Phenazine amide compound and application thereof in pesticide

Abstract

The invention relates to a phenazine amide compound and application thereof in pesticides, in particular to application of the phenazine amide compound in prevention and treatment of plant diseases caused by fungi. The structure of the phenazine amide compound is shown as a formula (I), wherein X is a nitrogen atom or an oxygen atom; r is at least one of fluorine atoms, chlorine atoms, bromine atoms, methyl, methoxyl, difluoromethyl, trifluoromethyl and trifluoromethoxyl. The phenazine amide compound disclosed by the invention has a relatively good inhibition effect on plant pathogenic fungi, and can be applied to prevention and treatment of plant diseases caused by fungi. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to phenazine amide compounds and their application in pesticides, in particular to their application in preventing and controlling plant diseases caused by fungi. Background Art

[0002] In recent years, with the global population growth and the intensive development of agriculture, crop disease prevention and control has become an important part of agricultural production. Pesticide companies have made significant progress in the development of new structural fungicides, especially fungicides with new mechanisms of action. These new fungicides have played an important role in improving crop yield and quality, but they have also brought about the problem of drug resistance. In particular, fungicides that act on mitochondrial cytochrome complexes, although they once occupied the forefront of market sales, have become increasingly serious due to their extensive use.

[0003] In this context, succinate dehydrogenase inhibitors (SDHIs) fungicides have attracted attention due to their unique mechanism of action. This type of fungicide acts on the succinate dehydrogenase of pathogens, inhibiting their respiration, thereby effectively controlling diseases. The SDHIs fungicides currently on the market all contain an amide group (-CONH-) in their chemical structure, such as boscalid, thiopyrad, furopyram and fluopyram. These fungicides have good preventive effects on plant diseases caused by fungi such as rice sheath blight, and due to their novel mechanism of action, they have no cross-resistance with most fungicides on the market.

[0004] The target of SDHIs fungicides is Complex II in the mitochondrial respiratory electron transport chain, which is composed of four subunits: flavin protein (Fp, SdhA), iron-sulfur protein (Ip, SdhB) and two other membrane-embedded proteins (SdhC and SdhD). Studies have found that the resistance of pathogens to SDHIs is mainly due to amino acid mutations in the target complex II, which leads to a decrease in the affinity of the agent and thus the loss of its fungicidal effect. The emergence of this resistance problem has challenged the long-term effectiveness of SDHIs fungicides. In order to meet this challenge, pesticide companies and scientific research institutions are actively developing new compounds and formulations to delay the development and development of resistance.

[0005] Globally, the market sales of SDHI fungicides continue to grow. This growth trend reflects the urgent market demand for new fungicides and highlights the importance of resistance management. As more SDHI fungicides expire, market competition will become more intense, which will also provide opportunities for the development of new compounds and formulations. Summary of the invention

[0006] The first object of the present invention is to provide a phenazine amide compound which can be used for preventing and treating plant diseases caused by fungi.

[0007] The structure of the phenazine amide compound of the present invention is shown in formula (I):

[0008]

[0009] in,

[0010] X is a nitrogen atom or an oxygen atom;

[0011] R is at least one of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a difluoromethyl group, a trifluoromethyl group, and a trifluoromethoxy group.

[0012] Preferably, X is an oxygen atom.

[0013] Preferably, R is at least one of a fluorine atom, a chlorine atom and a bromine atom.

[0014] Preferably, the R is a chlorine atom.

[0015] Preferably, the number of the chlorine atoms is 2.

[0016] The second object of the present invention is to provide the use of the above-mentioned phenazine amide compounds, wherein the use includes use in preventing and controlling plant diseases caused by fungi.

[0017] Preferably, the fungus is at least one of Rhizoctonia solani, Rhizoctonia solani, Gibberella fusca, Blight solani, Phytophthora infestans, Botrytis cinerea, or Sclerotinia sclerotiorum.

[0018] Preferably, the fungus is at least one of Rhizoctonia solani, Gibberella fusca, Blightia zea maydis, Botrytis cinerea, or Sclerotinia sclerotiorum.

[0019] Preferably, the fungus is at least one of Botrytis cinerea or Sclerotinia sclerotiorum.

[0020] The phenazine amide compounds of the present invention are easy to synthesize, low in cost, have good inhibitory effects on plant fungi, and have novel structures. They have not been reported in currently known compounds with good inhibitory effects on plant fungi.

[0021] The above contents of the present invention are further described in detail below through specific implementation modes, but this should not be construed as limiting the present invention. DETAILED DESCRIPTION

[0022] The phenazine amide compounds in the following examples were all sourced from Sichuan University, and the tested plant pathogens were sourced from Sichuan University and Sichuan Agricultural University.

[0023] Example 1 Compound 1 Preparation

[0024]

[0025] The synthesis method of phenazine acid chloride can be found in reference (Long Ye, et al, Novel Bioorganic & Medicinal Chemistry Letters, 2010, 7369-7371).

[0026] The synthesis method of amino diphenyl ether is shown in reference (Fang Wen, et al, European Journal of Medicinal Chemistry, 2016, 244-251)

[0027] 20 mmol of aminodiphenyl ether was placed in a three-necked flask, and then 25 mL of anhydrous dichloromethane and 5 mL of triethylamine were added thereto respectively. The mixture was stirred in an ice bath. Then 20 mmol of phenazine chloride was transferred to a constant pressure funnel and slowly added dropwise to the three-necked flask. The mixture was allowed to drip for 30 minutes. The mixture was then naturally warmed to room temperature. The reaction was completed in 3 hours. The generated salt was removed by filtration. The organic phases were combined and then washed with saturated NaHCO3 solution for 3 times and with clean water for 3 times respectively. The phases were separated, dried over anhydrous Na2SO4, and the solvent was removed by rotary evaporation to obtain a crude product. The crude product was passed through a normal pressure silica gel column (eluent: petroleum ether: ethyl acetate = 50:1 (V / V)) to obtain compound 1.

[0028] 1 H NMR (400MHz, CDCl3): δ9.46 (1H), 8.21-8.33 (2H), 7.76-7.96 (4H), 7.26-7.36 (4H), 7.11-7.20 (4H). HRMS (ESI) m / z calcd for C 25 H 16 FN3O2(M+H) + 409.1227, found 409.1234.

[0029] Example 2 Compound 2 Preparation

[0030] The preparation method of compound 2 is the same as the synthesis method of compound 1.

[0031] 1 H NMR (400MHz, CDCl3): δ9.45(1H),8.35(1H),8.21-33(2H),7.75-7.95(4H),7.25-7.35(4H),7.11-7.20(5H).HRMS(ESI)m / z calcd for C 25 H 18 FN4O(M+H)+ 409.1465, found 409.1510.

[0032] Example 3 Compound 3 Preparation

[0033] The preparation method of compound 3 is the same as the synthesis method of compound 1.

[0034] 1 H NMR (400MHz, CDCl3): δ9.46 (1H), 8.22-8.31 (2H), 7.74-7.91 (4H), 7.22-7.38 (4H), 7.10-7.21 (4H). HRMS (ESI) m / z calcd for C 25 H 16 Cl2N3O2(M+H) + 460.0620, found 460.0635.

[0035] Example 4 Compound 4 Preparation

[0036] The preparation method of compound 4 is the same as the synthesis method of compound 1.

[0037] 1 H NMR (400MHz, CDCl3): δ9.46(1H),8.36(1H),8.20-8.31(2H),7.72-7.85(4H),7.23-7.31(4H),7.10-7.18(4H).HRMS(ESI)m / z calcd for C 25 H 17 ClN4O(M+H) + 459.0779,found459.0785.

[0038] Example 5 Compound 5 Preparation

[0039] The preparation method of compound 5 is the same as the synthesis method of compound 1.

[0040] 1 H NMR (400MHz, CDCl3): δ9.45(1H),8.20-8.30(2H),7.72-7.81(4H),7.20-7.28(4H),7.12-7.22(4H).HRMS(ESI)m / z calcd for C 25 H 16 Cl2N3O2(M+H) +460.0620,found460.0627.

[0041] Example 6 Compound 6 Preparation

[0042] The preparation method of compound 6 is the same as the synthesis method of compound 1.

[0043] 1 H NMR (400MHz, CDCl3): δ9.44(1H),8.34(1H),8.20-8.30(2H),7.71-7.81(4H),7.22-7.31(4H),7.12-7.18(4H).HRMS(ESI)m / z calcd for C 25 H 17 Cl2N4O(M+H) + 459.0779, found 459.0781.

[0044] Example 7 Determination of fungicidal activity of phenazine amide compounds against plant pathogenic fungi

[0045] 1. Plant pathogenic fungi

[0046] Rice sheath blight (Rhizoctonia solani), wheat fusarium (Fusarium graminearum), corn leaf blight (Bipolaris maydis), potato late blight (Phytophthora infestans), tomato gray mold (Botrytis cirerea), rapeseed sclerotinia (Sclerotinia sclerotiorum).

[0047] 2. Experimental Methods

[0048] Determination of relative inhibition rate of mycelium by toxic medium method (%):

[0049] First, the phenazine amide compounds were diluted with sterile water and then mixed with PDA medium. The final concentration of the phenazine amide compounds was determined by double dilution method to prepare a series of drug-containing plates with uniform thickness. Sterile water was used as a blank control, and each treatment was repeated 3 times. After the culture medium solidified, the plant pathogenic fungus test cake was inoculated on the solidified culture medium and cultured at 27-28℃ for 3-5 days. The diameter of the cake was 0.4cm. The colony diameter was measured by the cross method to calculate the mycelial growth inhibition rate.

[0050]

[0051] 3. Experimental results

[0052] The results of the inhibitory activity of phenazineamide compounds on plant pathogenic fungi are shown in Table 1. As shown in Table 1, phenazineamide compounds also have a good inhibitory effect on plant pathogenic fungi.

[0053] Table 1 Relative inhibition rate of compounds 1-7 at 20 mg / L on plant pathogenic fungi (%)

[0054]

[0055]

[0056] Note: Chemical structure of compound 7: In the general formula (1), X is an oxygen atom and R is a hydrogen atom.

[0057] In summary, the phenazine amide compounds of the present invention have good broad-spectrum fungicidal activity against plant pathogenic fungi, and developing them into new green pesticides with high efficiency has broad prospects.

Claims

1. A phenazine amide compound, characterized in that: The structure of the phenazine amide compound is shown in formula (I): in, X is a nitrogen atom or an oxygen atom; R is at least one of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a difluoromethyl group, a trifluoromethyl group, and a trifluoromethoxy group.

2. The phenazine amide compound according to claim 1, characterized in that: The X is an oxygen atom.

3. The phenazine amide compound according to claim 1 or 2, characterized in that: The R is at least one of a fluorine atom, a chlorine atom, and a bromine atom.

4. The phenazine amide compound according to claim 1 or 2, characterized in that: The R is a chlorine atom.

5. The phenazine amide compound according to claim 4, characterized in that: The number of the chlorine atoms is 2.

6. The use of the phenazine amide compound according to any one of claims 1 to 5, characterized in that: The application includes application in controlling plant diseases caused by fungi.

7. The use according to claim 6, characterized in that: The fungus is at least one of rice sheath blight, wheat sheath blight, wheat fusarium rust, corn leaf blight, potato infestation, tomato gray mold, or rapeseed sclerotinia.

8. The use according to claim 7, characterized in that: The fungus is at least one of rice sheath blight, wheat fusarium rust, corn leaf blight, tomato gray mold, or rapeseed sclerotinia.

9. The use according to claim 7, characterized in that: The fungus is at least one of Botrytis cinerea or Sclerotinia sclerotiorum.

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