An anti-plant virus pesticide composition containing benzylthio-condensed oxathiine

Abstract

The present application provides an anti-plant virus pesticide composition containing fluazuron. The pesticide composition is made of raw materials including fluazuron and amino-oligosaccharide. The mass ratio of fluazuron and amino-oligosaccharide is 100:1-1:100. Compared with fluazuron single agent, the composition of the present application can significantly improve the use effect of fluazuron, and can greatly reduce the dosage under the same prevention effect. Fluazuron and amino-oligosaccharide have a synergistic effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of agricultural technology, and particularly relates to an anti-plant virus pesticide composition containing fluorobenzyl thio-condensed induc ether. BACKGROUND

[0002] Vanillin, also known as vanillin, CAS No. 121-33-5, chemical name 3-methoxy-4-hydroxybenzaldehyde, is an organic substance extracted from vanilla beans. At present, it is mainly synthesized by artificial synthesis and is an important chemical raw material, which is applied in the fields of food, agriculture, medicine and the like.

[0003] Fluorobenzyl thio-condensed induc ether is a newly developed drug based on the structure of vanillin. Its structure is disclosed for the first time in Chinese Patent CN109134327A, and it has a certain growth-promoting effect on crops such as corn, cucumber, rice, wheat and tomato. Its synthesis method is disclosed in Chinese Patent CN106467478A. At the same time, Chinese Patent CN112244011A discloses a method for preparing a suspension thereof, and indicates that the compound has an anti-plant virus effect.

[0004]

[0005] Plant virus is also known as plant "cancer", which is a relatively difficult problem in the field of plant protection. Although Chinese Patent CN106467478A discloses that some compounds have better anti-disease effect than Ningnanmycin, which is a widely used anti-virus agent on the market, but seeking a method to improve the efficacy and reduce the dosage is still the direction that the technical personnel need to research. SUMMARY

[0006] The present application aims to provide an anti-plant virus pesticide composition. The composition contains fluorobenzyl thio-condensed induc ether. Compared with fluorobenzyl thio-condensed induc ether single agent, the composition can significantly improve the use effect of fluorobenzyl thio-condensed induc ether, can greatly reduce the dosage under the same prevention effect, and has a synergistic effect.

[0007] The anti-plant virus pesticide composition provided by the present application is made of raw materials including the following components:

[0008] Fluorobenzyl thio-condensed induc ether and amino oligosaccharide.

[0009] The mass ratio of flubendiamide and amino oligosaccharide in the composition can be 100:1-1:100, specifically, the mass ratio of flubendiamide and amino oligosaccharide can be 50:1-1:100, 50:1-1:1, 10:1-1:10, 9:1-1:9, more specifically, the mass ratio of flubendiamide and amino oligosaccharide can be 50:1, 10:1, 9:1, 4:1, 3:2, 5:1, 5:2, 1:1, 2:3, 1:4, 1:9, 1:10, 1:50, 1:100.

[0010] The plant virus can be tobacco mosaic virus, potato Y virus, and cucumber mosaic virus.

[0011] In addition to flubendiamide and amino oligosaccharide, the above-mentioned pesticide composition can be processed into various dosage forms by adding an auxiliary agent (such as a surfactant, a carrier).

[0012] The dosage form can be an aqueous solution, an aqueous emulsion, a wettable powder, a soluble powder, a soluble granule, a water-dispersible granule, a suspension, a soluble solution, an oil suspension, a tablet, or an effervescent granule.

[0013] The suitable concentration of the active ingredient in the dosage form can be 0.1-60wt%, specifically, 0.5-15wt%, 0.6-5.1wt%, 2-52wt%, 11-21wt%.

[0014] The present application has the following advantages by compounding amino oligosaccharide and flubendiamide:

[0015] 1. The compounding components have obvious synergistic effect compared with single agents, which can reduce the use amount of pesticides while ensuring the control effect.

[0016] 2. Preliminary studies have shown that flubendiamide improves the plant's ability to resist viruses in a hormone-dependent manner, and neither flubendiamide nor amino oligosaccharide directly targets viruses, thereby avoiding the emergence of resistance and being more in line with the requirements of ecological prevention and control. DETAILED DESCRIPTION

[0017] The present application will be further described in detail below in conjunction with specific embodiments. The examples provided below are only intended to illustrate the present application, and are not intended to limit the scope of the present application. The examples provided below can serve as a guide for further improvement by those skilled in the art, and do not in any way constitute a limitation on the present application.

[0018] In the following examples, the experimental methods are conventional methods, and are performed according to the techniques or conditions described in the literature in the art or according to the product instructions, unless otherwise specified. The materials, reagents, etc. used in the following examples can be obtained from commercial channels, unless otherwise specified.

[0019] Example 1, formula screening experiment

[0020] The experiment was carried out according to the method of NY / T 1156.6-2006. The half-leaf dry spot method was used to screen the synergistic formula with heart leaf tobacco as the experimental material.

[0021] The TMV virus solution was provided by the Fine Chemical Research Center of Guizhou University and was stored in a freezer.

[0022] Experimental reagents: 95% flubendiamide technical material (CN109134327A, provided by Hebi Quantong Biological Technology Co., Ltd.), 85% amino oligosaccharide mother drug (purchased on the market)

[0023] Test method: Select heart leaf tobacco with consistent growth at the 5-6 leaf stage, trim the plant body, remove old leaves, and retain 3 healthy leaves. Use a brush to dip different treatments with different reagents on the left half leaf, and the right half leaf is coated with the corresponding concentration of solvent as a control. After 24 hours, evenly sprinkle the whole leaf with corundum, dilute the TMV virus solution 500 times, and use a brush to dip the virus solution for whole leaf virus inoculation. After 30 minutes, rinse with water, and when the disease spot is obvious (usually 72h), investigate the left and right leaf spots, and record the number of disease spots. Calculate the inhibition rate according to the following formula:

[0024]

[0025] Among them, the average dry spot number is the average of three replicates per group.

[0026] Bioassay results:

[0027] Table 1, preliminary activity test results

[0028]

[0029] From the above preliminary screening activity of amino oligosaccharide, it can be seen that the addition of amino oligosaccharide can improve the protection effect of flubendiamide on tobacco mosaic virus.

[0030] Example 2, synergistic screening experiment

[0031] The experiment was carried out by the half-leaf dry spot method, and the specific conditions were referred to Example 1. The difference is that this experiment increases the sample size, i.e. three tobacco plants are treated for each treatment, and each tobacco plant retains 3 leaves. Use DPS for data processing, and use Sun Yunpei method to evaluate the synergistic effect.

[0032] The bioassay results are shown in Table 2.

[0033] Table 2, synergistic experiment results

[0034]

[0035] From the above data, it can be seen that the addition of amino oligosaccharide has a promoting effect on the control effect of fluorobenzyl thioindoxyl on tobacco mosaic virus. When fluorobenzyl thioindoxyl and amino oligosaccharide are compounded at a ratio of 10:1, 5:1 and 5:2 respectively, the co-toxicity coefficients are all greater than 120, indicating that amino oligosaccharide has a synergistic effect on fluorobenzyl thioindoxyl.

[0036] Example 3, synergistic screening experiment

[0037] According to the above experimental results, the compounding mechanism of fluorobenzyl thioindoxyl and amino oligosaccharide is explored.

[0038] The experiment was carried out according to "Pesticide Indoor Biological Assay Experiment Standard NY / T1156.6-2006". The whole leaf spot method was used, and heart leaf tobacco was used as the experimental material to carry out synergistic formula screening work.

[0039] TMV virus liquid was provided by Guizhou University Fine Chemical Research Center, and the virus liquid was stored in a freezer.

[0040] Experimental reagents: 95% fluorobenzyl thioindoxyl technical material (CN109134327A, provided by Hebi Quantong Biological Technology Co., Ltd.), 85% amino oligosaccharide mother drug (marketed)

[0041] Test method: Select heart leaf tobacco with consistent growth at 5-6 leaf stage, trim the plant body, remove old leaves, and reserve 3 healthy leaves. Dip the drug into the paintbrush and apply it to each treated leaf. The control group is coated with the corresponding concentration of solvent. After 24 hours, evenly sprinkle the whole leaf with emery, dilute the TMV virus liquid 500 times, and use the pen to dip the virus liquid for whole leaf virus inoculation. Thirty minutes later, rinse with water, and when the disease spot is obvious (usually 72h), record the number of disease spots on the left and right leaves, and calculate the inhibition rate according to the following formula:

[0042]

[0043] Among them, the average number of spots is the average number of three repeats in each group.

[0044] The biological assay results are shown in Table 3.

[0045] Table 3, synergistic experiment results

[0046]

[0047]

[0048] From the above results, it can be seen that the compatibility of fluazuron and amino-oligosaccharide shows a certain synergistic effect on TMV. When the ratio of fluazuron to amino-oligosaccharide is 100:1, the CTC value is between 80-120, which is additive effect. When the ratio of fluazuron to amino-oligosaccharide is 1:100, the CTC value is 221.58, which is synergistic effect. However, the control effect of the ratio of fluazuron to amino-oligosaccharide at 1:1 is much higher than that of the ratio of fluazuron to amino-oligosaccharide at 1:100. Combined with the previous experiment, it can be seen that in the process of preventing and controlling viral diseases by fluazuron and amino-oligosaccharide, fluazuron is the main effective factor.

[0049] Example 4, synergistic screening experiment

[0050] The method in Example 3 was used to adjust the compatibility design of the pesticides for the experiment.

[0051] The bioassay results are shown in Table 4.

[0052] Table 4, synergistic experiment results

[0053]

[0054] From the above results, it can be seen that when the ratio of fluazuron to amino-oligosaccharide is 50:1, the CTC is 122.57, showing synergistic effect. When the ratio of fluazuron to amino-oligosaccharide is 1:10 and 1:50, the CTC is 134.56 and 140.38 respectively, showing synergistic effect.

[0055] From the above results, it can be seen that fluazuron and amino-oligosaccharide show good synergistic effect in the range of 50:1 to 1:100.

[0056] Example 5, anti-potato Y virus experiment

[0057] The experiment was carried out according to the "Pesticide Indoor Biological Assay Experiment Standard NY / T1156.6-2006". The semi-leaf spot method was used, and amaranth was used as the experimental material to carry out synergistic formula screening work.

[0058] The PVY virus solution was provided by the Fine Chemical Research Center of Guizhou University.

[0059] Experimental pesticides: 95% fluazuron technical (CN109134327A, provided by Hebi Quantong Biological Technology Co., Ltd.), 85% amino-oligosaccharide mother drug (marketed)

[0060] Test method: Select 5-6 leaf stage of consistent growth of amaranth, remove old leaves, keep 3 healthy leaves, dip different treatments with a brush, and apply the left half leaf with the drug, and apply the right half leaf with the corresponding concentration of solvent as control. 24 hours later, evenly sprinkle the whole leaf with corundum, dilute the PVY virus liquid 300 times, and use a brush to dip the virus liquid for whole leaf inoculation. Wash with water after 30 minutes, and investigate when the disease spot is obvious (usually 72h), record the number of disease spots on the left and right leaves, and calculate the inhibition rate according to the following formula:

[0061]

[0062] Among them, the average number of withered spots is the average of three replicates in each group.

[0063] The biological assay results are shown in Table 5.

[0064] Table 5, anti-potato Y virus experiment results

[0065]

[0066] From the above results of the effect of PVY virus, it can be seen that the effect of amino-oligosaccharin complex fluorobenzyl sulfide is better than that of fluorobenzyl sulfide alone. The scheme of TMV as a screening object is verified on PVY.

[0067] During the test process of the scheme, amino-oligosaccharin showed a certain resistance to TMV, but the control effect was not ideal. The synergistic screening experiment of fluorobenzyl sulfide and amino-oligosaccharin determined that it had good synergistic effect in the range of 50:1-1:100. According to the CTC value, it can be seen that fluorobenzyl sulfide as the main effective factor, its presence or absence obviously improves the overall control effect. For example, fluorobenzyl sulfide with low dose of amino-oligosaccharin (1:100) makes the CTC value much higher than 1:1.

[0068] Although the CTC value can reflect the synergistic effect between drugs, in actual agricultural control work, the final control effect still needs to be considered. More preferably, the synergistic scheme of fluorobenzyl sulfide as the main component and amino-oligosaccharin as the auxiliary component.

[0069] Example 6, cucumber virus disease control experiment

[0070] Test conditions: When facing high temperature and drought environment, summering cucumber is prone to virus disease. The test was carried out in a vegetable greenhouse in Luocheng Street, Shouguang City, Weifang City. Cucumber was planted on May 31, with row spacing of 60 cm and plant spacing of 25 cm. The previous crop was cucumber.

[0071] Test agents: 95% flubendiamide TC (CN109134327A, provided by Hebi Quanfeng Biological Technology Co., Ltd.), 85% amino-oligosaccharide TC (purchased)

[0072] Table 6, test design and arrangement

[0073] Treatment No. Flucycloxuron Amino oligosaccharides CK / / 1 100 mg / L / 2 / 100 mg / L 3 90 mg / L 10 mg / L 4 80 mg / L 20 mg / L 5 60 mg / L 40 mg / L 6 50 mg / L 50 mg / L 7 40 mg / L 60 mg / L 8 20 mg / L 80 mg / L 9 10 mg / L 90 mg / L

[0074] The above-mentioned TC was dissolved using a small amount of DMSO, and the TC was configured into a 2000 mg / L stock solution using a 0.1% Tween 80 aqueous solution, and then diluted into the required concentration of pesticide solution according to the proportion. Each treatment has 4 repeats, and each repeat is treated with a single row of 8m. The test was sprayed on July 22, and the virus disease control effect was investigated after 10 days.

[0075] Single plant disease grading standards:

[0076] 0 level: no disease symptoms on the whole plant;

[0077] 1 level: a few chlorotic spots appear on the leaves or the midrib of the heart leaf;

[0078] 3 level: leaf mosaic in the middle and upper parts;

[0079] 5 level: heavy leaf mosaic in the middle and upper parts, a few leaf wrinkles or deformities;

[0080] 7 level: most leaf heavy mosaic, partial leaf wrinkles, deformities or necrotic spots, and slightly dwarfed plants;

[0081] 9 level: most leaf heavy mosaic, deformities or necrotic spots, and significantly dwarfed plants or even death.

[0082] Disease index = Σ number of diseased plants x disease level representative value / total number of plants surveyed x highest level representative value x 100

[0083]

[0084] Table 7, results and analysis

[0085]

[0086] Field tests show that the synergistic effect of amino-oligosaccharide and flubendiamide on cucumber virus disease is better than that of single agent control, and the synergistic effect is in the range of 9:1 to 1:9, and the best effect is obtained when the ratio is 1:1. When the proportion of amino-oligosaccharide exceeds that of flubendiamide, the overall control effect will decrease, indicating that flubendiamide is the main effective factor in this synergistic compound.

[0087] The application has been described in detail. For those skilled in the art, the application can be implemented in a wider range under the same parameters, concentrations and conditions without departing from the spirit and scope of the application and without unnecessary experiments. Although the application gives a special example, it should be understood that the application can be further improved. In summary, according to the principle of the application, the application intends to include any change, use or improvement of the application, including the change made by the conventional technology known in the art, which is out of the range disclosed in the application.

Claims

1. A pesticidal composition made from raw materials comprising: flubendiamide and amino oligosaccharide. The mass ratio of flubendiamide and amino oligosaccharide in the composition is 100:1 to 1:

100.

2. The pesticidal composition according to claim 1, characterized in that, The mass ratio of flubendiamide and amino oligosaccharide in the composition is 50:1 to 1:

100.

3. The pesticidal composition according to claim 1, characterized in that, The pesticidal composition is processed into various dosage forms by adding an auxiliary agent in addition to flubendiamide and amino oligosaccharide.

4. The pesticidal composition according to claim 3, characterized in that, The dosage form is an aqueous agent, an emulsion in water, a wettable powder, a soluble powder, a soluble granule, a water dispersible granule, a suspension, a soluble liquid, an oil suspension, a tablet, or an effervescent granule.

5. The pesticidal composition according to claim 3, characterized in that, The concentration of the active ingredient in the dosage form is 0.1 to 60 wt%.

6. Use of the pesticidal composition according to any one of claims 1 to 5 for combating plant viruses; the plant viruses are tobacco mosaic virus, potato virus Y, and cucumber mosaic virus.

Images