Alkylamidoalkyl (meth)acrylates, their preparation and use

Abstract

The application discloses enoxamacetone diamine salts, a preparation method and application thereof. The stability of enoxamacetone diamine salts (enoxamacetone 1,4-butane diamine salt, enoxamacetone 1,5-pentane diamine salt and enoxamacetone 1,6-hexane diamine salt) is better than that of enoxamacetone and enoxamacetone monoamine salt (for example, enoxamacetone tert-butylamine salt); meanwhile, the weeding activity of the enoxamacetone diamine salt (enoxamacetone ethylenediamine salt, enoxamacetone 1,4-butane diamine salt and enoxamacetone 1,5-pentane diamine salt) is better than that of enoxamacetone tert-butylamine salt, wherein the weeding activity of enoxamacetone 1,5-pentane diamine salt is better than that of enoxamacetone. Most of the enoxamacetone diamine salts have low degradation rate during high-temperature heat storage, are easier to be stored for a long time, have higher melting point than enoxamacetone monoamine salt (for example, enoxamacetone tert-butylamine salt), are more convenient for granulation and crushing, are more convenient for being processed into solid dosage forms such as water dispersible granules as weeding agents, have better physical properties of preparations, and have good commercialization prospect.

Description

Clethodim diamine salt, preparation method and uses Technical Field

[0001] This invention relates to clethodim diamine salt, its preparation method, and its uses, belonging to the field of agricultural herbicides technology. Background Technology

[0002] Clethodim, chemically known as 2-{1-[(3-chloro-2-allyl)oxy]iminopropyl}-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one, is a cyclohexanedione herbicide with excellent herbicidal activity. Currently, commercially available industrial clethodim products are liquids, typically containing 86-93% clethodim. The clethodim structure contains multiple non-adjacent carbon-carbon double bonds and oxime functional groups, resulting in poor stability, easy configuration inversion, and sensitivity to ultraviolet light and heat. Therefore, it is prone to decomposition during long-term transportation and storage, leading to a decrease in clethodim content and reduced herbicidal efficacy in the product. Once clethodim decomposes, the content of its active ingredient decreases, which seriously affects subsequent formulation processing and efficacy. Therefore, it is very important to reduce the decomposition rate of clethodim technical and formulations during storage, improve stability, and increase the content of active ingredients. At the same time, currently available clethodim formulations are all emulsifiable concentrates (EC), such as 240EC and 360EC formulations, and there are no solid formulations, such as water-dispersible granules (WG) or wettable powders (WP), which also limits the application scenarios and commercial use of clethodim.

[0003] Different clethodim salts have different levels of stability, physicochemical properties, herbicidal activity, and efficacy. Different clethodim salts will bring different efficacy and effects, and the formulations and properties of economically important preparations may be different.

[0004] Patent CN102382023A discloses a method for improving the stability of clethodim, which discloses various monoamine salts of clethodim, all of which are monoamine salts of clethodim. The amine compounds used in the examples are primary amines (such as ethylamine and n-butylamine) and secondary amines (such as isopropylamine). However, diamine salts of clethodim (i.e., clethodim diamine salts) have not been reported, and their thermal decomposition rate, herbicidal activity, and physical properties have not been reported.

[0005] Patent CN119390631A discloses clethodim tert-butylamine salt, its preparation method and uses, but as a herbicidal active ingredient, clethodim tert-butylamine salt is not entirely satisfactory. For example, although its stability is better than that of other monoamine salts of clethodim (such as sec-butylamine salt), there is still room for improvement in terms of its thermal decomposition rate, herbicidal activity and physical properties.

[0006] Therefore, there is a need to develop new clethodim derivatives that exhibit one or more improved properties, such as improved storage stability, improved physical properties, improved herbicidal activity, and improved efficacy. Summary of the Invention

[0007] The purpose of this invention is to address the technical problems of poor stability, rapid weakening of herbicidal efficacy, and lack of solid formulation of clethodim. This invention provides clethodim diamine salt, its preparation method, and its uses.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides the use of clethodim diamine salt in improving the stability of clethodim and / or in herbicides, wherein the chemical structural formula of the clethodim diamine salt is as follows:

[0010]

[0011] Wherein, n is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8. Preferably, n is selected from 2, 3, or 4, that is, the preferred clethodim diamine salts are clethodim 1,4-butanediamine salt (n=2), clethodim 1,5-pentanediamine salt (n=3), or clethodim 1,6-hexanediamine salt (n=4).

[0012] More preferably, n is selected from 2 or 3, namely, clethodim 1,4-butanediamine salt or clethodim 1,5-pentanediamine salt.

[0013] The most preferred option is where n is selected from 3, which is clethodim 1,5-pentanediamine salt.

[0014] This invention has confirmed the structures of various clethodim diamine salts, including but not limited to high performance liquid chromatography (HPLC), nuclear magnetic resonance (HNMR), differential scanning calorimetry (DSC), and microscopic melting point analyzer.

[0015] The clethodim diamine salt prepared by this invention is a diamine salt formed by combining clethodim and a diamine in a molar ratio of 2:1. Clethodim exhibits different physicochemical properties and thermal stability after combining with different diamines. The melting range of the clethodim diamine salt prepared by this invention starts at temperatures exceeding 105°C, reaching a maximum of 134.1–135.5°C. Surprisingly, the thermal stability of clethodim ethylenediamine salt is poor, lower than that of clethodim and also lower than that of various clethodim monoamine salts. In contrast, the thermal stability of clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, and clethodim 1,6-hexanediamine salt is excellent, significantly superior to that of various clethodim monoamine salts. The clethodim diamine salts (clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, and clethodim 1,6-hexanediamine salt) prepared by this invention exhibit good stability, which is superior to that of clethodim and various clethodim monoamine salts (including clethodim tert-butylamine salt). Furthermore, the clethodim diamine salts (clethodim ethylenediamine salt, clethodim 1,4-butanediamine salt, and clethodim 1,5-pentanediamine salt) prepared by this invention show superior herbicidal activity compared to clethodim tert-butylamine salt. Specifically, the herbicidal activity of clethodim 1,5-pentanediamine salt is slightly better than that of clethodim, while the herbicidal activity of clethodim 1,6-hexanediamine salt is significantly worse than that of other clethodim diamine salts. The clethodim diamine salts (clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, and clethodim 1,6-hexanediamine salt) prepared by this invention exhibit a lower degradation rate during high-temperature thermal storage compared to clethodim and other clethodim amine salts (including clethodim tert-butylamine salt), and are easier to store for extended periods than clethodim and clethodim tert-butylamine salts.

[0016] Preferably, the preparation method of the clethodim diamine salt includes the following steps:

[0017] S1: Dissolve clethodim in a solvent to obtain mixture A;

[0018] S2: Add a diamine compound or its solution to mixture A to carry out the reaction. After the reaction is completed, clethodim diamine salt is precipitated out of the reaction system.

[0019] S3: Separate the precipitate to obtain clethodim diamine salt.

[0020] By adopting the above technical solution, the method for preparing clethodim diamine salt is simple, mature, stable, and has a high yield and low production cost. Compared with the currently commercialized clethodim technical, the content of clethodim diamine salt product can be significantly improved. The preferred clethodim diamine salt of this invention has a salt content of more than 96.0%, and the more preferred clethodim diamine salt has a salt content of more than 97.5%.

[0021] Preferably, the solvent is selected from one or more of aliphatic alkanes, chlorinated alkanes, ethers, alkyl ketones, and benzene solvents.

[0022] More preferably, the solvent is selected from one or more of toluene, 1,2-dichloroethane, and dichloromethane.

[0023] By adopting the above technical solution, the product yield is higher.

[0024] Preferably, the reaction temperature in S2 is 5°C to 80°C; more preferably, the reaction temperature in S2 is 5°C to 50°C.

[0025] By adopting the above technical solution, the reaction conditions are mild, and the process is mature and safe.

[0026] Preferably, the molar ratio of clethodim to diamine compound is (1:0.5) to (1:0.8).

[0027] By adopting the above technical solution, the yield and content of clethodim diamine salt product are high.

[0028] Preferably, the clethodim salt obtained in S3 is further washed with a solvent.

[0029] By adopting the above technical solution, the content of clethodim salt is high.

[0030] Thirdly, the present invention provides clethodim diamine salt, the chemical structural formula of which is as follows:

[0031]

[0032] Where n is selected from 2, 3, or 4, that is, the clethodim diamine salts are respectively clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, or clethodim 1,6-hexanediamine salt.

[0033] Preferably, n is selected from 2 or 3, that is, clethodim 1,4-butanediamine salt or clethodim 1,5-pentanediamine salt.

[0034] More preferably, n is selected from 3, namely clethodim 1,5-pentanediamine salt.

[0035] Thirdly, the present invention provides a method for improving the stability of clethodim, wherein clethodim is reacted with a diamine compound in an organic solvent at a temperature of 5°C to 50°C to generate clethodim diamine salt as described in the second aspect of the present invention, and then stored in the form of clethodim diamine salt as described in the second aspect of the present invention, wherein the diamine compound is selected from 1,4-butanediamine, 1,5-pentanediamine, or 1,6-hexanediamine.

[0036] Preferably, the diamine compound is selected from 1,4-butanediamine or 1,5-pentanediamine;

[0037] More preferably, the diamine compound is selected from 1,5-pentanediamine.

[0038] Preferably, the solvent is selected from one or more of aliphatic alkanes, chlorinated alkanes, ethers, alkyl ketones, and benzene solvents.

[0039] More preferably, the solvent is selected from one or more of toluene, 1,2-dichloroethane, and dichloromethane.

[0040] Fourthly, the present invention provides the use of the above-mentioned clethodim diamine salt in herbicidal compositions.

[0041] Clethodim's use as a herbicide is well-known in the art and is used on a commercial scale. The clethodim diamine salt described in this invention is also active in controlling harmful weeds. Therefore, techniques known in the art for the formulation and application of clethodim can be applied in a similar manner to the clethodim diamine salt of this invention.

[0042] Therefore, the present invention provides a herbicide composition comprising clethodim diamine salt as described above.

[0043] The composition containing the above-mentioned clethodim diamine salt comprises the clethodim diamine salt of the present invention and at least one adjuvant selected from one or more of the following: surfactants, diluents, dispersants, wetting agents, antioxidants, defoamers, etc.

[0044] Preferably, the composition is in the following forms: suspension concentrate (SC), soluble concentrate (SL), dispersible liquid (DC), emulsifiable concentrate (EC), emulsion seed dressing agent, granules (GR), suspension emulsion (SE), oil-based suspension concentrate (OD), soluble granules (SG), microparticles (MG), water-dispersible granules (WG), or wettable powder (WP).

[0045] More preferably, the composition is in the form of water-dispersible granules (WG) or wettable powder (WP).

[0046] In this invention, clethodim diamine salt is present at a concentration sufficient to achieve the desired dosage when applied to the plant or its location, preferably at a concentration of about 1% to about 95% by weight of the total mixture, more preferably at a concentration of about 5% to about 85% by weight of the total mixture, and more preferably at a concentration of about 10% to about 80% by weight of the total mixture. Formulations are prepared, for example, by incorporating a carrier and / or solvent into the clethodim diamine salt, and, if suitable, using emulsifiers and / or dispersants and / or other adjuvants.

[0047] Surfactants can be ionic or nonionic emulsifiers, dispersants, or wetting agents. Examples that can be used include, but are not limited to, salts of polyacrylic acid, lignin sulfonates, salts or naphthalene sulfonates of benzene sulfonic acid or naphthalene sulfonic acid, condensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols), sulfosuccinate salts, taurine derivatives (especially alkyl taurine), nonylphenol polyoxyethylene ethers, or phosphate esters of polyethoxylated phenols or alcohols, sodium docusate, polycarboxylate complexes, etc.

[0048] Diluents include, but are not limited to, water, N,N-dimethylamide, ethylene glycol, polypropylene glycol, propylene carbonate, diesters, paraffin wax, alkylbenzenes, alkylnaphthalenes, glycerin, olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, and coconut oil, ketones (such as cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone), acetates (such as hexyl acetate, heptyl acetate, and octyl acetate), water, and alcohols (such as methanol, cyclohexanol, decanol, benzyl alcohol, and tetrahydrofurfuryl alcohol), salts such as alkali metal phosphates (e.g., sodium dihydrogen phosphate), alkaline earth metal phosphates, sulfates of sodium, potassium, magnesium, and zinc, sodium chloride, potassium chloride, sodium acetate, sodium carbonate, and sugars and sugar derivatives such as sorbitol, lactose, sucrose, and mannitol, clay, synthetic silica and diatomaceous earth, kaolin, calcium silicate, titanium dioxide, aluminum oxide, calcium oxide, and zinc oxide, and mixtures thereof.

[0049] Wetting agents include, but are not limited to: phosphate esters, acetylenic glycol, ethoxylated silicone, sodium lauryl sulfate, separating powder, soap powder, detergent LS (sodium p-methoxy fatty amide benzenesulfonate), alkyl-substituted naphthalene sulfonates, alkylphenol polyoxyethylene ethers, and polyalkylene glycol ethers. Preferred wetting agents are selected from alkyl-substituted naphthalene sulfonates, polyalkylene glycol ethers, sodium lauryl sulfate, and soap powder.

[0050] Dispersants include, but are not limited to: polycarboxylates or polycarboxylate complexes, alkylphenol polyoxyethylene ether formaldehyde condensate sulfates, sodium salts of naphthalene sulfonate formaldehyde condensate, naphthalene sulfonate condensates, calcium salts of alkylbenzene sulfonate, alkylphenol polyoxyethylene ethers, nonylphenol polyoxyethylene ethers, fatty amine polyoxyethylene ethers, fatty acid polyoxyethylene esters and glycerol fatty acid polyoxyethylene ethers, sodium, calcium and ammonium salts of lignin sulfonate, and naphthalene sulfonate formaldehyde condensates. Preferred dispersants are selected from naphthalene sulfonate condensates (such as sodium salts of naphthalene sulfonate formaldehyde condensate), lignin sulfonates (such as calcium lignin sulfonate), calcium salts of alkylbenzene sulfonate, nonylphenol polyoxyethylene ethers, polycarboxylates or polycarboxylate complexes (such as TERSPERSE 2700, Agrilan 700, SP-2836, GeroponT / 36).

[0051] Defoamers encompass all substances commonly used for this purpose in agricultural chemical compositions. Suitable defoamers are known in the art and are commercially available. Preferred defoamers include polydimethylsiloxanes, mixtures of perfluoroalkylphosphonic acids, polyether-modified silicones, silicone compounds, C8-C10 fatty alcohols, etc.

[0052] Disintegrants include all substances that can typically be used for this purpose in agrochemical compositions. Suitable disintegrants are known in the art and are commercially available. Preferred disintegrants are bentonite, urea, ammonium sulfate, aluminum chloride, citric acid, succinic acid, and sodium bicarbonate.

[0053] Other formulation components can also be used in this invention, such as preservatives, penetrants, antifreeze agents, thickeners, etc. Herbicides can also be added to the composition containing clethodim diamine salt according to this invention. Suitable combinations of herbicides, such as adding appropriate amounts of one or more herbicide components, may result in better combined weed control effects. These components are known to those skilled in the art.

[0054] Under the same formulation and dosage form, the various clethodim diamine salts described in this invention have better formulation physical properties than clethodim tert-butylamine salts, and are easier to process into solid dosage forms such as water-dispersible granules (WG) as herbicides, thus having better commercial prospects.

[0055] Fourthly, the present invention provides the application of the clethodim diamine salt or the clethodim diamine salt composition of the present invention in the control of harmful weeds.

[0056] The clethodim diamine salt or the clethodim diamine salt composition of the present invention can be used to control harmful weeds, which are selected from grass weeds and broadleaf weeds.

[0057] Preferably, the harmful weeds are selected from *Alopecurus aequalis*, *Galium aparine*, *Galium affine*, *Sesamum indicum*, *Forget-me-not*, *Stellaria media*, *Ivy*, *Barnyard grass*, *Digitaria sanguinalis*, *Veronica persica*, *Eleusine indica*, *Sonchus oleraceus*, and *Viola yedoensis*.

[0058] Preferably, the clethodim diamine salt or clethodim diamine salt composition is used to control harmful weeds in ornamental plants, fruit trees, vegetables, legumes, and cereal crops.

[0059] Preferably, the clethodim diamine salt or clethodim diamine salt composition is used to control harmful weeds in winter wheat, potatoes, sunflowers, sugar beets, sugarcane, carrots, corn, and soybeans.

[0060] Furthermore, the present invention also provides a method for controlling weeds, comprising applying to the plant, plant parts, or the environment surrounding the plant an effective amount of the aforementioned clethodim diamine salt or the aforementioned clethodim diamine salt composition. Therefore, this provides a method for controlling weeds on a plant, plant parts, and / or its surrounding environment, comprising applying to the roots of the plant, plant parts, or the environment surrounding the plant an effective amount of clethodim diamine salt or the clethodim diamine salt composition.

[0061] As used herein, the term “about” when used in conjunction with a numerical quantity or range means slightly greater than or slightly less than the numerical quantity or range, and deviating from the endpoints of the numerical quantity or range by ±10%.

[0062] Treatment of plants and plant parts with the compositions or formulations of the present invention is carried out directly or by conventional treatment methods that allow the compositions or formulations to act on their surrounding environment, habitat, or storage space. Examples of such conventional treatment methods include impregnation, spraying, vaporization, atomization, broadcasting, brushing, mixing (such as soil treatment), etc.

[0063] The term "room temperature" as used in this article refers to a temperature range of approximately 20°C to 25°C.

[0064] By adopting the above technical solution, clethodim diamine salt has good stability and herbicidal efficacy, and it is expected to be prepared into a commercially viable formulation with excellent storage stability and good efficacy.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] 1. This invention provides for the first time multiple clethodim diamine salts and characterizes them by various means. The long-term storage stability of the clethodim diamine salts (clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, and clethodim 1,6-hexanediamine salt) of this invention is improved, which is not only superior to clethodim but also superior to other monoamine salts of clethodim reported in the literature (including clethodim tert-butylamine salt). At the same time, most of the clethodim diamine salts maintain herbicidal activity no weaker than clethodim. The clethodim diamine salts (clethodim ethylenediamine salt, clethodim 1,4-butanediamine salt, and clethodim 1,5-pentanediamine salt) prepared by this invention have better herbicidal activity against a variety of weeds than clethodim tert-butylamine salt. Among them, the herbicidal activity of clethodim 1,5-pentanediamine salt against a variety of weeds (barnyardgrass, crabgrass, and goosegrass) is slightly better than that of clethodim.

[0067] 2. The clethodim diamine salt of this application is beneficial for the preparation of commercially viable formulations with economic value, and has superior storage stability and good efficacy; the high-temperature thermal storage process of the multiple clethodim diamine salts of this application has a lower degradation rate than clethodim and other clethodim amine salts reported in the literature, and is easier to store for a long time than clethodim, which is beneficial to the shelf-life stability of commercial products.

[0068] 3. The clethodim diamine salt prepared by the method of the present invention has a high melting point and more suitable physical properties for preparation into solid formulations. The solid formulations of clethodim diamine salt prepared by the method of the present invention have better physical properties than those of clethodim tert-butylamine salt, and provide solid formulations of clethodim such as water-dispersible granules (WG), which have better commercial prospects. Attached Figure Description

[0069] Figure 1 shows the 1H NMR spectrum of clethodim ethylenediamine salt.

[0070] Figure 2 is a differential scanning calorimetry (DSC) graph of clethodim ethylenediamine salt.

[0071] Figure 3 shows the 1H NMR spectrum of clethodim 1,4-butanediamine salt.

[0072] Figure 4 is a differential scanning calorimetry (DSC) chromatogram of clethodim 1,4-butanediamine salt.

[0073] Figure 5 shows the 1H NMR spectrum of clethodim 1,5-pentanediamine salt.

[0074] Figure 6 is a differential scanning calorimetry (DSC) chromatogram of clethodim 1,5-pentanediamine salt.

[0075] Figure 7 shows the 1H NMR spectrum of clethodim 1,6-hexanediamine salt.

[0076] Figure 8 is a differential scanning calorimetry (DSC) chromatogram of clethodim 1,6-hexanediamine salt. Detailed Implementation

[0077] To make the present invention more apparent and understandable, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0078] Example 1

[0079] A clethodim diamine salt has the following chemical structural formula:

[0080]

[0081] Where n is selected from 0, that is, the clethodim diamine salt is clethodim ethylenediamine salt.

[0082] The preparation method of this clethodim ethylenediamine salt is as follows:

[0083] S1: At a temperature of 12℃, 40.2g of clethodim technical (89.5%, 0.10mol) and 25g of solvent A were stirred and mixed evenly. The temperature was raised to a mixing temperature of 15℃, and 3.64g of ethylenediamine (99%, 0.06mol) was slowly added. After the addition was complete, the mixture was stirred at 15℃ for 1.0h, and then 125.0g of solvent B was added to obtain mixture A.

[0084] S2: Continue stirring the reaction at 15℃ for 6.0 h to obtain the reaction mixture;

[0085] S3: Filter the reactants to obtain a solid;

[0086] S4: The solid is washed with solvent B at a mass ratio of 6, and then dried under vacuum at 10-15℃ to obtain the product clethodim ethylenediamine salt.

[0087] Solvent A is toluene, and solvent B is n-hexane.

[0088] Examples 2-8

[0089] The preparation method of clethodim diamine salt differs from that in Example 1 in that the process parameters of the preparation method are different, and the specific differences are shown in Table 1.

[0090] Table 1. Preparation method parameters for Examples 1-8

[0091]

[0092] The products obtained in Examples 1 to 8 were analyzed by high performance liquid chromatography (HPLC) and the yield was calculated. The results are shown in Table 2.

[0093] Table 2. Product purity and yield of Examples 1-8

[0094]

[0095]

[0096] As can be seen from Tables 1 and 2, and through Examples 1 to 8, the preparation method of this application controls the reaction temperature within the range of 5 to 50°C when obtaining the clethodim diamine salt of this application. Considering both the production cost and the final product quality indicators, the molar ratio of clethodim to tert-butylamine in this application is controlled at (1:0.4) to (1:0.8). With appropriate adjustment of the reaction time, the target product with high purity can be obtained in high yield. This preparation method has low production cost, is mature and simple, has good stability, and high yield.

[0097] Samples obtained from Examples 1, 3, 5, and 7 were selected as test samples and tested using a microscopic melting point analyzer. The melting range and other information of the obtained clethodim diamine salt are shown in Table 3.

[0098] Table 3. Melting range information of clethodim diamine salt in the examples

[0099] Comparative Example No. Clethodim Diamine Salt Name Clethodim Diamine Salt Content (%) Product Melting Range (°C) Example 1 Clethodim Ethylenediamine Salt 98.17 106.1~107.8 Example 3 Clethodim 1,6-Hexanediamine Salt 99.71 134.1~135.5 Example 5 Clethodim 1,4-Butanediamine Salt 99.01 132.1~133.9 Example 7 Clethodim 1,5-Pentanediamine Salt 99.43 126.6~129.5 surface

[0100] The clethodim ethylenediamine salt prepared in the above embodiments of the present invention can be characterized by the 1H NMR spectrum of clethodim ethylenediamine salt shown in Figure 1; and / or, by the differential scanning calorimetry (DSC) spectrum of clethodim ethylenediamine salt basically shown in Figure 2; and / or, by comparing the chromatogram of clethodim with that of clethodim standards using high performance liquid chromatography (HPLC); and / or, by the melting range shown by a microscopic melting point detector. The clethodim 1,4-butanediamine salt prepared in the above embodiments of the present invention can be characterized by the 1H NMR spectrum of clethodim butyldiamine salt shown in Figure 3; and / or, by the differential scanning calorimetry (DSC) spectrum of clethodim butyldiamine salt basically shown in Figure 4; and / or, by comparing the chromatogram of clethodim with that of clethodim standards using high performance liquid chromatography (HPLC); and / or, by the melting range shown by a microscopic melting point detector. The 1,5-pentanediamine salt of clethodim prepared in the above embodiments of the present invention can be characterized by the 1H NMR spectrum of clethodim pentanediamine salt shown in Figure 5; and / or, by the differential scanning calorimetry (DSC) spectrum of clethodim pentanediamine salt basically shown in Figure 6; and / or, by comparing the chromatogram of clethodim with that of clethodim standards using high performance liquid chromatography (HPLC); and / or, by the melting range shown by a microscopic melting point detector. The 1,6-hexanediamine salt of clethodim prepared in the above embodiments of the present invention can be characterized by the 1H NMR spectrum of clethodim hexanediamine salt shown in Figure 7; and / or, by the differential scanning calorimetry (DSC) spectrum of clethodim hexanediamine salt basically shown in Figure 8; and / or, by comparing the chromatogram of clethodim with that of clethodim standards using high performance liquid chromatography (HPLC); and / or, by the melting range shown by a microscopic melting point detector.

[0101] Comparative Example 1

[0102] A clethodim monoamine salt, which differs from Example 1 in that the amine used in S1 is 1,2-dimethylpropylamine, and the molar ratio of clethodim to 1,2-dimethylpropylamine is 1:1.1. The specific details of the obtained clethodim monoamine salt are shown in Table 4.

[0103] Comparative Examples 2-6

[0104] A clethodim monoamine salt differs from Example 1 in that the amine used in S1 is different. The molar ratio of clethodim to amine is 1:1.1. The specific clethodim monoamine salt obtained is shown in Table 4.

[0105] Table 4. Information on amines used in Comparative Examples 1–6, including product content and yield.

[0106] Comparative Example No. Amine Name Clethodim Amine Salt Content (%) Product Melting Point (°C) Clethodim Amine Salt Yield (%) Comparative Example 1 1,2-Dimethylpropylamine 94.6 978 -8390 Comparative Example 2 Tert-amylamine 95.6 675 -7892 Comparative Example 3 Cyclohexylamine 94.5 182 -8791 Comparative Example 4 n-Hexylamine 97.9 889 -9285 Comparative Example 5 n-Butylamine 90.5 2 / *87 Comparative Example 6 Tert-Butylamine 99.3 92 -9495.7 surface

[0107] *The melting point of the clethodim-n-butylamine salt obtained in Comparative Example 5 fluctuated by more than 10°C during the melting point test, and multiple resampling measurements could not obtain test results within the fluctuation range of 5°C. Analysis showed that this was because the clethodim-amine salt was too low, and the decomposition of clethodim or other byproducts during heating triggered the decomposition of the clethodim-amine salt.

[0108] The stability of the samples in Examples 1, 3, 5, 7 and Comparative Examples 1 to 6 was tested by accelerated storage testing.

[0109] According to the international method for the physicochemical determination of pesticide technicals and formulations—CIPAC method—CIPAC MT46.4 Accelerated Storage procedure specifies that pesticide technicals and formulations have a shelf life of at least 2 years under standard operating conditions. The shelf life of pesticide technicals and formulations under standard operating conditions can be determined through accelerated storage testing. Accelerated storage testing is performed according to the following six combinations of storage temperature and storage period specified in CIPAC MT 46.4 Accelerated Storage procedure. The test results for residual active ingredients in the samples can be considered as predictive values ​​for 2-year storage:

[0110] (1) 54±2℃, for 14 consecutive days;

[0111] (2) 50±2℃, for 4 weeks;

[0112] (3) 45±2℃, for 6 weeks;

[0113] (4) 40±2℃, for 8 weeks;

[0114] (5) 35±2℃, for 12 weeks;

[0115] (6) 30±2℃, for 18 weeks;

[0116] That is, storing at 54±2℃ for 14 days is equivalent to storing at 50±2℃ for 4 weeks, and so on.

[0117] In the combination of storage temperature and storage period, storage temperature has a significant impact on the accelerated storage testing of pesticide technicals and formulations, determining the accelerated storage testing cycle and reflecting the upper limit of extreme conditions that pesticide technicals and formulations can tolerate during storage.

[0118] This application selects "54±2℃ for 14 days" as the test parameter. The CIPAC method, the international standard for the physicochemical determination of pesticide technicals and formulations, is cited here. The rate of change curves of samples differ under different parameters, making conversion impractical. For example, the results of a sample at 54±2℃ for 7 days are not the same as those of a sample at 35℃±2℃ for 6 weeks.

[0119] The specific testing method was as follows: the sample was sealed in ampoules and stored in a constant temperature chamber at 54±2℃ for 14 days. Then, high performance liquid chromatography (HPLC) was used to analyze the change in purity of the active ingredient before and after heat storage. A commercially available clethodim sample (mass content 89.50%) was used as a control. The test results are shown in Table 5.

[0120] Table 5. Stability test results of Examples 1-6 and Comparative Examples 1-6

[0121]

[0122]

[0123] Note: The sample content refers to the content of the corresponding active ingredient (clethodim amine salt or clethodim) in the sample after heat storage; the decomposition rate is calculated as follows: Decomposition rate (%) = heat storage sample content / (initial sample - heat storage sample content) × 100%.

[0124] During the research process of this application, it was found that some of the samples in Comparative Examples 1 to 6 decomposed relatively quickly when stored at 54±2℃. In order to better and more comprehensively compare the examples and Comparative Examples 1 to 6, this application conducted additional independent tests with the same samples at 54±2℃ for a full 7 days, in addition to the 14 days required by the CIPAC MT 46.4 Accelerated Storage procedure, to better indicate the decomposition during storage and reflect the stability performance of each sample.

[0125] As shown in Table 5, after 14 days of accelerated storage at 54±2℃, the samples of Comparative Examples 1-6 and the Control Example all showed significant decomposition. The decomposition rate of Comparative Example 6, clethodim tert-butylamine salt, was relatively low, but still exceeded 10%. Surprisingly, Example 1 showed a similar decomposition rate to Comparative Examples 3-5, exhibiting significant decomposition. Surprisingly, the decomposition in Examples 3, 5, and 7 was gradual, and the final decomposition rate after 14 days was much lower than that of Comparative Examples 1-6 and the Control Example. The decomposition rate of Example 3 was less than 3%, at 2.51%, and the decomposition rate of Example 5 was less than 4%, at 3.56%. Therefore, the stability of the clethodim diamine salts (clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, clethodim 1,6-hexanediamine salt) prepared in this invention is superior to that of clethodim and clethodim monoamine salts (such as clethodim tert-butylamine salt). It is reasonable to infer that the prepared technical grade or formulation is less prone to decomposition during long-term storage.

[0126] Herbicidal activity test

[0127] The test was conducted according to the herbicide section 4 of the pesticide indoor bioassay test guidelines: activity assay test by foliar spraying (NY / T 1155.4-2006). The test targets were barnyard grass (Echinochloa Beauv.), crabgrass (Digitaria sanguinalis (L.) Scop.), and goosegrass (Eleusine indica (L.) Gaertn.). A commercially available sample of clethodim technical (content 90.0%) was used as a control. The test results were the fresh weight control efficacy against weeds at different application rates over 20 days.

[0128] The information table of the test samples is shown in Table 6 below:

[0129] Table 6. Information on test samples for weed control test

[0130] Serial Number | Sample Number | Sample Salt Content Conversion | Clethodim Content in Sample | 1 | Clethodim tert-butylamine salt A | 97.7% | 81.2% | 2 | Clethodim 1,6-hexamethylenediamine salt B | 97.6% | 84.0% | 3 | Clethodim 1,4-butanediamine salt C | 98.3% | 87.6% | 4 | Clethodim ethylenediamine salt D | 99.8% | 92.1% | 5 | Clethodim 1,5-pentanediamine salt E | 99.9% | 87.5% | 6 | Clethodim technical grade (90%) F / 90.0% | 7 | CK (blank control) / / / surface

[0131] The weed control test results are as follows:

[0132] The herbicidal effects of each herbicide on barnyard grass are shown in Tables 7 and 8 below:

[0133] Table 7. Results of barnyardgrass fresh weight control efficacy (%) 20 days after herbicide application

[0134]

[0135] Table 8. Regression equations for the inhibitory concentrations of various herbicides on barnyardgrass in the herbicide test.

[0136] The regression equation for the inhibitory concentration of the herbicide on barnyardgrass is ED50R. 2 95% confidence interval: Ay = 8.24 + (100.37 - 8.24) / (1 + (x + 64.36) * 1.37) = 64.36 * 0.97 * 2.82 ~ 125.91; By = 7.01 + (99.14 - 7.01) / (1 + (x + 74.92) * 1.56) = 74.92 * 0.96 - 10.24 ~ 160.07; Cy = -3.63 + (96.16 + 3.63) / (1 + (x + 38.72) * 2.37) = 38.72 * 0.97 * 30.25 ~ 4 7.18Dy=0.24+(1001.29-0.24) / (1+(x+33.10)2.98)33.100.9930.61~35.59Ey=0.21+(100.62-0.21) / (1+( x+24.14)3.10)24.140.9922.31~25.98Fy=0.77+(99.81-0.77) / (1+(x+30.96)3.86)30.960.9929.18~32.74 surface

[0137] Analysis of the experimental results in Tables 7 and 8: 20 days after application, pesticide E showed the best visual control efficacy, followed by pesticides F and D, while pesticides A and B showed the worst visual control efficacy. 20 days after application, pesticide E showed the best inhibition of barnyard grass fresh weight, with an ED50 value of 24.14, followed by pesticides F and D, with ED50 values ​​of 30.96 and 33.10 respectively. Pesticide B showed the worst inhibition of barnyard grass fresh weight, with an ED50 value of 74.92. The 20-day fresh weight control efficacy against barnyard grass was: Pesticide E > Pesticide F > Pesticide D > Pesticide C > Pesticide A > Pesticide B.

[0138] The herbicidal effects of each herbicide on crabgrass are shown in Tables 9 and 10 below:

[0139] Table 9. Results of fresh weight control efficacy (%) of crabgrass 20 days after herbicide application

[0140]

[0141] Table 10. Regression equations for the inhibitory concentration of each herbicide on crabgrass in the herbicide test.

[0142] The regression equation for the inhibitory concentration of the drug on Digitaria rubra is ED50R. 2 95% confidence interval: Ay = -0.99 + (100.81 + 0.99) / (1 + (x + 27.63) + 1.35) = 27.63 + 0.97 = 16.29 ~ 38.97; By = -16.62 + (98.50 + 16.62) / (1 + (x + 40.75) + 1.38) = 40.75 + 0.98 = 22.81 ~ 58.69; Cy = -17.54 + (101.58 + 17.54) / (1 + (x + 22.77) + 1.05) = 22.77 + 0.98 = 10.61 ~34.93Dy=-19.54+(100.28+19.54) / (1+(x+16.60)0.96)16.600.999.67~23.53Ey=-9.69+(100.60+9.69) / (1 +(x+9.72)1.06)9.720.986.69~12.74Fy=-24.56+(100.18+24.56) / (1+(x+13.00)0.71)13.000.982.59~23.42 surface

[0143] Analysis of the experimental results in Tables 9 and 10: 20 days after application, pesticide E showed the best visual control efficacy, followed by pesticides F and D, while pesticides A and B showed the worst visual control efficacy. 20 days after application, pesticide E showed the best inhibition of fresh weight of crabgrass, with an ED50 value of 9.72, followed by pesticides F and D, with ED50 values ​​of 13.00 and 16.60 respectively. Pesticide B showed the worst inhibition of fresh weight of crabgrass, with an ED50 value of 40.75. The 20-day fresh weight control efficacy against crabgrass was: Pesticide E > Pesticide F > Pesticide D > Pesticide C > Pesticide A > Pesticide B.

[0144] The herbicidal effects of each herbicide on crabgrass are shown in Tables 11 and 12 below:

[0145] Table 11. Results of herbicide efficacy (%) against fresh weight of goosegrass 20 days after application

[0146]

[0147]

[0148] Table 12. Regression equations for the inhibitory concentrations of various herbicides on *Eleusine indica* in herbicide tests.

[0149] The regression equation for the inhibitory concentration of the herb on *Eleusine indica* is ED50R. 2 95% confidence intervals: Ay = -13.06 + (100.07 + 13.06) / (1 + (x + 6.34) + 0.77) = 6.34 + 0.99 = 4.54 ~ 8.13; By = -7.14 + (100.13 + 7.14) / (1 + (x + 19.67) + 1.72) = 19.67 + 0.99 = 17.45 ~ 21.90; Cy = -3.25 + (100.10 + 3.25) / (1 + (x + 14.16) + 1.90) = 14.16 + 0.99 = 12. 64~15.68Dy=-0.87+(101.36+0.87) / (1+(x+9.55)1.76)9.550.998.83~10.27Ey=-0.74+(100.09+0.74) / (1+(x+4.31)1.19)4.310.994.02~4.60Fy=-5.58+(100.13+5.58) / (1+(x+5.40)0.83)5.400.994.11~6.69 surface

[0150] Analysis of the experimental results in Tables 11 and 12: 20 days after application, pesticides E and A showed the best visual control efficacy, followed by pesticides F and D, while pesticide B showed the worst visual control efficacy. 20 days after application, pesticide E showed the best inhibitory effect on the fresh weight of *Eleusine indica*, with an ED50 value of 4.31, followed by pesticides F and A, with ED50 values ​​of 5.40 and 6.34 respectively. Pesticide D also showed a good inhibitory effect on the fresh weight of *Eleusine indica*, with an ED50 value of 9.55. Pesticide B showed the worst inhibitory effect on the fresh weight of *Eleusine indica*, with an ED50 value of 19.67. The control efficacy against the fresh weight of *Eleusine indica* at 20 days was: Pesticide E > Pesticide F > Pesticide A > Pesticide D > Pesticide C > Pesticide B.

[0151] As shown in Tables 6-12, the six tested clethodim samples exhibited varying degrees of inhibition against barnyard grass, crabgrass, and goosegrass. Clethodim 1,5-pentanediamine salt (e.g., agent E) showed the best fresh weight inhibition against all three weeds, and its visual control efficacy was also good, exceeding that of the control agent clethodim technical (e.g., agent F). Clethodim ethylenediamine salt (e.g., agent D) also showed good fresh weight inhibition and visual control efficacy against all three weeds, but its inhibition effect was slightly lower than that of the control agent clethodim technical (e.g., agent F). Clethodim tert-butylamine salt (e.g., agent A) showed good visual control and fresh weight inhibition against goosegrass, but relatively poor visual control and fresh weight inhibition against barnyard grass and crabgrass.

[0152] Formulation Examples

[0153] Formulation Example 1: 40 parts of clethodim 1,6-hexanediamine salt, 10 parts of calcium dodecylbenzenesulfonate salt, 10 parts of nonylphenol polyoxyethylene ether, 5 parts of soapberry powder, 25 parts of diatomaceous earth, and 10 parts of sodium sulfate were mixed and stirred evenly in a stirring tank. The mixture was then further stirred evenly using an air jet mill to obtain the wettable powder of the herbicidal composition of the present invention.

[0154] Formulation Example 2: 48 parts of clethodim 1,6-hexanediamine salt, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of sodium naphthalenesulfonic acid formaldehyde condensate, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin were mixed evenly, pulverized using an ultra-micro airflow pulverizer, kneaded, and then added to a fluidized bed granulator for granulation, drying, and sieving. After sampling and analysis, the water-dispersible granules of the herbicidal composition of the present invention were obtained.

[0155] Formulation Example 3: 48 parts of clethodim 1,5-pentanediamine salt, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of sodium naphthalenesulfonic acid formaldehyde condensate, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin were mixed evenly, pulverized using an ultra-micro airflow pulverizer, kneaded, and then added to a fluidized bed granulator for granulation, drying, sieving, and sampling analysis to obtain the water-dispersible granules of the herbicidal composition of the present invention.

[0156] Formulation Example 4: 50 parts of clethodim 1,5-pentanediamine salt, 10 parts of calcium dodecylbenzenesulfonate salt, 10 parts of nonylphenol polyoxyethylene ether, 10 parts of soapberry powder, 15 parts of diatomaceous earth, and 5 parts of sodium sulfate were mixed and stirred evenly in a stirring tank, and then mixed evenly again after passing through an air jet mill to obtain the wettable powder of the herbicidal composition of the present invention.

[0157] Formulation Example 5: 48 parts of clethodim ethylenediamine salt, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of sodium naphthalenesulfonic acid formaldehyde condensate, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin were mixed evenly, pulverized using an ultra-micro airflow pulverizer, kneaded, and then added to a fluidized bed granulator for granulation, drying, and sieving. After sampling and analysis, the water-dispersible granules of the herbicidal composition of the present invention were obtained.

[0158] Formulation Example 6: 48 parts of clethodim 1,4-butanediamine salt, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of sodium naphthalenesulfonic acid formaldehyde condensate, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin were mixed evenly, pulverized using an ultra-micro airflow pulverizer, kneaded, and then added to a fluidized bed granulator for granulation, drying, sieving, and sampling analysis to obtain the water-dispersible granules of the herbicidal composition of the present invention.

[0159] Formulation Comparative Example 1: 48 parts of clethodim tert-butylamine salt, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of sodium naphthalenesulfonic acid formaldehyde condensate, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin were mixed evenly, pulverized using an ultra-micro airflow pulverizer, kneaded, and then added to a fluidized bed granulator for granulation, drying, sieving, and sampling analysis to obtain water-dispersible granules of the clethodim tert-butylamine salt herbicidal composition.

[0160] Formulation samples obtained from Formulation Example 2, Formulation Example 3, Formulation Example 6, and Comparative Example 1 were selected and their physical properties were compared and tested. The test results are shown in Table 13 below:

[0161] Table 13. Results of physical property tests for formulation examples and comparative samples

[0162] Formulation Sample | Particle Strength | Particle Viscosity | Granulation Suspension Rate Test | Thermal Decomposition Rate (14 days) | Formulation Example 2 | Strong Particle Strength, Qualified | Low Viscosity, Easy to Qualify | ≥90% | ≤5% | Formulation Example 3 | Strong Particle Strength, Qualified | Low Viscosity, Easy to Qualify | ≥90% | ≤5% | Formulation Example 6 | Strong Particle Strength, Qualified | Low Viscosity, Easy to Qualify | ≥90% | ≤5% | Formulation Comparative Example 1 | Weak Particle Strength, Unqualified | Sticky, Unqualified | Difficult to Qualify | ≥90% | ≥10% surface

[0163] Based on the test results in Table 13, under the same formulation and dosage form, clethodim 1,6-hexanediamine salt, clethodim 1,5-pentanediamine salt, and clethodim 1,4-butanediamine salt have better formulation physical properties than clethodim tert-butylamine salt. They are also easier to process into solid dosage forms such as water-dispersible granules (WG) as herbicides, and have better commercial prospects.

[0164] The above data shows that different clethodim diamine salts exhibit varying physicochemical properties, leading to significant differences in their stability and herbicidal activity. Even diamines (e.g., 1,6-hexanediamine) and monoamines (e.g., n-hexylamine) with the same carbon chain exhibit significant differences in storage stability when combined with clethodim. Furthermore, the processing difficulty and formulation performance of different clethodim amine salts vary significantly. The clethodim diamine salts disclosed in this invention, such as clethodim 1,4-butanediamine, clethodim 1,5-pentanediamine, and clethodim 1,6-hexanediamine, are compounds with good overall performance. In particular, clethodim 1,5-pentanediamine exhibits exceptionally excellent overall performance and has broad commercial prospects.

[0165] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any form or substance. It should be noted that those skilled in the art can make several improvements and additions without departing from the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. The application of clethodim diamine salt in i) improving the stability of clethodim and / or ii) in herbicides, characterized in that: The chemical structural formula of the clethodim diamine salt is as follows: Where n is selected from 2, 3, or 4, that is, the clethodim diamine salts are respectively clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, or clethodim 1,6-hexanediamine salt.

2. The application according to claim 1, characterized in that: wherein, n is selected from 2 or 3, that is, clethodim 1,4-butanediamine salt or clethodim 1,5-pentanediamine salt.

3. The application according to claim 1, characterized in that: in, n is selected from 3, namely clethodim 1,5-pentanediamine salt.

4. The application according to any one of claims 1 to 3, characterized in that: The clethodim diamine salt is characterized by one or more of the following methods: high performance liquid chromatography (HPLC), nuclear magnetic resonance (HNMR), differential scanning calorimetry (DSC) curves, and microscopic melting point detector.

5. The application according to any one of claims 1 to 3, characterized in that: The preparation method of clethodim diamine salt includes the following steps: S1: Dissolve clethodim in a solvent to obtain mixture A; S2: Add a diamine compound or its solution to mixture A to react, and after the reaction is completed, precipitate clethodim diamine salt from the reaction system; S3: Separate the precipitate to obtain clethodim diamine salt.

6. The application according to claim 5, characterized in that: The reaction temperature in S1 is 5℃ to 50℃; and / or the solvent in S1 is selected from one or more of aliphatic alkanes, chlorinated alkanes, ethers, alkyl ketones and benzene solvents; and / or the molar ratio of clethodim to diamine in S2 is (1:0.5)-(1:0.8).

7. The application according to any one of claims 1 to 3, characterized in that, The herbicide is formulated as water-dispersible granules (WG) or wettable powder (WP).

8. Clethodim diamine salt, characterized in that, Its chemical structural formula is as follows: Where n is selected from 2, 3, or 4, that is, the clethodim diamine salts are respectively clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, or clethodim 1,6-hexanediamine salt.

9. The clethodim diamine salt according to claim 8, characterized in that, in, n is selected from 2 or 3, that is, clethodim 1,4-butanediamine salt or clethodim 1,5-pentanediamine salt.

10. A method for improving the stability of clethodim, characterized in that: The method involves reacting clethodim with a diamine compound in an organic solvent at a temperature of 5°C to 50°C to generate the clethodim diamine salt as described in claim 8 or 9, and then storing it in the form of the clethodim diamine salt as described in claim 8 or 9, wherein the diamine compound is selected from 1,4-butanediamine, 1,5-pentanediamine, or 1,6-hexanediamine.

11. A herbicidal composition, characterized in that, It contains the clethodim diamine salt as described in claim 8 or 9 and at least one adjuvant.

12. The herbicidal composition according to claim 11, characterized in that, The herbicidal composition is in the form of water-dispersible granules (WG) or wettable powder (WP).

13. The use of the clethodim diamine salt according to claim 8 or 9, or the herbicidal composition according to claim 11 or 12, in the control of harmful weeds.

14. A method for controlling weeds, characterized in that, Apply to plants, plant parts or the environment surrounding the plants an effective amount of clethodim diamine salt according to claim 8 or 9, or to the herbicidal composition according to claim 11 or 12.

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