CN115340483A - Naphthyl pyrrolindione compound, preparation method and application thereof - Google Patents
Naphthyl pyrrolindione compound, preparation method and application thereof Download PDFInfo
- Publication number
- CN115340483A CN115340483A CN202211052833.3A CN202211052833A CN115340483A CN 115340483 A CN115340483 A CN 115340483A CN 202211052833 A CN202211052833 A CN 202211052833A CN 115340483 A CN115340483 A CN 115340483A
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- CN
- China
- Prior art keywords
- naphthyl
- pyrrolindione
- pyrrole
- dione
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
- C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01P3/00—Fungicides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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Abstract
The invention relates to a naphthyl pyrrolindione compound, which has the following chemical general formula (I):
Description
Technical Field
The invention belongs to the technical field of agricultural chemistry. More specifically, the present invention relates to a naphthyl pyrrolindione compound, and also relates to a preparation method of the naphthyl pyrrolindione compound, and also relates to an application of the naphthyl pyrrolindione compound.
Background
With the development of agriculture towards modernization and commercialization, the occurrence and harm of various crop diseases become more serious. The crop disease control in modern agricultural production is not safe, efficient and low-toxic, and a large amount of selective bactericides are used. However, at present, more than 400 compounds are registered as bactericides for controlling crop diseases, but the rapid genetic variation and the huge reproductive capacity of pathogenic microorganisms and other biological characteristics cause the generation of high-level drug-resistant pathogen populations on the production of various selective bactericides soon after the application, and often cause the sudden failure of the bactericide control. The epidemic harm of the drug-resistant diseases often causes the problem of inexhaustible prevention and control, and farmers often increase the dosage blindly, so that the diseases cannot be effectively controlled, and pesticide residues and pesticide damages are easy to cause. Therefore, the novel bactericide is a great demand for treating drug resistance, ensuring sustainable green development of agriculture and technological progress of modern bactericides.
The drug resistance of plant pathogenic bacteria is usually medium and high level drug resistance caused by point mutation of action targets of the bactericide. The drug-resistant germs have high suitability, the bactericides with resistance can not be reused even if the bactericides are stopped for years, and the drug resistance mechanism of the molecular target point mutation determines that after one bactericide has resistance, the bactericide can simultaneously express orthogonal mutual drug resistance to a plurality of bactericides with the same action mode, so that the plurality of bactericides simultaneously lose use value. Therefore, the development of new chemical structure types and new mechanisms of action of fungicides is necessary to treat biocide resistance. The search for compounds which have antibacterial activity against plant pathogens and can be used for controlling plant diseases and methods of using the compounds are urgent to ensure sustainable green development of agricultural production.
Based on the summary of the prior art, the present inventors have completed the present invention by a large number of experimental studies and analytical summaries for the technical defects of the prior art.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a naphthyl pyrrolindione compound.
It is another object of the present invention to provide a method for preparing the naphthyl pyrrolindione compound.
It is another object of the present invention to provide the use of the naphthyl pyrrolindione compound.
Technical scheme
The invention is realized by the following technical scheme.
The invention relates to a naphthyl pyrrolindione compound.
The naphthyl pyrrolindione compound has the following chemical general formula (I):
in the formula:
R 1 and R 2 Is 1-3 selected from H and CH 3 、C 2 H 5 、n-C 3 H 7 、i-C 3 H 7 、CF 3 Cyclopropyl, OCH 3 、COOCH 3 、 COOC 2 H 5 、NHCOOCH 3 、NHCOCH 3 、OH、NH 2 、NO 2 、SH、SO 3 H. CN, cl, br, F, O =, pyrrolylamino or pyridylamino groups.
In the present invention, the O = group is understood to mean that both the 3-and 4-positions of naphthalene are carbonyl groups to form 3, 4-dioxo-3, 4-dihydronaphthalene, or that both the 5-and 8-positions of naphthalene are carbonyl groups to form 5, 8-dioxo-5, 8-dihydronaphthalene;
R 3 is 1-2 selected from H and CH 3 、C 2 H 5 、n-C 3 H 7 、i-C 3 H 7 、CF 3 Cyclopropyl, OCH 3 、COOCH 3 、 COOC 2 H 5 、NHCOOCH 3 、NHCOCH 3 、OH、NH 2 、NO 2 、SH、SO 3 H. CN, cl, br, F, but R 1 、R 2 And R 3 Not H at the same time.
According to a preferred embodiment of the present invention, the naphthyl pyrrolindione compound is selected from the group consisting of 1- (4-chloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-bromonaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-bromonaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2, 4-dichloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-trifluoromethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-trifluoromethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, and mixtures thereof 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-ethoxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-cyclopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable salt thereof, 1- (4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-methyl-1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (6-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione 1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-ethyl-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-bromo-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-di-ketone Ketones, 1- (5-bromo-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4, 5-dichloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-propyl-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-bromo-2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (-4-chloro-2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione 1- (5-chloro-2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-bromo-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (6-bromo-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-chloro-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloro-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-nitro-1- (2-nitro-3, 4-dioxo-3, 4-dione -dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-methyl-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-nitro-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-bromo-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, di-or tri-ketone 1- (5-bromo-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-mercapto-1- (5-bromo-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, methyl (6-methyl-5- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalen-1-yl) carbamate, 1- (6-chloro-2- ((5- (trifluoromethyl) pyridin-2-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (6-chloro-2- ((4- (trifluoromethyl) -1H-pyrazol-3-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-methoxy-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione and 4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalene-1-sulfonic acid.
The invention also relates to a preparation method of the naphthyl pyrrolindione compound.
The preparation method comprises the following preparation steps:
A. heating reflux reaction
Mixing a naphthylamine compound (II), a maleic anhydride compound (III) and glacial acetic acid according to a molar ratio of 1: 1.0-2.0: 1.0-100.0, heating and refluxing for 0.41-24.0 h under stirring by using a heating and refluxing device, wherein the chemical reaction equation is as follows:
r in the chemical reaction equation 1 、R 2 Or R 3 The radicals are as defined above;
in this step, when glacial acetic acid is used in an amount within the range, if the molar ratio of the naphthylamine compound (II) to the maleic anhydride compound (III) is more than 1:1.0, the naphthylamine compound (II) is remained, the post-treatment is difficult, and the synthesis cost is increased; if the molar ratio of the naphthylamine compound (II) to the maleic anhydride compound (III) is less than 1:2.0, the product yield cannot be further improved, and the synthesis cost is also improved; therefore, the molar ratio of the naphthylamine compound (II) to the maleic anhydride compound (III) is 1:1.0 to 2.0 is reasonable, preferably 1:1.2 to 1.8;
when the amounts of the naphthylamine compound (II) and the maleic anhydride compound (III) are within the above range, if the amount of glacial acetic acid is less than 1.0, insufficient dissolution of the raw materials is caused, and the product yield is lowered; if the dosage of the glacial acetic acid is more than 100.0, the yield of the product cannot be further improved, and the synthesis cost is increased; accordingly, glacial acetic acid is suitably used in an amount of from 1.0 to 100.0, preferably from 20.0 to 80.0;
in this step, it is not preferable that the reaction time of the naphthylamine compound (II) and the maleic anhydride compound (III) in the glacial acetic acid solvent is heated under reflux for more than the above range, because the reaction does not proceed completely and the product yield is lowered because the reaction time is shorter than 0.41 hour, and the reaction time is longer than 24.0 hours, which does not further increase the product yield and the synthesis cost is increased.
The naphthylamine compound (II), the maleic anhydride compound (III) and glacial acetic acid used in the present invention are commercially available products, such as 4-bromonaphthalene-1-amine sold under the trade name 4-bromo-1-naphthylamine by Nanjing lattice chemical Co., ltd, 2-methylnaphthalene-1-amine sold under the trade name 1-amino-2-methylnaphthalene by Shanghai Haohong biomedical science Co., ltd, 3-methylmaleic anhydride sold under the trade name citraconic anhydride by Nanjing lattice chemical Co., ltd, and glacial acetic acid sold under the trade name glacial acetic acid by Nanjing Nippon glass instruments Co., ltd.
Then, cooling the reaction solution, distilling under reduced pressure to remove acetic acid, namely distilling by using a rotary evaporator under the conditions of pressure of 0.1-100 KPa and temperature of 30-100 ℃ until the acetic acid content of the reaction product mixture is below 1.0 percent by weight to obtain a reaction product mixture;
in the present invention, when the reduced pressure distillation temperature is within the above range, if the reduced pressure distillation pressure is less than 0.1KPa, the actual need for distilling off acetic acid is exceeded; if the reduced pressure distillation pressure is higher than 100KPa, it is difficult to distill off acetic acid; accordingly, the reduced pressure distillation pressure is suitably from 0.1 to 100KPa, preferably from 0.5 to 95KPa, more preferably from 1 to 90KPa;
when the reduced pressure distillation pressure is within the above range, it is difficult to distill off acetic acid if the reduced pressure distillation temperature is lower than 30 ℃; if the reduced pressure distillation temperature is higher than 100 ℃, the actual requirement of distilling to remove acetic acid is exceeded; accordingly, a reduced pressure distillation temperature of 30 to 100 ℃ is suitable, preferably 35 to 90 ℃, more preferably 40 to 85 ℃;
the acetic acid content in the reaction product mixture was determined according to the standard analytical method of GB/T1628-2008.
The rotary evaporator used in the present invention is a product currently on the market, for example, a product sold under the trade name of N-1100S-WD rotary evaporator by Tokyo chemical and physical instruments.
B. Extraction of
According to the weight ratio of the reaction product mixture to water of 1: 1-50, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then mixing according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1: 0.1-5.0, extracting the aqueous solution of the reaction product mixture for 2-4 times by using an extracting agent, and merging the extraction phases to obtain a merged extraction phase;
in the present invention, the main purpose of adding water to the reaction product mixture is to dissolve and remove impurities dissolved in water. Amounts of water added above the stated range are not desirable because the weight ratio of reaction product mixture to water is greater than 1:1, the purpose of dissolving and removing impurities dissolved in water is not achieved, and the weight ratio of the reaction product mixture to water is less than 1:5.0, water waste can result.
The main purpose of the extraction of the aqueous reaction product mixture with the extractant is to extract the reaction product of step a. The extractant used in the invention is diethyl ether, ethyl acetate, dichloromethane, trichloromethane or carbon tetrachloride, which are all products sold on the market at present.
In the present invention, the volume ratio of the aqueous reaction product mixture solution to the extractant is 1:0.1 to 5.0. If the volume ratio of the aqueous reaction product mixture to the extractant is greater than 1:0.1, the reaction product cannot be effectively dissolved and extracted; if the volume ratio of the aqueous reaction product mixture solution to the extractant is less than 1:5.0, the post-treatment difficulty is increased, and the treatment cost is increased; thus, the volume ratio of the aqueous reaction product mixture solution to the extractant is 1: from 0.1 to 5.0 is appropriate, preferably 1:0.2 to 4.0, more preferably 1:0.5 to 3.0;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1: 0.5-2.0, and the combined extract phase obtained in the step B is sequentially saturated NaHCO 3 Washing the solution with HCl solution with the concentration of 0.1-5.0N for 2-4 times, and repeatedly washing with distilled water in the same way until the washing combined extract phase is neutral;
in the present invention, saturated NaHCO is used 3 The main function of the solution washing is to remove acidic impurities; the main function of washing by using HCl solution with the concentration of 0.1-5.0N is to remove alkaline impurities and residual NaHCO 3 ；
In the present invention, the main purpose of repeated washing with distilled water until the extract phase is neutral is to remove residual HCl.
D. Drying the mixture
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying, and distilling under reduced pressure to remove solvent to obtain a solid or liquid;
in this step, the neutral combined extract phase was extracted with anhydrous Na 2 SO 4 Drying is primarily to remove water contained in the neutral combined extract phase.
In the present invention, the reduced pressure distillation is carried out by using a rotary evaporator under a pressure of 0.1 to 100KPa and a temperature of 30 to 100 ℃ until the solvent content of the residual solid or liquid becomes 1.0% by weight or less.
When the temperature is in the range, the pressure is lower than 0.1KPa, the practical need of distilling to remove the solvent is exceeded; if it is higher than 100KPa, it is difficult to distill off the solvent; therefore, it is reasonable that the pressure is 0.1 to 100KPa, preferably 0.5 to 95KPa, more preferably 1.0 to 90KPa; when the pressure is within the above range, if the temperature is lower than 30 ℃, it is difficult to distill off the solvent; if the temperature is higher than 100 ℃, the actual requirement of distilling to remove the solvent is exceeded; therefore, a temperature of 30 to 100 ℃ is suitable, preferably 38 to 90 ℃, more preferably 46 to 80 ℃;
the rotary evaporator used in the present invention is a product currently on the market, for example, a product sold under the trade name of N-1100S-WD rotary evaporator by Tokyo chemical and physical instruments.
E. Recrystallization or column chromatography
And D, mixing the solid obtained in the step D with petroleum ether and ethyl acetate according to the volume ratio of 100: recrystallizing in a mixed solution of 0-100 at room temperature, filtering, and drying to obtain the naphthyl pyrrolindione compound;
the drying is carried out by drying in an oven at the temperature of 30-100 ℃ until the content of the solvent or water in the naphthyl pyrrolindione compound product is below 0.5 percent by weight. The solvent content is analyzed and detected according to a national standard analysis method, for example, the ethyl acetate content is analyzed and detected according to GB/T12717-2007 standard, and the water content is detected according to GB/T2366-2008 standard analysis method.
Or
The solid obtained in step D was mixed in a ratio of solid in grams to solvent in milliliters of 1: 1-20 is dissolved by ethyl acetate to obtain a solution, the solution or the liquid obtained in the step D is separated by a silica gel chromatographic column, and petroleum ether and ethyl acetate are used according to the volume ratio of 100: 0-100 as eluent, eluting under the pressure of 0.1-5.0 MPa, collecting eluate, and distilling under reduced pressure to remove solvent to obtain the naphthyl pyrrolindione compound.
The silica gel chromatographic column used in the invention is a silica gel chromatographic column with the diameter to height ratio of 1:1 to 50 and a separation column filled with 100 to 600 meshes of silica gel.
Using a rotary evaporator vacuum distillation apparatus as described above, the collected leachate is further vacuum distilled under a pressure of 0.1 to 100KPa at a temperature of 30 to 100 ℃ until the solvent content of the residue detected according to the method described in the specification of the present application is 1.0% by weight or less, whereby the naphthyl pyrrolindione compound is obtained as a white, yellow, tan, brown, etc. colored crystal, solid, powder or oily liquid.
The yield of the preparation method of the naphthyl pyrrolindione compound is calculated according to the following calculation formula:
(moles of naphthyl pyrrolindione compound (I) ÷ moles of naphthylamine compound (II) × 100%
The naphthyl pyrrolindione diketone compound is detected by adopting a conventional nuclear magnetic resonance detection method 1 See the examples of the examples section for data on H-NMR spectra.
The invention relates to application of a naphthyl pyrrolindione compound in preventing and treating plant diseases.
According to the invention, the plant diseases are wheat scab, powdery mildew, rust disease, stem base rot, rice blast, banded sclerotial blight, false smut, bakanae disease, bacterial streak disease, bacterial leaf blight, big leaf spot of corn, small leaf spot, gray mold of melons, fruits, vegetables and flowers, sclerotinia sclerotiorum, anthracnose, early blight, late blight, brown spot, rust disease, southern blight, powdery mildew, downy mildew, scab, ring rot, leaf spot, gummy stem blight, bacterial canker, angular leaf spot, fruit spot, soft rot and root cancer.
The present invention refers to documents such as "pesticide bioassay" by Shenjin Ministry (Chinese agricultural Press, 2013, beijing) and the like, and the biological activity of the naphthyl pyrrolindione compound of the present invention on important plant pathogenic bacteria is measured by using plant pathogenic bacteria materials stored in the laboratory. Specifically, the naphthyl pyrrolindione compound of the invention is dissolved in dimethyl sulfoxide (DMSO) to obtain a medicament mother solution with the concentration of the compound being 50mg/mL or 20mg/mL, then the medicament mother solution is diluted to the concentration of 10000 mug/mL and 1000 mug/mL by sterile water, then potato glucose agar (PDA) culture medium cooled to the temperature of about 45 ℃ is added and evenly mixed to prepare an arithmetic series medicament-containing concentration culture medium with the final concentration of the compound being 100, 75, 50 and 25 mug/mL respectively, or a series medicament-containing concentration culture medium with the ratio of 50 mug/mL, 25 mug/mL, 12.5 mug/mL, 6.25 mug/mL and the like is prepared according to the activity of the initially screened compound and the sensitivity of pathogenic bacteria, and a culture medium without the compound and with the same amount of solvent is used as a blank control. The Minimum Inhibitory Concentrations (MICs) for the growth of Botrytis cinerea (Botrytis cinerea), rhizoctonia solani (Rhizoctonia solani) and Gibberella tritici (Fusarium graminearum) were determined according to the method described in Wiegand et al, "ear and bromine two different methods of the Minimal Inhibition Concentrations (MICs)," Nature protocols ", 3 (2), pp163-175 (2008), wherein in determining the activity against Botrytis cinerea, wild susceptible strain B10 and multiply resistant strain B5 having a high level of resistance to five types of fungicides such as carbendazim, pythium, pyronil, azoxystrobin, boscalid and the like were used; the sensitive strain 2021 and the strain 2021R showing dual resistance to carbendazim and phenamacril are used in the determination of the activity to gibberella zeae.
The Minimum Inhibitory Concentration (MIC) of the naphthylpyrrolindione compound of the invention in NB (beef gravy) medium at a concentration of 25, 12.5, 6.25. Mu.g/mL was determined according to the method described in Wiegand et al and Liang et al, "Two thiadiazol compounds present themselves, inorganic salts, pv. Oryzae by applying the same, molecular's production of extracellular polysaccharides", molecular plant Pathology, 16 (8), pp882-892 (2015), and the like, in particular in the examples.
The Minimum Inhibitory Concentrations (MIC) of the naphthyl pyrrolindiones of the present invention against the growth of ralstonia solanacearum (Pseudomonas solanacearum), fusarium solanacearum (Xanthomonas oryzae), xanthomonas citri canker (Xanthomonas citri), and Rhizopus persicus (Agrobacterium tumefaciens) in NB (beef broth) medium at concentrations of 10, 5, 1 μ g/mL were further determined according to the activity of the initially screened compounds and the sensitivity of pathogenic bacteria, as described in the above example, including wild-sensitive strains and double resistant strains against thiazoxazole and streptomycin.
The research of the inventor discovers that the naphthyl pyrrolindione compound has no cross resistance with benzimidazoles, dicarboximides, qoIs, SDHIs, phenylpyrroles and phenylaminopyrimidines bactericides, and has good control effect on strawberry gray mold; has no cross resistance with thiazole bactericides and agricultural streptomycin and has good control effect on the bacterial blight of rice; the bactericide has no cross resistance with cyanoacrylate bactericides and has a control effect on wheat scab, and particularly, refer to pesticide effect example 7, example 15 and example 16.
According to the invention, technicians in the technical field can use the existing auxiliary agents or auxiliary materials according to actual needs to process the naphthyl pyrrolindione compound into various dosage forms such as Wettable Powder (WP), suspending agent (SC), water dispersible granule (WG) and the like by adopting the existing pesticide production technology.
For example, according to Shenjin Liang Ming, processing and management of pesticide dosage form, china agricultural Press, beijing (2002), wangkiyuan Ming, pesticide formulation, china agricultural Press, beijing (2002)
The methods described prepare these formulations.
Wettable powders (50% WP) were prepared as follows:
weighing 50% of naphthyl pyrrolindione compound sample, 38-45% of carriers such as kaolin, diatomite, white carbon black, light calcium carbonate and the like and 5-12% of surfactants such as lignosulfonate, alkylphenol polyoxyethylene phosphate, sodium tripolyphosphate, fatty acid polyoxyalkylene ester, polyethylene glycol, polyvinyl alcohol, sodium oleate, nekal, peregal, lauric acid, fatty alcohol, stearic acid and the like according to the effective content of the preparation to be processed by the weight of the effective components, mixing, airflow crushing, sieving and collecting a mixture passing through 44 mu m. According to the detection of the GB/T14825-1993 standard method, the sample mass reaches the wetting time of less than 2 minutes, the suspension rate is more than 70 percent after the stirring and the standing for 1 hour, and the pH value is 6.8-7.2.
The suspension (35% SC) was prepared as follows:
weighing a sample of naphthyl pyrrolindione compound with 35-300 mesh or less, a water-soluble wetting agent such as sodium dodecyl sulfate, sodium dodecyl benzene sulfate, alkyl polyoxyethylene ether sulfonate, peregal, concentrated milk 100, tween, sorbitol, polyoxyethylene ether and the like, a dispersing and suspending agent such as NNO, nekal, polycarboxylate sodium salt, ethylenediamine tetraacetic acid sodium salt and the like, a tackifier such as acacia, xanthan gum, alginic acid and the like, a stabilizer such as bentonite, diatomaceous earth and the like, an antifreezing agent such as polyethylene glycol 400, glycerol, urea and the like, an antifoaming agent such as lauric acid, stearic acid, sulfonamide, fatty alcohol and the like, and an auxiliary agent such as mineral oil and the like, in an amount of 0.2-1.0%, 0.3-5.0%, based on the effective component weight of the preparation to be processed, mixing with water to prepare slurry, grinding for 2-3 times by a sand mill, finally regulating and controlling technical indexes such as pH, fluidity, wettability and the like, detecting according to a NY/T4014-2021 standard method, wherein the content of active ingredients of the prepared suspending agent is +/-0.1-0.5%, the suspending agent is not layered and precipitated after being placed indoors for 30 days, can keep a stable suspension state after being diluted with water, and the effective suspension rate after standing for 1 hour is more than 90%.
Water dispersible granules (25% WG) were prepared as follows:
weighing 25% sample of naphthyl pyrrolindione compound, 45-70% carrier such as kaolin, diatomite, pottery clay, white carbon black and the like, and 5-30% auxiliary agents and disintegrating agents such as sodium dodecyl sulfate, lignosulfonate, peregal, nekal, urea, fatty acid, lauric acid, stearic acid, silica gel, ammonium sulfate, potassium sulfate, sodium chloride and the like according to the effective content of the preparation to be processed by the weight of the effective components; mixing, jet milling, collecting the mixture with particle size below 10 μm, extruding, granulating, and drying. According to detection of HG/T4463-2012 standard method, the prepared water dispersible granule has the wet disintegration time less than 2 minutes, the suspension rate after stirring and standing for 1 hour is more than 70 percent, and the pH value is 6.8-7.2.
Advantageous effects
The beneficial effects of the invention are: the naphthyl pyrrolindione compound has the biological activity of broad-spectrum plant pathogenic fungi, bacteria and root-knot nematodes, is safe to plants, has selectivity and has adaptability to the environment; the bactericide has selectivity when being used for preventing and controlling diseases of crops and garden crops, accords with the development direction of a novel bactericide which is safe, efficient, low in toxicity, low in residue and compatible with the environment, and accords with the requirement of environmental protection quality; the bactericide has no cross resistance with the existing bactericide, can prevent and treat drug-resistant diseases, and particularly can solve the problem that multiple drug-resistant diseases can not be treated by medicines; the antibacterial agent has the advantages of high antibacterial activity, long lasting period, small dosage per unit area, low use cost, long suitable medication time, high input-output ratio and good economic benefit, and meets the requirement of high-quality green development of boosting agriculture.
Detailed Description
The invention will be better understood by the following examples.
Example 1: preparation of 1- (4-bromonaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-11)
The implementation steps of this example are as follows:
A. heating reflux reaction
Mixing 4-bromonaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.2:24, uniformly mixing, and heating and refluxing for reaction for 3.8 hours by using a heating reflux device under stirring;
then, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 28KPa and a temperature of 55 ℃ until the acetic acid content of the reaction product mixture was 0.5% by weight according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1:22, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then mixing according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:4.0, extracting the reaction product mixture aqueous solution for 3 times by using an ether extracting agent, and merging the extraction phases to obtain a merged extraction phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1:1.2, the combined extracts obtained in step B are successively treated with saturated NaHCO 3 Washing the solution with 1.8N HCl solution for 3 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying the mixture
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 52KPa and a temperature of 32 ℃ until the content of the residual solid solvent is 0.8% by weight as measured by the detection method described in the specification of the present application, thereby obtaining a solid;
E. recrystallization
And D, mixing the solid obtained in the step D with petroleum ether and ethyl acetate according to the volume ratio of 100:20 at room temperature, then filtered, and dried in an oven at a temperature of 46 c until the content of the solvent in the product of the naphthyl pyrrolindione compound detected according to the method described in the specification of the present application is 0.2% by weight, thereby obtaining the naphthyl pyrrolindione compound which is in the form of yellow crystals.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.33(d,J＝8.5Hz,1H,ArH),7.88(d,J＝7.9Hz,1H, ArH),7.66(t,J＝8.2Hz,1H,ArH),7.58(t,J＝7.5Hz,1H,ArH),7.53(d,J＝8.2Hz,1H,ArH), 7.23(d,J＝7.9Hz,1H,ArH),6.99(s,2H,COCH＝CHCO)；
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 83%.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing culture medium plate for the growth of botrytis cinerea, rice sheath blight fungus, wheat scab fungus and citrus canker fungus are respectively 50, 75, 100 and 25 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 25, 1, 5 and 25 mu g/mL respectively.
Example 2: preparation of 1- (5-bromonaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-12)
The implementation steps of this example are as follows:
A. heating reflux reaction
Mixing 5-bromonaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.3:32, uniformly mixing, and heating and refluxing for reaction for 4.9 hours by using a heating reflux device under stirring;
subsequently, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 34KPa and a temperature of 68 ℃ until the acetic acid content of the reaction product mixture was 0.5% by weight as measured according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1: and 33, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:2.5, extracting the reaction product mixture aqueous solution for 2 times by using a dichloromethane extracting agent, and merging extract phases to obtain a merged extract phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1:1.0, the combined extracts obtained in step B were successively subjected to saturated NaHCO 3 Washing the solution with 2.2N HCl solution for 2 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying the mixture
Step C obtainingThe obtained neutral combined extract phase uses anhydrous Na 2 SO 4 Drying and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 42KPa and a temperature of 35 deg.C until the solvent content of the residue liquid measured according to the measuring method described in the present specification is 0.6% by weight, thereby obtaining a viscous liquid;
E. column chromatography
Allowing the liquid obtained in step D to pass through a reactor having a diameter to height ratio of 1: 10. and (3) packing a silica gel chromatographic column of 300-mesh silica gel for separation, wherein petroleum ether and ethyl acetate are used according to the volume ratio of 100:5 as an eluting solution, eluting under a pressure of 0.1MPa, and distilling the collected eluate under reduced pressure at a pressure of 70KPa and a temperature of 60 ℃ by using a rotary evaporator until the solvent content of the residue detected according to the method described in the specification of the present application is 0.6% by weight, thereby obtaining the naphthyl pyrrolindione diketone compound as a pale yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.41(d,J＝8.6Hz,1H,ArH),7.84(d,J＝8.2Hz,1H,ArH), 7.71-7.63(m,1H,ArH),7.51(d,J＝8.5Hz,1H,ArH),7.46-7.41(m,1H,ArH),7.36(dd,J＝8.4, 7.5Hz,1H,ArH),6.98(s,2H,COCH＝CHCO)。
this example produced the naphthyl pyrrolindione compound in a yield of 89% as calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani, fusarium graminearum and citrus canker are 50, 75 and 25 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 10, 5, 1 and 10 mu g/mL respectively.
Example 3: preparation of 1- (2, 4-Dichloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-13)
The implementation steps of this example are as follows:
A. heating reflux reaction
Mixing 2, 4-dichloronaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.4:89, uniformly mixing, and heating and refluxing for reaction for 12.2 hours under stirring by using a heating reflux device;
then, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 58KPa and a temperature of 76 ℃ until the acetic acid content of the reaction product mixture was 0.9% by weight according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1:48, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:1.5, extracting the aqueous solution of the reaction product mixture for 4 times by using an ethyl acetate extractant, and merging extract phases to obtain a merged extract phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1:0.9, the combined extracts from step B were successively treated with saturated NaHCO 3 Washing the solution with 3.1N HCl solution for 3 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying the mixture
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 58KPa and a temperature of 62 ℃ until the solvent content of the residue solid measured according to the detection method described in the present specification is 0.9% by weight, thereby obtaining a solid;
E. column chromatography
The solid obtained in step D was mixed in a ratio of solid in grams to solvent in milliliters of 1:1 dissolving with ethyl acetate to give a solution, passing the solution through a die with a diameter to height ratio of 1: 25. and (3) packing a silica gel chromatographic column of 400-mesh silica gel for separation, wherein petroleum ether and ethyl acetate are used according to the volume ratio of 100:100 as a mixed solvent, eluting under a pressure of 1.3MPa, collecting the eluate, and distilling the eluate under reduced pressure at a pressure of 28KPa and a temperature of 54 deg.C by using a rotary evaporator until the solvent content of the residue is 0.9% by weight according to the method described in the specification of the present application, thereby obtaining the naphthyl pyrrolindione compound as a pink powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.31(dd,J＝7.6,1.4Hz,1H,ArH),7.74(s,1H,ArH), 7.70-7.60(m,2H,ArH),7.57(d,J＝9.1Hz,1H,ArH),7.01(s,2H,COCH＝CHCO)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, is 71%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani, fusarium graminearum and citrus canker are 75, 50, 100 and 25 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 1 and 5 mu g/mL respectively.
Example 4: preparation of 1- (4-nitronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-14)
The implementation steps of this embodiment are as follows:
A. heating reflux reaction
Mixing 4-nitronaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.8:100, uniformly mixing, and heating and refluxing for reaction for 0.41h under stirring by using a heating reflux device;
then, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 82KPa and a temperature of 92 ℃ until the acetic acid content of the reaction product mixture was 0.7% by weight according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1:50, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:1.0, extracting the aqueous solution of the reaction product mixture for 3 times by using a trichloromethane extracting agent, and merging the extracting phases to obtain a merged extracting phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1:1.8, the combined extracts obtained in step B are successively treated with saturated NaHCO 3 Washing the solution with 0.8N HCl solution for 3 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying the mixture
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 70KPa and a temperature of 50 ℃ until the solvent content of the residue solid is 0.5% by weight as measured by the detection method described in the specification of the present application, thereby obtaining a solid;
E. recrystallization
And D, allowing the solid obtained in the step D to react in a reaction tank with petroleum ether and ethyl acetate according to the volume ratio of 100:100 at room temperature, then filtered, and dried in an oven at 74 c until the solvent content in the product naphthyl pyrrolindione compound detected according to the method described in the specification of the present application is 0.3% by weight, thereby obtaining the naphthyl pyrrolindione compound as a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.57(d,J＝8.8Hz,1H,ArH),8.26(d,J＝8.1Hz,1H, ArH),7.83-7.75(m,1H,ArH),7.71-7.62(m,2H,ArH),7.47(d,J＝8.1Hz,1H,ArH),7.04(s, 2H,COCH＝CHCO)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 66%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate on the growth of botrytis cinerea, rhizoctonia solani, fusarium graminearum and canker citrus are 75, 100 and 25 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 10, 5, 1 and 5 mu g/mL respectively.
Example 5: preparation of 1- (2-Nitro-3, 4-dioxo-3, 4-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-15)
The implementation steps of this embodiment are as follows:
A. heating reflux reaction
Mixing 2-nitro-3, 4-dioxo-3, 4-dihydronaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0: 2.0:46, uniformly mixing, and heating and refluxing for reaction for 1.1h by using a heating reflux device under stirring;
subsequently, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 92KPa and a temperature of 100 ℃ until the acetic acid content of the reaction product mixture was 0.5% by weight as measured according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1: adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture obtained in the step A according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:3.0, extracting the reaction product mixture aqueous solution for 3 times by using a carbon tetrachloride extracting agent, and merging the extracting phases to obtain a merged extracting phase;
C. washing machine
According to the volume ratio of the combined extraction phase to the washing liquid of 1:2.0, the combined extracts from step B were successively treated with saturated NaHCO 3 Washing the solution with 4.8N HCl solution for 3 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 82KPa and a temperature of 64 ℃ until the solvent content of the residue solid or liquid is 0.8% by weight according to the detection method described in the specification of the present application, thereby obtaining a viscous liquid;
E. column chromatography
Allowing the liquid obtained in step D to pass through a reactor having a diameter to height ratio of 1:1. and (3) filling a silica gel chromatographic column of 100-mesh silica gel for separation, wherein petroleum ether and ethyl acetate are used according to the volume ratio of 100:0 as a leacheate, eluting under the condition of pressure of 3.9MPa, and distilling the collected leacheate under reduced pressure by using a rotary evaporator under the conditions of pressure of 82KPa and temperature of 72 ℃ until the solvent content of the residue is 0.8 percent by weight according to the method described in the specification of the application, thereby obtaining the naphthyl pyrrolindione diketone compound which is yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.85(d,J＝8.0Hz,1H,ArH),8.52(d,J＝8.0Hz,1H, ArH),8.03-7.94(m,1H,ArH),7.91-7.79(m,1H,ArH),7.01(s,2H,COCH＝CHCO)。
this example produced the naphthyl pyrrolindione compound in a 60% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani, fusarium graminearum and citrus canker are 25, 50, 75 and 25 μ g/mL, respectively.
Example 6: preparation of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-16)
The implementation steps of this embodiment are as follows:
A. heating reflux reaction
Mixing 2-methylnaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.5:58, uniformly mixing, and heating and refluxing for reaction for 2.1 hours under stirring by using a heating and refluxing device;
subsequently, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 22KPa and a temperature of 50 ℃ until the acetic acid content of the reaction product mixture was 0.8% by weight according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1:15, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:1.9, extracting the aqueous solution of the reaction product mixture for 4 times by using a carbon tetrachloride extracting agent, and merging the extracting phases to obtain a merged extracting phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1:1.5, the combined extracts obtained in step B are successively treated with saturated NaHCO 3 Washing the solution with 1.0N HCl solution for 2 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying the mixture
The neutral combined extract phase obtained in the step C uses anhydrous Na 2 SO 4 Drying, distilling under reduced pressure at a pressure of 0.1KPa and a temperature of 30 deg.C by using a rotary evaporator until the solvent content of the residue solid or liquid is 0.9% by weight according to the detection method described in the specification of the present application, thereby obtaining a productA seed liquid;
E. column chromatography
Allowing the liquid obtained in step D to pass through a reactor with a diameter to height ratio of 1: 50. and (3) separating by using a silica gel chromatographic column filled with 600-mesh silica gel, wherein petroleum ether and ethyl acetate are mixed according to the volume ratio of 100:32 as an eluent, under a pressure of 2.6MPa, and the collected eluate was distilled under reduced pressure using a rotary evaporator under a pressure of 0.1KPa and a temperature of 30 c until the solvent content of the residue was 0.9% by weight as measured by the method described in the specification of the present application, thereby obtaining the naphthyl pyrrolindione compound as a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:7.87(d,J＝8.6Hz,2H,ArH),7.55-7.40(m,4H,ArH), 6.99(s,2H,COCH＝CHCO),2.31(s,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared in this example, calculated according to the methods described in the specification of this application, was 85%
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani, fusarium graminearum and canker citrus are 25, >100 and 25 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 1 and 5 mu g/mL respectively.
Example 7: preparation of 1- (4-Cyclopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-17)
The implementation steps of this example are as follows:
A. heating reflux reaction
Mixing 4-cyclopropylnaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.0:1.0, uniformly mixing, and heating and refluxing for 8.0h under stirring by using a heating and refluxing device;
subsequently, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 0.1KPa and a temperature of 40 ℃ until the acetic acid content of the reaction product mixture was detected to be 0.6% by weight according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1:50, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:0.1, extracting the aqueous solution of the reaction product mixture for 4 times by using an ether extractant, and merging extract phases to obtain a merged extract phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1:0.5, the combined extracts from step B were successively saturated with NaHCO 3 Washing the solution with 0.1N HCl solution for 3 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying
The neutral combined extract phase obtained in the step C uses anhydrous Na 2 SO 4 Drying, and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 45KPa and a temperature of 30 ℃ until the solvent content of the residual solid or liquid is 0.7% by weight according to the detection method described in the specification of the present application, thereby obtaining a solid;
E. recrystallization
And D, allowing the solid obtained in the step D to react in a reaction tank with petroleum ether and ethyl acetate according to the volume ratio of 100:0 at room temperature, then filtered, and dried using an oven at 30 c until the content of the solvent or water in the product of the naphthyl pyrrolindione compound detected according to the method described in the specification of the present application is 0.1% by weight, thereby obtaining the naphthyl pyrrolindione compound as a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.49(dt,J＝8.5,1.0Hz,1H,ArH),7.58(ddd,J＝8.3,5.4, 2.7Hz,1H,ArH),7.53-7.49(m,2H,ArH),7.34(dd,J＝7.6,1.1Hz,1H,ArH),7.27(s,1H,ArH), 6.95(s,2H,COCH＝CHCO),2.44-2.27(m,1H,Ar-CH),1.13-1.07(m,2H,CH 2 ),0.80(td,J＝ 6.0,4.3Hz,2H,CH 2 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 76%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani, fusarium graminearum and citrus canker are 50, 75 and 25 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 25, 1, 5 and 5 mu g/mL respectively.
Example 8: preparation of 1- (2-hydroxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-19)
The implementation steps of this example are as follows:
A. heating reflux reaction
Mixing 2-hydroxynaphthalene-1-amine (II), maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.6:66, uniformly mixing, and heating and refluxing for reaction for 6.9 hours under stirring by using a heating and refluxing device;
subsequently, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 80KPa and a temperature of 85 ℃ until the acetic acid content of the reaction product mixture was 0.7% by weight according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1:46, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:1, extracting the aqueous solution of the reaction product mixture for 2 times by using an ethyl acetate extractant, and merging extract phases to obtain a merged extract phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1:0.8, the combined extracts from step B were successively saturated with NaHCO 3 Washing the solution with 5.0N HCl solution for 4 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying, and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 100KPa and a temperature of 100 deg.C until the solvent content of the residue solid or liquid is 0.7% by weight according to the detection method described in the specification of the present application, thereby obtaining a solid;
E. column chromatography
The solid obtained in step D was mixed in a ratio of solid in grams to solvent in milliliters of 1:20 dissolution with ethyl acetate gives a solution which is passed through a reactor with a diameter to height ratio of 1: 36. and (3) packing a silica gel chromatographic column of 500-mesh silica gel for separation, wherein petroleum ether and ethyl acetate are used according to the volume ratio of 100:70 as a eluent, under a pressure of 5.0MPa, and the collected eluate was distilled under reduced pressure using a rotary evaporator under a pressure of 100KPa and a temperature of 100 ℃ until the solvent content of the residue was 0.7% by weight as measured by the method described in the specification of the present application, thereby obtaining the naphthyl pyrrolindione compound as a brown powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H NMR(500MHz,CDCl 3 )δ:7.81-7.78(m,1H,ArH),7.73(d,J＝8.9Hz,1H,ArH), 7.46(ddd,J＝8.1,6.7,1.3Hz,1H,ArH),7.42-7.32(m,2H,ArH),7.06(d,J＝8.9Hz,1H,ArH), 6.93(s,2H,COCH＝CHCO),6.05(s,1H,Ar-OH)。
the yield of the naphthyl pyrrolindione compound prepared in this example, calculated according to the method described in the specification of the application, is 58%
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani, gibberella cerealis and Sclerotinia citrea are >100, >100 and > 100. Mu.g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria hypha in the drug-containing culture solution are respectively more than 100, more than 100 and more than 100 mu g/mL.
Example 9: preparation of 3-methyl-1- (naphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-21)
The implementation steps of this example are as follows:
A. heating reflux reaction
Mixing naphthalene-1-amine (II), 3-methyl maleic anhydride (III) and glacial acetic acid according to a molar ratio of 1.0:1.2:32, uniformly mixing, and heating and refluxing for reaction for 24.0 hours by using a heating reflux device under stirring;
then, the reaction liquid was cooled and distilled using a rotary evaporator under a pressure of 44KPa and a temperature of 72 ℃ until the acetic acid content of the reaction product mixture was 0.8% by weight according to the detection method described in the specification of the present application, thereby obtaining a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1:50, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then adding water into the reaction product mixture according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:0.5, extracting the reaction product mixture aqueous solution for 3 times by using an ether extracting agent, and merging the extraction phases to obtain a merged extraction phase;
C. washing machine
According to the volume ratio of the combined extraction phase to the washing liquid of 1:1.5, the combined extracts obtained in step B are successively treated with saturated NaHCO 3 Washing the solution with 3.5N HCl solution for 3 times, and repeatedly washing with distilled water in the same manner until the combined extract phase is neutral;
D. drying the mixture
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying, and distilling under reduced pressure using a rotary evaporator under conditions of a pressure of 100KPa and a temperature of 40 deg.C until the solvent content of the residual solid or liquid is 0.6% by weight according to the detection method described in the specification of the present application, thereby obtaining a solid;
E. recrystallization
And D, allowing the solid obtained in the step D to react in a reaction tank with petroleum ether and ethyl acetate according to the volume ratio of 100: the mixed solution of 50 was recrystallized at room temperature, then filtered, and dried in an oven at a temperature of 100 c until the content of the solvent in the product of the naphtyl pyrrolindione compound was 0.3% by weight as measured according to the method described in the specification of the present application, thereby obtaining the naphtyl pyrrolindione compound as a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:7.97-7.90(m,2H,ArH),7.53(dtd,J＝12.5,6.9,3.1Hz, 4H,ArH),7.35(d,J＝7.2Hz,1H,ArH),6.62(dd,J＝10.9,1.7Hz,1H,COCH),2.25(s,3H, CH 3 )。
this example produced the naphthyl pyrrolindione compound in a 88% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the growth of botrytis cinerea, rhizoctonia solani, fusarium graminearum and citrus canker on drug-containing medium plates were 50, 75 and >100 μ g/mL, respectively.
The naphthyl pyrrolindione compound prepared in the embodiment has the lowest inhibition concentration of more than 100, >100 and >100 mu g/mL for the growth of bacterial filaments of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution respectively.
Example 10: preparation of 3-methyl-1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-22)
The embodiment of this example is the same as that of example 6, except that the maleic anhydride compound (III) used in this example is 3-methylmaleic anhydride:
the naphthyl pyrrolindione compound prepared in this example is a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H NMR(400MHz,CDCl 3 )δ:7.86(d,J＝8.3Hz,2H,ArH),7.53-7.40(m,4H,ArH),6.62 (d,J＝1.7Hz,1H,COCH),2.31(s,3H,COCCH 3 ),2.26(d,J＝1.7Hz,3H,Ar-CH 3 )。
this example produced the naphthyl pyrrolindione compound in 83% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 25 and 50 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 100, 10 and 75 mu g/mL respectively.
Example 11: preparation of 3-nitro-1- (2-nitro-3, 4-dioxo-3, 4-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-23)
This example is the same as example 5 except that the maleic anhydride compound (III) used is 3-nitromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.88(d,J＝8.0Hz,1H,ArH),8.56(d,J＝8.0Hz,1H, ArH),8.09-7.96(m,1H,ArH),7.92-7.81(m,1H,ArH),7.13(s,1H,COCH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 58%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the growth of Botrytis cinerea, rhizoctonia solani and Gibberella tritici are 25, 50 and 100 μ g/mL, respectively.
Example 12: preparation of methyl (4-methyl-1- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalen-2-yl) carbamate (test No.: YNT 21-24)
This example is carried out in the same manner as in example 1 except that the naphthylamine compound (II) used is methyl (1-amino-4-methylnaphthalen-2-yl) carbamate;
the naphthyl pyrrolindione compound prepared in this example is a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:9.76(s,1H,NH),7.74(dd,J＝7.6,4.0Hz,2H,ArH), 7.46-7.38(m,2H,ArH),7.26(s,1H,ArH),6.95(m,2H,COCH＝CHCO),3.68(s,3H,OCH 3 ), 2.20(s,3H,Ar-CH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 72% calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 50, 50 and 100 mu g/mL respectively.
Example 13: preparation of 3, 4-dimethyl-1- (naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-25)
The embodiment of this example is the same as that of example 9 except that the maleic anhydride compound (III) used is 3, 4-dimethylmaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:7.92(t,J＝8.6Hz,2H,ArH),7.59-7.47(m,4H,ArH),7.34 (d,J＝6.5Hz,1H,ArH),2.13(s,6H,2CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 95%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are >100, >100 and >100 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria hypha in the drug-containing culture solution are respectively more than 100, more than 100 and more than 100 mu g/mL.
Example 14: preparation of 3, 4-dimethyl-1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-26)
This example is the same as example 6 except that the maleic anhydride compound (III) used is 3, 4-dimethylmaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:7.85(dd,J＝6.6,4.0Hz,2H,ArH),7.48-7.40(m,4H, ArH),2.30(s,3H,Ar-CH 3 ),2.14(s,6H,2CH 3 )。
this example produced the naphthyl pyrrolindione compound in 83% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 50, 50 and >100 mug/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are respectively 25, 10 and 75 mu g/mL.
Example 15: preparation of 2- (Naphthalen-1-yl) -4,5,6, 7-tetrahydro-1H-isoindole-1, 3 (2H) -dione (test No.: YNT 21-27)
This example is the same as example 9 except that the maleic anhydride compound (III) used is 4,5,6,7-tetrahydroisobenzofuran-1, 3-dione;
the naphthyl pyrrolindione compound prepared in this example was a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H NMR(400MHz,CDCl 3 )δ:7.92(t,J＝8.4Hz,2H,ArH),7.62-7.47(m,4H,ArH),7.35 (d,J＝7.3Hz,1H,ArH),2.50(br,4H,2CH 2 ),1.88(br,4H,CH 2 CH 2 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 75%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are respectively more than 100, >100 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria hypha in the drug-containing culture solution are respectively more than 100, more than 100 and more than 100 mu g/mL.
Example 16: preparation of 2- (2-methylnaphthalen-1-yl) -4,5,6, 7-tetrahydro-1H-isoindole-1, 3 (2H) -dione (test code: YNT 21-28)
This example is the same as example 6 except that the maleic anhydride compound (III) used is 4,5,6, 7-tetrahydroisobenzofuran-1, 3-dione;
the naphthyl pyrrolindione compound prepared in this example is a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:7.87(m,2H,ArH),7.52-7.42(m,4H,ArH),2.52-2.45(m, 4H,2CH 2 ),2.33(s,3H,CH 3 ),1.91-1.88(m,4H,CH 2 CH 2 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 70%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 100, 100 and >100 mug/mL, respectively.
The naphthyl pyrrolindione compound prepared in the embodiment has the lowest inhibition concentration of more than 100, >100 and >100 mu g/mL for the growth of bacterial filaments of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution respectively.
Example 17: preparation of 3, 4-dichloro-1- (naphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-29)
This example is the same as example 9 except that the maleic anhydride compound (III) used is 3, 4-dichloromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.02-7.91(m,2H,ArH),7.61-7.52(m,4H,ArH),7.40(d,J ＝7.3Hz,1H,ArH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 77%.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound on the drug-containing culture medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are respectively 100, 100 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 50, 10, 5 and 100 mu g/mL respectively.
Example 18: preparation of 3, 4-dichloro-1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-30)
This example is the same as example 6 except that the maleic anhydride compound (III) used is 3, 4-dichloromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.97-7.87(m,2H,ArH),7.60-7.42(m,4H,ArH),2.37(s, 3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 64%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 50, 50 and 100 mu g/mL respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 25, 5 and 50 mu g/mL respectively.
Example 19: preparation of 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-31)
This example is the same as example 6 except that the naphthylamine compound (II) used is 4-chloro-2-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a brown powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.29(d,J＝10.6Hz,1H,ArH),7.62-7.52(m,3H,ArH), 7.45(d,J＝10.1Hz,1H,ArH),7.00(s,2H,COCH＝CHCO),2.29(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 79%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the growth of Botrytis cinerea, rhizoctonia solani and Gibberella tritici are 12.5, 6.25 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound on the growth of bacterial filaments of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer are 5, 1 and 5 mu g/mL respectively.
Example 20: preparation of 3-methyl-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-32)
This example is the same as example 9 except that the naphthylamine compound (II) used is 4-chloro-2-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.28(d,J＝9.0Hz,1H,ArH),7.60-7.51(m,3H,ArH), 7.46(d,J＝8.3Hz,1H,ArH),6.62(q,J＝1.6Hz,1H,COCH),2.29(s,3H,COCCH 3 ),2.26(s, 3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 79%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 25, 12.5 and 50 mu g/mL respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 1 and 5 mu g/mL respectively.
Example 21: preparation of 3, 4-dichloro-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-33)
This example is the same as example 9 except that the naphthylamine compound (II) is 4-chloro-2-methylnaphthalen-1-amine and the maleic anhydride compound (III) is 3, 4-dichloromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is an orange crystal.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.27(d,J＝9.8Hz,1H,ArH),7.60-7.45(m,4H,ArH),2.28 (s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 61%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 50, 25 and 75 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 1, 5 and 5 mu g/mL respectively.
Example 22: preparation of 3, 4-dimethyl-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-34)
This example is the same as example 9 except that the naphthylamine compound (II) is 4-chloro-2-methylnaphthalen-1-amine and the maleic anhydride compound (III) is 3, 4-dimethylmaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.27(d,J＝10Hz,1H,ArH),7.58-7.46(m,4H,ArH),2.28 (s,3H,Ar-CH 3 ),2.13(s,6H,2COCCH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 52%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 50, 75 and 100 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are respectively 25, 10 and 5 mu g/mL.
Example 23: preparation of 1- (5-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-35)
This example is the same as example 6 except that the naphthylamine compound (II) used is 5-chloro-2-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a light yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.90(d,J＝8.0,1H,ArH),7.80(d,J＝8.1Hz,1H,ArH), 7.55(d,J＝7.5Hz,1H,ArH),7.49(d,J＝8.4Hz,1H,ArH),7.36-7.32(m,1H,ArH),7.00(s, 2H,COCH＝CHCO),2.32(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 68%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 12.5 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are respectively 1, 1 and 1, and are more than 5 mu g/mL.
Example 24: preparation of 1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-36)
This example is the same as example 6 except that the naphthylamine compound (II) used is 2, 4-dimethylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.01-7.97(m,1H,ArH),7.52-7.40(m,3H,ArH),7.28(s, 1H,ArH),6.95(s,2H,COCH＝CHCO),2.69(d,J＝1.0Hz,3H,Ar-CH 3 ),2.26(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 63%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella tritici are 12.5, 12.5 and 50 μ g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 1, 5 and 1 mu g/mL respectively.
Example 25: preparation of 3-methyl-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-37)
This example is the same as example 9 except that the naphthylamine compound (II) used is 2, 4-dimethylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.12-8.03(m,1H,ArH),7.50-7.38(m,3H,ArH),7.27(s, 1H,ArH),6.65(s,1H,COCH),2.65(d,J＝1.0Hz,3H,Ar-CH 3 ),2.28(s,3H,COCCH 3 ),2.25(s, 3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 62%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella tritici are 12.5, 12.5 and 50 μ g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 1, 1 and 10 mu g/mL respectively.
Example 26: preparation of 3-methyl-1- (2-amino-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-38)
This example is the same as example 9 except that the naphthylamine compound (II) used is 4-methylnaphthalene-1, 2-diamine;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.22(dd,J＝8.0,4.0Hz,2H,ArH),7.83-7.76(m,2H, ArH),7.51(s,1H,ArH),6.67(s,1H,COCH),4.19(s,2H,NH 2 ),2.36(s,3H,Ar-CH 3 ),2.29(s, 3H,COCCH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 56%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 50, 50 and >100 mug/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 5 and 25 mu g/mL respectively.
Example 27: preparation of 4-methyl-1- (3-methyl-2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) -2-naphthalenecarbonitrile (test code: YNT 21-39)
This example is the same as example 9 except that the naphthylamine compound (II) used is 1-amino-4-methyl-2-naphthalenecarbonitrile;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.36(dd,J＝8.0,4.0Hz,2H,ArH),7.73-7.65(m,2H, ArH),7.38(s,1H,ArH),6.64(s,1H,COCH),2.38(s,3H,Ar-CH 3 ),2.23(s,3H,COCCH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, is 71%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 12.5 and 25 mug/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 1, 5 and 5 mu g/mL respectively.
Example 28: preparation of 3-methyl-4- (3-methyl-2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) -1-naphthalenecarbonitrile (test code: YNT 21-40)
This example is the same as example 9 except that the naphthylamine compound (II) used is 4-amino-3-methyl-1-naphthalenecarbonitrile;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.21(dd,J＝8.0,4.0Hz,2H,ArH),7.66-7.58(m,2H, ArH),7.42(s,1H,ArH),6.64(s,1H,COCH),2.28(s,3H,COCCH 3 ),2.25(s,3H,Ar-CH 3 )。
this example produced the naphthyl pyrrolindione compound in a 65% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 6.25 and 25 mug/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 1, 1 and 5 mu g/mL respectively.
Example 29: preparation of 3-methyl-1- (2-methyl-4-nitronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-41)
This example is the same as example 9 except that the naphthylamine compound (II) used is 2-methyl-4-nitronaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.00(dd,J＝7.6,4.2Hz,2H,ArH),7.61-7.52(m,2H, ArH),7.35(s,1H,ArH),6.63(s,1H,COCH),4.19(s,2H,NH 2 ),2.26(s,3H,COCCH 3 ),2.22(s, 3H,Ar-CH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 64%, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 12.5 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 1, 5 and 10 mu g/mL respectively.
Example 30: preparation of 3-methyl-1- (2-hydroxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-42)
This example is the same as example 9 except that the naphthylamine compound (II) used is 2-hydroxynaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a brown powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H NMR(500MHz,CDCl 3 )δ:7.78-7.74(m,1H,ArH),7.70(d,J＝8.6Hz,1H,ArH), 7.43(d,J＝8.0Hz,1H,ArH),7.40-7.33(m,2H,ArH),7.11(d,J＝8.2Hz,1H,ArH),6.63(s,1H, COCH),6.20(s,1H,Ar-OH),2.29(s,3H,COCCH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 68%.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound on the drug-containing culture medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are respectively 100, 100 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 10, 10 and 25 mu g/mL respectively.
Example 31: preparation of 1- (2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-43)
This example is the same as example 6 except that the naphthylamine compound (II) used is 2-ethylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.92(d,J＝8.0,1H,ArH),7.89-7.86(m,1H,ArH), 7.50-7.45(m,3H,ArH),7.43-7.40(m,1H,ArH),6.99(s,2H,COCH＝CHCO),2.61(q,J＝7.7 Hz,2H,CH 2 ),1.23(t,J＝7.7Hz,3H,CH 3 )。
this example produces the naphthyl pyrrolindione compound in a yield of 81% as calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 12.5 and 50 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 1 and 5 mu g/mL respectively.
Example 32: preparation of 1- (2-Methoxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-44)
This example is the same as example 6 except that the naphthylamine compound (II) used is 2-methoxynaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a brown powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.95(d,J＝9.1Hz,1H,ArH),7.83(dt,J＝8.1,1.0Hz,1H, ArH),7.50-7.45(m,2H,ArH),7.40-7.32(m,2H,ArH),6.95(s,2H,COCH＝CHCO),3.90(s,3H, CH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 60%, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 25, 12.5 and 50 mu g/mL respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 25, 10 and 25 mu g/mL respectively.
Example 33: preparation of 3-methyl-1- (2-mercapto-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-45)
This example is the same as example 9 except that the naphthylamine compound (II) used is 2-mercapto-4-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a brown powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H NMR(500MHz,CDCl 3 )δ:7.78-7.74(m,1H,ArH),7.70(d,J＝8.6Hz,1H,ArH), 7.43(d,J＝8.0Hz,1H,ArH),7.33(s,1H,ArH),7.11(d,J＝8.2Hz,1H,ArH),6.63(s,1H, COCH),6.20(s,1H,SH),2.38(s,3H,Ar-CH 3 ),2.25(s,3H,COCCH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 60%, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 50, 100 and 100 μ g/mL, respectively.
Example 34: preparation of 1- (5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-46)
This example is the same as example 5 except that the naphthylamine compound (II) used is 5, 8-dioxo-5, 8-dihydronaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.15(d,J＝8.0Hz,1H,ArH),7.84(t,J＝8.6Hz,1H, ArH),7.74(d,J＝8.0Hz,1H,ArH),6.94(s,2H,NCOCH＝CHCO),6.92(d,J＝10.3Hz,1H, COCH),6.79(d,J＝10.3Hz,1H,COCH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 68%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 50, 50 and 100 μ g/mL, respectively.
Example 35: preparation of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-47)
This example is the same as example 5 except that the naphthylamine compound (II) used is 2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a tan solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.16(d,J＝8.0Hz,1H,ArH),7.75(d,J＝8.3Hz,1H, ArH),6.96(s,2H,NCOCH＝CHCO),6.93(d,J＝10.3Hz,1H,COCH),6.80(d,J＝10.3Hz,1H, COCH),2.33(s,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 59%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella tritici are 12.5, 12.5 and 50 μ g/mL respectively.
Example 36: preparation of 3-nitro-1- (2-nitro-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-48)
This example is the same as example 5 except that naphthylamine compound (II) used is 2-nitro-5, 8-dioxo-5, 8-dihydronaphthalene-1-amine, maleic anhydride compound (III) used is 3-nitromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.36(d,J＝8.2Hz,1H,ArH),7.99(d,J＝8.2Hz,1H, ArH),6.91(d,J＝10.1Hz,1H,COCH),6.78(s,2H,NCOCH),6.80(d,J＝10.1Hz,1H, COCH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 50%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 50, 50 and >100 mug/mL, respectively.
Example 37: preparation of 3-methyl-1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-49)
This example is the same as example 5 except that naphthylamine compound (II) is 2-methyl-5, 8-dioxo-5, 8-dihydronaphthalene-1-amine and maleic anhydride compound (III) is 3-methylmaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example was a reddish brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.11(d,J＝8.0Hz,1H,ArH),7.70(d,J＝8.0Hz,1H, ArH),6.92(d,J＝10.3Hz,1H,COCH),6.79(d,J＝10.3Hz,1H,COCH),6.69(s,1H, NCOCH),2.32(s,3H,Ar-CH 3 ),2.27(s,3H,COCCH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 67%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 25 and 50 mug/mL, respectively.
Example 38: preparation of 1- (2-methyl-3, 4-dioxo-3, 4-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-50)
This example is carried out in the same manner as in example 5 except that the naphthylamine compound (II) used is 2-methyl-3, 4-dioxo-3, 4-dihydronaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a reddish brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.98-7.89(m,2H,ArH),7.78(d,J＝8.2Hz,1H,ArH), 7.46(d,J＝8.0Hz,1H,ArH),6.96(s,2H,COCH＝CHCO),2.39(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 54%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 12.5 and 50 μ g/mL, respectively.
Example 39: preparation of 3-methyl-1- (6-chloro-2-methyl-3, 4-dioxo-3, 4-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-51)
This example is carried out in the same manner as in example 5 except that the naphthylamine compound (II) used is 6-chloro-2-methyl-3, 4-dioxo-3, 4-dihydronaphthalen-1-amine and the maleic anhydride compound (III) used is 3-methylmaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.38-8.31(m,1H,ArH),8.23(d,J＝7.2Hz,1H,ArH), 7.74(d,J＝7.0Hz,1H,ArH),6.64(s,1H,COCH),2.38(s,3H,Ar-CH 3 ),2.24(s,3H, COCCH 3 )。
this example produced the naphthyl pyrrolindione compound in a 51% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella tritici are 12.5, 12.5 and 50 μ g/mL respectively.
Example 40: preparation of methyl 1- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) -2-naphthoate (test code: YNT 21-52)
This example is the same as example 8 except that the naphthylamine compound (II) used is methyl 1-amino-2-naphthoate;
the naphthyl pyrrolindione compound prepared in this example is a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,DMSO-d 6 )δ:8.23(d,J＝6.9Hz,1H,ArH),8.14(d,J＝6.6Hz,1H, ArH),8.08(d,J＝6.9Hz,1H,ArH),7.97(d,J＝6.7Hz,1H,ArH),7.76(t,J＝5.5Hz,1H,ArH), 7.68(t,J＝5.5Hz,1H,ArH),7.37(s,2H,COCH＝CHCO),3.80(s,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 84%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 100, 100 and >100 mug/mL, respectively.
Example 41: preparation of ethyl 1- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) -2-naphthoate (test No.: YNT 21-53)
This example is the same as example 8 except that the naphthylamine compound (II) used is ethyl 1-amino-2-naphthoate;
the naphthyl pyrrolindione compound prepared in this example is a light yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,DMSO-d 6 )δ:8.22(d,J＝6.8Hz,1H,ArH),8.14(d,J＝6.6Hz,1H, ArH),8.07(d,J＝6.9Hz,1H,ArH),7.96(d,J＝6.8Hz,1H,ArH),7.76(t,J＝5.5Hz,1H,ArH), 7.68(t,J＝5.5Hz,1H,ArH),7.38(s,2H,COCH＝CHCO),4.24(q,J＝5.7Hz,2H,OCH 2 ),2.24 (t,J＝5.7Hz,3H,CH 3 )。
this example produced the naphthyl pyrrolindione compound in a yield of 80% calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 100, 100 and >100 mug/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 50, 50 and more than 50 mu g/mL respectively.
Example 42: preparation of methyl (5- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalen-1-yl) carbamate (test No.: YNT 21-54)
This example is carried out in the same manner as in example 1 except that the naphthylamine compound (II) used is methyl (5-aminonaphthalen-1-yl) carbamate;
the naphthyl pyrrolindione compound prepared in this example is a light yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,DMSO-d 6 )δ:10.50(s,1H,NH),8.12(d,J＝8.4Hz,1H,ArH), 7.68-7.63(m,1H,ArH),7.58(dd,J＝8.4,7.2Hz,1H,ArH),7.50-7.42(m,3H,ArH),7.28(s,2H, COCH＝CHCO),3.69(s,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 64%.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound on the drug-containing culture medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are respectively 100, 50 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 25, 10 and 25 mu g/mL respectively.
Example 43: preparation of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-55)
This example is the same as example 2 except that the naphthylamine compound (II) is 2, 4-dimethylnaphthalen-1-amine and the maleic anhydride compound (III) is 3-nitromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.04-7.99(m,1H,ArH),7.58-7.45(m,3H,ArH),7.32(s, 1H,ArH),6.99(s,1H,COCH),2.65(d,J＝1.0Hz,3H,Ar-CH 3 ),2.25(s,3H,Ar-CH 3 )。
this example produced the naphthyl pyrrolindione compound in a 60% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 25 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 1, 1 and 5 mu g/mL respectively.
Example 44: preparation of 3-nitro-1- (4-methyl-2-nitronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-56)
This example is the same as example 2 except that naphthylamine compound (II) is 4-methyl-2-nitronaphthalene-1-amine and maleic anhydride compound (III) is 3-nitromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,DMSO-d 6 )δ:8.07(d,J＝8.0Hz,1H,ArH),7.98(s,1H,ArH), 7.85-7.75(m,2H,ArH),7.57(d,J＝7.2Hz,1H,ArH),7.29(s,1H,COCH),2.46(s,3H, Ar-CH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 55%, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 25 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 10 and 5 mu g/mL respectively.
Example 45: preparation of 1- (4-chloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-57)
This example is the same as example 1 except that the naphthylamine compound (II) used is 4-chloronaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is in the form of yellow crystals.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.35(d,J＝8.2Hz,1H,ArH),7.80(d,J＝7.9Hz,1H, ArH),7.62(t,J＝8.2Hz,1H,ArH),7.52(t,J＝7.8Hz,1H,ArH),7.50(t,J＝8.0Hz,1H,ArH), 7.28(d,J＝7.8Hz,1H,ArH),7.01(s,2H,COCH＝CHCO)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 93%.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound on the drug-containing culture medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are respectively 100, 100 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 10, 10 and 25 mu g/mL respectively.
Example 46: preparation of 1- (5-chloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-58)
This example is the same as example 1 except that the naphthylamine compound (II) used is 5-chloronaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.00(dd,J＝8.30,1.3Hz,1H,ArH),7.86(dd,J＝8.2,1.1 Hz,1H,ArH),7.59(t,J＝7.9Hz,1H,ArH),7.58(dd,J＝8.7,1.2Hz,1H,ArH),7.42(t,J＝8.0 Hz,1H,ArH),7.39(dd,J＝7.3,1.3Hz,1H,ArH),6.98(s,2H,COCH＝CHCO)。
this example produces a naphthyl pyrrolindione compound with a yield of 68% calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 100, 100 and >100 mug/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 10, 5, 10 and 25 mu g/mL respectively.
Example 47: preparation of 6-methyl-5- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalene-1-sulfonic acid (test code: YNT 21-59)
This example is the same as example 4 except that the naphthylamine compound (II) used is 5-amino-6-methylnaphthalene-1-sulfonic acid;
the naphthyl pyrrolindione compound prepared in this example is a light yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,DMSO-d 6 )δ:8.86(d,J＝8.86Hz,1H,ArH),8.09(d,J＝7.2Hz,1H, ArH),8.06(d,J＝8.0Hz,1H,ArH),7.66(d,J＝8.0Hz,1H,ArH),7.48(t,J＝7.8Hz,1H,ArH), 7.28(s,2H,COCH＝CHCO),2.30(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 72%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 50, 50 and 50 mu g/mL respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 1, 5 and 10 mu g/mL respectively.
Example 48: preparation of 1- (4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-60)
This example is the same as example 6 except that the naphthylamine compound (II) used is 4-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.12-8.08(m,2H,ArH),7.67-7.58(m,3H,ArH),7.32(d,J ＝8.0Hz,1H,ArH),7.05(s,2H,COCH＝CHCO),2.36(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 66%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 50, 50 and >100 mug/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 10 and 10 mu g/mL respectively.
Example 49: preparation of 3-nitro-1- (4-chloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-61)
This example is the same as example 3 except that the naphthylamine compound (II) is 4-chloronaphthalene-1-amine and the maleic anhydride compound (III) is 3-nitromaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is in the form of yellow crystals.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.44(d,J＝8.6Hz,1H,ArH),8.07(d,J＝8.0Hz,1H, ArH),7.75(t,J＝8.0Hz,1H,ArH),7.68(t,J＝8.0Hz,1H,ArH),7.58(d,J＝8.2Hz,1H,ArH), 7.38(d,J＝7.4Hz,1H,ArH),6.65(s,1H,COCH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 91%.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound on the drug-containing culture medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are respectively 100, 100 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 10, 5, 10 and 25 mu g/mL respectively.
Example 50: preparation of 1- (5-chloro-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-62)
This example is the same as example 3 except that the naphthylamine compound (II) used is 5-chloro-4-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.80(d,J＝7.0Hz,1H,ArH),8.07(d,J＝8.6Hz,1H, ArH),7.98(d,J＝7.8Hz,1H,ArH),7.80-7.70(m,1H,ArH),7.54(d,J＝7.8Hz,1H,ArH),7.02 (s,2H,COCH＝CHCO),2.48(s,3H,Ar-CH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 65% calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 50, 50 and >100 mug/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 10 and 25 mu g/mL respectively.
Example 51: preparation of 1- (5-bromo-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-63)
This example is carried out in the same manner as in example 2 except that the naphthylamine compound (II) used is 5-bromo-2-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a light yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.85(d,J＝8.0,1H,ArH),7.74(d,J＝8.0Hz,1H,ArH), 7.52(d,J＝7.2Hz,1H,ArH),7.42(d,J＝8.2Hz,1H,ArH),7.35-7.30(m,1H,ArH),7.00(s, 2H,COCH＝CHCO),2.28(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 75%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 25 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 1, 5 and 5 mu g/mL respectively.
Example 52: preparation of 3-mercapto-1- (5-bromo-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-64)
This example is the same as example 8 except that naphthylamine compound (II) is 5-bromo-2-methylnaphthalen-1-amine and maleic anhydride compound (III) is 3-mercaptomaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.98(d,J＝8.0,1H,ArH),7.88(d,J＝8.0Hz,1H,ArH), 7.58(d,J＝7.6Hz,1H,ArH),7.52(d,J＝8.2Hz,1H,ArH),7.44-7.39(m,1H,ArH),6.72(s, 1H,COCH),6.17(s,1H,Ar-SH),2.30(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 64%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 12.5 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 1, 1 and 10 mu g/mL respectively.
Example 53: preparation of 3-methyl-1- (2, 4-dichloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-65)
This example is the same as example 3 except that the maleic anhydride compound (III) used is 3-methylmaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example was a pink powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.36(dd,J＝7.8,1.4Hz,1H,ArH),7.78(s,1H,ArH), 7.76-7.66(m,2H,ArH),7.62(d,J＝8.8Hz,1H,ArH),7.02(s,H,COCH),2.28(s,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 82%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 100, 100 and >100 mug/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 10 and 25 mu g/mL respectively.
Example 54: preparation of 1- (5-hydroxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT-21-66)
This example is the same as example 8 except that the naphthylamine compound (II) used is 5-hydroxynaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.15(d,J＝8.5Hz,1H,ArH),7.47(dd,J＝8.4,7.3Hz, 1H,ArH),7.35(dd,J＝7.2,1.1Hz,1H,ArH),7.14(t,J＝8.0Hz,1H,ArH),6.98(d,J＝8.5Hz, 1H,ArH),6.94(s,2H,COCH＝CHCO),6.52(d,J＝7.5Hz,1H,ArH),6.16(s,1H,Ar-OH)。
this example produced the naphthyl pyrrolindione compound in a yield of 84% as calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are respectively more than 100, >100 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 25, 10, 25 and 50 mu g/mL respectively.
Example 55: preparation of 1- (7-hydroxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-67)
This example is the same as example 8 except that the naphthylamine compound (II) used is 7-hydroxynaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a light yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,DMSO-d 6 )δ:9.88(s,1H,Ar-OH),7.91-7.83(m,2H,ArH),7.37-7.30 (m,2H,ArH),7.28(s,2H,COCH＝CHCO),7.10(ddd,J＝8.9,2.4,1.2Hz,1H,ArH),6.72(t,J＝ 2.0Hz,1H,ArH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 86%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are >100, >100 and >100 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 25, 10 and 25 mu g/mL respectively.
Example 56: preparation of 3-methyl-1- (2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-68)
This example is the same as example 6 except that the naphthylamine compound (II) used is 2-ethylnaphthalen-1-amine and the maleic anhydride compound (III) used is 3-methylmaleic anhydride;
the naphthyl pyrrolindione compound prepared in this example was a brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.91(d,J＝8.0,1H,ArH),7.88-7.85(m,1H,ArH), 7.50-7.41(m,4H,ArH),6.62(q,J＝1.8Hz,1H,COCH),2.61(q,J＝7.6Hz,2H,CH 2 ),2.26(t, J＝2.0Hz,3H,COCCH 3 ),1.22(t,J＝7.6Hz,3H,CH 3 )。
this example produces a naphthyl pyrrolindione compound in a yield of 92% as calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 25, 25 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 1 and 5 mu g/mL respectively.
Example 57: preparation of 1- (2-bromo-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-69)
This example is the same as example 6 except that the naphthylamine compound (II) used is 2-bromo-4-methylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,DMSO-d 6 )δ:8.80(d,J＝1.9Hz,1H,ArH),8.07(d,J＝8.5Hz,1H, ArH),7.94(s,1H,ArH),7.80-7.70(m,1H,ArH),7.54(d,J＝7.3Hz,1H,ArH),7.27(s,2H, COCH＝CHCO),2.43(s,3H,Ar-CH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 72% calculated according to the method described in the specification of the application.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound on the drug-containing culture medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are respectively 50, 100 and more than 100 mu g/mL.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 1, 5 and 5 mu g/mL respectively.
Example 58: preparation of N- (5- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalen-1-yl) acetamide (test No.: YNT 21-70)
This example is carried out in the same manner as in example 2 except that the naphthylamine compound (II) used is N- (5-aminonaphthalen-1-yl) acetamide;
the naphthyl pyrrolindione compound prepared in this example is a light yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,DMSO-d 6 )δ:10.01(s,1H,NH),8.16(d,J＝8.6Hz,1H,ArH), 7.70-7.66(m,1H,ArH),7.61(dd,J＝8.6,7.2Hz,1H,ArH),7.52-7.45(m,3H,ArH),7.26(s,2H, COCH＝CHCO),2.17(s,3H,CH 3 )。
this example produced the naphthyl pyrrolindione compound in a yield of 54% as calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are >100, >100 and >100 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 25, 25 and 50 mu g/mL respectively.
Example 59: preparation of 1- (6-chloro-2- (trifluoromethyl) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-71)
This example is the same as example 2 except that the naphthylamine compound (II) used is 6-chloro-2-trifluoromethylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,DMSO-d 6 )δ:7.96(d,J＝7.2Hz,1H,ArH),7.72(s,1H,ArH), 7.53-7.49(m,1H,ArH),7.63(d,J＝7.5Hz,1H,ArH),7.28(s,2H,COCH＝CHCO),6.89(d,J＝ 7.2Hz,1H,ArH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 73%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae on the drug-containing medium plate are 6.25, 12.5 and 12.5 mu g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 1, 1 and 1 mu g/mL respectively.
Example 60: preparation of 1- (6-chloro-2- ((5- (trifluoromethyl) pyridin-2-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-72)
This example is carried out in the same manner as in example 8 except that the naphthylamine compound (II) used is 6-chloro-N 2 - (5-trifluoromethylpyridin-2-yl) naphthalene-1, 2-diamine;
the naphthyl pyrrolindione compound prepared in this example was a brown-yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:9.89(s,1H,NH),8.67(s,1H,ArH),7.88-7.82(m,3H, ArH),7.63(d,J＝7.5Hz,1H,ArH),7.36-7.33(m,1H,ArH),7.21(s,1H,ArH),7.02(s,2H, COCH＝CHCO),6.69(d,J＝7.5Hz,1H,ArH)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 77%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae on the drug-containing medium plate are 6.25, 6.25 and 12.5 mu g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 1, 5 and 10 mu g/mL respectively.
Example 61: preparation of 1- (6-chloro-2- ((4- (trifluoromethyl) -1H-pyrazol-3-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-73)
This example is the same as example 8 except that the naphthylamine compound (II) used is 6-chloro-N 2 - (4-trifluoromethyl)-1H-pyrazol-3-yl) naphthalene-1, 2-diamine;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:13.02(s,1H,NH),8.25(d,J＝8.4Hz,1H,ArH),7.79-7.71 (m,3H,ArH),7.63(dd,J＝8.0,7.0Hz,1H,ArH),7.48-7.44(m,1H,ArH),7.25(s,1H,NH), 7.12(s,2H,COCH＝CHCO)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 61%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae on the drug-containing medium plate are 6.25, 6.25 and 12.5 mu g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 1, 1 and 5 mu g/mL respectively.
Example 62: preparation of methyl (6-methyl-5- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalen-1-yl) carbamate (test No.: YNT 21-74)
This example is carried out in the same manner as in example 1 except that the naphthylamine compound (II) used is methyl (5-amino-6-methylnaphthalen-1-yl) carbamate;
the naphthyl pyrrolindione compound prepared in this example is a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:10.55(s,1H,NH),8.19(d,J＝8.4Hz,1H,ArH),7.60-7.65 (m,1H,ArH),7.71(dd,J＝8.4,7.2Hz,1H,ArH),7.54-7.43(m,2H,ArH),7.10(s,2H, COCH＝CHCO),3.66(s,3H,CH 3 ),2.48(s,3H,Ar-CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 69%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and fusarium graminearum are 50, 50 and 100 μ g/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 1, 5 and 5 mu g/mL respectively.
Example 63: preparation of 1- (2-methoxy-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-75)
This example is the same as example 5 except that the naphthylamine compound (II) used is 2-methoxy-5, 8-dioxo-5, 8-dihydronaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a reddish brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.21(d,J＝8.2Hz,1H,ArH),7.78(d,J＝8.2Hz,1H, ArH),6.99(s,2H,NCOCH＝CHCO),6.94(d,J＝10.3Hz,1H,COCH),6.78(d,J＝10.3Hz,1H, COCH),3.70(s,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 59%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 25 and 50 mug/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 1 and 1 mu g/mL respectively.
Example 64: preparation of 1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-76)
This example is the same as example 3 except that the naphthylamine compound (II) used is 4-chloro-2-ethylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a light yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.00(d,J＝8.2Hz,1H,ArH),7.60(s,1H,ArH),7.59(td,J ＝8.4,1.4Hz,1H,ArH),7.58(td,J＝6.9,1.3Hz,1H,ArH),7.39(d,J＝7.7Hz,1H,ArH),6.99 (s,2H,COCH＝CHCO),2.58(q,J＝7.7Hz,2H,CH 2 ),1.23(t,J＝7.6Hz,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 87%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella tritici are 12.5, 12.5 and 50 μ g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 1, 1 and 5 mu g/mL respectively.
Example 65: preparation of 1- (5-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-77)
This example is the same as example 3 except that the naphthylamine compound (II) used is 5-chloro-2-ethylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.94(d,J＝8.6Hz,1H,ArH),7.79(dd,J＝8.1,1.2Hz,1H, ArH),7.55(dd,J＝7.6,1.3Hz,1H,ArH),7.53(d,J＝8.6Hz,1H,ArH),7.34(t,J＝7.8Hz,1H, ArH),6.99(s,2H,COCH＝CHCO),2.60(q,J＝7.7Hz,2H,CH 2 ),1.22(t,J＝7.6Hz,3H,CH 3 )
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 85%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 12.5 and 50 μ g/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 1, 1 and 1 mu g/mL respectively.
Example 66: preparation of 1- (2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-78)
This example is carried out in the same manner as in example 6 except that the naphthylamine compound (II) used is 2-isopropylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a yellowish brown powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:7.94(d,J＝8.7Hz,1H,ArH),7.85(dd,J＝7.0,2.3Hz,1H, ArH),7.54(d,J＝8.7Hz,1H,ArH),7.47-7.44(m,2H,ArH),7.40(dd,J＝7.3,2.4Hz,1H,ArH), 6.93(s,2H,NCOCH＝CHCO),2.93-2.84(m,1H,CH),1.26(d,J＝6.90Hz,6H,2CH 3 )。
this example produces the naphthyl pyrrolindione compound in a yield of 79%, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rhizoctonia solani and gibberella zeae are 12.5, 12.5 and 25 mug/mL respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 5 and 10 mu g/mL respectively.
Example 67: preparation of 1- (4-chloro-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-79)
This example is carried out in the same manner as in example 3 except that the naphthylamine compound (II) used is 4-chloro-2-isopropylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a yellow solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:8.29(d,J＝7.1Hz,1H,ArH),7.64(s,1H,ArH),7.59(td,J ＝5.5,1.0Hz,1H,ArH),7.54(td,J＝5.5,1.1Hz,1H,ArH),7.34(d,J＝6.0Hz,1H,ArH),7.00 (s,2H,COCH＝CHCO),2.87(septet,J＝5.5Hz,1H,CH),1.26(d,J＝5.5Hz,6H,2CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 67%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 12.5, 6.25 and 25 mu g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 1, 1 and 5 mu g/mL respectively.
Example 68: preparation of 1- (5-chloro-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (Experimental code: YNT 21-80)
This example is carried out in the same manner as in example 3 except that the naphthylamine compound (II) used is 5-chloro-2-isopropylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a brown solid.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:7.97(d,J＝8.7Hz,1H,ArH),7.79(d,J＝8.1Hz,1H, ArH),7.59(d,J＝8.7Hz,1H,ArH),7.55(d,J＝7.5Hz,1H,ArH),7.34(t,J＝7.9Hz,1H,ArH), 7.00(s,2H,COCH＝CHCO),2.92(septet,J＝6.7Hz,1H,CH),1.25(d,J＝6.8Hz,6H,2CH 3 )。
this example produces a naphthyl pyrrolindione compound with a yield of 76%, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 6.25 and 25 mug/mL, respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial filaments of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer bacteria in the drug-containing culture solution are 1, 1 and 1 mu g/mL respectively.
Example 69: preparation of 1- (2- (trifluoromethyl) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-81)
This example is the same as example 8 except that the naphthylamine compound (II) used is 2-trifluoromethylnaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example is a white powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(400MHz,CDCl 3 )δ:7.92(d,J＝7.2Hz,2H,ArH),7.53-7.41(m,4H,ArH), 7.00(s,2H,COCH＝CHCO)。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 77%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in this example on the drug-containing medium plate for the growth of Botrytis cinerea, rhizoctonia solani and Gibberella cerealis are 12.5, 12.5 and 25 mug/mL, respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 5 and 10 mu g/mL respectively.
Example 70: preparation of 1- (2-ethoxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-82)
This example is the same as example 8 except that the naphthylamine compound (II) used is 2-ethoxynaphthalen-1-amine;
the naphthyl pyrrolindione compound prepared in this example was a brown powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, which is detected by the conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,CDCl 3 )δ:8.04(d,J＝9.0Hz,1H,ArH),7.85(d,J＝8.0,1.0Hz,1H, ArH),7.52-7.44(m,2H,ArH),7.41-7.35(m,2H,ArH),6.97(s,2H,COCH＝CHCO),3.98(q,J ＝7.4Hz,2H,CH 2 ),1.34(t,J＝8.9Hz,3H,CH 3 )。
the yield of the naphthyl pyrrolindione compound prepared by this example, calculated according to the method described in the specification of the application, was 63%.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 25, 25 and 50 mu g/mL respectively.
The minimum inhibition concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of bacterial strains of tomato ralstonia solanacearum, rice bacterial blight, citrus canker and peach root cancer virus in the medicament-containing culture solution are 5, 1 and 1 mu g/mL respectively.
Example 71: preparation of 4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalene-1-sulfonic acid (test code: YNT 21-83)
This example is the same as example 4 except that the naphthylamine compound (II) used is 4-aminonaphthalene-1-sulfonic acid;
the naphthyl pyrrolindione compound prepared in this example was a yellow powder.
The nuclear magnetic resonance data of the naphthyl pyrrolindione compound prepared in this example, as detected by a conventional nuclear magnetic resonance detection method, are as follows:
1 H-NMR(500MHz,DMSO-d 6 )δ:8.95(d,J＝8.6Hz,1H,ArH),8.02(d,J＝7.6Hz,1H, ArH),7.63(d,J＝8.3Hz,1H,ArH),7.59(td,J＝6.8,1.4Hz,1H,ArH),7.52(td,J＝6.8,1.3Hz, 1H,ArH),7.44(d,J＝7.6Hz,1H,ArH),7.29(s,2H,NCOCH＝CHCO)。
this example produces the naphthyl pyrrolindione compound in a 69% yield, calculated according to the method described in the specification of the application.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the drug-containing medium plate for the growth of botrytis cinerea, rice sheath blight fungus and wheat scab fungus are 50, 50 and 100 mu g/mL respectively.
The minimum inhibitory concentrations of the naphthyl pyrrolindione compound prepared in the embodiment on the growth of ralstonia solanacearum, rice bacterial leaf blight, citrus canker and peach root cancer hypha in the drug-containing culture solution are 5, 10 and 1 mu g/mL respectively.
The in vitro activity preliminary screening result of the compound shows that the naphthyl pyrrolindione compound has antibacterial activity on tested plant pathogenic fungi and bacteria, and the activity is related to the structure; has different antibacterial activity to different plant pathogenic bacteria, and shows selectivity. The invention selects a part of compounds with higher primary screening activity, further performs in vivo efficacy tests on part of common diseases on plant tissues or plant seedlings or field crops, and compares the in vivo efficacy tests with the current common bactericides.
Drug efficacy test example 1: test for preventing and treating rice sheath blight disease and rice blast by naphthyl pyrroline dione compound
The implementation of this test example is as follows:
A. test compounds:
the test of the invention is 13 compounds with the test codes of YNT21-68, YNT21-71, YNT21-72, YNT21-73, YNT21-74, YNT21-75, YNT21-76, YNT21-77, YNT21-78, YNT21-79, YNT21-80, YNT21-81 and YNT 21-82;
the control test sample was pyraclostrobin prodrug sold by basf corporation.
B. Greenhouse pot experiment conditions:
rice seedlings in 3-leaf stage, about 15 seedlings per pot; culturing in a glass sunlight greenhouse at 20-30 deg.C.
C. The test method comprises the following steps:
I. preparing a test liquid medicine:
the above compounds were weighed out in amounts of 75mg each, dissolved in 3mL DMSO, and diluted with 297mL of tap water containing 0.1% by weight of Tween 40 to obtain 250mg/L solutions.
II. The test operation method comprises the following steps:
firstly, 2 pots of the seedlings are inoculated with sheath blight fungus hypha blocks with the diameter of 3mm at the stem parts of the rice seedlings, the stems are wrapped by absorbent cotton, and rice blast germs 10 are inoculated on the leaves of the rice seedlings in a spraying manner 5 /mL conidia, cultured in the dark at 25 ℃ for 3 hours;
secondly, spraying the prepared 250mg/L liquid medicine on the 2 inoculated pots and the 2 non-inoculated pots of rice seedlings in the 3-leaf stage at the same time, spraying the liquid medicine, airing, putting the 2 inoculated pots in a greenhouse for culturing, and determining the treatment effect of the compound; meanwhile, spraying clear water as a blank control. The uninoculated 2 pots of seedlings were sprayed with the pesticide and air-dried for 3 hours, inoculated with Rhizoctonia solani and Pyricularia oryzae in the same manner, placed at 25 ℃ in the dark for 3 hours, transferred to a greenhouse for culture, and the protective effect of the compound was measured.
Thirdly, the length of the sheath blight disease spot and the number of the rice blast disease spots on the 2 nd to 3 rd leaf surfaces were investigated 7 days after the inoculation, and the control effect was calculated by the following formula:
% of preventive effect = [1- (lesion length or lesion number treated ÷ blank control lesion length or lesion number) ] KHz 100.
D. And (3) test results:
the test results are shown in Table 1
Table 1: test results of prevention and treatment of rice sheath blight and rice blast by naphthyl pyrrolindione compound
The results listed in table 1 clearly show that the compounds of the invention have prevention and treatment effects on rice sheath blight and rice blast, the prevention effect is better than the treatment effect, the effect is similar to that of the control medicament pyraclostrobin with good use effect in the current production, and certain activity difference exists between different compounds. The test shows that the naphthyl pyrrole compound can be used for preventing and treating rice blast and sheath blight.
Pharmacodynamic test example 2: test for preventing and treating gray mold of tomatoes and strawberries by using naphthyl pyrrolindione compound
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-16) Suspension (SC);
(2) 50% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione Wettable Powder (WP);
(3) 50%1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granules (WG);
(4) 25%1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-31) water dispersible granules (WG);
(5) 35% 3-methyl-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-32) Suspension (SC);
(6) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-47) Suspension (SC);
(7) 50% 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-55) suspending agent (SC);
the control agent was a 50% boscalid water dispersible granule (WG) manufactured by basf.
B. The test conditions are as follows:
planting strawberries on ridges of a plastic greenhouse, and keeping the temperature of the greenhouse at 15-35 ℃;
and planting tomatoes on ridges of the field.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
a test medicament sample listed in A is mixed with water to prepare two liquid medicines with the effective component contents of 200mg/L and 500mg/L respectively.
II. The test operation method comprises the following steps:
each dose treatment is provided with 4 repeated cells, and each cell is 20 square meters; spraying the 1 st liquid medicine by using a knapsack electric sprayer about one week after the blooming of field tomatoes or greenhouse strawberries, and spraying the 2 nd and 3 rd liquid medicines at intervals of 7 days; the amount of the liquid medicine sprayed each time is 50 kg/mu, and meanwhile, clear water is sprayed to serve as a blank control. After 7 days after the 3 rd spraying treatment, randomly surveying 500 flowers and fruits finally, and calculating the disease and fruit rate (%) according to a formula of total number of diseased flowers and fruits/500 multiplied by 100;
the control effect is calculated according to the following formula:
preventing effect (%) = [1- (disease fruit rate of treatment ÷ blank control disease fruit rate) ] 100.
D. And (3) test results:
the test results are shown in Table 2.
Table 2: test result of naphthyl pyrroline diketone compound for preventing and treating gray mold of field tomatoes
The test results listed in table 2 show that 1- (2-methylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC), wettable Powder (WP) and water dispersible granules (WG) have biological activity for preventing and treating gray mold of crops, the prevention effect is not obviously different between dosage forms, but the concentration of the liquid medicine is obviously different; the effects of 200mg a.i./L and 500mg a.i./L on preventing and treating the tomato gray mold are 73.4-84.0% and 85.1-93.6% respectively. In addition, 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione had a slightly lower control effect (see Table 2). At the end of the test 7 of the 75 pathogenic bacterial strains isolated from the diseased fruit showed resistance to the commonly used boscalid, with 9.33% of resistant strains, but no resistance to the tested compounds.
The results of the naphthyl pyrrolines against the gray mold of strawberry protected by soil are shown in Table 3 below.
Table 3: test result of naphthyl pyrrolindione compound for preventing and treating gray mold of greenhouse strawberries
The results listed in Table 3 clearly show that the biological activity of the compounds for preventing and treating gray mold is not influenced by the processing dosage form, but the drug effect difference exists among different compounds, and the drug effect is positively correlated with the application dosage. The effects of preventing and treating strawberry gray mold of 200mg/L and 500mg/L of the four naphthyl pyrroline compounds are 69.4-83% and 77.6-94.6 respectively. Of these compounds tested, 3-methyl-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione was the most effective and 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione was somewhat less effective. At the end of the test 45 strains out of the 115 pathogenic bacteria strains isolated from the diseased fruit showed resistance to the commonly used fungicide boscalid, with the resistant strains accounting for 39.13%, so that the control agent was poor in effect.
The test shows that the naphthyl pyrrole compound can be used for preventing and treating gray mold of fruits and vegetables, in particular to gray mold with multiple drug resistance.
Drug efficacy test example 3: test for preventing and treating rice sheath blight disease by naphthyl pyrroline dione compound
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 50% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione Wettable Powder (WP);
(3) 50%1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granule (WG);
(4) 25%1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granule (WG);
(5) 35% 3-methyl-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(6) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(7) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control agent was a 24% thifluzamide Suspension (SC) made by Yinong Dow.
B. Greenhouse pot experiment conditions:
transplanting rice seedlings in pots with the diameter of 25cm into 4 holes, culturing under the conditions of sunshine in a glass greenhouse and 20-35 ℃, and using the 5-leaf stage for tests.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
mixing the test medicament sample listed in A with tap water to prepare two liquid medicines with the effective component contents of 200mg/L and 300mg/L respectively.
II. The test operation method comprises the following steps:
inoculating a leaf sheath of a 5-leaf stage potted rice seedling with a 3 mm-diameter Rhizoctonia solani hypha block one day before spraying, inoculating 10 strains in each pot, and wrapping with absorbent cotton for moisture preservation overnight; each test medicament sample is sprayed to 10 pots, liquid drops fall off when the test medicament sample is sprayed to a blade every time, and meanwhile, the test medicament sample is treated by spraying clear water to serve as a blank control. After being dried in the air, the mixture is placed in a greenhouse for culture, the length of the disease spot of the inoculated leaf sheath is checked 7 days later, and the prevention and treatment effect is calculated by the calculation method shown in the pesticide effect test example 1.
D. And (3) test results:
the test results are shown in Table 4.
Table 4: test result of naphthyl pyrroline diketone compound for preventing and treating sheath blight of potted rice
The results shown in table 4 show that 4 test naphthyl pyrrole compounds have ideal treatment effect activity for preventing and treating rice sheath blight, the prevention effect of high-concentration liquid medicine is better than that of low-concentration treatment, the prevention effect of 3-methyl-1- (4-chloro-2-methylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione is the best, and the naphthyl pyrrole compounds can be used for preventing and treating rice sheath blight similar to a control medicament thifluzamide with good common effect.
Pharmacodynamic test example 4: test for preventing and treating tomato early blight by naphthyl pyrrolindione compound
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 50% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione Wettable Powder (WP);
(3) 50%1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granules (WG);
(4) 25%1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granules (WG);
(5) 35% 3-methyl-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(6) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(7) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(8) 20%1- (2-methoxy-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-75) Suspension (SC);
the control agent was 50% procymidone Wettable Powder (WP) (manufactured by sumitomo chemical co., ltd., commercially available).
B. The test conditions are as follows:
tomato seedlings are planted in pots with the diameter of 20cm, 2 seedlings are planted in each pot, and the seedlings are cultured in a glass sunlight greenhouse at the temperature of 20-35 ℃ until the leaf stage is 5.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
mixing the test medicament sample listed in A with tap water to prepare two kinds of liquid medicines with the effective component contents of 500mg/L and 1000mg/L respectively.
II. The test operation method comprises the following steps:
spraying the above medicinal liquid to potted 5-leaf stage tomato seedlings until water drops flow down on leaf surfaces, spraying tap water as control, inoculating leaf blades with 5 mm-diameter tomato early blight (Alternaria solani) hypha blocks after 1 day, wrapping with absorbent cotton, and keeping moisture, wherein each plant is inoculated with 4 leaves, and each treatment is carried out in 10 pots. The treated potted seedlings were cultivated in a greenhouse, and after 10 days, the length of the inoculated leaf lesions was checked and the control effect was calculated by the method described in test example 1.
D. And (3) test results:
the test results are shown in Table 5.
Table 5: test result of naphthyl pyrrolindione compound for preventing and treating early blight of potted tomato
The results shown in Table 5 clearly show that the 5 naphthyl pyrrole compounds have prevention effect on tomato early blight and are positively correlated with treatment concentration. Wherein the activity of the 3-nitro-1- (2, 4-dimethylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione and the 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalene-1-yl) -1H-pyrrole-2, 5-dione is slightly lower, and the control effect of the other 3 compounds is slightly better than that of a control medicament procymidone treated at the same concentration, which indicates that the naphthyl pyrrole compound can be used for controlling early blight caused by alternaria.
Pharmacodynamic test example 5: test for preventing and treating rice bakanae disease by naphthyl pyrrolindione compound
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 50% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione Wettable Powder (WP);
(2) 25%1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granule (WG);
(3) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(4) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control agent was 25% cyhalothrin Suspension (SC) provided by jiangsu pesticide research institute limited.
B. The test conditions are as follows:
culturing rice seedlings in a glass sunlight greenhouse at the temperature of 20-30 ℃ and the relative humidity of 45-90%.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
mixing the test medicament sample listed in A with tap water to prepare two liquid medicines with the effective component contents of 250mg/L and 500mg/L respectively.
II. The test operation method comprises the following steps:
putting the rice seeds with the bakanae disease into the liquid medicine and stirring, and simultaneously soaking the seeds in clear water for blank control treatment; soaking seeds for 72 hours at the temperature of 15-20 ℃, taking out the seeds, placing the seeds in a closed glass container, preserving moisture and accelerating germination for 48 hours at the temperature of 25-30 ℃, then sowing the seeds in a plastic basin containing culture soil, placing the plastic basin in a greenhouse, culturing for 21 days at the temperature of 20-30 ℃ and the relative humidity of 45-90%, checking the incidence rate of the seedlings, calculating the prevention and treatment effect, and referring to the pesticide effect test example 2 in the calculation method.
D. And (3) test results:
the test results are shown in Table 6.
Table 6: test result for preventing and treating rice bakanae disease by naphthyl pyrroline diketone compound seed soaking
The test results shown in Table 6 clearly show that the accumulated disease rate of bakanae disease of the seedlings soaked in clear water reaches 21.3 percent after 21 days of sowing. The 4 kinds of naphthyl pyrrole compounds have good prevention and treatment effects on bakanae disease after seed soaking, the prevention effect of high-concentration liquid medicine is better than that of low-concentration treatment, and the prevention and treatment effects of the 1- (2-methylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione and the 1- (4-chloro-2-methylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione on bakanae disease of rice are not obviously different from that of a contrast medicament, namely the cyanestrel, with the best using effect at present. In addition, all the seeds treated by seed soaking germinate and emerge normally without any phytotoxicity influence, which indicates that the naphthyl pyrrole compound can be used for seed treatment to prevent and treat rice bakanae disease.
Drug efficacy test example 6: test for preventing and treating tomato bacterial wilt by using naphthyl pyrrolindione compound
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 50% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione Wettable Powder (WP);
(3) 50%1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granules (WG);
(4) 25%1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granule (WG);
(5) 35% of 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(6) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(7) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(8) 20%1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-76) suspending agent (SC);
the control agent was 20% zinc thiazole Suspension (SC) provided by xinnong gmbh of zhejiang.
B. The test conditions are as follows:
3 tomato seedlings are potted in pots with the diameter of 20cm, and are cultured under the conditions of 20-30 ℃ of temperature and 50-90% of relative humidity to reach the 4-leaf stage for testing under the condition of a glass sunlight greenhouse.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
the test medicament sample listed in A is mixed with tap water to prepare two liquid medicines with the effective component contents of 250mg/L and 500mg/L respectively.
II. The test operation method comprises the following steps:
the root soil of potted tomato seedlings was irrigated with 50mL of the prepared liquid, and tap water was used as a control. After 1 day of irrigation treatment, the composition is applied to the affected part 10 7 The bacterial suspension of cfu/mL bacterial Ralstonia solanacearum (Pseudomonas solanacearum) was inoculated by pouring, 10mL per pot, 10 pots each treatment. The treated potted seedlings are placed in a greenhouse and cultured under the conditions that the temperature is 20-30℃ and the relative humidity is 45-85%, the morbidity of 30 plants is checked after 10 days, and the prevention and treatment effects are calculated according to the calculation method in the pharmacodynamic test example 2.
D. And (3) test results:
the test results are shown in Table 7.
Table 7: test result of naphthyl pyrrolindione compound for preventing and treating bacterial wilt of potted tomato
The test results listed in table 7 clearly show that 4 test naphthyl pyrrole compounds in the test have ideal control effect, the control effect of the high-concentration liquid medicine is better than that of the low-concentration liquid medicine, and the effect of the compounds is obviously better than that of the control medicament zinc thiazole treated at the same concentration. All the test chemical treatments have no obvious adverse effect on the growth of tomato seedlings, which indicates that the naphthyl pyrrole compound can prevent and treat bacterial wilt of melons, fruits and vegetables through soil treatment.
Drug efficacy test example 7: test for preventing and treating bacterial leaf blight of rice by using naphthyl pyrroline diketone compound
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 25%1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granule (WG);
(3) 25%1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-76) Suspension (SC);
(4) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione Suspension (SC);
(5) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control agent was 20% zinc thiazole Suspension (SC) provided by xinnong gmbh of zhejiang.
B. The test conditions are as follows:
rice plants were transplanted into 4-hole pots of 25cm, and cultured in a glass sunlight greenhouse at 20-35 ℃ and 50-85% relative humidity until the tillering stage of 5 leaves was reached, and the rice plants were used in this experiment.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
the test medicament sample listed in A is mixed with tap water to prepare two liquid medicines with the effective component contents of 250mg/L and 500 mg/L.
II. The test operation method comprises the following steps:
spraying the prepared medicinal liquid on the leaf surface of rice seedling by using a knapsack electric sprayer until water drops on the leaf surface, spraying tap water as a control treatment, air-drying the leaf surface, cutting the leaf, and inoculating X.oryzae10 7 cfu/mL of bacterial suspension of rice bacterial blight fungus, 10 leaves were inoculated per pot, 10 pots were treated each, of which 5 pots were inoculated with wild sensitive strain and 5 pots were inoculated with thiabendazole and streptomycin resistant strain. The treated potted seedlings are placed in a greenhouse and cultured under the conditions that the temperature is 20-35℃ and the relative humidity is 50-85%, the length of disease spots is checked after 10 days, the prevention and treatment effect is calculated, and the calculation method refers to the pesticide effect test example 1.
D. And (3) test results:
the test results are shown in Table 8.
Table 8: test result of naphthyl pyrrolindione compound for preventing and treating bacterial leaf blight of potted rice
The test results listed in Table 8 clearly show that the 5 naphthyl pyrrole compounds have ideal control effect on bacterial blight of rice, and the control effect of high-concentration liquid medicine is better than that of low-concentration treatment; the lesion length of the inoculated wild sensitive strain and the disease-resistant strain has no obvious difference, and the wild sensitive strain and the disease-resistant strain have no cross resistance with the thiacumconazole and the streptomycin, so that the results of inoculating the two strains are combined and calculated; the activity of different compounds for preventing and treating the bacterial leaf blight of rice has obvious selectivity difference, wherein the preventing and treating effect of 1- (4-chloro-2-ethylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione and 1- (4-chloro-2-methylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione on the bacterial leaf blight is obviously better than that of a control medicament zinc thiazole treated at the same concentration. All treatments had no visible adverse effect on rice growth, indicating that the naphthyl pyrrole compounds can be used for spray control of rice bacterial diseases.
Drug efficacy test example 8: the naphthyl pyrroline diketone compound of the invention is used for preventing and controlling the cucumber angular leaf spot and the strawberry gray mold field test
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 25%1- (5-bromo-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione water dispersible granule (WG);
(3) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione Suspension (SC);
(4) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC); (5) 25% of 1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control agents were 20% zinc thiazole Suspension (SC) sold by xinnong gmbh of zhejiang and 50% procymidone Wettable Powder (WP) manufactured and sold by sumitomo chemical co.
B. The test conditions are as follows:
a field pesticide effect test is carried out in the Yangshi village in Nanjing, cucumbers cultivated in the field are cultivated and managed according to a conventional method, and the test is started when the vines are about 2 meters.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
a, mixing the test medicament samples listed in A with tap water to prepare three liquid medicines with the effective component contents of 200, 400 and 800mg/L respectively, wherein the three liquid medicines are used for preventing and treating cucumber angular leaf spot (Pseudomonas syringae);
the test medicament samples listed in A are mixed with tap water to prepare three liquid medicines with the effective component contents of 250, 500 and 1000mg/L respectively, and the three liquid medicines are used for preventing and treating strawberry gray mold (Botrytis cinerea).
II. The test operation method comprises the following steps:
the method comprises the steps of respectively carrying out cell division on cucumber and strawberry cultivation fields, processing 3 repeated cells respectively, carrying out spraying treatment by using a knapsack electric sprayer according to the spraying amount of 50 kg/mu, and meanwhile, spraying tap water as a blank control. Spraying the pesticide twice at intervals of 7 days, calculating the average disease and fruit rate of each treated strawberry and the disease index of angular leaf spot on the 10 th day after the pesticide is sprayed for the second time, and calculating the control effect. The control effect of the gray mold disease rate of the strawberries is calculated according to the pharmacodynamic test example 2; the disease index survey and the control effect calculation of the cucumber angular leaf spot are calculated according to the national standard GB/T17980.110-2004.
D. And (3) test results:
the test results are shown in Table 9.
Table 9: test result of prevention effect of naphthyl pyrrolindione compound on gray mold of strawberry and angular leaf spot of cucumber
The test results shown in Table 9 clearly show that the disease rate of gray mold of strawberry without drug treatment is 9.32%, the disease index of cucumber angular leaf spot without drug treatment is 2.70, and the test results of the five test drug samples show that the control effect of naphthyl pyrrole dione compound on gray mold and angular leaf spot is obviously better than that of the current common bactericide in production, wherein the control effect of 1- (4-chloro-2-ethylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione on two diseases is the best.
Pharmacodynamic test example 9: the naphthyl pyrrolindione compound of the invention is used for preventing and treating wheat scab and powdery mildew in field test
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 35% of 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(3) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione Suspension (SC);
(4) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control agent was a 43% tebuconazole Suspension (SC) manufactured by nicotineau green cloud biotechnology limited.
B. The test conditions are as follows:
the test is carried out on a Zhuchunhua family farm in Qian cancun of Liuhe area in Nanjing, a field pesticide effect plot test is carried out at the early flowering stage and the full flowering stage of wheat (Ningmai 13), and the cultivation management is carried out according to a conventional method.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
three treatment liquid medicines are prepared according to the dosage of 20, 30 and 40g of effective components per mu and the liquid medicine spraying amount of 50kg per mu, and are used as the medicine for the present application.
II. The test operation method comprises the following steps:
spraying the wheat twice by using an electric sprayer (5 days at an interval) in the initial flowering period and the full flowering period of the wheat, spraying water for 3 times at an interval of 2 hours after spraying the wheat for 2 hours in the test period due to dry weather, investigating the disease condition 20 days after spraying the wheat for 2 times, and calculating the disease index and prevention effect of the gibberellic disease according to the pesticide field efficacy test criterion industry standard NY/T1464.15-2007; and calculating the disease index and the prevention effect of the powdery mildew according to the national standard GB/T17980.22-2000.
D. And (3) test results:
the test results are shown in Table 10.
Table 10: test result of prevention and treatment of wheat scab and powdery mildew by naphthyl pyrrolindione compound
The test results shown in Table 10 clearly show that the test medicament has relatively ideal control effects on two diseases, and the control effect on the gibberellic disease of 20-40 g/mu reaches 64.9-89.2% under the condition that the blank control disease index of the non-medication treatment reaches 4.16; under the condition that the disease index of the non-medication treatment is 6.32, the effect of preventing and treating powdery mildew reaches 64.9-88.4 percent. Compared with a control medicament tebuconazole, the test medicament has the advantages of equivalent effect of preventing and treating gibberellic disease and slightly lower effect of preventing and treating powdery mildew.
Pharmacodynamic test example 10: the field test of the naphthyl pyrrolindione compound for preventing and treating sclerotinia rot of colza of the invention
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 20% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 35% of 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(3) 20% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(4) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control agent was a 25% boscalid Suspension (SC) manufactured and sold by basf;
B. the test conditions are as follows:
the test of the drug effect is carried out in the rape field of Qian Bicun in Liuhe district of Nanjing, 15 square meters per district.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
three treatment liquid medicines are prepared according to the dosage of 10g, 15g and 20g of effective components per mu and the liquid medicine spraying amount of 50kg per mu.
II. The test operation method comprises the following steps:
spraying the first Sclerotinia sclerotiorum (sclerotiorum) preventing and treating medicine when about 80% of main stems of rape bloom 95%, and spraying the second medicine after 7 days. Each treatment was set to 3 replicate cells, each 15 square meters, with spray tap water as a blank control.
The disease condition is investigated and the disease index and the prevention effect are calculated according to the GB/T17980.35-2000 regulation on the 30 th day after the 2 nd spray.
D. And (3) test results:
the test results are shown in Table 11.
Table 11: test result of prevention and treatment of sclerotinia rot of colza by naphthyl pyrrolindione compound
The field test results shown in table 11 indicate that the index of the condition of tap water treatment is 9.74, the effect of the naphthyl pyrrolindione compound on preventing and treating sclerotinia rot of rape is shown in table 11, the field test results indicate that the naphthyl pyrrolindione compound has good prevention and treatment effect on sclerotinia of rape, the prevention and treatment effect of the naphthyl pyrrolindione compound on the sclerotinia of rape can reach 77.8-88% only in 10 g/mu, the prevention and treatment effect of the naphthyl pyrrolindione compound on the sclerotinia of rape can reach more than 90%, and the prevention and treatment effect of the naphthyl pyrrolindione compound on the sclerotinia of rape is similar to that of boscalid, a bactericide with the best effect, which is commonly used at present.
Drug efficacy test example 11: the field test of the naphthyl pyrrolindione compound for preventing and treating kiwifruit canker disease
The implementation of this test example is as follows:
A. test agent samples:
20% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione Suspension (SC).
B. The test conditions are as follows:
in the 2-year-old kiwi fruit planting field test in Qian Bicun of Liuhe region of Nanjing, each 3 seedlings are 1 plot.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
the test agent samples were diluted 250, 500 and 1000 times with tap water and were ready for use.
II. The test operation method comprises the following steps:
spraying before germination in spring and spraying with electric sprayer for 3 times with 10 days interval, and treating with tap water as control. According to pesticide field efficacy test criteria NY/T1464.72-2018, the disease condition of kiwi fruit canker (Pseudomonas syringae pv. Actiniae) leaves is investigated, and the disease index and the control effect of 100 leaves are calculated.
D. And (3) test results:
the test results are shown in Table 12.
Table 12:20%1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione SC test results for prevention and treatment of kiwifruit canker
| Test drug sampleDilution multiple of product | Index of disease condition | Control effect% |
| 250 | 1.15 | 86.7 |
| 500 | 2.19 | 74.6 |
| 1000 | 3.19 | 63.0 |
| Tap water control | 8.62 | / |
The test results shown in Table 12 indicate that the test agent 20%1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione SC was diluted 250 times and treated with 500 times of the drug solution, and the therapeutic effect on ulcer diseases was more satisfactory.
Drug efficacy test example 12: the field test of the naphthyl pyrrolindione compound for preventing and treating the red spot and brown spot of broad beans
The implementation of this test example is as follows:
A. test agent samples:
(1) 20% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 35% of 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione Suspension (SC);
(3) 20% of 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(4) 50% of 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control agent was a 50% boscalid water dispersible granule (WG) manufactured by basf corporation.
B. The test conditions are as follows:
the field efficacy test for preventing and treating brown spot disease (Borytis fabae) and brown spot disease (Ascochyta fabae, A.vitae) is carried out on the broad bean field in the China agricultural high region of white horse in Lishu region of Nanjing City. Each test cell was 20 square meters and 3 repeat cells were set per treatment.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
three treatment liquid medicines are prepared according to the dosage of 35g, 25g and 15g of effective components per mu and the liquid medicine spraying amount of 50kg per mu, and are prepared for use at present.
II. The test operation method comprises the following steps:
spraying the liquid medicine for the 1 st time in the full-bloom stage of the broad beans and before the disease attack, spraying the liquid medicine for the 2 nd time at intervals of 10 days, and simultaneously spraying tap water as a blank control. The number of lesions on the upper 3 leaves of each of the 100 treated broad bean plants was examined 10 days after the 2 nd treatment, and the control effect was calculated according to the method described in test example 1.
D. And (3) test results:
the test results are shown in Table 13.
Table 13: test results of naphthyl pyrrolindione compounds for preventing and treating red spot and brown spot of broad beans
The test results shown in Table 13 clearly show that 4 naphthyl pyrrolindiones have control effect on both broad bean red spot disease and brown spot disease, and 1- (2-methylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione and 1- (4-chloro-2-methylnaphthalene-1-yl) -1H-pyrrole-2, 5-dione have the highest control effect. Meanwhile, the compounds have obvious selective activity and good control effect on the alternaria leaf spot, and the effect difference of 25g and 35g per mu on the alternaria leaf spot is small, so that the control effect on the alternaria leaf spot is low.
All treatments had no visible adverse effect on the growth of the broad beans.
Drug efficacy test example 13: test for preventing and treating potato late blight by using naphthyl pyrrolindione compound
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35%1- (6-chloro-2- (trifluoromethyl) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-71) Water dispersible granules (WG);
(2) 25%1- (6-chloro-2- ((5- (trifluoromethyl) pyridin-2-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-72) suspending agent (SC);
(3) 20%1- (6-chloro-2- ((4- (trifluoromethyl) -1H-pyrazol-3-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-73) Suspension (SC);
the control agent was 50% dimethomorph Wettable Powder (WP) produced by Hanbang plant protectant, inc., tianjin.
B. The test conditions are as follows:
2 potato seedlings are planted in pots with the diameter of 20cm, and the seedlings are cultured in a glass sunlight greenhouse at the temperature of 20-35 ℃ and the relative humidity of 50-85% until the 5-leaf stage for carrying out the efficacy test.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
the test medicament sample listed in A is prepared into two liquid medicines with the active ingredient contents of 500mg/L and 1000mg/L respectively by adding water, and the liquid medicines are used as the medicine.
II. The test operation method comprises the following steps:
the prepared liquid medicine is sprayed on the surfaces of the potato seedlings by using an electric sprayer until the surfaces of the potato seedlings are completely wet, 3 pots are processed for each time, potato late blight (Phytophthora infestans) hypha blocks with the diameter of 3mm are inoculated on the blades after air drying, 24 leaves are inoculated for each time, the inoculated leaves are placed in a greenhouse to be subjected to moisture preservation and culture for 7 days under the conditions that the temperature is 20-35 ℃ and the relative humidity is 50-85%, the length of disease spots is measured, and the control effect is calculated according to the method described in the test example 1.
D. And (3) test results:
the test results are shown in Table 14.
Table 14: test result of naphthyl pyrrolindione diketone compound for preventing and treating potato late blight
The test results listed in table 14 clearly show that the 3 naphthyl pyrrolindione compounds have good control effects on potato late blight, and the control effects are better than those of common control agents when the liquid medicine is treated by 1000 mg/L.
Drug efficacy test example 14: the naphthyl pyrrolindione diketone compound of the invention is used for preventing and controlling wheat sharp eyespot and root rot (stem root rot) disease in field test
The implementation of this test example is as follows:
A. test agent samples:
test agent samples prepared according to the methods described in the specification of the present application:
(1) 35% of 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
(2) 25% of 1- (5-bromo-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-63) Wettable Powder (WP);
(3) 25% of 1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione suspending agent (SC);
the control formulation was a 10% dulbeck suspension seed coating produced by syngenta corporation.
B. The test conditions are as follows:
the field efficacy plot experiment is carried out in Qian storehouse village of Liuhe district in Nanjing, and the conventional cultivation management is carried out according to winter wheat.
C. The test method comprises the following steps:
I. the medicament seed dressing treatment method comprises the following steps:
according to the technical scheme, the naphthyl pyrrolindione compound and the contrast medicament respectively account for 0.05 percent and 0.15 percent of the weight of the seeds, the compound and the contrast medicament for treating 2kg of wheat seeds are respectively weighed, mixed with 30-40 mL of water into paste, poured on the wheat seeds in a plastic bag, immediately and uniformly dried, and sowed in 5 days in 11 months. Each process set up 3 repeating cells, each cell being 20 square meters.
II. The investigation and prevention effect calculation method comprises the following steps:
investigation of the occurrence of sheath blight: investigating the wheat jointing stage in 4 months of the next year, wherein the disease-free period is 0 grade; the disease spots below 0.5cm on the stem base part and the disease spots above 0.5cm are grade 1 and grade 2; the disease spots appearing below 0.5cm on the stem are grade 3, the disease spots appearing above 0.5cm are grade 4, and the surrounding disease spots on the stem and the dead seedlings appear grade 5; calculating disease index and prevention and treatment effect according to GB/T17980.108-2004.
Investigation of occurrence of root rot or stem base rot: the percentage of 500 plants affected was investigated at the time of ear emergence, and the control effect was calculated by the method of test example 2.
D. And (3) test results:
the test results are shown in Table 15.
Table 15: test result of naphthyl pyrroline diketone compound for preventing and treating wheat sharp eyespot and root rot
The field test results shown in table 15 indicate that the 3 naphthyl pyrrolindione compounds have control effects on wheat sharp eyespot and root rot through seed treatment, and have better control effects on sharp eyespot.
Drug efficacy test example 15: determination of prevention and treatment effects of naphthyl pyrrolindione compound on wheat scab
The implementation of this test example is as follows:
A. test compounds:
(1) 1- (6-chloro-2- (trifluoromethyl) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-71);
(2) 1- (6-chloro-2- ((5- (trifluoromethyl) pyridin-2-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-72);
(3) 1- (6-chloro-2- ((4- (trifluoromethyl) -1H-pyrazol-3-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (test No.: YNT 21-73);
(4) 1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (test code: YNT 21-76);
the control agents are 96% of the raw pesticide Cyanoxastrobin sold by Jiangsu pesticide research institute, inc. and 98% of the carbendazim sold by Jiangsu Lanfeng chemical industry, inc.
B. The test conditions are as follows:
culturing in an illumination incubator at 25 deg.C under illumination of 10000Lux and relative humidity of 70-85%.
C. The test method comprises the following steps:
I. preparing a liquid medicine:
dissolving the test compound in DMSO to prepare a mother solution of the compound with the concentration of 50 mg/mL; carbendazim is dissolved in 0.1N hydrochloric acid to prepare mother liquor with the concentration of 10mg/mL carbendazim, and when the mother liquor is used, the mother liquor is diluted to 250mg/L and 1000mg/L by using tap water containing 0.1% Tween 40 by weight to obtain two liquid medicines for subsequent inoculation tests.
II. Spray treatment:
cutting wheat ear in flowering stage from field, inserting into 10mL water containing test tubes on the test tube rack, respectively spraying the liquid medicine to wet the ear, treating 10 ears with each concentration of liquid medicine, spraying tap water as control, air drying, and inoculating.
III, inoculation:
10 mu L of small ear drop inoculation is carried out in the middle of the wheat ear by a liquid transfer device 5 A conidia suspension of a/mL wheat scab sensitive strain 2021, carbendazim and a cyhalothrin double-resistant strain 2021R, each strain inoculated with 5 ears.
IV, recording culture and results:
and (4) transferring the inoculated wheat ears to a light incubator, preserving moisture and culturing for 7 days at the temperature of 25 ℃ and the relative humidity of 70-85%, and checking and recording the disease condition of the wheat ears. The disease is recorded as-without-inoculation-point disease +, the disease spot is expanded to 1/2 or less and recorded as +++, the disease spot is expanded to 1/2 or more and recorded as ++++, and the disease is fully developed.
D. And (3) test results:
the test results are shown in Table 16.
Table 16: naphthyl pyrrolindione compound for treating wheat scab
The results shown in table 16 indicate that the compounds of the invention have good control effect on gibberellic disease, the effect of different compounds is obviously different, and the compounds have no cross resistance with phenamacril and carbendazim.
Drug effect test example 16: antibacterial spectrum determination of plant pathogens by naphthyl pyrrolindione compound
The implementation of this test example is as follows:
A. test compounds:
(1) 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-16);
(2) 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-31);
(3) 3-methyl-1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-32);
(4) 1- (5-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-35);
(5) 1- (2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-43);
(6) 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-47);
(7) 3-nitro-1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-55);
(8) 1- (6-chloro-2- (trifluoromethyl) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-71);
(9) 1- (6-chloro-2- ((5- (trifluoromethyl) pyridin-2-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-72);
(10) 1- (6-chloro-2- ((4- (trifluoromethyl) -1H-pyrazol-3-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-73);
(11) 1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-76);
(12) 1- (4-chloro-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione (YNT 21-79);
B. test of pathogens:
(1) The plant pathogenic fungi can be cultured:
wheat leaf blight (Septoria tritici), rice false smut (Ustilaginoidea virens), corn northern leaf blight (Exserohilum turcicum), peanut leaf spot (Cercospora spp.), watermelon vine blight (Didymela bryoniae), melon and fruit anthracnose (Colletotrichum gloeosporioides), apple ring rot (Physalospora piricola), botrytis cinerea (Boytis cinerea, wild sensitive strain B10, multi-drug resistant strain B5);
(2) Plant obligate parasitic pathogenic oomycetes:
plasmopara viticola (Plasmopara viticola), pseudoperonospora cubensis (Pseudoperonospora cubensis);
(3) Plant pathogenic bacteria:
rice bacterial leaf spot (Xanthomonas oryzae pv. Oryzae) bacteria, chinese cabbage soft rot (Erwinia spp.), peach root cancer (Agrobacterium radiobacter), cucurbitaceous fruit spot (Acidovorax avenae subsp. Citrulli) bacteria, and citrus canker (Xanthomonas citri);
(4) Plant pathogenic nematodes:
meloidogyne incognita (Meloidogyne incognita).
C. The test conditions are as follows:
the indoor isolated test or the test on plant tissues, and the control condition is different according to pathogens, particularly a test method.
D. The test method comprises the following steps:
test compounds were dissolved in DMSO to prepare a test compound stock solution having a concentration of 50mg/mL, and stored at low temperature.
I. Determination of the biological Activity of fungi:
determined by colony growth on media containing drugs.
Media containing 100, 25, 6.25mg/L of test compound were prepared. The mother solution of the test compound at a concentration of 50mg/mL was transferred by a pipette and added to a PDA medium cooled to 45 ℃ and mixed well, poured into a 90mm diameter petri dish, cooled statically to make a drug-containing plate, then a 5mm diameter dish was cut from the edge of a colony pre-cultured on the PDA medium at 25 ℃ for 2-5 days, inoculated in the center of the plate containing the compound medium, cultured at 25 ℃ for 5 days, and the inhibitory effect of the test compound on growth was observed and recorded. The growth is completely failed to be marked with "-", the growth is 25% below the growth rate on a drug-free plate is marked with "+", the growth is about 25% -50% on the drug-free plate is marked with "+", the growth is about 50% -75% on the drug-free plate is marked with "+ + +", and the colony which is not obviously different from the colony grown on the drug-free plate is marked with "+ + + + +";
II. And (3) measuring the biological activity of the obligate parasitic pathogenic oomycete:
cleaning downy mildew leaves of fructus Vitis Viniferae or fructus Cucumidis Sativi, culturing at 18 deg.C for 24 hr in dark, washing fresh sporangium with 4 deg.C purified water, and making into 10 5 The spore capsule suspension is dipped by a writing brush and smeared on the back of a healthy leaf blade which is soaked in a compound solution of 100, 25 and 6.25mg/L for 2 minutes and then dried, and then the leaf blade is placed on wet filter paper of a culture dish, is cultured in the dark at the temperature of 18 ℃ for 24 hours, is placed in the light and dark at the temperature of 18 ℃ for alternate culture for 7 days, and the inhibition effect on the scab is observed and recorded. The leaves which can not be attacked are marked as < - >, the disease spots which are smaller than 25% of the disease spots on the leaves which are treated by the non-medicinal clear water are marked as < + >, the disease spots which are about 25% -50% of the size of the disease spots on the leaves which are treated by the non-medicinal clear water are marked as < + >, the disease spots which are about 50% -75% of the size of the disease spots on the leaves which are treated by the non-medicinal clear water are marked as < + >, and the disease spots which are not obviously different from the size of the disease spots on the leaves which are treated by the non-medicinal clear water are marked as < + >;
III, measuring the biological activity of the plant pathogenic bacteria:
dipping 10 with the inoculating ear 7 cfu/mL of bacterial suspension inNA media plates containing 25, 6.25, 1.56mg/L of test compound (prepared as drug-containing PDA media plates) were streaked and incubated at 28 ℃ for 48 hours, and inhibition of bacterial colony growth was observed and recorded. The complete failure to grow was marked with "-", 25% below was marked with "+" on drug-free plates, about 25% to 50% was marked with "+", about 50% to 75% was marked with "+ + +", and no significant difference from the colonies on drug-free plates was marked with "+ + + +";
IV, measuring the biological activity of the plant root-knot nematode:
removing the outer oocysts of the root knots on the roots of the tomatoes or the cucumbers by using stainless steel tweezers, putting the obtained products into a sodium hypochlorite solution with the concentration of 1% by weight, shaking for 3 minutes, sequentially sieving through 200-mesh and 500-mesh sieves, washing the eggs on the 500-mesh sieves by using clear water, putting the collected eggs on filter paper of the 200-mesh sieves, putting the sieves into a culture dish with clear water (the eggs slightly overflow through water), incubating at the temperature of 25 ℃, collecting the second-instar larvae every 24 hours, preserving at the temperature of 4 ℃, preparing a second-instar larva suspension by using distilled water, mixing the second-instar larva suspension with an isovolumetric compound diluent to enable the final concentration of the test compound to reach 100, 25 and 6.25mg/L, then culturing at the temperature of 25 ℃ for 36 hours, and checking the death rate of the larvae. The worm body is dead in a linear state, and is live in a bent or spiral state. All deaths were designated "-", less than 25% survivors as "+", 25% to 50% survivors as "+ + +", 50% to 75% survivors as "+ + + + + +", and all survivors as with the clear water treatment were designated "+ + + + + + + +".
E. And (3) test results:
the test results are shown in tables 17, 18 and 19, respectively.
Table 17: growth test results of plant pathogenic fungi on culture medium containing 25mg/L naphthyl pyrrolindione compound
Table 18: growth test results of plant pathogenic bacteria on a medium containing 6.25mg/L of naphthyl pyrrolindione compound
Table 19: grape and cucumber downy mildew occurrence and root-knot nematode survival test results under treatment of 25mg/L naphthyl pyrrolindione compound
| Compound (I) | P.viticola | P.cubensis | M.incognita |
| YNT21-16 | + | + | + |
| YNT21-31 | + | + | + |
| YNT21-32 | ++ | ++ | ++ |
| YNT21-35 | + | + | + |
| YNT21-43 | + | + | - |
| YNT21-47 | ++ | +++ | ++ |
| YNT21-55 | ++ | ++ | +++ |
| YNT21-71 | - | - | - |
| YNT21-72 | - | - | - |
| YNT21-73 | - | - | - |
| YNT21-76 | - | - | + |
| YNT21-79 | - | - | ++ |
The test results shown in tables 17, 18 and 19 clearly show that 12 naphthyl pyrrolindione compounds have certain broad spectrum antibiotic activity on different pathogens, the inhibition effect of the naphthyl pyrrolindione compounds is increased along with the increase of the treatment dosage, and different compounds have certain selectivity on the biological activities of fungi, bacteria and nematodes, wherein the naphthyl pyrrolindione compounds have the highest activity on pathogenic bacteria, have high activity on fungi such as green smut, gray mold, watermelon rambutan and the like, and have no cross resistance with other bactericides.
Claims (10)
1. A naphthyl pyrrolindione compound characterized in that the compound has the following general chemical formula (I):
in the formula:
R 1 and R 2 Is 1-3 selected from H and CH 3 、C 2 H 5 、n-C 3 H 7 、i-C 3 H 7 、CF 3 Cyclopropyl, OCH 3 、COOCH 3 、COOC 2 H 5 、NHCOOCH 3 、NHCOCH 3 、OH、NH 2 、NO 2 、SH、SO 3 H. A group of CN, cl, br, F, O =, pyrrolylamino or pyridylamino;
R 3 is 1-2 selected from H and CH 3 、C 2 H 5 、n-C 3 H 7 、i-C 3 H 7 、CF 3 Cyclopropyl, OCH 3 、COOCH 3 、COOC 2 H 5 、NHCOOCH 3 、NHCOCH 3 、OH、NH 2 、NO 2 、SH、SO 3 H. CN, cl, br, F, with the proviso that R 1 、R 2 And R 3 Not H at the same time.
2. The naphthyl pyrrolindione compound according to claim 1, characterized in that the naphthyl pyrrolindione compound is selected from the group consisting of 1- (4-chloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-bromonaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-bromonaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2, 4-dichloronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-trifluoromethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, a salt thereof, and a pharmaceutically acceptable salt thereof 1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-ethoxynaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-cyclopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione 1- (4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-methyl-1- (2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (6-chloro-2-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, a salt thereof, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable salt thereof 1- (2-methyl-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2, 4-dimethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-ethyl-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-bromo-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5- Diketones, 1- (5-bromo-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4, 5-dichloro-2-ethylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-propyl-4-methylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-bromo-2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-chloro-2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, di-and tri-carboxylic acids 1- (5-chloro-2-propylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-bromo-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (6-bromo-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (4-chloro-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (5-chloro-2-isopropylnaphthalen-1-yl) -1H-pyrrole-2, 5-dione, 3-nitro-1- (2-nitro-3, 4-dioxo-3, 4- <xnotran> -1- ) -1H- -2,5- ,3- -1- (2,4- -1- ) -1H- -2,5- ,3- -1- (4- -2- -1- ) -1H- -2,5- ,3- -1- (2,4- -1- ) -1H- -2,5- ,1- (4- -2- -1- ) -1H- -2,5- ,1- (5- -2- -1- ) -1H- -2,5- ,3- -1- (5- -2- -1- ) -1H- -2,5- , (6- -5- (2,5- -2,5- -1H- -1- ) -1- ) ,1- (6- -2- ((5- ( ) -2- ) ) -1- ) -1H- -2,5- ,1- (6- -2- ((4- ( ) </xnotran> -1H-pyrazol-3-yl) amino) naphthalen-1-yl) -1H-pyrrole-2, 5-dione, 1- (2-methoxy-5, 8-dioxo-5, 8-dihydronaphthalen-1-yl) -1H-pyrrole-2, 5-dione and 4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) naphthalene-1-sulfonic acid.
3. The method for producing a naphthylpyrrolindione compound according to claim 1, characterized by the production steps of the production method:
A. heating reflux reaction
Mixing a naphthylamine compound (II), a maleic anhydride compound (III) and glacial acetic acid according to a molar ratio of 1:1.0 to 2.0: 1.0-100.0, heating and refluxing for 0.41-24.0 h under stirring by using a heating and refluxing device, wherein the chemical reaction equation is as follows:
r in the chemical reaction equation 1 、R 2 Or R 3 The radicals are as defined in claim 1;
then, cooling the reaction liquid, and removing acetic acid by reduced pressure distillation to obtain a reaction product mixture;
B. extraction of
According to the weight ratio of the reaction product mixture to water of 1: 1-50, adding water into the reaction product mixture obtained in the step A, uniformly mixing, and then mixing according to the volume ratio of the aqueous solution of the reaction product mixture to the extracting agent of 1:0.1 to 5.0, extracting the reaction product mixture aqueous solution for 2 to 4 times by using an extracting agent, and merging the extraction phases to obtain a merged extraction phase;
C. washing machine
According to the volume ratio of the combined extraction phase and the washing liquid of 1: 0.5-2.0, the combined extract phase obtained in the step B uses saturated NaHCO successively 3 Washing the solution with HCl solution with the concentration of 0.1-5.0N for 2-4 times, and repeatedly washing with distilled water in the same way until the washing combined extract phase is neutral;
D. drying the mixture
Anhydrous Na for neutral combined extract phase obtained in step C 2 SO 4 Drying, and distilling under reduced pressure to remove solvent to obtain a solid or liquid;
E. recrystallization or column chromatography
And D, mixing the solid obtained in the step D with petroleum ether and ethyl acetate according to the volume ratio of 100: recrystallizing in a mixed solution of 0-100, filtering, and drying to obtain the naphthyl pyrrolindione compound; or
The solid obtained in step D was mixed in a ratio of solid in grams to solvent in milliliters of 1: 1-20 is dissolved by ethyl acetate to obtain a solution, the solution or the liquid obtained in the step D is separated by a silica gel chromatographic column, and petroleum ether and ethyl acetate are used according to the volume ratio of 100: 0-100 as eluent, eluting under the pressure of 0.1-5.0 MPa, collecting eluate, and distilling under reduced pressure to remove solvent to obtain the naphthyl pyrrolindione compound.
4. The process according to claim 3, wherein in the step A, the distillation under reduced pressure is carried out by using a rotary evaporator under a pressure of 0.1 to 100KPa and a temperature of 30 to 100 ℃ until the acetic acid content of the reaction product mixture becomes 1.0% by weight or less.
5. The method according to claim 3, wherein in step B, the extractant is diethyl ether, ethyl acetate, dichloromethane, chloroform or carbon tetrachloride.
6. The process according to claim 3, wherein in the steps D and E, the distillation under reduced pressure is carried out by using a rotary evaporator under a pressure of 0.1 to 100KPa and at a temperature of 30 to 100 ℃ until the solvent content of the residual solid or liquid becomes 1.0% by weight or less.
7. The method according to claim 3, wherein in the step E, the drying is performed by drying in an oven at a temperature of 30 to 100 ℃ until the content of the solvent or water in the product of the naphtyl pyrrolindione compound is 0.5% by weight or less.
8. The method according to claim 3, wherein in step E, the silica gel column is a column having a diameter to height ratio of 1:1 to 50 and a separation column filled with 100 to 600 meshes of silica gel.
9. Use of the naphthyl pyrrolindione compound according to any one of claims 1 to 2 or the naphthyl pyrrolindione compound prepared by the preparation method according to any one of claims 3 to 8 for controlling plant diseases.
10. The use according to claim 9, characterized in that the plant diseases are wheat scab, powdery mildew, rust disease, stem base rot, rice blast, sheath blight, false smut, bakanae disease, bacterial streak disease, bacterial leaf blight, corn northern leaf blight, southern leaf blight, gray mold of fruits and vegetables and flowers, sclerotinia, anthracnose, early blight, late blight, brown spot, rust disease, southern leaf blight, powdery mildew, downy mildew, scab, ring spot, leaf spot, gummy stem blight, bacterial canker, angular leaf spot, fruit spot, soft rot and root cancer.
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