Application of substituted phenylhydrazine copper salt complex as agricultural bactericide

Abstract

The invention belongs to the technical field of pesticide chemistry, and particularly relates to an application of a substituted phenylhydrazine copper salt complex as an agricultural fungicide, the structural general formula of the substituted phenylhydrazine copper salt complex is [Cu (ArNHNH2) 2] Xn, Ar is selected from 3-chlorphenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, 2, 4-dichlorophenyl-, the compound is prepared from 2, 6-dichlorophenyl, p-trichloromethoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 4-bromophenyl, 4-nitrophenyl, 4-cyanophenyl and 4-carboxyphenyl, and the compound is prepared from 2, 6-dichlorophenyl, p-trichloromethoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 4-bromophenyl, 4-nitrophenyl, 4-cyanophenyl and 4-carboxyphenyl. X is selected from SO4 <->, Cl <-> and NO3 <->; n is equal to 1-2. The substituted phenylhydrazine copper salt complex disclosed by the invention has remarkable inhibitory activity on plant pathogenic bacteria, has very high inhibition rate on three plant pathogenic fungi, namely fusarium graminearum, rhizoctonia solani and sclerotium rolfsii, can be used as a safe and efficient novel bactericide, and is applied to prevention and treatment of various crop diseases.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of pesticide chemistry, and particularly relates to application of a substituted phenylhydrazine copper salt complex as an agricultural fungicide. BACKGROUND

[0002] In agricultural production, the prevention and treatment of plant diseases has been a key link to guarantee the healthy growth of crops and improve yield. Plant fungal diseases are particularly common and serious. Traditional agricultural fungicides are mainly divided into two categories: inorganic fungicides and organic fungicides. Inorganic fungicides such as copper preparations (Bordeaux mixture, copper hydroxide, etc.) have broad-spectrum, long-acting and other advantages, but have the problems of high risk of phytotoxicity, easy to produce drug resistance, and certain pollution to the environment; organic fungicides are various, such as benzimidazole, triazole, etc., although they have good efficacy, but the cost is high and some varieties have potential risks to the ecological environment and human health.

[0003] Phenylhydrazine compounds are a class of organic compounds containing phenylhydrazine groups (-NH-NH2). Their structural diversity and biological activity make them have important application value in the field of pesticides. Due to the intramolecular hydrogen bond and the characteristics of the conjugated structure, phenylhydrazine compounds are often used as enzyme inhibitors or neurotoxins in the field of pesticides. Copper salt is an inorganic compound with broad-spectrum antibacterial performance. However, there is currently no product that effectively combines phenylhydrazine and copper salt and applies it to agricultural fungicides. Therefore, based on this technical gap, the present application aims to explore a new type of efficient, environmentally friendly and economical agricultural fungicide to provide a new disease control solution for agricultural production, which has important practical significance and broad application prospects. SUMMARY

[0004] The present application provides a kind of substituted phenylhydrazine copper salt complex, which has significant fungistatic activity against a variety of plant pathogenic fungi and can be used as an agricultural fungicide in the prevention and treatment of various plant fungal diseases.

[0005] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] The present application provides the application of a substituted phenylhydrazine copper salt complex as an agricultural fungicide, and the structure of the complex is as follows: [Cu(ArNHNH2)2]X n wherein Ar is selected from 3-chlorophenyl-, 2,4-dichlorophenyl-, 2,6-dichlorophenyl-, p-trichloromethoxyphenyl-, 4-trifluoromethylphenyl-, 4-trifluoromethoxyphenyl-, 4-bromophenyl-, 4-nitrophenyl-, 4-cyanophenyl-, 4-carboxyphenyl-; X is selected from SO4-, Cl-, NO3-; n = 1-2.

[0007] Preferably, the structure of the complex is as follows: [Cu(ArNHNH2)2]Xn wherein Ar is selected from 3-chlorophenyl-, 4-trifluoromethylphenyl-, 4-cyanophenyl-; X is selected from SO4-; n = 1.

[0008] Preferably, the structure general formula of the complex is: [Cu(ArNHNH2)2]X n wherein Ar is selected from 3-chlorophenyl-; X is selected from SO4-; n = 1.

[0009] The second aspect of the present application provides an agricultural fungicide comprising the substituted phenylhydrazine copper salt complex of the first aspect.

[0010] Preferably, the substituted phenylhydrazine copper salt complex can be used as a single effective ingredient, or can be used as a synergistic ingredient together with other drugs.

[0011] The third aspect of the present application provides an application of the agricultural fungicide in preventing and treating plant pathogenic fungi.

[0012] Preferably, the plant pathogenic fungi are Fusarium graminearum, Rhizoctonia solani or Sclerotium rolfsii.

[0013] Compared with the prior art, the present application has the following beneficial effects:

[0014] (1) The substituted phenylhydrazine copper salt complex of the present application has good prevention and treatment effects on Sclerotium rolfsii, Fusarium graminearum and Rhizoctonia solani, and the inhibition rate of the substituted phenylhydrazine copper salt complex 1 on the three kinds of bacteria reaches 100.0% at a concentration of 100 μg / mL.

[0015] (2) Compared with the substituted phenylhydrazine hydrochloride compound, the substituted phenylhydrazine copper salt complex of the present application has significant bacteriostatic activity on a variety of plant pathogenic fungi, can be used as a safe and efficient new type of plant fungicide, and can be applied in the prevention and treatment of a variety of plant fungal diseases, and has potential research and development value. DETAILED DESCRIPTION

[0016] The embodiments of the present application are further described. The following examples are intended to better illustrate the technical solutions of the present application, but not to limit the protection scope of the present application.

[0017] The substituted phenylhydrazine copper salt complex of the present application has good prevention and treatment effects on agricultural fungal diseases, which are described in more detail below, but the protection scope of the present application is not limited to the following examples.

[0018] Example 1: Bacteriostatic activity test of the substituted phenylhydrazine copper salt complex

[0019] I. Experimental materials

[0020] Test strains: Sclerotium rolfsii, Fusarium graminearum, Rhizoctonia solani;

[0021] Test agents: [Cu(ArNHNH2)2]SO4 substituted phenylhydrazine copper salt complex 1-10 in Table 1;

[0022] Wherein the substituted phenylhydrazine copper salt complex can be prepared by known method: add substituted phenylhydrazine ethanol solution to 0.1M copper sulfate solution drop by drop with a dropper, shake the test tube while adding, a deep blue flocculent precipitate will be produced in the solution, centrifuge the precipitate, and wash with distilled water, and dry to obtain the complex solid.

[0023] II. Experimental method

[0024] The inhibitory activity of the target compound on plant pathogenic fungi was determined by using toxic medium method. Substituted phenylhydrazine copper salt complex 1-10 was prepared into a mother liquor with a concentration of 10 mg / mL, 1.515 mL of the compound mother liquor was added to 150 mL of PDA medium cooled to about 50°C, so that the final concentration of the compound in each bottle of medium was 100 μg / mL. After the compound and the medium were mixed evenly, they were poured into plates, which were recorded as the treatment group. At the same time, a control group plate was prepared by adding the same amount of sterile water to the PDA medium. A 5.0 mm diameter Sclerotium rolfsii, Fusarium oxysporum, and Rhizoctonia solani cake was inoculated in the center of each prepared treatment and control group plate, and each concentration was repeated 3 times, and then placed in a 25°C constant temperature incubator for incubation. After the blank control colonies covered the plate, the colony diameters of each plate were measured, and the inhibition rate was calculated. Inhibition rate (%) = (control colony diameter - treatment colony diameter) / (control colony diameter - cake diameter) x 100.

[0025] III. Experimental results

[0026] The inhibition rates of [Cu(ArNHNH2)2]SO4 substituted phenylhydrazine copper salt complex 1-10 on Sclerotium rolfsii, Fusarium oxysporum, and Rhizoctonia solani at 100 μg / mL are shown in Table 1, wherein the structural formula of ArNHNH2 is shown in Table 1.

[0027] Table 1. Inhibition activity of [Cu(ArNHNH2)2]SO4 substituted phenylhydrazine copper salt complex on pathogenic fungi (100 μg / mL)

[0028]

[0029]

[0030]

[0031]

[0032] As shown in Table 1, at the concentration of 100 μg / mL, the substituted phenylhydrazine copper salt complex 1-10 all showed high inhibition rates on F. graminearum, R. solani and S. minor, especially the substituted phenylhydrazine copper salt complex 1, the inhibition rates on F. graminearum, R. solani and S. minor all reached 100.0 ± 0.0%; followed by the substituted phenylhydrazine copper salt complex 9, the substituted phenylhydrazine copper salt complex 5 and the substituted phenylhydrazine copper salt complex 6, the inhibition rates on the three pathogenic fungi were all above 92.9%; the rest of the substituted phenylhydrazine copper salt complexes also showed high inhibition rates. The experimental results show that the ten kinds of substituted phenylhydrazine copper salt complexes have high antifungal activity on the three pathogenic fungi (F. graminearum, R. solani and S. minor), and the present application relates to the pathogenic fungi of three different crops, which also reflects the broad-spectrum bactericidal property of the substituted phenylhydrazine copper salt complex.

[0033] Example 1: Inhibition activity of substituted phenylhydrazine copper salt complexes on pathogenic fungi

[0034] The substituted phenylhydrazine hydrochloride compounds 11-20 were tested for inhibition activity on pathogenic fungi in Comparative Example 1, and the experimental method was the same as that in Example 1. The structural formula of ArNHNH2 in the substituted phenylhydrazine hydrochloride compounds 11-20 corresponded to that of the compounds 1-10 in Example 1 (see Table 1 for the specific structural formula), and the inhibition rates of the substituted phenylhydrazine hydrochloride compounds 11-20 on S. minor, F. graminearum and R. solani at 100 μg / mL were shown in Table 2.

[0035] Table 2. Inhibition activity of ArNHNH2HCl substituted phenylhydrazine hydrochloride on pathogenic fungi (100 μg / mL)

[0036]

[0037] As shown in Table 2, at the concentration of 100 μg / mL, the inhibition rates of the ten phenylhydrazine hydrochloride compounds on F. graminearum, R. solani and S. minor were significantly lower than those of the ten substituted phenylhydrazine copper salt complexes with the same substituent group in Example 1, which indicated that the substituted phenylhydrazine copper salt complex had good prevention and control effect on plant pathogenic fungi.

[0038] In summary, the substituted phenylhydrazine copper salt complex involved in the present application can be applied as a new broad-spectrum and high-efficiency plant fungicide in plant pest control, especially in economic crop disease control, and has good market promotion and development value.

[0039] The above-described embodiments are merely intended to explain the present application, and are not intended to limit the scope of the present application. It is obvious to those skilled in the art that other embodiments can be made according to the technical content disclosed in the present specification, by means of substitution or change, and thus, any changes and improvements made within the principles and technical content of the present application should be included in the scope of the present application.

Claims

1. Use of a substituted phenylhydrazine copper salt complex as an agricultural fungicide, characterized in that The structural formula of the complex is: [Cu(ArNHNH2)2]X n wherein Ar is selected from the group consisting of 3-chlorophenyl-, 2,4-dichlorophenyl-, 2,6-dichlorophenyl-, p-trichloromethoxyphenyl-, 4-trifluoromethylphenyl-, 4-trifluoromethoxyphenyl-, 4-bromophenyl-, 4-nitrophenyl-, 4-cyanophenyl-, 4-carboxyphenyl-; X is selected from the group consisting of SO4-, Cl-, NO3-; n = 1-2.

2. Use of a substituted phenylhydrazine copper salt complex according to claim 1 as an agricultural fungicide, characterized in that, The structure general formula of the complex is: [Cu(ArNHNH2)2]X n wherein Ar is selected from the group consisting of 3-chlorophenyl-, 4-cyanophenyl-, 4-trifluoromethylphenyl-, 3-trifluoromethoxyphenyl-; X is selected from the group consisting of SO4-; n = 1.

3. Use of a substituted phenylhydrazine copper salt complex according to claim 2 as an agricultural fungicide, characterized in that, The structure general formula of the complex is: [Cu(ArNHNH2)2]X n wherein Ar is selected from 3-chlorophenyl-; X is selected from SO4-; n = 1.

4. An agricultural fungicide, characterized by comprising: A substituted phenylhydrazine copper salt complex comprising the copper salt of a substituted phenylhydrazine according to any one of claims 1 to 3.

5. Use of an agrofungicide according to claim 4 for the control of phytopathogenic fungi.

6. The use of a fungicide according to claim 5 for controlling plant pathogenic fungi, characterized by The phytopathogenic fungi are Fusarium graminearum, Rhizoctonia solani or Sclerotium rolfsii.

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