阅读说明：本技术 1-芳基-4-吡啶酮类化合物的应用 (Application of 1-aryl-4-pyridone compounds ) 是由 孙然锋 俞秀强 朱新月 周杨 李庆林 于 2019-11-06 设计创作，主要内容包括：本发明为1-芳基-4-吡啶酮类化合物的应用,提供了式(I)所示结构化合物在抑制植物病原菌活性中的应用。本发明式(I)所示结构化合物对农业生产中的植物病原真菌具有出色的广谱抗真菌活性,同时对于作物的细菌性病害也具有防治效果。体内生物测定证明式(I)所示结构化合物对黄瓜霜霉病、黄瓜靶斑病、小麦赤霉病和番茄灰霉病实现了超过95％的防治效果。同时,芒果采后保鲜实验结果表明,化合物在能有效控制芒果采后病害并且延长芒果了保鲜时间。此外,发现上述化合物还可以在盆栽试验中有效控制水稻细菌性叶枯病,这比商用杀菌剂中生菌素更有效。综上所述,式(I)所示的1-芳基-4-吡啶酮衍生物具有广谱抗植物病原真菌和细菌活性,是一类具有广泛生物活性的先导化合物。(The invention provides application of a 1-aryl-4-pyridone compound and provides application of a compound with a structure shown in a formula (I) in inhibiting activity of phytopathogen. The compound with the structure shown in the formula (I) has excellent broad-spectrum antifungal activity on plant pathogenic fungi in agricultural production, and simultaneously has control effect on bacterial diseases of crops. In vivo bioassay proves that the structural compound shown in the formula (I) realizes the prevention and treatment effects of more than 95 percent on cucumber downy mildew, cucumber target spot, wheat scab and tomato gray mold. Meanwhile, the mango postharvest preservation experiment result shows that the compound can effectively control mango postharvest diseases and prolong the mango preservation time. In addition, the compound can be found to be effective in controlling bacterial leaf blight of rice in a pot experiment, which is more effective than zhongshengmycin serving as a commercial bactericide. In conclusion, the 1-aryl-4-pyridone derivative shown in the formula (I) has broad-spectrum activity against plant pathogenic fungi and bacteria, and is a lead compound with wide biological activity.)

1. The application of the compound with the structure shown in the formula (I) in inhibiting the activity of phytopathogen;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

2. Use according to claim 1, wherein R is¹Selected from H, hydroxyl or alkoxy of C1-C6; r²Is C1-C6 alkyl; r³Selected from H, C1-C6 alkyl; x is selected from H, C1-C6 alkyl, C6-C20 aryl and C6-C30 aryl heterocyclic group.

3. Use according to claim 2, wherein R is¹Selected from H, hydroxy or methoxy; r²Is methyl or ethyl; r³Selected from H or methyl; x is selected from H, methyl or one of the following a-1-a-29 structures:

4. use according to claim 3, wherein the phytopathogen is a phytopathogenic fungus or a phytopathogenic bacterium.

5. The use according to claim 4, the phytopathogenic fungus being selected from the group consisting of mango stem rot (Botryodipterodia theobroma), Gibberella zeae (Fusarium graminearum), Pityrosporum ovale (Neospora dimyrium), Magnaporthe oryzae (Pyricularia oryzae), Musa cinerea (Fusarium oxysporum), Musa paradisiaca (Colletotrichum musae), Phytophthora capsici (Phytophthora capsici), Botrytis cinerea (Botrytis cinerea), Sclerotia sclerotiorum (Sclerotinia sclerotiorum), Pseudoperonospora cubensis (Pseudoperonospora cubensis), Pseudoperonospora cucumis (Corynespora cassoides), and Rhizoctonia solani (Rhizoctonia solani);

the plant pathogenic bacteria are Xanthomonas oryzae pv.

6. The application of the compound with the structure shown in the formula (I) in preventing and treating plant diseases caused by phytopathogens;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

7. The use according to claim 6, wherein the plant disease is selected from the group consisting of mango base rot, wheat scab, dragon fruit canker, rice blast, banana wilt, banana anthracnose, phytophthora capsici, tomato gray mold, rape sclerotinia rot, cucumber downy mildew, cucumber target spot, rice sheath blight and rice bacterial leaf blight.

8. The application of the compound with the structure shown in the formula (I) in preparing an inhibitor for inhibiting the activity of phytopathogen;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from alkyl of H, C1-C10Aryl of C6-C30, and heterocyclic radical of C6-C30.

9. A plant pathogenic bacteria activity inhibitor is characterized by comprising a compound with a structure shown in a formula (I);

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

10. A method for controlling a plant disease, characterized by applying the inhibitor of claim 9.

Technical Field

The invention relates to the technical field of biology, in particular to application of a 1-aryl-4-pyridone compound.

Background

For decades, phytopathogenic fungi have caused serious damage to crop production. Over 8000 known fungal species can cause plant disease. Diseases caused by plant pathogenic fungi are important factors for restricting agricultural production in China, and the diseases are often generated in a large scale and cause huge loss on agricultural production in China. The existing agricultural pesticide mainly comprises chemical synthetic pesticides, chemical bactericide pesticides are required to be produced and used by China for more than 80 ten thousand tons every year, the loss caused by diseases is reduced to a great extent by using the pesticides, but a series of problems and hidden dangers are caused by the large-scale use of the chemical pesticides, such as: pesticide residue, environmental pollution, ecological balance damage, drug resistance generation and the like. In the control of agricultural diseases, many strains of phytopathogenic fungi that are resistant or cross-resistant to some commonly used pesticides (e.g., carbendazim, thiophanate-methyl, thiabendazole, benomyl, metalaxyl, oxadixyl, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, famoxadone, etc.) have been found to be up to several hundred times more resistant. The development of these resistances has caused a great hindrance to the production of agricultural chemicals and the control of agricultural diseases, and therefore, the development of novel fungicides is urgently required to solve these problems.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a compound having excellent broad-spectrum antifungal activity against plant pathogenic fungi in agricultural production and simultaneously having control effect against bacterial diseases of crops.

The invention provides application of a structural compound shown in a formula (I) in inhibiting the activity of phytopathogen;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

Preferably, said R is¹Selected from H, hydroxyl or alkoxy of C1-C6; r²Is C1-C6 alkyl; r³Selected from H, C1-C6 alkyl; x is selected from H, C1-C6 alkyl, C6-C20 aryl and C6-C30 aryl heterocyclic group.

Preferably, said R is¹Selected from H, hydroxy or methoxy; r²Is methyl or ethyl; r³Selected from H or methyl; x is selected from H, methyl or one of the following a-1-a-29 structures:

preferably, the phytopathogen is a phytopathogenic fungus or a phytopathogenic bacterium.

Preferably, the phytopathogenic fungus is selected from the group consisting of mango stem rot (Botryodiplodia theobromae), Fusarium graminearum (Fusarium graminearum), dragon fruit canker (neospora dimyrium), rice blast (Pyricularia oryzae), banana wilt (Fusarium oxysporum), banana anthracnose (Colletotrichum musae), Phytophthora capsici (Phytophthora capsici), Botrytis cinerea (Botrytis cinerea), Sclerotinia sclerotiorum (sclerotiorum), cucumber downy mildew (Pseudoperonospora cubensis), cucumber target spot (Corynespora cassiacola) and rice sheath blight (Rhizoctonia solani) and the plant pathogen is Xanthomonas flava xanthosa pvaeae.

The invention provides application of a compound with a structure shown in a formula (I) in preventing and treating plant diseases caused by phytopathogens;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

Preferably, the plant disease is selected from the group consisting of mango base rot, wheat scab, dragon fruit canker, rice blast, banana wilt, banana anthracnose, phytophthora capsici leonian, tomato gray mold, sclerotinia rot of colza, cucumber downy mildew, cucumber target spot, rice sheath blight, and rice bacterial leaf blight.

The invention provides application of a compound with a structure shown in a formula (I) in preparation of an inhibitor for inhibiting activity of phytopathogen;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

The invention provides a plant pathogenic bacteria activity inhibitor, which comprises a structural compound shown in a formula (I);

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

The invention provides a method for preventing and treating plant diseases, which applies the inhibitor in the technical scheme.

Compared with the prior art, the invention provides the application of the structural compound shown in the formula (I) in inhibiting the activity of phytopathogen. The compound with the structure shown in the formula (I) has excellent broad-spectrum antifungal activity on plant pathogenic fungi in agricultural production, and simultaneously has control effect on bacterial diseases of crops. In vivo bioassay proves that the structural compound shown in the formula (I) realizes the prevention and treatment effects of more than 95 percent on cucumber downy mildew, cucumber target spot, wheat scab and tomato gray mold. Meanwhile, the mango postharvest preservation experiment result shows that the structural compound shown in the formula (I) can effectively control mango postharvest diseases and prolong the mango preservation time. In addition, the compound can be found to be effective in controlling bacterial leaf blight of rice in a pot experiment, which is more effective than zhongshengmycin serving as a commercial bactericide. In conclusion, the 1-aryl-4-pyridone derivative shown in the formula (I) has broad-spectrum activity against plant pathogenic fungi and bacteria, and is a lead compound with wide biological activity.

Detailed Description

The invention provides an application of 1-aryl-4-pyridone compounds, and persons skilled in the art can use the contents to appropriately modify other related applications to realize the application. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

The invention provides application of a structural compound shown in a formula (I) in inhibiting the activity of phytopathogen;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; h, hydroxyl or alkoxy of C1-C6 is preferred; more preferably H, hydroxy or alkoxy of C1-C3; most preferably H, hydroxy, methoxy or ethoxy; h, hydroxyl and methoxy are particularly preferred.

R²Is C1-C10 alkyl; preferably C1-C6 alkyl; more preferably a C1-C3 alkyl group; most preferably methyl or ethyl.

R³An alkyl group selected from H, C1 to C10; preferably H, C1 to C6 alkyl; more preferably H, C1 to C3 alkyl; most preferably H, methyl or ethyl; h or methyl is particularly preferred.

X is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical. Preferably, X is selected from H, C1-C6 alkyl, C6-C20 aryl, and C6-C30 aryl heterocyclic group, more preferably, X is selected from H, methyl or one of the following a-1-a-29 structures:

in a part of preferable embodiments of the invention, the structural compound shown in the formula (I) is specifically a structure shown in the following I-1 to I-37 (the following examples are abbreviated as 1 to 37):

the invention also provides a preparation method of the compound with the structure shown in the formula (I), which comprises the following steps:

heating pyrone with a structure shown in a formula (II) and amine compound with a structure shown in a formula (III) in water for reflux reaction to obtain a compound with a structure shown in a formula (I); or

Reacting pyrone with a structure shown in a formula (II) and amine compound with a structure shown in a formula (III) in a mixed solution of water, ethanol and hydrochloric acid under high pressure and heating to obtain a compound with a structure shown in a formula (I);

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

One preparation method of the compound with the structure shown in the formula (I) provided by the invention preferably comprises the following steps: heating pyrone with a structure shown in a formula (II) and amine compound with a structure shown in a formula (III) in water for reflux reaction to obtain a compound with a structure shown in a formula (I).

The method specifically comprises the following steps: dissolving pyrone with the structure of formula (II) in water, adding excessive amine with the structure of formula (III), and refluxing the reaction mixture to obtain the 1-aryl-4-pyridone derivative

Wherein the heating reflux reaction is carried out for overnight; preferably 10-15 h;

after the reflux reaction, ammonia and solvent were also removed under reduced pressure and the mixture was cooled to room temperature overnight. The solid product obtained was recrystallized from a 50% water/methanol mixture in the presence of activated carbon. The activated carbon was filtered off and the product was concentrated under reduced pressure. The final product was dried in a desiccator with phosphorous pentoxide.

The invention provides a compound with a structure shown in formula (I), wherein another preparation method preferably comprises the following steps:

and (2) reacting pyrone with a structure shown in a formula (II) and amine compound with a structure shown in a formula (III) in a mixed solution of water, ethanol and hydrochloric acid under high pressure and heating to obtain the compound with the structure shown in the formula (I).

Dissolving pyrone with a structure shown in formula (II) and amine with a structure shown in formula (III) in an acidic mixed solution of water, ethanol and hydrochloric acid, and heating the reaction mixture in a high-pressure reaction kettle for reaction.

According to the invention, the pressure of the high-pressure heating reaction is 0.15MPa, and the heating temperature is 160-170 ℃; the reaction time is 10-12 h.

The pyrone of formula (II) is not limited in the source, and may be commercially available or prepared by methods known to those skilled in the art.

According to the invention, the phytopathogen is a phytopathogenic fungus or a phytopathogenic bacterium.

Specifically, the phytopathogenic fungi include, but are not limited to, mango stem rot (botryodiodia theobroma), gibberella zeae (Fusarium graminearum), dragon fruit canker (neospora dimyritum), Pyricularia oryzae (Pyricularia oryzae), banana Fusarium oxysporum (Fusarium oxysporum), banana anthracnose (Colletotrichum muscae), Phytophthora capsici (Phytophthora capsici), Botrytis cinerea (Botrytis cinerea), Sclerotinia sclerotiorum (sclerotiotrium sclerotiorum), cucumber downy mildew (Pseudoperonospora cubensis), cucumber target spot (Corynespora cassiaca), and rice sheath blight (Rhizoctonia solani) including, but not limited to, Xanthomonas oryzae orazaya oryzae.

The invention provides application of a compound with a structure shown in a formula (I) in preventing and treating plant diseases caused by phytopathogens;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

According to the present invention, the plant diseases include, but are not limited to, mango base rot, wheat scab, dragon fruit canker, rice blast, banana wilt, banana anthracnose, phytophthora capsici, tomato gray mold, sclerotinia rot of colza, cucumber downy mildew, cucumber target spot, rice sheath blight and rice bacterial leaf blight.

The invention provides application of a compound with a structure shown in a formula (I) in preparation of an inhibitor for inhibiting activity of phytopathogen;

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

The compound with the structure can be used as an inhibitor for inhibiting the activity of phytopathogen, an antibacterial agent and the like.

The invention provides a plant pathogenic bacteria activity inhibitor, which comprises a structural compound shown in a formula (I);

in the formula, R¹Selected from H, hydroxyl or alkoxy of C1-C10; r²Is C1-C10 alkyl; r³An alkyl group selected from H, C1 to C10; x is selected from H, C1-C10 alkyl, C6-C30 aryl and C6-C30 heterocyclic radical.

The structural compound shown in the formula (I) is clearly described in the invention, and the description is omitted. The inhibitor may comprise the above compound and conventional adjuvants and ingredients.

The invention provides a method for preventing and treating plant diseases, which applies the inhibitor in the technical scheme.

The method for preventing and treating the plant diseases comprises the steps of applying the inhibitor in the technical scheme; the above application method is preferably embodied as follows:

spray treatment: the sprayer is a crop sprayer with a spray pressure of 1.5kg/cm²The amount of the sprayed liquid is about 675L/hm². After the test material is treated, the test material is naturally dried and inoculated with pathogenic bacteria after 20-24 hours.

The invention provides application of a structural compound shown in a formula (I) in inhibiting activity of phytopathogen. The compound with the structure shown in the formula (I) has excellent broad-spectrum antifungal activity on plant pathogenic fungi in agricultural production, and simultaneously has control effect on bacterial diseases of crops. In vivo bioassay proves that the structural compound shown in the formula (I) realizes the prevention and treatment effects of more than 95 percent on cucumber downy mildew, cucumber target spot, wheat scab and tomato gray mold. Meanwhile, the mango postharvest preservation experiment result shows that the structural compound shown in the formula (I) can effectively control mango postharvest diseases and prolong the mango preservation time. In addition, the compound can be found to be effective in controlling bacterial leaf blight of rice in a pot experiment, which is more effective than zhongshengmycin serving as a commercial bactericide. In conclusion, the 1-aryl-4-pyridone derivative shown in the formula (I) has broad-spectrum activity against plant pathogenic fungi and bacteria, and is a lead compound with wide biological activity.

In order to further illustrate the present invention, the following examples are provided to describe the application of the 1-aryl-4-pyridone compounds provided by the present invention in detail.