Application of material containing arylboronic acid compound in prevention and treatment of crop diseases

Abstract

The invention provides application of a material containing an arylboronic acid compound in prevention and treatment of crop diseases. The arylboronic acid compound is selected from one of # imgabs 0 #, # imgabs 1 #, # imgabs 2 # and # imgabs 3 #. A is selected from one of substitution structures of # imgabs 4 #, # imgabs 5 #, # imgabs 6 # or # imgabs 7 #, and B is selected from one of substitution structures of # imgabs 4 #, # imgabs 5 #, # imgabs 6 # and # imgabs 7 #; r1, R2, R3, R4 and R5 are independently selected from hydrogen, halogen, alkoxy with the carbon atom number of 1-6, aldehyde group, carboxyl, cyano, trifluoromethyl, alkyl with the carbon atom number of 1-6 or alkoxy carbonyl with the carbon atom number of 1-6, R1, R2, R3, R4 and R5 are not hydrogen at the same time, and at least two groups in R1, R2, R3, R4 and R5 are hydrogen; r6, R7, R8, R9 and R10 are independently selected from hydrogen or halogen respectively; m is sulfur or oxygen; and R11 and R12 are respectively and independently hydrogen, alkyl with 1-8 carbon atoms, phenyl or substituted phenyl, or R11 and R12 are bonded to form a ring. The material has a remarkable inhibition effect on a plurality of pathogenic bacteria causing agricultural plant diseases.

Description

Technical Field

[0001] The present invention relates to the technical field of agricultural pathogen prevention and control, and in particular to the application of materials containing arylboronic acid compounds in preventing and controlling crop diseases. Background Art

[0002] Plant pathogens are microorganisms that parasitize plants and cause plant diseases. They persist for a long time, are difficult to completely eliminate, and are contagious, resulting in significant economic losses in agricultural production. In today's agricultural sector, irrational use of pesticides or the long-term use of a single fungicide has led to the development of resistance to a wide range of agents in some bacterial and fungal diseases, posing a significant challenge in agricultural sterilization. The development of new pesticides not only carries significant investment risks but also faces increasing environmental and food safety requirements and stricter regulations, leading to lengthy development cycles. As plant pathogens develop resistance to a wide range of agents, identifying new, effective, and broadly applicable pesticides is crucial. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems in the prior art to a certain extent. To this end, one object of the present invention is to propose the use of materials containing arylboronic acid compounds in preventing and controlling crop diseases.

[0004] The present invention proposes the use of materials containing aryl boronic acid compounds in preventing and controlling crop diseases, wherein the aryl boronic acid compounds are selected from 、 、 、 One of the following; A is selected from 、 、 or One of the substitution structures; R1, R2, R3, R4, and R5 are independently selected from hydrogen, halogen, alkoxy having 1 to 6 carbon atoms, aldehyde, carboxyl, cyano, trifluoromethyl, alkyl having 1 to 6 carbon atoms, or alkoxycarbonyl having 1 to 6 carbon atoms, and R1, R2, R3, R4, and R5 are not hydrogen at the same time, and at least two of R1, R2, R3, R4, and R5 are hydrogen; R6, R7, R8, R9, R 10 are independently selected from hydrogen or halogen; M is sulfur or oxygen; R 11 、R 12 are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a substituted phenyl group, or R 11 and R 12 Bond to form a ring.

[0005] According to the application of the aryl boronic acid compounds provided by the present invention in preventing and controlling crop diseases, the above-mentioned aryl boronic acid compounds have a significant inhibitory effect on various pathogenic bacteria that cause agricultural plant diseases, can effectively prevent and inhibit the occurrence of plant diseases, and can be used as highly effective active pesticides in agricultural production to increase agricultural production output.

[0006] In some embodiments of the present invention, at least one of R1, R2, R3, R4, and R5 is a halogen, preferably two of R1, R2, R3, R4, and R5 are halogens, and more preferably three of R1, R2, R3, R4, and R5 are halogens.

[0007] In some embodiments of the present invention, R6, R7, R8, R9, R 10 At least one of the groups is halogen, preferably R6, R7, R8, R9, R 10 Two of the groups are halogen, more preferably R6, R7, R8, R9, R 10 Three of the groups are halogens.

[0008] In some embodiments of the present invention, The substitution structure is selected from At least one hydrogen on the benzene ring is replaced by R 13 Substituted, the R 13 Selected from carboxyl, hydroxyl, aldehyde or carboxyl-substituted vinyl.

[0009] In some embodiments of the present invention, The substitution structure is selected from One hydrogen on the benzene ring is replaced by R 13 Substituted, the R 13 Selected from carboxyl, hydroxyl, aldehyde or carboxyl-substituted vinyl.

[0010] In some embodiments of the present invention, The substitution structure is selected from The two hydrogen atoms on the benzene ring are replaced by R 13 Substitute, two of the R 13 Each is independently selected from a carboxyl group, a hydroxyl group, an aldehyde group or a carboxyl-substituted vinyl group.

[0011] In some embodiments of the present invention, the substituted phenyl group is selected from an alkyl substituted phenyl group having 1 to 3 carbon atoms, such as a methyl substituted phenyl group, an ethyl substituted phenyl group, or a propyl substituted phenyl group.

[0012] In some embodiments of the present invention, R 11 and R 12 The rings are bonded to form a five-membered ring or a six-membered ring, preferably a five-membered ring.

[0013] In some embodiments of the present invention, the halogen is at least one of chlorine, fluorine or bromine, preferably chlorine.

[0014] In some embodiments of the present invention, at least one of R1 and R3 is hydrogen.

[0015] In some embodiments of the present invention, one of R1 and R3 is hydrogen.

[0016] In some embodiments of the present invention, R1 and R3 are hydrogen.

[0017] Preferably, three of R1, R2, R3, R4 and R5 are chlorine.

[0018] More preferably, R1 is hydrogen, three of R2, R3, R4, and R5 are chlorine, and one of R2, R3, R4, and R5 is hydrogen.

[0019] In some embodiments of the present invention, the alkoxy group having 1 to 6 carbon atoms is selected from methoxy, ethoxy, propoxy, butoxy or pentoxy.

[0020] In some embodiments of the present invention, the alkoxycarbonyl group having 1 to 6 carbon atoms is selected from methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or butoxycarbonyl, preferably methoxycarbonyl.

[0021] In some embodiments of the present invention, the alkyl group having 1 to 6 carbon atoms is selected from methyl, ethyl, propyl or butyl, preferably methyl.

[0022] In some embodiments of the present invention, the alkyl group having 1 to 8 carbon atoms is selected from methyl, ethyl, propyl, butyl or pentyl, preferably methyl or ethyl.

[0023] In some embodiments of the present invention, the aryl boronic acid compound comprises at least the following structure: In some embodiments of the present invention, the crop disease is caused by crop pathogenic fungi.

[0024] In some embodiments of the present invention, the crop pathogenic fungi include at least one of rapeseed sclerotinia disease, wheat ergot, pepper blight, rice blast, rice sheath blight, corn leaf blight, peanut white spot, Panax notoginseng root rot, tobacco brown spot, gray mold, and late blight, preferably wheat ergot or rice sheath blight.

[0025] In some embodiments of the present invention, the material is a compound preparation.

[0026] In some embodiments of the present invention, the compound formulation further includes at least one of bethamyl, carbendazim, and thiabendazole.

[0027] The present invention has at least the following technical effects: The aryl boronic acid compounds of the present invention have significant prevention and control and inhibitory effects on crop diseases caused by pathogenic fungi of crops. The aryl boronic acid compounds of the present invention have broad-spectrum antibacterial activity and high activity, and particularly have significant inhibitory effects on rapeseed sclerotinia, wheat ergot, pepper blight, rice damping-off, rice blast, rice sheath blight, corn leaf blight, peanut white spot, Panax notoginseng root rot, tobacco brown spot, gray mold, late blight, etc. The aryl boronic acid compounds broaden the use and scope of agricultural disease-inhibiting active substances. DETAILED DESCRIPTION

[0028] Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative work shall fall within the scope of protection of the present invention. The present invention will be described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0029] Example 1 (1) Compound 33 ( ) is prepared as follows: Take 10 mmol of compound 22 ( ), dissolved in methanol, added with catechol (10 mmol), protected by nitrogen, heated under reflux, and after TLC detection of the completion of the reaction of the raw materials, cooled to room temperature, filtered, and the solid was collected to obtain the product.

[0030] (2) Compound 34 ( ) is prepared as follows: Take 10 mmol of compound 22 ( ), dissolved in methanol, and added catechol compounds ( ) (10 mmol), under nitrogen protection, heated to reflux, and after TLC detection, the reaction of the raw materials was completed, cooled to room temperature, filtered, and the solid was collected to obtain the product.

[0031] (3) Compound 82 ( ) is prepared as follows: Take 10 mmol of compound 72 ( ), dissolved in methanol, potassium bifluoride (30 mmol) was added thereto, a large amount of white solid precipitated, and the mixture was stirred at room temperature for 1 h. After TLC detection, the reaction of the raw material was completed, and the methanol was removed under reduced pressure. The solid was collected, washed with ether, dried, and recrystallized from acetone to obtain the product.

[0032] (4) Compound 83 ( ) is prepared as follows: Take 10 mmol of compound 72 ( ), dissolved in methanol, and added catechol compounds ( ) (10 mmol), under nitrogen protection, heated to reflux, and after TLC detection, the reaction of the raw materials was completed, cooled to room temperature, filtered, and the solid was collected to obtain the product.

[0033] (5) Compound 84 ( ) is prepared as follows: Take 10 mmol of compound 72 ( ), dissolved in methanol, and added catechol compounds ( ) (10 mmol), under nitrogen protection, heated to reflux, and after TLC detection, the reaction of the raw materials was completed, cooled to room temperature, filtered, and the solid was collected to obtain the product.

[0034] (6) Compound 85 ( ) is prepared as follows: Take 10 mmol of compound 72 ( ), dissolved in methanol, and added catechol compounds ( ) (10 mmol), under nitrogen protection, heated to reflux, and after TLC detection, the reaction of the raw materials was completed, cooled to room temperature, filtered, and the solid was collected to obtain the product.

[0035] Example 2 Test compound 1 ( ) to compound 88 ( ) against rapeseed sclerotinia disease, wheat ergot, pepper blight, rice damping-off, rice blast, rice sheath blight, corn leaf blight, peanut white rot, Panax notoginseng root rot, tobacco brown spot, gray mold, and late blight.

[0036] Comparative Example 1 The inhibitory effect of carbendazim (methyl N-(2-benzimidazolyl)carbamate) on rapeseed sclerotinia disease, wheat ergot, pepper blight, rice damping-off, rice blast, rice sheath blight, corn leaf blight, peanut white spot, Panax notoginseng root rot, tobacco brown spot, gray mold, and late blight was tested.

[0037] The bactericidal activity test method is as follows: In vitro fungal activity was determined using the in vitro growth rate method. Potato dextrose agar (PDA) medium (200 g potatoes, 18 g agar, 20 g glucose, 1000 mL distilled water) was heated until molten (40-60°C). The synthesized compound and a commercial control agent were prepared into 100 μg / mL solutions. Then, 10 mL of the solution (10 times the final concentration) was added to 90 mL of PDA medium, shaken thoroughly, and evenly poured into a 9 cm diameter Petri dish. The dish was placed horizontally and allowed to cool to solidify. A 5 mm diameter plate was punched from the edge of a fresh pathogen colony that had been incubated for 5 days. This plate was inverted and placed in the center of the PDA plate containing the agent. The plate was then incubated in a 26°C constant temperature and humidity incubator. The blank control colony was observed when it reached approximately two-thirds of the plate. The colony diameters were measured using the cross-hatch method and the average value was calculated. The blank control was treated with no drug but with the same concentration of solvent solution. Each treatment was repeated three times. The inhibition rate of the drug on mycelial growth was calculated by the formula. Evaluation was based on the inhibition rate, where 1 means the inhibition rate is less than 20%; 2 means the inhibition rate is 20% to 39%; 3 means the inhibition rate is 40% to 59%; 4 means the inhibition rate is 60% to 79%; and 5 means the inhibition rate is 80% to 100%. The bactericidal test results of compound 1-88 and carbendazim are shown in Table 1.

[0038] Table 1 As shown in Table 1, the arylboronic acid compounds of the present invention exhibit significant inhibitory effects against a variety of plant pathogens, including Sclerotinia sclerotiorum, Gibberella zeae, Phytophthora capsici, Rhizoctonia solani, and Pyricularia oryzae. The fungicidal activity of the compounds is closely related to the substituent groups and positions on the aromatic rings. Phenylboronic acid has a relatively weak fungicidal effect, but the introduction of substituent groups on the benzene ring significantly improves its fungicidal activity. Compounds 2-4, each containing only one chlorine atom, exhibit higher fungicidal activity than compound 1. Compounds 21-26, each containing two chlorine atoms, exhibit significantly improved fungicidal activity against the tested bacteria compared to compounds 2-4. Further increasing the number of chlorine atoms yielded phenylboronic acid compounds 69-75 containing three chlorine atoms. Fungicidal activity tests revealed that phenylboronic acids containing three chlorine atoms exhibited the highest fungicidal activity. Compounds 70-73, in particular, showed high activity against all 12 tested bacteria, demonstrating the broad fungicidal activity of this class of compounds. Compounds 69 and 74 also have three chlorine atoms, but their activity is significantly lower than that of other phenylboronic acids containing three chlorine atoms. This suggests that the position of the substituent has a strong influence on the activity of phenylboronic acid. When both ortho positions of boronic acid are replaced by chlorine atoms, the activity of the compound is inhibited, possibly due to steric hindrance. Replacing the chlorine atoms with fluorine atoms or other groups significantly reduces the fungicidal activity of the boronic acid.

[0039] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. Application of materials containing arylboronic acid compounds in preventing and controlling crop diseases, characterized in that: The aryl boronic acid compound is selected from 、 、 、 One of the following; A is selected from 、 、 or One of the substitution structures; R1, R2, R3, R4, and R5 are independently selected from hydrogen, halogen, alkoxy having 1 to 6 carbon atoms, aldehyde, carboxyl, cyano, trifluoromethyl, alkyl having 1 to 6 carbon atoms, or alkoxycarbonyl having 1 to 6 carbon atoms, and R1, R2, R3, R4, and R5 are not hydrogen at the same time, and at least two of R1, R2, R3, R4, and R5 are hydrogen; R6, R7, R8, R9, R 10 are independently selected from hydrogen or halogen; M is sulfur or oxygen; R 11 、R 12 are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a substituted phenyl group, or R 11 and R 12 Bond to form a ring.

2. The application according to claim 1, characterized in that At least one of R1, R2, R3, R4, and R5 is a halogen, preferably two of R1, R2, R3, R4, and R5 are halogens, and more preferably three of R1, R2, R3, R4, and R5 are halogens; and / or, R6, R7, R8, R9, R 10 At least one of the groups is halogen, preferably R6, R7, R8, R9, R 10 Two of the groups are halogen, more preferably R6, R7, R8, R9, R 10 Three of the groups are halogens.

3. The application according to claim 1, characterized in that The substitution structure is selected from At least one hydrogen on the benzene ring is replaced by R 13 Substituted, the R 13 Selected from carboxyl, hydroxyl, aldehyde or carboxyl substituted vinyl; and / or, the substituted phenyl group is selected from an alkyl-substituted phenyl group having 1 to 3 carbon atoms; and / or, R 11 and R 12 The rings are bonded to form a five-membered ring or a six-membered ring, preferably a five-membered ring.

4. The use according to any one of claims 1 to 3, characterized in that: The halogen is at least one of chlorine, fluorine or bromine, preferably chlorine; And / or, at least one of R1 and R3 is hydrogen.

5. The application according to claim 1, characterized in that: The alkoxy group having 1 to 6 carbon atoms is selected from methoxy, ethoxy, propoxy, butoxy or pentoxy; And / or, the alkoxycarbonyl group having 1 to 6 carbon atoms is selected from methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or butoxycarbonyl, preferably methoxycarbonyl.

6. The use according to any one of claims 1 to 3, characterized in that The alkyl group having 1 to 6 carbon atoms is selected from methyl, ethyl, propyl or butyl, preferably methyl; And / or, the alkyl group having 1 to 8 carbon atoms is selected from methyl, ethyl, propyl, butyl or pentyl, preferably methyl or ethyl.

7. The use according to claim 1, characterized in that The arylboronic acid compound comprises at least the following structure: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 8. The use according to any one of claims 1, 2, 5 or 7, characterized in that: The crop diseases are caused by pathogenic fungi of crops.

9. The application according to claim 8, characterized in that: The crop pathogenic fungi include at least one of rapeseed sclerotinia disease, wheat ergot, pepper blight, rice damping-off, rice blast, rice sheath blight, corn leaf blight, peanut white spot, Panax notoginseng root rot, tobacco alternating spot, gray mold, and late blight, preferably wheat ergot or rice sheath blight.

10. The use according to any one of claims 1, 2, 5 or 7, characterized in that: The material is a composite preparation; Preferably, the compound formulation further comprises at least one of bethamyl, carbendazim and thiabendazole.

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