Application of weeding composition containing quizalofop-p-ethyl and bispyribac-sodium in ACCase and ALS inhibitor resisting rice

Abstract

The invention provides a weeding composition containing quizalofop-p-ethyl and bispyribac-sodium, the mass ratio of quizalofop-p-ethyl to bispyribac-sodium is (1-6): (1-10), and auxiliary agents such as an emulsifier, a dispersing agent, a stabilizer, a thickening agent, vegetable oil and deionized water are added to prepare a dispersible oil suspending agent. By utilizing different action mechanisms of quizalofop-p-ethyl and bispyribac-sodium, the composition is compounded and used for non-transgenic ACCase and ALS inhibitor resistant rice, can effectively kill difficult-to-prevent gramineous weeds such as rice, barnyard grass and leersia oryzae in a rice field and annual weeds such as cyperus iria and monochoria vaginalis, and has a remarkable effect.

Description

Technical Field

[0001] This invention belongs to the field of herbicides, specifically relating to a herbicidal composition comprising quizalofop-P-ethyl and bispyribac-sodium and its application in rice resistant to ACCase and ALS inhibitors. Background Technology

[0002] Quizalofop-P-ethyl is a systemic arylphenoxypropionic acid herbicide applied foliarly. It inhibits fatty acid synthesis by suppressing acetyl-CoA carboxylase. It exhibits high selectivity between monocot and dicot crops. Weed stems and leaves can absorb the herbicide within hours, and it is translocated upwards and downwards within the plant. Annual weeds are translocated throughout the plant within 24 hours of application and die within 10 days. Perennial weeds are rapidly translocated to the underground rhizomes after application, losing their regenerative capacity. Quizalofop-P-ethyl is highly effective against grassy weeds in broadleaf crop fields and is frequently used on broadleaf crops such as soybeans and peanuts. Its efficacy is more stable and less affected by factors such as temperature, humidity, and rainfall.

[0003] Bismuth subsalicylate is a pyrimidine salicylic acid herbicide. Its core mechanism of action is to inhibit the activity of acetolactate synthase (ALS) in plants. ALS is a key enzyme in the biosynthesis of branched-chain amino acids (valine, leucine, and isoleucine). Inhibition of this enzyme prevents the synthesis of branched-chain amino acids, thereby blocking protein synthesis and cell division in plants, ultimately causing weeds to stop growing and die. Bismuth subsalicylate can be rapidly absorbed through the stems and leaves of weeds and translocated throughout the entire plant via the vascular bundle system. This characteristic makes it highly effective against existing weeds (such as barnyard grass, bermudagrass, and duckweed), especially barnyard grass at the 3-6 leaf stage.

[0004] In rice paddies, it is common to see a variety of grasses, broadleaf weeds, and weedy rice coexisting. Using a single type of herbicide alone will not achieve the desired weed control effect due to its narrow spectrum of activity. Furthermore, long-term use of chemical herbicides can easily lead to herbicide resistance in weeds, causing growers to increase the dosage and resulting in environmental pollution. Using herbicide combinations, however, helps to broaden the weed control spectrum, killing multiple weeds at once, improving weed control efficacy, and reducing the dosage of active ingredients.

[0005] Because quizalofop-P-ethyl has phytotoxic effects on ordinary rice, there are currently no reports of using quizalofop-P-ethyl in combination with bispyribac-sodium in rice fields.

[0006] Researchers obtained rice mutant plants resistant to ACCase and ALS inhibitor herbicides (patent number: ZL201210037789.9) by EMS chemical mutagenesis, and further selected the polymer-resistant line Jietiandao 001. Its resistance originates from mutations in the ACCase gene (wild-type sequences as shown in SEQ ID NO: 1 and 3) and the ALS gene (wild-type sequences as shown in SEQ ID NO: 5 and 7). Specifically, point mutations occurred at positions 5372 and 5374 of the ACCase gene coding frame, changing from A to G and from A to T, respectively (as shown in SEQ ID NO: 2). This resulted in the amino acid at position 1791 of the protein encoded by this gene changing from asparagine to serine and the amino acid at position 1792 changing from isoleucine to leucine (as shown in SEQ ID NO: 4), thus acquiring resistance to ACCase inhibitor herbicides such as quizalofop-P-ethyl. A point mutation occurred at position 1644 of the ALS gene coding frame, changing from G to T (as shown in SEQ ID NO: 6). This resulted in the amino acid at position 621 of the protein encoded by this gene changing from tryptophan to cysteine ​​(as shown in SEQ ID NO: 8), thus acquiring resistance to ALS inhibitor herbicides such as methoxyfenozide and imidacloprid.

[0007] Since rice resistant to ACCase and ALS inhibitors exhibits good resistance to quizalofop-P-ethyl and bispyribac-sodium, it is possible to apply a combination of quizalofop-P-ethyl and bispyribac-sodium in the field when planting ACCase and ALS inhibitor-resistant rice. Summary of the Invention

[0008] This invention comprises a herbicidal composition of quizalofop-P-ethyl and bispyribac-sodium and its application. The herbicidal composition of this invention has a significant synergistic effect and is effective in managing weeds in rice fields.

[0009] A herbicide composition comprising quizalofop-P-ethyl and bispyribac-sodium, wherein the active ingredients comprise quizalofop-P-ethyl and bispyribac-sodium, and the mass ratio of quizalofop-P-ethyl to bispyribac-sodium is 1-10:1-15. Preferably, the mass ratio of quizalofop-P-ethyl to bispyribac-sodium is 1-6:1-10. More preferably, the mass ratio of quizalofop-P-ethyl to bispyribac-sodium is 4-6:8-10.

[0010] The herbicidal composition contains an active ingredient at a mass percentage of 1-20%. Preferably, the active ingredient mass percentage is 12-16%.

[0011] The herbicidal composition is mixed with common pesticide excipients to prepare any formulation suitable for use in agricultural production. Preferably, the formulation is a dispersible oil suspension.

[0012] The dispersible oil suspension also includes additives, such as solvents, emulsifiers, dispersants, wetting agents, disintegrants, thickeners, stabilizers, antifreeze agents, or carriers.

[0013] The emulsifiers include, but are not limited to, calcium dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate, alkyl sulfate, etc.; the dispersants include, but are not limited to, polycarboxylate, lignin sulfonate, alkylnaphthalene sulfonate, etc.; the thickeners include, but are not limited to, silica, fumed silica, magnesium aluminum silicate, etc.; the stabilizers include, but are not limited to, butylated hydroxyanisole, epichlorohydrin, etc.; the vegetable oils include, but are not limited to, epoxidized soybean oil, corn oil, paraffin oil, etc.; the carriers include, but are not limited to, kaolin, diatomaceous earth, light calcium carbonate, etc.

[0014] The herbicide composition is used to control annual weeds and weedy rice in the field of "Jietiandao 001" rice, which is resistant to ACCase and ALS inhibitors.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] 1. The combination of quizalofop-P-ethyl and bispyribac-sodium has an effective control effect on difficult-to-control annual grass weeds. Specifically, when the ratio of quizalofop-P-ethyl to bispyribac-sodium is (90+120) g ai / ha or (90+150) g ​​ai / ha, it has a good control effect on weeds such as barnyard grass, barnyard grass, rice barnyard grass, duckweed, and rice sedge in paddy fields.

[0017] 2. The herbicide composition of quizalofop-P-ethyl and bispyribac-sodium prepared in this invention has a field control efficacy of over 85% against weeds and rice in the ACCase and ALS inhibitor rice variety Jietiandao 001, which can effectively reduce weed damage and has a significant synergistic effect. Detailed Implementation

[0018] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the scope of the invention as detailed in the claims.

[0019] Example 1: Preparation of 12% quizalofop-p-ethyl dispersible oil suspension (i.e., 60 + 120 g ai / ha)

[0020] The following ingredients were added: 4% quizalofop-P-ethyl, 8% bispyribac-sodium, 10% calcium lignosulfonate, 5% sodium dodecylbenzenesulfonate, 3% magnesium aluminum silicate, 4% butylated hydroxyanisole, 0.5% kaolin, and 100% epoxidized soybean oil. A 12% (w / w) quizalofop-P-ethyl·bispyribac-sodium dispersible oil suspension was prepared using conventional methods.

[0021] Example 2: Preparation of 14% quizalofop-P-ethyl·bispyribac-sodium dispersible oil suspension (i.e., 60 + 150 g ai / ha)

[0022] The following ingredients were added: 4% quizalofop-P-ethyl, 10% bispyribac-sodium, 7% sodium dodecylbenzenesulfonate, 10% calcium lignosulfonate, 3% magnesium aluminum silicate, 4% butylated hydroxyanisole, 0.5% kaolin, and 100% epoxidized soybean oil. A 14% (w / w) quizalofop-P-ethyl·bispyribac-sodium dispersible oil suspension was prepared using conventional methods.

[0023] Example 3: Preparation of 14% quizalofop-P-ethyl·bispyribac-sodium dispersible oil suspension (i.e., 90 + 120 g ai / ha)

[0024] The following ingredients were added: 6% quizalofop-P-ethyl, 8% bispyribac-sodium, 10% fatty alcohol polyoxyethylene ether, 15% alkyl naphthalene sulfonate, 3% magnesium aluminum silicate, 4% epichlorohydrin, 0.5% kaolin, and 100% epoxidized soybean oil. A 14% (w / w) quizalofop-P-ethyl·bispyribac-sodium dispersible oil suspension was prepared using conventional methods.

[0025] Example 4: Preparation of 16% quizalofop-P-ethyl·bispyribac-sodium dispersible oil suspension (i.e., 90 + 150 g ai / ha)

[0026] The following ingredients were added: 6% quizalofop-P-ethyl, 10% bispyribac-sodium, 10% fatty alcohol polyoxyethylene ether, 15% alkyl naphthalene sulfonate, 3% magnesium aluminum silicate, 4% epichlorohydrin, 0.5% kaolin, and 100% epoxidized soybean oil. These were then formulated into a 16% (w / w) quizalofop-P-ethyl·bispyribac-sodium dispersible oil suspension using conventional methods.

[0027] Example 5: Indoor toxicological assays of quizalofop-P-ethyl and bispyribac-sodium against weeds such as rice, barnyard grass, rice barnyardgrass, duckweed, and rice sedge.

[0028] The tested weeds were: weedy rice, barnyard grass, rice barnyard grass, duckweed, and rice sedge. They were collected from rice fields and preserved in the laboratory weed seed bank for future use.

[0029] Test reagents: quizalofop-P-ethyl technical grade and bispyribac-sodium technical grade, which were purchased commercially.

[0030] Experimental Method: 15cm diameter plastic flowerpots were filled 4 / 5 with potting soil. Twenty mature and plump weed seeds were selected, soaked in a 200mg / L gibberellin solution for 24 hours, and then sown in the flowerpots. After sowing, the seeds were covered with 2cm of soil, moistened, and placed in a 28℃ greenhouse for conventional cultivation. When the weeds reached the 3-5 leaf stage, seedlings were thinned, leaving 10 plants of similar growth per pot. Foliar spraying was performed according to the experimental design. The experiment was replicated three times. After spraying, the weeds were dried at room temperature before being moved to the greenhouse for further cultivation. Symptoms of herbicide damage were observed and recorded. Twenty-one days after spraying, the above-ground parts of the weed plants were harvested, their fresh weight was measured, and the fresh weight inhibition rate was calculated.

[0031] Evaluation criteria for synergistic effects of herbicides: Calculate the fresh weight inhibition rate (E) and theoretical fresh weight inhibition rate (E0) of each herbicide in single-agent and binary combination treatments. The synergistic effect type of binary herbicide combination is evaluated as follows: when E-E0>10%, it indicates that the two herbicides in the combination have a synergistic effect; when E-E0<-10%, it indicates that the superior herbicide has an antagonistic effect; when 10%>E-E0>-10%, it indicates that the effect between the two herbicides is additive.

[0032] Fresh weight inhibition rate E = (Fresh weight of blank control group - Fresh weight of treatment group) / Fresh weight of blank control group × 100%

[0033] The theoretical fresh weight inhibition rate E0 = X + Y - XY / 100, where X is the fresh weight inhibition rate of quizalofop-P-ethyl and Y is the fresh weight inhibition rate of bispyribac-sodium.

[0034] Test Result Analysis:

[0035] Table 1 shows that when quizalofop-P-ethyl is used alone, it has good control efficacy against rice weeds, barnyard grass, and *Leymus chinensis*, with a control efficacy of over 84% at a dosage of 90 g ai / ha. However, its control efficacy against duckweed and *Cyperus difformis* is very low, with a control efficacy of less than 1% at a dosage of 90 g ai / ha, similar to the herbicidal spectrum of quizalofop-P-ethyl. When bispyribac-sodium is used alone, its control efficacy against rice weeds is low, with a control efficacy of only 44.22% at a dosage of 150 g ai / ha. However, it has good control efficacy against barnyard grass and *Leymus chinensis*, with a control efficacy of over 83% at a dosage of 150 g ai / ha, especially reaching 90% against *Leymus chinensis*. When the two are used in combination, the control effect on weeds such as rice, barnyard grass, rice barnyard grass, duckweed, and rice sedge is improved. At a dosage of (90+150) g ​​ai / ha, the fresh weight inhibition rate of rice, barnyard grass, and rice barnyard grass reaches more than 98%, and the fresh weight inhibition rate of duckweed and rice sedge reaches more than 91%.

[0036] Tables 2 and 3 show that by comparing the fresh weight inhibition rate and theoretical fresh weight inhibition rate of quizalofop-P-ethyl and bispyribac-sodium when used in combination, different synergistic effects were observed between the quizalofop-P-ethyl and bispyribac-sodium combinations against weeds such as rice, barnyard grass, *Leymus chinensis*, duckweed, and *Cyperus difformis*. Specifically, when the ratio of quizalofop-P-ethyl to bispyribac-sodium was (90+120) g ai / ha and (90+150) g ​​ai / ha, the combination showed a significant synergistic effect against rice, barnyard grass, and *Leymus chinensis*, and effectively controlled difficult-to-control grassy weeds. The four quizalofop-P-ethyl and bispyribac-sodium combinations showed a synergistic effect against duckweed and *Cyperus difformis*, and compared with the effect of bispyribac-sodium alone, there was no reduction in efficacy.

[0037] Table 1. Fresh weight inhibition rate (%) of different ratios of quizalofop-p-ethyl and bispyribac-sodium combination on annual weeds.

[0038]

[0039] Note: All values ​​above are actual measured values.

[0040] Table 2. Theoretical fresh weight inhibition rate (%) of different compound treatments on annual weeds

[0041]

[0042] Table 3 Combined effects of different compound treatments on annual weeds (E-E0)

[0043]

[0044] Example 6: Efficacy determination of different combinations of quizalofop-P-ethyl and bispyribac-sodium against weeds in the field of rice variety Jietiandao 001, which has both anti-ACCase and ALS inhibitors.

[0045] Implementation agents: the formulations of Examples 1-4 prepared in this invention; 6% quizalofop-P-ethyl and 10% bispyribac-sodium, commercially available.

[0046] Experimental crop field: Jietian Rice 001 field.

[0047] Grasses: weeds, barnyard grass, rice grass, duckweed, and rice sedge.

[0048] Application method: Eight pesticide treatments and one water control were set up, with each treatment replicated three times; each treatment covered an area of ​​20m². 2 The plots were randomly arranged. Foliar spraying was performed using a backpack sprayer. Twenty-one days after application, the weed fresh weight control efficacy, the fresh weight inhibition rate of Jietiandao 001, and the extent of herbicide damage were assessed.

[0049] Fresh weight inhibition rate = (Fresh weight of blank control group - Fresh weight of treatment group) / Fresh weight of blank control group × 100%

[0050] Test Result Analysis:

[0051] As shown in Table 4, the herbicide composition of the present invention can significantly improve herbicidal activity and reduce weed damage. 21 days after application, the fresh weight inhibition rate of each compound herbicide treatment on Jietian Rice 001 was <3%, indicating that it did not affect the growth of Jietian Rice 001, meaning that each compound herbicide is safe for the growth of Jietian Rice 001.

[0052] Table 4. Fresh weight control efficacy of different herbicides 20 days after treatment.

[0053]

[0054] The above are merely preferred embodiments of the present invention. For those skilled in the art, appropriate modifications can be made without departing from the materials described in the present invention, and these modifications are also within the protection scope of the present invention.

Claims

1. A herbicidal composition comprising quizalofop-P-ethyl and bispyribac-sodium, characterized in that, The mass ratio of quizalofop-P-ethyl to bispyribac-sodium is 1-10:1-15.

2. The herbicidal composition according to claim 1, characterized in that, The preferred mass ratio of quizalofop-P-ethyl to bispyribac-sodium is 1-6:1-10.

3. The herbicidal composition according to claim 2, characterized in that, The preferred mass ratio of quizalofop-P-ethyl to bispyribac-sodium is 4-6:8-10.

4. The herbicidal composition according to any one of claims 1-3, characterized in that, The mass percentage of quizalofop-P-ethyl and bispyribac-sodium is 1-20%.

5. The herbicidal composition according to claim 4, characterized in that, The preferred percentage content of the active ingredient is 12-16%.

6. The herbicidal composition according to claim 1, characterized in that, The herbicidal composition also includes adjuvants, said adjuvants being at least one of solvents, emulsifiers, dispersants, wetting agents, disintegrants, thickeners, stabilizers, antifreeze agents, or carriers.

7. As described in claim 6, characterized in that, The emulsifiers include, but are not limited to, calcium dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate, alkyl sulfate, etc.; the dispersants include, but are not limited to, polycarboxylate, lignin sulfonate, alkylnaphthalene sulfonate, etc.; the thickeners include, but are not limited to, silica, fumed silica, magnesium aluminum silicate, etc.; the stabilizers include, but are not limited to, butylated hydroxyanisole, epichlorohydrin, etc.; the vegetable oils include, but are not limited to, epoxidized soybean oil, corn oil, paraffin oil, etc.; the carriers include, but are not limited to, kaolin, diatomaceous earth, light calcium carbonate, etc.

8. The use of the herbicidal composition according to claim 1 for controlling annual weeds and weedy rice in non-GMO ACCase- and ALS-inhibiting rice "Jietiandao 001" fields.

9. The herbicidal composition according to claim 8, characterized in that, The ACCase protein of Jietian Rice 001 has a mutation in which amino acid 1791 is changed from asparagine to serine and amino acid 1792 is changed from isoleucine to leucine.

10. The herbicidal composition according to claim 8, characterized in that, The ALS protein of Jietian Rice 001 has a mutation at amino acid position 621, where tryptophan is changed to cysteine.

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