Anti-amide herbicide benzyl pyrimidine compound suitable for seed coating and application thereof

Abstract

The invention discloses an anti-amide herbicide benzyl pyrimidine compound suitable for seed coating and application of the anti-amide herbicide benzyl pyrimidine compound. The invention relates to a benzyl pyrimidine compound, in particular to 4, 6-dichloro-5-benzyl-2-methylpyrimidine, C11H8Cl2N2, and the molecular weight of the benzyl pyrimidine compound is 239.10. The benzyl pyrimidine compound is applied to preparation of a seed coating agent for resisting amide herbicides. The invention fully focuses on how mechanically sown and directly sown seeds in the middle and lower reaches of Yangtze River to resist phytotoxicity of herbicides in a field stress environment, and designs a novel amide herbicide resistant compound 4, 6-dichloro-5-benzyl-2-methylpyrimidine suitable for seed coating in a targeted manner through an artificial synthesis mode. The compound is subjected to nanocrystallization grinding to prepare a seed coating agent, finally, through a coating mode, the seeds achieve the remarkable herbicide phytotoxicity resistance, the emergence rate and the seedling rate of the seeds are increased, and the method is simple, clear, easy to master and high in operability.

Description

Technical Field

[0001] The invention belongs to the field of small molecule compounds and relates to an amide herbicide-resistant benzyl pyrimidine compound suitable for seed coating and application thereof. Background Art

[0002] Rice and wheat are the main crop rotation patterns for grain production in the middle and lower reaches of the Yangtze River. Due to the production problems of tight rotation and short cycle in rice and wheat production, coupled with factors such as returning straw to the field and insufficient labor, various simple rice and wheat cultivation methods such as machine sowing and direct seeding that save labor and cost have been widely accepted and applied. However, the problems brought about by them, such as many weeds and severe weed damage, have become the pain points of agricultural production, seriously affecting the economic benefits of farmers and food safety production. In production, the use of a large number of amide herbicides, especially pretilachlor and butachlor, for weed control before seed germination and in the seedling stage is currently the most economical and effective way to solve the weed problem. However, there are still the following key problems that need to be solved in the large-scale production application of herbicides: (1) Excessive use of herbicides inhibits the normal growth of crops. At present, although amide herbicides such as pretilachlor and butachlor have the advantages of a wide spectrum of weed control and outstanding effects, they are widely used in rice and wheat weed control. However, this type of herbicide has a short duration of efficacy and high environmental residues. In production, in order to achieve effective weed control, there are characteristics and disadvantages such as multiple applications and large dosages. Excessive use of herbicides can easily cause phytotoxicity and environmental pollution, resulting in growth inhibition of crops, especially in the seedling stage, yellowing and stunting of seedlings, and large-scale yield reduction. How to overcome herbicide toxicity and achieve efficient weed control without affecting the normal growth of crops is a key issue that needs to be solved; (2) There is a lack of amide-resistant herbicide compounds that can be made into seed coating agents and are suitable for seed coating. Antiamide-resistant herbicide compounds are a special class of compounds that selectively protect crops from herbicide toxicity without affecting the activity of herbicides on target weeds. Polymerizing amide-resistant herbicide compounds into slow-release seed coating agents and achieving seedling protection and long-term weed control through slow release after sowing is a hot topic in the research and development of new and efficient seed coating agents. However, the current amide-resistant herbicide compounds are relatively simple in terms of molecular configuration and resistance mode, and there is a phenomenon of inhibiting root growth after coating. Therefore, the development of amide-resistant herbicide compounds that do not inhibit root growth is the key to creating new slow-release coating agents. In response to the above problems, the development of new amide-resistant herbicide compounds with low environmental risks and suitable for coating provides a new and effective way to solve the problem of pesticide damage and selectivity problems in the process of weed control in light cultivation.

[0003] Seed coating agents are compositions containing one or more active ingredients, and play an important role in seed disinfection, slow-release fertilizers, pest control, improving crop resistance, and reducing environmental pollution. Seed coating agents are advanced preparations processed using high-tech nanotechnology. They can evenly adhere to the outer surface of seeds to form a protective film, with the drug power concentrated around the seeds. The drug effect is slowly released, and it is not easily affected by the external environment, making it difficult for surrounding pests to survive. It can achieve a good prevention and control effect without other drugs, with high utilization efficiency and extended drug efficacy. After the seeds are coated, the surface is smooth, which is conducive to mechanical sowing. At the same time, the coating agent can adjust the size of seeds from different sources, which can improve the efficiency and quality of mechanical sowing.

[0004] After checking, it is found that there are currently no similar patents on the synthesis of new compounds resistant to amide herbicides such as pretilachlor and butachlor, and their development into nano-type seed coating agents. In particular, there is a lack of corresponding technologies and methods for how to enhance the herbicide resistance of seeds, promote seed germination, and increase the emergence rate in fields with complex environments such as machine sowing and straight rice. Summary of the invention

[0005] The object of the present invention is to address the above-mentioned deficiencies in the prior art and to provide a benzyl pyrimidine compound.

[0006] Another object of the present invention is to provide the application of the benzyl pyrimidine compound.

[0007] Another object of the present invention is to provide a rice seed coating agent.

[0008] The fourth object of the present invention is to provide the application of the rice seed coating agent.

[0009] The purpose of the present invention can be achieved through the following technical solutions:

[0010] A benzyl pyrimidine compound, the structure of which is shown below:

[0011]

[0012] 4,6-Dichloro-5-benzyl-2-methylpyrimidine, C 11 H8Cl2N2, molecular weight 239.10.

[0013] Application of the benzyl pyrimidine compound in the preparation of a seed coating agent.

[0014] The benzyl pyrimidine compound is used in preparing a seed coating agent resistant to amide herbicides.

[0015] A rice seed coating agent is composed of the benzyl pyrimidine compound, a film former, a wetting agent, a dispersant, a thickener and purified water, wherein the film former is polyvinyl alcohol, the wetting agent is sodium lauryl sulfate, the dispersant is sodium methylene dinaphthalene sulfonate, and the thickener is xanthan gum.

[0016] As a preferred embodiment of the present invention, the concentration of the benzyl pyrimidine compound in the rice seed coating agent is 6-8g / 100ml, the concentration of the film-forming agent in the rice seed coating agent is 2-3g / 100ml, the concentration of the wetting agent in the rice seed coating agent is 1-1.5g / 100ml, the concentration of the dispersant in the rice seed coating agent is 1-3g / 100ml, and the concentration of the thickener in the rice seed coating agent is 0.5-1g / 100ml.

[0017] As a preferred embodiment of the present invention, the rice seed coating agent is prepared by mixing the benzyl pyrimidine compound, film former, wetting agent, dispersant, thickener and purified water, and then grinding the mixture repeatedly to finally form a 6-8% concentration benzyl pyrimidine compound nano-type stable suspension.

[0018] As a preferred embodiment of the present invention, the benzyl pyrimidine compound, film-forming agent, wetting agent, dispersant, thickener and purified water are mixed and then repeatedly circulated and ground to finally form a 6-8% concentration of benzyl pyrimidine compound nano-type stable suspension, which is the rice seed coating agent.

[0019] As a preferred embodiment of the present invention, the benzyl pyrimidine compound, film-forming agent, wetting agent, dispersant, thickener and purified water are mixed, and are repeatedly cyclically ground for 100-120 minutes by a grinder, a chiller and a nano sand mill in sequence, and the indoor ambient temperature of all machines is maintained at 20-25° C., and finally a nano-type stable suspension of the benzyl pyrimidine compound with a concentration of 6-8% is formed.

[0020] The rice seed coating agent of the invention is used in protecting crop seeds from the damage of amide herbicides.

[0021] A method for protecting crops from amide herbicide damage and enhancing the tolerance of protected crops to amide herbicides, comprising coating rice seeds with a germination rate of more than 90% using the rice seed coating agent, wherein the volume mass ratio of the rice seed coating agent to the rice seeds is 1:30-50 (mL:g), and the coating is followed by drying for standby use.

[0022] As a preferred embodiment of the present invention, the volume mass ratio of the rice seed coating agent to the rice seeds is 1:30-40 (mL:g).

[0023] Beneficial effects:

[0024] The present invention fully focuses on how to resist herbicide damage in the adverse field environment of machine-sown and direct-seeded seeds in the middle and lower reaches of the Yangtze River. A new amide herbicide-resistant compound 4,6-dichloro-5-benzyl-2-methylpyrimidine suitable for seed coating is designed by artificial synthesis, and the compound is nano-ground to make a seed coating agent. Finally, by coating, the seeds can achieve significant resistance to herbicide damage, improve seed germination rate and seedling rate, and the method is simple, easy to master, and highly operable. The present invention has the following advantages:

[0025] (1) Create compounds that are highly effective, low toxic, and broad-spectrum safe and resistant to amide herbicides.

[0026] (2) The developed safe and highly effective herbicide-resistant compounds can be used in seed formulations to protect crops from herbicide damage and enhance the tolerance of protected crops to specific herbicides, thereby increasing crop safety and improving weed control effects.

[0027] (3) The benzyl pyrimidine compound can be made into a nano-type rice seed coating agent. A relatively low dosage can solve the problem of low germination rate and low emergence rate of seeds caused by herbicide damage under light and simple cultivation, thereby increasing the seed germination rate and seedling rate, reducing the amount of seeds used, and saving costs.

[0028] (4) The nano rice seed coating agent is easy to use. It can be used immediately after packaging, or it can be coated in advance and stored for later use without affecting the germination potential and germination rate of seeds in the later stage.

[0029] (5) The benzyl pyrimidine compounds can be successfully synthesized in high yield via an efficient and economical “one-pot” method. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Electron micrograph of 4,6-dichloro-5-benzyl-2-methylpyrimidine

[0031] Figure 2 4,6-Dichloro-5-benzyl-2-methylpyrimidine H spectrum

[0032] Figure 3 4,6-Dichloro-5-benzyl-2-methylpyrimidine C spectrum

[0033] Figure 4 Germination rate of different treatments

[0034] Figure 5 Comparison of germination rates under different treatments

[0035] Figure 6 Plant height 12d and 20d after germination

[0036] Figure 7 Dry matter weight per plant at seedling stage DETAILED DESCRIPTION

[0037] Example 1 Synthesis of 4,6-dichloro-5-benzyl-2-methylpyrimidine

[0038] Sodium metal (3.04 g, 0.13 mol) and anhydrous ethanol (200 mL) were used to prepare sodium ethoxide solution, and acetamidine hydrochloride (6.619 g, 0.07 mol) and diethyl benzylmalonate (17.520 g, 0.07 mol) were added to reflux at 90°C for 4 h; after the reaction was completed and cooled to room temperature, the solvent was distilled off under reduced pressure, the crude sodium salt was added to 1 L of distilled water to dissolve, and concentrated hydrochloric acid (10 mL) was added to the solution to precipitate the intermediate product. After separation of the precipitate, it was washed with distilled water and dried under vacuum at 80°C for 6 h. Phosphorus oxychloride (80 mL) was then added, heated at 100°C for 48 h, the excess phosphorus oxychloride was treated with 2 L of ice water, and then extracted with dichloromethane (30 mL × 3), the organic phases were combined, dried with anhydrous MgSO4, filtered, and finally distilled under reduced pressure. The crude product was purified by column chromatography (V 乙酸乙酯 :V 石油醚 =1:2) to give the final product 4,6-dichloro-5-benzyl-2-methylpyrimidine (9.707 g, 58%). 1 H NMR (400MHz, DMSO-d6) δ7.31(t,J=7.4Hz,2H),7.23(dd,J=13.9,6.5Hz,1H),7.17(d,J=7.4Hz,2H),4.21(s,2H),2.60(s,3H). 13 C NMR (100MHz, DMSO-d6) δ166.63(s), 161.48(s), 136.52(s), 128.83(s), 128.12(s), 127.93(s), 126.90(s), 34.74(s), 24.89(s).

[0039] By nuclear magnetic resonance spectroscopy ( 1 H NMR, 13 C NMR) was used to verify the structure of 4,6-dichloro-5-benzyl-2-methylpyrimidine. Figure 2 It can be seen from the hydrogen spectrum that the single signal peak of the compound at 2.60ppm is attributed to the three hydrogens on the methyl group of the compound, the signal peak at 4.21ppm is attributed to the two hydrogens on the benzyl methylene group of the compound, the signal peak at 7.16-7.18ppm is attributed to the two hydrogens at the ortho position on the benzene ring, the signal peak at 7.22-7.25ppm is attributed to the one hydrogen at the para position on the benzene ring, and the signal peak at 7.29-7.33ppm is attributed to the two hydrogens at the meta position on the benzene ring; Figure 3It can be seen from the carbon spectrum that the appearance of characteristic peaks of the compound at 166.63, 161.48, 136.52, 128.83, 128.12, 127.93, 126.90, 34.74, and 24.89 ppm indicates that the compound contains a benzene ring and a pyrimidine skeleton.

[0040] Example 2

[0041] (1) Preparation of seed coating solution

[0042] Add auxiliary agents, including film-forming agent: polyvinyl alcohol (2.00 g, purity Mw 9000-10000, 80% hydrolysis, produced by Shanghai McLean Biochemical Technology Co., Ltd.); wetting agent: sodium dodecyl sulfate (1.00-1.50 g, purity 92.5-100%, produced by Shanghai McLean Biochemical Technology Co., Ltd.); dispersant: sodium methylene dinaphthalene sulfonate (1.50 g, purity 95%, produced by Shanghai McLean Biochemical Technology Co., Ltd.); thickener: xanthan gum (0.72 g, USP grade, produced by Shanghai McLean Biochemical Technology Co., Ltd.), and "Wahaha" brand purified water is added to 100 ml. The powder was repeatedly ground in an electric lifting blue grinder (model: LZLM-3L, produced by Changzhou Lezu Machinery Technology Co., Ltd.), a chiller (model: ZP, produced by Changzhou Lezu Machinery Technology Co., Ltd.), and a nano sand mill (model: LZNSM-0.3L, produced by Changzhou Lezu Machinery Technology Co., Ltd.) for 150 minutes. The indoor ambient temperature of all machines was maintained at 25°C, and a 6% concentration of a fluoropyrimidine compound nano-type stable suspension was finally formed as a coating liquid. The same method was used to prepare a coating liquid without 4,6-dichloro-5-benzyl-2-methylpyrimidine and the other components were the same as the control for subsequent experiments.

[0043] (2) Seed coating

[0044] In 2023, at the Wanfu Experimental Base of the Lixiahe Agricultural Science Institute in Yangzhou City, Jiangsu Province, a 50-acre wheat straw return to the field machine-sown rice variety, Yangxiangyu 200, was set up.

[0045] Select seeds with a germination rate of more than 90%, and coat them evenly at a drug-seed ratio of 1:30 (mL:g).

[0046] (3) Field sowing

[0047] The coated seeds are sown according to the normal field seed rate, 15 catties per mu.

[0048] (4) Field management

[0049] After sowing, the field management is the same as that of normal fields. The herbicide used is pretilachlor. The application method is a one-time machine or manual spraying after seed sowing. The amount per mu is 350g / mu, which is 5 times the normal field amount. The amount and time are the same for indoor and field use.

[0050] ① Improve the germination rate of seeds

[0051] After 5 days of germination, the germination rate of the benzyl pyrimidine compound (M15) treated as a seed coating agent was higher than that of the control in both the field and indoors, reaching a significant difference ( Figure 4 ).

[0052] ② Improve the seedling rate

[0053] After a complete germination cycle, the investigation showed that after the 12th and 20th days of seed germination, the germination had basically stabilized, and the seedling rate in the field and indoor pots was higher than the control ( Figure 5 ).

[0054] ③Increase plant height

[0055] like Figure 6 As shown, the investigation showed that after the 12th and 20th days of seed germination, the plant height after M15 treatment as a seed coating agent was higher than that of the control, and the difference between the two was significant, indicating that the seed coating agent can promote the growth of plant height.

[0056] ④Significantly reduce the incidence of yellow and dead seedlings

[0057] The impact of herbicide damage on seeds and seedlings can easily lead to yellowing and dead seedlings, resulting in large-scale yield reduction. As shown in Table 1, compared with the untreated control, the incidence of yellowing seedlings and dead seedlings of M15 treated as a seed dressing agent decreased by 81.54% and 93.58% respectively, and the incidence of sheath blight in the later stage decreased by 67.70%.

[0058] Table 1 Effect of M1 coating on yellow seedlings, stunted seedlings and sheath blight

[0059]

[0060] The data are mean values, and different lowercase letters indicate significant differences among treatments at the 0.05 level.

[0061] ⑤ Promote the accumulation of dry matter in the seedling stage

[0062] Depend on Figure 7 It can be seen that the dry matter content of the materials treated with M15 as a seed dressing agent exceeded that of the control and reached a significant level, indicating that the substance has the function of promoting material transport.

[0063] ⑨Significant increase in production

[0064] As can be seen from Table 2, the number of effective ears per mu of rice treated with the above technical formula increased by 5.50% compared with the untreated control, the number of grains per ear increased by 4.06%, the fruit setting rate and 1000-grain weight had no significant differences, and the theoretical yield and actual yield increased by 9.12% and 10.99% respectively (see Table 2).

[0065] Table 2 Effect of M15 coating on rice yield

[0066]

[0067] The data are mean values, and different lowercase letters indicate significant differences among treatments at the 0.05 level.

Claims

1. A benzyl pyrimidine compound, the structure of which is shown below:

2. Use of the benzyl pyrimidine compound according to claim 1 in the preparation of a seed coating agent.

3. Use of the benzyl pyrimidine compound according to claim 1 in the preparation of a seed coating agent resistant to amide herbicides.

4. A rice seed coating agent, characterized in that: The invention is composed of the benzyl pyrimidine compound according to claim 1, a film-forming agent, a wetting agent, a dispersant, a thickener and purified water, wherein the film-forming agent is polyvinyl alcohol, the wetting agent is sodium lauryl sulfate, the dispersant is sodium methylene dinaphthalene sulfonate, and the thickener is xanthan gum.

5. The rice seed coating agent according to claim 4, characterized in that: The concentration of the benzyl pyrimidine compound in the rice seed coating agent is 6-8g / 100ml, the concentration of the film-forming agent in the rice seed coating agent is 2-3g / 100ml, the concentration of the wetting agent in the rice seed coating agent is 1-1.5g / 100ml, the concentration of the dispersant in the rice seed coating agent is 1-3g / 100ml, and the concentration of the thickener in the rice seed coating agent is 0.5-1g / 100ml.

6. The rice seed coating agent according to claim 4, characterized in that: The rice seed coating agent is prepared by mixing the benzyl pyrimidine compound, film-forming agent, wetting agent, dispersant, thickener and purified water, and then grinding them repeatedly to finally form a 6-8% concentration benzyl pyrimidine compound nano-type stable suspension.

7. The method for preparing the rice seed coating agent according to any one of claims 4 to 6, characterized in that: The benzyl pyrimidine compound, film-forming agent, wetting agent, dispersant, thickener and purified water are mixed and then repeatedly circulated and ground to finally form a 6-8% concentration benzyl pyrimidine compound nano-type stable suspension, which is the rice seed coating agent.

8. The preparation method according to claim 7, characterized in that: The benzyl pyrimidine compound, film-forming agent, wetting agent, dispersant, thickener and purified water are mixed, and then repeatedly circulated and ground for 100-120 minutes by a grinder, a water chiller and a nano sand mill in sequence. The indoor ambient temperature of all machines is maintained at 20-25° C., and finally a nano-type stable suspension of the benzyl pyrimidine compound with a concentration of 6-8% is formed.

9. Use of the rice seed coating agent according to any one of claims 4 to 6 for protecting crop seeds from damage by amide herbicides.

10. A method for protecting crops from toxicity of amide herbicides and enhancing tolerance of protected crops to amide herbicides, characterized in that: The rice seed coating agent according to any one of claims 4 to 6 is used to coat rice seeds with a germination rate of more than 90%, wherein the volume mass ratio of the rice seed coating agent to the rice seeds is 1:30 to 50 (mL:g), and the rice seeds are dried after coating for later use.

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