CN109400588B - Fluorine-containing triazole quinoxaline bactericide, preparation method and application thereof - Google Patents

Fluorine-containing triazole quinoxaline bactericide, preparation method and application thereof Download PDF

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CN109400588B
CN109400588B CN201811496330.9A CN201811496330A CN109400588B CN 109400588 B CN109400588 B CN 109400588B CN 201811496330 A CN201811496330 A CN 201811496330A CN 109400588 B CN109400588 B CN 109400588B
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azidoaniline
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任志林
贺依民
乔玥
苏蕾
和平
王龙
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Shandong Kanghui Plant Protection Co.,Ltd.
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Hubei University of Arts and Science
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
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Abstract

The invention discloses a fluorine-containing triazole quinoxaline sterilizationThe quinoxaline bactericide has a structure shown as a formula I:

Description

Fluorine-containing triazole quinoxaline bactericide, preparation method and application thereof
Technical Field
The invention relates to the technical field of bactericides, and in particular relates to a fluorine-containing triazole quinoxaline bactericide, a preparation method and application thereof.
Background
Crop diseases caused by various bacteria and fungi cause a great amount of yield reduction of grains every year, and the problem is very serious, so that the problem that people eat well is seriously influenced. Therefore, in order to solve the above problems, the development of a high-efficiency, broad-spectrum bactericide is very urgent. Researches and develops more novel bactericides with better antibacterial activity, and is the key for promoting the development of the bactericides.
Disclosure of Invention
The invention aims to provide a fluorine-containing triazole quinoxaline bactericide, a preparation method and application thereof, and the method prepares a novel trifluoromethyl-containing N-substituted triazole acetyl dihydroquinoxaline derivative.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a fluorine-containing triazole quinoxaline bactericide, which has a structure shown in a formula I:
Figure BDA0001896983380000021
in the formula I, R groups are independently selected from hydrogen, fluorine, chlorine, trifluoromethyl or methyl, and the substitution position of the R groups is at least one of four unbound sites on a benzene ring.
The invention also provides a preparation method of the fluorine-containing triazole quinoxaline bactericide, which comprises the following steps:
Figure BDA0001896983380000022
mixing and dissolving an o-azidoaniline derivative, alpha-bromotrifluoroacetone and alkali with a first solvent, carrying out a first reaction, mixing with triphenylphosphine, carrying out a second reaction, removing the first solvent under reduced pressure to obtain an intermediate, mixing and dissolving the intermediate, triphenylphosphine, hexachloroethane and a second solvent, mixing with triazoleacetic acid, carrying out a third reaction, removing the second solvent under reduced pressure to obtain a primary product, and carrying out column chromatography on the primary product to obtain a final product.
The embodiment of the invention also provides a sterilization preparation, which consists of the fluorine-containing triazole quinoxaline bactericide and acceptable auxiliary materials, wherein the weight ratio of the fluorine-containing triazole quinoxaline bactericide to the total weight of the sterilization preparation is 1:1.5-1:4.5, and is preferably 1: 3.
The invention also provides an application of the fluorine-containing triazole quinoxaline bactericide or bactericide in inhibiting at least one of rice blast fungus, penicillium digitatum and penicillium italicum.
The invention has the beneficial effects that:
the invention provides a fluorine-containing triazole quinoxaline bactericide, a preparation method and application thereof, and synthesizes a novel trifluoromethyl-containing N-substituted triazole acetyl dihydroquinoxaline derivative, which has excellent effect on inhibiting fungi such as rice blast fungus, penicillium digitatum, penicillium italicum and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The fluorine-containing triazole quinoxaline bactericide provided by the embodiment of the invention, the preparation method and the application thereof are specifically explained below.
The embodiment of the invention provides a fluorine-containing triazole quinoxaline bactericide, which has the following structural formula:
Figure BDA0001896983380000031
in the formula I, R groups are independently selected from hydrogen, fluorine, chlorine, trifluoromethyl or methyl, and the substitution position of the R groups is at least one of four unbound sites on a benzene ring.
The embodiment of the invention also provides a preparation method of the fluorine-containing triazole quinoxaline bactericide, which comprises the following steps:
Figure BDA0001896983380000041
mixing and dissolving an o-azidoaniline derivative, alpha-bromotrifluoroacetone and alkali with a first solvent, carrying out a first reaction, mixing with triphenylphosphine, carrying out a second reaction, removing the first solvent under reduced pressure to obtain an intermediate, mixing and dissolving the intermediate, triphenylphosphine, hexachloroethane and a second solvent, mixing with triazoleacetic acid, carrying out a third reaction, removing the second solvent under reduced pressure to obtain a primary product, and carrying out column chromatography on the primary product to obtain a final product.
The embodiment of the invention also provides a preparation method of the fluorine-containing triazole quinoxaline bactericide, which comprises the following steps: the o-azido aniline derivative and alpha-bromotrifluoroacetone are subjected to a first reaction under the action of alkali, the first reaction is a nucleophilic substitution reaction, a first reaction product is mixed with triphenylphosphine to perform a second reaction, the second reaction is subjected to a Staudinger reaction and an intramolecular aza Wittig reaction to generate a cyclic intermediate, and the intermediate and triazoleacetic acid are subjected to a third reaction under the action of triphenylphosphine and hexachloroethane to generate a novel N-substituted triazoleacetyldihydroquinoxaline derivative containing trifluoromethyl.
In some embodiments, the ortho-azidoaniline derivative comprises at least one of ortho-azidoaniline, 4-fluoro-azidoaniline, 4-chloro-ortho-azidoaniline, 4-trifluoromethyl-ortho-azidoaniline, 4-methyl-ortho-azidoaniline, 6-fluoro-ortho-azidoaniline, and 4, 6-difluoro-ortho-azidoaniline.
In some embodiments, the base comprises at least one of triethylamine, sodium hydroxide, 4-dimethylaminopyridine, and potassium carbonate, preferably potassium carbonate; the first solvent and the first solvent are the same or different, and the first solvent and the second solvent comprise at least one of chloroform, methanol, ethyl acetate and chloroform, preferably dichloromethane.
The base in the preparation process of the fluorine-containing triazole quinoxaline bactericide in the embodiment of the invention comprises at least one of triethylamine, sodium hydroxide, 4-dimethylamino pyridine and potassium carbonate, preferably potassium carbonate, and the yield is reduced by using other bases or changing the using amount of the bases.
The first solvent and the second solvent are the same or different, and include at least one of chloroform, methanol, ethyl acetate and chloroform, preferably dichloromethane, and the other solvent is used instead, the conversion rate is reduced, resulting in a low yield. The solvent dichloromethane which is useful is anhydrous and contains water in the solvent results in a significant reduction in yield.
In some embodiments, the feed molar ratio of ortho-azidoaniline derivative, α -bromotrifluoroacetone, and base is from 0.5 to 2: 1: 0.5-2, the feeding molar ratio of the alpha-bromotrifluoroacetone to the triphenylphosphine is 1: 0.5-2, the feeding molar ratio of the alpha-bromotrifluoroacetone to the triphenylphosphine and the hexachloroethane is 1: 0.5-6: 0.5-6, the feeding molar ratio of the alpha-bromotrifluoroacetone to the triazolic acid is 1: 0.5-2.
The preparation method of the fluorine-containing triazole quinoxaline bactericide in the embodiment of the invention comprises 3 reaction processes, the material amount in each reaction process is limited, and the feeding ratio of the added materials and the alpha-bromotrifluoroacetone in the subsequent reaction process is sequentially limited by taking the alpha-bromotrifluoroacetone in the first reaction process as a reference so as to ensure that each reaction is fully carried out.
In some embodiments, the first, second, and third reactions are all at a temperature of 22 to 50 ℃ for 1 to 5 hours.
The preparation method of the fluorine-containing triazole quinoxaline bactericide in the embodiment of the invention comprises 3 reaction processes, wherein the reaction temperature in the 3 reaction processes is 22-50 ℃, the reaction is incomplete when the temperature is too low, the conversion rate is very low, the temperature is high, the side reaction is aggravated, and the yield is reduced.
In some embodiments, the temperature of the first solvent removal under reduced pressure and the second solvent removal under reduced pressure are both 30-40 ℃.
The embodiment of the invention also provides a sterilization preparation, which consists of the fluorine-containing triazole quinoxaline bactericide and acceptable auxiliary materials, wherein the weight ratio of the fluorine-containing triazole quinoxaline bactericide to the total weight of the sterilization preparation is 1:1.5-1:4.5, and is preferably 1: 3.
In some embodiments, the germicidal formulation includes at least one of a wettable powder, a suspension, a suspoemulsion, a microemulsion, a mixture, and a granule, preferably a mixture and a granule.
The bactericidal preparation provided by the embodiment of the invention consists of the bactericide and acceptable auxiliary materials, and can be processed into any pesticide acceptable dosage form according to the requirement, wherein the common dosage form can be as follows: wettable powder, suspending agent, suspoemulsion, water dispersible granule, microemulsion, microcapsule suspending agent, microcapsule suspension-suspending agent, preferably mixture and granule.
The embodiment of the invention also provides an application of the fluorine-containing triazole quinoxaline bactericide or the bactericide in inhibiting at least one of rice blast fungus, penicillium digitatum and penicillium italicum.
The features and properties of the present invention are described in further detail below with reference to examples.
Instruments and reagents:
melting point X4 type melting point apparatus (Beijing third optics)Manufactured by instrument factory), the thermometer is not corrected;1HNMR and13CNMR was determined using a Varian Mercury400 model 400MHz NMR spectrometer or a Varian Mercury600 model 600MHz NMR spectrometer using deuterated chloroform (CDCl)3) Or deuterated dimethyl sulfoxide (DMSO-d6) is used as a solvent, and TMS is used as an internal standard; MS was determined using a finnigan trace mass spectrometer; elemental analysis was determined using a VarioELIII elemental analyzer; the reagent is chemically pure or analytically pure. The solvent toluene was dried by redistilling, and triethylamine was also treated by redistilling.
Example 1
Figure BDA0001896983380000071
Preparation of
O-azidoaniline (1.1mmol), alpha-bromotrifluoroacetone (1mmol) and potassium carbonate (1.3mmol) were added to a 50mL flask and reacted at 45 ℃ in dichloromethane (10mL) as the reaction solvent, after 1 hour of reaction, triphenylphosphine (1.2mmol) was added, reacted at 45 ℃ for 3 hours, after which the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a solution of triphenylphosphine (3mmol) and hexachloroethane (3mmol) in dichloromethane (10mL), triazoleacetic acid (1.1mmol) was added and reacted at 45 ℃ for 2 hours, after completion of the reaction, the solvent dichloromethane was removed under reduced pressure and the crude product was subjected to column chromatography to give 0.244g of the title compound 5a in 79% yield.
Example 2
Figure BDA0001896983380000081
Preparation of
To a 500mL flask were added o-azidoaniline (11mmol), α -bromotrifluoroacetone (10mmol) and potassium carbonate (13mmol) and reacted at 45 ℃ in dichloromethane (100mL) as a reaction solvent, after 1 hour of reaction, triphenylphosphine (12mmol) was added and reacted at 45 ℃ for 3 hours, after which the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a solution of triphenylphosphine (30mmol) and hexachloroethane (30mmol) in dichloromethane (100mL) and then triazoleacetic acid (11mmol) was added and reacted at 45 ℃ for 2 hours, after completion of the reaction, the solvent dichloromethane was removed under reduced pressure and the crude product was subjected to column chromatography to give 2.35g of the title compound 5a in 76% yield.
Example 3
Figure BDA0001896983380000082
Preparation of
A5 mL flask was charged with o-azidoaniline (0.11mmol), α -bromotrifluoroacetone (0.1mmol) and potassium carbonate (0.13mmol) and reacted at 45 ℃ in dichloromethane (1mL) as a reaction solvent for 1 hour, then triphenylphosphine (0.12mmol) was added and reacted at 45 ℃ for 3 hours, then the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a solution of triphenylphosphine (0.3mmol) and hexachloroethane (0.3mmol) in dichloromethane (1mL), then triazoleacetic acid (0.11mmol) was added and reacted at 45 ℃ for 2 hours, and after completion of the reaction, the solvent dichloromethane was removed under reduced pressure by column chromatography to give 0.025g of the title compound 5a in 81% yield.
Example 4
Figure BDA0001896983380000091
Preparation of
O-azidoaniline (1.1mmol), alpha-bromotrifluoroacetone (1mmol) and potassium carbonate (1.3mmol) were added to a 50mL flask and reacted at 15 ℃ in dichloromethane (10mL) as the reaction solvent, after 1 hour of reaction, triphenylphosphine (1.2mmol) was added and reacted at 15 ℃ for 3 hours, after which the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a solution of triphenylphosphine (3mmol) and hexachloroethane (3mmol) in dichloromethane (10mL), triazoleacetic acid (1.1mmol) was added and reacted at 15 ℃ for 2 hours, after completion of the reaction, the solvent dichloromethane was removed under reduced pressure and the crude product was subjected to column chromatography to give 0.108g of the title compound 5a in 35% yield.
Example 5
Figure BDA0001896983380000101
Preparation of
O-azidoaniline (1.1mmol), alpha-bromotrifluoroacetone (1mmol) and potassium carbonate (1.3mmol) were added to a 50mL flask and reacted at 45 ℃ in dichloromethane (10mL) as the reaction solvent, after 1 hour of reaction, triphenylphosphine (1.2mmol) was added, reacted at 45 ℃ for 3 hours, after which the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a solution of triphenylphosphine (3mmol) and hexachloroethane (3mmol) in dichloromethane (10mL), triazoleacetic acid (0.9mmol) was added and reacted at 45 ℃ for 2 hours, after completion of the reaction, the solvent dichloromethane was removed under reduced pressure and the crude product was subjected to column chromatography to give 0.185g of the title compound 5a in 60% yield.
Example 6
Figure BDA0001896983380000102
Preparation of
4-fluoro-2-azidoaniline (1.1mmol), alpha-bromotrifluoroacetone (1mmol) and potassium carbonate (1.3mmol) were added to a 50mL flask and reacted at 45 ℃ in dichloromethane (10mL) as a reaction solvent, triphenylphosphine (1.2mmol) was added after 1 hour of reaction, reaction was continued at 45 ℃ and after 3 hours of reaction continued, the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a dichloromethane (10mL) solution containing triphenylphosphine (3mmol) and hexachloroethane (3mmol), and then triazoleacetic acid (1.1mmol) was added and reacted at 45 ℃ for 2 hours, after completion of the reaction, the column chromatography solvent dichloromethane was removed under reduced pressure, and the crude product was subjected to column chromatography to give 0.252g of the objective compound 5b in 77% yield.
Example 7
Figure BDA0001896983380000111
Preparation of
A50 mL flask was charged with 4-trifluoromethyl-2-azidoaniline (1.1mmol), α -bromotrifluoroacetone (1mmol) and potassium carbonate (1.3mmol) and reacted at 45 ℃ in dichloromethane (10mL) as a reaction solvent, after 1 hour of reaction, triphenylphosphine (1.2mmol) was added and reacted at 45 ℃ for 3 hours, the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a solution of triphenylphosphine (3mmol) and hexachloroethane (3mmol) in dichloromethane (10mL), triazoleacetic acid (1.1mmol) was added and reacted at 45 ℃ for 2 hours, after completion of the reaction, the column chromatography solvent dichloromethane was removed under reduced pressure and the crude product was passed through to give 0.192g of the objective compound 5c in 51% yield.
Example 8
Figure BDA0001896983380000112
Preparation of
4-methyl-2-azidoaniline (1.1mmol), alpha-bromotrifluoroacetone (1mmol) and potassium carbonate (1.3mmol) were added to a 50mL flask, and reacted at 45 ℃ in dichloromethane (10mL) as a reaction solvent, after 1 hour of reaction, triphenylphosphine (1.2mmol) was added, reacted at 45 ℃ for 3 hours, the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a dichloromethane (10mL) solution containing triphenylphosphine (3mmol) and hexachloroethane (3mmol), and then triazoleacetic acid (1.1mmol) was added, reacted at 45 ℃ for 2 hours, after completion of the reaction, the column chromatography solvent dichloromethane was removed under reduced pressure, and the crude product was subjected to column chromatography to give 0.216g of the objective compound 5d in 67% yield.
Example 9
Figure BDA0001896983380000121
Preparation of
4, 6-difluoro-2-azidoaniline (1.1mmol), alpha-bromotrifluoroacetone (1mmol) and potassium carbonate (1.3mmol) were added to a 50mL flask, and reacted at 45 ℃ in dichloromethane (10mL) as a reaction solvent, after 1 hour of the reaction, triphenylphosphine (1.2mmol) was added, reacted at 45 ℃ for 3 hours, the solvent dichloromethane was removed under reduced pressure, the intermediate was transferred to a dichloromethane (10mL) solution containing triphenylphosphine (3mmol) and hexachloroethane (3mmol), and then triazoleacetic acid (1.1mmol) was added, reacted at 45 ℃ for 2 hours, after completion of the reaction, the solvent dichloromethane was removed under reduced pressure, and the crude product was subjected to column chromatography to give 0.224g of the objective compound 5e in 65% yield.
Example 10
Bactericidal activity test (with toxic medium)
The liquid medicine concentration is 200ppm, strain agar sheet is taken by a 5mm puncher, the hypha face downwards is inoculated on a PDA culture medium containing the drug to be detected, the PDA culture medium is placed in the center of a circular culture medium, and the strain agar sheet is cut without sliding so as to avoid polluting the culture medium. Three samples to be tested are inoculated, the culture medium without drugs and containing DMSO with the same concentration is used as an air-white illumination, the samples are placed in a biochemical incubator to be cultured for 3-5 days at 25 ℃, and then the diameters of colonies on the culture medium are measured. And (3) observing the influence of the sample to be detected on the growth of hyphae by comparing with the blank control group, and calculating the inhibition rate of the sample to be detected on the growth of colonies under 200 mg/L. Inhibition (%) × (blank colony diameter-diameter of sample colony to be tested)/(blank colony diameter-diameter of punch) ] × 100%. Table 1 shows the results of the assay for a portion of compound I.
Table 1: results of bacteriostatic activity test of Compound I
Figure BDA0001896983380000131
As can be seen from table 1 above, the compounds represented by formula I in the examples of the present invention have good inhibitory activity against penicillium digitatum (penicillium digitatum), penicillium italicum (penicillium italicum), and pyricularia oryzae (magnaporthisea). Of these, the compounds numbered 3 and 5 are most effective.
The embodiment of the invention provides a fluorine-containing triazole quinoxaline bactericide, a preparation method and application thereof, wherein the preparation method is to prepare a novel trifluoromethyl-containing N-substituted triazole acetyl dihydroquinoxaline bactericide by carrying out a series condensation reaction on an o-azidoaniline derivative, alpha-bromotrifluoroacetone, triazoleacetic acid and triphenylphosphine under the action of a dehydrating agent. The embodiment of the invention provides a novel efficient synthesis method for synthesizing N-substituted triazole acetyl dihydroquinoxaline derivatives containing trifluoromethyl, and the derivatives show good antibacterial activity and are beneficial to being used as bactericides.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (15)

1. The fluorine-containing triazole quinoxaline bactericide is characterized by having a structure shown in a formula I:
Figure 995399DEST_PATH_IMAGE001
I
in the formula I, the R groups are independently selected from hydrogen, fluorine, chlorine, trifluoromethyl or methyl, and the substitution position of the R groups is at least one of four unbound sites on a benzene ring.
2. The method for preparing a fluorine-containing triazole quinoxaline bactericide according to claim 1, which comprises the steps of:
Figure 775136DEST_PATH_IMAGE002
mixing and dissolving an o-azidoaniline derivative, alpha-bromotrifluoroacetone, alkali and a first solvent, carrying out a first reaction, mixing with triphenylphosphine, carrying out a second reaction, removing the first solvent under reduced pressure to obtain an intermediate, mixing and dissolving the intermediate, the triphenylphosphine, hexachloroethane and a second solvent, mixing with triazoleacetic acid, carrying out a third reaction, removing the second solvent under reduced pressure to obtain a primary product, and carrying out column chromatography on the primary product to obtain a final product.
3. The method according to claim 2, wherein the o-azidoaniline derivative is at least one of o-azidoaniline, 4-fluoro-o-azidoaniline, 4-chloro-o-azidoaniline, 4-trifluoromethyl-o-azidoaniline, 4-methyl-o-azidoaniline, 6-fluoro-o-azidoaniline, and 4, 6-difluoro-o-azidoaniline.
4. The method according to claim 2, wherein the base is at least one of triethylamine, sodium hydroxide, 4-dimethylaminopyridine, and potassium carbonate.
5. The method of claim 4, wherein the base is potassium carbonate.
6. The method according to claim 2, wherein the first solvent and the second solvent are the same or different, and the first solvent and the second solvent are at least one of dichloromethane, methanol, ethyl acetate, and chloroform.
7. The method of claim 6, wherein the first solvent and the second solvent are both methylene chloride.
8. The production method according to claim 2,
the feeding molar ratio of the o-azidoaniline derivative to the alpha-bromotrifluoroacetone to the alkali is 0.5-2: 1: 0.5-2,
the feeding molar ratio of the alpha-bromotrifluoroacetone to the triphenylphosphine in the second reaction is 1: 0.5-2,
the feeding molar ratio of the triphenylphosphine to the hexachloroethane in the third reaction of the alpha-bromotrifluoroacetone is 1: 0.5-6: 0.5-6, the feeding molar ratio of the alpha-bromotrifluoroacetone to the triazoleacetic acid is 1: 0.5-2.
9. The method according to claim 2, wherein the first, second and third reactions are carried out at a temperature of 22 to 50 ℃ for 1 to 5 hours.
10. The method according to claim 2, wherein the temperature of the first solvent removal under reduced pressure and the temperature of the second solvent removal under reduced pressure are both 30 to 40 ℃.
11. The bactericidal preparation is characterized by consisting of the fluorine-containing triazole quinoxaline bactericide of any one of claims 1 to 10 and acceptable auxiliary materials, wherein the weight ratio of the fluorine-containing triazole quinoxaline bactericide to the total weight of the bactericidal preparation is 1:1.5-1: 4.5.
12. The bactericidal formulation of claim 11, wherein the weight ratio of the fluorine-containing triazole quinoxaline bactericide to the total weight of the bactericidal formulation is 1: 3.
13. The bactericidal formulation of claim 11, wherein the bactericidal formulation is at least one of a wettable powder, a suspension, a suspoemulsion, a microemulsion, and a granule.
14. The bactericidal formulation of claim 13, wherein the bactericidal formulation is a granule.
15. Use of the fluorine-containing triazole quinoxaline bactericide according to any one of claims 1 to 10 or the bactericidal preparation according to any one of claims 11 to 14 for inhibiting at least one of pyricularia oryzae, penicillium digitatum and penicillium italicum.
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