agent becomes concentrated into a precipitate, it will be prevented from being evenly distributed when sprayed on a field. Thus, surfactants may be included in the formulation to improve the solubility, wetting, and spreadability of the active agent.

[0004] The surfactants may be uncharged, zwitterionic, cationic or anionic. In principle any surfactant class (e.g., cationic, anionic, nonionic, amphoteric) is suitable, but it is possible that a formulation may contain a combination of two or more surfactants from two or more surfactant classes.

[0005] Surfactants are often amphiphilic molecules with a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can adsorb at interfaces, for example, between two liquids, a liquid and a gas, or a liquid and a solid. In systems that contain relatively polar and relatively non-polar components, the hydrophobic tail preferentially interacts with the relatively non-polar component, while the hydrophilic head preferentially interacts with the relatively polar component. In the case of an interface between water and oil, the hydrophilic head group preferentially penetrates the water, while the hydrophobic tail preferentially penetrates the oil. When added to a water-gas interface, the hydrophilic head group preferentially penetrates the water, while the hydrophobic tail preferentially penetrates the gas. The presence of the surfactant disrupts at least some of the intermolecular interactions between the water molecules and replaces them with generally weaker interactions between at least some of the water molecules and the surfactant. This can also lower the surface tension and serve to stabilize the interface.

[0006] At high enough concentrations, surfactants can form aggregates that serve to limit the exposure of the hydrophobic tails to polar solvents. One such aggregate is a micelle. In a typical micelle, the molecules are arranged as a sphere, with the hydrophobic tails of the surfactant preferentially located inside the sphere and the hydrophilic heads of the surfactant preferentially located outside the micelle, where the heads preferentially interact with more polar solvents. The effect that a given compound has on surface tension and the concentration at which it forms micelles can serve as a determining property of the surfactant. Summary of the Invention

[0007] The present disclosure provides formulations for 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 Agents may be used as emulsifiers, wetting agents, dispersing agents, and / or agents that improve spreadability. Additionally, surfactants may be used as adjuvants and agents to control spin drift.

[0008] The present disclosure provides produce surfactants in the form of derivatives of amino acids with surface active properties. The amino acids can be naturally occurring or synthetic amino acids, or they are obtained via a ring-opening reaction of molecules such as lactams, e.g. caprolactam. The amino acids can be functionalized with different types of groups to form compounds with surface active properties. Characteristically, these compounds can have a low critical micelle concentration (CMC) and / or the ability to reduce the surface tension of liquids.

[0009] The present disclosure provides a pesticide or plant growth regulator formulation comprising a compound of Formula I:

[0010] [ka]

[0011] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5is selected from hydrogen, an oxygen atom and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counter ion may be associated with the compound, which counter ion, if present, may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate), a pesticide or plant growth regulator, and a water insoluble solvent.

[0012] The present disclosure provides a fungicide formulation comprising a compound of formula I:

[0013] [ka]

[0014] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, where C1-C6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, and The present invention further provides a formulation comprising at least one surfactant, wherein the counterion, if present, may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate, an optional co-surfactant, and an optional carrier agent, such as a solvent or solid carrier.

[0015] The present disclosure provides a herbicidal formulation comprising a compound of formula I:

[0016] [ka]

[0017] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, where C1-C6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, where the counterion, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate), one or more herbicides, a water-insoluble solvent, and water.

[0018] The present disclosure provides a pesticide formulation comprising a compound of formula I:

[0019] [ka]

[0020] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counter ion may be associated with the compound, which counter ion, if present, may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate), a pesticide, an optional antifoam agent, an optional antifreeze agent, and water.

[0021] The above mentioned and other features of the present disclosure and the means for achieving the same will become more apparent and better understood with reference to the following description of the embodiments taken in conjunction with the accompanying drawings. will be done. [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 shows a plot of surface tension versus concentration measured at pH=7, as described in Example 1B, where the Y-axis depicts surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts concentration (c) in millimolar (mM). [Figure 2A] FIG. 2A shows a plot of surface tension versus concentration measured at pH=7, as described in Example 2B, where the Y-axis depicts surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts concentration (c) in millimolar (mM). [Figure 2B] FIG. 2B is a plot of dynamic surface tension as change in surface tension versus time, as described in Example 2C, where the Y-axis depicts surface tension in milliNewtons per meter (mN / m) and the X-axis depicts surface elapsed time in milliseconds (ms). [Diagram 3]FIG. 3 shows a plot of surface tension versus concentration measured at pH=7, as described in Example 3B, where the Y-axis depicts surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts concentration (c) in millimolar (mM). [Figure 4A] FIG. 4A shows a plot of surface tension versus concentration measured at pH=7 as described in Example 4B, where the Y-axis depicts surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts concentration (c) in millimolar (mM). [Figure 4B] FIG. 4B is a plot of dynamic surface tension as change in surface tension versus time, as described in Example 4C, where the Y-axis depicts surface tension in milliNewtons per meter (mN / m) and the X-axis depicts surface elapsed time in milliseconds (ms). [Figure 5A] FIG. 5A shows a plot of surface tension versus concentration measured at pH=7 as described in Example 5B, where the Y-axis depicts surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts concentration (c) in millimolar (mM). [Figure 5B] FIG. 5B is a plot of dynamic surface tension as change in surface tension versus time, as described in Example 5C, where the Y-axis depicts surface tension in milliNewtons per meter (mN / m) and the X-axis depicts surface elapsed time in milliseconds (ms). [Figure 6A] FIG. 6A shows a plot of surface tension versus concentration measured at pH=7 as described in Example 6B, where the Y-axis depicts surface tension (γ) in milliNewtons per meter (mN / m) and the X-axis depicts concentration (c) in millimolar (mM). [Figure 6B] FIG. 6B is a plot of dynamic surface tension as change in surface tension versus time, as described in Example 6C, where the Y-axis depicts surface tension in milliNewtons per meter (mN / m) and the X-axis depicts surface elapsed time in milliseconds (ms). [Figure 7A]FIG. 7A shows a plot of surface tension versus concentration measured at pH=7 as described in Example 7B, where the Y-axis depicts surface tension (γ) in millinewtons per meter (mN / m) and the X-axis depicts concentration (c) in millimolar (mM). [Figure 7B] FIG. 7B is a plot of dynamic surface tension as change in surface tension versus time, as described in Example 7C, where the Y-axis depicts surface tension in milliNewtons per meter (mN / m) and the X-axis depicts surface elapsed time in milliseconds (ms). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] I. Definition As used herein, the phrase "within any range using these endpoints" literally means that any range may be selected from any two of the values ​​listed before such phrase, regardless of whether the values ​​are at the lower end of the recitation or the values ​​are at the upper end of the recitation. For example, a pair of values ​​may be selected from two lower values, two upper values, or a lower value and an upper value.

[0024] As used herein, the term "alkyl" means either a saturated carbon chain which may be a straight chain or branched chain.

[0025] As used herein, the phrase "surface active" means that the associated compound is capable of lowering the surface tension of the medium in which it is at least partially dissolved and / or the interfacial tension with other phases and thus may be at least partially adsorbed at liquid / vapor and / or other interfaces. The term "surfactant" may be applied to such compounds.

[0026] With respect to non-strict terminology, the terms "about" and "approximately" can be used interchangeably to refer to measurements that include the stated measurement and also include any measurements that are reasonably close to the stated measurement. Measurements that are reasonably close to the stated measurement deviate from the stated measurement by a reasonably small amount that is understood and easily ascertained by a person skilled in the relevant industry. Such deviations may be due to measurement errors or fine-tuning made, for example, to optimize performance. In cases where it is determined that a person skilled in the relevant industry would not be able to easily ascertain values ​​for such reasonably small differences, the terms "about" and "approximately" can be understood to mean plus or minus 10% of the stated value.

[0027] The present disclosure provides agricultural formulations such as pesticides, plant growth regulators, fungicides, insecticides and herbicides.

[0028] II. Pesticide and Plant Growth Regulator Formulations Agricultural active agents, such as pesticides, have traditionally been provided to end users in various concentrated forms that are diluted in water or other suitable media that end users dilute into ready-to-use formulations. Such concentrated forms include solid formulations, such as powders, and liquid formulations. In many applications, liquid formulations are preferred because they avoid the problems of toxic powder drift and slow dissolution in diluents.

[0029] Liquid concentrate formulations include so-called emulsion concentrates and soluble liquid concentrates. Emulsion concentrates contain a pesticide, a water-insoluble solvent and an emulsifier, which when added to water, spontaneously or after mixing, forms an oil-in-water emulsion, with the agricultural active being mainly present in the emulsion droplets. This type of concentrated formulation is particularly suitable for agricultural actives that are water-insoluble / have low water solubility and whose concentrations recommended for ready-to-use formulations exceed the solubility of the agricultural active.

[0030] The present disclosure provides pesticide or plant growth regulator formulations with high concentrations of agricultural active agents suitable for long-term storage and delivery to an end user, who ultimately treats the plant by contacting the plant with an agricultural formulation prepared from the concentrated pesticide formulation described herein.

[0031] The pesticidal formulations of the present disclosure comprise an agricultural active agent (a pesticide or a plant growth regulator), It may include one or more surfactants or co-surfactants selected from one or more surfactant classes, and a water insoluble solvent.

[0032] 1. Pesticides The term "pesticide" as used herein is well known in the art and described by the Environmental Protection Agency (EPA) at least in the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA), in the Insecticide and Environmental Pesticide Management section (7 USC §136(u)), in the Code of Federal Regulations (CFR) on "Environmental Protection", and in EPA regulations at 40 CFR §152.3. A pesticide is typically recognized in the art as a substance used to prevent, exterminate, repel, control, and / or ameliorate any pest. A pest 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 on or within a living human or other living animal. In other words, the term "pest" typically does not include any organism that infects or makes a human or animal sick. Additionally, the term "pesticides" as used herein typically does not include any human or animal drugs or pharmaceuticals, any articles that are "animal drugs" as defined in the art, any liquid sterilants applied to devices used on the human body, and / or any products intended for use against fungi, bacteria, viruses, or other microorganisms in or on living humans or living animals. Additionally, pesticides of the present disclosure typically do not include drugs or pharmaceuticals used to control disease in humans or animals (e.g., livestock and pets).

[0033] As used herein, the term "plant growth regulator" refers to a compound that, through a physiological action, accelerates or retards the rate of growth or maturation, or otherwise alters the behavior of ornamental or crop plants or their products.

[0034] In particular, the pesticides and plant growth regulators contemplated for use in the present 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, pyridine carboxylic acids, neonicotinides, amidines, organic phosphates and pyrethroids.The pesticides may have a water solubility of 1 g / L or less.

[0035] In concentrated formulations of the present disclosure, the pesticide or plant growth regulator may be present in an amount of about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or more, or about 25 wt.% or less, about 30 wt.% or less, about 35 wt.% or less, about 40 wt.% or less, or within any range using these endpoints, based on the weight of the composition.

[0036] 2. Surfactants The pesticide formulation of the present disclosure comprises one or more surfactants, also referred to as surfactant system. The surfactant system is included to emulsify the composition and / or act as an adjuvant. The surfactant system comprises at least one surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, and optionally comprises at least one other surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof. Such surfactant should be physically and chemically compatible with the essential ingredients described herein, or should not otherwise unduly impair the stability, aesthetics or performance of the product.

[0037] Suitable surfactants for use in the pesticide formulations of the present disclosure have Formula I:

[0038] [ka]

[0039] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, which, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate.

[0040] Specifically, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-7 described herein.

[0041] The concentration of the surfactant system in the pesticide formulation may range from about 20 wt.% or more, to about 30 wt.% or more, to about 40 wt.% or more, or to about 50 wt.%, to about 60 wt.%, to about 70 wt.%, or to about 80 wt.%, or any of the ranges using these endpoints, based on the weight of the composition.

[0042] 3. Water-insoluble solvents The pesticidal formulation of the present disclosure may include a water-insoluble solvent. A solvent is considered water-insoluble if its water solubility at 20° C. is about 10 g / L water or less, about 5 g / L water or less, about 1 g / L water or less, or about 0.1 g / L water or less.

[0043] 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.

[0044] 4. Other Additives The pesticide formulation may contain other additives such as additional surfactants, water, thickeners, deposition enhancers, drift control agents, salts, stabilizers, penetrants, spreading agents, wetting agents, builders, etc. agents, extending agents, emulsifiers, dispersants, suspending agents, plant penetrants, translocators, oils, activators, foliar nutrients, compatibilizers, drift retardants, foam retardants, buffers, inverting agents, soil penetrants, stabilizers, UV screening agents, feeding stimulants, detergents, settling agents, binders, liquid carriers, dry carriers such as attapulgite, kaolinite, vermiculite, starch polymers, corncob and combinations thereof. Pesticide formulations may contain additional chemical compounds that are not pesticides, such as activators, feeding deterrents, stain inhibitors, attractants, sterilants, disinfectants, fumigants, pheromones, repellents, defoliants, drying agents, insect growth regulators, plant ... Length regulators, synergistic additives, adjuvants and combinations thereof may also be included.

[0045] These additives may be independently present in the pesticide formulation in amounts of about 0 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, or about 20 wt.% or less, about 25 wt.% or less, about 30 wt.% or less, or within any range using these endpoints.

[0046] Additional surfactants, such as additional anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, may be present in concentrated compositions at concentrations of about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or more, or about 25 wt.% or less, about 30 wt.% or less, about 35 wt.% or less, about 40 wt.% or less, by weight of the composition, or within any range using these endpoints.

[0047] Water may be present in the concentrated composition at a concentration of about 0 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 20 wt.% or more, about 30 wt.% or more, or about 35 wt.% or less, about 45 wt.% or less, about 55 wt.% or less, about 65 wt.% or less, based on the weight of the composition, or within any range using these endpoints.

[0048] Polymers may be included in the concentrated compositions as thickeners, deposition enhancers, or drift control agents. Suitable polymers may include polysaccharide ethers and synthetic polymers.

[0049] Water-soluble organic solvents, such as glycol ethers, e.g., butyl diglycol, N-formyl-morpholine, shorter aliphatic alcohols, propylene carbonate, and the like, may be present in the pesticide formulation in a weight ratio of at most 1:2 water-soluble organic solvent:water-insoluble organic solvent.

[0050] 5. Preparation method The method includes combining a surfactant system, a pesticide, and optionally a solvent. This step may also include adding any of the additives described above. The aforementioned components and compounds may be added to each other in one or more of any order, in any amount, and in one or more separate steps, for example in whole or in part.

[0051] 6.How to use The concentrated pesticidal formulations of the present disclosure may be in liquid form at room temperature and atmospheric pressure in which the agriculturally active ingredients are solubilized.

[0052] Concentrated pesticidal formulations are intended to be mixed with an aqueous medium, typically tap water, before final use. The concentrated compositions are added to the tank before, at the same time as, or after the aqueous medium (water) is added to the tank. The concentrated pesticidal compositions are then diluted to the appropriate concentration of agriculturally active ingredient.

[0053] The amount of water in the diluted pesticidal formulations of the present disclosure can be from about 75 wt.% or more, to about 90 wt.% or more, to about 99 wt.% or more, or to about 99.9 wt.% or more, based on the total weight of the diluted composition, ultimately depending on the amount of water required to dilute the agriculturally active ingredient in the concentrated pesticidal formulations of the present disclosure to the desired concentration in the ready-to-use composition.

[0054] When mixed with an aqueous medium and diluted therein, the agriculturally active ingredient distributes evenly throughout the aqueous medium in the form of a solution or fine emulsion and can be diluted substantially without any crystal growth occurring.

[0055] Plants can be treated with the diluted, ready-to-use pesticidal formulation by contacting the plant to be treated with the diluted composition by any means conventionally used. The term "plant" as used herein refers to the stems, leaves and fruits of plants that can be seen above ground, as well as the roots and seeds. The amount of active ingredient that contacts the plant is preferably sufficient for the active ingredient to exert its pesticidal or plant growth regulating activity, i.e., an effective amount.

[0056] III. Fungicide Formulations The present disclosure provides a fungicide formulation. The fungicide formulation can be in solid or liquid form. The fungi for which the formulation can be used include: Basidiomycetes, Ascomycetes, Adalomycetes or Fungi imperfecti-type fungi, especially Heifers, powdery mildew, eyespot, fusarioses, Fusarium roseum, Fusarium nivale, net blotch, leaf spot, Septoria spot, and sin Rhizoctonia. These harmful fungi can cause disease in most vegetables and plants, but especially in cereals such as wheat, barley, rye, oats or hybrids thereof, as well as rice and corn.

[0057] The 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 agent, such as a solvent or solid carrier.

[0058] 1. Fungicides The fungicide formulation comprises a fungicide. Suitable fungicides include, but are not limited to, azoxystrobin, benalaxyl, carbendazim, chlorothalonil, cupfer, cymoxanil, cyproconazol, diphenoconazol, dinocap, epoxyconazol, fluazinam, flusilazole, flutriafol, forper, fosetyl alumnium, kresoxim methyl, hexaconazol, mancozeb, metalaxyl, metconazole, myclobutanil, ofurase, triphenyltin hydroxide, prochloraz, pyrimethanil, soufre, tebuconazol and tetraconazol and mixtures thereof. Suitable herbicides include alachlor, aclonifen, acetochlor, amidosulfuron, aminotriazol, atrazine, bentazon, bifenox, bromoxyl octanoate, bromoxynil, clethodim, chlodinafop-propargyl, chloridazon, chlorsulfuron, chlortoluron, clomazone, cycloxydim, desmedipham, dicamba, dicyclofop-methyl, diurea, difluphenicanil, dimethenamid ... imithenamid, etofumesat, fluazifop, fluazifop-p-butyl, fluorochloridon, fluroxypyr, glufosinate, glyphosate, haloxyfop-R, ioxynil octanoate, isoproturon, isoxaben, metamitron, metazachlor, metolachlor, metsulfuron-methyl, nicosulfuron Examples of suitable antiseptics include, but are not limited to, flusulfon, norflurazon, oryzalin, oxadiazon, oxyfluorphen, paraquat, pendimethalin, phenmedipham, phenoxyprop-p-ethyl, propaquizafop, prosulfocarb, quizalofop, sulcotrione, sulphosat, terbutylazin, triasulfuron, triclopyr, trifluralin, and triflusulfon-methyl, which may be used individually or in admixture with one another.

[0059] The amount of fungicide can be about 1 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 20 wt.% or more, about 30 wt.% or more, about 40 wt.% or more, or about 50 wt.% or less, about 60 wt.% or less, or about 70 wt.% or less, about 80 wt.% or less, about 90 wt.% or less, based on the total weight of the liquid fungicide formulation, or any combination of ranges using these endpoints.

[0060] 2. Surfactants The fungicide formulation of the present invention comprises one or more surfactants, also referred to as surfactant system. The surfactant system may be used as a dispersing agent or wetting agent. The surfactant system may also be used as an emulsifier component to form a stable emulsion of the liquid fungicide form when prepared for agricultural use. The emulsifier component may also be used to form a stable emulsion concentrate. The surfactant system comprises at least one surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, and optionally at least one other surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof.

[0061] Surfactants suitable for use in the fungicidal formulations of the present disclosure have Formula I:

[0062] [ka]

[0063] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, which, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate.

[0064] Specifically, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-7 described herein.

[0065] The total amount of one or more surfactants in the fungicidal formulation can be about 1 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, or about 15 wt.% or less, about 20 wt.% or less, about 25 wt.% or less, about 30 wt.% or less, about 35 wt.% or less, or within any range using these endpoints.

[0066] 3. Co-emulsifiers or co-surfactants The fungicide composition may include an optional co-emulsifier or co-surfactant. The optional co-surfactant may be an anionic surfactant and / or a non-ionic surfactant, and may include the surfactants of the present disclosure, as well as others. For example, the anionic surfactant may include the surfactants of the present disclosure or any known in the art, and may include the alkali, alkaline earth or ammonium salts of fatty acids, such as potassium stearate, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates or iso-alkyl sulfonates, alkyl naphthalene sulfonates, alkyl methyl ester sulfonates, acyl glutamates, alkyl sulfosuccinates, sarcosine salts, such as sodium lauroyl sarcosine or taurine salts, and combinations thereof. The anionic surfactant may be present in an amount in the emulsifier component.

[0067] Nonionic emulsifiers may include surfactants of the present disclosure or any 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 fatty ethoxylates, glycerol esters, such as glycerol monostearate, fatty alcohol alkoxylates and oxoalcohol 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 sorbitan fatty acid esters (e.g., sorbitan monooleate, and sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkyl gluconamides, alkyl methyl sulfoxides, alkyl dimethyl phosphine oxides, such as tetradecyl dimethyl phosphine oxide, and combinations thereof.

[0068] 4. Carrier Agent The fungicide formulation of the present disclosure may contain a carrier agent. The term "carrier" as used herein refers to a material in natural or synthetic, organic or inorganic form that, when combined with the active ingredient, facilitates application to plants, seeds or soil. Thus, this carrier is usually inert, but must also be agriculturally acceptable, especially to the plants to be treated. Carriers can be solids (such as clays, natural or synthetic silicates, silicon dioxide, resins, waxes or solid fertilizers), or liquids (such as water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.).

[0069] 5. Other Additives Fungicide formulations may contain other additives such as stabilizers, penetrants, spreading agents, wetting agents, builders, extenders, emulsifiers, dispersants, suspending agents, plant penetrants, translocators, oils, activators, foliar nutrients, compatibilizers, drift retardants, antifoam agents, buffers, inverting agents, soil penetrants, stabilizers, UV filters, feeding stimulants, detergents, settling agents, binders, liquid carriers, dry carriers such as attapulgite, kaolinite, vermiculite, starch polymers, corncobs, and combinations thereof. Pesticide formulations may also contain additional chemical compounds that are not pesticides, such as activators, feeding deterrents, stain inhibitors, attractants, sterilizers, disinfectants, fumigants, pheromones, repellents, defoliants, desiccant agents, insect growth regulators, plant growth regulators, synergistic additives, adjuvants, and combinations thereof.

[0070] These additives may be independently present in the pesticide formulation in amounts of about 0 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, or about 20 wt.% or less, about 25 wt.% or less, about 30 wt.% or less, or within any range using these endpoints.

[0071] 6.Fungicidal emulsion The liquid fungicidal formulation may be added to water or another solvent to form an agricultural emulsion at the time of sale and / or use. Typically, a properly formed agricultural emulsion is milky white in color, blooms (i.e. forms) naturally, and has sufficient stability for effective use. However, the fungicidal emulsions of the present disclosure are not limited to such parameters and may have other characteristics indicative of proper emulsion formation.

[0072] The present disclosure provides an aqueous fungicide formulation comprising the aforementioned fungicide formulation and water. The liquid fungicide formulation may be combined with water in the spray tank or in a separate tank prior to addition to the spray tank. For example, the liquid fungicide formulation may be added to a separate container and / or spray tank with or without water. The term "diluted" describes that the agricultural liquid fungicide formulation comprises water.

[0073] Water in the diluted fungicidal formulation may be present in an amount of about 5 wt.% or more, about 10 wt.% or more, about 20 wt.% or more, about 30 wt.% or more, about 40 wt.% or more, about 50 wt.% or more, or about 60 wt.% or less, about 70 wt.% or less, about 80 wt.% or less, about 90 wt.% or less, about 99 wt.% or less, about 99.5 wt.% or less of the diluted fungicidal formulation, or within any range using these endpoints.

[0074] The fungicide may be present in the diluted fungicidal formulation in an amount within a range from about 0.00001 wt.% or more, to about 0.0001 wt.% or more, to about 0.001 wt.% or more, to about 0.01 wt.% or more, to about 0.1 wt.% or more, to about 1 wt.% or more, or to about 2 wt.% or less, to about 4 wt.% or less, to about 6 wt.% or less, to about 8 wt.% or less, to about 10 wt.% or less, or using any of these endpoints.

[0075] The fungicide may be present in an amount of (or equal to) about 100 g / hectare or more, about 200 g / hectare or more, about 300 g / hectare or more, about 400 g / hectare or more, about 500 g / hectare or more, or about 600 g / hectare or less, about 700 g / hectare or less, about 800 g / hectare or less, about 900 g / hectare or less, about 1000 g / hectare or less, or any range using these endpoints.

[0076] 7. Emulsion concentrate The present disclosure provides fungicidal emulsions that may be formed using emulsion concentrates (also known in the art as "EC"). The liquid fungicidal compositions described above may be further described as EC or may not be EC. The emulsion concentrates may be liquids having a viscosity of about 1 cps or more, 20 cps or more, 40 cps or more, 60 cps or more, 80 cps or more, 100 cps or more, 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 about 200 cps or less at 25°C. Without intending to be bound by any particular theory, it is believed that a viscosity of about 200 cps or less at 25°C promotes bloom and efficient formation of the emulsion when emulsion concentrates are used.

[0077] The emulsion concentrate itself may be anhydrous, i.e., free of water. The emulsion concentrate may contain water. The emulsion concentrate may contain water in an amount of 5 wt.% or less, 2.5 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less. The emulsion concentrate may contain less than 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 parts by weight of water per 100 parts by weight of the emulsion concentrate. The emulsion concentrate is a single oily, e.g., hydrophobic, phase that does not contain water. When added to water or another solvent, the emulsion concentrate may form a milky white agricultural emulsion that blooms and shows little to no phase separation, as described in more detail below.

[0078] The emulsion concentrate may include a single phase. In other words, the emulsion concentrate may not include a separate non-polar phase and a separate polar phase, but instead may include a single phase including the active ingredient (fungicide), surfactant system, optional co-surfactant and / or optional water-insoluble solvent. It is recognized that the single phase may include partial phase separation, but typically does not include total phase separation. At low temperatures, phase separation may occur. The emulsion concentrate may include or be described as including the aforementioned surfactant system and fungicide (e.g., without the optional solvent and / or without the optional co-surfactant).

[0079] 8. Solid formulation By solid form compositions, mention may be made of powders or dispersions suitable for scattering, in particular extruded, extruded or extruded particulate compositions.Solid formulations may be formed through impregnation of a carrier powder with the active agent or by granulating the powder.

[0080] The amount of active agent in these granular compositions can be about 1 wt.% or more, 10 wt.% or more, 20 wt.% or more, 30 wt.% or more, or about 40 wt.% or less, about 50 wt.% or less, about 60 wt.% or less, about 70 wt.% or less, about 80 wt.% or less, or within any range using these endpoints.

[0081] Wettable powder formulations (or spray powders) may contain the active agent in an amount of about 20 wt.% or more, about 30 wt.% or more, about 40 wt.% or more, or about 50 wt.% or more, about 60 wt.% or less, about 70 wt.% or less, about 80 wt.% or less, about 90 wt.% or less, about 95 wt.% or less, or within any range using these endpoints.

[0082] Wettable powder formulations may include a wetting agent, such as a surfactant, and the formulation may include a surfactant of the present disclosure in an amount of about 0 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, or about 3 wt.% or less, about 4 wt.% or less, about 5 wt.% or less, or within any range using these endpoints.

[0083] Wettable powder formulations may include a dispersant, such as a surfactant, and the formulation may include a surfactant of the present disclosure in an amount of about 3 wt.% or more, about 4 wt.% or more, about 5 wt.% or more, about 6 wt.% or more, or about 7 wt.% or less, about 8 wt.% or less, about 9 wt.% or less, or about 10 wt.% or less, or within any range using these endpoints.

[0084] The wettable powder formulation may include a solid carrier, the formulation may include any solid carrier known in the art in an amount of about 0 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, about 3 wt.% or more, about 4 wt.% or more, about 5 wt.% or more, or about 6 wt.% or less, about 7 wt.% or less, about 8 wt.% or less, about 9 wt.% or less, about 10 wt.% or less, or within any range using these endpoints.

[0085] The wettable powder formulation may contain one or more stabilizers and / or other additives, such as pigments, colorants, penetrants, adhesion promoters or anti-caking agents.

[0086] To produce these wettable powder formulations or sprayable powders, the active agent(s) are intimately mixed with other ingredients in a suitable mixing device, and the resulting mixture is ground in a mill or other suitable grinding equipment. Thus, sprayable powders with wettable and suspendable properties are obtained. Thus, they can be suspended in water at any concentration, and these suspensions are particularly useful, in particular for the treatment of seeds.

[0087] 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 or sprayable powders.

[0088] Dispersible granular compositions, similar to wettable powder formulations, can be prepared by agglomeration in a suitable granulating system to give powder compositions.

[0089] IV. Herbicide Formulations The present disclosure further provides herbicide formulations that can be applied to plants in a herbicidally effective amount to effectively control one or more plant species in one or more of the following genera without restriction: Abutilon, Amaranth, Artemisia, Milkweed, Avena, Axonops, Borrelia, Brachiaria, Brassica, Bromelia, Chenopodium, Cirsium, Commelina, Field mustard, Cyperus, Cyperus, Digitaria, Echinochloa, and Goosegrass. The genera are: Ewes, Equisetum, Geranium, Helianthus, Imperata, Ipomoea, Brussels spp., Cornus spp., Malva spp., Oryza spp., Ottochloa, Millet, Paspalum spp., Reed canary, Phragmites spp., Polygonum spp., Portulaca spp., Bracken spp., Pueraria spp., Rubus spp., Setaria spp., Scutellaria spp., Sorghum spp., Triticum spp., Cattail spp., Gorse spp., Xanthium spp. and Maize spp.

[0090] The herbicidal formulations of the present disclosure may include a herbicide, as well as an optional second herbicide, one or more surfactants selected from one or more surfactant classes, a water-insoluble solvent, and water.

[0091] 1. Herbicides The herbicide formulation of the present disclosure may include a herbicide or a water-soluble salt thereof. 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.

[0092] The water-soluble salts of the herbicides may include salts containing one or more cations selected from the class of organic ammonium cations, which may have from 1 to about 12 carbon atoms, such as organic ammonium cations including, for example, isopropylammonium, diglycolammonium (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).

[0093] Additionally, water-soluble salts of the herbicides may include salts containing one or more cations selected from inorganic cations, such as sodium and / or potassium.

[0094] In the case of an acidic herbicide, e.g., an auxin herbicide, the herbicide can be present in the herbicide formulation in an amount of about 100 grams 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 within any range using these endpoints.

[0095] Some herbicidal actives described herein do not contain acid-type functional groups, and the terms "acid equivalent" and "on an acid equivalent basis" for these active ingredients are not accurate in describing the amount of the second herbicide present. In general, in such instances, the terms "active ingredient" or "on an active ingredient basis" can be used to describe the amount of the second herbicide active ingredient present. For example, grams active ingredient per liter (g ai / L) can be used instead of grams acid equivalent per liter (g ae / L), or grams active ingredient per kilogram (g ai / kg) can be used instead of grams acid equivalent per kilogram (g ae / kg) if the active ingredient does not have an acid equivalent.

[0096] 2. Optional Second Herbicide Suitable second herbicides include 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, aridochlor, acetochlor, acifluorfen, aclonifen, alachlor, alloxydim, arorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor esters, aminopyralide esters, amipropionate ... s-methyl, amitrole, anilofos, anisrone, ashram, atraton, atrazine, azafenidine, azimsulfuron, aziprothrin, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazon, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, viranaphos, bispyribac, Bromacil, bromobonyl, bromobutide, bromofenoxime, bromoxynil, bromopyrazone, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butyrate, cafenstrole, cafenstrole, cambendichlor, carbasulam, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlormethoxyphen, chloramben, chloranocryl, chlorradifop, chlorazine, chlorbromuron, Chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, clomeprop, cloprop, cloproxydim, clopyralid ester,Cloransulam, CPMF, CPPC, Cledazin, Cumiluron, Cyanatrin, Cyanazine, Cycloate, Cyclosulfamuron, Cycloxydim, Cycluron, Cyhalofop, Cyperquat, Cyprazine, Cyprazole, Cypromide, Dimron, Dalapon, Dazomet, Delachlor, Desmedipham, Desmetrin, Diallate, Dicambaester, Dichlobenil, Dichloralurea, Dichlor Mate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamcort, diethyl, diphenopentene, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinitramine, dinofenate, dinoprop, P, dinosamu, dinoseb, dinoterb, diphenamide, dipropetrine, diquat, disul, dithiopyr, diuron, DMPA, DNOC, EBEP, eglinadin, endothal, epronaz, epronaz, EPTC, ervon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyphene, ethoxysulfuron, ethinofen, ethonipromide, ethonipromide, etobenzanide, EXD, fenasulam, fenasulam, fenasulam, fenasulam Noprop, Fenoxaprop, Fenoxaprop-P, Fenoxasulfone, Fenteracol, Fentiaprop, Fentrazamide, Fenuron, Flamprop, Flamprop-M, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazolate, Flucarbazone, Flucetosulfuron, Fluchloralin, Flufenacet, Flufenican, Flufenpyr, Flumetsulam, Flumezin, Flumicrac, Flumioxazin, Flumipropine, Fluometuron, Fluorodifen, Fluoroglycofen , fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, fluorochloridone, non-liquid fluroxypyr ester, fluroxypyr-meptyl, flurtamone, fluthiacet, fomesafen, fomesafen, foramsulfuron, fosamine, furyloxyfen, glyphosate, halauxfen, halauxfen-methyl, halosafen, halosafen, halosulfuron, hal Roxyzine, Haloxyfop, Haloxyfop-P, Hexazinone, Imazamethabenz, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Indanofan, Indaziflam, Iodobonyl, Iodosulfuron, Ioxynil, Ipazine, Ipfencarbazone, Iprimidum, Isocarbamide, Isosil, Isomethiozine, Isonorurone, Isopolynate, Isoproparin, Isoproturon, Isouron, Isoxaben, Isoxachlorthor, Isoxaflutole, Isoxapyrifop, Carbutilate,Ketospiradox potassium, lactofen, lenacil, linuron, MCPA ester, MCPA-thioethyl, MCPA-EHE, MCPB ester, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamifop, metamitron, metazachlor, metazosulfuron, metoflurazone, methabenzthiazuron, methaproparin, methazole, methiobencarb, methiozoline, methiouron, methionone, methoprothrin, meto ... Tildaimuron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, methoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monolinuron, monuron, morphamcort, naproanilide, napropamide, naptalam, nebulon, nicosulfuron, nipiraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, norlon, OCH, orbencarb, orthosulfamuron, oryzalin, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, Oxasulfuron, oxaziclomefone, oxyfluorfen, parafluoron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamide, phenisofam, phenmedipham, phenmedipham-ethyl, fenobenzuron, picloram ester, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, procyazin, prodiamine, prodiamine, proflurazole, profluralin, profoxidi , proglinadin, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfarin, prosulfocarb, prosulfuron, proxan, purinachlor, pidanone, pyraclonil, pyraflufen, pyrasulfotole, pyrazolinate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyrichlor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan,Pyrithiobac, Pi, pyrosulfotole, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamide, quizalofop, quizalofop-P, rodetanil, rimsulfuron, saflufenacil, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, sulcotrione, sulfurate, sulfentrazone, sulfometuron, sulfosulfuron, sulglicapin, swep, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoroone, thenylchlor, thiazafluron, The benzodiazepine may be selected from, but is not limited to, thiazopyr, non-liquid triclopyr esters, thidiazimine, thidiazuron, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, thiocarbazil, tioclorim, topramezone, tralkoxydim, triallate, triasulfuron, triaziflam, tribenuron, tricamba, tridiphan, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, triphop, trifopsim, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, xylachlor, and mixtures and derivatives thereof.

[0097] The second herbicide, when used, is present in an amount of about 0 g ae / L or more, 0.1 g ae / L or more, 10 g ae / L or more, 50 g ae / L or more, 100 g ae / L or more, or 200 g ae / L or less, about 300 g ae / L or less, about 400 g ae / L or less, or within any range using these endpoints.

[0098] Some second herbicide actives described herein do not contain acid-type functional groups, and for these active ingredients, the terms "acid equivalent" and "acid equivalent basis" are not accurate to describe the amount of the second herbicide present. Generally, in such instances, the terms "active ingredient" or "active ingredient basis" can be used to describe the amount of the second herbicide active ingredient present. For example, grams active ingredient per liter (g ai / L) can be used instead of grams acid equivalent per liter (g ae / L), or grams active ingredient per kilogram (g ai / kg) can be used instead of grams acid equivalent per kilogram (g ae / kg) if the active ingredient does not have an acid equivalent.

[0099] 3. Surfactants Surfactants suitable for use in the herbicide formulations of the present disclosure have Formula I:

[0100] [ka]

[0101] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, where C1-C6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counter ion may be associated with the compound, and When present, counterions include one or more surfactants and / or co-surfactants, which may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate.

[0102] Specifically, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-7 described herein.

[0103] The herbicidal formulation may contain one or more surfactants in an amount of about 0 wt.% or more, about 2 wt.% or more, about 4 wt.% or more, about 6 wt.% or more, about 8 wt.% or more, or about 10 wt.% or less, about 12 wt.% or less, about 14 wt.% or less, about 16 wt.% or less, or within any range using these endpoints.

[0104] 4. Water-insoluble solvents Suitable water-insoluble, immiscible organic solvents include those derived or made from natural non-petroleum sources, such as plants and animals, and vegetable oils, seed oils, animal oils, and the like, such as N,N-dimethylcaprylamide (N,N-dimethyloctanamide), N,N-dimethylcapramide (N,N-dimethyldecanamide) and mixtures thereof, which are available under the names Agnique® AMD 810 and Agnique® AMD 10 from BASF Corp. (Florham Park, NJ), Genegen® 4166, Genegen® 4231 and Genegen® 4296 from Clariant (Charlotte, NC), Hallcomid M-8-10 and Hallcomid M-10 from Stepan (Northfield, Ill.), and Amid® from AkzoNobel (Chicago, Ill.). It is commercially available as DM10 and DM810. Further examples of naturally derived organic solvents include morpholine amides of caprylic / capric fatty acids (C8 / C10), commercially available as JEFFSOL® AG-1730 solvent from Huntsman International LLC (The Woodlands, Tex.).

[0105] Other suitable water-insoluble solvents are aromatic hydrocarbons, mixed naphthalene and alkyl naphthalene fractions, aromatic solvents, especially alkyl-substituted benzenes, such as xylene or propylbenzene fractions; C1-C6 esters of fatty acids derived from plants, seeds or animal oils, such as methyl caproate, methyl caprylate, methyl caprate, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, and the like; ketones, such as isophorone and trimethylcyclohexanone (dihydroisophorone); acetates, such as methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl acetate; and the like, as described by Huntsman (The Journal of Chemical Society of America). and cyclic alkyl carbonates, such as propylene carbonate and butylene carbonate, also available as JEFFSOL® alkylene carbonates from The Woodlands, Tex., and dibutyl carbonate from Huntsman, with any of the water-immiscible organic solvents described herein. The water-insoluble solvent may be present in the herbicidal formulation in an amount of about 0 wt.% or more, about 10 wt.% or more, about 20 wt.% or more, or about 30 wt.% or less, about 40 wt.% or less, about 50 wt.% or less, or within any range using these endpoints.

[0106] 5.Water Water is present in the herbicidal formulations of the present disclosure and can serve as both an aqueous solvent and a carrier for the ingredients in the described compositions.

[0107] The herbicidal formulation of the present disclosure may be applied at a concentration of at least about 200 g / L of water, at least about 300 g / L, at least about 400 g / L The composition may comprise an amount of about 500 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 within any range using these endpoints.

[0108] 6. Other Additives The herbicidal formulation may contain one or more additional compatible raw materials. These additional raw materials may include, for example, one or more pesticides or other raw materials, which may be dissolved or dispersed in the composition, and may be selected from acaricides, algaecides, feeding deterrents, birdicides, bactericides, bird repellents, sterilants, defoliants, dry blighters, disinfectants, fungicides, herbicide toxicity safeners, herbicides, insect attractants, insecticides, insect repellents, mammal repellents, mating disruptants, molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, information materials, synergistic additives, and viricides. Any other additional ingredients with functional utility may also be included in these compositions, such as antifoam agents, antimicrobial agents, buffers, corrosion inhibitors, dispersants, dyes, fragrances, freezing point depressants, neutralizing agents, odorants, penetration aids, sequestering agents, spray drift control agents, spreading agents, stabilizers, sticking agents, viscosity modifying additives, water soluble solvents, and the like.

[0109] When the herbicidal formulations described are used in combination with additional active ingredients, e.g., herbicidal active ingredients, the compositions described herein can be combined with the other active ingredient(s) as a premix concentrate, tank-mixed with the other active ingredient(s) in water for spray applications, or applied sequentially with the other active ingredient(s) in a separate spray application.

[0110] 7. Preparation method The herbicide formulations of the present disclosure may be prepared by: 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 with sufficient mixing to form a clear solution; and 3) optionally adding any additional compatible active or inactive ingredients.

[0111] Alternatively, the herbicide formulation of the present disclosure may be prepared by: 1) providing a second herbicide that is 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 a water-soluble salt of the herbicide in water with sufficient mixing to form a clear solution; and 3) optionally adding any additional compatible active or inactive ingredients.

[0112] Suitable water-compatible ingredients that may be added to the herbicide formulation include, but are not limited to, water-soluble or water-insoluble dispersing surfactants, such as the surfactants of the present disclosure, water-insoluble active ingredients, and, optionally, other inert ingredients, such as pH buffers, wetting agents, antifreeze agents, defoamers, and biocides.

[0113] 8. How to Use The aqueous herbicidal formulations described herein can be optionally diluted in aqueous spray mixtures for agricultural applications, such as controlling weeds in crop fields or lawns. Such herbicidal formulations are typically diluted with an inert carrier, such as water, before application. For example, diluted herbicidal formulations that are typically applied to weeds, weed locations, or locations where weeds may eventually appear can contain agricultural active agents (herbicides) in amounts of about 0.0001 wt.% or more, about 0.001 wt.% or more, about 0.01 wt.% or more, about 0.1 wt.% or more, about 1 wt.% or more, or about 2 wt.% or less, about 3 wt.% or less, about 4 wt.% or less, or about 5 wt.% or less, or within any range using these endpoints. The herbicidal formulations of the present disclosure can be applied to weeds or locations, for example, by using conventional ground or aerial sprayers, by adding to irrigation water, and by other conventional means known to those skilled in the art.

[0114] The herbicide formulations of the present disclosure may be used to control undesirable vegetation in crops that possess single, multiple or stacked genomic traits that confer resistance to one or more herbicide chemicals with single or multiple modes of action, and / or inhibitors.

[0115] V. Insecticide Formulations The present disclosure also provides formulations of the pesticides. Such formulations can be in liquid or solid form, such as emulsifiable concentrates, oil-in-water (O / W) emulsions, suspension concentrates, and wettable powders.

[0116] The pesticide formulation may include a pesticide, one or more surfactants selected from one or more surfactant classes, an optional defoamer, an optional antifreeze agent, and water.

[0117] 1. Insecticides Suitable insecticides may include one or more pyrethroids, such as synthetic pyrethroids; organophosphate compounds, such as chlorpyrifos-ethyl, chlorpyrifos-methyl, pirimiphos-methyl, fenitrothion; phenyl ethers, such as pyriproxyfen; benzoylureas, such as flufenoxuron; carbamates, such as fenoxycarb, carbosulfan; nicotinoids, such as acetamiprid; pyridinecarboxamides, such as flonicamid; and / or others. The pyrethroid may be selected from one or more of bifenthrin, zeta-cypermethrin, alpha-cypermethrin, tetra-methrin, lambda-cyhalothrin, fenvalerate, cyfluthrin, bio-resmethrin, permethrin, delta-methrin.

[0118] The pesticide may be present in the pesticide formulation in an amount, measured by weight per volume, of about 1% or more, about 5% or more, about 10% or more, or about 15% or less, about 20% or less, or within any range using these endpoints.

[0119] 2. Surfactants The pesticide formulation may include one or more surfactants selected from one or more surfactant classes collectively referred to as a surfactant system.

[0120] Suitable surfactants for use in the pesticide formulations of the present disclosure have Formula I:

[0121] [ka]

[0122] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, where C1-C6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, where the counterion, if present, is selected from chloride, bromide, iodide, and 4-methyl. The surfactants and / or co-surfactants may be selected from the group consisting of benzenesulfonate ions.

[0123] Specifically, suitable surfactants or co-surfactants may include any one or more of Surfactants 1-7 described herein.

[0124] The surfactant system may be present in the pesticide formulation in an amount, measured by weight per volume, of about 1% or more, about 5% or more, about 10% or more, about 15% or more, or about 20% or less, about 25% or less, about 30% or less, about 35% or less, about 40% or less, or within any range using these endpoints.

[0125] 3. Optional Defoamer Optional antifoam agents in the insecticide formulation may include silicone emulsions, and / or surfactants, such as those of the present disclosure.

[0126] The antifoaming agent may be present in the insecticide formulation in an amount, measured by weight per volume, 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 within any range using these endpoints.

[0127] 4. Optional antifreeze The insecticide formulation may include an optional antifreeze agent. Suitable antifreeze agents may include diols, such as alkyl diols or dialkyl diols.

[0128] The pesticide formulation may contain an antifreeze agent in an amount, measured by weight per 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 within any range using these endpoints.

[0129] 5.Water The insecticide formulation may contain water in an amount, measured by weight per volume, of about 25% or more, about 30% or more, about 35% or more, about 40% or more, about 45% or more, about 50% or more, about 55% or more, or about 60% or less, about 65% or less, about 70% or less, about 75% or less, about 80% or less, about 85% or less, about 90% or less, about 95% or less, about 98% or less, or within any range using these endpoints.

[0130] 6. Other Additives The pesticide formulations of the present disclosure may include viscosity modifiers. Such viscosity modifiers may include thickening agents such as cellulose derivatives, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, and natural gums.

[0131] The viscosity modifier may be present in the pesticide formulation in any amount suitable for modifying the viscosity to a desired level.

[0132] The insecticide formulations of the present disclosure may also include a preservative. Suitable preservatives include methylparaben.

[0133] Preservatives may be present in the pesticide formulation in an amount measured as weight per volume of from 0.0% or more, from 0.1% or more, or from 0.2% or less, or within any range using these endpoints.

[0134] VI. Adjuvants In addition to the above uses, the surfactant of the present disclosure can be used as an adjuvant in the formulation of agricultural active agents, such as pesticides, plant growth regulators, herbicides, fungicides and insecticides.Adjuvant compounds can be used to improve one or more properties of the formulation of agricultural active agents, such as storage stability, easy handling, pesticidal efficacy against target organisms.

[0135] VII. Spray drift reducer Spray drift refers to the unintended dispersion of pesticides and other agricultural active agents, including off-target contamination. This can cause damage to human health, environmental pollution, and property damage. The surfactants of the present disclosure can be used to reduce the amount of driftable fines in agricultural active agent formulations in both aerial and ground spray applications.

[0136] The surfactants of the present disclosure, and mixtures thereof, can be incorporated into aqueous spray mixtures, for example, by tank mixing directly with a dilute formulation of an agricultural active agent, such as a pesticide, plant growth regulator, fungicide, herbicide or insecticide.

[0137] The optimal spray droplet size depends on the application for which the composition is used. If the droplets are too large, the spray coverage will be reduced, for example, large droplets will reach some areas, while the areas in between will receive little or no spray coverage. The maximum acceptable droplet size may depend on the amount of composition applied per unit area and the need for uniformity of the spray coverage. Smaller droplets will provide more uniform coverage, but will tend to drift more during spraying. Thus, the application parameters in the spray coverage, such as uniformity, must be balanced against the tendency of smaller droplets to drift. For example, if it is windy, especially during spraying, larger droplets may be required to reduce drift, whereas on calm days, smaller droplets may be acceptable. In addition to the physical properties of the detailed aqueous composition, the size of the spray droplets may also depend on the spraying equipment, such as the size and arrangement of the nozzle.

[0138] The reduction in spray drift can be attributed to a variety of factors, including a reduction in the production of fine spray droplets (minimum diameter <150 μm) and an increase in the volume median diameter (VMD) of the spray droplets. In any case, for a given spray device, application and conditions, and based on the surfactant used, the median diameter of the spray droplets produced using the surfactants described herein will be increased over that of the surfactant-free spray composition of the present disclosure.

[0139] VIII. Surfactants The present disclosure provides surfactants for use on agricultural products in the form of derivatives of amino acids. The amino acids can be naturally occurring or synthetic, or they can be obtained from the ring-opening reaction of lactams, such as caprolactam. The compounds of the present disclosure have been shown to have surface active properties and can be used, for example, as surfactants and wetting agents. In particular, the present disclosure provides compounds of formula I:

[0140] [ka]

[0141] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, where C1-C6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counter ion may be associated with the compound, where the counter ion, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate.

[0142] One particular compound (Surfactant 1) provided by the present disclosure has the following formula:

[0143] [ka]

[0144] The compound is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula:

[0145] A second specific compound (surfactant 2) obtained according to the present disclosure has the following formula:

[0146] [ka]

[0147] The compound is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate having the formula:

[0148] A third specific compound (surfactant 3) available from the present disclosure has the following formula:

[0149] [ka]

[0150] The compound is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0151] A fourth specific compound (surfactant 4) available from the present disclosure has the following formula:

[0152] [ka]

[0153] The compound is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0154] A fifth specific compound (surfactant 5) available from the present disclosure has the following formula:

[0155] [ka]

[0156] The compound is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide.

[0157] A sixth specific compound (surfactant 6) obtained according to the present disclosure has the following formula:

[0158] [ka]

[0159] The compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula:

[0160] A seventh specific compound (surfactant 7) available from the present disclosure has the following formula:

[0161] [ka]

[0162] The compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

[0163] These surfactants can be synthesized by a variety of methods. One such method involves opening a lactam to give an amino acid with an N-terminus and a C-terminus. The N-terminus can be reacted with one or more alkylating agents and / or acids to give a quaternary ammonium salt. Alternatively, the N-terminus can be reacted with an oxidizing agent to give an amine N-oxide. The C-terminus can be reacted with an alcohol in the presence of an acid to give an ester.

[0164] The amino acids may be naturally occurring or synthetic, or may be derived from a ring-opening reaction of a lactam, such as caprolactam. The ring-opening reaction may be an acid or alkali catalyzed reaction, an example of an acid catalyzed reaction is shown below in Scheme 1.

[0165] [ka]

[0166] The amino acid may have as few as one or as many as twelve carbons between the N- and C-termini. The alkyl chain may be branched or straight. The alkyl chain may be interrupted at nitrogen, oxygen, or sulfur. The alkyl chain may be further substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen may be acylated or alkylated with one or more alkyl groups. For example, the amino acid may be 6-(dimethylamino)hexanoic acid or 6-aminohexanoic acid.

[0167] Surfactant 1 can be synthesized as shown below in Scheme 2. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is alkylated with methyl iodide in the presence of sodium carbonate.

[0168] [ka]

[0169] Surfactant 2 can be synthesized as shown below in Scheme 3. As shown, the C-terminus of 6-(dimethylamino)hexanoic acid is treated with 2-butyloctanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, 2-butyloctyl 6-(dimethylamino)hexanoate, as the 4-methylbenzenesulfonate salt.

[0170] [ka]

[0171] Surfactant 3 can be synthesized as shown below in Scheme 4. As shown, 2-butyloctyl 6-(dimethylamino)hexanoate is treated with one equivalent of hydrochloric acid to give 2-butyloctyl 6-(dimethylamino)hexanoate as the chloride salt.

[0172] [ka]

[0173] Surfactant 4 can be synthesized as shown below in Scheme 5. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is treated with 1,4-butanesultone in refluxing ethyl acetate to give the desired sulfonate.

[0174] [ka]

[0175] Surfactant 5 can be synthesized as shown below in Scheme 6. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is treated with hydrogen peroxide in water to give the desired N-oxide.

[0176] [ka]

[0177] Surfactant 6 can be synthesized as shown below in Scheme 7. As shown, the N-terminus of 2-butyloctyl 6-aminohexanoate is treated with one equivalent of hydrochloric acid to give the corresponding chloride salt.

[0178] [ka]

[0179] Surfactant 7 can be synthesized as shown below in Scheme 8. As shown, 6-aminohexanoic acid is treated with 2-butyloctanol and p-toluenesulfonic acid (PTSA) in benzene to give the corresponding 4-methylbenzenesulfonate salt.

[0180] [ka]

[0181] The compounds of the present disclosure demonstrate surface active properties. These properties can be measured and described in various ways. One way that surfactants can be described is by the critical micelle concentration (CMC) of the molecule. CMC is the concentration of surfactant at which micelles form, and can be defined as the concentration at which all the additional surfactants mentioned above are incorporated into the micelle.

[0182] As the surfactant concentration increases, the surface tension decreases. When the surface is completely covered with surfactant molecules, micelles begin to form. This point represents the CMC, as well as the minimum surface tension. Adding more surfactant does not further affect the surface tension. The CMC can therefore 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 a thin iridium-platinum plate that is usually placed perpendicular to the air-liquid interface, attached to a balance by wires. The balance is used to measure the force exerted on the plate by wetting. This value is then calculated using Equation 1: Equation 1: γ = F / l cosθ where l is equal to the wetting length (2w+2d, w and d are the thickness and width of the plate, respectively), and the contact angle cosθ between the liquid and the plate is assumed to be 0 if there is no existing literature value.

[0183] Another parameter used to evaluate the performance of surfactants is the dynamic surface tension. Dynamic surface tension is the value of the surface tension for a particular surface or interface lifetime. In the case of liquids to which surfactants are added, this may differ from the equilibrium value. Immediately after the surface is created, the surface tension is equal to that of the pure liquid. As mentioned above, surfactants reduce the surface tension, so the surface tension falls until it reaches the equilibrium value. The time required to reach equilibrium depends on the diffusion and adsorption rates of the surfactant.

[0184] One method by which dynamic surface tension is measured relies on a bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble formed in a liquid by a capillary. The measured value corresponds to the surface tension at a certain surface time, which is the time from the start of bubble formation to the occurrence of maximum pressure. The dependence of surface tension on surface time can be measured by the variation of the speed at which the bubble is generated.

[0185] Surface active compounds can also be evaluated by their ability to wet solid substrates, as measured by contact angle. When a liquid drop contacts a solid surface under a third medium, e.g. air, a three-phase line occurs between the liquid, the gas and the solid. The angle between the surface and a unit vector acting at the three-phase line and being the tangent surface tension at the drop, is described as the contact angle. The contact angle (also known as the wetting angle) is a measure of the degree of wetting of a solid by a liquid. In the case of complete wetting, the liquid is completely spread on the solid and the contact angle is 0°. Wettability is typically measured at concentrations of 1-10×CMC for a given compound, but since it is not a concentration-dependent property, wettability measurements can be measured at higher or lower concentrations.

[0186] In one method, an optical contact angle goniometer can be used to measure contact angles. This device uses a digital camera and software to extract the contact angle by analyzing the contour shape of a stationary liquid drop on a surface.

[0187] Potential applications for the surface active compounds of the present disclosure include formulations for use as shampoos, hair conditioners, detergents, spot free rinse solutions, floor and carpet cleaners, graffiti removal cleaners, crop protection wetting agents, crop protection adjuvants, and wetting agents for aerosol spray coatings.

[0188] It will be appreciated by those skilled in the art that small differences between compounds can result in significantly different surfactant properties, such that different compounds can be used with different substrates in different applications.

[0189] The following non-limiting embodiments are provided to demonstrate the different properties of different surfactants. In Table 1 below, the surfactant abbreviations correlate with their corresponding chemical structures.

[0190] [Table 1-1]

[0191] [Table 1-2]

[0192] Each of the seven compounds is effective as a surfactant, useful in wetting or foaming agents, dispersants, emulsifiers and detergents, among other uses.

[0193] Surfactant 1, Surfactant 2, Surfactant 3, Surfactant 6, and Surfactant 7 are cationic. These surfactants are useful in both the above applications and in some more specialized applications, such as in personal hair care products, for example, for surface treatments, and can also be used to create water repellent surfaces.

[0194] Surfactant 4 is zwitterionic. These surfactants are useful as co-surfactants in all of the above applications.

[0195] Surfactant 5 is non-ionic and can be used in shampoos, detergents, hard surface cleaners, and a variety of other surface cleaning formulations.

[0196] Working Example Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. Critical micelle concentration (CMC) was determined by the Wilhelmy plate method at 23 °C on a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate. Dynamic surface tension was measured using a bubble pressure tensiometer (Kruss BP100, Kruss GmbH) at 23° C. Contact angles were determined with an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

[0197] Example 1a: Synthesis of 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide 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. Methyl iodide (6.12 mmol, 0.38 mL) was added and the mixture was heated to 40° C. for 24 h and then cooled to room temperature. The mixture was filtered and the solvent removed under vacuum to give 6-((2-butyloctyl)oxy) -N,N,N-trimethyl-6-oxohexan-1-aminium iodide was obtained as a yellow solid in 90% yield. 1 H NMR (500 MHz, DMSO) δ 3.93 (d, J = 5.7 Hz, 2H), 3.29 - 3.22 (m, 2H), 3.04 (s, 9H), 2.34 (t, J = 7.4 Hz, 2H), 1.73 - 1.53 (m, 5H), 1.33-1.25 (m, 18H), 0.88-0.85 (m, 6H).

[0198] Example 1b: Critical micelle concentration (CMC) determination The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide from Example 1a was tested. From the plot of results shown in FIG. 1, it is clear that the CMC value cannot be determined at concentrations as low as 10 mg / mL, and the surface tension asymptotically approaches a value of about 27 mN / m. FIG. 1 is a plot of these results showing surface tension versus concentration. From the plot of results, it is clear that the surface tension at the CMC is below about 27 mN / m.

[0199] Example 2a: Synthesis of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate 6-(Dimethylamino)hexanoic acid was treated with 2-butyloctan-1-ol and p-toluenesulfonic acid in benzene for 12 hours at 120° C. 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate was isolated as a white waxy solid and recrystallized from acetone in 49% yield. 1 H NMR (500 MHz, DMSO) δ 7.48 (dd, J = 8.4, 0.6 Hz, 2H), 7.12 (dd, J = 8.4, 0.6 Hz, 1H), 3.93 (d, J = 5.7 Hz, 2H), 3.02 - 3.00 (m, 2H), 2.76 (d, J = 5.0 Hz, 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, 2.7 Hz, 6H).

[0200] Example 2b: Critical micelle concentration (CMC) determination The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate from Example 2a was tested. From the change in surface tension with concentration in water, the CMC was determined to be about 0.97 mmol. The minimum surface tension plateau value that can be reached by this surfactant is about 27 mN / m, i.e., 27 mN / m±3 mN / m. FIG. 2A is a plot of these results showing surface tension versus concentration. From the plot of results, the surface tension at the CMC is about 30 mN / m or less.

[0201] Example 2c: Determination of dynamic surface tension The dynamic surface tension of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate from Example 2a was determined with a bubble pressure tensiometer, which measures the change in surface tension of a freshly created air-water interface over time. FIG. 2B presents a plot of surface tension versus time, showing the surface tension rapidly dropping from about 46 mN / m to about 30 mN / m in the time interval between 10 and 100 ms. In the time interval from 100 to 8,000 ms, the surface tension slowly drops from 30 mN / m to about 27 mN / m, asymptotically approaching the saturation value of the surface tension at the CMC.

[0202] Example 2d: Wettability assessment In addition to the surface tension and surface dynamics, 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzene from Example 2a The wetting of the sulfonates was tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit surface wetting with a contact angle of 24.3°. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was much smaller at 48.2° than the contact angle of water at 119° (Table 2).

[0203] [Table 2]

[0204] Example 3a: Synthesis of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride 2-Butyloctyl 6-(dimethylamino)hexanoate was treated with one equivalent of hydrochloric acid to give 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium chloride.

[0205] Example 3b: Critical micelle concentration (CMC) determination The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride from Example 3a was tested. From the change in surface tension with concentration in water, the CMC was determined to be about 27.47 mmol. The minimum surface tension that can be reached by this surfactant is about 29 mN / m, i.e., 29 mN / m±3 mN / m. FIG. 3 is a plot of these results showing surface tension versus concentration. From the plot of results, it is clear that the CMC value cannot be determined at concentrations as high as 27.4 mmol, with the surface tension asymptotically approaching a value of about 29 mN / m.

[0206] Example 4a: Synthesis of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate 2-Butyloctyl 6-(dimethylamino)hexanoate (2.04 mmol, 700 mg) was dissolved in ethyl acetate (30 mL). 1,4-butanesultone (3.06 mmol, 0.31 mL) was added. The mixture was heated to reflux for 12 hours and evaporation of the solvent was continued. The resulting white waxy solid was washed with acetone to give 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate in 89% yield. 1 H NMR (500 MHz, DMSO) δ 3.93 (d, J = 5.7 Hz, 2H), 3.30-3.28 (m, 4H), 2.97 (s, 3H), 2.49 - 2.43 (m, 2H), 2.34 (t, J = 7.4 Hz, 2H), 1.96- 1.76 (m, 9H), 1.27-1.25 (m, 18H), 0.88 - 0.85 (m, 6H).

[0207] Example 4b: Critical micelle concentration (CMC) determination The critical micelle concentration (CMC) of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate from Example 4a was tested. From the change in surface tension with concentration in water, the CMC was determined to be about 0.54 mmol. The minimum surface tension plateau value achievable by this surfactant is about 32 mN. / m, i.e., 32 mN / m ± 3 mN / m. Figure 4A is a plot of these results showing surface tension versus concentration. From the resulting plot, it can be seen that the surface tension at the CMC is approximately 32 mN / m or less.

[0208] Example 4c: Determination of dynamic surface tension The dynamic surface tension of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate from Example 4a was determined with a bubble pressure tensiometer, which measures the change in surface tension of a freshly created air-water interface over time. FIG. 4B presents a plot of surface tension versus time showing that in the time interval between 10 and 100 ms, the surface tension drops rapidly from about 66 mN / m to about 36 mN / m. In the time interval from 100 to 8,000 ms, the surface tension drops slowly from 36 mN / m to about 32 mN / m, asymptotically approaching the saturation value of surface tension at the CMC.

[0209] Example 4d: Wettability assessment In addition to surface tension and surface dynamics, the wettability of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate from Example 4a was tested on various surfaces. For example, hydrophobic substrates, such as polyethylene-HD, exhibit surface wetting with a contact angle of 44.4°. On oleophobic and hydrophobic substrates, such as Teflon, the measured contact angle was much smaller at 62.2° than the water contact angle of 119° (Table 3).

[0210] [Table 3]

[0211] Example 5a: Synthesis of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide 2-Butyloctyl 6-(dimethylamino)hexanoate was treated with hydrogen peroxide in water at 70° C. for 24 hours to give 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide as an oil in 90% yield. 1 H NMR (500 MHz, DMSO) δ 3.93 (d, J = 5.7 Hz, 2H), 3.30-3.28 (m, 4H), 2.97 (s, 3H), 2.49 - 2.43 (m, 2H), 2.34 (t, J = 7.4 Hz, 2H), 1.96- 1.76 (m, 9H), 1.27-1.25 (m, 18H), 0.88 - 0.85 (m, 6H).

[0212] Example 5b: Critical micelle concentration (CMC) determination The critical micelle concentration (CMC) of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was tested. From the change in surface tension with concentration in water, the CMC was determined to be about 0.29 mmol. The plateau value of the minimum surface tension that can be reached by this surfactant is about 28 mN / m, i.e., 28 mN / m±3 mN / m. Figure 5A is a plot of these results showing surface tension versus concentration. From the plot of results, the surface tension at the CMC is about 28 mN / m or less.

[0213] Example 5c: Determination of dynamic surface tension The dynamic surface tension of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was determined with a bubble pressure tensiometer, which measures the change in surface tension of a freshly created air-water interface over time. Figure 5B presents a plot of surface tension versus time showing that in the time interval between 10 and 1,000 ms, the surface tension rapidly drops from about 60 mN / m to about 30 mN / m. In the time interval between 1,000 and 8,000 ms, the surface tension slowly drops from 30 mN / m to about 28 mN / m, asymptotically approaching the saturation value of surface tension at the CMC.

[0214] Example 5d: Wettability assessment In addition to surface tension and surface dynamics, the wettability of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was tested on various surfaces. For example, hydrophobic substrates, such as polyethylene-HD, exhibit surface wetting with a contact angle of 31.6°. On oleophobic and hydrophobic substrates, such as Teflon, the measured contact angle was much smaller at 41.5° than the water contact angle of 119° (Table 4).

[0215] [Table 4]

[0216] Example 6a: Synthesis of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride 2-Butyloctyl 6-(dimethylamino)hexanoate was treated with one equivalent of hydrochloric acid to give 6-((2-butyloctyl)oxy)-6-oxohexan-1-aminium chloride.

[0217] Example 6b: Critical micelle concentration (CMC) determination The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride from Example 6a was tested. From the change in surface tension with concentration in water, the CMC was determined to be about 0.15 mmol. The minimum surface tension plateau value that can be reached by this surfactant is about 27 mN / m, i.e., 27 mN / m±3 mN / m. FIG. 6A is a plot of these results showing surface tension versus concentration. From the resulting plot, the surface tension at the CMC is about 30 mN / m or less.

[0218] Example 6c: Determination of dynamic surface tension The dynamic surface tension of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride from Example 6a was determined with a bubble pressure tensiometer, which measures the change in surface tension of a freshly created air-water interface over time. Figure 6B shows that the surface tension slowly changes from about 69 mN / m to about 29 mN / m over time intervals between 10 and 8,000 ms. A plot of surface tension versus time is presented showing a drop, and a slight plateau of about 49 mN / m at a surface lapse time of 1,000 ms, approaching the saturation value of surface tension at the CMC.

[0219] Example 6d: Wettability assessment In addition to surface tension and surface dynamics, the wettability of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride from Example 6a was tested on various surfaces. For example, hydrophobic substrates, such as polyethylene-HD, exhibit surface wetting with a contact angle of 25.8°. On oleophobic and hydrophobic substrates, such as Teflon, the measured contact angle was much smaller at 48.7° than the water contact angle of 119° (Table 5).

[0220] [Table 5]

[0221] Example 7a: Synthesis of 6-((2-butyloctyl)oxy)-6-oxohexan-1-aminium 4-methylbenzenesulfonate 6-Aminohexanoic acid (38.11 mmol, 5 g) was dissolved in benzene (50 mL) in a 100 mL round bottom flask equipped with a Dean Stark trap. p-Toluenesulfonic acid monohydrate (38.11 mmol, 7.25 g) and 2-butyloctanol (38.11 mmol, 7.1 g, 8.5 mL) were added and the mixture was heated to reflux for 1 week until no further water was separated in the Dean Stark trap. The solvent was removed under vacuum and the product was crystallized from acetone at -20°C to remove residual unreacted alcohol. The resulting white waxy solid was filtered to give 2-butyloctyl)oxy)-6-oxohexan-1-aminium 4-methylbenzenesulfonate in 82% yield. 1 H NMR (500 MHz, DMSO) δ 7.49 (d, J = 8.0 Hz, 2H), 7.12 (dd, J = 8.4, 0.6 Hz, 2H), 3.93 (d, J = 5.7 Hz, 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).

[0222] Example 7b: Critical micelle concentration (CMC) determination The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-6-oxohexan-1-aminium 4-methylbenzenesulfonate from Example 7a was tested. From the change in surface tension with concentration in water, the CMC was determined to be about 2.12 mmol. The minimum surface tension plateau value that can be reached by this surfactant is about 27 mN / m, i.e., 27 mN / m±3 mN / m. FIG. 7A is a plot of these results showing surface tension versus concentration. From the plot of results, the surface tension at the CMC is about 30 mN / m or less, and the surface tension is about 28.5 mN / m or less at concentrations of about 1.0 mmol or more.

[0223] Example 7c: Determination of dynamic surface tension The dynamic surface tension of 6-((2-butyloctyl)oxy)-6-oxohexan-1-aminium 4-methylbenzenesulfonate from Example 7a was determined with a bubble pressure tensiometer, which measures the change in surface tension of a freshly created air-water interface over time. FIG. 7B presents a plot of surface tension versus time showing that in the time interval between 10 and 100 ms, the surface tension drops rapidly from about 46 mN / m to about 30 mN / m. In the time interval between 100 and 8,000 ms, the surface tension drops slowly from 30 mN / m to about 27 mN / m, asymptotically approaching the saturation value of surface tension at the CMC.

[0224] Example 7d: Wettability assessment In addition to surface tension and surface dynamics, the wettability of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate from Example 7a was tested on various surfaces. For example, hydrophobic substrates, such as polyethylene-HD, exhibit surface wetting with a contact angle of 14.6°. On oleophobic and hydrophobic substrates, such as Teflon, the measured contact angle was much smaller at 49.4° than the water contact angle of 119° (Table 6).

[0225] [Table 6]

[0226] Example 8: Pesticide Formulations In this example, a concentrated formulation is provided for use as a pesticide. The components of the formulation are shown below in Table 7. The formulation may also include additional surfactants, water, thickeners, deposition enhancers, drift control agents and salts.

[0227] [Table 7]

[0228] Example 9: Formulations for liquid fungicidal compositions In this example, formulations are provided for use as liquid fungicidal compositions. The formulations are shown below in Table 8.

[0229] [Table 8]

[0230] Example 10: Herbicide formulations In this example, formulations are provided for use as herbicides. The formulations are shown below in Table 9.

[0231] [Table 9]

[0232] Example 11: Insecticide formulations In this example, formulations are provided for use as insecticides. The formulations are shown below in Table 10.

[0233] [Table 10]

[0234] Aspects Aspect 1 is a pesticide formulation comprising the following formula:

[0235] [ka]

[0236] (In the formula, R 1 and R 2are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, which counterion, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate, and a pesticide.

[0237] Example 2 is the formulation of Example 1, further comprising a water insoluble solvent.

[0238] Aspect 3 is directed to a surfactant having the following formula:

[0239] [ka]

[0240] The formulation according to embodiment 1 or embodiment 2, wherein the compound is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula:

[0241] Aspect 4 is a surfactant having the following formula:

[0242] [ka]

[0243] The formulation according to embodiment 1 or embodiment 2, wherein the compound is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate having the formula:

[0244] Aspect 5 is a method for preparing a surfactant having the following formula:

[0245] [ka]

[0246] The formulation according to embodiment 1 or embodiment 2, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0247] Aspect 6 is a method for preparing a surfactant having the following formula:

[0248] [ka]

[0249] The formulation according to embodiment 1 or embodiment 2, wherein the compound is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0250] Aspect 7 is a method for preparing a surfactant having the following formula:

[0251] [ka]

[0252] The formulation according to embodiment 1 or embodiment 2, wherein the compound is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula:

[0253] In an eighth aspect, the surfactant has the following formula:

[0254] [ka]

[0255] The formulation according to embodiment 1 or embodiment 2, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula:

[0256] Aspect 9 is a method for preparing a surfactant having the formula:

[0257] [ka]

[0258] The formulation according to embodiment 1 or embodiment 2, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexan-1-aminium 4-methylbenzenesulfonate having the formula:

[0259] Aspect 10 is a fungicide formulation comprising the following formula:

[0260] [ka]

[0261] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, which counterion, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate, and a fungicide.

[0262] Example 11 is the formulation of Example 10, further comprising a co-surfactant.

[0263] Example 12 is the formulation of Example 10 or Example 11, further comprising a carrier agent.

[0264] Aspect 13 is directed to a surfactant having the following formula:

[0265] [ka]

[0266] 13. The formulation according to any of aspects 10-12, wherein the compound is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula:

[0267] Aspect 14 is a method for preparing a surfactant having the formula:

[0268] [ka]

[0269] 13. The formulation according to any of aspects 10-12, wherein the compound is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate having the formula:

[0270] Aspect 15 is directed to a surfactant having the following formula:

[0271] [ka]

[0272] 13. The formulation according to any of aspects 10-12, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0273] Aspect 16 is directed to a surfactant having the following formula:

[0274] [ka]

[0275] 13. The formulation according to any of aspects 10-12, wherein the compound is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0276] Aspect 17 is directed to a surfactant having the following formula:

[0277] [ka]

[0278] 13. The formulation according to any of aspects 10-12, wherein the compound is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula:

[0279] An eighteenth aspect is a method for preparing a surfactant comprising the steps of:

[0280] [ka]

[0281] 13. The formulation according to any of aspects 10-12, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula:

[0282] Aspect 19 is directed to a surfactant having the following formula:

[0283] [ka]

[0284] 13. The formulation according to any of aspects 10-12, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

[0285] Aspect 20 is a herbicidal formulation comprising a compound of the formula:

[0286] [ka]

[0287] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, which counterion, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate, and a herbicide.

[0288] Embodiment 21 is the formulation of embodiment 20, further comprising a second herbicide.

[0289] Example 22 is the formulation of Example 20 or Example 21, further comprising a water insoluble solvent.

[0290] Example 23 is the formulation of any of Examples 20-22, further comprising water.

[0291] Aspect 24 is a method for preparing a surfactant having the formula:

[0292] [ka]

[0293] 24. The formulation according to any of aspects 20-23, wherein the compound is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula:

[0294] Aspect 25 is directed to a surfactant having the following formula:

[0295] [ka]

[0296] 24. The formulation according to any of aspects 20-23, wherein the compound is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate having the formula:

[0297] Aspect 26 is directed to a surfactant having the formula:

[0298] [ka]

[0299] 24. The formulation according to any of aspects 20-23, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0300] Aspect 27 is directed to a surfactant having the formula:

[0301] [ka]

[0302] 24. The formulation according to any of aspects 20-23, wherein the compound is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0303]

[0023] Aspect 28 is directed to a surfactant having the formula:

[0304] [ka]

[0305] 24. The formulation according to any of embodiments 20-23, wherein the compound is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula:

[0306] Aspect 29 is directed to a surfactant having the formula:

[0307] [ka]

[0308] 24. The formulation according to any of aspects 20-23, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula:

[0309]

[0023] Aspect 30 is directed to a surfactant having the formula:

[0310] [ka]

[0311] 24. The formulation according to any of aspects 20-23, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

[0312] Aspect 31 is an insecticide formulation comprising the following formula:

[0313] [ka]

[0314] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate; n is an integer from 2 to 5, inclusive; R 3 is C5~C 12 is alkyl, R 4 is C3~C 10 alkyl, the terminal nitrogen is R 5 may be further substituted with R 5 is selected from hydrogen, an oxygen atom, and C1-C6 alkyl, which may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, which counterion, if present, may be selected from the group consisting of chloride, bromide, iodide, and 4-methylbenzenesulfonate, and a pesticide.

[0315] Example 32 is the formulation of Example 31, further comprising an antifoaming agent.

[0316] Example 33 is the formulation of Example 31 or Example 32, further comprising an antifreeze agent.

[0317] Example 34 is the formulation of any of Examples 31-33, further comprising water.

[0318]

[0023] Aspect 35 is directed to a surfactant having the following formula:

[0319] [ka]

[0320] 35. The formulation according to any of Aspects 31-34, wherein the compound is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula:

[0321] Aspect 36 is directed to a surfactant having the formula:

[0322] [ka]

[0323] 35. The formulation according to any of aspects 31-34, wherein the compound is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

[0324]

[0023] Aspect 37 is directed to a surfactant having the formula:

[0325] [ka]

[0326] 35. The formulation according to any of Aspects 31-34, wherein the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0327]

[0023] Aspect 38 is directed to a surfactant having the following formula:

[0328] [ka]

[0329] 35. The formulation according to any of aspects 31-34, wherein the compound is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0330] Aspect 39 is directed to a surfactant having the formula:

[0331] [ka]

[0332] 35. The formulation according to any of embodiments 31-34, wherein the compound is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula:

[0333]

[0036] Aspect 40 is a method for preparing a surfactant having the formula:

[0334] [ka]

[0335] 35. The formulation according to any of Aspects 31-34, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula:

[0336] Aspect 41 is directed to a surfactant having the following formula:

[0337] [ka]

[0338] 35. The formulation according to any of aspects 31-34, wherein the compound is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

Claims

1. A pesticide formulation comprising: The following formula: 【Chemistry 1】 (In the formula, R １ and R ２ represents hydrogen, oxygen and C １ ~C ６ alkyl; １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; n is an integer from 2 to 5, inclusive; R ３ is C ５ ~C １２ is alkyl, R ４ is C ３ ~C １０ is alkyl, Terminal nitrogen is R ５ may be further substituted with R ５ represents hydrogen, oxygen and C １ ~C ６ alkyl, C １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; at least one surfactant of the formula (I), wherein an optional counterion may be associated with the compound, and when present, the counterion may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate; A formulation comprising a pesticide.

2. The formulation of claim 1 further comprising a water insoluble solvent.

3. The surfactant is The following formula: 【Chemistry 2】 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula The following formula: 【Chemistry 3】 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula The following formula: 【Chemistry 4】 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemistry 5】 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula The following formula: 【Chemistry 6】 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula The following formula: 【Chemistry 7】 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemistry 8】 2. The formulation of claim 1, comprising at least one of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

4. A fungicide formulation comprising: The following formula: 【Chemistry 9】 (In the formula, R １ and R ２ represents hydrogen, oxygen and C １ ~C ６ alkyl; １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; n is an integer from 2 to 5, inclusive; R ３ is C ５ ~C １２ is alkyl, R ４ is C ３ ~C １０ is alkyl, Terminal nitrogen is R ５ may be further substituted with R ５ represents hydrogen, oxygen and C １ ~C ６ alkyl, C １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; at least one surfactant of the formula (I), wherein an optional counterion may be associated with the compound, and when present, the counterion may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate; A formulation comprising a fungicide.

5. The formulation of claim 4 further comprising a co-surfactant.

6. The formulation of claim 4 further comprising a carrier agent.

7. The surfactant is The following formula: 【Chemistry 10】 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula The following formula: 【Chemistry 11】 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula The following formula: 【Chemistry 12】 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemistry 13】 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula The following formula: 【Chemistry 14】 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula The following formula: 【Chemistry 15】 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemistry 16】 5. The formulation of claim 4, comprising at least one of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

8. 1. A herbicide formulation comprising: The following formula: 【Chemistry 17】 (In the formula, R １ and R ２ represents hydrogen, oxygen and C １ ~C ６ alkyl; １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; n is an integer from 2 to 5, inclusive; R ３ is C ５ ~C １２ is alkyl, R ４ is C ３ ~C １０ is alkyl, Terminal nitrogen is R ５ may be further substituted with R ５ represents hydrogen, oxygen and C １ ~C ６ alkyl, C １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; at least one surfactant of the formula (I), wherein an optional counterion may be associated with the compound, and when present, the counterion may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate; A formulation, including a herbicide.

9. 10. The formulation of claim 8 further comprising a second herbicide.

10. The formulation of claim 8 further comprising a water insoluble solvent.

11. 9. The formulation of claim 8 further comprising water.

12. The surfactant is: The following formula: 【Chemistry 18】 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula The following formula: 【Chemistry 19】 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula The following formula: 【Chemistry 20】 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemistry 21】 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula The following formula: 【Chemical 22】 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula The following formula: 【Chemistry 23】 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemistry 24】 9. The formulation of claim 8, comprising at least one of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

13. 1. A formulation for an insecticide comprising: The following formula: 【Chemistry 25】 (In the formula, R １ and R ２ represents hydrogen, oxygen and C １ ~C ６ alkyl; １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; n is an integer from 2 to 5, inclusive; R ３ is C ５ ~C １２ is alkyl, R ４ is C ３ ~C １０ is alkyl, Terminal nitrogen is R ５ may be further substituted with R ５ represents hydrogen, oxygen and C １ ~C ６ alkyl, C １ ~C ６ The alkyl may be substituted with a carboxylate, hydroxyl, or sulfonate; at least one surfactant of the formula (I), wherein an optional counterion may be associated with the compound, and when present, the counterion may be selected from the group consisting of chloride, bromide, iodide and 4-methylbenzenesulfonate; A formulation that contains an insecticide.

14. 14. The formulation of claim 13 further comprising an antifoaming agent.

15. 14. The formulation of claim 13 further comprising an antifreeze agent.

16. 14. The formulation of claim 13 further comprising water.

17. The surfactant is The following formula: 【Chemistry 26】 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the formula The following formula: 【Chemical 27】 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula The following formula: 【Chemistry 28】 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemical 29】 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula The following formula: 【Chemistry 30】 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the formula The following formula: 【Chemistry 31】 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the formula The following formula: 【Chemistry 32】 14. The formulation of claim 13, comprising at least one of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

18. 2. The formulation of claim 1, wherein n is 5.

19. The formulation of claim 4 wherein n is 5.

20. 9. The formulation of claim 8, wherein n is 5.

21. 14. The formulation of claim 13, wherein n is 5.

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