CN115124462B - 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound and preparation method and application thereof - Google Patents
2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound and preparation method and application thereof Download PDFInfo
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- CN115124462B CN115124462B CN202210865872.9A CN202210865872A CN115124462B CN 115124462 B CN115124462 B CN 115124462B CN 202210865872 A CN202210865872 A CN 202210865872A CN 115124462 B CN115124462 B CN 115124462B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
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- 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
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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Abstract
The invention discloses a 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound, a preparation method and application thereof, wherein the compound is prepared by reacting 2, 4-difluoro aniline with 2-methyl acetoacetic acid ethyl ester to prepare 2, 3-dimethyl-6, 8-difluoro-4-hydroxyquinoline, and then reacting the 2, 3-dimethyl-6, 8-difluoro-4-hydroxyquinoline with various chlorobenzenes to prepare the 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound. The preparation method of the invention is simple and convenient to operate, and 17 prepared compounds are all subjected to the following steps 1 HNMR and HRMS were characterized and tested for bactericidal activity at a concentration of 50 ppm. The results show that: the 16 compounds have bactericidal activity, the inhibition rate of I-10 to sclerotinia sclerotiorum and Rhizoctonia solani is over 60 percent, and the inhibition rates of I-2 and I-4 to botrytis cinerea are 63.3 percent and 60.0 percent respectively.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis and pharmaceutical application, and particularly relates to a 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound, and a preparation method and application thereof.
Background
Grain and environmental problems remain a major problem in today's world. The Chinese amplitude-officials are wide, the people and the agricultural large country are from ancient times, and the agricultural production is self-evident to the meaning of China. In the development of heterocyclic pesticides, the heterocyclic pesticides have important roles in the development of novel pesticides. Quinoline is a common and very important nitrogen-containing heterocyclic structure, and is extracted from coal tar by Runge in 1834. Many heterocyclic compounds containing quinoline structures have very important biological and pharmacological activities, and therefore, the heterocyclic compounds are of course the most common use in the creation of new pesticides.
In recent years, various quinoline compounds have been reported for synthesis, and many quinoline structure-containing compounds are put on the market as commercial pesticides. Moreover, the development of safer pesticides with higher activity and lower toxicity by structural modification of known natural products or commercial compounds has become a hotspot for the research direction of agropharmaceutical manufacturers.
Disclosure of Invention
The invention aims to provide a 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound, a preparation method and application thereof.
The invention discloses a 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound, the structural formula of which is shown as formula (I):
in the formula (I), R is alkyl, phenyl, substituted phenyl, benzoyl, substituted benzoyl, cyano or 2-chlorothiazole-5-yl, the substituent of the substituted phenyl is alkyl or halogen, and the substituent of the substituted benzoyl is halogen, alkoxy or substituted alkyl; preferably, the substituents of the substituted phenyl groups are 2-chloro, 4-bromo, 2-fluoro, 4-fluoro, 2-methyl, 2, 4-dichloro, 3-fluoro; the substituent of the substituted benzoyl is 4-bromo, 4-methoxy, 4-chloro, 4-fluoro, 4-trifluoromethyl.
Further, the invention also discloses a preparation method of the 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound, which comprises the following steps of;
1) Reacting 2, 4-difluoroaniline with ethyl 2-methylacetoacetate by taking polyphosphoric acid as a cyclizing agent to generate a compound shown as a formula (II);
2) Stirring and reacting the compound shown in the formula (II) obtained in the step 1) with the compound shown in the formula (III) at room temperature under the condition that DMF is taken as a solvent and NaH is provided with alkaline environment to obtain the 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound shown in the formula (I);
in the formula (I), R is alkyl, phenyl, substituted phenyl, benzoyl, substituted benzoyl, cyano or 2-chlorothiazole-5-yl, the substituent of the substituted phenyl is alkyl or halogen, and the substituent of the substituted benzoyl is halogen, alkoxy or substituted alkyl; preferably, the substituents of the substituted phenyl groups are 2-chloro, 4-bromo, 2-fluoro, 4-fluoro, 2-methyl, 2, 4-dichloro, 3-fluoro; the substituent of the substituted benzoyl is 4-bromo, 4-methoxy, 4-chloro, 4-fluoro, 4-trifluoromethyl.
The reaction process is as follows:
further, in the case of synthesizing the compound represented by the formula (II) in the step 1), the mass ratio of 2, 4-difluoroaniline to ethyl 2-methylacetoacetate is 1:1 to 1:1.5, preferably 1:1.
Further, in the synthesis of the 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound in the step 2), the mass ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is 1:1 to 1:1.4, preferably 1:1.1.
Further, in the step 2), when the 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound is synthesized, the mass ratio of the compound shown as the formula (II) to NaH is 1:1-1:1.5, preferably 1:1.3.
Furthermore, the invention also discloses application of the 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound in preparing bactericides.
The invention has the beneficial effects that:
the preparation method of the invention is simple and convenient to operate, and the structure of the obtained product is improved 1 H NMR and HRMS were confirmed and the resulting 17 target products were tested for bactericidal activity, indicating that: all the compounds have certain antibacterial activity, and the inhibition rate of the compound I-14 to the tomato early blight bacteria is 41.7% in 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compounds; the inhibition rates of the compounds I-2, I-3 and I-10 on the wheat scab bacteria reach 54.2%,58.3% and 50.0%, respectively, and the compounds I-4 and I-8 reach 45.8%; the inhibition rate of the compounds I-4, I-10 and I-16 on rice blast bacteria reaches more than 40.0 percent; chemical combinationThe inhibition rate of the compound I-10 to phytophthora capsici is up to 58.1%, and the compound I-14 is up to 41.9%; the inhibition rate of the compounds I-2, I-8 and I-16 on Sclerotinia sclerotiorum reaches 50.0%, the compound I-10 reaches 66.7%, and the compound I-1 reaches 41.7%; the inhibition rates of the compounds I-2 and I-4 on the botrytis cinerea are 63.3% and 60.0%, respectively, and the compounds I-10 and I-13 reach 50.0%; the inhibition rate of the compound I-10 to the Rhizoctonia solani reaches 63.6%, and the compounds I-5, I-8 and I-16 reach 45.5%; the inhibition rate of the compound I-8 to cucumber fusarium wilt bacteria reaches 47.6%; the inhibition rate of the compounds I-8 and I-9 on the apple ring rot germs reaches 57.7 percent.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1 preparation of Compounds of formula (II)
Into a 100mL three-necked flask, 2, 4-difluoroaniline (5.16 g,40.00 mmol), ethyl 2-methylacetoacetate (5.77 g,40.00 mmol) and polyphosphoric acid (20.28 g,60.00 mmol) were sequentially added, and the mixture was heated and stirred at 150℃under controlled temperature to react with each other by TLC (V EA /V PE =1/1) tracking the reaction progress, stopping the reaction after 5 hours, cooling to room temperature, putting the reaction bottle into an ice bath, adjusting the pH to 7-8 with 10% sodium hydroxide aqueous solution, precipitating a large amount of solid, suction-filtering, taking a filter cake, and drying to obtain a compound shown as a formula (II), white solid and yield: 83.2%, melting point: 241-243 ℃.
EXAMPLE 2 preparation of Compounds of formula (I)
In 17 50mL round bottom flasks, the compound (0.20 g,0.96 mmol) of formula (II), sodium hydride (0.03 g,1.25 mmol) and DMF (10 mL) obtained in example 1 were reacted by stirring at room temperature for 0.5h, then the compound (1.06 mmol) of formula (III) was added, stirring was continued, TLC (V) EA /V PE After completion of the reaction, the reaction mixture was transferred to a separating funnel, extracted with water (30 mL), ethyl acetate (10 ml×3), the organic phases were combined, washed with saturated brine (10 ml×3), dried over anhydrous sodium sulfate, filtered, and the solvent was dried by spin-drying, followed by column chromatography (flowPhase V EA /V PE =1/4) purification to give the target compounds I-1 to I-17, the specific data are shown in tables 1 and 2.
TABLE 1 physical data of 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound
Table 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound 1 H NMR and HRMS data
Example 3 bactericidal activity test
Test method
(1) Test object: tomato early blight (Alternaria asalolani), wheat scab (Gibberella zeae), rice blast (Pyricularia Grisea), pepper phytophthora capsici (Phytophthora capsici), rape sclerotinia (Sclerotinia sclerotiorum), cucumber gray mold (Botrytis cinerea), sheath blight (Riziocotinia solani), cucumber fusarium wilt (Fusarium oxysporum), peanut brown spot (Cercospora arachidicola), apple ring rot (Physalosporium cucumericola).
(2) Each test compound was dissolved in DMSO to 1% ec stock solution for use. The indoor bactericidal activity of the compound to be tested on the test target at the dose of 50ppm is evaluated by adopting a bacteriostasis circle method, and a water control (QCK) is additionally arranged.
(3) The test method comprises the following steps: 150. Mu.l of the EC mother solution thus prepared was sucked by a pipette and dissolved in 2.85mL of warm water to prepare a drug solution having an effective concentration of 500ppm of the compound to be tested. 1ml of the liquid medicine is sucked by a pipette, placed in a sterilized culture dish, placed in 9ml of PDA culture medium, shaken uniformly and cooled. After taking out the circular bacterial cake by a puncher, picking up the circular bacterial cake to the center of a culture dish by an inoculating needle, then placing the culture dish in an incubator at 27 ℃ for culturing, and measuring the colony diameter after 48 hours. The pure growth of the bacterial colony is the difference value between the average diameter of the bacterial colony and the diameter of a bacterial cake, and the calculation method of the bacteriostasis rate (%) refers to the following formula.
The activity test results are shown in table 3:
table 3 bactericidal activity of 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound
The 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether 17 compounds all show a certain bactericidal activity, and the inhibition rate of the compound I-14 to the tomato early blight bacteria is 41.7%; the inhibition rates of the compounds I-2, I-3 and I-10 on the wheat scab bacteria reach 54.2%,58.3% and 50.0%, respectively, and the compounds I-4 and I-8 reach 45.8%; the inhibition rate of the compounds I-4, I-10 and I-16 on rice blast bacteria reaches more than 40.0 percent; the inhibition rate of the compound I-10 to phytophthora capsici is up to 58.1%, and the compound I-14 is up to 41.9%; the inhibition rate of the compounds I-2, I-8 and I-16 on Sclerotinia sclerotiorum reaches 50.0%, the compound I-10 reaches 66.7%, and the compound I-1 reaches 41.7%; the inhibition rates of the compounds I-2 and I-4 on the botrytis cinerea are 63.3% and 60.0%, respectively, and the compounds I-10 and I-13 reach 50.0%; the inhibition rate of the compound I-10 to the Rhizoctonia solani reaches 63.6%, and the compounds I-5, I-8 and I-16 reach 45.5%; the inhibition rate of the compound I-8 to cucumber fusarium wilt bacteria reaches 47.6%; the inhibition rate of the compounds I-8 and I-9 on the apple ring rot germs reaches 57.7 percent.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept, and the scope of protection of the present invention should not be construed as limited to the specific forms set forth in the examples, nor is it intended that the scope of protection of the present invention be limited to only equivalent technical means as would occur to those skilled in the art based on the inventive concept.
Claims (6)
1.2,3-dimethyl-6, 8-difluoro quinoline-4-ether compound, its structural formula is shown in formula (I):
；
in the formula (I), the substituent R is 2-chlorophenyl, 4-bromophenyl, 2-fluorophenyl, 3, 4-dichlorophenyl, 3-fluorophenyl or cyano.
2. A process for producing the 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound according to claim 1, comprising the steps of;
1) Reacting 2, 4-difluoroaniline with ethyl 2-methylacetoacetate by taking polyphosphoric acid as a cyclizing agent to generate a compound shown as a formula (II);
2) Stirring and reacting the compound shown in the formula (II) obtained in the step 1) with the compound shown in the formula (III) at room temperature under the condition that DMF is taken as a solvent and NaH is provided with alkaline environment to obtain the 2, 3-dimethyl-6, 8-difluoro quinoline-4-ether compound shown in the formula (I);
；
in the formula (I) and the formula (III), the substituent R is 2-chlorophenyl, 4-bromophenyl, 2-fluorophenyl, 3, 4-dichlorophenyl, 3-fluorophenyl or cyano.
3. The method for producing a 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound according to claim 2, wherein the mass ratio of 2, 4-difluoroaniline to ethyl 2-methylacetoacetate is 1:1 to 1:1.5 when the compound represented by the formula (II) is synthesized in step 1).
4. The method for producing a 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound according to claim 2, wherein the mass ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is 1:1 to 1:1.4 in the synthesis of the 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound in the step 2).
5. The method for producing 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound according to claim 2, wherein the mass ratio of the compound represented by the formula (II) to NaH is 1:1 to 1:1.5 in the synthesis of 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound in step 2).
6. Use of a 2, 3-dimethyl-6, 8-difluoroquinoline-4-ether compound according to claim 1 for preparing a bactericide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034924A (en) * | 1988-01-29 | 1989-08-23 | 伊莱利利公司 | quinoline, quinazoline and cinnoline derivatives |
| CN1893949A (en) * | 2003-12-24 | 2007-01-10 | 默克专利有限公司 | Acidic quinoline derivatives and their use for the prevention and/or treatment of hyperglycaemia-related pathologies |
| CN101426486A (en) * | 2005-12-01 | 2009-05-06 | 先灵公司 | Compounds for the treatment of inflammatory disorders and microbial diseases |
| CN109320452A (en) * | 2017-07-31 | 2019-02-12 | 东莞东阳光科研发有限公司 | Quinoline derivatives and its preparation method and application |
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- 2022-07-22 CN CN202210865872.9A patent/CN115124462B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034924A (en) * | 1988-01-29 | 1989-08-23 | 伊莱利利公司 | quinoline, quinazoline and cinnoline derivatives |
| CN1893949A (en) * | 2003-12-24 | 2007-01-10 | 默克专利有限公司 | Acidic quinoline derivatives and their use for the prevention and/or treatment of hyperglycaemia-related pathologies |
| CN101426486A (en) * | 2005-12-01 | 2009-05-06 | 先灵公司 | Compounds for the treatment of inflammatory disorders and microbial diseases |
| CN109320452A (en) * | 2017-07-31 | 2019-02-12 | 东莞东阳光科研发有限公司 | Quinoline derivatives and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 范文玉，等.2,3-二甲基喹啉类化合物的合成及其生物活性.《农药》.2013,第52卷(第3期),171-173. * |
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