Clethodim diamine salt, preparation method and application thereof

Abstract

The invention discloses clethodim diamine salt as well as a preparation method and application thereof. The stability of the clethodim diamine salt (clethodim 1, 4-butanediamine salt, clethodim 1, 5-pentanediamine salt and clethodim 1, 6-hexamethylenediamine salt) provided by the invention is superior to that of clethodim and clethodim monoamine salt (such as clethodim tert-butylamine salt); meanwhile, the herbicidal activity of the clethodim diamine salt (clethodim ethylenediamine salt, clethodim 1, 4-butanediamine salt and clethodim 1, 5-pentanediamine salt) is superior to that of clethodim tert-butylamine salt, and the herbicidal activity of the clethodim 1, 5-pentanediamine salt is superior to that of clethodim. Most clethodim diamine salt is low in degradation rate in the high-temperature heat storage process and easier to store for a long time, the clethodim diamine salt is higher in melting point than clethodim monoamine salt (such as clethodim tert-butylamine salt), granulation and smashing are more convenient, the clethodim diamine salt can be used as a herbicide to be processed into solid dosage forms such as water dispersible granules and the like, the physical performance of the preparation is better, and the preparation has good application prospects. The commercialization prospect is good.

Description

TECHNICAL FIELD

[0001] The present application relates to an enoxamide diamine salt, a preparation method and a use thereof, and belongs to the technical field of agricultural herbicides. BACKGROUND

[0002] Enoxamide, the Chinese name of which is 2-{1-[(3-chloro-2-allyl)oxy] iminylpropyl}-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one. It is a cyclohexanedione herbicide with excellent herbicidal activity. The currently marketed enoxamide industrial product is a liquid, and its ingredient content is usually 86-93%. Enoxamide contains multiple non-adjacent carbon-carbon double bonds, oxime and other functional groups in its structural formula. It has poor stability, is prone to configuration inversion, and is sensitive to ultraviolet light and heat. Therefore, it is prone to decomposition during long-term transportation and long-term storage, resulting in a decrease in the content of enoxamide in the product and a decrease in herbicidal efficacy. Once enoxamide decomposes, the content of the active ingredient decreases, which has a serious impact on subsequent dosage form processing and efficacy. Therefore, it is very important to reduce the decomposition rate of enoxamide technical material and preparation during storage, improve stability, and increase the content of the active ingredient. At present, the commercially available enoxamide preparation is an emulsifiable concentrate (EC) product, such as 240EC and 360EC dosage forms. There is no solid dosage form, such as water dispersible granules (WG) or wettable powder (WP), which also limits the application scenarios and commercial uses of enoxamide.

[0003] Different enoxamide amine salts have different stabilities, different physicochemical properties, and different herbicidal activities and efficacies. Different enoxamide amine salts have different efficacies and effects, and the dosage forms and properties of the economically important preparations may be different.

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

[0005] Patent CN119390631A discloses enoxamide tert-butylamine salt, a preparation method and a use thereof. However, as a herbicidal active ingredient, enoxamide tert-butylamine salt is not completely satisfactory. For example, although its stability is better than that of the reported monoamine salts of enoxamide (such as sec-butylamine salt), there is still room for improvement in terms of thermal storage decomposition rate, herbicidal activity, and physical properties.

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

[0007] The present application aims to solve the technical problems of poor stability, fast reduction of herbicidal efficacy and no solid dosage form of clethodim, and provides a clethodim diamine salt, a preparation method and uses thereof.

[0008] To achieve the above-mentioned object, the present application adopts the following technical solutions:

[0009] In a first aspect, the present application provides the use of a clethodim diamine salt in improving the stability of clethodim and / or herbicides, the chemical structure 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, i.e. preferably the clethodim diamine salt is 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, i.e. the clethodim diamine salt is clethodim 1,4-butanediamine salt or clethodim 1,5-pentanediamine salt.

[0013] Most preferably, n is selected from 3, i.e. the clethodim diamine salt is clethodim 1,5-pentanediamine salt.

[0014] The present application confirms the structure of various clethodim diamine salts, including but not limited to high performance liquid chromatography (HPLC), nuclear magnetic resonance (HNMR), differential scanning calorimetry (DSC), microscopic melting point detector, etc.

[0015] The alkene grass ketone diamine salt prepared by the present application is a diamine salt combined by alkene grass ketone and diamine with a molar ratio of 2:1; alkene grass ketone combined with different diamines shows different physicochemical properties and different thermal storage stability; the starting temperature of the melting range of the alkene grass ketone diamine salt prepared by the present application is more than 105℃, and the highest temperature is 134.1-135.5℃. Surprisingly, the thermal storage stability of the alkene grass ketone ethylenediamine salt is poor, which is lower than that of alkene grass ketone and various alkene grass ketone monoamine salts; the thermal storage stability of the alkene grass ketone 1,4-butanediamine salt, alkene grass ketone 1,5-pentanediamine salt and alkene grass ketone 1,6-hexanediamine salt is very excellent, which is obviously better than that of various alkene grass ketone monoamine salts. The alkene grass ketone diamine salt (alkene grass ketone 1,4-butanediamine salt, alkene grass ketone 1,5-pentanediamine salt and alkene grass ketone 1,6-hexanediamine salt) prepared by the present application has good stability, which is better than that of alkene grass ketone and various alkene grass ketone monoamine salts (including alkene grass ketone tert-butylamine salt); at the same time, the herbicidal activity of the alkene grass ketone diamine salt (alkene grass ketone ethylenediamine salt, alkene grass ketone 1,4-butanediamine salt and alkene grass ketone 1,5-pentanediamine salt) prepared by the present application is better than that of alkene grass ketone tert-butylamine salt, among which the herbicidal activity of the alkene grass ketone 1,5-pentanediamine salt is slightly better than that of alkene grass ketone; the herbicidal activity of the alkene grass ketone 1,6-hexanediamine salt is obviously poorer than that of other alkene grass ketone diamine salts. The alkene grass ketone diamine salt (alkene grass ketone 1,4-butanediamine salt, alkene grass ketone 1,5-pentanediamine salt and alkene grass ketone 1,6-hexanediamine salt) prepared by the present application has a lower degradation rate during high-temperature thermal storage than alkene grass ketone and other alkene grass ketone amine salts (including alkene grass ketone tert-butylamine salt), and is easier to be stored for a long time than alkene grass ketone and alkene grass ketone tert-butylamine salt.

[0016] Preferably, the preparation method of the alkene grass ketone diamine salt comprises the following steps:

[0017] S1: dissolving alkene grass ketone in a solvent to obtain a mixture A;

[0018] S2: adding a diamine compound or a solution thereof into the mixture A for reaction, and after the reaction is completed, precipitating and separating the alkene grass ketone diamine salt from the reaction system;

[0019] S3: separating the alkene grass ketone diamine salt from the precipitate.

[0020] By using the above technical scheme, the method for preparing the alkene grass ketone diamine salt is simple, the process is mature and stable, the yield is high, the production cost is low, the content of the alkene grass ketone diamine salt product can be obviously improved compared with the current commercial alkene grass ketone original drug, the content of the preferred alkene grass ketone diamine salt of the present application is greater than 96.0% by salt, and the content of the more preferred alkene grass ketone diamine salt is greater than 97.5% by salt.

[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 technical scheme, the product yield is higher.

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

[0025] By adopting the technical scheme, the reaction condition is mild, and the process is mature and safe.

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

[0027] By adopting the technical scheme, the product yield and content of alkenylcyclohexanone diamine salt are high.

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

[0029] By adopting the technical scheme, the product content of alkenylcyclohexanone amine salt is high.

[0030] In a third aspect, the present application provides an alkenylcyclohexanone diamine salt, which has the following chemical structure:

[0031]

[0032] Preferably, n is selected from 2, 3 or 4, i.e. the alkenylcyclohexanone diamine salt is alkenylcyclohexanone 1,4-butanediamine salt, alkenylcyclohexanone 1,5-pentanediamine salt or alkenylcyclohexanone 1,6-hexanediamine salt.

[0033] Preferably, n is selected from 2 or 3, i.e. the alkenylcyclohexanone diamine salt is alkenylcyclohexanone 1,4-butanediamine salt or alkenylcyclohexanone 1,5-pentanediamine salt.

[0034] More preferably, n is selected from 3, i.e. the alkenylcyclohexanone diamine salt is alkenylcyclohexanone 1,5-pentanediamine salt.

[0035] In a third aspect, the present application provides a method for improving the stability of alkenylcyclohexanone, which comprises reacting alkenylcyclohexanone with a diamine compound in an organic solvent at a temperature of 5-50°C to obtain an alkenylcyclohexanone diamine salt as described in the second aspect of the present application, and then storing the alkenylcyclohexanone diamine salt, 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 alkane, chlorinated alkane, ether, alkyl ketone and benzene solvents.

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

[0040] In a fourth aspect, the present application provides use of the above-mentioned allidochlor diamin salt in a herbicidal composition.

[0041] The use of allidochlor as a herbicide is well known in the art and is used on a commercial scale. The allidochlor diamin salt of the present application is also active in controlling harmful weeds. Therefore, the techniques known in the art for formulating and applying allidochlor can also be applied in a similar manner to the allidochlor diamin salt of the present application.

[0042] Accordingly, the present application provides a herbicidal composition comprising the allidochlor diamin salt as described hereinabove.

[0043] The composition comprising the above-mentioned allidochlor diamin salt comprises the allidochlor diamin salt of the present application and at least one adjuvant selected from one or more of the following: surfactants, diluents, dispersants, wetting agents, antioxidants, antifoams and the like.

[0044] Preferably, the composition is in the form of a suspension concentrate (SC), a soluble liquid (SL), a dispersible concentrate (DC), an emulsifiable concentrate (EC), an emulsion seed dressing, a granule (GR), a suspoemulsion (SE), an oil miscible flowable concentrate (OD), a water soluble granule (SG), a microgranule (MG), a water dispersible granule (WG) or a wettable powder (WP).

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

[0046] In the present application, the allidochlor diamin salt can be present in a concentration sufficient to deliver the desired dosage when applied to the plant or locus thereof, desirably in a concentration of from about 1% to about 95% by weight of the total mixture, preferably in a concentration of from about 5% to about 85% by weight of the total mixture, more preferably in a concentration of from about 10% to about 80% by weight of the total mixture. The formulation is prepared, for example, by incorporating a carrier and or solvent, as appropriate, using emulsifiers and / or dispersants and / or other adjuvants, into the allidochlor diamin salt.

[0047] The surfactant can be an emulsifying, dispersing or wetting agent which can be ionic or non-ionic. Examples which can be used include, but are not limited to, salts of polyacrylic acid, lignosulfonates, salts of benzene or naphthalene sulfonic acids or naphthalene sulfonate condensates, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols), sulfosuccinic ester salts, taurine derivatives (especially alkyl taurines), nonylphenol polyethoxylates, or phosphoric esters of polyethoxylated phenols or alcohols, sodium docusate, polycarboxylate salts complexes and the like.

[0048] Diluents include, but are not limited to, water, N,N-dimethylamide, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffin, alkylbenzene, alkylnaphthalene, glycerol, 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 (for example sodium dihydrogen phosphate), alkaline earth metal phosphates, sodium, potassium, magnesium and zinc sulfates, sodium chloride, potassium chloride, sodium acetate, sodium carbonate, and sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol, clays, synthetic silicas and siliceous earths, kaolin, calcium silicate, titanium dioxide, aluminium oxide, calcium oxide and zinc oxide and mixtures thereof.

[0049] Wetting agents include, but are not limited to, phosphoric esters, acetylenic diols, ethoxylated silicones, sodium lauryl sulfate, talc, and soapstone, TWEEN® LS (sodium p-methoxy fatty amido benzenesulfonate), alkyl-substituted naphthalene sulfonates, alkylphenol polyoxyethylene ethers, polyalkylene glycol ethers. Preferred wetting agents are selected from the group consisting of alkyl-substituted naphthalene sulfonates, polyalkylene glycol ethers, sodium lauryl sulfate, soapstone.

[0050] Dispersants include, but are not limited to, polycarboxylate salts or polycarboxylate salt complexes, alkylphenol polyoxyethylene formaldehyde condensate sulfates, naphthalene sulfonate formaldehyde condensate sodium salts, naphthalene sulfonate condensates, calcium alkylbenzene sulfonates, 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 lignosulfonic acid and naphthalene sulfonate formaldehyde condensates. Preferred dispersants are selected from the group consisting of naphthalene sulfonate condensates (such as naphthalene sulfonate formaldehyde condensate sodium salts), lignosulfonates (such as calcium lignosulfonate), calcium alkylbenzene sulfonates, nonylphenol polyoxyethylene ethers, polycarboxylate salts or polycarboxylate salt complexes (such as TERSPERSE 2700, Agrilan 700, SP-2836, Geropon T / 36).

[0051] Antifoaming agents include all substances which are generally used for this purpose in agrochemical compositions. Suitable antifoaming agents are known in the art and are commercially available. Preferred antifoaming agents are polydimethylsiloxanes, mixtures of perfluoroalkylphosphonic acids, polyether-modified silicones, silicone-based compounds, C8-C10 fatty alcohol-based compounds and the like.

[0052] Disintegrants include all substances which are generally 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, sodium bicarbonate.

[0053] Other formulation ingredients can also be used in the present application, such as preservatives, penetrants, antifreezes, thickeners and the like. Also, herbicides can be added to the composition containing the oxadiargyl diamine salt according to the present application. Suitable herbicide combinations, such as adding an appropriate amount of one or more herbicide ingredients, can result in better herbicidal effects. These ingredients are known to those skilled in the art.

[0054] The various oxadiargyl diamine salts described in the present application have better formulation physical properties than oxadiargyl tert-butylamine salt, and are more convenient to be processed into solid formulations such as water dispersible granules (WG) and the like, and have better commercial prospects under the same formulation and the same dosage form.

[0055] In a fourth aspect, the present application provides the use of the oxadiargyl diamine salt or the composition containing the oxadiargyl diamine salt according to the present application in controlling harmful weeds.

[0056] The oxadiargyl diamine salt or the composition containing the oxadiargyl diamine salt according to the present application can be used to control harmful weeds, and the harmful weeds are selected from grass weeds and broadleaf weeds.

[0057] Preferably, the harmful weeds are selected from Alopecurus myosuroides, Apera spica-venti, Galium aparine, Lamium purpureum, Lepidium apetalum, Matricaria inodora, Hedera helix, Echinochloa crus-galli, Digitaria sanguinalis, Veronica persica, Eupatorium odoratum and Cineraria japonica.

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

[0059] Preferably, the oxadiargyl diamine salt or the composition containing the oxadiargyl diamine salt is used to control harmful weeds in winter wheat, potato, sunflower, sugar beet, sugarcane, carrot, corn, soybean.

[0060] Further, the present application also provides a method for controlling weeds, which comprises applying to a plant, plant part, or the surrounding environment of the plant an effective weed- controlling amount of the aforedescribed cloproxydim diamine salt or the composition of the cloproxydim diamine salt. Thus, this provides a method for controlling weeds in a plant, plant part, and / or the surrounding environment thereof, which comprises applying to the roots of the plant, plant part, or the surrounding environment of the plant an effective amount of the cloproxydim diamine salt or the composition of the cloproxydim diamine salt.

[0061] The term "about" as used herein in connection with a numerical quantity or range means slightly more or slightly less than the numerical quantity or range, i.e., ±10% of the end points of the numerical quantity or range.

[0062] The treatment of plants and plant parts with the compositions or formulations of the present application is carried out directly or by allowing the compositions or formulations to act on their surroundings, habitat, or storage space by conventional treatment methods. Examples of such conventional treatment methods include dipping, spraying, vaporizing, atomizing, spreading, brushing, mixing (e.g., soil treatment), and the like.

[0063] The term "room temperature" as used herein means a temperature range of about 20-25°C.

[0064] By adopting the above technical solutions, the cloproxydim diamine salt has good stability and herbicidal effect, and is expected to be prepared into a commercialized, economically valuable formulation with superior storage stability and good herbicidal effect.

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

[0066] 1. The present application first provides a plurality of cloproxydim diamine salts, and characterizes them by various means; the cloproxydim diamine salts (cloproxydim 1,4-butanediamine salt, cloproxydim 1,5-pentanediamine salt, cloproxydim 1,6-hexanediamine salt) of the present application have improved long-term storage stability, which is superior not only to cloproxydim, but also to other monoamine salts of cloproxydim (including cloproxydim tert-butylamine salt) reported in the literature; at the same time, most of the cloproxydim diamine salts also maintain herbicidal activity that is not weaker than that of cloproxydim, and the cloproxydim diamine salts (cloproxydim ethylenediamine salt, cloproxydim 1,4-butanediamine salt, cloproxydim 1,5-pentanediamine salt) prepared by the present application have herbicidal activity against a plurality of weeds that is superior to that of cloproxydim tert-butylamine salt, wherein the cloproxydim 1,5-pentanediamine salt has herbicidal activity against a plurality of weeds (echinochloa crus-galli, digitaria sanguinalis, erythronium japonicum) that is slightly superior to that of cloproxydim;

[0067] 2. The oxadiazyl diamine salt of the present application is beneficial to prepare into commercialized formulation with economic value, and has superior storage stability and good efficacy; the degradation rate of the oxadiazyl diamine salt of the present application during high-temperature heat storage is lower than that of oxadiazyl and other oxadiazyl amine salts reported in the literature, and the oxadiazyl is easier to store for a long time, which is beneficial to the shelf life stability of commercialized products;

[0068] 3. The oxadiazyl diamine salt prepared by the method of the present application has a high melting point, and the physical properties are more suitable for preparation into solid formulations; the solid formulation of the oxadiazyl diamine salt prepared by the method of the present application has better physical properties than the formulation of oxadiazyl tert-butylamine salt, and provides solid dosage forms of oxadiazyl such as water dispersible granules (WG) and the like, which has a better commercial prospect. BRIEF DESCRIPTION OF DRAWINGS

[0069] Figure 1 is the nuclear magnetic hydrogen spectrum (HNMR) graph of oxadiazyl ethylenediamine salt.

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

[0071] Figure 3 is the nuclear magnetic hydrogen spectrum (HNMR) graph of oxadiazyl 1,4-butanediamine salt.

[0072] Figure 4 is the differential scanning calorimetry (DSC) graph of oxadiazyl 1,4-butanediamine salt.

[0073] Figure 5 is the nuclear magnetic hydrogen spectrum (HNMR) graph of oxadiazyl 1,5-pentanediamine salt.

[0074] Figure 6 is the differential scanning calorimetry (DSC) graph of oxadiazyl 1,5-pentanediamine salt.

[0075] Figure 7 is the nuclear magnetic hydrogen spectrum (HNMR) graph of oxadiazyl 1,6-hexanediamine salt.

[0076] Figure 8 is the differential scanning calorimetry (DSC) graph of oxadiazyl 1,6-hexanediamine salt. DETAILED DESCRIPTION

[0077] In order to make the present application more apparent and easy to understand, the preferred embodiments are described in detail below with the aid of the accompanying drawings.

[0078] Example 1

[0079] An oxadiazyl diamine salt, the chemical structural formula of which is as follows:

[0080]

[0081] wherein n is selected from 0, i.e. the clethodim diamine salt is clethodim ethylene diamine salt.

[0082] The preparation method of the clethodim ethylene diamine salt is as follows:

[0083] S1: 40.2 g of clethodim technical material (89.5%, 0.10 mol) and 25 g of solvent A were stirred and mixed uniformly at a temperature of 12°C, the temperature was raised to a mixing temperature of 15°C, and 3.64 g of ethylene diamine (99%, 0.06 mol) was slowly added. After the addition was completed, the mixture was stirred at 15°C for 1.0 h, and then 125.0 g of solvent B was added to obtain a reaction mixture A;

[0084] S2: the reaction was continued to be stirred at 15°C for 6.0 h to obtain a reaction material;

[0085] S3: the reaction material was filtered to obtain a solid;

[0086] S4: the solid was washed with 6 times the mass of solvent B, and then vacuum dried at 10-15°C to obtain the product clethodim ethylene diamine salt.

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

[0088] Examples 2-8

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

[0090] Table 1. Preparation method parameter table of Examples 1-8

[0091]

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

[0093] Table 2. Purity and yield table of products of Examples 1-8

[0094]

[0095]

[0096] From Table 1 and Table 2, it can be seen that, by Examples 1-8, the preparation method of the present application can control the reaction temperature within 5-50°C when obtaining the alkoxycarbonyl ketone diamine salt of the present application, and considering the product production cost and the final product quality index, the molar ratio of alkoxycarbonyl ketone and tert-butylamine in the present application is controlled to be (1:0.4)-(1:0.8), and by appropriately adjusting the reaction time, the target product with high purity can be obtained in high yield, and the preparation method has low production cost, mature and simple preparation method, good stability and high yield.

[0097] The samples obtained from Examples 1, 3, 5 and 7 were selected as test samples and tested by a microscopic melting point detector, and the melting range information of the alkoxycarbonyl ketone diamine salt obtained is shown in Table 3.

[0098] Table 3. Melting range information table of alkoxycarbonyl ketone diamine salt of examples

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

[0100] The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 1 The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 2 The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 3 The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 4 The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 5 The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 6 The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 7 The alkoxycarbonyl ketone ethylenediamine salt prepared in the above examples of the present application can be characterized by the nuclear magnetic hydrogen spectrum (HNMR) of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 1; and / or, characterized by the differential scanning calorimetry (DSC) spectrum of the alkoxycarbonyl ketone ethylenediamine salt shown in Figure 2; and / or, characterized by the comparison of the chromatogram of high performance liquid chromatography (HPLC) with that of the alkoxycarbonyl ketone standard; and / or, characterized by the melting range shown by a microscopic melting point detector. Figure 8The differential scanning calorimetry (DSC) pattern of the shown oxadiazylidene cyclohexenone monoamine salt is characterized; and / or, characterized by comparing the chromatogram of the oxadiazylidene cyclohexenone monoamine salt with the chromatogram of the oxadiazylidene cyclohexenone standard by high performance liquid chromatography (HPLC); and / or, characterized by the melting range shown by the microscopic melting point detector.

[0101] Comparative Example 1

[0102] An oxadiazylidene cyclohexenone monoamine salt, which is different from Example 1 in that the amine used in S1 is 1,2-dimethylpropylamine, and the molar ratio of oxadiazylidene cyclohexenone to 1,2-dimethylpropylamine is 1:1.1, and the obtained oxadiazylidene cyclohexenone monoamine salt is shown in Table 4.

[0103] Comparative Examples 2-6

[0104] An oxadiazylidene cyclohexenone monoamine salt, which is different from Example 1 in that the amine used in S1 is different, and the molar ratio of oxadiazylidene cyclohexenone to amine is 1:1.1, and the obtained oxadiazylidene cyclohexenone monoamine salt is shown in Table 4.

[0105] Table 4. Information table of amine used in Comparative Examples 1-6, product content, yield table

[0106] Comparative Example No. Name of Amine Salt of Clethodim Content of Amine Salt of Clethodim (%) Melting Point of Product (°C) Yield of Amine Salt of Clethodim (%) Comparative Example 1 1,2-Dimethylpropylamine 94.69 78-83 90 Comparative Example 2 Tert-amylamine 95.66 75-78 92 Comparative Example 3 Cyclohexylamine 94.51 82-87 91 Comparative Example 4 n-Hexylamine 97.98 89-92 85 Comparative Example 5 n-Butylamine 90.52 / * 87 Comparative Example 6 Tert-butylamine 99.3 92-94 95.7

[0107] *The oxadiazylidene cyclohexenone n-butylamine salt obtained in Comparative Example 5 has a melting point fluctuation range of more than 10°C in the melting point test process, and multiple re-sampling measurements cannot obtain a detection result with a fluctuation range of within 5°C. After analysis, it is found that the oxadiazylidene cyclohexenone amine salt is too low, and the decomposition of oxadiazylidene cyclohexenone or other by-products during heating causes the decomposition of the oxadiazylidene cyclohexenone amine salt.

[0108] The samples of Example 1, Example 3, Example 5, Example 7 and Comparative Examples 1-6 are tested for stability by accelerated storage test.

[0109] According to the international method for physical and chemical determination of pesticide crude drugs and preparations-CIPAC method-CIPAC MT46.4 Accelerated Storage procedure, the storage shelf life of pesticide crude drugs and preparations under standard operation is at least 2 years, and the storage shelf life of pesticide crude drugs and preparations under standard operation can be tested by accelerated storage test. According to the following 6 groups of storage temperature and storage period combinations specified in CIPAC MT 46.4 Accelerated Storage procedure, the accelerated storage test is carried out, and the test results of the residual active ingredients in the sample can be regarded as the predictive value of 2 years of storage:

[0110] (1) 54±2°C, for 14 days;

[0111] (2) 50±2°C, 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] i.e. 54±2℃ for 14 days is equivalent to 50±2℃ for 4 weeks, and so on.

[0117] In the combination of storage temperature and storage period, the storage temperature has a great influence on the accelerated storage test of pesticide technical and preparation, determines the accelerated storage test period and reflects the upper limit of the extreme condition of the storage tolerance of pesticide technical and preparation.

[0118] The present application selects "54±2℃, for 14 days" as the test parameter. Here, the provisions of the test experiment in the international method-CIPAC method for the determination of the physical and chemical properties of pesticide technical and preparation are cited. The change rate curves of samples are different between different parameters, and there is no feasibility of conversion. For example, the sample of 54±2℃ for 7 days is not the same as the sample of 35℃±2℃ for 6 weeks.

[0119] The specific detection method is: the sample is sealed with an ampoule, stored in a constant temperature oven at 54±2℃ for 14 days, then the purity change of the active ingredient before and after heat storage is analyzed and detected by high performance liquid chromatography analysis method, and the sample of clethodim purchased on the market (mass content of 89.50%) is used as a control example. The test results are shown in Table 5.

[0120] Table 5. Stability test results of examples and comparative examples 1-6

[0121]

[0122]

[0123] Note: The sample content is the content of the corresponding active ingredient (clethodim amine salt or clethodim) in the sample after heat storage; the decomposition rate calculation formula is: decomposition rate (%) = heat storage sample content / (initial sample-heat storage sample content) x 100%.

[0124] During the research process of the present application, it was found that some samples in Comparative Examples 1-6 decomposed relatively fast when stored at 54±2℃. In order to better and comprehensively compare the stability of the samples in Example 1-6 and Comparative Examples 1-6, in addition to the 14-day accelerated storage at 54±2℃ required by CIPAC MT 46.4 Accelerated Storage procedure, the present application additionally independently stored the same samples at 54±2℃ for 7 days to better remind the decomposition during the storage process and reflect the stability performance of the samples.

[0125] As can be seen from Table 5, after 14 days of accelerated storage at 54±2℃, the samples in Comparative Examples 1-6 and the control sample all showed significant decomposition; the decomposition rate of the clomazone tert-butylamine salt in Comparative Example 6 was relatively low, but still exceeded 10%; surprisingly, the decomposition rates of Example 1 and Comparative Examples 3-5 were similar, and significant decomposition occurred; surprisingly, the decomposition in Example 3, Example 5 and Example 7 was smooth, and the final decomposition rate after 14 days was much lower than that of Comparative Examples 1-6 and the control sample, wherein the decomposition rate of Example 3 was less than 3%, i.e. 2.51%, and the decomposition rate of Example 5 was less than 4%, i.e. 3.56%. Therefore, the stability of the clomazone diamine salt (clomazone 1,4-butanediamine salt, clomazone 1,5-pentanediamine salt, clomazone 1,6-hexanediamine salt) prepared by the present application is better than that of clomazone and clomazone monoamine salt (such as clomazone tert-butylamine salt, etc.), and it is reasonably inferred that the prepared technical material or preparation is not easy to decompose during long-term storage.

[0126] Herbicidal activity test

[0127] The test was performed according to the method of Herbicides-Part 4: Determination of Activity-Method of Stem-Leaf Spray (NY / T 1155.4-2006) in the Guidelines for Pesticide Indoor Biological Test, and the test targets were Echinochloa Beauv., Digitariasanguinalis (L.) Scop., and Eleusine indica (L.) Gaertn. The clomazone technical material sample (content 90.0%) purchased on the market was used as a control sample, and the test results were the fresh weight control effects of the weeds after 20 days of treatment at different dosages.

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

[0129] Table 6. Information table of test samples for herbicidal activity test

[0130] No. Test Sample No. Sample Salt Content Clethodim Content in Sample 1 Tert-butylamine salt of clethodim A 97.7％ 81.2％ 2 1,6-Hexanediamine salt of clethodim B 97.6％ 84.0％ 3 1,4-Butanediamine salt of clethodim C 98.3％ 87.6％ 4 Ethylene diamine salt of clethodim D 99.8％ 92.1％ 5 1,5-Pentanediamine salt of clethodim E 99.9％ 87.5％ 6 Clethodim TC (90%) F / 90.0％ 7 CK (blank control) / / /

[0131] The herbicidal activity test results are as follows:

[0132] The herbicidal activity test results of each pesticide on Echinochloa Beauv. are shown in Tables 7-8:

[0133] Table 7. Fresh weight control effect (%) of Echinochloa crus-galli of each herbicide after 20 days of application

[0134]

[0135] Table 8. Regression equation of inhibition concentration of Echinochloa crus-galli of each herbicide

[0136] Pesticide Regression Equation of Inhibition Concentration on Barnyardgrass ED50 [R 2 ]] 95% Confidence Interval A y = 8.24 + (100.37 - 8.24) / (1 + (x + 64.36)1.37) 64.36 0.97 2.82～125.91 B y = 7.01 + (99.14 - 7.01) / (1 + (x + 74.92)1.56) 74.92 0.96 -10.24～160.07 C y = -3.63 + (96.16 + 3.63) / (1 + (x + 38.72)2.37) 38.72 0.97 30.25～47.18 D y = 0.24 + (1001.29 - 0.24) / (1 + (x + 33.10)2.98) 33.10 0.99 30.61～35.59 E y = 0.21 + (100.62 - 0.21) / (1 + (x + 24.14)3.10) 24.14 0.99 22.31～25.98 F y = 0.77 + (99.81 - 0.77) / (1 + (x + 30.96)3.86) 30.96 0.99 29.18～32.74

[0137] Based on the results of Tables 7 and 8, the visual control effect of E was the best, followed by F and D, and A and B were the worst. The fresh weight inhibition effect of E was the best, followed by F and D, and B was the worst. The fresh weight control effect of Echinochloa crus-galli after 20 days was E > F > D > C > A > B.

[0138] The results of the herbicidal test of each herbicide on Digitaria sanguinalis are as follows in Tables 9 and 10:

[0139] Table 9. Fresh weight control effect (%) of Digitaria sanguinalis of each herbicide after 20 days of application

[0140]

[0141] Table 10. Regression equation of inhibition concentration of Digitaria sanguinalis of each herbicide

[0142] Pesticide Regression Equation of Inhibition Concentration on Large Crabgrass ED50 [R 2 ]] 95% Confidence Interval A y = -0.99 + (100.81 + 0.99) / (1 + (x + 27.63)1.35) 27.63 0.97 16.29～38.97 B y = -16.62 + (98.50 + 16.62) / (1 + (x + 40.75)1.38) 40.75 0.98 22.81～58.69 C y = -17.54 + (101.58 + 17.54) / (1 + (x + 22.77)1.05) 22.77 0.98 10.61～34.93 D y = -19.54 + (100.28 + 19.54) / (1 + (x + 16.60)0.96) 16.60 0.99 9.67～23.53 E y = -9.69 + (100.60 + 9.69) / (1 + (x + 9.72)1.06) 9.72 0.98 6.69～12.74 F y = -24.56 + (100.18 + 24.56) / (1 + (x + 13.00)0.71) 13.00 0.98 2.59～23.42

[0143] Based on the results of Tables 9 and 10, the visual control effect of E was the best, followed by F and D, and A and B were the worst. The fresh weight inhibition effect of E was the best, followed by F and D, and B was the worst. The fresh weight control effect of Digitaria sanguinalis after 20 days was E > F > D > C > A > B.

[0144] The results of the herbicidal test of each herbicide on Digitaria sanguinalis are as follows in Tables 11 and 12:

[0145] Table 11. Fresh weight control effect (%) of Eleusine indica of each herbicide after 20 days of application

[0146]

[0147]

[0148] Table 12. Regression equation of inhibition concentration of each herbicide on E. crus-galli

[0149] Pesticide Regression Equation of Inhibition Concentration on Chinese Violet ED50 [R 2 ]] 95% Confidence Interval A y = -13.06 + (100.07 + 13.06) / (1 + (x + 6.34)0.77) 6.34 0.99 4.54～8.13 B y = -7.14 + (100.13 + 7.14) / (1 + (x + 19.67)1.72) 19.67 0.99 17.45～21.90 C y = -3.25 + (100.10 + 3.25) / (1 + (x + 14.16)1.90) 14.16 0.99 12.64～15.68 D y = -0.87 + (101.36 + 0.87) / (1 + (x + 9.55)1.76) 9.55 0.99 8.83～10.27 E y = -0.74 + (100.09 + 0.74) / (1 + (x + 4.31)1.19) 4.31 0.99 4.02～4.60 F y = -5.58 + (100.13 + 5.58) / (1 + (x + 5.40)0.83) 5.40 0.99 4.11～6.69

[0150] Based on the results of Tables 11 and 12, the following can be concluded: 20 days after application, the E and A herbicides had the best visual control effect, followed by the F and D herbicides, and the B herbicide had the worst visual control effect. 20 days after application, the E herbicide had the best fresh weight inhibition effect on E. crus-galli, with an ED50 value of 4.31, followed by the F and A herbicides, with ED50 values of 5.40 and 6.34, respectively. The D herbicide also had a good fresh weight inhibition effect on E. crus-galli, with an ED50 value of 9.55, and the B herbicide had the worst fresh weight inhibition effect on E. crus-galli, with an ED50 value of 19.67. The 20-day fresh weight control effect on E. crus-galli was: herbicide E > herbicide F > herbicide A > herbicide D > herbicide C > herbicide B.

[0151] Based on Tables 6-12, the following can be concluded: the six cloproxydim samples had different inhibition effects on E. crus-galli, D. sanguinalis, and E. crus-galli. The cloproxydim 1,5-pentanediamine salt (E herbicide) had the best fresh weight inhibition effect on the three weeds, and also had the best visual control effect, which was better than the control herbicide cloproxydim technical material (F herbicide). The cloproxydim ethylenediamine salt (D herbicide) also had good fresh weight inhibition and visual control effects on the three weeds, but the inhibition effect was slightly lower than that of the control herbicide cloproxydim technical material (F herbicide). The cloproxydim tert-butylamine salt (A herbicide) had good visual control and fresh weight inhibition effects on E. crus-galli, but had relatively poor visual control and fresh weight inhibition effects on E. crus-galli and D. sanguinalis.

[0152] Preparation Examples

[0153] Preparation Example 1: 40 parts of cloproxydim 1,6-hexanediamine salt, 10 parts of calcium dodecylbenzenesulfonate, 10 parts of nonylphenol polyoxyethylene ether, 5 parts of soapnut powder, 25 parts of diatomite, and 10 parts of sodium sulfate were mixed and uniformly stirred in a stirring tank, and then mixed uniformly after passing through an air flow crusher, thereby obtaining the wettable powder of the herbicidal composition according to the present application.

[0154] Preparation Example 2: 48 parts of cloproxydim 1,6-hexanediamine salt, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of naphthalene sulfonate formaldehyde condensate sodium salt, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin were mixed uniformly, crushed by an ultra-micro air flow crusher, kneaded, and then added to a fluidized bed granulator, dried, sieved, and sampled and analyzed, thereby obtaining the water dispersible granule of the herbicidal composition according to the present application.

[0155] Preparation Example 3: 48 parts of the 1,5-pentanediamine salt of propynylcarbamic acid (3- ethyl-2-oxo-2H-chromen-5-yl) ester, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of naphthalene sulfonic acid formaldehyde condensate sodium salt, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin are mixed uniformly, and then are pulverized by using an ultrafine airflow pulverizer. After kneading, the mixture is added into a fluidized bed granulation dryer to perform granulation, drying, and sieving. After sampling and analysis, the water dispersible granules of the herbicidal composition are obtained.

[0156] Preparation Example 4: 50 parts of the 1,5-pentanediamine salt of propynylcarbamic acid (3- ethyl-2-oxo-2H-chromen-5-yl) ester, 10 parts of calcium dodecylbenzenesulfonate, 10 parts of nonylphenol polyoxyethylene ether, 10 parts of soapstone powder, 15 parts of diatomite, and 5 parts of sodium sulfate are mixed and stirred uniformly in a stirring kettle. After being pulverized by using an airflow pulverizer, the mixture is mixed uniformly, and then the wettable powder of the herbicidal composition is obtained.

[0157] Preparation Example 5: 48 parts of the ethylenediamine salt of propynylcarbamic acid (3- ethyl-2-oxo-2H-chromen-5-yl) ester, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of naphthalene sulfonic acid formaldehyde condensate sodium salt, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin are mixed uniformly, and then are pulverized by using an ultrafine airflow pulverizer. After kneading, the mixture is added into a fluidized bed granulation dryer to perform granulation, drying, and sieving. After sampling and analysis, the water dispersible granules of the herbicidal composition are obtained.

[0158] Preparation Example 6: 48 parts of the 1,4-butanediamine salt of propynylcarbamic acid (3- ethyl-2-oxo-2H-chromen-5-yl) ester, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of naphthalene sulfonic acid formaldehyde condensate sodium salt, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin are mixed uniformly, and then are pulverized by using an ultrafine airflow pulverizer. After kneading, the mixture is added into a fluidized bed granulation dryer to perform granulation, drying, and sieving. After sampling and analysis, the water dispersible granules of the herbicidal composition are obtained.

[0159] Preparation Comparative Example 1: 48 parts of the tert-butylamine salt of propynylcarbamic acid (3- ethyl-2-oxo-2H-chromen-5-yl) ester, 5 parts of polycarboxylate (TERSPERSE 2700), 10 parts of naphthalene sulfonic acid formaldehyde condensate sodium salt, 6 parts of calcium lignosulfonate, 6 parts of sodium dodecyl sulfate, and 25 parts of kaolin are mixed uniformly, and then are pulverized by using an ultrafine airflow pulverizer. After kneading, the mixture is added into a fluidized bed granulation dryer to perform granulation, drying, and sieving. After sampling and analysis, the water dispersible granules of the tert-butylamine salt of propynylcarbamic acid (3-ethyl-2-oxo-2H-chromen-5-yl) ester are obtained.

[0160] The samples of the preparations obtained in Preparation Example 2, Preparation Example 3, Preparation Example 6, and Preparation Comparative Example 1 are selected, and the physical properties of the samples are compared and tested. The test results are shown in Table 13.

[0161] Table 13. Test results of the physical properties of the samples of the preparations and the preparation comparative example

[0162] Formulation sample Particle strength of formulation particles Viscosity of formulation particles Granulation Suspension rate test Thermal storage decomposition rate (14 days) Formulation Example 2 Strong particle strength, passed Small viscosity, passed Easy ≥90％ ≤5％ Formulation Example 3 Strong particle strength, passed Small viscosity, passed Easy ≥90％ ≤5％ Formulation Example 6 Strong particle strength, passed Small viscosity, passed Easy ≥90％ ≤5％ Formulation Comparative Example 1 Weak particle strength, failed Tacky, failed Difficult ≥90％ ≥10％

[0163] In combination with the test results in Table 13: under the same formulation and the same dosage form, the physical properties of the clethodim 1,6-hexanediamine salt, clethodim 1,5-pentanediamine salt, and clethodim 1,4-butanediamine salt are better than those of the clethodim tert-butylamine salt, and they are more convenient to process into solid dosage forms such as water dispersible granules (WG) and other dosage forms, and have better commercial prospects.

[0164] From the above data, it can be seen that the physicochemical properties of different clethodim diamine salts are different, resulting in significant differences in stability and herbicidal activity. Even if the diamines with the same carbon chain (such as 1,6-hexanediamine) and the monoamines with the same carbon chain (such as n-hexylamine) form clethodim diamine salts and monoamine salts, respectively, there will be significant differences in storage stability. In addition, the process difficulty of different clethodim amine salts into various dosage forms and the performance of the preparation products also have significant differences. The clethodim diamine salts disclosed in the present application, such as clethodim 1,4-butanediamine salt, clethodim 1,5-pentanediamine salt, and clethodim 1,6-hexanediamine salt, are compounds with good comprehensive performance, and in particular, the clethodim 1,5-pentanediamine salt has particularly excellent comprehensive performance and has a broad commercial prospect.

[0165] The above description is only a preferred embodiment of the present application, and is not a limitation on the form and essence of the present application. It should be noted that, for ordinary skilled persons in the art, without departing from the present application, several improvements and supplements can be made, and these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. The application of clethodim diamine salt in improving the stability of clethodim and / or 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 can be characterized by one or more of the following methods, including but not limited to 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 the 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 carry out the reaction. After the reaction is completed, clethodim diamine salt is precipitated out of the reaction system. S3: Separate the precipitate to obtain clethodim diamine salt.

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

7. The application according to any one of claims 1 to 6, 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; Preferably, n is selected from 3, that is, 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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