A herbicidal combination for gramineous crops against fenclorim phytotoxicity

Abstract

The present application provides a kind of herbicide composition for anti-benzoxyacetone phenoxy acid double oxygenase inhibitor and the herbicide safener containing quinoline structure;The herbicide composition prepared by the present application can reduce the phytotoxicity of herbicide to gramineous crops such as wheat, rice and millet without affecting the efficacy of herbicide;For three different gramineous crops such as wheat, rice and millet, the composition of the present application is significantly better than the composition for reducing the phytotoxicity of herbicide to rice and millet in reducing the phytotoxicity of herbicide to wheat.

Description

[0001] This application is a divisional application of the invention patent application entitled "A herbicide combination for resisting benzoxazine damage to gramineous cereals", application number "202311249928.9". Technical Field

[0002] This invention relates to the field of herbicide safeners, and more specifically to a herbicide composition for resisting benzoxazine damage in gramineous cereals. Background Technology

[0003] Due to the irrational use of herbicides and the selectivity of weeds themselves, an increasing number of weeds are exhibiting high herbicide resistance, making their control extremely difficult. One common solution is to increase the dosage and use multi-component mixtures, but this can further increase weed resistance and increase the risk of herbicide damage to crops. The causes of herbicide damage are particularly complex, mainly including inappropriate herbicide selection, failure to follow correct application methods and dosage standards, unreasonable application timing, incorrect application methods, and uneven spraying.

[0004] The emergence of herbicide safeners has effectively solved the problem of herbicide damage. Herbicide safeners, also known as antidotes or protectants, are compounds used to protect crops from herbicide damage, thereby increasing crop safety and improving weed control. They protect crops by accelerating metabolism, increasing enzyme activity, and upregulating related genes. Adding safeners to herbicides is a way to artificially impart selectivity to them, thereby improving crop tolerance. Their function also includes acting as selective herbicide synergists, broadening the spectrum of herbicide activity without increasing crop damage. Currently, more than 30 herbicide safener varieties and their commercially available combinations with herbicides are in practical application, protecting gramineous crops such as rice, wheat, corn, and sorghum, and broadleaf crops such as soybeans and cotton.

[0005] Selecting appropriate herbicides and safeners for different growth stages of different crops, the types of weeds at special growth stages, and the sensitivity of plants to different herbicides, and screening existing herbicides and safeners to obtain the optimal combination and relative proportions for application to specific crops is a technical problem that urgently needs to be solved in the field of herbicides. Summary of the Invention

[0006] p-Hydroxypyruvate dioxygenase (EC 1.13.11.27, HPPD) is one of the most important herbicide targets. HPPD-inhibiting herbicides inhibit HPPD activity, thus blocking the conversion of p-hydroxypyruvate to hydantoin, which in turn affects the synthesis of plastoquinones and tocopherols in plants, leading to bleaching symptoms and plant death. These herbicides have advantages such as high efficiency, low toxicity, broad-spectrum weed control, and slow resistance development.

[0007] This invention addresses the shortcomings of existing technologies by providing a herbicidal composition for gramineous crops, wherein the composition can be used to control weeds on gramineous crops; the herbicidal composition comprises a p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor and a safener having the structure described in formula (1): R is selected from hydrogen, C1-C8 alkyl, C1-C8 alkoxy, hydroxyl, halogen, nitro, and phenyl.

[0008] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the selected grain is preferably one or more of wheat, rice, or millet; more preferably wheat.

[0009] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein R is selected from one of C2-C7 alkyl, nitro, and phenyl; preferably, R is selected from n-pentyl.

[0010] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein R is selected from n-pentyl.

[0011] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the mass ratio of the safener active ingredient to the herbicide active ingredient is 1:(0.7-70.0), preferably 1:(2-60.0), more preferably 1:(5-40.0), and most preferably 1:10 or 1:30.

[0012] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor is selected from at least one of isoxaflutole, benzoxazine, thiamethoxam, and cyclosulfonamide, preferably benzoxazine.

[0013] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the herbicide composition further comprises other herbicides, preferably selected from one or more of clopyralid, sodium MCPA, cyclohexane, diflubenzuron, and isoproturon.

[0014] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the herbicide composition is compounded with clopyralid for post-emergence control of annual broadleaf weeds such as shepherd's purse, shepherd's purse, speedwell, and sedge in wheat fields. The ratio of p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to clopyralid is 1:(0.5-50), preferably 1:(1-40), more preferably 1:(3-20), and most preferably 1:5.

[0015] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the herbicide composition is compounded with sodium 2,4-D for post-emergence control of annual broadleaf weeds such as shepherd's purse, shepherd's purse, speedwell, and sedge in wheat fields. The mass ratio of p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to sodium 2,4-D is 1:(1-100), preferably 1:(5-80), more preferably 1:(10-40), and most preferably 1:30.

[0016] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the herbicide composition is compounded with oxychloride for post-emergence control of annual broadleaf weeds such as shepherd's purse, shepherd's purse, speedwell, and sedge in wheat fields. The mass ratio of p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to oxychloride is 1:(0.1-10), preferably 1:(0.2-5), more preferably 1:(0.8-2), and most preferably 1:1.

[0017] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the herbicide composition is compounded with diflubenzuron for post-emergence control of annual broadleaf weeds such as shepherd's purse, shepherd's purse, speedwell, and sedge in wheat fields. The mass ratio of p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to diflubenzuron is 1:(0.01-1), preferably 1:(0.02-0.5), more preferably 1:(0.05-0.2), and most preferably 1:0.1.

[0018] Furthermore, the present invention provides a herbicidal composition for gramineous crops as described above, wherein the herbicide composition is compounded with isoproturon for post-emergence control of annual gramineous weeds such as Alopecurus aequalis, Alopecurus japonicus, and Bromus esculentus in wheat fields. The mass ratio of p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to isoproturon is 1:(2-200), preferably 1:(10-100), more preferably 1:(5-50), and most preferably 1:7.33.

[0019] Furthermore, the present invention provides the use of the herbicidal composition described above in controlling weeds in gramineous crops, wherein the gramineous crop is preferably selected from one or more of wheat, rice or millet, more preferably wheat.

[0020] The compositions of the present invention preferably further comprise an agriculturally acceptable carrier. The compositions of the present invention can be formulated into granules, wettable granules, emulsifiable concentrates, powders or dusts, liquids, solutions, suspensions or emulsions, or controlled-release forms such as microcapsules.

[0021] Wettable powders are finely dispersed granules that readily disperse in water or other liquid carriers. These granules contain the active ingredient retained in a solid matrix. Typical solid matrices include bleaching clay, kaolin, silica, and other readily wettable organic or inorganic solids. Wettable powders generally contain approximately 5% to approximately 95% of the active ingredient plus small amounts of wetting agents, dispersants, or emulsifiers.

[0022] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids. They may consist entirely of an active ingredient and a liquid or solid emulsifier, and may also contain liquid carriers such as xylene, heavy aromatic naphtha, isophorone, and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquids and are typically applied by spray to the area to be treated. The amount of active ingredient can range from approximately 0.5% to approximately 95% of the concentrate.

[0023] Granules include extrudates and coarser granules, typically undiluted and used in areas where plant growth is desired to be suppressed. Typical carriers for granules include sand, bleaching powder, magnesia, bentonite, montmorillonite, vermiculite, perlite, and other organic or inorganic materials that can absorb or coat the active ingredient. Granules generally contain approximately 5% to approximately 95% of the active ingredient and may contain surfactants such as heavy aromatic naphtha, kerosene, and other petroleum distillates or vegetable oils; and / or binders such as dextrin, gum, or synthetic resins.

[0024] Powders are free-flowing mixtures of active ingredients with finely dispersed solids such as talc, clay, flour, and other organic and inorganic solids that act as dispersants and carriers.

[0025] Compared with the prior art, the present invention has the following beneficial effects: 1. The quinoline-containing herbicide safener, methylparaben, is used to protect cereal crops from HPPD-type herbicides like benzoxazole. It reduces the damage caused by herbicides to crops without affecting their efficacy. The combination of methylparaben and benzoxazole is used for weed control in cereal crops such as wheat, rice, and millet. It has excellent weed-control capabilities and protects crops from herbicide damage.

[0026] 2. The herbicide combination agent containing a quinine structure described in this invention, which is a combination of the HPPD herbicide benzoxazine, is feasible. On the basis of being safe for wheat, rice, and millet, the herbicide-relieving effect on wheat is far superior to that on rice and millet. This shows that the combination herbicide of this invention has achieved unexpected technical effects in the field of wheat weed control. Attached Figure Description

[0027] Figure 1 Safety tests were conducted on wheat at different concentrations of benzoyl permethrin. Figure 2 Feasibility verification of herbicide combination formulation of glyphosate, a herbicide safener containing quinoline structure, and benzoxazine, an HPPD-type herbicide; Figures 3-4 To verify the efficacy of a combination herbicide combination of quinoline-containing herbicide safener methylparaben and HPPD-type herbicide benzoate with different treatment groups sown with Artemisia annua. Figures 5-6 The efficacy of a combination herbicide, methyl parathion, a safener for herbicides containing a quinoline structure, and benzoxazine, an HPPD-type herbicide, in different treatment groups of shepherd's purse was verified through experiments. Figure 7 For detailed comparison of single plants under different mixed treatments (1. Blank control 2. Bismuth subtilis + clopyralid 3. Bismuth subtilis single agent 4. Bismuth subtilis + bismuth subtilis 5. Bismuth subtilis + clopyralid 6. Bismuth subtilis + 2,4-D sodium); Figures 8-9 This study aims to verify the efficacy of Veronica persica in combination with the quinoline-containing herbicide safener methylparaben and the HPPD-type herbicide benzoxazine, and to evaluate the efficacy of different treatment groups. Detailed Implementation

[0028] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0029] In addition to the raw materials, active ingredients and / or safeners mentioned above, the products used in the embodiments of this invention also contain 85% sodium dimethyl ether EP, 20% clopyralid AS, 5% diflubenzuron SC, 10% cyclopyralid EP, 5.5% diflubenzuron SC + 16.5% clopyralid SC, 22% isoproturon EP, and 6% cyclopyralid OD.

[0030] The formulation information of this invention is as follows: 30% Benzoflubenzuron SC: Benzoflubenzuron technical grade 30%, fatty alcohol polyoxyethylene ether phosphate 3%, tristyrene phenol polyoxyethylene ether 3%, nonylphenol polyoxyethylene ether 1%, magnesium aluminum silicate 1.5%, xanthan gum 0.1%, sodium sulfite 0.3%, ethylene glycol 5%, Kathon 0.1%, silicone defoamer 0.3%, water to make up 100%.

[0031] 20% Chloropyroxyacetic Acid AS: 20% chloropyroxyacetic acid, 5% fatty alcohol polyoxyethylene ether, 5% ethylene glycol, 0.2% silicone defoamer, water to make up 100%.

[0032] 5% Diflubenzuron SC: Diflubenzuron 5%, fatty alcohol polyoxyethylene ether phosphate 3%, calcium dodecylbenzenesulfonate 2%, magnesium aluminum silicate 2.5%, xanthan gum 0.2%, ethylene glycol 5%, Kathon 0.1%, silicone defoamer 0.3%, water to make up 100%.

[0033] 10% cyclohexane EP: cyclohexane 10%, organosilicon 2%, silica 20%, calcium lignosulfonate 10%, sodium maleate-acrylate 2%, sodium gluconate to make up 100%.

[0034] 85% Sodium Dimethyl Tetrachlorophosphate SP: Sodium dimethyl tetrachlorophosphate 85%, Naphthalene sulfonate formaldehyde condensate 8%, Sodium dodecylbenzene sulfonate 2%, Silica to make up 100%.

[0035] 22% Isoproturon EP: Isoproturon 22%, Acrylic acid methacrylate copolymer 8%, Fatty alcohol polyoxyethylene ether 3%, Silica 10%, Sodium lignosulfonate 10%, Ammonium sulfate to make up 100%.

[0036] For pharmaceutical preparations not mentioned here, when the active pharmaceutical ingredient and the preparation type are the same but the content is different, the content should be adjusted according to the content of the specific active ingredient, and other excipients should be adjusted accordingly. All other pharmaceutical preparations not mentioned here are commercially available products, and should be diluted with water according to the dosage before use and experimentation.

[0037] The following embodiments are descriptive only and not limiting, and should not be construed as limiting the scope of protection of this invention. The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, endpoint values ​​of various ranges, endpoint values ​​of various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0038] Example 1: Safety study of HPPD herbicide benzoxazole on indoor wheat and the effect of different herbicide safeners on mitigating phytotoxicity of HPPD herbicide benzoxazole in indoor wheat. To investigate the safety of the HPPD herbicide benzoxazole on wheat and the mitigation of herbicide damage by different safeners, 800 potted wheat plants were cultivated in a greenhouse at the Pangjiasheng Testing Base of Shandong Jingbo Agricultural Chemical Technology Co., Ltd. Each pot was sown with at least 50 seeds, and all 800 pots were managed uniformly. 495 potted plants with similar growth stages were selected as experimental subjects for indoor safety testing of benzoxazole on wheat and for studying the mitigation effects of different herbicide safeners on indoor wheat resistance to benzoxazole herbicide damage.

[0039] I. Indoor safety study of HPPD herbicide benzoxazole on wheat: To investigate the safety of the HPPD herbicide benzoxazole on indoor wheat, a two-stage dilution method was used. For each treatment area, the herbicide sample was diluted with water and then injected into a sprayer. The water volume was adjusted according to the plot's water usage to prepare effective ingredient dosages of 9.00 g / ha, 13.50 g / ha, 18.00 g / ha, 22.50 g / ha, 27.00 g / ha, 31.50 g / ha, 36.00 g / ha, 54.00 g / ha, and 81.00 g / ha. 120 potted wheat plants selected as the experimental subjects were divided into 8 groups (treatments 1-8), with 5 pots in each group. The experiment was repeated three times during the wheat's growth period, and the potted wheat was sprayed via foliar spraying. The results were collected on day 14, and the inhibition rate of the herbicide content based on fresh weight / plant height was calculated using the formula. The results were rounded to two decimal places. The results are shown in Table 1. Figure 1 As shown.

[0040] ×100 In the formula: R—Growth inhibition rate, expressed as a percentage (%); X0 — Control fresh weight (or plant height), in grams or centimeters (g or cm); X1 — Processed fresh weight (or plant height), in grams or centimeters (g or cm).

[0041] Table 1 Safety test of different concentrations of benzoxazine on wheat

[0042] The results showed that when HPPD herbicides such as benzoxazole were applied to wheat at a concentration of 18 g / ha or higher of active ingredient, they caused phytotoxicity to wheat, affecting the growth rate of wheat plant height and the inhibition rate of fresh weight.

[0043] II. Study on the effect of different herbicide safeners on mitigating phytotoxicity of HPPD-resistant wheat by benzoxazine in indoor experiments: To investigate the effects of different herbicide safeners on mitigating phytotoxicity of the HPPD-resistant herbicide benzoxazole in indoor wheat cultivation, benzoxazole was diluted using a two-stage dilution method. For each treatment area, the herbicide sample was diluted with water and mixed thoroughly before being introduced into a sprayer. Water was added according to the water usage of each plot to prepare effective ingredient dosages of 18.00 g / ha, 27.00 g / ha, 36.00 g / ha, 54.00 g / ha, and 81.00 g / ha. A safener was added during the preparation process, with a mass ratio of the safener active ingredient to the herbicide active ingredient of 1:10. 375 potted wheat plants selected as the experimental subjects were divided into 25 groups (treatments 9-33), with 5 pots in each group, and the treatment was repeated three times. During the wheat's growth period, the potted wheat was sprayed via foliar spraying. The statistical methods for the results are described in Example 1, and the results are shown in Table 2.

[0044] Table 2. Comparative Study of the Effects of Different Herbicide Safeguards on Herbicide Damage Relief in Indoor Wheat Resistant to Benzoxam

[0045] The results showed that different safeners had significantly different effects on alleviating herbicide damage to wheat. Among them, the herbicide safener containing quinoline structure, chlorpyrifos, had the greatest protective effect. When the mass ratio of the active ingredient of the herbicide safener to the active ingredient of the herbicide was 1:10, there was no significant difference in the indicators between wheat and the control group.

[0046] Example 2: Study on the phytotoxicity of different concentrations of quinoline-containing herbicide safener methylparaben against HPPD-resistant wheat in indoor environments: To investigate the effects of different concentrations of the quinoline-containing herbicide safener, methylparaben, on the phytotoxicity of HPPD-type herbicide benzoyl permethrin in indoor wheat cultivation, benzoyl permethrin was diluted using a two-stage method. For each treatment area, the herbicide sample was diluted with water and mixed thoroughly before being sprayed. Water was added according to the water usage of each plot to prepare effective ingredient dosages of 18.00 g / ha, 27.00 g / ha, and 36.00 g / ha. The mass ratio of the active ingredient in the herbicide safener to the active ingredient in the herbicide was set at three levels: 1:10, 1:20, and 1:30, respectively. Two hundred pots of wheat were planted in a greenhouse, with at least 50 seeds sown in each pot. During the wheat's growth period, 180 pots of wheat with similar growth were selected and divided into 12 groups of 5 pots each, with three replicates. The potted wheat was sprayed via foliar spraying. The results were collected on day 14, and the inhibition rate of the fresh weight / plant height content for each treatment was calculated using the formula. The results were rounded to two decimal places. The statistical methods for the results are described in Example 1, and the experimental results are shown in Table 3.

[0047] Table 3 Comparison of different concentrations of glyphosate in alleviating wheat herbicide damage

[0048] The results showed that low, medium, and high concentrations of the quinoline-containing herbicide safener, tebufenozide, could protect wheat to some extent. Furthermore, at low concentrations of benzoxazole, there was no significant difference in the mitigation effect of the three concentrations of tebufenozide on phytotoxicity. When mixed with low concentrations of benzoxazole (active ingredient below 27 g / ha), the optimal ratio of tebufenozide to benzoxazole active ingredient was 1:30; when mixed with high concentrations of benzoxazole (active ingredient above 27 g / ha), the optimal ratio was 1:10.

[0049] Example 3: Study on the phytotoxicity effect of quinoline-containing herbicide safener methylparaben on the HPPD-type herbicide benzoxazole in wheat fields in major wheat-producing areas. To investigate the efficacy of the quinoline-containing herbicide safener, methylparaben, against the HPPD-type herbicide benzoyl permethrin in major wheat-producing areas, benzoyl permethrin was diluted using a two-stage method. The herbicide was selected for treatment areas, and the sample was diluted with water and mixed thoroughly before being injected into a sprayer. Water was added according to the plot's water usage to prepare effective ingredient dosages of 18.00 g / ha and 27.00 g / ha. The mass ratio of the active ingredient in the herbicide safener to the active ingredient in the herbicide was 1:30. Experiments were conducted in major wheat-producing areas: Fugou County in Henan Province, Taihe County in Anhui Province, Lianshui County in Jiangsu Province, and Tancheng County in Shandong Province. Each treatment covered 20 square meters, and each treatment was replicated three times. During the wheat's growth period, the herbicide was sprayed via foliar spraying. Results were collected on day 14, and the inhibition rate of the herbicide content (fresh weight / plant height) for each treatment was calculated using the formula. Results were rounded to two decimal places. The statistical methods for the results are described in Example 1, and the experimental results are shown in Table 4.

[0050] Table 4. Comparison of the efficacy of glyphosate in alleviating wheat herbicide damage in different regions.

[0051] The results showed that trials conducted in major wheat-producing areas across the country revealed that the quinoline-containing herbicide safener, methylparaben, had a significant protective effect on wheat.

[0052] Example 4: Efficacy study of a herbicide combination of quinoline-containing herbicide safener methylparaben and HPPD-type herbicide benzoxazine against weeds in wheat fields in major wheat-producing areas. To investigate whether the addition of acetamiprid affected the efficacy of benzoxazine, a two-stage dilution method was used. For each treatment area, the herbicide sample was diluted with water, mixed thoroughly, and then injected into a sprayer. The water volume was adjusted according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the herbicide safener active ingredient to the herbicide active ingredient was 1:30. The experiment was conducted in Taihe County, Anhui Province, with each treatment covering 20 square meters and repeated three times. During the wheat growth period, *Shepherd's Purse*, *Veronica persica*, and *Capsella bursa-pastoris* were sprayed via foliar spraying. The results were assessed on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. The results were rounded to two decimal places. The statistical method for the results is described in Example 1, and the experimental results are shown in Table 5.

[0053] Table 5. Feasibility verification of a herbicide combination formulation of quinoline-containing herbicide safener methylparaben and HPPD-type herbicide benzoxazole.

[0054] The results showed that when a quinoline-containing herbicide safener was added, the HPPD herbicide benzoxazole had no significant effect on the efficacy of major weeds in wheat fields, such as shepherd's purse, speedwell, shepherd's purse, and pigweed. Therefore, the herbicide combination of the quinoline-containing herbicide safener oxychloride and the HPPD herbicide benzoxazole described in this invention is feasible.

[0055] Example 5: Efficacy test results of a combination of a quinine-containing herbicide safener, methylparaben, an HPPD-type herbicide, and clopyralid against annual broadleaf weeds.

[0056] To investigate the efficacy of this combination agent against annual broadleaf herbicides, treatment areas were selected. Samples were diluted with water, mixed thoroughly, and then introduced into sprayers. Water was added according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the active ingredients of acetamiprid to benzoyl permethrin was 1:30, and the mass ratio of benzoyl permethrin to clopyralid was 1:5. The experiment was conducted in Taihe County, Anhui Province, with each treatment covering 20 square meters and repeated three times. During the wheat growth period, the herbicides were applied to *Desmodium styracifolium*, *Veronica persica*, *Capsella bursa-pastoris*, and *Phyllostachys edulis* via foliar spraying. The results were assessed on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. Calculation results were rounded to two decimal places. The statistical method for the results is described in Example 1, and the experimental results are shown in Table 6.

[0057] Table 6. Efficacy test results of a combination of a quinolin-containing herbicide safener, fenpropathrin, an HPPD-type herbicide, and clopyralid against different broadleaf weeds in wheat fields.

[0058] The results showed that a combination of a quinine-containing herbicide safener, methyl parathion, HPPD herbicide benzoate, and clopyralid significantly improved plant control efficacy and fresh weight inhibition rate on *Cephalotaxus fortunei*, *Capsella bursa-pastoris*, and *Phyllostachys edulis* compared to benzoate alone or clopyralid alone.

[0059] Example 6: Efficacy test results of a combination of a quinine-containing herbicide safener, methyl parathion, an HPPD-type herbicide, and sodium 2,4-D, against annual broadleaf weeds. To investigate the efficacy of this combination agent against annual broadleaf herbicides, treatment areas were selected. Samples were diluted with water, mixed thoroughly, and then introduced into sprayers. Water was added according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the active ingredients of methyl parathion to benzoyl permethrin was 1:30, and the mass ratio of benzoyl permethrin to sodium 2,4-D was 1:30. The experiment was conducted in Taihe County, Anhui Province, with each treatment covering 20 square meters and repeated three times. During the wheat growth period, *Shepherd's Purse*, *Veronica persica*, and *Capsella bursa-pastoris* were sprayed via foliar spraying. The results were investigated on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. The results were rounded to two decimal places. The statistical method for the results is described in Example 1, and the experimental results are shown in Table 7.

[0060] Table 7. Efficacy test results of a combination of a quinoline-containing herbicide safener, methyl parathion, an HPPD-type herbicide, and sodium 2,4-D, against different broadleaf weeds in wheat fields.

[0061] The results showed that a combination of a quinoline-containing herbicide safener, methyl parathion, an HPPD-type herbicide, and sodium 2,4-D significantly improved plant control efficacy and fresh weight inhibition rate on *Cephalotaxus fortunei*, *Capsella bursa-pastoris*, and *Phyllostachys edulis* compared to methyl parathion or sodium 2,4-D alone.

[0062] Example 7: Efficacy test results of a combination of a quinine-containing herbicide safener, methylparaben, and HPPD-type herbicides benzoxazine and methylparaben against annual broadleaf weeds. To investigate the efficacy of this combination agent against annual broadleaf herbicides, treatment areas were selected. Samples were diluted with water, mixed thoroughly, and then introduced into sprayers. Water was added according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the active ingredients of methyl parathion to benzoyl permethrin was 1:30, and the mass ratio of benzoyl permethrin to methyl parathion was 1:1. The experiment was conducted in Taihe County, Anhui Province, with each treatment covering 20 square meters and repeated three times. During the wheat growth period, *Shepherd's Purse*, *Veronica persica*, and *Capsella bursa-pastoris* were sprayed via foliar spraying. The results were investigated on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. The calculation results were rounded to two decimal places. The statistical method for the results is described in Example 1, and the experimental results are shown in Table 8.

[0063] Table 8. Efficacy test results of a quinine-containing herbicide safener, fenproxate, and a combination of HPPD herbicides benzoxazole and fenproxate against different broadleaf weeds in wheat fields.

[0064] The results showed that oxadiazon is prone to phytotoxicity in wheat when used improperly, but it has strong efficacy. When mixed with oxadiazon, it has excellent control effects on common broadleaf weeds in wheat fields. A combination of quinoline-containing herbicide safener oxadiazon, HPPD herbicide oxadiazon, and oxadiazon can be used to control highly resistant broadleaf weeds in wheat fields.

[0065] Example 8: Efficacy test results of a combination of a quinine-containing herbicide safener, methylparaben, an HPPD-type herbicide, and diflubenzuron against annual broadleaf weeds. To investigate the efficacy of this combination agent against annual broadleaf herbicides, treatment areas were selected. Samples were diluted with water, mixed thoroughly, and then introduced into sprayers. Water was added according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the active ingredients in the combination was 1:10 (methylparaben to benzoyl permethrin), and the mass ratio of benzoyl permethrin to diflubenzuron was 1:0.1. The experiment was conducted in Taihe County, Anhui Province, with each treatment covering 20 square meters and repeated three times. During the wheat growth period, *Shepherd's Purse*, *Veronica persica*, and *Capsella bursa-pastoris* were sprayed via foliar spraying. The results were assessed on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. Calculation results were rounded to two decimal places. The statistical method for the results is described in Example 1, and the experimental results are shown in Table 9.

[0066] Table 9. Efficacy test results of a combination of a quinine-containing herbicide safener, fenproxetil, an HPPD-type herbicide, and diflubenzuron against different broadleaf weeds in wheat fields.

[0067] The results showed that a combination of a quinoline-containing herbicide safener, methylparaben, and HPPD-type herbicides benzoxazine and diflubenzuron significantly improved plant control efficacy and fresh weight inhibition rate on Veronica persica and swamp vines compared to benzoxazine and diflubenzuron alone.

[0068] Example 9: Efficacy test results of a combination of a quinine-containing herbicide safener, methyl parathion, an HPPD-type herbicide, and isoproturon against bromelain.

[0069] To study the efficacy of this combination agent against annual grass herbicides, treatment areas were selected. Samples were diluted with water, mixed thoroughly, and then introduced into sprayers. Water was added according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the active ingredients, methyl parathion and benzoyl permethrin, was 1:30, and the mass ratio of benzoyl permethrin to isoproturon was 1:27.5. The experiment was conducted in Tancheng County, Shandong Province, with each treatment covering 20 square meters and repeated three times. During the wheat's growth period, the herbicide was applied via foliar spraying. Results were assessed on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. Results were rounded to two decimal places. The statistical methods for the results are described in Example 1, and the experimental results are shown in Table 10.

[0070] Table 10. Efficacy test results of a quinine-containing herbicide safener, fenpropathrin, HPPD-type herbicides benzoxazine and isoproturon against mature bromeliad.

[0071]

[0072] The results showed that a combination of a quinoline-containing herbicide safener, methyl parathion, an HPPD-type herbicide, and isoproturon had a certain effect on the control of older bromeliads, and that methyl parathion was no less effective than cyclopyridoxine under the same dosage of active ingredient.

[0073] Example 10: Efficacy test results of a combination of a quinine-containing herbicide safener, methyl parathion, an HPPD-type herbicide, and isoproturon against Japanese wild oats.

[0074] To study the efficacy of this combination agent against annual grassy weeds, treatment areas were selected. Samples were diluted with water, mixed thoroughly, and then introduced into sprayers. Water was added according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the active ingredients, methyl parathion and benzoyl permethrin, was 1:30, and the mass ratio of benzoyl permethrin to isoproturon was 1:27.5. The experiment was conducted in Lianshui County, Jiangsu Province, with each treatment covering 20 square meters and repeated three times. During the wheat's growth period, the Japanese wild oats were sprayed via foliar spraying. The results were assessed on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. Calculation results were rounded to two decimal places. The statistical methods for the results are described in Example 1, and the experimental results are shown in Table 11.

[0075] Table 11. Efficacy test results of a quinine-containing herbicide safener, fenproxetil, HPPD-type herbicide benzoxazine, and isoproturon against *Oregano* spp.

[0076] Example 11: Efficacy test results of a quinine-containing herbicide safener, methyl parathion, HPPD herbicide benzoxazine, and isoproturon against bromelain.

[0077] To investigate the efficacy of this combination agent against annual broadleaf herbicides, treatment areas were selected. Samples were diluted with water, mixed thoroughly, and then introduced into sprayers. Water was added according to the plot's water usage to prepare an effective ingredient dosage of 27.00 g / ha. The mass ratio of the active ingredients, methyl parathion and benzoyl permethrin, was 1:10, and the mass ratio of benzoyl permethrin to isoproturon was 1:18.33, 1:9.17, and 1:7.33. The experiment was conducted in Boxing County, Shandong Province, with each treatment covering 20 square meters and repeated three times. During the wheat's growth period, the herbicide was applied via foliar spraying. Results were assessed on day 14, and the plant control efficacy and fresh weight inhibition rate for each treatment were calculated using the formula. Calculation results were rounded to two decimal places. The statistical methods for the results are described in Example 1, and the experimental results are shown in Table 12.

[0078] Table 12. Efficacy test results of a combination of a quinine-containing herbicide safener, methyl parathion, HPPD herbicide benzoxazine, and isoproturon against bromelain.

[0079]

[0080] The results showed that a combination of a quinoline-containing herbicide safener, fenproxetine, an HPPD-type herbicide, and isoproturon had a certain effect on the control of Japanese wild oats. Fenproxetine showed stronger activity than cyclopyrfluthrin. Both alone and in combination, fenproxetine had good control efficacy against wild oats, proving the feasibility of using fenproxetine for grass weeds in wheat fields.

[0081] Example 12: Study on the phytotoxicity of different concentrations of quinoline-containing herbicide safener oxychloride against HPPD-type herbicide benzoxazole in indoor rice: To investigate the effects of different concentrations of the quinoline-containing herbicide safener, methylparaben, on the phytotoxicity of the HPPD herbicide benzoyl permethrin in indoor rice cultivation, benzoyl permethrin was diluted using a two-stage method. For each treatment area, the herbicide sample was diluted with water and then injected into a sprayer. Water was added according to the plot's water usage to prepare effective ingredient dosages of 18.00 g / ha, 27.00 g / ha, and 36.00 g / ha. The mass ratio of the active ingredient in the herbicide safener to the active ingredient in the herbicide was set at three levels: 1:10, 1:20, and 1:30, respectively. Two hundred rice pots were planted in a greenhouse, each containing at least 50 seeds, divided into 12 groups of 5 pots each, with three replicates. During the rice's growth period, the potted sorghum was sprayed via foliar spraying. The results were assessed on day 14, and the inhibition rate of fresh weight / plant height content for each treatment was calculated using the formula. The results were rounded to two decimal places. The statistical methods for the results are described in Example 1, and the experimental results are shown in Table 13.

[0082] Table 13 Comparison of different concentrations of glyphosate in alleviating herbicide damage in rice

[0083] The results showed that low, medium and high concentrations of the quinoline-containing herbicide safener, methyl parathion, had a certain mitigating effect on benzoxazole herbicide damage to rice, but the mitigation effect was generally limited.

[0084] Example 13: Study on the phytotoxicity of different concentrations of quinoline-containing herbicide safener oxychloride to millet in indoor soil against HPPD-type herbicide benzoxazole. To investigate the effects of different concentrations of the quinoline-containing herbicide safener, methylparaben, on the phytotoxicity of the HPPD herbicide benzoyl permethrin in indoor millet, a two-stage dilution method was used. For each treatment area, the herbicide sample was diluted with water and mixed thoroughly before being sprayed. Water was added according to the water usage of each plot to prepare effective ingredient dosages of 18.00 g / ha, 27.00 g / ha, and 36.00 g / ha. The mass ratio of the active ingredient in the herbicide safener to the active ingredient in the herbicide was set at three levels: 1:10, 1:20, and 1:30, respectively. Two hundred pots of millet were planted in a greenhouse, with at least 50 seeds sown per pot, divided into 12 groups of 5 pots each, with three replicates. During the millet's growth period, the potted millet was sprayed via foliar spraying. The results were assessed on day 14, and the inhibition rate of the fresh weight / plant height content for each treatment was calculated using the formula. The results were rounded to two decimal places. The statistical methods for the results are described in Example 1, and the experimental results are shown in Table 14.

[0085] Table 14 Comparison of different concentrations of acetamiprid in alleviating herbicide damage in millet

[0086] The results showed that low, medium and high concentrations of the quinoline-containing herbicide safener, methyl parathion, could protect millet to a certain extent.

[0087] In summary, quinoline-containing herbicide safeners can alleviate the phytotoxicity of HPPD herbicides on cereal crops such as wheat, rice, and millet, with particularly significant effects on wheat. When the mass ratio of the active ingredients is 1:(0.7-70.0), the herbicide combination of the quinoline-containing herbicide safener, fenpropathrin, and the HPPD herbicide benzoyl permethrin described in this invention is feasible, ensuring safety for wheat, rice, and millet without affecting efficacy.

[0088] Furthermore, this invention describes its relevant compound formulations and experimental results, demonstrating its feasibility for application under specific conditions. The effect of acetamiprid on alleviating HPPD herbicide damage in wheat is far superior to that in rice and millet, possibly related to the interaction between the target and the crop.

[0089] Although embodiments of the present invention have been disclosed for illustrative purposes, various simple modifications can be made to the technical solutions of the present invention within the scope of the inventive concept, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention. Various substitutions, variations, and modifications are possible without departing from the spirit and scope of the present invention and the appended claims; therefore, the scope of the present invention is not limited to the content disclosed in the embodiments.

Claims

1. A herbicidal composition for use on gramineous crops, characterized in that, The herbicidal composition comprises a p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor and a safener having the structure of formula (1): （I） R is selected from one of hydrogen, C1-C8 alkyl, C1-C8 alkoxy, hydroxyl, halogen, nitro, and phenyl.

2. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The R is selected from C2-C7 alkyl, nitro, and phenyl; preferably, the R is selected from n-pentyl.

3. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The mass ratio of the safener to the p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor is 1:(0.7-70.0), preferably 1:(2-60.0), more preferably 1:(5-40.0), and most preferably 1:30 or 1:

10.

4. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor is selected from at least one of isoxazolidinone, benzoxazolidinone, thiamethoxam, and cyclosulfonamide, preferably benzoxazolidinone.

5. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The herbicide composition further comprises other herbicides, preferably selected from one or more of clopyralid, sodium MCPA, cyclohexane, diflubenzuron, and isoproturon.

6. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The herbicide composition is further compounded with clopyralid, wherein the ratio of the p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to clopyralid is 1:(0.5-50), preferably 1:(1-40), more preferably 1:(3-20), and most preferably 1:

5.

7. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The herbicide composition is further compounded with sodium 2,4-D, wherein the mass ratio of the p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to sodium 2,4-D is 1:(1-100), preferably 1:(5-80), more preferably 1:(10-40), and most preferably 1:

30.

8. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The herbicide composition is further compounded with oxychloride, and the mass ratio of p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to oxychloride is 1:(0.1-10), preferably 1:(0.2-5), more preferably 1:(0.8-2), and most preferably 1:

1.

9. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The herbicide composition is further compounded with diflubenzuron, wherein the mass ratio of the p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to diflubenzuron is 1:(0.01-1), preferably 1:(0.02-0.5), more preferably 1:(0.05-0.2), and most preferably 1:0.

1.

10. The herbicidal composition for gramineous crops according to claim 1, characterized in that, The herbicide combination is further compounded with isoproturon, and the mass ratio of p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor to isoproturon is 1:(2-200), preferably 1:(10-100), more preferably 1:(30-50), and most preferably 1:7.33.

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