Diphenyl ether ester compounds and their uses as pesticides and fungicides

Abstract

The present application discloses a diphenyl ether ester compound and its use in the prevention and treatment of rice blast disease caused by the rice blast fungus. The compound has the following structural formula: TIFF2024539274000020.tif28170The compounds of the present application have strong inhibitory activity and specificity against the virulence of blast fungus, and are of great utility.

Description

[Technical field]

[0001] The present invention belongs to the fields of organic chemicals and plant protection, and specifically relates to the use of diphenyl ether ester compounds as fungicides, particularly for controlling rice blast disease caused by the rice blast fungus. [Background technology]

[0002] Rice is one of the most important food crops with the largest cultivation area in the world, feeding more than half of the world's population. With the rapid growth of the world's population, the demand and safety of rice production are becoming increasingly important. Rice blast disease caused by Magnaporthe oryzae is the most important devastating fungal disease that occurs widely in rice areas in China and around the world, and seriously threatens the safety of food production worldwide. Rice blast disease causes 3 billion kilograms of food loss every year in China, and the annual production loss in the world is enough to feed a population of 60 million people. Currently, the prevention and treatment of this disease are mainly based on disease-resistant varieties and chemical prevention and treatment. Due to the complex field pathotype of the rice blast fungus and the rapid change in population composition, disease resistance is lost 3 to 5 years after the spread of disease-resistant varieties. Chemical control is usually expensive, and due to the constant development of pathogen resistance, the control effect of current fungicides is limited, and at the same time, it is prone to environmental pollution.

[0003] Currently, the fungicides used to control rice blast are mainly steroid demethylation inhibitors (DMIs), mitochondrial respiratory inhibitors (QoIs), and melanin biosynthesis inhibitors (melanin biosynthesis inhibitors). However, the above fungicides have been used for a long time, and the rice blast fungus has gradually developed drug resistance. Therefore, there is an urgent need to develop new, highly efficient, and low-toxicity fungicide targets.

[0004] In the long-term cooperative evolution process between plants and pathogenic microorganisms, a complex and precise arms race of attack, defense, re-attack, and re-defense has been formed between the two. Recent research has revealed that plants have an innate immune system similar to that of animals, which induces two levels of immune responses, PTI (PAMP-triggered immunity) and ETI (Effector-triggered immunity), by pathogen-associated model molecules PAMPs (pathogen-associated molecular patterns) and effector molecules, respectively. The basal disease resistance (PTI) that plants use to deal with pathogens is produced by recognizing conserved model molecules (PAMPs) of pathogens by receptors on the cell membrane, and is characterized by stability, persistence, and broad spectrum. Effectors are important weapons that pathogenic microorganisms use to attack plants. When rice is infected by the rice blast fungus, it secretes a large amount of effectors to interfere with the anti-disease response in rice cells. Therefore, analyzing effectors and inhibiting the molecular mechanisms of host PTI is not only of great significance in understanding the pathogenic mechanisms of pathogenic microorganisms, but also enables the design of new low-toxicity, highly efficient bactericides that target the structural features of effectors specific to pathogenic microorganisms. Summary of the Invention

[0005] The object of the present invention is to provide a green, highly efficient and low-toxicity fungicide for the prevention and management of rice blast disease, which addresses the problems of drug resistance, environmental pollution, etc., present in existing blast fungicides. The present invention relates to the use of a diphenyl ether compound for the control of disease caused by the rice blast fungus.

[0006] In order to achieve the above object, a first aspect of the present invention provides a diphenyl ether ester compound represented by structural formula I: TIFF2024539274000002.tif27170

[0007] However, in formula [I], R 1 is H, hydroxyl group, amino group, mercapto group, halogen, C1-C 12 Alkyl groups, C1-C12 Alkoxy groups, C1-C 12 Alkylamino group, C1-C 12 Alkylmercapto group, C2-C6 alkenyl group, C2-C6 alkynyl group, C1-C substituted with halogen 12 Alkyl groups, C1-C 12 Alkoxy groups, C1-C 12 Phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C1-C substituted with alkoxy group 12 selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted by an alkyl group and / or a halogen atom; R 1 is located at any substitution position of the aromatic ring or aromatic heterocycle and is mono- or polysubstituted; R 2 is H, hydroxyl group, amino group, mercapto group, halogen, C1-C 12 Alkyl groups, C1-C 12 Alkoxy groups, C1-C 12 Alkylamino group, C1-C 12 Alkylmercapto group, C2-C6 alkenyl group, C2-C6 alkynyl group, C1-C substituted with halogen 12 Alkyl groups, C1-C 12 Alkoxy groups, C1-C 12 Phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C1-C substituted with alkoxy group 12 selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted by an alkyl group and / or a halogen atom; R 2 is located at any substitution position of the aromatic ring or aromatic heterocycle and is mono- or polysubstituted; R 1 and R 2 are the same or different, and X is either C or N, In addition, diphenyl ether ester compounds having the following structural formula are excluded: TIFF2024539274000003.tif27170

[0008] Preferably, the diphenyl ether ester compound of the present invention is specifically Compound FY21001: X is C and R 1 is 4-OH, R 2 is H, Compound FY21003: X is C and R 1 is 4-OCH2Ph, R 2 is H, Compound FY21004: X is C and R 1 is 4-CH3, R 2 is H, Compound FY21005: X is C and R 1 is 4-F, R 2 is H, Compound FY21006: X is C and R 1 is 4-Cl, R 2 is H, Compound FY21007: X is C and R 1 is 4-Br, R 2 is H, Compound FY21008: X is C and R 1 is 4-OH, R 2 is 4-OPh, Compound FY21009: X is C and R 1 is 4-OH, R 2 is 4-CH3, Compound FY21010: X is C and R 1 is 4-OH, R 2 is 4-F, Compound FY21011: X is C and R 1 is 4-OH, R 2 is 4-Cl, Compound FY21012: X is C and R 1 is 4-OH, R 2 is 4-Br, Compound FY21013: X is C and R 1 is 4-OH, R 2 is 4-OCH3, Compound FY21014: X is C and R 1 is 4-SH, R 2 is H, Compound FY21015: X is N and R 1 is 4-OH, R 2 is H, Compound FY21016: X is C and R 1 is 4-OCH3, R 2 is H, Compound FY21017: X is C and R 1 is 4-OCH2Ph, R 2 is 4-Cl, Compound FY21018: X is C and R 1 is 4-OCH2Ph, R 2 is 4-OCH3, Compound FY21019: X is C and R 1 is 4-OCH3, R 2 is 4-OCH3, Compound FY21020: X is C and R 1 is 4-CH3, R 2 is 4-Cl.

[0009] The present invention synthesizes the diphenyl ether ester compound of the present invention according to the following scheme: TIFF2024539274000004.tif26170

[0010] In the above synthesis scheme, the substituents in formulae I, II and III have the same definitions as the corresponding groups in formula "1" of the present invention.

[0011] In the above synthesis scheme, in step a, the synthesis method of formula II can be, for example, by dissolving raw material I in a solvent, adding oxalyl chloride, and reacting by stirring at a low temperature. After the reaction is completed, the solvent is removed and the remaining solid is dissolved in a solvent and prepared. At a low temperature, for example -5°C to 5°C, most preferably 0°C, phenylpropanol is dissolved in the solvent, triethylamine is added, and after stirring, the acid chloride solution dissolved in the solvent is dropped into the reaction system, and the reaction is monitored by TLC. After the reaction is completed, a saturated NaHCO3 solution is added to the reaction system, and the organic layer is extracted and combined, dried and concentrated, and then subjected to column chromatography to obtain intermediate II.

[0012] In the above synthesis scheme, in step b, the synthesis method of formula III can be, for example, by putting intermediate II, a solvent, and a base into a flask, and heating the mixture to 80° C. to 120° C., most preferably 100° C., while stirring. The reaction is monitored by TLC, and after the reaction is completed, water is added to the reaction system, extraction is performed, and the organic layer is combined, dried and concentrated, and then subjected to column chromatography to obtain derivative III.

[0013] The present invention will now be described in more detail with reference to the following examples, in which all the various raw materials used were purchased commercially unless otherwise specified.

[0014] The terms used in the present invention will be explained below. "C 1-12The alkyl group referred to here is an alkyl group having a total of 1 to 12 carbon atoms, including a linear alkyl group, a branched alkyl group, or a cycloalkyl group, and may be, for example, a linear alkyl group, a branched alkyl group, or a cycloalkyl group having a total of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isoamyl group, a tertiary butyl, an n-pentyl group, an isopentyl group, an n-hexyl group, a cyclopropyl group, a methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a methylcyclobutyl group, a cyclopentyl group, a methylcyclopentyl group, an ethylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, or an ethylcyclohexyl group.

[0015] In the present invention, "C 1-12 The "alkoxy group" refers to an alkoxy group having 1 to 12 carbon atoms and may be, for example, a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tertiary butyloxy group, an n-pentyloxy group, an isoamyloxy group, an n-hexyloxy group, a cyclopropyloxy group, a methylcyclopropyloxy group, an ethylcyclopropyloxy group, a cyclopentyloxy group, a methylcyclopentyloxy group, or a cyclohexyloxy group.

[0016] In the present invention, "C 1-12 The term "alkylamino" refers to an alkyl-substituted amino group having 1 to 12 carbon atoms that may be monoalkyl and / or dialkyl substituted, where the alkyl groups in the dialkyl substitution may be the same and / or different.

[0017] In the present invention, "C 1-12The "alkyl mercapto group" refers to an alkyl mercapto group having 1 to 12 carbon atoms, and may be, for example, a methyl mercapto group, an ethyl mercapto group, an n-propyl mercapto group, an isopropyl mercapto group, an n-butyl mercapto group, an isobutyl mercapto group, a tertiary butyl mercapto group, an n-pentyl mercapto group, an isoamyl mercapto group, an n-hexyl mercapto group, a cyclopropyl mercapto group, a methyl cyclopropyl mercapto group, an ethyl cyclopropyl mercapto group, a cyclopentyl mercapto group, a methyl cyclopentyl mercapto group, or a cyclohexyl mercapto group.

[0018] In the present invention, "C 2-6 The "alkenyl group" refers to a monoalkenyl group, bisalkenyl group or polyalkenyl group having 1 to 6 carbon atoms, and may be, for example, a vinyl group, an n-propenyl group, an isopropenyl group, an n-butenyl group, a normal butenyl group, an isobutyryl group, a tertiary butyl group, an n-pentenyl group, a 1,3-pentadiene group, an isoamyl group, a hexenyl group, a 1,3-hexadiene group, a cyclopropenyl group, a methylcyclopropenyl group, an ethylcyclopropenyl group, a cyclopentenyl group, a methylcyclopentenyl group or a cyclohexenyl group.

[0019] In the present invention, "C 2-6 The alkynyl group" represents a monoalkynyl group, bisalkynyl group or polyalkynyl group having 1 to 6 carbon atoms, and may be, for example, an ethynyl group, a propynyl group, an isopropenyl group, a normal butynyl group, a normal butynyl group, an isobutynyl group, a t-butynyl group, a pentapropanyl group, a 1,3-pentynyl group, an isoamyl group, a propynyl group, a 1,3-caprodiethynyl group, a cyclopropargyl group, a methylcyclopropargyl group, an ethylcyclopropargyl group, a cyclopentanyl group, a methylcyclopentanyl group, or a cyclohexenyl group.

[0020] In the present invention, the term "substituted or unsubstituted five-membered heterocycle" refers to a heterocycle containing at least one element selected from the group consisting of N, O and S.

[0021] In the present invention, the term "substituted or unsubstituted six-membered heterocycle" refers to a heterocycle containing at least one element selected from the group consisting of N, O and S.

[0022] In the present invention, "halogen" means at least one element selected from fluorine, chlorine, bromine and iodine.

[0023] In the present invention, the method for synthesizing the diphenyl ether ester compound represented by formula [I] is not particularly limited, and those skilled in the art can obtain a suitable method for producing the derivative represented by formula (I) by the synthesis method in the field of compound structure bonding chemistry provided by the present invention, but the present invention will not be described here.

[0024] A second aspect of the present invention provides use of the diphenyl ether ester compound according to the first aspect for suppressing the function of a target protein MoErs1 in blast fungus.

[0025] A third aspect of the present invention provides use of the diphenyl ether ester compound according to the first aspect for preventing rice blast disease.

[0026] A fourth aspect of the present invention provides the use of a diphenyl ether ester compound according to the first aspect as an agricultural fungicide.

[0027] A fifth aspect of the present invention provides an agricultural chemical fungicide comprising an active ingredient containing at least one of the diphenyl ether ester compounds according to the first aspect and an auxiliary material.

[0028] The diphenyl ether ester compounds provided by the present invention have shown excellent crop safety in plants, including rice.

[0029] The present invention has the following advantages: 1) Simple structure and easy production The diphenyl ether ester compound of the present invention has a simple chemical formula and is easy to produce. 2) High specificity The diphenyl ether ester compound has high specificity The diphenyl ether ester compound of the present invention is designed based on the effector protein specific to the blast fungus, and has high specificity. 3) High safety. Diphenyl ether ester compounds were developed against effectors specific to the rice blast fungus, and since they have no homologues in other species, they have the characteristics of low toxicity and high safety as fungicides. 4) Strong fungicidal activity. Diphenyl ether ester compounds have strong inhibitory activity against the virulence of rice blast fungus. In particular, compound FY21001 has a high EC 50 At the same time, compound FY21001 can inhibit the germination of conidia and the formation of adhesins of the blast fungus. [Brief description of the drawings]

[0030] [Figure 1] This is a cross-validation of MoErs1 and compound FY21001. Using microsensor thermophoresis (MST) technology, the binding ability of MoErs1 with diphenyl ether ester compounds was verified in vitro, and the Kd reaction dissociation constant, the smaller the value, the stronger the binding. [Diagram 2] Measurement of MoErs1 inhibitory function by diphenyl ether ester compound FY21001. Biotin-labeled DCG-04 is used in combination with Western hybridization technology to detect the inhibitory effect of diphenyl ether ester compounds on MoErs1 function. [Diagram 3]The MoErs1 inhibitory function of diphenyl ether ester compounds FY21002 and FY21003 is measured. A is the mutual authentication of MoErs1, FY21002, and FY21003. Using microsensor thermophoresis (MST) technology, the binding ability of MoErs1 and diphenyl ether ester compounds is verified in vitro, and the Kd reaction dissociation constant is determined; the smaller the value, the stronger the binding. B is the MoErs1 inhibitory function of diphenyl ether ester compounds FY21002 and FY21003. Using biotin-labeled DCG-04 in combination with Western hybridization technology, the inhibitory effect of diphenyl ether ester compounds on MoErs1 function is detected. [Figure 4] Inhibitory effect of diphenyl ether ester compounds on conidial germination and adhesin formation of blast fungus. Guy11 is a wild-type strain of blast fungus.

[0031] Detailed Description of the Application The endpoints of the ranges and any values ​​disclosed herein are not limited to the exact ranges or values, but should be understood to include the values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, and the endpoints and individual points of each range, and the individual points of each range, which are to be considered as specifically disclosed herein, can be combined with each other to obtain one or more new numerical ranges.

[0032] Example 1: Synthesis of Compound II-1 The intermediate I used in this embodiment can be purchased directly and has the following structure: TIFF2024539274000005.tif31170

[0033] Intermediate I (5 mmol) was placed in a 50 mL monocoque, 18 mL of dichloromethane was added, and (COCl)2 (8 mmol) was slowly added dropwise at room temperature. After the addition, the reaction was refluxed for about 1.5 hours. TLC was used to monitor the progress of the reaction, and the solvent was removed after the reaction was completed. 20 mL of dried CH2Cl2, phenylpropanol (6 mmol), and Et3N (10 mmol) were added, and the reaction was continued for about 0.5 hours. TLC was used to monitor the progress of the acyl chloride until it disappeared. After the reaction was completed, the reaction was washed once with 20 mL, twice with 10 mL of 1 mol / L HCl, and twice with 10 mL of saturated NaHCO3. The organic phase was collected and combined, dried over anhydrous Na2SO4, and intermediate II-1 was separated and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent.

[0034] Example 2: Synthesis of compound FY21001 The intermediate II-1 (5 mmol) prepared in Example 1, DMF (40 mL), potassium carbonate (10 mmol), and hydroquinone (10 mmol) are placed in a flask, stirred, and heated to 100 ° C. The reaction is monitored by TLC. After the reaction is completed, water (100 ml) is added to the reaction system, and the reaction is extracted three times with ethyl acetate (30 mL). The organic layers are combined, the organic phase is dried and concentrated, and then column chromatography is performed to obtain compound FY21001. The nuclear magnetic resonance spectrum is as follows.

[0035] 1 H NMR (500 MHz, DMSO-d6) δ 9.47 (s, 1H), 7.90 - 7.84 (m, 2H), 7.27 - 7.22 (m, 2H), 7.21 - 7.17 (m, 2H), 7.17 - 7.13 (m, 1H), 6.95 - 6.88 (m, 4H), 6.81 - 6.76 (m, 2H), 4.18 (t, J = 6.5 Hz, 2H), 2.71 - 2.65 (m, 2H), 2.00 - 1.91 (m, 2H).

[0036] Example 3: Synthesis of compound FY21002 The intermediate II-1 (5 mmol) prepared in Example 1, DMF (40 ml), potassium carbonate (10 mmol), and orthomethylphenol (10 mmol) are placed in a flask, stirred, and heated to 100°C. The reaction is monitored by TLC. After the reaction is completed, water (100 ml) is added to the reaction system, and the reaction is extracted three times with ethyl acetate (30 mL). The organic layers are combined, the organic phase is dried and concentrated, and then column chromatography is performed to obtain compound FY21002. The nuclear magnetic resonance spectrum is as follows.

[0037] Example 4: Synthesis of compound FY21003 The intermediate II-1 (5 mmol) prepared in Example 1, DMF (40 ml), potassium carbonate (10 mmol), and p-benzyl alcohol (10 mmol) are placed in a flask, stirred, and heated to 100°C. The reaction is monitored by TLC. After the reaction is completed, water is added to the reaction system, the organic layer is extracted and combined, the organic phase is dried and concentrated, and column chromatography is performed to obtain compound FY21003. The nuclear magnetic resonance spectrum is as follows:

[0038] 1 H NMR (500 MHz, Chloroform-d) δ 7.98 - 7.95 (m, 2H), 7.46 - 7.42 (m, 2H), 7.41 - 7.37 (m, 2H), 7.37 - 7.31 (m, 2H), 7.30 - 7.25 (m, 2H), 7.22 - 7.18 (m, 3H), 7.00 - 6.98 (m, 3H), 6.95 - 6.90(m, 2H), 5.05 (s, 2H), 4.31 (t, J = 6.5 Hz, 2H), 2.80 - 2.73 (m, 2H), 2.11 - 2.03 (m, 2H).

[0039] Example 5: Synthesis of compound FY21008 TIFF2024539274000006.tif34170

[0040] Place intermediate I (5 mmol) in a 50 mL monocoque, add 18 mL of dichloromethane, slowly add (COCl)2 (8 mmol) at room temperature, and reflux for about 1.5 hours after the dropwise addition. TLC will follow the progress of the reaction, and after the reaction is completed, the solvent will be dehydrated. Add 20 mL of dried CH2Cl2, 4-phenoxyphenylpropanol (6 mmol), and Et3N (6 mmol), and react for about 0.5 hours. TLC will follow until no acyl chloride remains. After the reaction is completed, wash once with 20 mL, twice with 10 mL of 1 mol / L HCl, and twice with 10 mL of saturated NaHCO3. The organic phase is collected and combined, dried over anhydrous Na2SO4, and intermediate II-2 is separated and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent.

[0041] The intermediate II-2 (5 mmol) prepared in the previous step, DMF (40 mL), potassium carbonate (10 mmol), and hydroquinone (10 mmol) are placed in a flask, stirred, and heated to 100 ° C. The reaction is monitored by TLC, and after the reaction is completed, water is added to the reaction system, extracted, and the organic layer is combined. The organic phase is dried and concentrated, and then subjected to column chromatography to obtain compound FY21008.

[0042] Example 6: Synthesis of compound FY21011 TIFF2024539274000007.tif33170

[0043] Intermediate I (5 mmol) was placed in a 50 mL monocoque, 18 mL of dichloromethane was added, and (COCl)2 (8 mmol) was slowly added dropwise at room temperature. After the addition, the mixture was refluxed for about 1.5 hours. TLC was used to monitor the progress of the reaction. After the reaction was completed, the solvent was removed by drying. 20 mL of dried CH2Cl2, 4-chlorophenylpropanol (6 mmol), and Et3N (10 mmol) were added, and the mixture was reacted for about 0.5 hours. TLC was used to monitor the disappearance of the acid chloride. After the reaction was completed, the mixture was washed once with 20 mL, twice with 10 mL of 1 mol / L HCl, and twice with 10 mL of saturated NaHCO3. The organic phase was collected and combined, dried over anhydrous Na2SO4, and intermediate II-3 was separated and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent.

[0044] The intermediate II-3 (5 mmol) prepared in the previous step, DMF (40 mL), potassium carbonate (10 mmol), and hydroquinone (10 mmol) are placed in a flask, stirred, and heated to 100 ° C. The reaction is monitored by TLC, and after the reaction is completed, water is added to the reaction system, extracted, and the organic layer is combined. The organic phase is dried and concentrated, and then subjected to column chromatography to obtain compound FY21011.

[0045] Example 7: Synthesis of compound FY21015 The intermediate II-1 (5 mmol) prepared in Example 1, DMF (40 mL), potassium carbonate (10 mmol), and 3-hydroxypyridine (10 mmol) are placed in a flask, stirred, and heated to 100° C. The reaction is monitored by TLC. After the reaction is completed, water is added to the reaction system, and the organic layers are combined after extraction. The organic phase is dried and concentrated, and then subjected to column chromatography to obtain compound FY21015.

[0046] Example 8: Synthesis of compound FY21017 The intermediate II-3 (5 mmol) prepared in Example 6, DMF (40 mL), potassium carbonate (10 mmol), and p-benzyl alcohol (10 mmol) are placed in a flask, stirred, and heated to 100°C. The reaction is monitored by TLC. After the reaction is completed, water is added to the reaction system, the organic layer is extracted and combined, the organic phase is dried and concentrated, and then subjected to column chromatography to obtain compound FY21017. The nuclear magnetic resonance spectrum is as follows:

[0047] 1 H NMR (500 MHz, Chloroform-d) δ 7.88 (s, 2H), 7.37 - 7.34 (m, 2H), 7.33 - 7.29 (m, 2H), 7.25 (d, J = 7.5 Hz, 1H), 7.20(d, J = 7.5 Hz, 2H), 7.12-7.10(m, 3H), 6.91-6.90(m, 3H), 6.84 (s, 2H), 4.97 (s, 2H), 4.22 (t, J = 4.5 Hz, 2H), 2.69-2.66 m, 2H), 1.99-1.95 (m, 2H).

[0048] Example 9: Synthesis of compound FY21018 TIFF2024539274000008.tif34170

[0049] The intermediate I (5 mmol) prepared in Example 1 is placed in a 50 mL monocoque, 18 mL of dichloromethane is added, and (COCl)2 (8 mmol) is slowly dropped at room temperature. After the dropwise addition, the reaction is refluxed for about 1.5 hours, the progress of the reaction is tracked by TLC, and the dry solvent is drained after the reaction is completed. 20 mL of dry CHCl, 4-methoxyphenylpropanol (6 mmol), and EtN) 6 mmol are added, and the reaction is performed for about 0.5 hours. TLC is followed until no acyl chloride remains. After the reaction is completed, the mixture is washed once with 20 mL, twice with 10 mL of 1 mol / L HCl, and twice with 10 mL of saturated NaHCO3. The organic phase is collected and combined, dried over anhydrous Na2SO4, and intermediate II-4 is separated and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent.

[0050] The intermediate II-4 (5 mmol) prepared in the previous step, DMF (40 mL), potassium carbonate (10 mmol), and p-benzyl alcohol (10 mmol) are placed in a flask, stirred, and heated to 100° C. The reaction is monitored by TLC, and after the reaction is completed, water is added to the reaction system, extracted, and the organic layer is combined. The organic phase is dried and concentrated, and then subjected to column chromatography to obtain compound FY21018.

[0051] Example 10: Measurement of the inhibitory function of the target protein MoErs1 of the rice blast fungus by diphenyl ether ester compounds The MoErs1 protein secreted by the blast fungus has cysteine ​​protease inhibitory activity, and the blast fungus MoErs1 protein, which is the target of the diphenyl ether ester compound, specifically binds to it. The amino acid sequence of the MoErs1 protein is shown in SEQ ID NO:1, and the coding nucleotide sequence is shown in SEQ ID NO:2.

[0052] In this example, to verify that diphenyl ether ester compounds significantly suppress the function of MoErs1 and thereby relieve the inhibition of rice cysteine ​​protease activity by MoErs1, rice cysteine ​​protease activity is measured using biotin-labeled DCG-04.

[0053] Microthermophoresis (MST) experiment method: MoErs1-His protein is expressed and purified in E. coli BL21, and the interaction strength between the compound and MoErs1 is measured by using the Monolith NT.LabelFree (Nano Temper Technologies GMBH) instrument using the microthermophoresis method. First, MoErs1-His protein is labeled with a fluorescent probe and stored in a buffer solution; Compounds FY21001, FY21002 and FY21003 are diluted to different concentration gradients and incubated with the labeled MoErs1-His protein for 10 minutes; The above sample is placed in the NT.LabelFree labeled capillary and the values ​​are measured with 20% LED and 40% MST parameters. The curve is created using the KD fitting function of the Nano Temper analysis software (version 1.5.41) and the dissociation constant (Kd) value is calculated. The smaller the Kd value, the stronger the interaction.

[0054] Cysteine ​​protease activity measurement method: 0.5mg of rice cysteine ​​protease is dissolved in 50mM sodium acetate solution, pH 6.0 is prepared, and 10mM L-cysteine ​​and 2M DCG-04 are added. 0.2mM E-64 (E3132, sigma) is added to the control, and MoErs1 protein is incubated at room temperature for 5 hours. The incubated protein is added to 2 volumes of pre-cooled acetone precipitated protein, centrifuged at 10000g for 1 minute, the supernatant is removed, washed twice with 70% acetone, and dried. The precipitate is dissolved in TBS, protein sample buffer is added, and boiled for 5 minutes. Activity is measured by western hybridization method using streptavidin-coupled HRP, which proves that the strap has cysteine ​​protease activity after western hybridization.

[0055] As a result of the MST experiment, the Kd values ​​of compounds FY21001 and FY21002 and MoErs1 protein were 0.32 μM, which was approximately 1 / 20 of the control Kd value of 6.8 μM, and the Kd value of FY21003 and MoErs1 protein was 0.51 μM, indicating that both the diphenyl ether ester compounds and MoErs1 protein have strong binding ability (Figures 1 and 3A). In addition, further enzyme activity measurements showed that without the addition of diphenyl ether ester compounds FY21001, FY21002 and FY21003, MoErs1 could obviously inhibit the activity of rice cysteine ​​protease, and no bands were detected in the corresponding lanes; on the other hand, after gradually increasing the concentration of diphenyl ether ester compounds, the inhibitory effect of MoErs1 on the activity of rice cysteine ​​protease was significantly reduced, and the detection bands in the corresponding lanes gradually became deeper (B in Figures 2 and 3), indicating that diphenyl ether ester compounds could significantly inhibit the function of MoErs1.

[0056] Example 11: Measurement and results of indoor activity to suppress virulence of blast fungus The wild-type strain Guy11 of blast fungus used in this example is stored in this laboratory. The blast fungus strain is placed on complete medium (CM) and cultured in the dark at 28°C. The strain is stored on potato glucose agar medium (PDA) at 10°C and transferred every 3 months; the strain is stored long-term on dry filter paper strips and kept in a refrigerator at -20°C.

[0057] PDA medium arrangement method: Wash and peel the potatoes, cut 200g into small pieces, add water and boil (boil for 30 minutes), filter through four-layer gauze into a beaker, add 20g of glucose and 15-20g of agar powder, add water to measure up to 1L, stir to dissolve thoroughly, then divide into small portions in Erlenmeyer flasks, sterilize at 121℃ for 20 minutes, cool and reserve.

[0058] CM medium arrangement: 50ml of 20x nitrates (120g sodium nitrate, 10.4g potassium chloride, 10.4g Epsom salt, 30.4g potassium dihydrogen phosphate, add distilled water to make 1L), 1ml of 1000x trace elements (2.2g zinc sulfate, 1.1g boric acid, 0.5g manganese chloride tetrahydrate, 0.5g ferrous sulfate heptahydrate, 0.17g cobalt chloride hexahydrate, 0.16g copper sulfate pentahydrate, 0.15g sodium manganate dihydrate, 5g tetrasodium EDTA, add distilled water to make 100ml. Weigh out 1 ml of vitamin solution (0.01 g biotin, 0.01 g vitamin B6, 0.01 g riboflavin B1, 0.01 g riboflavin, 0.01 g para-aminobenzoic acid, 0.01 g nicotinic acid, add distilled water to make 100 ml), weigh out 10 g glucose, 2 g peptone, 1 g yeast extract, 1 g casein amino acid, and 15 g agar powder, add distilled water to make 1 L, dispense into Erlenmeyer flasks, sterilize at 121°C for 20 minutes, cool, and use as spare.

[0059] Mortierella medium arrangement method: Prepare with corn flour and rice stalk. Take 100g of rice stalk, add 1L of water and boil for 30 minutes, add 40g of corn flour and 15g of agar powder and boil for 20 minutes, finally add distilled water to the final volume of 1L, divide into small portions into triangular bottles, sterilize at 121℃ for 20 minutes, cool and reserve.

[0060] Testing Method: This method involves inoculating rice leaves with a blast fungus spore liquid spray, and the specific method is as follows.

[0061] 1. First, conidia were produced in the blast fungus, and a hyphal block (2mm x 2mm) of the blast fungus strain Guy11 on CM medium was inoculated onto SDC medium and cultured in the dark at 28°C for 4 days. After that, the surface hyphae were scraped off and the fungus was induced under black light for 3 days to obtain conidia. 2. 14-day-old greenhouse-cultured rice seedlings were used for spray inoculation experiments, and 4 ml of conidia on the above SDC plate, containing 1×105 conidia / ml and 0.2% (w / v) total gelatin, were added with different concentrations of diphenyl ether ester compounds. They were sprayed on rice leaves, kept moist in the dark for 24 hours, and then cultured at 25°C for 5-7 days, alternating between light and dark. 3. Statistic the diseased area, calculate the inhibition rate, and calculate the preventive treatment effect (%) as follows: diseased area of ​​control rice - diseased area of ​​treated rice / (disease area of ​​control rice) x 100. 4. Each treatment was repeated three times. At the same time, a parallel experiment was carried out with triconazole pesticide. The control effect of diphenyl ether ester compounds against rice blast is shown in Table 1.

[0062] Table 1. Control effect of diphenyl ether ester compounds against rice blast disease TIFF2024539274000009.tif65170Note: Three replicates were performed for each treatment in the test, and data in the table are the average of the three replicates.

[0063] From the results in Table 1, it can be seen that the diphenyl ether ester compounds according to the present invention have a high control effect against the virulence of blast fungus. At the same time, based on the results in Table 1, the EC 50 The values ​​were calculated and the results are shown in Table 2.

[0064] Table 2. EC of diphenyl ether ester compounds against rice blast fungus 50 TIFF2024539274000010.tif71170Note: Three replicates were performed for each treatment in the study, and data in the table are the average of the three replicates.

[0065] As a result, diphenyl ether ester compounds had strong inhibitory activity against the virulence of rice blast fungus, and among them, FY21001 had the best inhibitory activity and its EC 50 The EC value was 231.07 m (80.445 μg / mL), which is the EC 50The EC value was 224.08μM (42.405μg / mL), which is close to the concentration used for FY21001, and shows that it has excellent preventive effect against rice blast disease. 50 The value was 246.69 μM (96.813 μg / mL). Therefore, diphenyl ether ester compounds can be used to manufacture fungicides.

[0066] Example 12: Activity measurement and results of diphenyl ether ester compounds for inhibiting germination of conidia and formation of adhesins of rice blast fungus 1. First, obtain conidia according to the method of Example 9. 2. Centrifuge the above spore liquid at 4000 rpm for 3 minutes, wash with sterilized ddH2O three times, and adjust the concentration to 2-5 × 10 4 The mixture was adjusted to 100 / ml, and different concentrations of diphenyl ether ester compounds FY21001 or FY21019 were added, and 20 μl of the mixture was aspirated and dropped onto a hydrophobic glass (12-540-A, Fisherbrand, USA), moistened, and cultured in a dark incubator at 28°C. After 24 hours of culture, the spore germination and the formation of attached spores were observed. 3. Statistically measure the spore germination and attached spore formation rates, and calculate the inhibition rate. Inhibition rate (%) (control spore germination or attached spore formation rate - treatment group spore germination or attached spore formation rate) / (control spore germination or attached spore formation rate) x 100. 4. Repeat each treatment three times. The inhibitory activities of the diphenyl ether ester compounds FY21001 and FY21019 against spore germination and adherent spore formation of blast fungus are shown in Table 3 and FIG. 4, while the other compounds do not have any significant effect on spore germination and adherent spore formation of blast fungus.

[0067] Table 3. Inhibitory activity of diphenyl ether ester compounds against blast fungus spore germination TIFF2024539274000011.tif31170Note: Three replicates were performed for each treatment in the test, and data in the table are the average of the three replicates.

[0068] Table 4. Inhibitory activity of diphenyl ether ester compounds against sporulation of rice blast fungus TIFF2024539274000012.tif30170Note: Three replicates were performed for each treatment in the study, and data in the table are the average of the three replicates.

[0069] From the results of Tables 3 and 4, it can be seen that the diphenyl ether ester compounds of the present invention exhibit strong inhibitory activity against the germination and adhering spore formation of blast fungus. At the same time, based on the results of Tables 3 and 4, the EC of the diphenyl ether ester compounds against the conidial germination and adhering spore formation of blast fungus was 50 The values ​​were calculated and the results are shown in Table 5.

[0070] Table 5. EC of diphenyl ether ester compounds on germination and adhesiospore formation of conidia of rice blast fungus 50 TIFF2024539274000013.tif38170Note: Three replicates were performed for each treatment in the study, and data in the table are the average of the three replicates.

[0071] As a result, diphenyl ether ester compounds had strong inhibitory activity against blast fungus spore germination and adherent spore formation, and among them, the EC 50 The values ​​were 102.57 μM (35.76 μg / mL) and 53.03 μM (18.48 μg / mL), respectively, and the C 50 The values ​​are 166.42 μM (65.31 g / mL) and 68.58 μM (26.91 μg / mL), respectively. Therefore, diphenyl ether ester compounds can be used to manufacture fungicides.

[0072] As described above, the diphenyl ether ester compound of the present invention has the characteristics of simple structure, easy production, low cost, strong specificity, etc., and also shows good inhibitory effect against rice blast fungus, and is worthy of further research and development.

[0073] Although the preferred embodiment of the present invention has been described in detail above, the present invention is not limited thereto. Many simple modifications are possible in the technical aspects of the present invention, including combining the technical features of the present invention in other suitable ways, within the scope of the technical idea of ​​the present invention, and these simple modifications and combinations are also considered to be the contents disclosed in the present invention, and all of them should be considered to fall within the protection scope of the present invention.

Claims

1. Formula [I], [In the formula, R １ is H, hydroxyl group, amino group, mercapto group, halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R １ is mono- or polysubstituted at any substitution position of the aromatic ring or aromatic heterocycle, R ２ is H, hydroxyl group, amino group, mercapto group, halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R ２ is located at any substitution position of the aromatic ring or aromatic heterocycle and is mono- or polysubstituted, R １ and R ２ are the same or different, X is either C or N], In addition, diphenyl ether ester compounds are compounds of the following structural formula: is eliminated, In formula [I], each substituent is as follows: Compound FY21001: X is C, R 1 is 4-OH, and R 2 is H; Compound FY21002: X is C, R 1 is CH 3 , and R 2 is H; Compound FY21003: X is C, R 1 is 4-OCH 2 Ph, and R 2 is H; Compound FY21004: X is C, R 1 is 4-CH 3 , and R 2 is H; Compound FY21005: X is C, R 1 is 4-F, and R 2 is H; Compound FY21006: X is C, R 1 is 4-Cl, and R 2 is H; Compound FY21007: X is C, R 1 is 4-Br, and R 2 is H; Compound FY21009: X is C, R 1 is 4-OH, and R 2 is 4-CH 3 ; Compound FY21010: X is C, R 1 is 4-OH, and R 2 is 4-F; Compound FY21011: X is C, R 1 is 4-OH, and R 2 is 4-Cl; Compound FY21012: X is C, R 1 is 4-OH, and R 2 is 4-Br; Compound FY21013: X is C, R 1 is 4-OH, and R 2 is 4-OCH 3 ; Compound FY21014: X is C, R 1 is 4-SH, and R 2 is H; Compound FY21015: X is N, R 1 is 4-OH, and R 2 is H; Compound FY21016: X is C, R 1 is 4-OCH 3 , and R 2 is H; Compound FY21017: X is C, R 1 is 4-OCH 2 Ph, and R 2 is 4-Cl; Compound FY21018: X is C, R 1 is 4-OCH 2 Ph, and R 2 is 4-OCH 3 ; Compound FY21019: X is C, R 1 is 4-OCH 3 , and R 2 is 4-OCH 3 ; Compound FY21020: A diphenyl ether ester compound, characterized in that X is C, R 1 is 4-CH 3 , and R 2 is 4-Cl.

2. The compound of formula III can be obtained through the following two steps, step a and step b:

2. The method for producing a diphenyl ether ester compound according to claim 1, wherein the target compound is

3. In step a, the synthesis method of formula II is as follows: raw material I is dissolved in a solvent, oxalyl chloride is added, and the reaction is carried out under stirring at -5°C to 5°C; after the reaction is completed, the solvent is removed and the remaining solid is dissolved in a solvent to prepare the reaction mixture; At low temperature, phenylpropanol is dissolved in a solvent, triethylamine is added, and after stirring, acyl chloride dissolved in a solvent is added dropwise to the reaction system; when the reaction is completed, saturated NaHCO ３ The process according to claim 2, characterized in that the organic layer is extracted and combined, dried and concentrated, and then subjected to column chromatography to obtain intermediate II.

4. The method of claim 3, wherein in step b, the synthesis of the compound of formula III is carried out by adding the intermediate II, a solvent, and a base to a flask, stirring, and heating to 80-120°C; after the reaction is completed, water is added to the reaction system, and the organic layer is extracted and combined, dried, concentrated, and then subjected to column chromatography to obtain the compound of formula III.

5. Use of the diphenyl ether ester compound according to claim 1 or 2 for inhibiting the function of the rice blast fungus target protein MoErs1.

6. The diphenyl ether ester compound has a structure represented by formula [I]: During the ceremony, R １ is a hydroxyl group, an amino group, a mercapto group, a halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R １ is mono- or polysubstituted at any substitution position of the aromatic ring or aromatic heterocycle, R ２ is H, hydroxyl group, amino group, mercapto group, halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R ２ is mono- or polysubstituted at any substitution position of the aromatic ring or aromatic heterocycle, R １ and R ２ are the same or different, 1. Use of a diphenyl ether ester compound for controlling rice blast, wherein X is either C or N.

7. 7. The use according to claim 6, wherein the diphenyl ether ester compound is a compound represented by formula (I) in which each substituent is as follows: Compound FY21001: X is C and R １ is 4-OH, and R ２ is H, Compound FY21002: X is C and R １ is CH ３ and R ２ is H, Compound FY21003: X is C and R １ is 4-OCH ２ Ph and R ２ is H, Compound FY21004: X is C and R １ is 4-CH ３ and R ２ is H, Compound FY21005: X is C and R １ is 4-F and R ２ is H, Compound FY21006: X is C and R １ is 4-Cl, and R ２ is H, Compound FY21007: X is C and R １ is 4-Br, and R ２ is H, Compound FY21009: X is C and R １ is 4-OH, and R ２ is 4-CH ３ and Compound FY21010: X is C and R １ is 4-OH, and R ２ is 4-F, Compound FY21011: X is C and R １ is 4-OH, and R ２ is 4-Cl, Compound FY21012: X is C and R １ is 4-OH, and R ２ is 4-Br, Compound FY21013: X is C and R １ is 4-OH, and R ２ is 4-OCH ３ and Compound FY21014: X is C and R １ is 4-SH, and R ２ is H, Compound FY21015: X is N and R １ is 4-OH, and R ２ is H, Compound FY21016: X is C and R １ is 4-OCH ３ and R ２ is H, Compound FY21017: X is C and R １ is 4-OCH ２ Ph and R ２ is 4-Cl, Compound FY21018: X is C and R １ is 4-OCH ２ Ph and R ２ is 4-OCH ３ and Compound FY21019: X is C and R １ is 4-OCH ３ and R ２ is 4-OCH ３ or Compound FY21020: X is C and R １ is 4-CH ３ and R ２ is 4-Cl, 7. The use according to claim 6.

8. Use of a diphenyl ether ester compound as an agricultural fungicide, the diphenyl ether ester compound being represented by the formula [I]: [In the formula, R １ is a hydroxyl group, an amino group, a mercapto group, a halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R １ is mono- or polysubstituted at any substitution position of the aromatic ring or aromatic heterocycle, R ２ is H, hydroxyl group, amino group, mercapto group, halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R ２ is mono- or polysubstituted at any substitution position of the aromatic ring or aromatic heterocycle, R １ and R ２ are the same or different, X is either C or N.

9. The use according to claim 8, wherein the diphenyl ether ester compound is a compound of formula [I], wherein each substituent is as follows: Compound FY21001: X is C and R １ is 4-OH, and R ２ is H, Compound FY21002: X is C and R １ is CH ３ and R ２ is H, Compound FY21003: X is C and R １ is 4-OCH ２ Ph and R ２ is H, Compound FY21004: X is C and R １ is 4-CH ３ and R ２ is H, Compound FY21005: X is C and R １ is 4-F and R ２ is H, Compound FY21006: X is C and R １ is 4-Cl, and R ２ is H, Compound FY21007: X is C and R １ is 4-Br, and R ２ is H, Compound FY21009: X is C and R １ is 4-OH, and R ２ is 4-CH ３ and Compound FY21010: X is C and R １ is 4-OH, and R ２ is 4-F, Compound FY21011: X is C and R １ is 4-OH, and R ２ is 4-Cl, Compound FY21012: X is C and R １ is 4-OH, and R ２ is 4-Br, Compound FY21013: X is C and R １ is 4-OH, and R ２ is 4-OCH ３ and Compound FY21014: X is C and R １ is 4-SH, and R ２ is H, Compound FY21015: X is N and R １ is 4-OH, and R ２ is H, Compound FY21016: X is C and R １ is 4-OCH ３ and R ２ is H, Compound FY21017: X is C and R １ is 4-OCH ２ Ph and R ２ is 4-Cl, Compound FY21018: X is C and R １ is 4-OCH ２ Ph and R ２ is 4-OCH ３ and Compound FY21019: X is C and R １ is 4-OCH ３ and R ２ is 4-OCH ３ or Compound FY21020: X is C and R １ is 4-CH ３ and R ２ The use according to claim 8, wherein is 4-Cl.

10. An agricultural chemical fungicide comprising an active ingredient containing a diphenyl ether ester compound and an auxiliary material, wherein the diphenyl ether ester compound is represented by the formula [I]: [In the formula, R １ is a hydroxyl group, an amino group, a mercapto group, a halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R １ is mono- or polysubstituted at any substitution position of the aromatic ring or aromatic heterocycle, R ２ is H, hydroxyl group, amino group, mercapto group, halogen, C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkylamino group, C １ ~C １２ Alkylmercapto group, C ２ ~C ６ Alkenyl group, C ２ ~C ６ Alkynyl group, halogen-substituted C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C １ ~C １２ Alkoxy-substituted phenyl group, naphthyl group, pyridyl group, furyl group, thienyl group, pyrazole group, imidazole group, C １ ~C １２ selected from a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, a furyl group, a thienyl group, a pyrazole group, an imidazole group, a substituted or unsubstituted 5-membered heterocycle, and a substituted or unsubstituted 6-membered heterocycle, each of which is substituted with an alkyl group and / or a halogen atom, R ２ is mono- or polysubstituted at any substitution position of the aromatic ring or aromatic heterocycle, R １ and R ２ are the same or different, X is either C or N.

11. The use according to claim 10, wherein the diphenyl ether ester compound is a compound of formula [I], wherein each substituent is as follows: Compound FY21001: X is C and R １ is 4-OH, and R ２ is H, Compound FY21002: X is C and R １ is CH ３ and R ２ is H, Compound FY21003: X is C and R １ is 4-OCH ２ Ph and R ２ is H, Compound FY21004: X is C and R １ is 4-CH ３ and R ２ is H, Compound FY21005: X is C and R １ is 4-F and R ２ is H, Compound FY21006: X is C and R １ is 4-Cl, and R ２ is H, Compound FY21007: X is C and R １ is 4-Br, and R ２ is H, Compound FY21009: X is C and R １ is 4-OH, and R ２ is 4-CH ３ and Compound FY21010: X is C and R １ is 4-OH, and R ２ is 4-F, Compound FY21011: X is C and R １ is 4-OH, and R ２ is 4-Cl, Compound FY21012: X is C and R １ is 4-OH, and R ２ is 4-Br, Compound FY21013: X is C and R １ is 4-OH, and R ２ is 4-OCH ３ and Compound FY21014: X is C and R １ is 4-SH, and R ２ is H, Compound FY21015: X is N and R １ is 4-OH, and R ２ is H, Compound FY21016: X is C and R １ is 4-OCH ３ and R ２ is H, Compound FY21017: X is C and R １ is 4-OCH ２ Ph and R ２ is 4-Cl, Compound FY21018: X is C and R １ is 4-OCH ２ Ph and R ２ is 4-OCH ３ and Compound FY21019: X is C and R １ is 4-OCH ３ and R ２ is 4-OCH ３ or Compound FY21020: X is C and R １ is 4-CH ３ and R ２ The use according to claim 10, wherein is 4-Cl.

12. The pesticide fungicide according to claim 10 or 11, wherein the content of the active ingredient is 1 to 99.9999% by weight.

13. 12. The pesticide fungicide according to claim 10 or 11, wherein the formulation of the pesticide fungicide is one selected from an emulsifiable concentrate, a suspension concentrate, a dust concentrate, a granule concentrate, a wettable powder, a poison bait, a mother liquor, and a mother powder.

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