Carboline derivative containing substituted phenoxy pyridine structure as well as preparation method and application of carboline derivative

Abstract

The invention relates to a carboline derivative containing a substituted phenoxy pyridine structure as well as a preparation method and application of the carboline derivative. The compound is obtained by reacting substituted phenoxy pyridine formyl chloride with a substituted carboline compound. The carboline derivative containing the substituted phenoxy pyridine structure shows an excellent control effect on phytopathogen, and the compound can be used for preparing bactericides in the fields of agriculture, horticulture and the like.

Description

Technical Field

[0001] This invention relates to the field of chemical pesticides, specifically to carboline derivatives containing substituted phenoxypyridine structures, their preparation methods, and applications. Background Technology

[0002] The control of plant pathogens is a crucial area of ​​pesticide research, as the use of fungicides has effectively controlled many plant diseases. However, in recent years, with the increasing use of fungicides, some plant pathogens have developed significant resistance to traditional fungicides. Therefore, it is essential to continuously develop new and highly effective fungicides.

[0003] Substituted pyridine compounds are an important class of heterocyclic compounds with wide applications in agricultural production.

[0004] Carboline derivatives are also an important class of heterocyclic compounds, and they have important applications in plant protection.

[0005] Therefore, in order to further explore novel compounds with excellent bactericidal effects from carboline derivatives, this invention discloses a class of carboline derivatives with bactericidal application value containing substituted phenoxypyridine structures, organically linking substituted pyridine units with the carboline skeleton. Summary of the Invention

[0006] The purpose of this invention is to provide carboline derivatives containing substituted phenoxypyridine structures that have good inhibitory activity against plant pathogens, in order to meet the demand for highly efficient fungicides in crop protection.

[0007] Another object of the present invention is to provide a method for preparing the above-mentioned compound.

[0008] Another object of the present invention is to provide the use of the above-mentioned compounds in the preparation of bactericides.

[0009] To solve the above-mentioned technical problems, a first aspect of the present invention provides a carbline derivative containing a substituted phenoxypyridine structure, which has the following structure: or

[0010] A second aspect of the present invention provides a method for preparing the above-mentioned carboline derivatives containing substituted phenoxypyridine structures, comprising the following reaction steps: or

[0011] The substituted phenoxypyridine carboxyl chloride and substituted carboline compounds were prepared using conventional methods.

[0012] The compounds of this invention exhibit good bactericidal effects against plant pathogens, and therefore can be used to prepare fungicides to protect agricultural and horticultural plants. The plant pathogens mentioned include *Cucumber blight*, etc. Of course, the harmful organisms that the compounds of this invention can control are not limited to the examples mentioned above.

[0013] When the compounds of the present invention are used as fungicides in agriculture, horticulture and other fields, they can be used alone or in the form of fungicidal compositions. For example, the compounds of the present invention can be used as active ingredients and combined with commonly used pesticide adjuvants in the field to process them into emulsions, suspensions, water-dispersible granules, emulsifiable concentrates, etc.

[0014] Commonly used pesticide adjuvants include: liquid carriers, such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; commonly used surface agents such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; and other adjuvants such as wetting agents and thickeners.

[0015] When the compounds of the present invention are used as active ingredients in bactericides, their content in the bactericide is selected within the range of 0.1% to 99.5%, and the appropriate content of the active ingredient can be determined according to the formulation and application method. Typically, the active ingredient is contained in aqueous emulsions at 5% to 50% (weight percentage, the same below), preferably at 10% to 40%; and in suspensions at 5% to 50%, preferably at 5% to 40%.

[0016] For the use of the fungicide of the present invention, commonly used application methods can be selected, such as foliar spraying, water surface application, soil treatment, and seed treatment. For example, when using foliar spraying, the usable concentration range of the compound of the present invention as the active ingredient is 1 to 1000 μg / mL in water emulsions, suspensions, water-dispersible granules, and emulsifiable concentrates, preferably 1 to 200 μg / mL.

[0017] The carboline derivatives containing substituted phenoxypyridine structures disclosed in this invention exhibit good bactericidal effects against plant pathogens, and therefore can be used to prepare bactericides for use in agriculture, horticulture and other fields. Detailed Implementation

[0018] To facilitate a further understanding of the present invention, the following embodiments are provided for more detailed description. These embodiments are for illustrative purposes only and are not intended to limit the scope or implementation principles of the present invention.

[0019] Example 1:

[0020] 1 mmol of intermediate IIIa, 1 mL of pyridine, and 20 mL of tetrahydrofuran were added to a reaction flask. Under ice bath conditions, 1 mmol of intermediate II was added dropwise, and the mixture was stirred at room temperature for 15 hours. The reaction was stopped, and the solvent was removed. The residue was purified by silica gel column chromatography to obtain the target compound Ia. 1 H NMR (400 MHz, DMSO- d 6): δ 11.81 (s, 1H), 8.88 (t, J =6.00 Hz, 1H), 8.81 (s, 1H), 8.67 (t, J = 5.60 Hz, 1H), 8.60 (d, J = 2.00 Hz, 1H), 8.41 (d, J = 7.60 Hz, 1H), 8.25~8.28 (m, 1H), 8.10 (d, J = 8.00 Hz, 2H), 7.70 (d, J = 8.40 Hz, 1H), 7.58~7.62 (m, 1H), 7.45~7.49 (m, 4H), 7.31 (t, J =7.60 Hz, 1H), 7.19 (d, J = 8.80 Hz, 2H), 7.11 (d, J = 8.80 Hz, 1H), 3.45~3.50 (m,2H), 3.38~3.41 (m, 2H), 2.46 (s, 3H), 1.81~1.88 (m, 2H). Example 2:

[0021] 1 mmol of intermediate IIIb, 2 mL of triethylamine, and 25 mL of chloroform were added to a reaction flask. Under ice bath conditions, 1.2 mmol of intermediate II was added dropwise, and the mixture was stirred at room temperature for 11 hours. The reaction was stopped, and the solvent was removed. The residue was purified by silica gel column chromatography to obtain the target compound Ib. 1 H NMR (400 MHz, DMSO- d 6): δ 11.81 (s, 1H), 8.87 (t, J =6.00 Hz, 1H), 8.78 (s, 1H), 8.67 (t, J= 5.60 Hz, 1H), 8.60 (d, J = 2.00 Hz, 1H), 8.40 (d, J = 8.00 Hz, 1H), 8.25~8.28 (m, 1H), 8.18 (d, J = 8.80 Hz, 2H), 7.71 (d, J = 8.00 Hz, 1H), 7.57~7.61 (m, 1H), 7.48 (t, J =9.20 Hz, 2H), 7.31(t, J =7.60 Hz, 1H), 7.18~7.21 (m, 4H), 7.11 (d, J = 8.40 Hz, 1H), 3.89 (s,3H), 3.45~3.50 (m, 2H), 3.38~3.41 (m, 2H), 1.83~1.86 (m, 2H). Example 3: Fungicidal activity test of compounds against cucumber wilt pathogen The inhibitory effect of the synthesized compound on cucumber blight pathogens was tested using a toxic medium method. First, the compound solution was added to the culture medium, and the mycelial cake was placed on the medium. The petri dishes were then incubated at 25 ℃ in the dark. Based on the pathogen's growth rate, the inhibition rate (%) was calculated when the control group reached approximately 8 cm in diameter. The concentration used for determination was 200 μg / mL.

[0022] Table 1. Bactericidal activity data of compounds Ia–Ib compound Concentration (μg / mL) Cucumber vine blight (inhibition rate, %) Ⅰa 200 100 Ⅰb 200 100 As shown in Table 1, compounds Ia–Ib exhibited good antibacterial activity against *Agrostis cuspidatum*, the causal agent of cucumber anthracnose. At a concentration of 200 μg / mL, compounds Ia and Ib showed inhibition rates of 100% and 100%, respectively, against *Agrostis cuspidatum*.

[0023] The above experimental data show that the novel carboline derivatives obtained by rationally combining the substituted pyridine unit with the carboline skeleton exhibit good antibacterial effects.

[0024] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above examples; the examples and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A carbaline derivative (I) containing a substituted phenoxypyridine structure, characterized in that... The structure is as follows: or 。 2. The method for preparing the carboline derivative (I) containing a substituted phenoxypyridine structure as described in claim 1, characterized in that... The method is as follows: or 。 3. Use of the carboline derivative (I) containing a substituted phenoxypyridine structure as described in claim 1 in the preparation of bactericides.

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