CN102715176B - Bactericidal composition containing 2-cyano-3-amino-3-ethyl phenylacrylate and clorine-nalidixic-methyl - Google Patents

Abstract

The present invention discloses a bactericidal composition containing 2-cyano-3-amino-3-ethyl phenylacrylate and clorine-nalidixic-methyl. Active constituents of the bactericidal composition are 2-cyano-3-amino-3-ethyl phenylacrylate and clorine-nalidixic-methyl. The weight ratio of 2-cyano-3-amino-3-ethyl phenylacrylate to clorine-nalidixic-methyl is in the range of from 1:20 to 20:1, and the weight of the active constituents is 5-60% of that of the composition. The bactericidal composition has high bactericidal activity, can delay the production and development of pathogen resistance, and can reduce preventive dosage in the real production, which is economical, efficient, safe and environmentally friendly. The bactericidal composition has the higher control efficiency for crop diseases caused by fusarium, and particularly significant in wheat scab.

Description

A kind of bactericidal composition containing cyclostrobin and cloclostrobin

technical field

The invention relates to the field of agricultural fungicides, in particular to a fungicidal composition containing cyclostrobin and cloclostrobin.

Background technique

Wheat head blight is a widely distributed disease, which occurs in almost all wheat producing areas in the world, especially in mild and humid and semi-humid areas. To date, there are no resistant wheat varieties with complete immunity to head blight. Therefore, wheat head blight still depends on chemical control in production. At present, the main agent used to control wheat head blight in production is the benzimidazole fungicide represented by carbendazim. Since the world's first carbendazim-resistant strain of Fusarium graminearum was detected on wheat ears in Haining, Zhejiang in 1992, the resistance of the pathogen has been found in Zhejiang, Jiangsu, Lu, Anhui and other places. Moreover, the proportion of drug-resistant bacteria is rapidly increasing, and the distribution of drug-resistant pathogenic bacteria continues to expand. At present, East China is facing the danger of failure of existing fungicides such as carbendazim to control scab due to drug resistance. How to continue to control wheat scab, especially the epidemic hazard of carbendazim-resistant scab has become a major issue faced by scientific and technological workers and growers.

Cloclostrobin is a high-efficiency broad-spectrum fungicide, which is effective against wheat, cucumber powdery mildew, rice blast, rice smut, rice sheath blight, rice bakanae disease, wheat sheath blight, wheat head blight, wheat Pathogens such as root rot, corn big spot, small spot, rape sclerotinia, tomato gray mold, apple rot, melon anthracnose, cucumber wilt, cotton verticillium wilt, cotton wilt, etc. have high antibacterial active. Its main mechanism of action is to affect the respiration of bacteria, and it has no cross-resistance with carbendazim.

Chemical name: methyl N-methoxy-N-[2-[[(3,5,6-trichloropyridin-2-yl)oxy]methyl]phenyl]carbamate

The structural formula is shown in the figure below:

Cyclostrobin is a 2-cyanoacrylate fungicide. The appearance of the original drug is white solid powder; melting point 123-124°C; vapor pressure (25°C): 4.5*10 ⁵ Pa; solubility (20°C): hardly soluble in water, petroleum ether, toluene, easily soluble in chloroform, acetone, Dimethyl sulfoxide, N,N-dimethylformamide. Stability: stable in acidic and alkaline media, stable to light.

The structural formula is shown in the figure below:

Cyclostrobin is a new type of fungicide with strong specialization, which has the functions of protection, treatment, systemic absorption and transport, etc. High biological activity, suitable for effective prevention of crop diseases such as wheat head blight, rice bakanae disease and watermelon wilt, against cucumber downy mildew caused by Cuban pseudoperonospermum, and rice plant blight caused by Xanthomonas oryzae Anthracnose of capsicum, capsicum anthracnose caused by capsicum anthracnose, and sclerotinia sclerotiorum caused by Botrytis berenger also have a certain inhibitory effect. Cyclostrobin had no cross-resistance with five fungicides with different mechanisms of action: benzimidazoles, dithiocarbamates, ergosterol biosynthesis inhibitors, methoxyacrylates and aromatics, indicating that the Agents have novel mechanisms of action. Cyclostrobin belongs to the xylem transport agent, that is, this kind of agent mostly accumulates in the parts with high transpiration intensity (leaf edge, leaf tip), and hardly reaches the organs or parts with very weak transpiration (fruits, seeds, etc.). At the same time, it is found that the medicament is resistant to rain erosion, has good systemic penetration performance and excellent protective and therapeutic effects.

Chemical name: ethyl 2-cyano-3-amino-3-phenylacrylate

Chloroxystrobin is a methoxyacrylate compound, and its main mechanism of action is to affect the respiration of bacteria. However, many studies have shown that this agent can make pathogenic bacteria resistant to drugs in a short period of time when used alone to prevent and control diseases. Lead to the failure of disease control; there are also many studies have shown that wheat head blight is also easy to produce resistance to cyclostrobin. Clostristrobin and cyclostrobin used alone have a higher risk of drug resistance, making them ineffective in the short term. The Fungicide Resistance Action Committee (FRAC) suggested that the combined use of agents with different mechanisms of action can avoid or delay the emergence of drug resistance. Therefore, the combination of the two into a fungicidal composition can not only effectively solve the practical production problem of wheat head blight difficult to control in areas resistant to benzimidazole fungicides, but also delay the development of resistance of pathogens to it.

Contents of the invention

The invention provides a bactericidal composition containing cyclostrobin and chlorpyrastrobin, which has high bactericidal activity, delays the occurrence and development of drug resistance of pathogens, and reduces the total dosage per unit area, which is economical, efficient, and It is environmentally friendly and has special effects in the prevention and treatment of wheat scab.

The present invention combines two types of fungicides with different mechanisms of action, i.e., the methoxyacrylate fungicide chlorpyrastrobin and the 2-cyanoacrylate fungicide cyclostrobin, and processes them into a product that is easy to use in production. Compared with the two components used alone, the preparation has high biological activity, and the total dosage per unit area is reduced, which greatly reduces the cost of application, and at the same time delays the occurrence and development of drug resistance of pathogens to a greater extent, reducing the The risk of pathogenic fungi developing resistance to a single fungicide prolongs the service life of each component in the fungicidal composition, thereby achieving the purpose of the invention of economy, high efficiency and environmental protection.

Technical scheme of the present invention is:

A bactericide composition containing cyclostrobin and cloclostrobin, characterized in that, the active components of the bactericide composition are cyclostrobin and cloclostrobin, cloclostrobin and cyanene The mass ratio of strytostrobin is 1:20 to 20:1, and the mass percentage of active components in the composition is 5-60%.

The bactericidal composition containing cyclostrobin and cloclostrobin is characterized in that the mass ratio of the active component cloclostrobin to cyclostrobin is 1:10 to 10:1.

The bactericidal composition containing cyclostrobin and cloclostrobin is characterized in that the mass ratio of cloclostrobin to cyclostrobin is 1:3-8.

The bactericidal composition containing cyclostrobin and cloclostrobin is characterized in that the mass ratio of cloclostrobin to cyclostrobin is 1:4-6.

The bactericide composition containing cyclostrobin and cloclostrobin is characterized in that: the dosage form of the bactericide composition is a suspension concentrate or an emulsifiable concentrate.

The application of the fungicide composition containing cyclostrobin and chlorpyracillin is characterized in that: the fungicide composition has a higher control effect on various crop diseases caused by Fusarium, and has a higher control effect on wheat head blight The control effect is particularly remarkable.

Significant effect and advantage of the present invention are:

The present invention has a higher control effect on wheat fungal diseases, and there is an obvious synergistic effect between the two components; it can replace some high-priced pesticide varieties, reduce the dosage, effectively reduce ecological damage and environmental pollution, and can improve wheat Yield and quality; both cyprostrobin and clostristrobin in the present invention have low toxicity, and are safe to humans, animals, beneficial organisms, and the environment; they can delay the resistance of germs to a single agent.

First measure the EC ₅₀ (drug safety index) of two single compounds of cyprostrobin and cloclostrobin (hereinafter referred to as the medicament), and set the combination ratio of the two medicaments according to the Wadley method according to the EC ₅₀ of the two single medicaments, and according to Wadley The synergistic coefficient C value, determine the appropriate composition ratio, and then verify it according to Sun Yunpei's method.

The test object is, but not limited to, wheat scab. The test adopts mycelial growth assay method, and the drug-containing medium is prepared according to different treatments. Each treatment has 4 repetitions. After inoculation for 3 days, the growth inhibitory effect of each treatment on wheat head blight was investigated. Through the linear regression analysis between the probability value of the control effect and the logarithmic value of the serial drug concentration, the EC50 of each drug was obtained, and the synergistic coefficient (SR) was calculated according to the Wadley method, and a comprehensive evaluation was made accordingly. SR≤0.5 means antagonistic effect, 0.5<SR<1.5 means additive effect, SR≥1.5 means synergistic effect. The calculation method of SR value is as follows:

EC ₅₀ (theoretical value)=(a+b)/(a/EC _50A +b/EC _50B )

SR=EC ₅₀ (theoretical value)/EC ₅₀ (actual value)

SR ≤ 0.5, the two agents mixed with antagonistic effect

SR=0.5～1.5, the mixture of the two agents has an additive effect

SR ≥ 1.5, the combination of the two agents has a synergistic effect

The Wadley method determination result of table 1 Chloroprexstrobin and cyclostrobin composition to wheat head blight

Note: Q is cyclostrobin, L is chlorazoxystrobin, add 50ppm salicylic acid when preparing the drug-containing medium.

From the above data, it can be analyzed that the bacteriostasis effect of different ratios of the composition of Chloroprexstrobin and Cyclostrobin on wheat head blight is different, generally speaking, the ratio is in the range of 1:20 to 20:1 All have synergistic or additive effects, and the maximum synergistic ratio is 1:5.

The present invention will be further described below in conjunction with the examples, but not limited thereto.

Detailed ways

Embodiment 1 (60% clostrostrobin · cyclostrobin suspension concentrate)

Raw material formula: by mass percentage

Active ingredient Chloroprexate 10%

Active ingredient Cyclostrobin 50%

Calcium lignosulfonate 6%

BY140 4%

Xanthan Gum 0.1%

Propylene Glycol 1%

Phosphate ester defoamer 0.1%

Water balance.

The preparation method is as follows:

According to the formula, weigh each component in proportion, put it into a ball mill and mill it for 30 minutes, filter, pump it into the dispersion tank for 3 minutes at high speed and then grind it fully with a sand mill to control the particle diameter of the solid component within 2 microns, and the grinding is completed Finally, stir evenly to obtain the suspension concentrate product.

Embodiment 2 (the preparation method of 30% chlorazoxystrobin · cyclostrobin suspension concentrate)

Active ingredient Chloroprexate 15%

Active ingredient Cyclostrobin 15%

Sodium lignosulfonate 6%

BY140 4%

Xanthan Gum 0.1%

Propylene Glycol 1%

Phosphate ester defoamer 0.1%

Water balance.

Preparation method: same as Example 1.

Embodiment 3 (the preparation method of 40% clostristrobin · cyclostrobin suspension concentrate)

Active ingredient Chloroprexate 5%

Active ingredient Cyclostrobin 35%

Sodium lignosulfonate 5%

BY140 3%

Xanthan Gum 0.2%

Propylene Glycol 1%

Phosphate ester defoamer 0.1%

Water balance.

Preparation method: same as Example 1.

Embodiment 4 (20% clostrobin · cyclostrobin emulsifiable concentrate)

Active ingredient Chloroprexate 15%

Active ingredient Cyclostrobin 5%

Dimethylformamide DMF 30%

Anhydrous calcium salt 5%

NP-10 5%

Xylene balance.

Preparation method: Fully dissolve the active component chloranthistrobin in a xylene reactor to make liquid A; fully dissolve the active component cyclostrobin in a DMF reactor to make liquid B; keep stirring Mix liquid A into liquid B in the state, stir well, add anhydrous calcium salt and NP-10, and then adjust the content with solvent xylene.

Embodiment 5 (45% clostrostrobin · cyclostrobin emulsifiable concentrate)

Raw material formula: by mass percentage

Active ingredient Chloroprexate 35%

Active ingredient Cyclostrobin 10%

DMF 30%

Anhydrous calcium salt 5%

NP-10 5%

Xylene balance.

Preparation method: with embodiment 4.

Embodiment 6 (preparation method of 48% chlorazoxystrobin · cyclostrobin emulsifiable concentrate)

Raw material formula: by mass percentage

Active ingredient Chloroprexate 36%

Active ingredient Cyclostrobin 12%

DMF 30%

Anhydrous calcium salt 5%

NP-10 5%

Xylene balance.

Preparation method: with embodiment 4.

Control effect test:

The field control effect test of wheat head blight was carried out in the suburbs of Bengbu City, the test area was 0.3hm ² , each treatment was repeated three times, spraying control was carried out at the flowering stage of wheat, and the control effect investigation was carried out 15 days after spraying. The control results are shown in the table 2. The results show that the fungicidal composition containing cyclostrobin and chlorpyrexate has a good control effect on wheat head blight, and can achieve higher control effect at the same dosage or at a lower dosage, and the fungicidal composition The control bacteria of each treatment were more than 85%, which was significantly higher than that of the control agent.

Table 2 The field efficacy of the chloracrylostrobin-cyclostrobin fungicidal composition in the control of wheat head blight*

The field control experiment of rice bakanae disease was set up in the suburbs of Bengbu City, where rice bakanae disease occurred moderately every year on average, with a test area of 0.3hm ² , and each treatment was repeated three times. The volume ratio of the medicament mixture was 1:1, and the soaking time was 10 hours. The incidence of bakanae disease was investigated at the rice seedling stage, and the control results are shown in Table 3. The results showed that the fungicidal composition containing cyclostrobin and cclostrobin had a good control effect on rice bakanae disease, and the control effect of each treatment dose was higher than 83%, which was significantly higher than that of the control agent.

Table 3 The field efficacy of the chlorazoxystrobin-cyclostrobin fungicidal composition soaking treatment against rice bakanae disease (the volume ratio of seeds and pesticides is 1:1)*

From the data in Table 2 and Table 3, it can be seen that the fungicidal composition containing clostristrobin and cyclostrobin has good control effects on wheat head blight and rice bakanae disease caused by Fusarium, and different proportions The effectiveness of the defense is different. It is worth noting that when the ratio of cyclostrobin and clostristrobin is 5:1, compared with other treatments, it has a higher control effect on the two diseases at a lower dosage, showing that Good synergistic effect; and the indoor biotest results also showed that when the ratio of cyclostrobin and cloclostrobin was 5:1, the measured synergistic coefficient was the highest, and the results of the two were consistent.

Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Apparently, the present invention is not limited to the above embodiments, and many modifications are possible. All deformations that can be directly derived or associated by those skilled in the art from the content disclosed in the present invention are considered to be within the protection scope of the present invention.

Claims (5)

1. a bactericide composition containing cyclostrobin and cloclostrobin, it is characterized in that, the active component of described bactericide composition is cyclostrobin and cloclostrobin, cloclostrobin and The mass ratio of cyclostrobin is 1:20 to 10:1, and the mass percentage of active components in the composition is 5-60%. 2. The bactericidal composition containing cyclostrobin and cloclostrobin according to claim 1, characterized in that: the mass ratio of the active component cloclostrobin to cyclostrobin is 1:10 to 10:1. 3. The bactericidal composition containing cyclostrobin and cloclostrobin according to claim 1, characterized in that: the mass ratio of cloclostrobin to cyclostrobin is 1:3-8. 4. The bactericidal composition containing cyclostrobin and cloclostrobin according to claim 1, characterized in that: the mass ratio of cloclostrobin to cyclostrobin is 1:4-6. 5. The bactericide composition containing cyclostrobin and cloclostrobin according to claim 1, characterized in that: the dosage form of the bactericide composition is a suspension concentrate or an emulsifiable concentrate.