Benzoyl sulfadiazine organic salt and its application

Abstract

This invention belongs to the field of pesticides, specifically relating to benzoxazine organic salts and soluble homogeneous liquid herbicide formulations containing benzoxazine organic salts as active ingredients, as well as their preparation methods. The benzoxazine organic salts prepared by this invention, particularly the triethanolamine salt, exhibit good solubility and high herbicidal activity as a field weed control agent.

Description

Technical Field

[0001] This invention belongs to the field of pesticides, specifically relating to benzoxazine organic salt and soluble homogeneous liquid herbicide formulations in which benzoxazine organic salt is the active ingredient, as well as their preparation methods. Background Technology

[0002] Benzoate, chemically known as [3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)phenyl(]5-hydroxy-1-methyl-1H-pyrazole-4-yl) methyl ketone, belongs to the pyrazole class of herbicides. It inhibits 4-hydroxyphenylpyruvate dioxygenase (4-HPPD), thus suppressing and disrupting the biosynthesis and function of carotenoids and chlorophyll. This causes bleaching symptoms in sensitive weeds within 2-5 days, and plant death within 14 days. It has a broad spectrum of weed control, effectively controlling most grasses and broadleaf weeds in cornfields, including foxtail grass, goosegrass, lambsquarters, knotweed, velvetleaf, purslane, cocklebur, and black nightshade. It can be absorbed by the leaves, roots, and stems of weeds and transported within the plant, indirectly affecting the synthesis of carotenoids, interfering with the synthesis and function of chloroplasts under light, and ultimately leading to severe whitening of the weed's heart leaves, tissue necrosis, and weed death. At 20℃, the effects are generally visible within 2-4 days after spraying.

[0003] Due to the physicochemical properties of benzoxazine, common formulation types are suspension concentrates (SC) and oil suspension concentrates (OD), which are heterogeneous formulation systems. These formulations have high requirements for pourability, storage stability, and freeze-thaw stability, often leading to issues such as clumping and poor efficacy. Furthermore, benzoxazine suspension concentrates or oil suspension concentrates are difficult to premix with other soluble herbicides, and incompatibility issues arise when tank-mixed with other herbicides. In actual use, common suspension concentrate products usually require additional tank mixing with vegetable or mineral oil to ensure field efficacy, increasing farmers' costs and posing greater environmental risks.

[0004] Patent document CN112601457A discloses an aqueous composition containing 0.1-1.0% by weight of benzoxazine or its agriculturally usable salt based on the total weight of the aqueous composition, wherein the pH of the composition is in the range of 6.5-7.5, and the type of salt is not disclosed. Patent document CN115443990A discloses a soluble concentrate containing benzoxazine potassium salt, wherein the soluble concentrate contains 1-30% by weight of benzoxazine potassium salt (expressed as benzoxazine), 40-80% by weight of water, and one or more additives selected from synergists, pigments, preservatives, and antifreeze agents. Patent document TW202241878A discloses a crystalline hydrate of benzoxazine sodium salt, and also provides a method for preparing the crystalline hydrate of benzoxazine sodium salt and a herbicidal composition containing the crystalline hydrate of benzoxazine sodium salt. Patent document US 2010075853 A states that the monovalent cation of benzoxazine is an alkali metal ion selected from Li+, Na+, and K+. It is evident that existing literature only discloses the inorganic salt form of benzoxazine, and no literature has been found concerning the organic salts of benzoxazine, particularly benzoxazine triethanolamine salt and herbicide compositions containing benzoxazine triethanolamine salt. Summary of the Invention

[0005] The purpose of this invention is to find a benzoxazine organic salt and its herbicidal composition with good solubility and high herbicidal activity. The benzoxazine organic salt is benzoxazine dimethylamine salt, benzoxazine isopropylamine salt, or benzoxazine triethanolamine salt. Preferably, it is benzoxazine triethanolamine salt, and its chemical structure is as follows: .

[0006] The preparation method of benzoxazine triethanolamine salt is as follows: Add benzoxazine technical material to water, and add triethanolamine dropwise while stirring at a speed of 150-200 rpm until completely dissolved. Keep warm at 55-65℃ for 2-4 hours, then add disodium EDTA (optional, selected as needed), stir evenly, and cool to room temperature to obtain benzoxazine triethanolamine salt.

[0007] The present invention provides a composition comprising an organic salt of benzoxazine, preferably a homogeneous and stable herbicidal active liquid formulation containing an organic salt of benzoxazine a) and a solvent b), wherein the herbicidal active ingredient may comprise a) alone or one or more other herbicidal active ingredients d).

[0008] The mass concentration of a) in the composition of the present invention is 0.1%-50%.

[0009] In the composition described in this invention, b) may be selected from: water, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, amides (C6-C4) 10One or more of the following: diethylene glycol, cyclohexanone, isobutanol, cyclohexanone, and isophorone.

[0010] In the composition of the present invention, the mass ratio of a) and b) is from 1:1 to 1:1000.

[0011] The composition of the present invention may further include one or more additives (c), including: antifreeze c1, surfactant c2, pH adjuster c3, and defoamer c4.

[0012] The component c1 described in this invention may be selected from one or more of glycerol, ethylene glycol, and propylene glycol.

[0013] The component c2 of this invention may be selected from one or more combinations of: alkyl glycoside, fatty alcohol polyoxyethylene ether (AEO), styrene-phenol polyoxyethylene ether, EO / PO block polyether, coconut oil alkylamine ethoxylate, tridecyl alcohol polyether, fatty alcohol polyoxyethylene ether sulfate (AES), sodium fatty acid methyl ester sulfonate (MES), and cocamidopropyl dimethylamine.

[0014] The component c3 of this invention may be selected from one or more combinations of EDTA, citric acid, triethanolamine, triethylamine, dimethylamine, and isopropylamine.

[0015] The component c4 of this invention can be selected from one or a combination of two of the following: polysiloxane-based and polyether-modified silicone-based defoamers.

[0016] In the composition of the present invention, the mass ratio of a) and c) is from 1:0.001 to 1:1000.

[0017] The composition of the present invention may further contain one or more other herbicides (d), selected from cyclopyridone, thidiazuron, sulfadiazine, bromoxynil, acetochlor, metolachlor, S-metolachlor, glyphosate, glufosinate, S-metolachlor, dichloropyridine acid, bentazon, imazalil ethanoic acid, trifluralin, diquat, aminopyridine acid, dicamba, 2,4-D, 2,4-DP, 2,4-DP-p, 2,4-DB, MCPA, MCPB, flusulfanilamide, imazalil ethanoic acid, methoxyfenozide, trichloropyridine, imazalil ethanoic acid, imazalil quinolinic acid, bispyribac-sodium, ethanofluralin, chlorpyrifos, etc.

[0018] In the composition of the present invention, the mass ratio of a) and d) is from 1:0.01 to 1:200.

[0019] The composition described in this invention can be applied by pre-sowing, pre-emergence, or post-emergence spraying to various agricultural and non-agricultural crops that have been tolerant to herbicides through traditional breeding or genetic engineering, such as: coffee, palm, rubber, citrus, apple, banana, peanut, rapeseed, corn, soybean, sorghum, sugarcane, sunflower, cotton, rice, wheat, barley, millet, oats, rye, etc.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) It has better bioactivity than its suspension and inorganic salt forms; 2) The composition has better storage stability than its suspension and does not form precipitates; 3) It is easier to dilute, dissolve or disperse in water uniformly and homogeneously than its suspension, making it suitable for large spraying equipment and preventing nozzle clogging; 4) It can be formulated into homogeneous premixed liquid formulations with other herbicides, with better compatibility. Detailed implementation method: The present invention will be further explained below with reference to specific embodiments.

[0021] Example 1: Solubility test of benzoxazine salt Test method: The solubility test method for various salts of benzoxazine at room temperature (18.5℃) is as follows: In a sealed container, weigh 10.2g of 98% benzoxazine, add a certain mass of alkali at a 1:1 molar ratio, add 20g of water, start stirring until the mixture returns to room temperature, continue to slowly add water until benzoxazine is completely dissolved, and calculate the solubility of benzoxazine.

[0022]

[0023] Experimental steps: Benzoxam potassium salt: In a sealed container, add 10.2g of 98% benzoxam and 1.81g of 85% potassium hydroxide, add water to 20g, start stirring until the mixture returns to room temperature, continue to slowly add water until benzoxam is completely dissolved, total weight 43.5g, benzoxam solubility 23.0%.

[0024] Sodium benzoate: In a sealed container, add 10.2g of 98% benzoate and 1.25g of 96% sodium hydroxide, then add water to 20g. Stir until the mixture returns to room temperature, and continue to slowly add water until benzoate is completely dissolved. The total weight is 48.1g, and the solubility of benzoate is 20.8%.

[0025] Benzoate ammonium salt: In a sealed container, add 10.2g of 98% benzoate and 2.34g of 20% ammonia water, add water to 20g, start stirring until the mixture returns to room temperature, continue to slowly add water until benzoate is completely dissolved, the total weight is 90.1g, and the solubility of benzoate is 11.1%.

[0026] Benzoflubenzuron dimethylamine salt: In a sealed container, add 10.2g of 98% benzoflubenzuron and 3.10g of 40% dimethylamine, add water to 20g, start stirring until the mixture returns to room temperature, continue to slowly add water until benzoflubenzuron is completely dissolved, total weight 40g, benzoflubenzuron solubility 25.0%.

[0027] Benzoate isopropylamine salt: In a sealed container, add 10.2g of 98% benzoate and 2.37g of 70% isopropylamine, add water to 20g, start stirring until the mixture returns to room temperature, continue to slowly add water until benzoate is completely dissolved, total weight 37g, benzoate solubility 27.0%.

[0028] Benzoate triethanolamine salt: In a sealed container, add 10.2g of 98% benzoate and 4.08g of 99% triethanolamine, add water to 20g, start stirring until the mixture returns to room temperature, continue to slowly add water until benzoate is completely dissolved, total weight 25g, benzoate solubility 40.0%.

[0029] Experimental results: As shown in Table 1, preparing benzoxazole into organic salt form, especially into benzoxazole triethanolamine salt, can significantly increase the solubility of benzoxazole to 40% when combined with inorganic salts (sodium salt, potassium salt, ammonium salt) of benzoxazole.

[0030] Table 1: Solubility Data

[0031] Example 2: Field efficacy test report of different benzoyl sulfadiazine salt soluble formulations against weeds in corn fields Experimental objective: To test and compare the efficacy and safety of different forms of benzoxazine salt against major weeds in maize fields through field trials. Experimental crop: Xianyu 335; Weed types: annual grasses and broadleaf weeds; Cultivation conditions: The experiment was conducted at Qixingpao Farm in Nenjiang City. The soil at the experimental site was black soil of medium texture, with an organic matter content of 3.62% and a pH value of 6.79. The previous crop was corn. The soil was plowed and harrowed in the autumn, and ridges were made in the spring with a ridge spacing of 65 cm. Test reagents: 10% benzoxazine sodium salt soluble concentrate, 10% benzoxazine potassium salt soluble concentrate, 10% benzoxazine ammonium salt soluble concentrate, 10% benzoxazine isopropylamine salt soluble concentrate, 10% benzoxazine triethanolamine salt soluble concentrate, 10% benzoxazine sodium salt soluble concentrate, 10% benzoxazine dimethylamine salt soluble concentrate; Manufacturer: Nantong Taihe Chemical Co., Ltd. Reference agent: 30% benzoxazine suspension, commercially available; Table 2: Drug Dosage and Treatment Numbers:

[0032] Plot arrangement: The experiment consisted of 8 treatments, 4 replicates, and 32 plots, with each plot having an area of ​​25 m2. The first replicate was arranged in sequential order, and the other three replicates were arranged in randomized block design.

[0033] Application method: Apply the pesticide once after corn emergence, on June 8th. At the time of application, the corn should be at the 3.5-5 leaf stage and the weeds at the 2-4 leaf stage. Use a backpack compressor sprayer specifically designed for small plots, with a spray width of 2m, 4 flat fan-shaped nozzles, and an operating pressure of 4kg / cm². The spray volume should be 250 liters per hectare.

[0034] Investigation method: Observe crop safety after application of pesticide, and investigate the fresh weight of weeds and the control efficacy 28 days after application.

[0035] Experimental results: As shown in Table 3, benzoxazine organic salt has better biological activity than benzoxazine suspension and benzoxazine inorganic salt; in particular, benzoxazine triethanolamine salt has the best control effect on annual grass weeds and broadleaf weeds in maize fields.

[0036] Crop safety: No obvious phytotoxicity symptoms were found in corn in any treatment area at 3-5 days, 14 days and 28 days after application. The corn grew normally throughout the entire growth period, and there was no difference in corn growth between the treated area and the manually weeded area.

[0037] Table 3: Field efficacy of different benzoyl sulfadiazine salt soluble formulations against weeds in corn fields

[0038] Example 3: Preparation of Benzotriethanolamine Salt The following method is used: Add benzoxazine technical material to water, and while stirring at a speed of 150-200 rpm, add triethanolamine dropwise until completely dissolved. Keep it at 55-65℃ for 2-4 hours, then add disodium EDTA (optional), stir evenly, and cool to room temperature to obtain benzoxazine triethanolamine salt.

[0039] Example 4: Preparation of 20% Benzophenone Triethanolamine Salt Soluble Solution The following formulation was used: 20% benzoxazine triethanolamine salt, 8% alkyl glycosides (C10-C12), 5% fatty alcohol polyoxyethylene ether, 0.1% SAG-1572 defoamer, 0.1% tartrazine, and deionized water to bring the total to 100%. A 20% benzoxazine triethanolamine salt soluble concentrate was prepared using conventional soluble concentrate preparation methods. Samples were taken and analyzed according to the general indicators for soluble concentrates in NY / T2989-2016. The results are as follows:

[0040] Example 5: Preparation of 10.5% benzoxazine triethanolamine•glufosinate-ammonium salt soluble concentrate The following formulation was used: 0.5% benzoxazine triethanolamine salt, 10% glyphosate ammonium salt, 4% propylene glycol methyl ether, 15% sodium fatty alcohol polyoxyethylene ether sulfate, 0.07% ZY-8262 (organosilicone defoamer), 0.1% 1% brilliant blue aqueous solution, and deionized water to 100%. A 15.5% benzoxazine triethanolamine•glyphosate triethanolamine salt soluble concentrate was prepared using conventional formulation preparation methods. Samples were taken and analyzed according to the general indicators of soluble concentrates in NY / T2989-2016. The results are as follows:

[0041] Example 6: Preparation of 11.4% Benzotriethanolamine Salt•2,4-D Microemulsion The following formulation was used: containing 1.4% benzoxazine triethanolamine salt, 10% 2,4-D, 2% N-methylpyrrolidone, 4% cyclohexane, 8% amides (C6-C10), 12% arylphenol polyoxyethylene ether, 4% EO / PO block polyether, and deionized water to 100%. An 11.4% benzoxazine triethanolamine•2,4-D microemulsion was prepared using conventional formulation methods. Samples were taken and analyzed according to the general indicators of microemulsions in NY / T2989-2016. The results are as follows:

[0042] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it.

Claims

1. A benzalkonium chloride organic salt, characterized in that, The benzoxazine organic salt is benzoxazine triethanolamine salt, and its chemical structure is as follows: .

2. A herbicidal composition, characterized in that, It includes the benzoxazine organic salt as described in claim 1 and one or more other herbicides.

3. The composition according to claim 2, characterized in that, The mass ratio of benzoxazine organic salt to other herbicides is 1:0.01 to 1:

200.

4. The composition according to claim 3, characterized in that, The other herbicides mentioned are selected from cyclopyridone, thidiazuron, sulfadiazine, bromoxynil, acetochlor, metolachlor, S-metolachlor, glyphosate, glufosinate, S-metolachlor, dichloropyridine acid, bentazon, imazalil ethanoic acid, trifluralin, diquat, aminopyridine acid, dicamba, 2,4-D, MCPA, MCPB, flusulfanilamide, imazalil ethanoic acid, methoxyfenozide, trichloropyroxyacetic acid, imazalil ethanoic acid, imazalil quinolinic acid, bispyribac-sodium, ethanofluralin, or chlorpyridine acid.

5. The composition according to claim 3, characterized in that, It also contains pesticide adjuvant ingredients.

6. The composition according to claim 5, characterized in that, The mass concentration of benzoxazine organic salt is 0.1%-50%.

7. The composition according to claim 5, characterized in that, The composition is formulated as a soluble liquid or a microemulsion.

8. Use of the benzoxazine organic salt of claim 1 or the composition of any one of claims 2-7 for the control of crop weeds.

9. The use according to claim 8, characterized in that, The crop is corn, and the weeds are annual grasses and / or broadleaf weeds.

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