agricultural formulation

Abstract

Agricultural concentrates, particularly emulsifiable concentrates, are disclosed. The agricultural concentrates comprise a 3-alkyloxy-4-aryl-5-oxopyrazoline compound, an emulsifier, and an adjuvant comprising one or more C6-C14 triglycerides. The adjuvant surprisingly enhances the herbicidal efficacy of the oxopyrazoline compound while limiting its decomposition in the concentrate. The water-diluted formulations are resistant to phase separation and provide excellent control of grassy weeds without harming crops such as winter barley or winter wheat. The triglycerides are an effective, non-irritating, sustainable alternative to the phosphate esters currently used as adjuvants for the herbicide pyraclonil.

Description

Technical Field

[0001] This invention relates to herbicides, and more particularly to agricultural concentrates having good stability of active substances and herbicidal efficacy. Background Technology

[0002] Phenylacetic pyrazolines, particularly 3-alkoxy-4-aryl-5-oxopyrazoline compounds such as pinoxaden, target grassy weeds and are well-known herbicides for both wheat and barley (see, for example, U.S. Patent Nos. 6,410,180, 6,552,187, and 8,119,566). Pinoxaden-based products were initially developed by Syngenta.

[0003] Cloquinoline is often used with a "safety agent," which modulates the herbicide's activity to better protect the desired crop. Cloquintocet-mexyl, a 5-chloroquinoline derivative, is widely used as a safety agent for cloquinoline.

[0004] Phoxim is typically formulated as an emulsifiable concentrate. This concentrate contains phosmet, one or more emulsifiers, and one or more organic solvents in a major proportion, typically aromatic hydrocarbons.

[0005] When used alone, clodinafop-propargyl has limited efficacy, so it is normally used in combination with an adjuvant. Commercial formulations from Syngenta contain trialkyl phosphates such as tris(2-ethylhexyl) phosphate as adjuvants. Organophosphates have some drawbacks: they can irritate the skin, and they are petrochemical-based, meaning they are not biorenewable.

[0006] Few adjuvants can be "built-in" as part of a clodinafop-propargyl concentrate; most must be "canned-mixed" in spray water before use, which is inconvenient. Despite the potential convenience of built-in adjuvants, there are challenges in formulating clodinafop-propargyl concentrates containing them. For example, a high proportion of adjuvant is required because the built-in adjuvant will be applied at the same dilution as clodinafop-propargyl. Unfortunately, clodinafop-propargyl is prone to degradation when mixed with and stored with other chemicals, including large proportions of adjuvants. Furthermore, the concentrate requires long-term storage stability, such as at least two years under the various temperature and humidity conditions that may exist in warehouses without climate control.

[0007] Identifying adjuvants capable of successfully activating clodinafop-propargyl to maximize its herbicidal effect remains a challenge. Concentrates containing "built-in" adjuvants are needed that can be stored for years under alternating heat / humidity and freezing conditions while limiting the degradation of clodinafop-propargyl. Ideally, the adjuvant used would be an effective bio-based alternative to existing organophosphates. Summary of the Invention

[0008] On one hand, the present invention relates to agricultural concentrates. These concentrates comprise 3-alkoxy-4-aryl-5-oxopyrazoline compounds, emulsifiers, and one or more C6-C... 14 Adjuvants to triglycerides.

[0009] In some respects, agricultural concentrates further include safeners, one or more organic solvents, agricultural active substances other than 3-alkoxy-4-aryl-5-oxopyrazoline compounds, or some combination thereof.

[0010] In some applications, agricultural concentrates are combined with water to obtain emulsions, microemulsions, or suspensions that can be further diluted by the user.

[0011] In a preferred embodiment, the 3-alkoxy-4-aryl-5-oxopyrazoline compound is zoclomethasone.

[0012] We were surprised to find that it included one or more C6-C 14 The adjuvant effect of triglycerides enhances the herbicidal efficacy of 3-alkoxy-4-aryl-5-oxopyrazoline compounds, particularly clodinafop-propargyl, while limiting the degradation of agrochemical actives. The agricultural concentrate exhibits good high-temperature stability, indicating that concentrates containing "built-in" triglyceride adjuvants can be manufactured and stored long-term under ambient conditions. Dilution of the concentrate provides an oil-in-water emulsion with resistance to phase separation. This formulation effectively controls gramineous weeds without harming crops such as winter barley or winter wheat. Triglycerides are an effective, non-irritating, and sustainable alternative to phosphate esters currently used as adjuvants for clodinafop-propargyl. Attached Figure Description

[0013] Figure 1 This is a graph showing the stability of the clopyralid emulsifiable concentrate after storage at 54°C for 2 weeks with a range of adjuvants at 17 or 34 wt.% adjuvant.

[0014] Figure 2A and 2B The image shows (from left to right) the control sample of clodinafop-propargyl without adjuvant and the control sample containing 15 wt.% adjuvant. 108, 30 wt.% Photographs of phytotoxicity test results of 108 and 30 wt.% tri(2-ethylhexyl) phosphate formulations (as adjuvants) on winter barley and winter wheat.

[0015] Figures 3A to 3D These are photographs showing the herbicidal efficacy test results when the above-mentioned clopyralid formulation was used against the following weeds: Agrostis capillaris (AGRCA). Figure 3A), perennial ryegrass (Lolium perenne) (LOLPE, Figure 3B ), Alopecurus myosuroides (ALOMY, Figure 3C ) and wild oats (Avena fatua) (AVEFA, Figure 3D ). Detailed Implementation

[0016] Agricultural concentrate

[0017] In some aspects, the present invention relates to agricultural concentrates comprising a 3-alkoxy-4-aryl-5-oxopyrazoline compound, an emulsifier, and a triglyceride.

[0018] Oxypyrazoline compounds

[0019] Suitable oxopyrazoline compounds are 3-alkoxy-4-aryl-5-oxopyrazolines. The structures and suitable methods for synthesizing many of these compounds are described, for example, in U.S. Patent Nos. 6,410,180, 6,552,187, 7,915,199 and 8,119,566, the teachings of which are incorporated herein by reference.

[0020] In some respects, oxopyrazoline compounds have a general structure:

[0021]

[0022] Ar is an aryl group, which can be substituted with an alkoxy, alkyl, alkylaryl, amino, aryl, halogenated, hydroxyl, or nitro group, preferably substituted with a C1-C4 alkyl group; R 1 It is an alkyl, aryl, alkylaryl, or acyl group, especially a C2-C8 acyl group; and R 2 and R 3 It is an alkyl, alkoxy, aryl, or alkylaryl group, or it can be linked to form a 5-, 6-, 7-, or 8-membered ring optionally including O, N, or S.

[0023] In a preferred embodiment, the oxopyrazoline compound is cyclophosphamide, a well-characterized herbicide having the following structure:

[0024]

[0025] Clotrimazole was first commercialized by Syngenta and is applicable to non-oat grains such as wheat, barley, rye, and triticale, especially wheat and / or barley, as well as cotton, soybean, sugar beets, rice, and other crops, as described in U.S. Patent No. 7,815,199. It is typically applied post-emergence to control grass weeds of the genera *Alopecurus*, *Apera*, *Avena*, *Lolium*, *Phalaris*, *Setaria*, and other families (see, for example, column 27 of '199 patent).

[0026] In some respects, agricultural concentrates contain 1 to 20 wt.%, 2 to 10 wt.%, or 3 to 8 wt.% of an oxopyrazoline compound based on the amount of the concentrate.

[0027] safety agent

[0028] In some respects, agricultural concentrates contain “safeties” that modulate the activity of the herbicide. Suitable safeties are well known and have been described, for example, in U.S. Patent Nos. 6,555,499 and 7,915,199, the teachings of which are incorporated herein by reference. Suitable safeners include, for example, cloquintocet and cloquintocet salts, including alkali metal salts, alkaline earth metal salts, ammonium salts, and sulfonium salts; 2-heptyl sulfadiazine (cloquintocet 2-heptyl ester); mefenpyr and mefenpyr oxalate, including alkali metal salts, alkaline earth metal salts, ammonium salts, and sulfonium salts; mefenpyr-ethyl; bnoxacor, cyometrinil, 2,4-D, dichlormid, dymron, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, oxabetrinil, etc., and combinations thereof. Cloquintocet, cloquintocet salts, and cloquintocet are preferred.

[0029] Oxypyrazoline compounds and safeners can be used in a wide range of ratios. When using a safener, the molar ratio of the oxypyrazoline compound to the safener is typically in the range of 100:1 to 1:10 or 10:1 to 1:1.

[0030] In some respects, agricultural concentrates contain 0.1 to 4 wt.%, or 0.2 to 2 wt.%, or 0.4 to 1.5 wt.% of a safety agent based on the amount of the concentrate.

[0031] solvent

[0032] In some respects, agricultural concentrates contain one or more organic solvents, typically water-immiscible organic solvents. Suitable water-immiscible organic solvents include hydrocarbons, alcohols, ethers, glycols, glycol ethers, ketones, esters, ethers, alkylene carbonates, glycol ether esters, and mixtures thereof. For examples of suitable water-immiscible organic solvents, see U.S. Patent No. 10,314,305 and U.S. Publication No. 2009 / 0005246, the teachings of which are incorporated herein by reference.

[0033] In some applications, the solvent includes aromatic hydrocarbons, typically mixtures of two or more aromatic hydrocarbon compounds, usually "heavy" aromatic compounds. These mixtures are commonly sold by ExxonMobil, Shell, and numerous distributors based on the mixture's boiling range or flash point. Examples include ExxonMobil's SOLVESSO. TM Solvents, such as SOLVESSO TM 200 and SOLVESSO TM 200ND, etc. In some respects, organic solvents consist of or are essentially composed of aromatic hydrocarbons. In some respects, organic solvents have flash points greater than 80°C.

[0034] Organic solvents are often the main component of agricultural concentrates. Therefore, in some respects, agricultural concentrates contain 30 to 90 wt.%, 40 to 80 wt.%, or 50 to 70 wt.% of organic solvents based on the amount of the concentrate.

[0035] emulsifier

[0036] Agricultural concentrates contain emulsifiers. In some cases, the emulsifier is a combination of one or more anionic surfactants and one or more nonionic surfactants. The properties and proportions of the emulsifier used will depend on the nature of the agricultural active ingredient and any safeners used, the nature and proportions of any solvents, the nature and proportions of triglycerides, and other factors. Emulsifiers may include a certain proportion of amphoteric or cationic surfactants, but in many cases, a combination of anionic and nonionic surfactants will be preferred.

[0037] Suitable anionic surfactants include, for example, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, α-sulfonated alkyl esters (especially α-sulfonated methyl esters), α-sulfonated alkyl carboxylates, alkylbenzene sulfonates, sulfoacetates, sulfosuccinates, alkane sulfonates, alkylphenol alkoxylates, phosphate esters, and mixtures thereof. Suitable anionic surfactants include, for example, C5-C... 20 Straight-chain alkylbenzene sulfonates, alkyl ester sulfonates, C6-C 22Primary or secondary alkyl sulfonates, C6-C 24 Olefin sulfonates, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oil-based glycerol sulfonates, and mixtures thereof.

[0038] Many suitable anionic surfactants are commercially available from the Stepan Company, and and Sold under a trademark. For further examples of suitable anionic surfactants, see U.S. Patent No. 6,528,070, the teachings of which are incorporated herein by reference. Further examples of suitable anionic surfactants are described in U.S. Patent Nos. 3,929,678, 5,929,022, 6,399,553, 6,489,285, 6,511,953, 6,949,498 and U.S. Patent Application Publication No. 2010 / 0184855, the teachings of which are incorporated herein by reference.

[0039] In some respects, alkylbenzene sulfonates, such as 60EPG 401-A or 60E (Calcium Alkylbenzene Sulfonate, a product of Stepan Company).

[0040] Suitable nonionic surfactants include, for example, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated castor oil, ethoxylated fatty acids, ethoxylated fatty amines, ethoxylated sorbitol esters, block copolymers of EO and PO, ethoxylated alkanolamides, ethoxylated carbohydrate esters, and combinations thereof. Nonionic surfactants are typically alkoxylated using ethylene oxide units or combinations of ethylene oxide units with propylene oxide or other epoxides.

[0041] Many suitable nonionic surfactants are commercially available. Alcohol ethoxylates and alkylphenol ethoxylates, including those from Stepan, are available from [company name missing]. and Those obtained under the trademark. Suitable amine ethoxylates include ethoxylated coconut oil amines, such as Stepan's. CA-2 and CA-7.5. Suitable ethoxylated carbohydrate esters include ethoxylated sorbitol esters, such as Stepan's. SEE-340 and SEE-341. Suitable ethoxylated alkanolamides include PEG-cocamide and PEG-lauramide, for example, Stepan's. and L-5. Suitable ethoxylated oils include ethoxylated castor oil, for example, Stepan's. 8240 8241 and 8242. Suitable EO-PO block copolymers include those from Stepan. 8320 8323 / 33 26F, from BASF Copolymers, etc. Suitable ethoxylated fatty acids include Stepan's. Products, such as MT-603 MT-610 MT-615 and MT-630F, etc.

[0042] Some suitable surfactants are sold as anionic / nonionic blends. Examples include those available from Stepan. 3400 series blends, such as 3403F, 3453F, 3465F, 3479F, etc.

[0043] Specifically, the anionic surfactant is an alkylbenzene sulfonate and the nonionic surfactant is selected from fatty alcohol ethoxylates, castor oil ethoxylates, ethoxylated fatty acids and EO / PO block copolymers.

[0044] Agricultural concentrates contain 0.5 to 20 wt.%, or 1 to 10 wt.%, or 2 to 8 wt.% of emulsifiers.

[0045] Triglycerides

[0046] Agricultural concentrates contain adjuvants, which include one or more C6-C... 14 Triglycerides, also referred to as "medium-chain" triglycerides in this article, are fatty acid residues that can have a C6-C6 configuration. 14 Triglycerides can be any combination of straight or branched chains within a given range, and can be saturated, unsaturated, or some combination thereof. In some respects, triglycerides mainly or exclusively contain saturated C2O3. 10 -C 12 or saturated C8-C 10 Fatty acid residues. In some respects, adjuvants are composed of or are primarily composed of C6-C6 fatty acid residues. 14 Composition of triglycerides.

[0047] Those skilled in the art will understand that medium-chain triglycerides are typically manufactured and supplied as mixtures containing up to 15 mol% or 2 to 10 mol% diglycerides, and may contain up to 3 mol% or 0.1 to 2 mol% monoglycerides.

[0048] Suitable medium-chain triglycerides are commercially available. Examples include... 108, a triglyceride derived from coconut oil, which combines C8 and C2. 10 Fatty acid (octanoic acid and capric acid) residues; and M-5 is a triglyceride made using glycerol from vegetable oil sources and medium-chain fatty acids from coconut oil and palm kernel oil, both products of Stepan Corporation.

[0049] In some respects, C6-C 14 Triglycerides can be alkylated at the 2-position, as in similar triglycerides prepared from trimethylolethane or trimethylolpropane. In some cases, commercial products are available, such as... 3T, a C8-C compound made from a mixture of decanoic acid / octanoic acid and trimethylolpropane. 10 Composition.

[0050] In some respects, C6-C 14 Triglycerides contain C6-C 14 95 wt.% or more of C8-C triglycerides 12 Triglycerides. In other aspects, C6-C 14 Triglycerides contain C6-C 14 95 wt.% or more of C8-C triglycerides 10 Triglycerides.

[0051] Agricultural concentrates contain 5 to 50 wt.%, 10 to 35 wt.%, or 15 to 30 wt.% of one or more C6-C compounds, based on the amount of the concentrate. 14 Adjuvants to triglycerides.

[0052] In one specific aspect, the agricultural concentrate comprises 1 to 20 wt.% of a 3-alkoxy-4-aryl-5-oxopyrazoline compound; 0.1 to 4 wt.% of a safener; 30 to 90 wt.% of one or more organic solvents; 0.5 to 20 wt.% of an emulsifier; and 5 to 50 wt.% of a compound comprising one or more C6-C... 14 Adjuvants to triglycerides; wherein the wt.% amount is based on the amount of the concentrate.

[0053] In another specific aspect, the agricultural concentrate comprises 4 to 6 wt.% of cyclophosphamide; 1 to 1.5 wt.% of quinalazine; 50 to 70 wt.% of one or more organic solvents comprising aromatic hydrocarbons having a flash point greater than 80°C; 1 to 7 wt.% of a combination of a nonionic surfactant selected from fatty alcohol ethoxylates, castor oil ethoxylates, ethoxylated fatty acids, and EO / PO block copolymers with anionic surfactants selected from alkylbenzene sulfonates; and 10 to 35 wt.% of an adjuvant comprising one or more C8-C... 10 Triglycerides; where the wt.% amount is based on the amount of the concentrate.

[0054] Other herbicidal active substances

[0055] Oxypyrzoline compounds, emulsifiers, and triglyceride adjuvants can be combined with other agronomic active substances, which may include one or more other herbicides.

[0056] Generally, herbicides are characterized by their mode of action, their chemical classification, or both. Functionally, other suitable herbicides include acetyl-CoA carboxylase inhibitors (ACC herbicides), acetyllactase synthase inhibitors (ALS inhibitors), photosynthesis inhibitors, protoporphyrinogen-IX-oxidase inhibitors, bleaching herbicides, synthetic plant growth regulators, and other herbicides described in the HRAC and WSSA classification schemes (available at www.hracglobal.com and www.wssa.net, respectively).

[0057] Suitable herbicides include, for example, anilines such as diflufenican and propargite; arylcarboxylic acids such as dichloropyridinecarboxylic acid, dicamba, and chlorpyrifos; aryloxyalkyl acids such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP, and chlorpyrifos; aryloxyphenoxyalkyl esters such as quizalofop-ethyl, fenoxaprop-ethyl, fluazifop-butyl, fluazifop-methyl, and quizalofop-ethyl; pyrazines such as chlorpyrifos and chlorpyrifos; and benzamides such as dicamba. (flamprop); benzenesulfonamides, such as benfuresate and ethofumesate; benzoxazines, such as flumioxazin; benzoic acids; benzothiadiazines, such as bentazon; carbamates, such as chlorfenapyr, desmedipham, betaine, and chlorfenapyr; carboxamides, such as napropamide and n-(tetrazolyl)aryl carboxamides; chloroacetanilides, such as metolachlor, acetochlor, butachlor, pyrazosulfuron, metolachlor, propachlor, and cyclohexane; eucalyptols, such as cinmethylin; cyclohexane... Ketones; cyclohexenones, such as tralkoxydim; dinitroanilines, such as amoxicillin, pendimethalin, and trifluralin; diphenyl ethers, such as acifluorfen, methyl chlorpyrifos, fluazifop, ethoxyflufenoxam, flusulfanilamide, halosafen, lactofen, and ethoxyflufenoxam; dipyridyliums, such as paraquat; 1,1-disubstituted ethylene oxides, such as tridiphane; hydroxylamines, such as alloxydim, clethodim, thiamethoxam, clethodim, and tralkoxydim. Imidazolinones, such as imidacloprid, imidacloprid, methoxymicarboxylic acid, metribuzin, and quinalazine; indane, such as indoxime; isoxazoles, such as isoxaben; isoxazolidinones, such as isoxaflutole; nitriles, such as bromoxynil, diquat, and iodoxynil; organophosphonates, such as glyphosate and glufosinate; oxadiazonides, such as oxadiazon; oxyacetamides, such as benzalkonium chloride; oxazirones; phenoxyacetic acids; phenoxypropionates; pyridinecarboxylic acids, such as chlopyralid; pyrazolamides; pyrazolyloxyphenyls; pyrazoles, such as oat ash and pyrazolylpyrazoles; pyridinecarboxylic acids, such as clopyralid;Pyridazines, such as pyridafol, pyrazopyrazine metabolites, and imidazopyrazines; pyrimidines, such as pyrazosulfuron; pyrimidine diones, such as bensulfuron; quinoline carboxylic acids, such as quinchlorac and chloroquinolineac; sulfonamides, such as flumetsulam, flusulfonil, and flumetsulam; pyrrolidines, such as flurflufenoxuron; sulfonylureas; sulfonylureas, such as pyrimisulfuron, bensulfuron, chlorimuron, chlorsulfuron, cinosulfuron, formamidesulfuron, flupyrimisulfuron, mesosulfuron, nicosulfuron, flupyrimisulfuron, pyrimisulfuron, sulfonylsulfuron, thiamethoxam, methylthiophenesulfuron, and bensulfuron. The following are listed as examples of herbicides: methylsulfuron, trifluralin, and bensulfuron-methyl; thiocarbamates, such as butyrazosulfuron, cyclosulfuron, albendazole, EPTC, pendimethalin, chlorpyrifos, clethodim, and fenvalerate; thioesters, such as flusulfuron-methyl; thiophenes, such as thiophanate-methyl; triazines, such as atrazine, cypermethrin, simazine, cypermethrin, terbufenozide, and terbufenozide; triazoles, such as chlorpyrifos; triazinones, such as hexazinone, fenpyrazosulfuron, and fenpyrazosulfuron; triazopropanols; triones; uracils, such as cyclosulfuron, chlorpyrifos, or terbufenozide; ureas or azole-urea compounds, such as chlorpyrifos, diuron, fenpyrazosulfuron, isoproturon, linuron, fenpyrazosulfuron, cyclosulfuron, and methylbenzylthiazoline, and combinations thereof.

[0058] Other suitable herbicidal actives for use in combination with oxopyrazoline compounds are described in U.S. Patent No. 7,915,199 (especially columns 8-9); U.S. Patent No. 10,314,305; and U.S. Publication No. 2013 / 0310257, the teachings of which are incorporated herein by reference.

[0059] Other agricultural active substances

[0060] Oxypyrazoline compounds and safeners can be combined with agrochemical actives other than herbicides, which may include one or more insecticides, fungicides, bactericides, acaricides, nematicides, plant growth regulators, etc. Examples of agrochemical actives can be found in U.S. Patent Nos. 8,119,566 (particularly in columns 67-74) and 10,694,743, the teachings of which are incorporated herein by reference.

[0061] Stability of Concentrate

[0062] We found that, compared to many other potential adjuvants screened, including one or more C6-C... 14The triglyceride adjuvant imparts excellent chemical stability to the active substances in the agricultural concentrate. When heated at 54°C for two weeks (i.e., when tested under stress conditions designed to simulate long-term storage at warm ambient temperatures), the concentrates of this invention prepared with adjuvant contents of 17 wt.% or 34 wt.% retained high levels of clodinafop-propargyl and detoxifying quinalcohol active substances (see Adjuvant C, Table 3 below). In contrast, most other screened adjuvants significantly degraded the clodinafop-propargyl active substances. M-10 is an N,N-dimethyl fatty amide that also exhibits good chemical stability of the active substance in this test.

[0063] Water-diluted composition

[0064] Agricultural concentrates are diluted with a large proportion of water before use. Therefore, water-diluted compositions are expected to resist phase separation. In laboratory-scale experiments such as those described in Example 2 below, this means ideally little or no separation of oil, cream, or frost from the water-diluted composition within 24 hours. As shown in Example 2 and Tables 5 and 6, emulsifiable concentrates containing medium-chain triglycerides exhibit considerable flexibility in the combination of anionic and nonionic surfactants, enabling good stability when EC is diluted with water. Compared to ECs formulated with M-10 as an adjuvant, using The EC formulation with 108 is significantly more tolerant of phase separation.

[0065] Agricultural uses

[0066] When with Compared to Pratic (a commercial product combining oxychloride and tris(2-ethylhexyl) phosphate), the concentrate of this invention also showed good performance in greenhouse tests. The EC of this invention exhibited low phytotoxicity to winter barley and winter wheat. Figure 2A and 2B At a typical 30 wt.% adjuvant level, its efficacy in controlling perennial ryegrass (LOLPE), wild oat (AVEFA), large spike alopecuroides (ALOMY), and creeping bentgrass (AGRCA) was comparable to that of commercial samples.

[0067] Formulation designers may prefer to use products including C6-C 14 Triglyceride adjuvants are comparable to organophosphates in efficacy and formulation properties, but are non-irritating and sustainable alternatives.

[0068] The following examples are merely illustrative of the subject matter of this invention. Many similar variations within the scope of the claims will be apparent to those skilled in the art.

[0069] Example 1

[0070] Adjuvant screening for stability (2 weeks, 54°C)

[0071] The stability of clodinafop-methyl in emulsifiable concentrates and other agrochemical formulations depends in part on its resistance to degradation in the presence of other formulation components, including any adjuvants. In this study, various potential adjuvants were screened under stress conditions (stored at 54°C for 2 weeks) to assess their potential use in emulsifiable concentrates containing a mixture of clodinafop-methyl (50 g / L), a quinallic acid-safe agent (12.5 g / L), an aromatic hydrocarbon solvent, a glycol solvent, and a surfactant. Each adjuvant was evaluated at loadings of 17 wt.% or 34 wt.%. A summary of the tested formulations is as follows:

[0072]

[0073]

[0074] After storage in a 54°C oven for 2 weeks, some samples (not listed) crystallized and could not be further studied. Other samples were analyzed by high-performance liquid chromatography (HPLC) using an Agilent 1260 Infinity instrument and high-resolution mass spectrometry (HRMS) using a Bruker Impact HD instrument. The mobile phase for HPLC contained methanol and water, and 5 mM ammonium formate. The column was a silica-based stationary phase modified with branched octadecyl groups.

[0075] As shown in Table 3 below, the stress conditions for 34 wt.% adjuvant compositions are generally more severe. However, formulations containing adjuvants A through D and G, together with clodinafop-propargyl and a safener, provide optimal high-temperature storage stability. These adjuvants are considered suitable for facilitating the next series of tests that evaluate the ability of emulsifiable concentrates to produce stable aqueous emulsions.

[0076]

[0077]

[0078] Example 2

[0079] Performance of emulsifiable concentrates after dilution with water

[0080] In SOLVESSO TM An emulsifiable concentrate sample containing clopyralid (50 g / L) and quinalazine (12.5 g / L) was prepared in 200 ND, of which 34 wt.% M-10 or 108 was used as an adjuvant. The two emulsifiers were modified. 60-EPG (calcium dodecylbenzenesulfonate) and The proportion of 8241 (castor oil 30EO ethoxylate) was determined to determine the appropriate ratio for incorporating the adjuvant into the emulsifiable concentrate. Each EC formulation was diluted to 1 vol.% at 30°C in water with a hardness of 20 ppm or 342 ppm to assess emulsion stability.

[0081] The sample is prepared by first adding the emulsifier to an aromatic hydrocarbon solvent and stirring until homogeneous. If necessary, the emulsifier is heated in an oven at 50°C to 60°C before being combined with the hydrocarbon solvent. Then, clodinafop-propargyl and the safener are added and mixed until homogeneous.

[0082] To test emulsion stability, 100 mL graduated cylinders were filled with CIPAC standard water (20 or 342 ppm, 99 mL). EC (1 mL) was pipetted into each cylinder. The cylinders were plugged and inverted ten times, then allowed to stand at 30°C for 0.5, 1, 2, and 24 hours, recording the stability, type, and amount of separation each time. After 24 hours, the samples were inverted ten times again and allowed to stand for 0.5 hours before the final measurement.

[0083] Table 4 summarizes the emulsifiable concentrates used for stability testing of water-in-oil emulsions. The test results for M-10 (comparative example) are shown in Table 5, and The test results of 108 (example of the present invention) are shown in Table 6.

[0084]

[0085]

[0086]

[0087] Although in Example 1 M-10 and The high-temperature stability properties between 108 and 108 are similar, but the results in Tables 5 and 6 show that when the EC formulation is diluted with standard water at 20 ppm or 342 ppm total dissolved solids (TDS), 108 is a more forgiving adjuvant. A wider range of emulsifier combinations provides water-diluted formulations with no significant separation. Results show that... 108 would be an adjuvant that is easier to use in formulation.

[0088] Example 3: EC formulations used for greenhouse testing

[0089] Production containing clopyralid and 15 wt.% or 30 wt.% A formulation with adjuvant 108 was used for evaluation in greenhouse testing. EC formulation A contains clodinafop-propargyl (5.0 wt.%), quinalazine (1.2 wt.%), and... 60EPG anionic surfactant (2.0 wt.%), nonionic surfactant blend (2.0 wt.%) 108 adjuvant (15.0 wt.%) and SOLVESSO TM 200ND solvent (74.8 wt.%). EC formulation B contains clodinafop-propargyl (5.0 wt.%), quinalazine (1.2 wt.%), 60EPG anionic surfactant (2.6 wt.%), nonionic surfactant blend (2.4 wt.%) 108 adjuvant (30.0 wt.%) and SOLVESSO TM 200ND solvent (58.8 wt.%).

[0090] Storage stability

[0091] The high-temperature storage stability of the formulation was assessed by HPLC / UV after preparation and storage in a 54°C oven for 2 weeks. The mobile phase for HPLC was acetonitrile / aqueous gradient containing 10 mM ammonium formate and 0.1 wt.% formic acid. The column was a silica-based stationary phase modified with branched octadecyl groups. Reported values ​​are the average of measurements from five samples. EC Formulation A (15%) The clopyralid content (quantified based on the signal at 254 nm) of the 108 adjuvant ranged from 49.4 to 50.4 g / L, and the original clopyralid content was retained by an average of 98.2% after storage. This represents excellent storage stability.

[0092] Water-Emulsion Stability

[0093] The stability of water-diluted samples at 25°C was generally assessed as described in Example 2 with some modifications. First, 5 mL of test sample and 95 mL of standard water were used (instead of 1 mL and 99 mL). Second, the samples were evaluated only at 0.5, 1, and 2 hours. Third, experiments using 1000 ppm water were included. The results are shown in Table 7 below.

[0094]

[0095]

[0096] As shown in Table 7, the EC samples diluted with water exhibited excellent stability.

[0097] Example 4: Efficacy in greenhouse testing

[0098] The herbicidal efficacy of the formulation in Example 3 was evaluated in a greenhouse test. The control formulation was... Pratic (Syngenta product). The experimental plan is summarized in Table 8 below. Each formulation was administered in BBCH phases 20-22 and according to... The Pratic label recommends testing at the full dose (N = 1.2 L / ha). Each formulation was also tested at reduced doses (N / 4 = 0.3 L / ha and N / 10 = 0.12 L / ha). A control experiment was also conducted using water (Experiment No. 1). Application volume: 225 L / ha; temperature: 22.7 °C to 24.6 °C; relative humidity: 53% to 86%.

[0099] The efficacy of the formulation was evaluated against perennial ryegrass (LOLPE), wild oat (AVEFA), large-spike wild oat (ALOMY), and creeping bentgrass (AGRCA). Each experiment was repeated four times, with each replicate including three plants. Efficacy was evaluated by visual observation at 3, 7, 14, and 21 days after application, and scored from 0 to 100% efficacy.

[0100] In addition to herbicidal activity, the formulation of Example 3 was weighted and examined for signs of phytotoxicity on winter wheat and winter barley.

[0101]

[0102]

[0103] result :

[0104] like Figure 2A and 2B As shown, none of the tested formulations exhibited any effect on winter barley (N) at full dose. Figure 2A or winter wheat Figure 2B It exhibits significant phytotoxicity.

[0105] The results of the herbicidal efficacy test are as follows Figures 3A to 3D As shown in Table 9. At full dose, it contains 30 wt.% The performance of 108% clopyralid formulations is comparable to those containing 30 wt.% tri(2-ethylhexyl) phosphate. Pratic was just as good (Experiments 5 and 8); Figures 3A to 3D (The third and fourth samples from the left in the image). Contains clopyralid and 15 wt.% 108 formulation (Experiment 2, Figures 3A to 3D The second sample from the left in the picture performed well for AVEFA, but not as well for other weeds as clodinafop-propargyl and 30 wt.%. 108 or Just as good as Pratic. Reduced dosage. The 108 assay showed mixed results: it outperformed commercial samples for AVEFA; performed similarly for AGRCA; and performed poorly for LOLPE and ALOMY.

[0106] Overall, the results showed that, compared with commercial formulations containing 30 wt.% tris(2-ethylhexyl) phosphate, formulations containing 30 wt.% tris(2-ethylhexyl) phosphate were significantly better. The 108% oxadiazon formulation has good efficacy.

[0107]

[0108] The foregoing examples are for illustrative purposes only; the following claims define the scope of the invention.

Claims

1. An agricultural concentrate comprising a 3-alkoxy-4-aryl-5-oxopyrazoline compound, an emulsifier, and an adjuvant, said adjuvant comprising one or more C8-C... 10 Triglycerides; among which, Based on the amount of the agricultural concentrate, the agricultural concentrate contains 10 wt% to 35 wt% of the adjuvant; and the agricultural concentrate contains 3 to 8 wt.% of the 3-alkoxy-4-aryl-5-oxopyrazoline compound, wherein the 3-alkoxy-4-aryl-5-oxopyrazoline compound is cyclohexyl ester.

2. The concentrate according to claim 1, wherein the emulsifier is a combination of one or more nonionic surfactants and one or more anionic surfactants.

3. The concentrate according to claim 2, wherein the anionic surfactant is an alkylbenzene sulfonate and the nonionic surfactant is selected from the group consisting of: fatty alcohol ethoxylates, castor oil ethoxylates, ethoxylated fatty acids and EO / PO block copolymers.

4. The concentrate according to claim 1, further comprising a safener.

5. The concentrate according to claim 4, wherein the safener comprises antidote quinine.

6. The concentrate according to claim 1, further comprising one or more organic solvents.

7. The concentrate according to claim 6, wherein the organic solvent comprises an aromatic hydrocarbon having a flash point greater than 80°C.

8. The concentrate according to claim 1, further comprising one or more insecticides, fungicides, bactericides, acaricides, nematicides, plant growth regulators, or combinations thereof.

9. The concentrate according to claim 1, further comprising an agronomic active substance selected from the group consisting of: anilines; arylcarboxylic acids; aryloxyalkyl acids; aryloxyphenoxyalkyl esters; quinones; benzamides; benzenesulfonamides; benzofurans; benzoxazines; benzoic acids; benzothiadiazines; carbamates; benzoamides; chloroacetanilides; eucalyptols; cyclohexanediones; cyclohexenones; dinitroanilines; diphenyl ethers; bispyridinium compounds; 1,1-disubstituted ethylene oxides; hydroxylamines; imidazolinones; indene Ketones, isoxazoles; isoxazolidinones; nitriles; organophosphonates; oxadiazolones; oxyacetamides; oxazinazoles; phenoxyacetic acids; phenoxypropionates; pyridinecarboxylic acids; pyrazoleamides; pyrazolyloxyphenyls; pyrazoles; pyridazines; pyridinecarboxylic acids; pyrimidines; pyrimidinediones; quinolinecarboxylic acids; sulfonamides; pyrrolidines; sulfonylanilines; sulfonylureas; thiocarbamates; thioesters; thiophenes; triazines; triazoles; triazinones; triazolylpropanols; triones; uracils; ureas; and combinations thereof.

10. The concentrate according to claim 9, wherein the agrochemical active substance is selected from the group consisting of: pyrfluthrin, propargite, dichloropyridinecarboxylic acid, dicamba, chlorpyrifos, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP, chlorpyrifos, quizalofop-p-ethyl, quizalofop-p-ethyl, butylpyrfluthrin, fluroxypyr, quizalofop-p-ethyl, chlorpyrifos, chlorpyrifos, dicamba, methylparaben, ethoxysulfuron, propyzoxystrobin, metribuzin, chlorfenapyr, betaine, betaine, chlorfenapyr. Metolachlor, acetochlor, butachlor, pyrazosulfuron, metolachlor, propachlor, cyclohexane, oxadiazon, amyloliquefaciens, pendimethalin, fluroxypyr, trifluralin, methylflufenican, pyrfluthrin, ethoxysulfuron, flufenoxuron, flufenoxuron, sulfonylurea, oxyfluorfen, paraquat, metribuzin, clethodim, thiamethoxam, clethodim, oxadiazon, imazalil, imazalil, methoxysulfuron, methylfluthrin, metribuzin, quinalazine, indicarb, isoxaflutole, isoxaflutole Bromoxyfenozide, chlorpyrifos, iodofenozide, glyphosate, glufosinate, oxadiazon, bensulfuron-methyl, oxadiazon, chlorpyrifos, chlopyralid, oat ash, dichloropyridine, pyrazosulfuron, dapoxuron, pyrazosulfuron metabolites, pyrazosulfuron, bensulfuron-methyl, dichloroquinoline, chlorpyrifos, diflubenzuron, sulfadiazon, pyrazosulfuron-methyl, fluroxypyr, pyrazosulfuron, bensulfuron-methyl, chlorpyrifos, chlorpyrifos, sulfadiazon, flupyrazosulfuron, formamide, mesosulfuron-methyl, mesosulfuron-methyl, nicosulfuron, flupyrazosulfuron, pyrazosulfuron Sulfonylsulfuron, thiamethoxam, methyl thiophenesulfuron, benzylsulfuron, trifluralin, benzylsulfuron, butachlor, cyclosulfuron, oat sulfuron, EPTC, pendimethalin, chlorpyrifos, clethodim, fenproxetine, flufenoxuron, thiamethoxam, atrazine, cypermethrin, simazine, chlorpyrifos, terbuprofen, terbuprofen, cyclomethrin, fenproxetine, cyclomethrin, fenproxetine, cyclomethrin, chlorpyrifos, terbuprofen; chlorpyrifos, diuron, fenproxetine, isoproturon, linuron, chlorpyrifos, cyclomethrin, methyl thiamethoxam, and combinations thereof.

11. An agricultural concentrate comprising: (a) 3 to 8 wt.% of a 3-alkoxy-4-aryl-5-oxopyrazoline compound; wherein the 3-alkoxy-4-aryl-5-oxopyrazoline compound is cyclohexyl ester; (b) 0.1 to 4 wt.% of a safety agent; (c) 30 to 90 wt.% of one or more organic solvents; (d) 0.5 to 20 wt.% emulsifier; and (e) 10 wt% to 35 wt% of an adjuvant, said adjuvant comprising one or more C8-C 10 Triglycerides; wherein the wt.% amount is based on the amount of the concentrate.

12. The concentrate of claim 11, comprising 0.2 to 2 wt.% of the safener; 40 to 80 wt.% of the aromatic hydrocarbon solvent; and 4 to 10 wt.% of the emulsifier.

13. The concentrate of claim 11, comprising 4 to 6 wt.% of cyclophosphamide; 1 to 1.5 wt.% of quinacrine; 50 to 70 wt.% of an aromatic hydrocarbon solvent having a flash point greater than 80°C; 1 to 7 wt.% of an emulsifier comprising a combination of a nonionic surfactant selected from the group consisting of fatty alcohol ethoxylates, castor oil ethoxylates, ethoxylated fatty acids and EO / PO block copolymers and an anionic surfactant selected from alkylbenzene sulfonates; and 10 to 35 wt.% of the adjuvant, wherein the adjuvant comprises one or more C8-C10 triglycerides.

14. An emulsion, microemulsion or suspension comprising water and the agricultural concentrate according to claim 1.

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