Process for crystallizing amorphous pesticides and formulations thereof

Abstract

Described herein is a process for preparing an aqueous suspension of a crystalline organic pesticide from its amorphous form. Also described herein is an aqueous pesticide formulation comprising the prepared aqueous suspension.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 322,360, filed March 22, 2022.

[0002] The present disclosure relates to a process for preparing an aqueous suspension concentrate of a crystalline organic pesticide, which process involves inducing in situ crystallization of an amorphous organic pesticide with the crystalline organic pesticide in an aqueous system. [Background technology]

[0003] Suspension concentrate (SC) formulations contain crystalline solid active ingredients dispersed in water. SCs have gained popularity due to their many advantages when compared to formulation types such as emulsifiable concentrate (EC) and wettable powder (WP) formulations, including ease and effectiveness of use, elimination of dust, and elimination of solvent hazards.

[0004] Some pesticides are difficult to convert from amorphous to the crystalline form used in SC formulations. Crystalline forms are preferred over amorphous forms because a well-defined particle size range and stable formulation products can be achieved. Some pesticides, such as indoxacarb, are characterized by one or more of the following: a very steep temperature / viscosity curve, thus requiring a relatively high temperature to achieve flowability; the lack of a clear melting point, i.e., a large variation in melting point, which is an indication that the pesticide does not easily crystallize; decomposition begins at a relatively low temperature (e.g., about 100°C); and decomposition slowly up to a fairly high temperature (e.g., about 230°C) and almost complete decomposition at a higher temperature (e.g., about 310°C). Prior art methods for crystallizing such pesticides usually require complex processes using non-aqueous solvents, and the cost of the resulting crystalline pesticide is too high to be economically viable.

[0005] One alternative is to use a melt of the pesticide to form the SC formulation. Prior art melt processes for preparing SC formulations typically require forming a melt at high temperatures (above 100°C) so that the pesticide becomes flowable and then drips into an aqueous solution containing the SC formulation ingredients. This presents a significant safety issue when handling molten pesticides at temperatures above 100°C during manufacturing processes. An additional problem is that adding molten pesticide to an aqueous solution can result in incomplete crystallization, resulting in significant amounts of semi-solid amorphous material that must be isolated, reclaimed, or discarded, creating environmental and cost burdens. Furthermore, amorphous pesticides can have relatively low glass transition temperatures (e.g., about 25-35°C), and their presence during the subsequent milling process can lead to crushing of mill screens and the need for equipment cleaning, creating processing and material exposure issues. As an additional problem, the relatively long duration of dripping the hot pesticide melt into water, followed by milling that exposes a large surface area to hydrolysis conditions (especially at high temperatures), results in significant degradation of the pesticide by acid- or base-catalyzed aqueous-phase hydrolysis. As an additional problem, SC formulations formed by the above-described hot melt drip method are prone to crystal growth when stored above about 30°C. Crystal growth negatively impacts sprayability and overall product stability.

[0006] One prior art process for producing crystalline indoxacarb, described in WO 2018 / 137387 A1, requires the use of toxic halogenated hydrocarbons to dissolve and precipitate indoxacarb and isolate Isoflex therefrom. Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, there is a need for an improved process for preparing aqueous suspension concentrates of crystalline organic pesticides. [Means for solving the problem]

[0008] In one aspect, there is provided a process for preparing an aqueous suspension of an organic pesticide, comprising: I) forming a mixture comprising a source of at least one amorphous organic pesticide, water, and at least one formulation additive; II) adding at least one crystalline seed of an organic pesticide to the mixture; III) crystallizing at least one amorphous organic pesticide; IV) optionally homogenizing the mixture; V) optionally, grinding the mixture; and VI) Optionally, thickening the mixture Provided herein is a process comprising:

[0009] In one aspect, there is provided a process for preparing an aqueous suspension of an organic pesticide, comprising: I) A mixture comprising: A) compounding additives, B) at least one crystalline organic pesticide, and C) water forming a mixture comprising: II) adding at least one amorphous organic pesticide to the mixture under stirring conditions; III) crystallizing at least one amorphous organic pesticide; IV) optionally homogenizing the mixture; V) optionally, grinding the mixture; and VI) Optionally, thickening the mixture Provided herein is a process comprising: [Brief explanation of the drawings]

[0010] [Figure 1] 1 shows the particle size distribution of a suspension concentrate of crystallized indoxacarb of the present disclosure before milling. [Figure 2] 1 shows the particle size distribution of a suspension concentrate of milled crystallized indoxacarb of the present disclosure. [Figure 3]1 shows the particle size distribution of a suspension concentrate of milled crystallized indoxacarb of the present disclosure after 0 and 15 days of storage at room temperature. [Figure 4] 1 shows the particle size distribution of a suspension concentrate of milled crystallized indoxacarb of the present disclosure after two weeks of storage at room temperature and two weeks of storage at 54° C. [Figure 5] 1 shows the particle size distribution of a suspension concentrate of milled crystallized indoxacarb of the present disclosure after 4 weeks of storage at room temperature and after 2 weeks of storage at 54° C. [Figure 6] 1 shows XRD patterns of prior art crystalline indoxacarb (Samples 1 and 6) and crystalline indoxacarb prepared according to an example of the present disclosure (Sample 3). [Figure 7] 1 shows XRD patterns of a prior art crystalline indoxacarb suspension concentrate (Sample 8) and crystalline indoxacarb suspension concentrates made according to examples of the present disclosure (Samples 2 and 9). [Figure 8] 1 shows XRD patterns of prior art crystalline indoxacarb (Sample 1), prior art amorphous indoxacarb (Sample 7), and a crystalline indoxacarb suspension concentrate made according to an example of the present disclosure (Sample 9). [Figure 9] 1 shows XRD patterns of prior art crystalline indoxacarb (top line, Sample 1), crystalline indoxacarb made according to an example of the present disclosure (Sample 5), a prior art crystalline indoxacarb suspension concentrate (Sample 8), and crystalline indoxacarb suspension concentrates made according to an example of the present disclosure (Samples 4 and 9). [Figure 10] 1 shows a DSC diagram of prior art crystalline indoxacarb (sample 1). [Figure 11] FIG. 1 shows a DSC diagram of a crystalline indoxacarb suspension concentrate (Sample 2) prepared according to an example of the present disclosure. [Figure 12] FIG. 1 shows a DSC diagram of crystalline indoxacarb (Sample 3) prepared according to an embodiment of the present disclosure. [Figure 13] FIG. 1 shows a DSC diagram of a crystalline indoxacarb suspension concentrate (Sample 4) prepared according to an example of the present disclosure. [Figure 14] FIG. 1 shows a DSC diagram of crystalline indoxacarb (sample 5) prepared according to an example of the present disclosure. [Figure 15] 1 shows a DSC diagram of prior art crystalline indoxacarb (sample 6). [Figure 16] 1 shows an SEM image of prior art crystalline indoxacarb (Sample 1). [Figure 17] 1 shows an SEM image of a crystalline indoxacarb suspension concentrate (Sample 2) prepared according to an embodiment of the present disclosure. [Figure 18] 1 shows an SEM image of crystalline indoxacarb (Sample 3) prepared according to an embodiment of the present disclosure. [Figure 19] 1 shows an SEM image of a crystalline indoxacarb suspension concentrate (Sample 4) prepared according to an embodiment of the present disclosure. [Figure 20] 1 shows an SEM image of crystalline indoxacarb (Sample 5) prepared according to an embodiment of the present disclosure. [Figure 21] 1 shows an SEM image of prior art crystalline indoxacarb (Sample 6). DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure generally relates to a process for converting amorphous organic pesticides in situ to crystalline organic pesticides in an aqueous system and preparing high dose formulations therefrom.

[0012] As used herein, the terms "comprise," "including," "include," "including," "having," "having," "containing," "characterized by," or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitations expressly stated. For example, a composition, mixture, process, or method that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent in such composition, mixture, process, or method.

[0013] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. In the context of a claim, such excludes the inclusion of materials other than those recited, except for impurities normally associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim rather than immediately following a preamble, it limits only the elements recited in that clause; other elements are not excluded from the claim as a whole.

[0014] The transitional phrase "consisting essentially of" is used to define compositions or methods that include materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additional materials, steps, features, ingredients, or elements do not materially affect the basic and novel characteristics of the claimed disclosure. The term "consisting essentially of" occupies a middle ground between "comprising" and "consisting of."

[0015] It should be readily understood that where a disclosure or portion thereof is defined using open-ended terminology such as "comprising," this description should be construed as also describing such disclosure using the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0016] Furthermore, unless expressly stated to the contrary, "or" means an inclusive "or" and not an exclusive "or." For example, a condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0017] The indefinite articles "a" and "an" preceding an element or component of the present disclosure are also intended to be open-ended regarding the number of instances (i.e., occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural, unless the number is specifically intended to be singular.

[0018] Numerical ranges recited herein are also understood to encompass all values ​​between the lower and upper limits. For example, and without limitation, a range of 1 to 10 is intended to include all subranges between the stated minimum of 1 and the stated maximum of 10, including the stated minimum of 1 and the stated maximum of 10, i.e., to have a minimum of 1 or greater and a maximum of 10 or less. As a further non-limiting example, references herein to a range of "at least 50" include integers such as 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, etc., and decimals such as 50.1, 50.2, 50.3, 50.4, 50.5, 50.6, 50.7, 50.8, 50.9, etc. In a further non-limiting example, reference herein to a range of "less than 50" includes whole numbers such as 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, etc., and decimals such as 49.9, 49.8, 49.7, 49.6, 49.5, 49.4, 49.3, 49.2, 49.1, 49.0, etc. These are merely examples of what is specifically intended, and all possible combinations of numerical values ​​therebetween, including the lowest and highest values ​​recited, are considered to be expressly stated in this application.

[0019] As used herein, the term "about" means plus or minus 10% of a value.

[0020] In the context of the present invention, "crystalline" means that at least 90% by weight of the pesticidal compound present in the aqueous suspension is in a crystalline state and that less than 10% by weight of the pesticidal compound present in the aqueous suspension is non-crystalline, i.e. amorphous. The degree of crystallinity is easily determined by powder X-ray diffraction (powder XRD) of the pesticidal compound, by optical microscopy (due to the birefringence of the crystalline phase), in most cases also by DSC analysis (DSC = differential scanning calorimetry) and in some cases by spectroscopic measurements.

[0021] In the context of the present invention, "amorphous" means that the pesticidal compound present in the aqueous emulsion is essentially non-crystalline, i.e., contains less than 10% by weight of crystalline material based on the total amount of pesticidal compound, or contains no traceable amounts of crystalline material. Amorphous forms include liquid forms, i.e., melts and supercooled melts, solutions in water-miscible solvents, and solid amorphous forms.

[0022] In one embodiment, the amorphous organic pesticide has a relatively low melting point, such as about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, or any range consisting thereof, for example, about 55°C to about 100°C or about 65°C to about 90°C.

[0023] In one embodiment, the amorphous organic pesticide has a relatively low solubility in water. In one embodiment, the amorphous organic pesticide has a solubility in water at 25° C. of 0.001 mg / L or less, 0.01 mg / L or less, about 0.1 mg / L, about 0.2 mg / L, about 0.5 mg / L, about 1 mg / L, about 5 mg / L, about 10 mg / L, about 25 mg / L, about 50 mg / L, about 75 mg / L, or about 100 mg / L, and any range consisting thereof, for example, about 0.001 mg / L to about 100 mg / L or about 0.01 mg / L to about 100 mg / L.

[0024] In one embodiment, the amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a solid amorphous form, a liquid, a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof. In one embodiment, the amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a liquid, a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof. In one embodiment, the amorphous organic pesticide is in a form selected from a melt and a supercooled melt. In embodiments including two or more amorphous organic pesticides, such pesticides can each independently be selected from a melt, a supercooled melt, a solid amorphous form, a liquid, and a solution comprising an active ingredient and a water-miscible solvent. For example, one amorphous organic pesticide can be in the form of a melt and one amorphous organic pesticide can be in the form of a solid amorphous form.

[0025] In one embodiment, the amorphous organic pesticide is selected from an insecticide (such as an insecticide included in the list of insecticides disclosed elsewhere herein), a fungicide (such as a fungicide included in the list of fungicides disclosed elsewhere herein), a herbicide (such as a herbicide included in the list of herbicides disclosed elsewhere herein), and combinations thereof.

[0026] In one embodiment, the amorphous organic pesticide is an insecticide selected from indoxacarb, bifenthrin, gamma-cyhalothrin, and combinations thereof.

[0027] In one embodiment, the amorphous organic pesticide is a fungicide selected from difenoconazole, pyraclostrobin, picoxystrobin, and combinations thereof.

[0028] In one embodiment, the amorphous organic pesticide is a herbicide selected from beflubutamid, s-beflubutamid, rimisoxamide, bixlozone isoflex, napropamide, aclonifen, and combinations thereof.

[0029] In one embodiment, the crystalline organic pesticide has a melting point of about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and any range consisting thereof, for example, from about 55°C to about 100°C or from about 65°C to about 90°C.

[0030] In one embodiment, the crystalline organic pesticide has a relatively low solubility in water. In one embodiment, the amorphous organic pesticide has a solubility in water at 25° C. of 0.001 mg / L or less, 0.01 mg / L or less, about 0.1 mg / L, about 0.2 mg / L, about 0.5 mg / L, about 1 mg / L, about 5 mg / L, about 10 mg / L, about 25 mg / L, about 50 mg / L, about 75 mg / L, or about 100 mg / L, and any range consisting thereof, for example, about 0.001 mg / L to about 100 mg / L or about 0.01 mg / L to about 100 mg / L.

[0031] In one embodiment, the crystalline organic pesticide is selected from an insecticide (such as an insecticide included in the list of insecticides disclosed elsewhere herein), a fungicide (such as a fungicide included in the list of fungicides disclosed elsewhere herein), a herbicide (such as a herbicide included in the list of herbicides disclosed elsewhere herein), and combinations thereof.

[0032] In one embodiment, the crystalline organic pesticide is an insecticide, hi one embodiment, the insecticide is selected from indoxacarb, bifenthrin, gamma-cyhalothrin, and combinations thereof.

[0033] In some crystallization embodiments, the amorphous and crystalline organic pesticide may be the same pesticide.

[0034] In some crystallization embodiments, the at least one amorphous organic pesticide comprises two or more organic pesticide species, each independently in the form of (i) a melt, a supercooled melt, a solid amorphous form, a liquid, or a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof; (ii) a melt, a supercooled melt, a liquid, or a solution comprising an active ingredient and a water-miscible solvent; or (iii) a melt. In embodiments comprising two amorphous organic pesticides, the following combinations are within the scope of the present disclosure: (i) two insecticide species; (ii) two fungicide species; (iii) two herbicide species; (iv) an insecticide species and a fungicide species; (v) an insecticide species and a herbicide species; and (vi) a fungicide species and a herbicide species. In embodiments including three amorphous organic pesticides, the following non-limiting combinations are within the scope of this disclosure: (i) three insecticide species; (ii) three fungicide species; (iii) three herbicide species; (iv) an insecticide species, a fungicide species, and a herbicide species; (v) two insecticide species and a herbicide species; (vi) two insecticide species and a fungicide species, (vii) an insecticide species and two fungicide species; (vii) an insecticide species and two herbicide species; (viii) two herbicide species and a fungicide species; (viii) two fungicide species and a herbicide species. One non-limiting example of a combination of two organic pesticide species is indoxacarb and rynaxypyr.

[0035] In some crystallization embodiments, at least one crystalline organic pesticide comprises two or more organic pesticide species. In embodiments comprising two crystalline organic species, the combination of insecticides, fungicides, and herbicides described for the amorphous organic pesticide is within the scope of the present disclosure. Similarly, in embodiments comprising three crystalline organic species, the combination of insecticides, fungicides, and herbicides described for the amorphous organic pesticide is within the scope of the present disclosure.

[0036] In some crystallization embodiments, the at least one amorphous organic pesticide comprises two or more organic pesticide species, and the at least one crystalline organic pesticide comprises two or more organic pesticide species, each of the two or more amorphous organic pesticide species independently selected from the insecticides, fungicides, and herbicides described above, and each of the two or more crystalline organic pesticide species independently selected from the insecticides, fungicides, and herbicides described above.

[0037] In some aspects, formulation additives (also called adjuvants) may be used. In some aspects, one or more adjuvants are formulation aids. In some aspects, the adjuvants are selected from additional water, dispersants, surfactants, biocides, antifoaming agents, antifreeze agents, rheology modifiers (viscosity modifiers), wetting agents, non-aqueous solvents, and combinations thereof. In one embodiment, the formulation additives are selected from additional water, dispersants, antifreeze agents, viscosity modifiers, antifoaming agents, bactericides, surfactants, and combinations thereof.

[0038] In one embodiment, the compositions and formulations of the present disclosure may further comprise a dispersant. The dispersant can promote dispersion of the active ingredient in the formulation and prevent clumping after dispersion in water. The dispersant can be selected from any dispersant known in the art.

[0039] In some embodiments, the dispersing agent is selected from ethoxylated fatty alcohol phosphate esters such as Dextrol OC-180 (phosphate ester salt of ethoxylated alcohol, 39-43% alcohol, 4-6% ethoxylation), Dextrol OC-70, Dextrol OC-50, Dextrol OC-15, Stepfac 8181K, Stepfac 8181 PT3K, Surfom SC8216, Soprophor 3D33 (tristyrylphenol ethoxylate phosphate ester - acid form), Surfom 1323 SC, Stepfac TSP-PE, and naphthalenesulfonic acid derivatives or lignosulfonic acid derivatives. In one embodiment, the dispersing agent is Dextrol OC-180, Stepfac 8181K, Stepfac 8181 PT3K, Surfom SC8216, Soprophor 3D33, or Surfom 1323 SC. In one embodiment, the dispersing agent is Dextrol OC-180 or Soprophor 3D33.

[0040] In some embodiments, the dispersant may include at least one polymeric surfactant. Polymeric surfactants are classified into several categories, including, but not limited to, block copolymers, random copolymers, graft copolymers, and star polymers. Polymeric surfactants may be non-anionic or anionic. Non-limiting examples of block copolymers include Atlas™ G-5000 and Atlas™ G-5002L (butyl block copolymer). Non-limiting examples of graft copolymers include methacrylic acid-polyethylene oxide copolymers, such as Atlox® 4913 (acrylic copolymer solution containing propylene glycol, acrylic copolymer, water, and methyl ethyl ketone, 33% active, HLB=12) and STEP-FLOW® 4000. A non-limiting example of a nonionic polymer is Break Thru® DA647. Non-limiting examples of anionic polymers are modified styrene (meth)acrylic copolymers (eg, Metasperse™ 550s) or lignosulfonates (eg, Reax 88B or Borresperse NA).

[0041] In one embodiment, the dispersant is present in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, or about 15 wt%, and any range consisting thereof, for example, about 0.1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 3 wt%.

[0042] In one embodiment, the compositions and formulations of the present disclosure may further comprise a wetting agent. The wetting agent may facilitate the grinding process. In one embodiment, the wetting agent is selected from nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, and combinations thereof. In one embodiment, the wetting agent is an alkyl polyglycoside, non-limiting examples of which include Agnique PG9116, Agnique PG8107, Agnique PG8105, and alkyl ethoxylates.

[0043] In one embodiment, the humectant is present in an amount of about 0.01%, about 0.1%, about 1%, about 2%, about 3%, about 4%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, or about 35%, and any range consisting thereof, for example, about 0.01% to about 35% by weight, about 0.01% to about 25% by weight, about 0.01% to about 20% by weight, about 0.01% to about 15% by weight, about 0.01% to about 5% by weight, about 0.1% to about 5% by weight, about 0.1% to about 2% by weight, or about 0.1% to about 1% by weight.

[0044] Non-limiting examples of nonionic surfactants include alkoxylates, fatty alcohol alkoxylates, siloxanes / silicones, alkylphenol alkoxylates, fatty acid alkoxylates, alkoxylated amines, alkoxylated fatty acid amides, end-blocked alkoxylates, fatty acid esters of polyhydroxy compounds, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkyl polyglucosides, amine oxides, and combinations thereof. The alkoxy groups may suitably be ethoxy, propoxy, or a combination of ethoxy and propoxy groups in a random or block configuration.

[0045] More particularly, non-limiting examples of nonionic surfactants include alcohol alkoxylates (e.g., alcohol alkoxylates based on natural and synthetic alcohols, which may be branched or linear, and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides (e.g., ethoxylated soybean oil, castor oil, and rapeseed oil); alkylphenol alkoxylates (e.g., octyl- (e.g., Triton® X series), nonyl- (e.g., Tergitol® HP series), dinonyl-, or dodecyl-); ethoxylated fatty acids; ethoxylated fatty esters and oils (e.g., Break Thru® SP series, 133); ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers (e.g., block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers (wherein the end blocks are prepared from propylene oxide); ethoxylated fatty acids), alkyd PEG (polyethylene glycol) resins, alkyd-type copolyesters, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; sugar derivatives such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides; and combinations thereof. In one embodiment, the nonionic surfactant is Agnique PG 9116.

[0046] In some embodiments, the nonionic surfactant component comprises at least one nonionic surfactant selected from sorbitan fatty acid esters, polyethoxylated sorbitan fatty acid esters, sorbitol ethoxylate esters, and combinations thereof. Non-limiting examples of sorbitan fatty acid esters include sorbitan monolaurate (e.g., Span™ 20), sorbitan monopalmitate (e.g., Span™ 40), sorbitan monostearate (e.g., Span™ 60), sorbitan tristearate (e.g., Span™ 65), sorbitan monooleate (e.g., Span™ 80), sorbitan trioleate (e.g., Span™ 85), and combinations thereof. Non-limiting examples of polyethoxylated sorbitan fatty acid esters include Tween® 20, Tween® 21, Tween® 40, Tween® 60, Tween® 80, and Surfonic® L24-4. Non-limiting examples of sorbitol ethoxylate esters that may be suitable for the biopesticides described herein include polyoxyethylene sorbitol oleate (e.g., Arlatone® TV), polyoxyethylene sorbitol hexaoleate (e.g., Cirrasol® G-1086), polyoxyethylene sorbitol hexaoleate (e.g., Cirrasol® G-1096), polyoxyethylene oleate-laurate (e.g., Atlox 1045AR®), and combinations thereof. Polyethoxylated sorbitan fatty acid esters and sorbitol ethoxylate esters having a degree of ethoxylation of 20, 30, 40, 50, 60, 70 or 80 are generally suitable.

[0047] In some embodiments, the nonionic surfactant component may comprise at least one organosilicone surfactant. Non-limiting examples of organosilicone surfactants within the scope of the present disclosure include polyether siloxanes (e.g., Break Thru® OE441); polyether trisiloxanes (e.g., Break Thru® S240, Break Thru® S233); polyoxyethylene dimethyl siloxanes (e.g., Dyne-Amic® (mixture with methylated seed oil)); polyoxyethylene methyl polysiloxanes (e.g., KF-640 manufactured by Shin-Etsu Chemical Co., Ltd.); polyalkylene oxide-modified polymethyl siloxanes (e.g., Helena Kinetic manufactured by Chemical; polyoxyethylenepropylheptamethyltrisiloxane (e.g., Masil® SF19); polyether-modified polysiloxanes (e.g., Quark (mixtures with alkylphenol ethoxylates)); hydroxypropylheptamethyltrisiloxane (e.g., Silflow® (mixtures with ethoxylated acetate, polyethylene glycol monoallyl ether acetate, and polyethylene glycol diacetate)); polyalkylene oxide-modified heptamethyltrisiloxane (e.g., Silwet® L77); polyether / polymethylsiloxane copolymers (e.g., Syl-Coat®); polyoxyethylene-modified polydimethylsiloxanes (e.g., Xiameter®); polyoxyalkyleneoxypropylheptamethyltrisiloxane; siloxane / polyalkylene oxide copolymers (e.g., Vestis™ (mixtures with polyalkylene oxide)).In some embodiments, the nonionic surfactant organosilicone surfactant is a polyethertrisiloxane, such as Break Thru® S240 (a mixture of polyethertrisiloxane and alcohol ethoxylate (CAS 9043-30-5)), Break Thru® S321, Break Thru® S200, Break Thru® OE 441, Break Thru® S278, Break Thru® S243, Break Thru® S233, Silwet® L-77, Silwet® 408, Silwet® HS 429, Silwet® HS 312, Silwet® Y-12808, Silwet® L-7607, Silwet® L-7602, Silwet® L-7210, Silwet® L-7002, Silwet® L-720 and Silwet® L-7200, Sylgard® 309 and Silibase® 2848, and combinations thereof. In some embodiments, the organosilicone surfactant is Break Thru® S240. In some embodiments, the organosilicone surfactant is Silwet® HS 312.

[0048] In some aspects, the nonionic surfactant component may include at least one alcohol alkoxylate surfactant, at least one alkylphenol alkoxylate surfactant, at least one seed oil alkoxylate surfactant (e.g., Ecosurf® SA-4, Ecosurf® SA-7, Ecosurf® SA-9, and Ecosurf® SA-15), at least one alkylamine alkoxylate surfactant, at least one tallowamine alkoxylate surfactant, at least one fatty acid alkoxylate surfactant, and combinations thereof. In some aspects, the alkoxylates may be end-capped. Alcohol alkoxylates generally include a hydrophobic alkyl chain attached to a hydrophilic alkoxy chain by an ether linkage and have the general formula R-(OC 2~4 ) n -OH. R is C 6~18 It can be a straight or branched chain alkyl. The alkoxy moiety (OC 2~4 ) can be ethoxy, n-propyl, i-propyl, n-butyl, i-butyl, or tert-butyl. In some embodiments, the alkoxy moiety can be a block copolymer of polymeric ethoxy and polymeric propoxy or polymeric butoxy, where n can suitably be an integer from 2 to 100. Suitable alcohol alkoxylates include linear alcohol alkoxylates, branched alcohol alkoxylates, secondary alcohol alkoxylates, and mixtures thereof. Non-limiting examples of alcohol alkoxylates include: Plurafac® SL-42 (C 6~10 -(PO)3(EO)6); Plurafac (registered trademark) ) SL-62(C 6~10 -(PO)3(EO)8);General structure Guerbet C 10 -(PO) a (EO) bLutensol® XL series (including, but not limited to, Lutensol® XL-40, Lutensol® XL-50, Lutensol® XL-60, Lutensol® XL-70, Lutensol® XL-79, Lutensol® XL-80, Lutensol® XL-89, Lutensol® XL-90, Lutensol® XL-99, Lutensol® XL-100, and Lutensol® XL-140); general structure Guerbet C 10 -(EO) a Lutensol® XP series (including but not limited to Lutensol® XP-40, Lutensol® XP-50, Lutensol® XP-60, Lutensol® XP-70, Lutensol® XP-79, Lutensol® XP-80, Lutensol® XP-89, Lutensol® XP-90, Lutensol® XP-99, Lutensol® XP-100); 10 -(EO) a Lutensol® ON series (including but not limited to Lutensol® ON-30, Lutensol® ON-50, Lutensol® ON-60, Lutensol® ON-70, Lutensol® ON-80, Lutensol® ON-110); 13 / 15 -(EO) a Lutensol® AO series (including but not limited to Lutensol® AO-3, Lutensol® AO-5, Lutensol® AO-7, Lutensol® AO-79, Lutensol® AO-8, Lutensol® AO-11); 13 -(EO) aLutensol® TO series (including but not limited to Lutensol® TO-6, Lutensol® TO-65, Lutensol® TO-7, Lutensol® TO-79, Lutensol® TO-8, Lutensol® TO-89, Lutensol® TO-10, Lutensol® TO-109, Lutensol® TO-12, Lutensol® TO-129, Lutensol® TO-15, Lutensol® TO-20); 11~ C 14- -C 13 Rich (EO) a Lutensol® TD series (including but not limited to Lutensol® TDA-6, Lutensol® TDA 8, Lutensol® TDA-9, Lutensol® TDA-10); m (EO) n Ecosurf® EH series (including Ecosurf® EH-3, Ecosurf® EH-6 and Ecosurf® EH-9); Ecosurf® SA series (including Ecosurf® SA-4 (C 6~12 -(PO) 3~4 (EO)4), Ecosurf(registered trademark) SA-7(C 6~12 -(PO) 3~4 (EO)7 and Ecosurf® SA-9 (C 6~12 -(PO) 3~4(EO)9); Tergitol® 15-S-3, Tergitol® 15-S-5, Tergitol® 15-S-7, Tergitol® 15-S-9, Tergitol® 15-S-12, Tergitol® 15-S-15, Tergitol® 15-S-20, Tergitol® 15-S-30, and Tergitol® 15-S-40; Tergitol® L-61, Tergitol® L-62, Tergitol® L-64, Tergitol® L-81, and Tergitol® L-101; Tergitol® TMN-3, Tergitol® TMN-6, and Tergitol® TMN-10), and combinations thereof. In some embodiments, the alcohol alkoxylate is Lutensol® TDA 6. In some embodiments, the alcohol alkoxylate is Lutensol® TO 6. In some embodiments, the alcohol alkoxylate is Lutensol® TO 8.

[0049] In some embodiments, the nonionic surfactant component may include at least one polymeric surfactant. Polymeric surfactants are classified into several categories, including, but not limited to, block copolymers, random copolymers, graft copolymers, and star polymers. Non-limiting examples of polymeric monomer units include ethylene oxide, propylene oxide, acrylic, styrene, methacrylic, hydroxystearate, and esters (e.g., alkyd). Examples include, but are not limited to, EO / PO block copolymers, acrylic / styrene copolymers, methacrylic copolymers, polyhydroxystearate derivatives, alkyd PEG resin derivatives, and combinations thereof. Non-limiting examples of block copolymers include Atlas™ G-5000 and Atlas™ G-5002L (butyl block copolymer). Non-limiting examples include methacrylic acid-polyethylene oxide copolymers such as Atlox® 4913 (acrylic copolymer solution containing propylene glycol, acrylic copolymer, water, and methyl ethyl ketone, 33% active, HLB=12) and STEP-FLOW® 4000. In some embodiments, the nonionic surfactant component includes Atlox® 4913 or STEP-FLOW® 4000. In some embodiments, the nonionic surfactant component includes Atlas™ G-5000. In some embodiments, the nonionic surfactant component includes Atlox® 4913 or STEP-FLOW® 4000, Atlas™ G-5000, and Lutensol® TDA6.

[0050] In one embodiment, the nonionic surfactant is present in an amount ranging from about 0.01% to about 10% by weight. In another embodiment, the nonionic surfactant is present in an amount ranging from about 0.1% to about 5% by weight. In another embodiment, the nonionic surfactant is present in an amount ranging from about 0.1% to about 2% by weight. In another embodiment, the nonionic surfactant is present in an amount ranging from about 0.1% to about 1% by weight.

[0051] The composition prepared according to the present disclosure may contain one or more anionic surfactants.Non-limiting examples of anionic surfactants include alkylarylsulfonic acid and its salts; carboxylated alcohols; diphenylsulfonate derivatives; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; salts of sulfates of alkoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of fractionated petroleum; sulfosuccinamates; sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates; and combinations thereof. Non-limiting examples of cationic counterions of anionic surfactants in salt form include, but are not limited to, alkali metals, alkaline earth metals, ammonium or (C 1~6 ) alkylammonium cations may be included.

[0052] Non-limiting examples of anionic surfactants within the scope of the present disclosure include ammonium lauryl sulfate; magnesium lauryl sulfate; sodium 2-ethyl-hexyl sulfate; sodium octyl sulfate; sodium oleyl sulfate; sodium tridecyl sulfate; triethanolamine lauryl sulfate; ammonium nonylphenol ether sulfate; ammonium nonoxynol-4-sulfate sulfosuccinamate; N-(1,2-dicarboxyethyl)-N-octadecyl sulfo-succinamic acid tetrasodium; diamyl ester of sodium sulfosuccinate; dihexyl ester of sodium sulfosuccinate; dioctyl ester of sodium sulfosuccinate; dihexyl ester of sodium sulfosuccinate; dioctyl ester of sodium sulfosuccinate (Aerosol OT 75 PG); calcium naphthalene sulfonate (DAXAD® 19LCAD); sodium methyl oleyl taurate (Geropon® T-77); sodium dodecylbenzenesulfonate; sodium dodecyl sulfate; N-oleyl N-methyl taurate; 1,4-dioctoxy-1,4-dioxo-butane-2-sulfonic acid; sodium lauryl sulfate; sodium lauryl ether sulfate (Steol CS-370); calcium dodecylbenzenesulfonate (Rhodacal® 60BE and 70B); isopropylamine dodecylbenzenesulfonate (Bio-Soft® N-411); sodium diisopropyl naphthalenesulfonate (Morwet® IP); and combinations thereof. In one embodiment, the anionic surfactant is Aerosol OT 75 PG. In one embodiment, the anionic surfactant comprises a blend of sodium decyl sulfate and sodium dodecyl sulfate. In one such embodiment, the anionic surfactant is Polystep® B25U.

[0053] In some aspects of the present disclosure, the surfactant component may comprise a mixture of at least one nonionic surfactant and at least one anionic surfactant.

[0054] In one embodiment, the anionic surfactant is present in an amount ranging from about 0.01% to about 15% by weight. In another embodiment, the nonionic surfactant is present in an amount ranging from about 0.1% to about 2% by weight. In another embodiment, the nonionic surfactant is present in an amount ranging from about 0.1% to about 1% by weight.

[0055] In some embodiments of the present disclosure, surfactant component can optionally comprise at least one cationic surfactant.Non-limiting examples of cationic surfactant include amide and ethoxylated amide; amine (for example, N-alkylpropanediamine, tripropylenetriamine and dipropylenetetramine); ethoxylated amine, ethoxylated diamine and propoxylated amine (prepared from amine and ethylene oxide, propylene oxide, butylene oxide or their mixture); amine salt, for example, acetate amine and diamine salt; quaternary ammonium salt, for example, quaternary salt, ethoxylated quaternary salt and diquaternary salt; amine oxide, for example, alkyldimethylamine oxide and bis-(2-hydroxyethyl)-alkylamine oxide; and combinations thereof.

[0056] In some embodiments of the present disclosure, the surfactant component may optionally include at least one zwitterionic (amphoteric) surfactant. Non-limiting examples of zwitterionic (amphoteric) surfactants include betaine, N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid, C 8~18 Included are alkylaminoacetic acids containing alkyl groups and combinations thereof.

[0057] In embodiments in which the surfactant component comprises one or more nonionic surfactants and one or more anionic surfactants, the weight ratio of total nonionic surfactants to total anionic surfactants is suitably about 5:1, about 4:1, about 3.5:1, about 3.25:1, about 3:1, about 2.75:1, about 2.5:1, about 2.25:1, about 2:1, about 1.75:1, about 1.5:1, about 1.25:1, or about 1:1, and any range therein, such as from about 5:1 to about 1:1, from about 3.5:1 to about 1:1, from about 3.5:1 to about 1.5:1, from about 3.25:1 to about 1.75:1, from about 3:1 to about 1.75:1, from about 2.75:1 to about 1.75:1, or from about 2.75:1 to about 1.5:1. In such embodiments, the total nonionic surfactant content in the concentrate composition is suitably about 1 wt.%, about 2 wt.%, about 5 wt.%, about 10 wt.%, about 12.5 wt.%, about 15 wt.%, about 17.5 wt.%, about 20 wt.%, about 22.5 wt.%, about 25 wt.%, about 30 wt.%, or about 35 wt.%, and any range consisting thereof, such as about 1 wt.% to about 35 wt.%, about 1 wt.% to about 10 wt.%, about 2 wt.% to about 10 wt.%, about 2 wt.% to about 35 wt.%, about 5 wt.% to about 30 wt.%, about 10 wt.% to about 25 wt.%, about 12.5 wt.% to about 20 wt.%, or about 12.5 wt.% to about 17.5 wt.%. In such embodiments, the total anionic surfactant content in the concentrate composition is suitably about 0.1 wt.%, about 0.2 wt.%, about 0.3 wt.%, about 0.4 wt.%, about 0.5 wt.%, about 0.75 wt.%, about 1 wt.%, about 1.5 wt.%, about 2 wt.%, about 2.5 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 12.5 wt.%, about 15 wt.%, about 20 wt.%, or about 25 wt.%, and any range consisting thereof, such as about 2 wt.% to about 25 wt.%, about 2.5 wt.% to about 20 wt.%, about 2.5 wt.% to about 15 wt.%, about 2.5 wt.% to about 10 wt.%, or about 5 wt.% to about 10 wt.%.

[0058] In one embodiment, the compositions and formulations of the present disclosure may further comprise a cryoprotectant. The cryoprotectant may prevent the formulation from freezing. In one embodiment, the cryoprotectant is selected from inorganic salts selected from propylene glycol, glycerol, urea, ammonium, sodium, potassium, and lithium salts of sulfate, nitrate, chloride, citric acid, phosphoric acid, polyphosphate, acetate, tartaric acid, and succinate, calcium salts, and magnesium salts of nitrate, chloride, citric acid, acetate, tartaric acid, and succinate, and combinations thereof. In some aspects of the present disclosure, the cryoprotectant is propylene glycol. In some aspects of the present disclosure, the cryoprotectant is glycerol. In some aspects of the present disclosure, the cryoprotectant is ammonium sulfate. In some aspects of the present disclosure, the cryoprotectant is a mixture of glycerol and ammonium sulfate.

[0059] In one embodiment, the compositions and formulations of the present disclosure may further comprise a biocide. The biocide may prevent bacterial growth. Suitable biocides include, but are not limited to, germicides such as Legend™ MK (a mixture of 5-chloro-2-methyl-3(2H)-isothiazolone and 2-methyl-3(2H)-isothiazolone), EDTA (ethylenediaminetetraacetic acid), formaldehyde, benzoic acid, or 1,2-benzisothiazol-3(2H)-one or its salts, such as Proxel® BD or Proxel® GXL (Arch), Acticide LA 1209, Acticide LG, Acticide SPX, Proxel GXL, Kathon CG / ICP, and Kathon CG / ICP II. In one embodiment, the biocide is selected from 2-bromo-2-nitropropane-1,3-diol, 5-chloro-2-methyl-2H-isothiazol-3-one, 2-methyl-2H-isothiazol-3-one, and combinations thereof. In one embodiment, the biocide is Proxel GXL and / or Acticide LG.

[0060] In one embodiment, the biocide is present in an amount ranging from about 0.01% to about 2% by weight. In another embodiment, the biocide is present in an amount ranging from about 0.01% to about 1% by weight. In another embodiment, the biocide is present in an amount ranging from about 0.01% to about 0.5% by weight. In another embodiment, the biocide is present in an amount ranging from about 0.01% to about 0.1% by weight.

[0061] In one embodiment, the compositions and formulations of the present disclosure may further comprise an antifoaming agent. The antifoaming agent can prevent foaming during product manufacturing and handling. In one embodiment, the antifoaming agent is selected from silicone-based emulsions. In one embodiment, the antifoaming agent is a polydimethylsiloxane emulsion, such as, but not limited to, Xiameter AFE-0100, SAG 1572, Agnique DFM111S, Break Thru AF9903, or Silfoam SRE antifoam emulsion (polydimethylsiloxane emulsion, 35%). In one embodiment, the antifoaming agent is Silfoam SRE antifoam or Xiameter AFE-0100.

[0062] In one embodiment, the antifoaming agent is present in an amount ranging from about 0.01% to about 2% by weight. In another embodiment, the antifoaming agent is present in an amount ranging from about 0.01% to about 1% by weight. In another embodiment, the antifoaming agent is present in an amount ranging from about 0.01% to about 0.5% by weight.

[0063] In one embodiment, the compositions and formulations of the present disclosure may further comprise a rheology modifier. The rheology modifier can prevent settling and sedimentation. In one embodiment, the rheology modifier is a viscosity modifier. In one embodiment, the rheology modifier is selected from magnesium aluminosilicate hydrate, xanthan gum, amorphous silica, and combinations thereof. In one aspect, suitable commercially available rheology modifiers include, for example, VanGel B, Veegum K, Veegum HS, Veegum R, Veegum T, Veegum Pure, Acti-gel 208, Rhodopol 23, Kelzan S, Kelzan S plus, Aerosil, AEROSIL® R202, AEROSIL® R805, AEROSIL® R812S, AEROSIL® R816, AEROSIL® R972, AEROSIL® R974, AEROSIL® 200, AEROSIL® 300, AEROSIL® 380, and bentonite (e.g., Vanatural). In another aspect, suitable viscosity modifiers are sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. In one embodiment, the rheology modifier is Rhodopol 23 and / or Veegum R.

[0064] In one embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 5% by weight. In another embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 4% by weight. In another embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 3% by weight. In another embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 2% by weight. In another embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 1% by weight. In another embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 0.5% by weight. In another embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 0.25% by weight. In another embodiment, the rheology modifier is present in an amount ranging from about 0.01% to about 0.1% by weight.

[0065] In one embodiment, the crystalline pesticide formulation of the present disclosure may further comprise a safener. As used herein, the term "safener" refers to a substance that, when added to a herbicide formulation, eliminates or reduces the phytotoxic effect of the herbicide on a particular crop. Those skilled in the art will recognize that the selection of a safener will depend in part on the target crop and the particular pesticide or combination of pesticides. Suitable safeners include, for example, furilazole, AD67 (4-(dichloroacetyl)-1-oxa-4-azaspiro[4,5]decane), benoxacor, cloquintocet-mexyl, BCS (1-bromo-4-[(chloromethyl)sulfonyl]benzene), cyometrinil, cyprosulfamide, dichlormid, dicyclonone, dietholate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen, mefenpyr, mephenate, MG191 (2-(dichloromethyl)-2-methyl-1,3-dioxolane), methoxyphenone, naphthalic anhydride, oxabetrinil, and combinations thereof. In one embodiment, the safener is cloquintocet-mexyl.

[0066] In one embodiment, an aqueous suspension of a crystalline organic pesticide can be prepared as follows: A mixture is formed containing at least one source of amorphous organic pesticide, water, and at least one formulation additive. At least one crystalline organic pesticide is added to the mixture. The at least one amorphous organic pesticide is then crystallized from the mixture. In some embodiments, the at least one amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a solid amorphous form, a liquid, a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof. In some embodiments, the at least one amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a liquid, a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof. In some embodiments, a melt of the amorphous pesticide is formed in a first vessel at a temperature described elsewhere herein, such as about 55°C to about 100°C. In a second vessel, a mixture of formulation ingredients is formed, including water and at least one formulation additive (ingredient). The formulation additives are described elsewhere herein. In one embodiment, the additive comprises at least one dispersant, at least one surfactant, or a combination thereof. The weight ratio of the amorphous organic pesticide to the formulation additive, excluding water, is suitably about 1:1, about 1.25:1, about 1.5:1, about 1.75:1, about 2:1, about 2.25:1, about 2.5:1, about 3:1, about 3.5:1, about 4:1, about 4.5:1, or about 5:1, or any range therein, such as about 1:1 to about 5:1, about 1.25:1 to about 3:1, or about 1.5:1 to about 2.5:1. In some aspects, the temperature of the melt of the amorphous pesticide and the temperature of the mixture of formulation ingredients are approximately equal. The melt of the amorphous pesticide and the mixture of formulation ingredients are combined with stirring to form a mixture. In some embodiments, the temperature may be maintained at or near the melt temperature for a period of time, such as about 5 minutes, about 10 minutes, about 15 minutes, about 30 minutes, about 1 hour, about 2 hours or more, while stirring.

[0067] In some embodiments, the mixture of amorphous pesticides and the mixture of ingredients may optionally be cooled to an intermediate lower temperature with stirring before adding at least one crystalline organic pesticide to the mixture. For example, the temperature may be cooled to about 5°C, about 10°C, about 15°C, or about 20°C. In some aspects, the intermediate cooling temperature is a temperature above the supersaturation temperature. The temperature of the cooled mixture may be maintained around the cooling temperature with stirring for a period of time such as about 5 minutes, about 10 minutes, about 15 minutes, about 30 minutes, about 1 hour, about 2 hours, or more. In such embodiments, the cooled mixture of amorphous pesticides and the mixture of ingredients may optionally be further cooled with stirring before adding at least one crystalline organic pesticide to the mixture. In some aspects, the final intermediate cooling temperature is a temperature above the supersaturation temperature. In some optional embodiments, the mixture of amorphous pesticide and the mixture of formulation ingredients may be cooled to the final temperature stepwise, continuously, or semi-continuously with stirring over a period of time such as about 30 minutes, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, or more.

[0068] In some embodiments, at least one crystalline organic pesticide is added to the optionally cooled mixture of amorphous pesticide and the mixture of formulation ingredients with stirring. The resulting mixture is then further cooled to produce a supersaturated solution and induce crystallization of the amorphous pesticide, thereby forming a mixture comprising the crystalline organic pesticide, water, and at least one formulation additive. The final temperature can suitably be about 0°C, about 5°C, about 10°C, about 15°C, or about 20°C. Cooling to the final temperature can be carried out stepwise, semi-continuously, or continuously over a period of time, such as about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, or more.

[0069] In another embodiment for preparing an aqueous suspension of a crystalline organic pesticide, a mixture is formed containing at least one source of crystalline organic pesticide, water, and at least one formulation additive. At least one amorphous organic pesticide is added to the mixture. The at least one amorphous organic pesticide is then crystallized from the mixture. In some embodiments, the at least one amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a solid amorphous form, a liquid, a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof. In some embodiments, the at least one amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a liquid, a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof. In one such embodiment, a melt of the amorphous pesticide is formed in a first vessel at a temperature described elsewhere herein, such as about 55°C to about 100°C. In a second vessel, a mixture of formulation ingredients is formed, including water, at least one crystalline organic pesticide, and at least one formulation additive (ingredient). The formulation additives are suitably selected from additional water, dispersants, antifreeze agents, viscosity modifiers, antifoam agents, bactericides, surfactants, and combinations thereof. In one embodiment, the additives include at least one dispersant, at least one surfactant, or a combination thereof. The weight ratio of the amorphous organic pesticide to the formulation additives, excluding water, is suitably about 1:1, about 1.25:1, about 1.5:1, about 1.75:1, about 2:1, about 2.25:1, about 2.5:1, about 3:1, about 3.5:1, about 4:1, about 4.5:1, or about 5:1, or greater, and any range therein, for example, about 1:1 to about 5:1, about 1.25:1 to about 3:1, or about 1.5:1 to about 2.5:1. In some embodiments, the temperature of the melt of the amorphous pesticide and the temperature of the mixture of water, crystalline organic pesticide, and at least one formulation additive are approximately equal. The melt of the amorphous pesticide and the aqueous mixture containing the crystalline organic pesticide are combined with stirring to form a mixture, in some embodiments, the temperature can be maintained at about the temperature of the melt for a period of time, such as about 5 minutes, about 10 minutes, about 15 minutes, about 30 minutes, about 1 hour, about 2 hours, or more, while stirring.

[0070] Optionally, the mixture can be cooled to an intermediate lower temperature while stirring before adding at least one crystalline organic pesticide to the mixture. For example, the temperature can be cooled to about 5°C, about 10°C, about 15°C, or about 20°C. In some embodiments, the intermediate cooled temperature is a temperature above the supersaturation temperature. The temperature of the cooled mixture can be maintained around the cooling temperature while stirring for a period of time such as about 5 minutes, about 10 minutes, about 15 minutes, about 30 minutes, about 1 hour, about 2 hours, or more. In some embodiments, the final intermediate cooled temperature is a temperature above the supersaturation temperature. In some optional embodiments, the mixture can be cooled to the final intermediate temperature continuously or semi-continuously while stirring over a period of time such as about 30 minutes, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, or more. The mixture is then further cooled to produce a supersaturated solution and induce crystallization of the amorphous pesticide, thereby forming a mixture comprising a crystalline organic pesticide, water, and at least one formulation additive. The final temperature may suitably be about 0° C., about 5° C., about 10° C., about 15° C., or about 20° C. Cooling to the final temperature may be carried out stepwise, semi-continuously, or continuously over a period of time, such as about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, or more.

[0071] In some crystallization embodiments, at least a portion of the crystallized pesticide composition may be in the form of agglomerates that are generally not freely flowable. In such embodiments, the agglomerated crystallized pesticide may be suitably processed by methods known in the art to form a flowable suspension. For example, the composition may be homogenized, for example, by impacting the crystalline material to break up the agglomerates. In such an embodiment, the crystalline agglomerates may be homogenized using a high-shear mixer to form a flowable suspension.

[0072] In one embodiment, the crystalline pesticide formulation can be milled to a desired particle size. In one embodiment, the suspension concentrate formulation has an average D of about 0.5 μm, about 1 μm, about 2 μm, about 3 μm, about 4 μm, about 5 μm, about 10 μm, about 15 μm, or about 20 μm, and any range consisting thereof, such as about 0.5 μm to about 20 μm, about 0.5 μm to about 10 μm, about 0.5 μm to about 5 μm, or about 0.5 μm to about 3 μm. (90) It can be ground to a particle size.

[0073] In one embodiment, the crystalline pesticide formulation is optionally filtered and dried before being milled. In one embodiment, the crystalline pesticide formulation is filtered before being milled. In one embodiment, the crystalline pesticide formulation is dried before being milled.

[0074] In one embodiment, the process step of grinding the mixture is carried out using a device selected from an attritor mill, a bead mill, a colloid mill, a rotor stator, a jet mill, an air classifier mill, a ring mill, a hammer mill, a pin mill, a pack mill, and combinations thereof. In another embodiment, the process step of grinding the mixture is carried out in a mill selected from a ring mill, a bead mill, an attritor mill, a jet mill, an air classifier mill, and combinations thereof.

[0075] In one embodiment, the crystalline pesticide formulation is formed in a mixing vessel before being transferred to a grinding device. In one embodiment, the crystalline pesticide formulation is formed in the grinding device. In one embodiment, the crystalline pesticide formulation is transferred to a holding tank after grinding in the grinding device. In one embodiment, the crystalline pesticide formulation is prepared in a continuous process.

[0076] In one embodiment, one or more formulation additives may be combined with the crystalline pesticide formulation of the present disclosure, such as a ground crystalline pesticide formulation. The formulation additives are described elsewhere herein and are selected from additional water, dispersants, antifreeze agents, viscosity modifiers (e.g., thickeners), antifoam agents, fungicides, surfactants, and combinations thereof.

[0077] In any of the embodiments of the present disclosure, the crystalline pesticide formulation is a suspension concentrate. The total pesticide content of the suspension concentrate of the present disclosure, based on the active ingredient, is about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, or about 45% by weight, and any range consisting thereof, for example, about 10% to about 45%, about 20% to about 45%, or about 30% to about 45% by weight. Alternatively, the total pesticide content of the suspension concentrates of the present disclosure based on active ingredients is about 100 g / L, about 150 g / L, about 200 g / L, about 250 g / L, about 300 g / L, about 350 g / L, about 400 g / L, about 450 g / L, about 500 g / L, about 550 g / L, or about 600 g / L, and any range consisting therein, for example, about 200 g / L to about 600 g / L, about 300 g / L to about 600 g / L.

[0078] In some embodiments, the suspension concentrate compositions of the present disclosure can be diluted with water and optional additives and co-pesticides to form spray mixtures that can be used in accordance with the present disclosure. The concentration of the active compound in the spray mixtures of the present disclosure can vary within a specific range. Generally, the concentration of the active compound is from about 0.0003 to about 5% by weight of active ingredient, in one embodiment from about 0.003 to about 3% by weight, and in another embodiment from about 0.01 to about 0.06% by weight.

[0079] To prepare an aqueous spray mixture ready for application, the concentrated formulation can be mixed with a certain amount of water, stirring and / or pumping as necessary to evenly distribute the formulation in the water.

[0080] Conventional mixing and / or spray equipment suitable for the process can be used to prepare and apply the spray mixtures of the present disclosure.

[0081] Suspension concentrate compositions and / or aqueous spray mixtures produced in accordance with the present disclosure may optionally contain one or more additional pest control agents selected from insecticides, herbicides, biopesticides, nematicides, fungicides, and fungicides. General references for these pest control agents (i.e., insecticides, fungicides, nematicides, miticides, herbicides, and biological agents) include The Pesticide Manual, 13th Edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2004. nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0082] Non-limiting examples of additional insecticides include abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, acinonapyr, afidopyropen ([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylsilane, clopropanecarboxylate), amidoflumet, amitraz, avermectin, azadirachtin, azinphos methyl, benfuracarb, bensultap, benzpyrimoxane, bifenazate, bistrifluron, borate, brofuranilide, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carsol, chlorantraniliprole (Rynaxypyr®), chlorfenapyr, chlorfluazuron, chlorprallethrin, chlorpyrifos, chlorpyrifos-e, chlorpyrifos-methyl, chromafenozide, Clofentezine, chlorprallethrin, clothianidin, cycloprothrin, cycloxapride ((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine), cyenopyrafen, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin , diafenthiuron, diazinon, dichloromezothiaz, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinpropylidaz, dinotefuran, diofenolan, emamectin, emamectin benzoate, endosulfan, esfenvalerate, ethiprole, etofenprox, epsilon-metofluthrin, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin (2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), flonicamid, fluazaindolizine, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate), fluensulfone (5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole), fluhexafon, fluopyram, Flupiprole (1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile), flupyradifurone (4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), flupirimine, fluvalinate, tau-fluvalinate, fluxametamide, fonofos, formetanate, fosthiazate, gamma-cyhalothrin, halofenozide, Heptafluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soap, isofenphos, isocycloceram, kappa-tefluthrin, lambda-cyhalothrin, lufenuron, malathion, meperfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate), methyl)phenyl]methyl (1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide, epsilon-metofluthrin, epsilon-monfluorothrin, monocrotophos, monofluorothrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 3-(2-cyano-1-propen-1-yl)-2,2-Dimethylcyclopropanecarboxylate), nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, N-[1,1-dimethyl-2-(methylthio)ethyl]-7-fluoro-2-(3-pyridinyl)-2H-indazole-4-carboxamide, N-[1,1-dimethyl-2-(methylsulfinyl)ethyl]-7-fluoro-2-(3-pyridinyl)-2H-indazole-4-carboxamide, N-[1,1-dimethyl-2-(methylsulfonyl)ethyl]- 7-Fluoro-2-(3-pyridinyl)-2H-indazole-4-carboxamide, N-(1-methylcyclopropyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide, N-[1-(difluoromethyl)cyclopropyl]-2-(3-pyridinyl)-2H-indazole-4-carboxamide, oxamyl, oxazosulfil, parathion, parathion methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos , profluthrin, propargite, protrifenbute, piflubumid (1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide), pymetrozine, pyrafluprole, pyrethrins, pyridaben, pyridalyl, pyrifluquinazone, pyriminostrobin (methyl(αE)-2-[[[2-[ (2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate), pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spiropydione, spirotetramat, sulprofos, sulfoxaflor (N-[methyloxide[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-λ, 4-sulfanylidene]cyanamide), tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, kappa-tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2,3,3-tetramethylcyclopropanecarboxylate), thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, thioxazam Examples of insecticides that can be used include phen (3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin, triazameate, trichlorfon, triflumezopyrim (2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidinium inner salt), triflumuron, cyclopyrazoflurane, zeta-cypermethrin, Bacillus thuringiensis delta endotoxin, entomopathogenic bacteria, entomopathogenic viruses, or entomopathogenic fungi, and combinations thereof.

[0083] Non-limiting examples of additional fungicides include fungicides such as acibenzolar-S-methyl, aldimorph, ametoctrazine, aminopyrifen, amisulbrom, allilazine, azaconazole, azoxystrobin, benalaxyl (such as benalaxyl-M), bendanil, benomyl, benthiavalicarb (such as benthiavalicarb-isopropyl), benzovindiflupyr, bethoxadin, binapropacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, carboxymethylpropanol, ... Cin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride, copper sulfate, comoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, diclobenthiazox, dichlofluanid, diclocymet, diclomedine, dicloran, diethofencarb, difenoconazole, diflumetrim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole (diniconazole-M, etc.), dinocap, dipimethitron, di Thianon, dithiolane, dodemorph, dodine, econazole, etaconazole, edifenphos, enoxastrobin (also known as enestrobrin), epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, phenaminestrobin, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpicoxamide, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, fen Erimzone, flometoquin, florylpicoxamide, fluopimomide, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, flumorph, fluopicolide, fluopyram, fluoxapiprolin, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fthalide (also known as phthalide), fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazole, guazatine, imazalil,Imibenconazole, Iminoctadine albesilate, Iminoctadine triacetate, Inpirfluxam, Iodicarb, Ipconazole, Ipfentrifluconazole, Ipflufenoquine, Isofetamide, Iprobenfos, Iprodione, Iprovalicarb, Isoflucipram, Isoprothiolane, Isopyrazam, Isotianil, Kasugamycin, Kresoxim methyl, Lancotrione, Mancozeb, Mandipropamide, Mandestrobin, Maneb, Mapanipirin, Mefentrifluconazole, Mepronil, Meptyldinocap, Metalaxyl (Me Taraxyl-M / mefenoxam, etc.), metconazole, methasulfocarb, metiram, metominostrobin, methyltetraprole, metrafenone, myclobutanil, naphthitine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofrace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, penflufen, penthiopyrad, perfluazolate, phosphorous acid (its salts, e.g., fosetilure), Luminum, etc.), picoxystrobin, piperalin, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propiconazole, probineb, proquinazid, prothiocarb, prothioconazole, pydiflumetofen (Adepidyn®), pyraclostrobin, pyrametostrobin, pyrapropoin, pyroxystrobin, pyraziflumid, pyrazophos, pyribencarb, pyributacarb, pyridaclomethyl, pyrifenox, pyriophenone, perisoxazole, pyrimethanil, pyrifenox, pyrrole Lunitrin, pyroquilon, quinconazole, quinmethionate, quinofumelin, quinoxyfen, quintozene, silthiofam, sedaxane, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquine, teleclosalam, tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb, trifluanid, triadimefon, triadimenol, triarimol, triazoxide,tribasic copper sulfate, triclopyricarb, tridemorph, trifloxystrobin, triflumizole, trimofuramide tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, valifenalate (also known as valifenal), vinclozolin, zineb, ziram, zoxamide, 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, and combinations thereof.

[0084] Non-limiting examples of additional herbicides include cyclohexenone oxime ethers such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, butroxydim, clefoxydim or tepraloxydim; clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentiapropetyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl ... Phenoxyphenoxypropionic acid esters such as Quizalofop-P-methyl, Isoxapyrifop, Propaquizafop, Quizalofop-ethyl, Quizalofop-P-ethyl, or Quizalofop-tefuryl; Arylaminopropionic acids such as Flamprop-methyl or Flamprop-isopropyl; Acetolactate synthase inhibitors (ALS) such as Imazapyr, Imazaquin, Imazamethabenzmethyl (Imazame), Imazamox, Imazapic, or Imazethapyr; Pyrithiobac acid, Pyrithiobac sodium, Bispyribac sodium. KIH-6 Pyrimidyl ethers such as 127 or pyribenzoxim; sulfonamides such as florasulam, flumetsulam, or metosulam; amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfonamides sulfonylureas such as meturon-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, tritosulfuron, sulfosulfuron, foramsulfuron or iodosulfuron; amides such as aridochlor (CDAA), benzoylprop-ethyl, bromobutide, chioruthiamid, diphenamide, etobenzanidibenzchromate, fluthiamid, fosamin or monalid; auxin herbicides such as pyridine carboxylic acids, for example clopyralid or picloram; 2,4-D or benazolin;Auxin transport inhibitors such as napthalamethicone or diflufenzopyr; carotenoid biosynthesis inhibitors such as benzofenap, clomazone (dimethasone), diflufenican, fluorochloridone, fluridone, pyrazolinate, pyrazoxyfen, isoxaflutole, isoxachlorthole, mesotrione, sulcotrione (chlormethron), ketospiradox, flurtamone, norflurazon, or amitrole; enolpyruvylshikimate-3-phosphate synthase inhibitors (EPSPS) such as glyphosate or sulfosate; bialaphos or glyphosate Glutamine synthetase inhibitors such as ammonium fluorfosinate; lipid biosynthesis inhibitors such as anilides, for example anilofos or mefenacet; chloroacetanilides such as dimethenamid, S-dimethenamid, acetochlor, alachlor, butachlor, butenachlor, dietatylethyl, dimetolachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, prinachlor, terbuchlor, thenylchlor or xylaclor; butyrate, cycloate, diallate, dimepiperate, EP Thiourea such as TC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb (benthiocarb), triallate or vemonolate; or benfuresate or perfluidone; mitotic inhibitors such as asulam, carbetamide, chlorpropham, orbencarb, pronamide (propyzamide), propham or thiocarbazil; dinitroanilines such as benefin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine or trifluralin; dithiopyr or Pyridines such as thiazopyr; butamiphos, chlorthal dimethyl (DCPA), maleic hydrazide; protoporphyrinogen IX oxidase inhibitors such as acifluorfen, acifluorfen sodium, aclonifen, bifenox, chloronitrofen (CNP), ethoxyfen, fluorodifen, fluoroglycofen ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorofen, or oxyfluorofen; oxadiazoles such as oxadiargyl or oxadiazon;Cyclic imides such as azafenidin, butafenacil, carfentrazone ethyl, cinidon ethyl, flumiclorac pentyl, flumioxazin, flumipropin, flupropacil, fluthiacet methyl, sulfentrazone or thidiazimine; pyrazoles such as ET-751, JV485 or nipiraclofen; photosynthetic inhibitors such as propanil, pyridate or pyridafol; benzothiadiazinones such as bentazone; dinitrophenols such as bromofenoxime, dinoseb, dinoseb acetate, dinoterb or DNOC; dipyridylenes such as cyperquat chloride, difenzoquat methyl sulfate, diquat or paraquat dichloride; chlorobromuron, chlorotoluron, difenoxyuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazinone Ureas such as ron, methazole, methobenzuron, methoxyuron, monorinuron, nebron, siduron, or tebuthiuron; phenols such as bromoxynil or ioxynil; chloridazon; triazines such as ametryn, atrazine, cyanazine, desmaine, dimethametryn, hexazinone, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbuthylazine, or trietazine; triazinones such as metamitron or metribuzin; uracils such as bromacil, lenacil, or terbacil; or biscarbamates such as desmedipham or phenmedipham; synergists such as tridiphan; CIS cell wall synthesis inhibitors such as isoxaben or dichlobenil; dichloropropionic acids such as dalapon; dihydrobenzofurans such as ethofumesate; phenylacetic acids such as chlorfenac (fenac);Or aziprothrin, barban, beflubutamid, s-beflubutamid, beunsulide, benzthiazuron, benzofluor, bixlozone, buminafos, butidazole, buturon, cafenstrole, chlorbufam, chlorfenprop-methyl, chloroxuron, cinmethylin, cumyluron, cycluron, ciprazine, ciprazole, dibenzyluron, dipropetrin, dymron, eglinadin-ethyl, endothal, etiodin, flucabazone, fluoroventra In some embodiments, the herbicide is selected from the group consisting of beflubutamid, s-beflubutamid, rimisoxamid, bixlozone isoflex, napropamide, aclonifen, and combinations thereof.

[0085] Non-limiting examples of additional nematicides include fluopyram, spirotetramat, thiodicarb, fosthiazate, abamectin, iprodione, fluensulfone, dimethyl disulfide, thioxazaphen, 1,3-dichloropropene (1,3-D), metam (sodium and potassium), dazomet, chloropicrin, fenamiphos, ethoprophos, cadusafos, terbufos, imicyafos, oxamyl, carbofuran, thioxazaphen, Bacillus firmus, Pasteuria nishizawae, and combinations thereof. A non-limiting example of a fungicide is streptomycin. Non-limiting examples of additional acaricides include amitraz, thinomethionate, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben, tebufenpyrad, and combinations thereof.

[0086] One or more additives may optionally be combined with the aqueous spray mixture produced in accordance with the present disclosure. Examples of such additives include, for example and without limitation, safeners (described elsewhere herein), dispersants (described elsewhere herein), surfactants (described elsewhere herein), oils (e.g., crop oil concentrates and / or methylated seed oils), nitrogen-based fertilizers (e.g., ammonium sulfate and / or urea ammonium nitrate), antifoaming agents, suspending agents, buffers, conditioning or water softening agents, fixatives (spreading agents), drift control agents, and colorants.

[0087] herbivorous insects Phytophagous insects refer to invertebrate pests that cause damage to plants by feeding on them, for example, by feeding on the tissues of the foliage, stems, leaves, fruits, or seeds, or by sucking the vascular sap of the plant. Insects that feed on leaves may be external (epiparasitic), or they may sometimes specialize in particular cell types and bore holes into the tissue. Phytophagous insect species exist in most insect orders, including Hemiptera, Thysanoptera, Orthoptera, Lepidoptera, Coleoptera, Heteroptera, Hymenoptera, and Diptera.

[0088] Examples of agronomic or non-agronomic invertebrate pests include the noctuid moths, armyworms, loopers, and tobacco budworms (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), armyworm moth (Spodoptera eridania Cramer), fall armyworm (Spodoptera frugiperda J.E. Smith), beet armyworm (Spodoptera exigua Huebner), cotton leafworm (Spodoptera littoralis littoralis Boisduval), Yellow Stripped Armyworm (Spodoptera ornithogalli Guenee), Cutthroat Moth (Agrotis ipsilon Hufnagel), Mucuna Caterpillar (Anticarsia gemmatalis Huebner), Green Fruit Worm (Lithophane antennata Walker), Armyworm Moth (Barathra brassicae Linnaeus), Soybean Looper (Pseudoplusia includens Walker), Cabbage Looper (Trichoplusia ni Huebner), False Tobacco Moth (Heliothis virescens eggs, larvae and adults of Lepidoptera, such as the European corn borer (Ostrinia nubilis) Fabricius; borers from the family Pyralidae, case bearers, webworms, corn caterpillars, cabbage worms and skeletonizers (e.g. the European corn borer (Ostrinia nubilis)nubilalis Huebner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), turf worm (Herpetogramma licarsisalis Walker), sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer (Neoleucinodes elegantalis Guenee), green leafholder (Cnaphalocrocis medinalis), grape leafholder (Desmia funeralis Huebner), melon worm (Diaphania nitidaris) nitidalis Stoll), Cabbage center grub (Helluala hydralis Guenee), Yellow stem borer (Scirpophaga incertulas Walker), Early shoot borer (Scirpophaga infuscatellus Snellen), White stem borer (Scirpophaga innotata Walker), Top shoot borer (Scirpophaga nivella Fabricius), Dark-headed rice borer (Chilo polychrysus Meyrick), Striped rice borer (Chilo suppressalis Walker), Cabbage cluster caterpillar (Crocidolomia Sod webworms (Crambinae) such as Pyralidae (Cyperidae); leaf rollers (tortricidae); budworms (caterpillars that feed on plant buds); Seedworms and fruitworms (e.g., codling moth (Cydia pomonella Linnaeus), grapeberry moth (Endopiza viteana Clemens), pear fruit moth (Grapholita molesta Busck), citrus codling moth (Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantiana Lima), red-striped leafroller (Argyrotaenia velutinana Walker), diagonal-striped leafroller (Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postificittana postvittana Walker), European grapeberry moth (Eupoecilia ambiguella Huebner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leaf roller (Platynota stultana Walsingham), striped fruit tree tortrix moth (Pandemis cerasana Huebner), apple brown tortrix moth (Pandemis heparana Denis & Schiffermueller);as well as many other economically important Lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm moth larvae (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensis Walsingham), peach twig borer (Anarsia lineatella Zeller), potato leaf moth larvae (Phthorimaea operculella Zeller), spotted teniform leafminer (Lithocolletis blancardella)Fabricius), Asian apple leafminer (Lithocolletis ringoniella)Matsumura), rice leaf folder (Lerodea eufala)Edwards), apple leafminer (Leucoptera scitella)Zeller);Cockroaches from the families Blattidae and Blattidae (e.g., the Asian cockroach (Blatta orientalis Linnaeus), the Asian cockroach (Blatella asahinai Mizukubo), the German cockroach (Blattella germanica Linnaeus), the brown-striped cockroach (Supella longipalpa Fabricius), the American cockroach (Periplaneta americana Linnaeus), the brown brown cockroach (Periplaneta brunnea Burmeister), the Madeira cockroach (Leucophaea maderae) eggs, nymphs and adults of the order Blattella, including the brown cockroach (Periplaneta fuliginosa, Service), the Australian cockroach (Periplaneta australasiae, Fabr.), the lobster cockroach (Nauphoeta cinerea, Olivier) and the smooth cockroach (Symploce pallens, Stephens);Weevils from the families Pholioideae, Bruchidae and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), grain weevil (Sitophilus oryzae Linnaeus)), oak leaf weevil (Listronotus maculicollis Dietz), bluegrass weevil (Sphenophorus palustris) Coleoptera, including eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding, and vesicular-feeding larvae and adults, including the grass weevil (Sphenophorus parvulus Gyllenhal), the grass weevil (Sphenophorus venatus vestitus), and the Denverville bug (Sphenophorus cicatristriatus Fahraeus); Chrysomelidae, including bagworms, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers (e.g., the Colorado potato beetle (Leptinotarsa ​​decemlineata Say), and the western corn rootworm (Diabrotica virgifera LeConte));Scarab beetles and other beetles from the family Scarabaeidae (e.g., bean beetle (Popillia japonica Newman), red beetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse) Baraud), northern scarab beetle (Cyclocephala borealis Arrow), southern scarab beetle (Cyclocephala immaculata Olivier or C. lurida Bland), dung beetles and grubs (Scarabaeida spp.), dung beetle (Ataenius spretulus Haldeman); These include the greenish cockroach beetle (Cotinis nitida Linnaeus), the red-billed beetle (Maladera castanea Arrow), the May / June beetle (Phyllophaga spp.) and the European scarab beetle (Rhizotrogus majalis Razoumowsky); dermestidae beetles; click beetle larvae from the Elateridae family; bark beetles from the Scolytidae family and the red flour beetle from the Tenebrionidae family.

[0089] Further agronomic and non-agronomic pests include eggs, adults and larvae of Dermoptera, including earwigs from the family Dermoptera (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); mirid bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers from the family Cicadidae (e.g., Empoasca spp.), potato leafhoppers from the family Cimexidae, bedbugs (e.g., Cimex lectularius), lectularius Linnaeus), planthoppers from the superfamily Delphadoidea and Delphacidae, treehoppers from the family Cerambycidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, mealybugs from the family Pseudococcidae, scale insects from the families Coccidae, Diaspididae and Diaspididae, finches from the family Tingidae, stink bugs from the family Hemiptera, American long-horned stink bugs from the family Lygaeidae (e.g., the hairy American long-horned stink bug (Blissus leucopterus hirtus) Montandon) and the southern American long-horned stink bug (Blissus insularis) Insularis (Barber) and other seed pests from the Lygaeidae family, the foxtail bug from the Scypholidae family, the core bug from the Coreidae family, and the eggs, immatures, adults and larvae of the Hemiptera and Scypholidae suborders such as chigger larvae and cotton stainers from the Pyrrhocoridae family.

[0090] Agronomic and non-agronomic pests include eggs, larvae, nymphs and adults of the order Acari (mites), such as spider mites and red mites of the family Tetranychidae (e.g., apple red mite (Panonychus ulmi Koch), two-spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)); flat mites of the family Ornithine (e.g., citrus flat mite (Brevipalpus luisi)); lewisi McGregor); rust and bud mites of the family Eriophyidae and other foliar-feeding mites and mites important to human and animal health, namely house mites of the family Dermatophagoides, Demodex mites of the family Demodex mites, and acarid mites of the family Sarcophagidae; ticks of the family Ixodidae, commonly known as hard mites (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), Lone star tick (Amblyomma americanum Linnaeus)) and ticks of the family Ardisidae, commonly known as soft mites (e.g., relapsing fever tick (Ornithodoros tsurikata)). turicata), common poultry ticks (Argas radiatus); cricket mites, lice mites and scabies mites of the Sarcoptes scabra family;Grasshoppers, grasshoppers, and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locusts (Schistocerca gregaria Forskal), migratory locusts (Locusta migratoria Linnaeus), bush locusts (Zonocerus spp.), house crickets (Acheta domesticus Linnaeus), grasshoppers (e.g., tawny grasshoppers (Scapteriscus vicinae)), grasshoppers (e.g., brown ... Eggs, adults and nymphs of Orthoptera, including the Southern Mole Cricket (Scapteriscus borellii Giglio-Tos);Leafminers (e.g., Liriomyza spp., such as the bean leafminer (Liriomyza sativae Blanchard)), small insects, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), small house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp.), spp., Phormia spp.) and other blowfly pests, bot flies (e.g. Tabanus spp.), bot fly larvae (e.g. Gastrophilus spp., Oestrus spp.), cow flies (e.g. Hypoderma spp.), deer flies (e.g. Chrysops spp.), sheep lice (e.g. Melophagus ovinus Linnaeus) and other brachyhorns, mosquitoes (e.g. Aedes spp., Anopheles spp., Culex spp.), black flies (e.g. Prosimulium spp.), eggs, adults and nymphs of Diptera, including Culicoides (Culicoides spp.), Simulium spp., midges, sand flies, Sciaridae and other Mesoceratopsians; eggs, adults and nymphs of Thysanoptera, including onion thrips (Thrips tabaci Lindeman), broad-leaved flower thrips (Frankliniella spp.) and other foliar-feeding thrips;Florida carpenter ant (Camponotus floridanus Buckley), red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), white-legged ant (Technomyrmex albipes fr. Smith), large-headed ant (Pheidole sp.), ghost ant (Tapinoma melanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus), small fire ant (Wasmannia auropunctata) Also included are Hymenoptera pests, including ants of the family Formicidae, which include the fire ant (Solenopsis auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Foerster), and scented house ant (Tapinoma sessile Say). Other Hymenoptera, including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.);Termites of the families Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Isotermitidae (e.g., Cryptotermes sp.) and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen), Eastern Subterranean Termite (Reticulitermes flavipes Kollar), Western Subterranean Termite (Reticulitermes hesperus Banks), Formosan Termite (Coptotermes formosanus) formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), powder post termite (Cryptotermes brevis Walker), drywood termite (Incisitermes snyderi Light), southeastern subterranean termite (Reticulitermes virginicus Banks), western drywood termite (Incisitermes minor Hagen), arboreal termites such as Nasutitermes sp., as well as other isopteran pests including other termites of economic importance; saccharina Linnaeus) and spotted silverfish (Thermobia domestica Packard);From the order Ciliophaga, and head lice (Pediculus humanus capitis De Geer), human body lice (Pediculus humanus Linnaeus), chicken lice (Menacanthus stramineus Nitszch), dog biting lice (Trichodectes canis De Geer), downy lice (Goniocotes gallinae De Geer), sheep lice (Bovicola ovis Schrank), cattle lice (Haematopinus eurysternus pests including the oriental rat flea (Xenopsylla cheopis Rothschild), the cat flea (Ctenocephalides felis Bouche), the dog flea (Ctenocephalides canis Curtis), the chicken flea (Ceratophyllus gallinae Schrank), the sucking flea (Echidnophaga gallinacea Westwood), the human flea (Pulex irritans), Pests of the order Siphonaptera, including the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes of the order Scutigera, such as the house centipede (Scutigera coleoptrata Linnaeus);

[0091] Examples of invertebrate pests of stored grain include the boston beetle (Prostephanus truncatus), the mealybug (Rhyzopertha dominica), the grain weevil (Stiophilus oryzae), the maize weevil (Stiophilus zeamais), the cowpea weevil (Callosobruchus maculatus), the red flour beetle (Tribolium castaneum), the granary weevil (Stiophilus granarius), and the Indian meal moth (Plodia interpunctella). interpunctella), the Mediterranean red flour beetle (Ephestia kuhniella) and the rusty grain beetle (Cryptolestis ferrugineus).

[0092] Compositions produced in accordance with the present disclosure are effective against economically important agricultural pests (i.e., root-knot nematodes of the genus Meloidogyne, lesion nematodes of the genus Pratylenchus, stubby root nematodes of the genus Trichodorus, etc.) and animal and human health pests (i.e., Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, parasitic helminths Anoplocephala perfoliata in horses, Fasciola hepatica in ruminants, and the like). It may have activity against members of the classes Nematoda, Cestoda, Trematoda and Acanthocephala, including commercially important members of the orders Strongyloidea, Ascarida, Oxyzoida, Rhabdochida, Spiruura and Enoplus, such as all economically important trematodes, cestodes and roundworms (such as, but not limited to, Acanthochiida ...

[0093] Compositions prepared according to the present disclosure may be used to control lepidopteran pests (e.g., Alabama argillacea Huebner (cotton leafworm), Archips argyrospila Walker (fruit tree leafroller), A. rosan Linnaeus (European leafroller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leafroller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella pomonella Linnaeus (Codling Moth), Earias insulana Boisduval (Spiny Bowlworm), Earias vittella Fabricius (Spotted Bowlworm), Helicoverpa armigera Huebner (American Bowlworm), Helicoverpa zea Boddie (Tobacco Moth Larva), Heliothis virescens Fabricius (False Tobacco Moth), Herpetogramma licarsisalis Walker (Sod Webworm), Lobesia botrana Denis & Schiffermueller (Grapeberry Moth), Pectinophora gossypiera gossypiella Saunders (larvae of the pink bollworm moth), Phyllocnistis citrella Stainton (orange leafminer), Pieris brassicaeIt may have activity against Spodoptera exigua Huebner (beetle armyworm), Spodoptera litura Fabricius (common cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (stalk fall armyworm), Trichoplusia ni Huebner (cabbage looper), and Tuta absoluta Meyrick (tomato leafminer).

[0094] Compositions prepared in accordance with the present disclosure are effective against Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (Spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaehorii (apple aphid), Aphis cristatus var. ... fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov / Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (apple aphid), Hyalopterus pruni Geoffroy (mealie plum aphid), Lipaphis erysimi Kaltenbach (false radish aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiae euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum myzismaidis Fitch (corn aphid), Rhopalosiphum padi Linnaeus (bird cherry oat aphid), Schizaphis graminum Rondani (greengrass aphid), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid) and Toxoptera citricida citricida) Kirkaldy (brown citrus aphid); Adelges spp. (pillar aphid); Phylloxera devastatrix) Pergande (pecan phylloxera); Bemisia tabaci) Gennadius (tobacco whitefly, cotton whitefly), Bemisia argentifolii) Bellows & Perring (silverleaf whitefly), Dialeurodes citri) Ashmead (citrus whitefly) and Trialeurodes vaporariorum) Westwood (greenhouse whitefly); Empoasca fabae fabae) Harris (Potato Leafhopper), Laodelphax striatellus) Fallen (Small Brown Planthopper), Macrolestes quadrilineatus) Forbes (Aster Leafhopper), Nephotettix cinticeps) Uhler (Green Leafhopper), Nephotettix nigropictusnigropictus Stall (Rice Leafhopper), Nilaparvata lugens Stall (Brown Planthopper), Peregrinus maidis Ashmead (Corn Planthopper), Sogatella furcifera Horvath (White-backed Planthopper), Sogatodes orizicola Muir (Rice Delphacid), Typhlocyba pomaria McAtee (White Apple Leafhopper), Erythroneoura spp. (Grape Leafhopper); Magicidada septendecim Linnaeus (Periodic Cicada); Icerya purchasii It may have significant activity against members of the Homoptera, including (A. purchasi) Maskell (cotton scale), Quadraspidiotus perniciosus (Comstock) (San Jose scale); Planococcus citri (Risso) (citrus mealybug); Pseudococcus species (other mealybug complex); Cacopsylla pyricola (Foerster) (sunflower psylla), and Trioza diospyri (Ashmead) (persimmon psylla).

[0095] Compositions prepared in accordance with the present disclosure are effective against Acrosternum hilare Say (southern green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus Say (American long-horned stink bug), Cimex lectularius Linnaeus (bed bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaeffer (cotton stainer), Euchistus cervus (squash bug ... servus) Say (Brown Stink Bug), Euchistus variolarius) Palisot de Beauvois (One-Spotted Stink Bug), Graptosthetus spp. (Seed Bug Complex), Halymorpha halys) Stal (Brown Marbled Stink Bug), Leptoglossus corculus) Say (Leaf-Footed Pine Seed Bug), Lygus lineolaris) Palisot de Beauvois (Green Mirid Bug), Nezara viridula) Linnaeus (Southern Green Stink Bug), Oebalus pugnax It may also have activity against members of the Hemiptera order, including Oncopeltus fasciatus Dallas (large milkweed bug), and Pseudatomoscelis seriatus Reuter (cotton freehopper).Other insect orders controlled by the compounds of the present disclosure include Thysanoptera (e.g., Frankliniella occidentalis Pergande) (Occitrus flower thrips), Scirthothrips citri Moulton (Occitrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and Coleoptera (e.g., Leptinotarsa ​​decemlineata Say (Colorado potato beetle), Epilachna varivestis (Leptinotarsa ​​decemlineata Say (Colorado potato beetle), Epilachna varivestis (Leptinotarsa ​​decemlineata Say (Colorado potato beetle), Epilachna varivestis (Leptinotarsa ​​varivestis)). varivestis) Mulsant (heart beetle) and wireworms of the genera Agriotes, Athous or Limonius.

[0096] In some embodiments, compositions made in accordance with the present disclosure are useful for controlling western flower thrips (Frankliniella occidentalis). In some embodiments, compositions made in accordance with the present disclosure are useful for controlling potato leaf hoppers (Empoasca fabae). In some embodiments, compositions made in accordance with the present disclosure are useful for controlling cotton aphids (Aphis gossypii). In some embodiments, compositions made in accordance with the present disclosure are useful for controlling diamondback moths (Plutella xylostella L.). In some embodiments, compositions made in accordance with the present disclosure are useful for controlling silverleaf whiteflies (Bemisia argentifolii Bellows & Perring).

[0097] In the cyantraniliprole aspect of the present disclosure, compositions made in accordance with the present disclosure may be effective against insects from the Coleoptera, Chrysomelidae family, including Cerotoma trifurcata bean leaf beetle, Chaetocnema concinna beetle, Epilachna varivestis common ladybird beetle, Epitrix cucumeris potato leaf beetle, Leptinotarsa ​​decemlineata Colorado potato beetle, Oulema melanopus cereal leaf beetle, Oulema oryzae rice leaf beetle, Phyllotreta cruciiferae cabbage flea beetle, Phyllotreta striolata flea beetle, Psylliodes flea beetle, family Curculionidae, Anthonomus eugenii pepper weevil, Ceutorhynchus napi cabbage stem weevil, Ceutorhynchus quadridens cabbage root weevil, Conotrachelus nenuphar plum weevil, Hypera bruneipennis Egyptian alfalfa weevil, Hypera postica alfalfa weevil, Lissorhoptrus oryzophilus rice water weevils, Nitidulidae, Meligethes aeneus pollen beetles, blossom beetles, Scarabaeidae, Cotinis nitida blue cockroach beetles, Phyllophaga species cockroach beetles, maggots, Popilliajaponica) Japanese beetle, Diptera, Agromyzidae, Liromyza chinensis) Winter onion leaf miner, Liromyza huidobrensis) Pea leaf miner, Liriomyza sativae) Serpentine / vegetable leaf miner, Liromyza trifolii) American serpentine leaf miner, Anthomyiidae, Delia antiqua) Onion fly, Delia platura) Seed corn maggot, Muscidae, Atherigona oryzae oryzae rice seedling fly, Psilidae family, Psila rosae carrot fly, Tephritidae family, Anastrepha fraterculus South American fruit fly, Anastrepha ludens Mexican fruit fly, Anasterpha striata guava fruit fly, Bactrocera cucurbitae melon fly, Bactrocera dorsalis Oriental fruit fly, Bactrocera oleae olive fly, Ceratitis capitata Mediterranean fruit fly, Chromatomyia horticola) Garden pea leaf miner, Rhagoletis cerasi) Cherry fruit fly, Rhagoletis cingulata) Cherry fruit fly, Rhagoletis indifferens) Western cherry fruit fly, Rhagoletis pomonella) Apple maggot, Hemiptera, Aleyrodidae,Aleyrodes proletella (cabbage whitefly), Bemisia tabaci (sweet potato whitefly), cotton whitefly, Dialeurodes citri (citrus whitefly), Trialeurodes vaporariorum (greenhouse whitefly), greenhouse whitefly, Aphididae (family Aphididae), Acyrthosiphon pisum (pea aphid), Aphis craccivora (cowpea aphid), Aphis fabae (black bean aphid), Aphis glycines (soybean aphid), Aphis gossypii (aphis gossypii (cotton aphid), melon aphid, Aphis nasturtii (buckthorn aphid), Aphis pomi (green apple aphid), Aphis spiraceola (spira aphid), Aulacorthum solani (potato aphid), Brachycaudus persicae (black peach aphid), Brevicoryne brassicae (radish aphid), Chromaphis juglandicola (European walnut aphid), Dysaphis plantaginea (rosy apple aphid), Hyalopterus pruni), mealy plum aphid, false radish aphid (Lipaphis erysimi), mustard aphid, turnip aphid, tulip long-horn aphid (Macrosiphum euphorbiae), potato aphid, green peach aphid (Myzus persicae), green peach aphid, peach and potato aphid, wheat collar aphid (Rhopalosiphum padi), water cherry oat aphid, husk aphid (Rhopalosiphumnymphaeae plum aphid, Schizaphis graminum greenbug aphid, Sitobion avenae English grain aphid, Therioaphis maculata spotted alfalfa aphid, Toxoptera citricida brown citrus aphid, Oriental citrus aphid, Cicadellidae leafhopper / leafhopper complex, Empoasca fabae green frogfly, Hortensia similis similis (common green leafhopper), mango leafhopper (Idioscopus species), Jacobiasca lybica (cotton leafhopper), rice green leafhopper complex (Nephotettix species), rose leafhopper (Typhlocyba rosae), white apple leafhopper (Typhlocyba pomaria), rice bug (Leptocorisa oratorius) (Coreidae), rice ear bug, paddy bug, Delphacidae (planthoppers), Nilaparvata lugens (rice brown planthopper), Diaspididae (scale insect), Aonidiella aurantii citrus sky bug, Flatidae, Metcalfa pruinosa citrus sky bug, Pentatomidae, Euschistus species of brown stink bug, Edessa species of stink bug, Psyllidae, Diaphorina citri Asian citrus sky bug, Paratrioza cockerellicockerelli) potato psyllid, tomato psyllid, Trioza eugeniae Eugenia psyllid, Lily pilly psyllid, Hymenoptera Tenthredinidae, Hoplocampa testudinea European apple sawfly, Lepidoptera Crambidae, Scirpophaga incertulas Yellow (rice) stem borer, Gelechiidae, Anarsia lineatella Peach twig borer, Keiferia lycopersicella Tomato pinworm, Pectinophora gossipiera gossypiella Pink Bowl Worm, Tuta absoluta Tomato Leaf Miner, Gracilariariidae Tea Tortrix, Phyllonorycter blancardella Spotted Tenchform Leaf Miner, Phyllonorycter coryfoliella Nut Leaf Blister Moth, Phyllonorycter crataegella Apple Blotch Leaf Miner, Phyllonorycter ringoniella Apple Leaf Miner, Phyllonorycter elmaella Western Tenchform Leaf Miner, Hesperiidae Borer, Borbo cynara cinara) rice leafminer, Lyonetiidae (leucoptera coffeella) white coffee leafminer, Leucoptera scitella (leucoptera scitella) pear leafminer, Lyonetiidae (peach leafminer)clerkella) peach, leaf miner, Noctuidae, Agrotis segetum (spodoptera), Alabama argillacea (cotton leafworm), Autographa californica alfalfa looper, Barathra brassicae (cabbage cutworm), Chrysodeixis chalcites (green garden looper), Chrysodeixis eriosoma (green semilooper), Earias insulana (Egyptian bowlworm), Earias vittella (northern rough bowlworm), Feltia subterranea (granular cutworm), Helicoverpa armigera armigera American bowl worm, cotton bowl worm, Helicoverpa punctigera Climbing cutworm, Heliothis virescens Tobacco budworm, Helicoverpa zea Tobacco budworm larva, Prodenia ornithogalli Yellowstriped armyworm, Pseudaletia unipuncta True armyworm, Pseudoplusia includens Soybean looper, Sesamia inferens Pink (Rice) stem borer, Spodoptera eridania Southern armyworm, Spodoptera exigua exigua) beet armyworm, Spodoptera frugiperda) leaf fall armyworm, Spodoptera littoralis) Egyptian armyworm, Spodoptera litura) cluster caterpillar, Thermesia gemmatalis) peanut beetle, Trichoplusia nini) nettle silver moth, Phyllocnistidae (family of leafminers), Phyllocnistis citrella (citrus leafminer), Pieridae (family of butterflies), Colias eurytheme (alfalcon moth), Leptophobia aripa (green-eyed white), Pieris brassicae (cabbage butterfly), large cabbage white butterfly, Pieris rapae (nano green caterpillar), cabbage white butterfly, Plutellidae (family of moths), Plutella xylostella (diamond moth), Pyralidae (family of moths), Chilo suppressalis (rice suppressor moth), Cnaphalocerus medinaris medinalis rice leaf folder, Crocidolomia binotalis cabbage caterpillar, Desmia funeralis grape leaf folder, Diaphania indica cotton bollworm, Diaphania nitidaltis melon worm, Hellula hydralis cabbage center maggot, Hellula undalis cabbage webworm, Lerodea eufala rice leaf folder, Leucinodes orbonalis eggplant fruit borer, Maruca testulalis bean pod borer, Neoleucinodes elegantalis elegantalis small tomato borer, Nymphula depunctalis rice trichoderma larva, Ostrinia furnicalis Asian corn borer, Ostrinia nubilalis European corn borer, Sphingidae, Manduca sextaTomato caterpillar (Aedes sexta), tobacco caterpillar, Smerinthus hawkmoths, Tortricidae, Adoxophyes orana summer fruit tortrix moth, Argyrotaenia pulchellana grape tortrix moth, Argyrotaenia velutinana red-striped tortrix, Choristoneura rosaceana diagonal-striped tortrix, Eupoecilia ambiguella grapeberry moth, Cydia pomonella codling moth, Cydia prunivora small appleworm, Grapholita molesta) Pear fruit moth, Lobesia botrana Grapevine moth, Pandemis heparana Apple brown tortrix moth, Pandemis limitata Three-lined leafroller, Paramyelois transitella Navel orangeworm, Platynota idaeusalis Tufted applebud moth, Platynota stultana Omnivorous leafroller, Thysanoptera, Thripidae, Enneothrips flavens, Frankliniella fusca Tobacco thrips, Frankliniella intonsa) European flower thrips, Frankliniella occidentalis) Western flower thrips, Frankliniella schultzei) Common blossom thrips, Frankliniella triticitritici Eastern flower thrips, Megalurothrips sjostedti Cowpea thrips, Megalurothrips usitatus Bean blossom thrips, Scirthothrips citri Citrus thrips, Scirthothrips dorsalis Yellow tea thrips, Chili thrips, Sericothrips variabilis Soybean thrips, Stenchaetothrips biformis Oriental rice thrips, Thrips arizonensis Cotton thrips, Thrips meridionalis It is effective against peach thrips (Thrips meridionalis), melon thrips (Thrips palmi), onion thrips (Thrips tabaci), and common cotton thrips.

[0098] In some cyantraniliprole embodiments of the present disclosure, compositions made according to the present disclosure may be effective against insects such as Leptinotarsa ​​decemlineata Colorado potato beetle, Oulema oryzae rice leaf beetle, Phyllotreta cruciiferae cabbage flea beetle, Phyllotreta striolata striped flea beetle, Psylliodes species flea beetle, Anthonomus eugenii pepper weevil, Conotrachelus nenuphar plum weevil, Lissorhoptrus oryzophilus rice water weevil, Meligethes aenois aeneus pollen beetle, blossom beetle, Liromyza chinensis winter onion leaf miner, Liromyza huidobrensis pea leaf miner, Liriomyza sativae serpentine / vegetable leaf miner, Liromyza trifolii American serpentine leaf miner, Delia antiqua onion fly, Delia platura seed corn maggot, Psila rosae carrot fly, Bactrocera dorsalis oriental fruit fly, Bactrocera oleae olive fly, Ceratitis capitata capitata) Mediterranean fruit fly, Rhagoletis indifferens) Western cherry fruit fly, Rhagoletis pomonella) Apple maggot, Bemisia tabaci) Sweet potato whitefly, cotton whitefly, Trialeurodesvaporariorum), greenhouse whitefly, pea aphid (Acyrthosiphon pisum), pea aphid, bean aphid (Aphis craccivora), cowpea aphid, Aphis fabae, black bean aphid, Aphis gossypii, cotton aphid, melon aphid, Aphis pomi, green apple aphid, Aphis spiraceola, potato aphid (Aulacorthum solani), foxglove aphid, radish aphid (Brevicoryne brassicae), cabbage aphid, Dysaphis plantaginea plantaginea) Rosie apple aphid, False radish aphid (Lipaphis erysimi) Mustard aphid, Turnip aphid, Tulip long-horn aphid (Macrosiphum euphorbiae) Potato aphid, Green peach aphid (Myzus persicae) Peach aphid, Peach potato aphid, Wheat neck aphid (Rhopalosiphum padi) Cherry oat aphid, Schizaphis graminum Green wheat aphid, Sitobion avenae English grain aphid, Toxoptera citricida Brown citrus aphid, Oriental citrus aphid, Empoasca vitis vitis Green Frogfly, Idioscopus species of Mango Leafhopper, Nilaparvata lugens Rice Brown Planthopper, Aonidiella aurantii Citrus Sky Bug, Euschistus species of Brown Stink Bug, Diaphorina citri Asian Citrus Sky Bug, Paratrioza cockerelliicockerelli) potato psyllid, tomato psyllid, Scirpophaga incertulas) yellow (rice) stem borer, Anarsia lineatella) peach twig borer, Tuta absoluta) tomato leaf miner, Leucoptera coffeella) white coffee leaf miner, Alabama argillacea) cotton leafworm, Helicoverpa armigera) American bowl worm, cotton bowl worm, Helicoverpa punctigera) climbing cutworm, Heliothis virescens) tobacco budworm, Helicoverpa zea) tobacco budworm larvae, Pseudoplusia includens) soybean looper, Sesamia inferens) pink (rice) stem borer, Spodoptera eridania) southern armyworm, Spodoptera exigua) beet cutworm, Spodoptera frugiperda) rice armyworm, Spodoptera littoralis) Egyptian armyworm, Spodoptera litura) cluster caterpillar, Thermesia gemmatalis) vermiculata beetworm, Trichoplusia ni) nettle looper, citrus leafminer, Phyllocnistis citrella) Citrus leaf miner, Pieris brassicae (cabbage butterfly), large cabbage white butterfly, Pieris rapae (nano green caterpillar), cabbage white butterfly, Plutella xylostella (diamond moth), Chilo suppressalis (rice stem borer)Rice stem borer (Chloro suppressalis), rice leaf folder (Cnaphalocerus medinalis), eggplant fruit borer (Leucinodes orbonalis), Asian corn borer (Ostrinia furnicalis), European corn borer (Ostrinia nubilalis), diagonal striped leafroller (Choristoneura rosaceana), grapeberry moth (Eupoecilia ambiguella), codling moth (Cydia pomonella), pear fruit moth (Grapholita molesta), grapevine moth (Lobesia botrana), Frankliniella fusca It is effective against tobacco thrips (Frankliniella fusca), European flower thrips (Frankliniella intonsa), western flower thrips (Frankliniella occidentalis), citrus thrips (Scirthothrips citri), yellow tea thrips (Scirthothrips dorsalis), chili thrips, melon thrips (Thrips palmi), onion thrips (Thrips tabaci), and common cotton thrips.

[0099] In some cyantraniliprole embodiments of the present disclosure, compositions made according to the present disclosure may be effective against Conotrachelus nenuphar plum weevil, Liromyza huidobrensis pea leafminer, Liriomyza sativae serpentine / vegetable leafminer, Liromyza trifolii American serpentine leafminer, Bemisia tabaci sweet potato whitefly, cotton whitefly, Trialeurodes vaporariorum greenhouse whitefly, Acyrthosiphon pisum pea aphid, and bean aphid. craccivora (cowpea aphid), Aphis gossypii (cotton aphid), Melon aphid, Brevicoryne brassicae (cabbage aphid), Dysaphis plantaginea (rosy apple aphid), Myzus persicae (green peach aphid), Peach and potato aphid, Diaphorina citri (Asian citrus psyllid), Paratrioza cockerelli (potato psyllid), Tomato psyllid, Scirpophaga incertulas (yellow (rice) stem borer), Anarsia lineatella (peach twig borer), Tomato tusk moth, absoluta Tomato Leaf Miner, Leucoptera coffeella White Coffee Leaf Miner, Alabama argillacea Cotton Leafworm, Helicoverpa armigera American Bowl Worm, Cotton Bowl Worm, Helicoverpa punctatuspunctigera climbing cutworm, Heliothis virescens tobacco budworm, Helicoverpa zea tobacco budworm larvae, Pseudoplusia includens soybean looper, Sesamia inferens pink (rice) stem borer, Spodoptera eridania southern armyworm, Spodoptera exigua beet armyworm, Spodoptera frugiperda leafminer, Spodoptera littoralis Egyptian armyworm, Spodoptera litura cluster caterpillar, Phyllocnistis citri leafminer Citrus leaf miner (Plutella citrella), diamondback moth (Plutella xylostella), rice stem borer (Chilo suppressalis), rice leaf folder (Cnaphalocerus medinalis), diagonal striped leafroller (Choristoneura rosaceana), grapeberry moth (Eupoecilia ambiguella), codling moth (Cydia pomonella), pear fruit moth (Grapholita molesta), grapevine moth (Lobesia botrana), tobacco thrips (Frankliniella fusca), Frankliniella occidentalis It is effective against western flower thrips (Scirthothrips occidentalis), yellow tea thrips (Scirthothrips dorsalis), chili thrips, melon thrips (Thrips palmi), onion thrips (Thrips tabaci), and common cotton thrips.

[0100] In the chlorantraniliprole aspect of the present disclosure, compositions made in accordance with the present disclosure may be effective against insects of the following families: Coleoptera (Family: Chrysomelida, Leptinotarsa ​​decemlineata Colorado potato beetle, Family: Curculionidae, Lissorhoptrus oryzophilus rice water weevil, Listronotus maculicollis annual bluegrass weevil, Oryzophagus oryzae rice water weevil, Sphenophorus species weevils, Family: Scarabaeidae Ataenius spurturs spretulus, a species of scarab beetle, Aphodius, Cotinis nitida, Cyclocephala, Exomala orientalis, Maladera castanea, Phyllophaga, Popillia japonica, and Rhizotrogus majalis; Diptera (Family Agromyzidae, Chromatomyia horticola garden pea leaf miner and Liriomyza species leaf miner; Hemiptera (Family Aleyrodidae, Bemisia species whitefly, Trialeurodes abutiloneus banded-winged whitefly, Family Cicadellidae, and Typhlocyba pomariipomaria white apple leafhopper); Isoptera (Rhinotermitidae, Heterotermes tenuis sugarcane termite, Termitidae, Microtermes obesi sugarcane termite and Odontotermes obesus sugarcane termite); and Lepidoptera (Arctiidae, Estigmene acrea American tiger moth larvae, Crambidae, Achyra rantalis garden webworm, Desmia funeralis grape leaf folder, Ostrinia nubilalis nubilalis (European corn borer), Gelechiidae (Gelechiidae), Anarsia lineatella (Peach twig borer), Keiferia lycopersicella (Tomato pinworm), Phthorimaea operculella (Potato tooth moth larvae), Tuta absoluta S. (American tomato pinworm), Geometridae (Geometridae), Operophthera brumata (Winter geometrid), Gracilaridae (Gracilaridae), Phyllocnistis citrella (Citrus leafminer), Lithocolletis ringoniella (Apple leafminer), Phyllonorycter blancardella Spotted Tenchform Leafminer, Leucoptera species of the family Lyonetidae (i.e., malifoliella, coffeella) Coffee Leafminer, Pear Trifoliate Moth, Noctuidae Noctuidae Agrotisipsilon black cutworm, Alabama argillacea Egyptian armyworm, Amphipyra pyramidoides knob green fruitworm, Anticarsia gemmatalis lizard beetle, Autographa gamma common goldfly, Barathra brassica brassicae cabbage armyworm, Earias species (i.e., huegeliana, insulana, vitella) rough, spiny, and northern rough bowlworms, Helicoverpa species (i.e., armigera, punctigera, zea) bowlworms / budworms / fruitworms, Heliothis virescens tobacco budworm, Lithophane antennata green fruitworm, Mamestra brassicae cabbage moth, Orthosia hibisci green fruitworm, Phalaenoides glycinae grapevine moth, Phytometra acuta tomato semilooper, Pseudoplusia includens soybean looper, Spodoptera species (i.e., Exigua, Frugiperda, and Littoralis) beet armyworm, grass fall armyworm, Egyptian armyworm, Trichoplusia ni nettle looper, Pieridae, Pieris species (i.e., Brassica and Rapae) large white butterfly, nano caterpillar, Plutellidae, Plutella xylostellaxylostella diamondback moth, Pyralidae family, Amyelois transitella navel orangeworm, Chilo species (i.e., infuscatellus, polychrysus, and suppressalis) sugarcane / rice stem borer, Cnaphalocrocis medinalis rice leafroller, Crambus species cut grass webworm, Crocidolomia binotalis cabbage cluster caterpillar, Diaphania species (i.e., hyalinata and nitidalis) melon worm, pickle worm, Diatraea saccharalis saccharalis, Brazilian sugarcane borer, Elasmopalpus lignosellus small stalk borer, Evergestis rimosalis cross-striped leaf beetle, Hedylepta indicata soybean leaf folder, Hellula species (i.e., hydralis, undalis) cabbage center maggot, cabbage webworm, Leucinodes orbonalis eggplant shoot and fruit borer, Maruca species pod borer, Neoleucinodes elegantaliselegantalis tomato small borer, sugarcane / rice stem borer, Scirpophaga species, pink stem borer / cornstalk borer, Sesamia species (i.e., inferens, nonagrioides), tomato / tobacco caterpillar, Sphingidae, Manduca species (i.e., quinquemaculata, sexta), Tortricidae, Adoxophyes orana summer fruit tortrix, Argyrotaenia species (i.e., pulchellana, velutinana), red-striped leafroller, Bonagota cranaodes, cranaodes Brazilian apple leafroller, Carposina species (i.e., niponensis, sasaki) peach fruit borer, peach fruit moth, Choristoneura rosaceana diagonal striped leafroller, Cryptophlebia leucotreta false codling moth, Cydia pomonella codling moth, Ecdytolopha aurantiana citrus borer, Endopiza vitana grapeberry moth, Epiphyas postvittana light brown apple moth, Eupoecilia ambiguella European grapeberry moth, Grapholita molesta) Oriental fruit moth, Lobesia botolana (LobesiaThe compound is effective against the European grapevine moth (Pandemis spp.) (i.e., Cerasanella, Heparana, Striped fruit tree tortrix moth, Pyrusana spp.), the apple brown tortrix moth (Pandemis spp.), the three-striped leafroller moth (Pyrusana spp.), the apple pandemic moth (Platynota spp.), the tufted applebud moth (Platynota spp.), the omnivorous leafrollers (Platynota spp.), the grapeleaf / western grapevine leaf-feeding larvae (Zygaenidae) and the Harrisina spp. (i.e., Americana, Brilliants).

[0101] In some chlorantraniliprole embodiments of the present disclosure, compositions made according to the present disclosure may be effective against insects such as Leptinotarsa ​​decemlineata Colorado potato beetle, Liriomyza spp. leaf miner, Bemisia spp. whitefly, Trialeurodes abutiloneus banded-winged whitefly, Heterotermes tenuis sugarcane termite, Microtermes obesi sugarcane termite, and Odontotermes obesus sugarcane termite, Ostrinia nubilalis European corn borer, Anarsia lineatella peach twig borer, Phthorimaea operculella (potato tooth moth larvae), tomato tooth moth (Tuta absoluta S.) (American tomato pinworm), citrus leafminer (Phyllocnistis citrella), spotted tenchform leafminer (Phyllonorycter blancardella), coffee leafminer (Leucoptera species, i.e., malifoliella and coffeella), black cutworm (Agrotis ipsilon), Egyptian armyworm (Alabama argillacea), and Anticarsia gemmatalis (Anticarsia gemmatalis beetle, Helicoverpa species (i.e., armigera, punctigera, and zea) bowl worms / bud worms / fruit worms, Heliothis virescens tobacco budworm, and Pseudoplusia includens.includens soybean looper, Spodoptera species (i.e., Exigua, Frugiperda, and Littoralis) beet armyworm, grass fall armyworm, Egyptian armyworm, Trichoplusia ni nettle looper, Pieris species (i.e., Brassica and Rapa) large white butterfly, nano caterpillar, Plutella xylostella diamondback moth, Amyelois transluna transitella navel orangeworm, Chilo species (i.e., infuscatellus, polychrysus, and suppressalis) sugarcane / rice stem borers, Cnaphalocrocis medinalis rice leafroller, Diatraea saccharalis Brazilian sugarcane borer, and Leucinodes orbonalis orbonalis eggplant shoot and fruit borer, sugarcane / rice stem borer, which is a species of Scirpophaga, pink stem borer / cornstalk borer, which is a species of Sesamia (i.e., inferens, nonagrioides), peach fruit borer, which is a species of Carposina (i.e., niponensis, sasaki), peach fruit moth, Choristoneura rosaceana diagonal striped leafroller, Cydia pomonella codling moth, Eupoecilia ambiguella European grapeberry moth, Grapholita molesta pear fruit moth and Lobesia botolana botrana) is effective against the European grapevine moth.

[0102] In some chlorantraniliprole embodiments of the present disclosure, compositions made according to the present disclosure may be effective against Liriomyza species leaf miners, Bemisia species whiteflies, Trialeurodes abutiloneus banded-winged whitefly, Heterotermes tenuis sugarcane termites, Microtermes obesi sugarcane termites, and Odontotermes obesus sugarcane termites, Ostrinia nubilalis European corn borer, Anarsia lineatella peach twig borer, Tuta absoluta S.) American tomato pinworm, Anticarsia gemmatalis (a type of peanut moth), Helicoverpa species (i.e., armigera, punctigera, and zea) bowlworms / budworms / fruitworms, Heliothis virescens (a type of tobacco budworm), Pseudoplusia includens (a type of soybean looper), Spodoptera species (i.e., exigua, frugiperda, and littoralis) beet armyworm, Japanese armyworm, Egyptian armyworm, Plutella xylostella (a type of diamondback moth), Amyelois transluna (a type of beetworm), transitella navel orangeworm, sugarcane / rice stem borers that are species of the genus Chilo (i.e., infuscatellus, polychrysus, and suppressalis), rice leafroller Cnaphalocrocis medinalis, Brazilian sugarcane borer Diatraea saccharalis, sugarcane / rice stem borers that are species of the genus Scirpophaga, pinkstem borers / cornstalk borers that are species of the genus Sesamia (i.e., inferens and nonagrioides), codling moth Cydia pomonella, and pear fruit moth Grapholita It is effective against the pear fruit moth (Pear fruit moth) and the European grapevine moth (Lobesia botrana).

[0103] Compositions produced according to the present disclosure are useful for protecting agricultural crops and other non-agricultural horticultural crops and plants from herbivorous invertebrate pests. This utility includes protecting crops and other plants (i.e., both agronomic and non-agronomic) that contain genetic material introduced by genetic engineering (i.e., transgenic) or modified by mutagenesis to provide advantageous traits. Examples of such traits include herbicide tolerance, resistance to herbivorous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant pathogenic fungi, bacteria, and viruses), improved plant growth, increased tolerance to adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity, increased flowering or fruiting, increased harvest yield, more rapid maturation, higher quality and / or nutritional value of the harvested product, or improved storage or processing characteristics of the harvested product. Transgenic plants can be engineered to express multiple traits. Examples of plants containing traits achieved by genetic engineering or mutagenesis include corn, cotton, soybean, and potato varieties expressing insecticidal Bacillus thuringiensis toxins, such as YIELD GARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN®, and NEWLEAF®, INVICTA RR2PRO™, and herbicide-tolerant varieties of corn, cotton, soybean, and rapeseed, such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS®, and CLEARFIELD®, as well as crops expressing N-acetyltransferase (GAT) genes that confer resistance to glyphosate herbicides or containing HRA genes that confer resistance to herbicides that inhibit acetolactate synthase (ALS). Compositions produced in accordance with the present disclosure may interact synergistically with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing the phenotypic expression or efficacy of the trait or increasing the invertebrate pest control efficacy of the present compounds and compositions.In particular, compositions made in accordance with the present disclosure may act synergistically with the expression of proteins or other natural products that are toxic to invertebrate pests to achieve greater than additive control of these pests, i.e., produce a combined effect that is greater than the sum of their individual effects.

[0104] Plants within the scope of this disclosure include crops, vegetables, fruits, non-fruit trees, turf, and other uses (flowers, biofuel plants, and ornamental foliage). Crops include corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, beets, rapeseed, sunflowers, sugarcane, tobacco, and others known in the art. Vegetables include solanaceae vegetables (e.g., eggplant, tomato, bell pepper, pepper, and potato); cucurbitaceae vegetables (e.g., cucumber, pumpkin, zucchini, watermelon, and melon); cruciferous vegetables (e.g., radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard greens, broccoli, and cauliflower); Asteraceae vegetables (e.g., burdock, garland chrysanthemum, artichoke, and lettuce); liliaceae vegetables (e.g., leeks, onions, garlic, and asparagus); Apiaceae vegetables (e.g., carrots, parsley, celery, and parsnips); Chenopodiaceae vegetables (e.g., spinach and Swiss chard); and Lamiaceae vegetables (e.g., perilla (Perilla frutescens), mint, and basil). Fruits include pome fruits (e.g., apples, pears, Japanese pears, quince, and quince); stone fruits (e.g., peaches, plums, nectarines, Prunus mume, cherries, apricots, and prunes); citrus fruits (e.g., Citrus unshiu, oranges, lemons, limes, and grapefruit); tree nuts (e.g., chestnuts, walnuts, hazelnuts, almonds, pecans, pistachios, cashews, and macadamia nuts); berries (e.g., blueberries, cranberries, blackberries, strawberries, and raspberries); grapes; persimmons; persimmon trees; olives; plums; bananas; coffee; dates; coconuts; and oil palms.Non-fruit trees include tea; mulberry; and other trees (e.g., ash, birch, dogwood, eucalyptus, ginkgo (Ginkgo biloba), lilac, maple, oak (Quercus), poplar, Judas tree, liquidambar (Liquidambar formosana), plane tree, zelkova, arborvitae, fir tree, hemlock, juniper, pine (Pinus), spruce (Picea), yew (Taxus cuspidate), elm, and horse chestnut), coral tree, dogwood (Podocarpus macrophyllus), cedar, cypress, croton, Japanese einkorn, and Photinia glabra). Turf uses include grasses (e.g., Zoysia japonica, Zoysia matrella); barley; bentgrass; festuca; and ryegrass. Flower uses include roses, carnations, chrysanthemums, eustomas, gypsophila, gerberas, marigolds, salvia, petunias, verbena, tulips, asters, gentiana, lilies, pansies, cyclamen, orchids, lily of the valley, lavender, stocks, snapdragons, primulas, poinsettias, gladioli, cattleyas, daisies, cymbidiums, and begonias. Biofuel plants include jatropha, safflower, camelina, switchgrass, Miscanthus giganteus, Phalaris arundinacea, Arundo donax, kenaf, cassava, and willow.

[0105] All or any part of a plant can be treated with the composition produced according to the process of the present disclosure. As used herein, the term "plant" is understood to mean all plants and plant populations, such as desirable and undesirable wild plants or crops (including naturally occurring crops). Crops may be plants obtained by conventional breeding and optimization methods or biotechnology and genetic engineering methods, or a combination of these methods, including transgenic plants and plant cultivars that may or may not be protected by plant breeder's rights. Plant parts are understood to mean all parts and organs of plants above and below ground, such as shoots, leaves, flowers, and roots. Examples that may be mentioned are leaves, needles, stalks, stems, flowers, fruiting bodies, fruits, and seeds, as well as roots, tubers, and rhizomes. Plant parts also include collected materials and vegetative and generative propagation materials, such as cuttings, tubers, rhizomes, lateral shoots, and seeds.

[0106] Treatment of plants and plant parts with the compositions produced according to the process of the present disclosure is carried out by direct contact with the plants or plant parts or by acting on the plant's environment, habitat or storage space using customary treatment methods. For example, treatment as described herein can be by immersion, spraying, evaporation, atomization, dusting, spreading, injecting and, in the case of propagation material (especially seeds), by applying a layer of coating comprising the composition, optionally with further layers.

[0107] In one embodiment, the composition produced according to the process of the present disclosure is delivered to the plant via air. In another embodiment, the composition according to the present disclosure is delivered by an unmanned aerial vehicle (UAV). In yet another embodiment, the composition produced according to the process of the present disclosure is delivered by a helicopter or fixed-wing aircraft.

[0108] Wild plant species and plant cultivars or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof may be treated. Transgenic plants and plant cultivars (genetically modified organisms), obtained, where appropriate, by genetic engineering methods combined with conventional methods, and parts thereof, are also treated. In any case, plants of plant cultivars that are commercially available or in use are treated according to the present disclosure. Plant cultivars are understood to mean plants with novel properties ("traits") that have been obtained by conventional breeding, mutagenesis or recombinant DNA techniques. These may be cultivars, biotypes or genotypes.

[0109] Transgenic plants or plant cultivars (obtained by genetic engineering) that can be treated according to the present disclosure include all plants that have received genetic material that, through genetic modification, gives these plants particularly advantageous and useful traits.Examples of such traits are better plant growth, increased resistance to high or low temperatures, increased resistance to drought or water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher yields, higher quality and / or higher nutritional value of collected products, better storage stability and / or processability of collected products.Further particularly highlighted examples of such traits are better plant defense against animal and microbial pests, such as insects, mites, plant pathogenic fungi, bacteria and / or viruses, and increased plant resistance to certain herbicidal compounds. Examples of transgenic plants include important crops such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas, and other vegetable varieties, cotton, tobacco, rapeseed, and fruit plants (including the fruits apple, pear, citrus fruits, and grapes), with an emphasis on corn, soybeans, potatoes, cotton, tobacco, and rapeseed. Traits include increased plant defense against insects, arachnids, nematodes, and slugs and snails due to toxins formed in plants, particularly those formed in plants by genetic material from Bacillus thuringiensis (e.g., by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb, and CryIF, and combinations thereof) ("Bt plants"). Other traits include systemic acquired resistance (SAR), systemin, phytoalexins, elicitors, and increased plant defense against fungi, bacteria, and viruses due to resistance genes and the corresponding expressed proteins and toxins. Traits also include increased plant tolerance to certain herbicidally active compounds, such as imidazolinones, sulfonylureas, glyphosate, or phosphinothricin (e.g., the "PAT" gene). Genes conferring desirable traits of interest can also be present in combination with one another in transgenic plants.Examples of "Bt plants" include corn varieties, cotton varieties, soybean varieties, and potato varieties sold under the trade names YIELD GARD® (e.g., corn, cotton, soybean), KnockOut® (e.g., corn), StarLink® (e.g., corn), Bollgard® (cotton), Nucotn® (cotton), and NewLeaf® (potato). Examples of herbicide-tolerant plants are corn varieties, cotton varieties, and soybean varieties sold under the trade name Roundup Ready® (tolerant to glyphosate, e.g., corn, cotton, soybean). Liberty Link® (tolerant to phosphinothricin, e.g., rapeseed), IMI® (tolerant to imidazolinones), and STS® (tolerant to sulfonylureas, e.g., corn). Herbicide-resistant plants (plants conventionally bred for herbicide tolerance) include varieties sold under the name Clearfield® (e.g., corn). Agricultural crops are selected from the group consisting of cereals, fruit trees, citrus fruits, legumes, horticultural crops, cucurbits, oil plants, tobacco, coffee, tea, cocoa, sugar beet, sugarcane, and cotton.

[0110] Depending on the plant species or plant cultivars, their location and growing conditions (soil, climate, growing season, diet), the treatment according to the present disclosure can also produce superadditive ("synergistic") effects. Thus, for example, it is possible to reduce the application rate and / or widen the activity spectrum and / or increase the activity of the substances and compositions that can be used according to the present disclosure, improve plant growth, increase resistance to high or low temperatures, increase resistance to drought or water or soil salt content, increase flowering performance, easier harvesting, accelerated maturation, higher yield, higher quality and / or higher nutritional value of the collected product, better storage stability and / or processability of the collected product, which actually exceed the expected effects.

[0111] Crops that can be protected with the compositions produced according to the processes of the present disclosure include, for example, cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apples, pears, plums, peaches, almonds, cherries, bananas, grapes, strawberries, raspberries, blackberries, etc.), citrus trees (oranges, lemons, mandarins, grapefruit, etc.), legumes (green beans, beans, peas, lentils, soybeans, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, eggplant, peppers, etc.), cucurbitaceae (pumpkin, zucchini, cucumber, melon, watermelon, etc.), oleaginous plants (sunflower, rapeseed, peanuts, castor, coconut, etc.), tobacco, coffee, tea, cocoa, sugar beet, sugarcane, and cotton.

[0112] For the protection of agricultural crops, the compositions produced according to the processes of the present disclosure may be applied to any part of the plant, or onto the seed before sowing, or onto the soil in which the plants are growing.

[0113] Non-agricultural uses refer to invertebrate pest control in areas other than crop fields. Non-agricultural uses of the present compositions include pest control in stored grains, legumes, and other foodstuffs, as well as textile products, such as clothing and carpets. Non-agricultural uses of the present compositions also include invertebrate pest control in ornamental plants, forests, gardens, roadsides and railroads, and turf areas, such as lawns, golf courses, and pastures. Non-agricultural uses of compositions produced according to the present disclosure also refer to invertebrate pest control in homes and other buildings that may be occupied by humans and / or pets, livestock, farm animals, zoo animals, or other animals. Non-agricultural uses of compositions produced according to the present disclosure also include the control of pests, such as termites, that may damage wood or other structural materials used in buildings.

[0114] Non-agricultural uses of compositions produced according to the present disclosure also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. Control of animal parasites includes controlling ectoparasites that infest the surface of a host animal's body (e.g., shoulders, axillae, abdomen, inner thighs) and endoparasites that infest the interior of a host animal's body (e.g., stomach, intestines, lungs, veins, subcutaneous tissue, lymphatic tissue). Ectoparasitic or disease-vector pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites, and fleas. Endoparasites include heartworms, duodenal worms, and helminths. Compositions produced according to the present disclosure are suitable for systemic and / or non-systemic control of parasitic infestation or infection on animals. Compositions produced according to the present disclosure are particularly suitable for controlling ectoparasitic or disease-vector pests. The compositions of the present disclosure are suitable for controlling parasites in farm animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, hens, turkeys, ducks, geese, and bees; pet animals and livestock such as dogs, cats, pet birds, and ornamental fish; and so-called laboratory animals such as hamsters, guinea pigs, rats, and mice. Controlling these parasites reduces mortality and performance losses (in terms of meat, milk, wool, skin, eggs, honey, etc.), making it possible to farm animals more economically and easily by applying the compositions of the present disclosure.

[0115] Embodiments of the present disclosure include the following.

[0116] Embodiment 1. A process for preparing an aqueous suspension of an organic pesticide, comprising: I) forming a mixture comprising a source of at least one amorphous organic pesticide, water, and at least one formulation additive; II) adding at least one crystalline organic pesticide to the mixture; III) crystallizing at least one amorphous organic pesticide; IV) optionally homogenizing the mixture; V) optionally, grinding the mixture; and VI) Optionally, thickening the mixture A process involving:

[0117] Embodiment 2. A process for preparing an aqueous suspension of an organic pesticide, comprising: I) A mixture comprising: A) compounding additives, B) at least one crystalline organic pesticide, and C) water forming a mixture comprising: II) adding at least one amorphous organic pesticide to the mixture under stirring conditions; III) crystallizing at least one amorphous organic pesticide; IV) optionally homogenizing the mixture; V) optionally, grinding the mixture; and VI) Optionally, thickening the mixture A process involving:

[0118] Embodiment 3. The process of embodiment 1 or embodiment 2, wherein the formulation additives are selected from additional water, dispersants, antifreeze agents, viscosity modifiers, antifoam agents, bactericides, surfactants, and combinations thereof.

[0119] Embodiment 4. The process of any one of embodiments 1-3, wherein the at least one amorphous organic pesticide has a melting point in the range of about 55°C to about 100°C.

[0120] Embodiment 5. The process of any one of embodiments 1-4, wherein the at least one amorphous organic pesticide has a solubility in water at 25° C. of from about 0.001 mg / L to about 100 mg / L.

[0121] Embodiment 6. The process of any one of embodiments 1-5, wherein the at least one amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a solid amorphous form, a liquid, a solution comprising the active ingredient and a water-miscible solvent, and combinations thereof.

[0122] Embodiment 7. The process of any one of embodiments 1 to 6, wherein the at least one amorphous organic pesticide is selected from the group consisting of insecticides, fungicides, herbicides, and any combination thereof.

[0123] Embodiment 8. The process of embodiment 7, wherein the insecticide is selected from the group consisting of indoxacarb, bifenthrin, gamma-cyhalothrin, and combinations thereof.

[0124] Embodiment 9. The process of embodiment 7, wherein the fungicide is selected from the group consisting of difenoconazole, pyraclostrobin, picoxystrobin, and combinations thereof.

[0125] Embodiment 10. The process of embodiment 7, wherein the herbicide is selected from the group consisting of beflubutamid, s-beflubutamid, rimisoxamide, bixlozone isoflex, napropamide, aclonifen, and combinations thereof.

[0126] Embodiment 11. The process of any one of embodiments 1 to 10, wherein the aqueous suspension of the organic pesticide further comprises a safener.

[0127] Embodiment 12. The process of embodiment 11, wherein the safener is cloquintocet-mexyl.

[0128] Embodiment 13. The process of any one of embodiments 1 to 12, wherein the at least one crystalline organic pesticide has a melting point of from about 55°C to about 100°C.

[0129] Embodiment 14. The process of embodiment 13, wherein the at least one crystalline organic pesticide has a melting point of about 95°C.

[0130] Embodiment 15. The process of any one of embodiments 1 to 14, wherein the at least one crystalline organic pesticide has a solubility in water at 25° C. of from about 0.001 mg / L to about 100 mg / L.

[0131] Embodiment 16. The process of embodiment 15, wherein the at least one crystalline organic pesticide has a solubility in water of about 0.2 mg / L at 25° C.

[0132] Embodiment 17. The process of any one of embodiments 1 to 16, wherein the at least one crystalline organic pesticide is selected from insecticides, fungicides, herbicides, and combinations thereof.

[0133] Embodiment 18. The process of any one of embodiments 1 to 17, wherein the at least one crystalline organic pesticide is an insecticide.

[0134] Embodiment 19. The process of embodiment 18, wherein the crystalline organic insecticide is selected from the group consisting of indoxacarb, chlorantraniliprole, cyantraniliprole, bifenthrin, gamma-cyhalothrin, and combinations thereof.

[0135] Embodiment 20. The process of any one of embodiments 1 to 19, including a milling step, wherein the mixture is milled using a device selected from an attritor mill, a bead mill, a colloid mill, a rotor stator, a jet mill, an air classifier mill, a ring mill, a hammer mill, a pin mill, a pack mill, and combinations thereof.

[0136] Embodiment 21. The process of any one of embodiments 1 to 20, wherein the process step of adding at least one amorphous organic pesticide to the mixture is conducted at a temperature in the range of from about 50 to about 100°C.

[0137] Embodiment 22. The process of embodiment 21, wherein the process step of adding at least one amorphous organic pesticide to the mixture is conducted at a temperature in the range of from about 50 to about 95°C.

[0138] Embodiment 23. The process of any one of embodiments 1 to 22, wherein the at least one additive comprises at least one dispersant, at least one nonionic surfactant, and at least one anionic surfactant.

[0139] Embodiment 24. The process of embodiment 23, wherein the at least one dispersant is an acrylic copolymer solution.

[0140] Embodiment 25. The process of embodiment 24, wherein the acrylic copolymer solution comprises propylene glycol, about 30% to about 35% acrylic copolymer.

[0141] Embodiment 26 The process of embodiment 25, wherein the acrylic copolymer solution further comprises water and methyl ethyl ketone.

[0142] Embodiment 27. The process of any one of embodiments 23 to 26, wherein the dispersant content in the aqueous suspension of the organic pesticide is from about 0.1% to about 15% by weight, from about 1% to about 10% by weight, from about 0.5% to about 5% by weight, or from about 0.5% to about 3% by weight.

[0143] Embodiment 28. The process of any one of embodiments 23 to 27, wherein the at least one anionic surfactant is (1) a tristyrylphenol ethoxylate phosphate ester or a phosphate ester salt of an ethoxylated alcohol; (2) sodium decyl sulfate and sodium lauryl sulfate; or (3) a combination thereof.

[0144] Embodiment 29. The process of embodiment 28, wherein (1) the phosphate ester salt of an ethoxylated alcohol comprises about 39% to about 43% alcohol and about 4% to about 6% ethoxylated alcohol; and (2) the sodium decyl sulfate and sodium lauryl sulfate comprise about 28% to about 32% sodium decyl sulfate and about 5% to about 10% sodium lauryl sulfate, and further comprises about 50% to about 60% water.

[0145] Embodiment 30. The process of any one of embodiments 23 to 29, wherein the content of the at least one anionic surfactant in the aqueous suspension of the organic pesticide is from about 2% to about 25% by weight, from about 2.5% to about 20% by weight, from about 2.5% to about 15% by weight, from about 2.5% to about 10% by weight, or from about 5% to about 10% by weight.

[0146] Embodiment 31. The process of any one of embodiments 23 to 30, wherein the at least one nonionic surfactant is an alkyl polyglycoside.

[0147] Embodiment 32. The process of embodiment 31, wherein the at least one nonionic surfactant is an oligomeric D-glucopyranose, C9-11 alkyl glycoside.

[0148] Embodiment 33. The process of any one of embodiments 23 to 32, wherein the content of the at least one nonionic surfactant in the aqueous suspension of the organic pesticide is from about 1% to about 10% by weight, or from about 2% to about 10% by weight.

[0149] Embodiment 34. The process of any one of embodiments 23 to 33, wherein the ratio of the at least one nonionic surfactant to the at least one anionic surfactant is from about 5:1 to about 1:1, from about 3.5:1 to about 1:1, from about 3.5:1 to about 1.5:1, from about 3.25:1 to about 1.75:1, from about 3:1 to about 1.75:1, from about 2.75:1 to about 1.75:1, or from about 2.75:1 to about 1.5:1.

[0150] Embodiment 35. The process of any one of embodiments 23 to 34, wherein the at least one additive further comprises at least one antifreeze component and at least one antifoaming agent.

[0151] Embodiment 36. The process of embodiment 35, wherein the at least one antifreeze component is glycerin, propylene glycol, or a combination thereof.

[0152] Embodiment 37. The process of embodiment 35 or embodiment 36, wherein the at least one antifoaming agent is polydimethylsiloxane.

[0153] Embodiment 38. The process of embodiment 37, wherein the polydimethylsiloxane antifoam agent is an emulsion containing about 30 to about 40% solids.

[0154] Embodiment 39. The process step of crystallizing at least one amorphous organic pesticide comprises: A) mixing the mixture; and B) Optionally, cooling the mixture 39. The process of any one of embodiments 1 to 38, comprising:

[0155] Embodiment 40. The process of embodiment 39, wherein the crystallization step is carried out in the absence of a precipitation step.

[0156] Embodiment 41. The process of any one of embodiments 1 to 40, carried out in the absence of a non-aqueous solvent.

[0157] Embodiment 42. The process of any one of embodiments 1 to 41, wherein the at least one amorphous organic pesticide is the same pesticide as the at least one crystalline organic pesticide.

[0158] Embodiment 43. The process of embodiment 42, wherein the amorphous organic pesticide and the crystalline organic pesticide are each indoxacarb.

[0159] Embodiment 44. The process of any one of embodiments 1 to 41, wherein the at least one amorphous organic pesticide is a different pesticide from the at least one crystalline organic pesticide.

[0160] Embodiment 45. The process of any one of embodiments 1 to 44, wherein the aqueous suspension of the organic pesticide comprises at least 200, at least 250, or at least 300 grams per liter of the active ingredient of the crystalline organic pesticide.

[0161] Embodiment 46. An aqueous suspension of an organic pesticide prepared according to any one of embodiments 1 to 45.

[0162] Embodiment 47. An aqueous pesticide formulation prepared according to any one of embodiments 1 to 45. [Example]

[0163] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present disclosure to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative and not limiting of the disclosure in any way.

[0164] The following ingredients were used in Example 1:

[0165] [Table 1]

[0166] Particle size measurements were performed according to CIPAC method MT187. A beam of monochromatic light, usually a laser, is passed through a representative sample dispersed at an appropriate concentration in a suitable liquid or gas. The light scattered by the particles at various angles is measured by a multi-element detector, and numerical values ​​relating to the scattering pattern are then recorded for subsequent analysis. Using appropriate optical models and mathematical procedures, these scattered values ​​are then converted to the ratio of the total volume to a discrete number of particle size classes, forming a volumetric particle size distribution.

[0167] X-ray diffractometer samples were analyzed using a Bruker D2 Phase powder X-ray diffractometer in coupled 2θ / θ mode. The method involved (1) X-ray irradiation from copper at 1.5406 Å; (2) X-ray power at 30 kV and 10 mA; and (3) sample powder was dispersed on a standard PMMA sample holder (C79298A3244D82 / D84). Typical measurement conditions for pXRD were: 2θ start angle = 5°; 2θ stop angle = 35°; sampling = 0.02°; and scan rate = 2° / min.

[0168] Differential scanning calorimeter samples were analyzed using a TA Q20 differential scanning calorimeter. DSC sample pans were either Tzero aluminum hermetic pans or high-pressure, gold-plated crucibles (Fauske M20), and 4-6 mg of sample was used for each run. The method used a constant heating rate of 2 °C / min from 20 °C to 140 °C and nitrogen at 50 mL / min as the purge gas. Peaks were integrated over a linear, two-point baseline.

[0169] Microscopic analysis was performed using a Leica DMI3000B, manual inverted research microscope and a Leica DMC6200 digital camera.

[0170] Scanning electron microscopy imaging was performed on an FEI Quanta 205FEG under high vacuum at 6.00 kV using an Everhardt-Thornly secondary electron detector (ETD). Six white powder samples were dispensed in 100 μL aliquots into 1 mL of distilled water in Eppendorf tubes. Each sample was vortexed for 20 seconds and then sonicated in a water bath for 1 minute. A 100 μL drop of the diluted sample was dispensed onto carbon tape, centered on a 12 mm SEM aluminum specimen stage, and dried under vacuum for 1 hour. Each sample was coated with 4.0-5.0 nm of carbon using a Quorum 150RES carbon evaporator.

[0171] Example 1 Crystalline indoxacarb was prepared in situ from a melt of amorphous indoxacarb.

[0172] A blend of ingredients was prepared by combining Atlox 4913 (14.5 g), Dextrol OC-180 (10.1 g), Agnique PG9166 (28.0 g), Polystep B25U (26.4 g), glycerin (24.0 g), Xiameter AFE (1.0 g), and water (119 g) with stirring (approximately 300-500 rpm) in a jacketed beaker. The blend was heated to approximately 95°C.

[0173] Technical molten amorphous indoxacarb (184.0 g) was prepared by melting in an oven at about 95°C.

[0174] The blend of ingredients and the indoxacarb melt were combined with stirring (about 300-500 rpm) at about 95°C. The temperature was then reduced to about 85°C, and the mixture was maintained at that temperature with stirring for about 1 hour. The temperature was then reduced to about 70-75°C with stirring.

[0175] Technical crystalline indoxacarb (9.5 g) was added to the mixture with stirring (approximately 300 rpm) to form a slurry. Cooling was initiated, and the slurry formed crystalline clumps. Cooling was continued to approximately 5°C. The crystalline clumps were broken up and homogenized to form a flowable suspension. The particle size distribution of the crystalline indoxacarb and agglomerate suspension is shown in Figure 1. Water (70 g) was used to rinse the beaker and combined with the homogenized slurry. The resulting slurry was homogenized (deagglomerated) using a Silverson L4RT homogenizer at approximately 4.5K rpm for approximately 3 minutes. The deagglomerated slurry was transferred to an Eiger mill, circulated, and milled at approximately 2.5-3K rpm at approximately 5°C for approximately 40 minutes to produce a suspension of crystalline indoxacarb.

[0176] The milled suspension of crystalline indoxacarb was then thickened with 5.7 g of Veegum R (8%) and 19.0 g of Rhodophol 23 slurry (2%). Preservatives Proxel GXL (0.5 g) and Acticide LG (0.35 g) were added.

[0177] The composition of the final thickened milled suspension of crystalline indoxacarb is tabulated below and its particle size distribution is shown in FIG.

[0178] [Table 2]

[0179] The final thickened milled suspensions of crystalline indoxacarb were evaluated for particle size distribution on day 0, 15 days after storage at room temperature, and 15 days after storage at 54°C. The particle size results are shown in Figure 3 (blue line represents 15 days at room temperature, red line represents 0 days); Figure 4 (blue line represents 15 days at room temperature, red line represents 2 weeks at 54°C); and Figure 5 (blue line represents 2 weeks at 54°C, red line represents 30 days at room temperature). The results are also shown in the table below, along with particle size distribution results for the crystalline indoxacarb produced according to Example 1 and for a technical concentrate (TC) prepared from the crystalline indoxacarb produced according to Example 1. Each of the compositions evaluated was an off-white suspension. In the tables, "Indox.TC" means crystalline indoxacarb technical concentrate, "15 days at room temperature" means 15 days at room temperature, "15 days at 54°C" means 15 days at 54°C, and was evaluated by 75 μm (200 mesh) wet sieving.

[0180] [Table 3]

[0181] Example 2 Characterization by XRD, DSC and SEM Sample formulation numbers 1-8 listed in the table below were analyzed by XRD (X-ray diffraction), DSC (differential scanning calorimetry) thermal analysis and SEM (scanning electron microscopy) as shown in the table, and the results are reported in Figures 6-21.

[0182] In Figure 6, XRD data for prior art crystalline indoxacarb Samples 1 (black line) and 6 (yellow line) are reported; the yellow and black lines are essentially identical and may be fused as the top line in Figure 6. Figure 6 also reports XRD data for Sample 3 of the present disclosure (red line (bottom line)). Figure 6 shows that the prior art indoxacarb and the indoxacarb produced by Example 1 are crystalline and have similar XRD patterns. In Figure 7, XRD data for Sample 8 of the prior art (red line), Sample 2 of the present disclosure (orange line (middle line)), and Sample 9 of the present disclosure (blue line (bottom line)) are reported. Figure 7 shows that the prior art indoxacarb and the indoxacarb produced by Example 1 are crystalline and have similar XRD patterns. FIG. 8 reports the XRD data for prior art Sample 1 (black line (top line)), Sample 9 of the present disclosure (magenta line (middle line)), and Prior Art Sample 7 (brown line (bottom line)). FIG. 8 shows that the prior art indoxacarb and the indoxacarb produced by Example 1 are crystalline and have similar XRD patterns, and that the prior art molten material used as the starting material for Example 1 is amorphous. FIG. 9 reports the XRD data for prior art Sample 1 (black line (top line)), Sample 5 of the present disclosure (green line (second line from the top)), Prior art Sample 8 (pink line (third line from the top)), Sample 9 of the present disclosure (orange line (second line from the bottom)), and Sample 4 of the present disclosure (light blue line (bottom line)). FIG. 9 shows that the prior art indoxacarb and the indoxacarb produced by Example 1 are crystalline and have similar XRD patterns.

[0183] In Figure 10, DSC data for prior art Sample 1 is reported. In Figure 11, DSC data for Sample 2 of the present disclosure is reported. In Figure 12, DSC data for Sample 3 of the present disclosure is reported. In Figure 13, DSC data for Sample 4 of the present disclosure is reported. In Figure 14, DSC data for Sample 5 of the present disclosure is reported. In Figure 15, DSC data for prior art Sample 6 is reported.

[0184] Figure 16 shows an SEM scan of Sample 1 of the prior art. Figure 17 shows an SEM scan of Sample 2 of the present disclosure. Figure 18 shows an SEM scan of Sample 3 of the present disclosure. Figure 19 shows an SEM scan of Sample 4 of the present disclosure. Figure 20 shows an SEM scan of Sample 5 of the present disclosure. Figure 21 shows an SEM scan of Sample 6 of the prior art.

[0185] [Table 4]

[0186] Samples 3 and 5 demonstrate that indoxacarb produced by the disclosed in situ crystallization process is crystalline. Samples 2, 4, and 9 demonstrate that crystalline indoxacarb produced by the disclosed in situ crystallization process can be directly formulated into indoxacarb SC formulations. Samples 2, 4, and 9 further demonstrate that crystalline indoxacarb SC formulations produced by the disclosed in situ crystallization process are stable in accelerated storage stability tests.

[0187] XRD (X-ray diffraction), DSC (differential scanning calorimetry) thermal analysis, and SEM (scanning electron microscopy) analyses confirmed that the crystalline indoxacarb formed by the disclosed in situ crystallization and one-pot compounding process is consistent with commercially available crystalline indoxacarb.

[0188] Example 3 A mixture of crystalline indoxacarb and rynaxypyr was prepared in situ from a melt of amorphous indoxacarb and rynaxypyr.

[0189] A blend of ingredients was prepared by combining Atlox 4913 (19.07 g), Dextrol OC-180 (13.06 g), Agnique PG9166 (37.56 g), Polystep B25U (34.29 g), glycerin (31.39 g), Xiameter AFE (1.13 g), and water (202.12 g) in a jacketed beaker with stirring (approximately 300-500 rpm). The blend was heated to approximately 95°C.

[0190] Technical molten amorphous indoxacarb (178.00 g) was prepared by melting in an oven at about 95°C.

[0191] The blend of ingredients and the indoxacarb melt were combined with stirring (about 300-500 rpm) at about 95° C. The temperature was then reduced to about 85° C. and the mixture was maintained at that temperature with stirring for about 1 hour. The temperature can then be reduced to about 70-75° C. with stirring.

[0192] Technical crystalline rynaxypyr (2.35 g) was added to the mixture while stirring (approximately 300 rpm) to form a slurry. Cooling was initiated, and the slurry formed crystalline clumps. Cooling was continued to approximately 10°C. The crystalline clumps were broken up and homogenized to form a fluid suspension. Water (32.32 g) was used to rinse the beaker and combined with the homogenized slurry. The resulting slurry was homogenized (deagglomerated) for approximately 3 minutes at approximately 4.5K rpm using a Silverson L4RT homogenizer. Technical rynaxypyr (80.30 g) and Veegum® (0.65 g) were added to the deagglomerated slurry, and the entire slurry was transferred to an Eiger mill, circulated, and milled at approximately 2.5-3K rpm at approximately 5°C for approximately 40 minutes, producing a suspension containing crystalline indoxacarb and rynaxypyr.

[0193] The milled suspension was then thickened with 24.0 g of Rhodophol 23 slurry (2%). The preservative Acticide SPX (1.03 g) was added.

[0194] The composition of the final milled suspension of crystalline indoxacarb and rynaxypyr is summarized in the table below.

[0195] [Table 5]

[0196] Example 4 The insecticidal efficacy of a crystalline indoxacarb suspension concentrate prepared according to Example 1 was evaluated on cotton in comparison to a prior art Steward® indoxacarb emulsion concentrate. The insecticidal efficacy of a crystalline indoxacarb suspension concentrate prepared according to Example 1 was evaluated on cotton in comparison to a prior art Steward® indoxacarb emulsion concentrate after a simulated rainfall event.

[0197] Cotton plants were grown in a growth chamber until they reached the appropriate size. The test formulations were diluted and applied by spraying onto two sets of cotton plants using a Stine 215 Belt Sprayer (468 L / hectare, TwinJet 8002E, 2.1 bar, 19 cm, 43 meters / min). After a 2-hour dry-off period, one set of cotton plants was exposed to a "rainfall" event. Leaves were then cut and placed into impact-resistant styrene trays with agar. Insects (second-instar beet armyworms (Spodoptera exigua)) were placed into each cell, which was then covered. There were two trays per treatment. The trays were housed in a growth chamber under conditions of 16:8 light:dark, 25°C, and 70% relative humidity. Insect mortality was assessed in the trays 72 hours after infestation. A square nozzle was suspended approximately 3 meters above the greenhouse floor, and the rainfall (runoff) phenomenon was carried out at a pressure of approximately 0.28 bar and a rotation rate of 1 revolution per minute. The runoff volume was approximately 7.2 cm over 60 minutes.

[0198] The test sample formulations and associated evaluations are summarized in the following table, where "426 g / L SC" refers to the crystalline indoxacarb suspension concentrate prepared according to Example 1, "322.6 g / L SC" refers to the prior art suspension concentrate containing crystalline indoxacarb, and "EC" refers to the prior art indoxacarb emulsion concentrate containing 0.15 kg / L of amorphous indoxacarb.

[0199] [Table 6]

[0200] The results are shown in the table below: "Amount" means the amount applied, "Dead" means the number of dead insects, and "Total" means the total number of insects applied per test.

[0201] [Table 7]

[0202] The results are analyzed by LC 50 and L.C. 90 The following table shows the 50 " and "LC 90 " means the ppm concentrations at which 50% and 90% insect mortality is achieved, respectively.

[0203] [Table 8]

[0204] The results show that there was no significant difference in drying power, but there was a significant difference under run-off conditions. The SC formulation provided higher efficacy under run-off conditions compared to the EC formulation (EC 50(The confidence intervals do not overlap.) Two SC formulations (a 426 g / L formulation containing crystalline indoxacarb prepared according to the process of the present disclosure and a 322.6 g / L formulation containing crystalline indoxacarb prepared according to the prior art process) demonstrated greater efficacy (i.e., had lower LC values) than the prior art EC formulation. The results further show that there was no significant difference between the 426 g / L SC formulation of the present disclosure and the 322.6 g / L SC formulation of the prior art.

[0205] This written description uses examples to illustrate the disclosure, including the best mode, and also to enable any person skilled in the art to practice the disclosure, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they contain equivalent structural elements that have insubstantial differences from the literal language of the claims.

Claims

1. 1. A process for preparing an aqueous suspension of an organic pesticide comprising the steps of: I) forming a mixture comprising at least one source of amorphous organic pesticide, water, and at least one formulation additive; II) adding at least one crystal seed of an organic pesticide to the mixture; III) crystallizing the at least one amorphous organic pesticide; IV) optionally homogenizing the mixture; V) optionally grinding the mixture; and VI) Optionally, thickening the mixture. A process including.

2. 1. A process for preparing an aqueous suspension of an organic pesticide comprising the steps of: I) A mixture comprising: A) compounded additives, B) at least one crystalline organic pesticide, and C) water forming a mixture comprising: II) adding at least one amorphous organic pesticide to the mixture under stirring conditions; III) crystallizing the at least one amorphous organic pesticide; IV) optionally homogenizing the mixture; V) optionally grinding the mixture; and VI) Optionally, thickening the mixture. A process including.

3. 3. The process of claim 1 or 2, wherein the formulation additives are selected from additional water, dispersants, antifreeze agents, viscosity modifiers, antifoam agents, bactericides, surfactants, and combinations thereof.

4. 4. The process of any one of claims 1 to 3, wherein the at least one amorphous organic pesticide has a melting point in the range of about 55°C to about 100°C.

5. 5. The process of any one of claims 1 to 4, wherein the at least one amorphous organic pesticide has a solubility in water at 25°C from about 0.001 mg / L to about 100 mg / L.

6. 6. The process of any one of claims 1 to 5, wherein the at least one amorphous organic pesticide is in a form selected from a melt, a supercooled melt, a solid amorphous form, a liquid, a solution comprising an active ingredient and a water-miscible solvent, and combinations thereof.

7. 7. The process according to any one of claims 1 to 6, wherein the at least one amorphous organic pesticide is selected from the group consisting of insecticides, fungicides, herbicides and any combination thereof.

8. 8. The process of claim 7, wherein the insecticide is selected from the group consisting of indoxacarb, bifenthrin, gamma-cyhalothrin, and combinations thereof.

9. 8. The process of claim 7, wherein the fungicide is selected from the group consisting of difenoconazole, pyraclostrobin, picoxystrobin, and combinations thereof.

10. 8. The process of claim 7, wherein the herbicide is selected from the group consisting of beflubutamid, s-beflubutamid, rimisoxamide, bixlozone isoflex, napropamide, aclonifen, and combinations thereof.

11. 11. The process according to any one of claims 1 to 10, wherein the aqueous suspension of organic pesticide further comprises a safener.

12. 12. The process of claim 11, wherein the safener is cloquintocet mexyl.

13. 13. The process according to any one of claims 1 to 12, wherein the at least one crystalline organic pesticide has a melting point of from about 55°C to about 100°C.

14. 14. The process of claim 13, wherein the at least one crystalline organic pesticide has a melting point of about 95°C.

15. 15. The process of any one of claims 1 to 14, wherein the at least one crystalline organic pesticide has a solubility in water at 25°C from about 0.001 mg / L to about 100 mg / L.

16. 16. The process of claim 15, wherein the at least one crystalline organic pesticide has a solubility in water of about 0.2 mg / L at 25°C.

17. 17. The process according to any one of claims 1 to 16, wherein the at least one crystalline organic pesticide is selected from insecticides, fungicides, herbicides and combinations thereof.

18. The process according to any one of claims 1 to 17, wherein said at least one crystalline organic pesticide is an insecticide.

19. An aqueous suspension of an organic pesticide produced according to any one of claims 1 to 18.

20. An aqueous pesticide formulation prepared according to any one of claims 1 to 18.

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