CN108640871B - Fluorine-containing pyridine piperazine urea compound and application thereof - Google Patents
Fluorine-containing pyridine piperazine urea compound and application thereof Download PDFInfo
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- CN108640871B CN108640871B CN201810587098.3A CN201810587098A CN108640871B CN 108640871 B CN108640871 B CN 108640871B CN 201810587098 A CN201810587098 A CN 201810587098A CN 108640871 B CN108640871 B CN 108640871B
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- compound
- fluorine
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- containing pyridine
- urea compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
Abstract
The invention discloses a fluorine-containing pyridine piperazine urea compound with a structure shown as a formula IShown in the figure:
Description
Technical Field
The invention belongs to the field of acaricides in pesticides, and particularly relates to a fluorine-containing pyridine piperazine urea compound and application thereof.
Background
Because the existing acaricide is frequently used for a long time, the acarids generate different degrees of drug resistance to the acaricide, so that the development of the novel acaricide is an effective way for controlling the drug resistance of the acarids. CN102378754A discloses the research on the insecticidal and acaricidal activity of 3-aminooxalylaminobenzamide derivatives, and part of the compounds show high acaricidal activity. CN104285968A discloses the acaricidal activity of acaricide with tebufenpyrad as active ingredient, and shows excellent acaricidal activity at low concentration. The invention relates to a novel compound formed by connecting fluorine-containing pyridine and amide-containing compound by using piperazine as a bridge chain, and the compound of formula I and the application thereof as acaricide in the prior art are not disclosed.
Disclosure of Invention
The invention aims to provide a fluorine-containing pyridine piperazine urea compound used as an acaricide to prevent and treat agricultural or forestry pest mites.
The technical scheme of the invention is as follows:
the invention provides a fluorine-containing pyridine piperazine urea compound, which is shown as a formula I:
the compounds of formula I can be prepared by the following reaction:
III and II react in ethyl acetate or dichloromethane by taking triethylamine as an acid-binding agent to obtain I. The preparation of intermediate III is described in the examples of the invention.
The invention has the advantages and positive effects that:
the invention relates to a miticide with a novel structure, which is characterized in that piperazine is used as a bridge chain, fluorine-containing pyridine and an amide compound are spliced to generate a urea compound, and the acaricide has the advantages that the compound has a fluorine-containing pyridyl, piperazine and urea bond structure, so that the endotherm conduction effect is remarkably improved, the pesticide effect is remarkably improved (shown in table 1), the acaricide has unexpected acaricidal activity, and the high pesticide resistance problem of mites is avoided. Meanwhile, the compound of the formula I designed and synthesized by the invention has the advantages of wide raw material source, simple synthesis process, low production cost, low toxicity and small dosage, meets the requirements of modern agriculture on low pollution, super-high efficiency and long-lasting effect, and has commercial potential.
When the compound is used for preventing and treating mites, the compound can be used alone or combined with other active substances according to actual needs so as to improve the comprehensive performance of the product.
The invention also comprises a miticidal composition containing the compound shown in the formula I as an active ingredient, wherein the weight percentage of the active composition in the miticidal composition is 1-99%. The acaricidal composition also comprises a forestry and agricultural acceptable carrier.
The compositions of the invention may be used in the form of formulations: the compound of formula I as active component is dissolved or dispersed in carrier or solvent, and is added with proper amount of surfactant to prepare missible oil, suspending agent, microemulsion, etc.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Detailed Description
The following synthetic examples and results of the biological tests are provided to further illustrate the invention and are not meant to limit the invention.
Synthesis examples:
example 1, preparation of intermediate iii:
weighing 17.2g (0.2mol) of anhydrous piperazine, adding the anhydrous piperazine into a 250mL reaction bottle, adding 60mL of methanol, stirring for dissolving, heating to 40 ℃, dissolving 21.6g (0.1mol) of 2, 3-dichloro-5- (trifluoromethyl) pyridine by using 50mL of methanol, slowly dripping the dissolved solution into the reaction bottle, reacting at the constant temperature of 40 ℃ for 6 hours after finishing dripping, tracking the TLC until the raw materials are completely reacted, cooling to room temperature, performing suction filtration, performing rotary evaporation on the filtrate to remove the methanol, precipitating a white solid, adding water, stirring and dissolving the rest anhydrous piperazine, performing suction filtration, washing a filter cake for 2 times to obtain 22.6g of white solid, wherein the melting point is 65.8-67.3 ℃, and the yield is 85%.
1H NMR(500MHz,DMSO-d6),δ(ppm)8.53(s,1H),8.15(s,1H),3.37–3.35(t,4H),2.82–2.80(t,4H).
Example 2, preparation of compound I:
adding 5.3g (0.02mol) of the intermediate III into a 250mL reaction bottle, then adding 30g of ethyl acetate, then adding 2.22g of triethylamine, dropwise adding 1.98g (0.02mol) of n-butyl isocyanate under stirring, reacting at 60 ℃ for 40min after the dropwise adding is finished, tracking the completion of the reaction of the intermediate III by TLC, adding 100mL of water, stirring, separating, drying an organic phase by using anhydrous sodium sulfate, removing ethyl acetate by rotary evaporation, and cooling to obtain 6.8g of a white solid, wherein the melting point is 121.1-122.7 ℃, and the yield is 93%.
1H NMR(500MHz,DMSO-d6)，δ(ppm)：8.56(s,1H),8.20(s,1H),6.54～6.52(t,1H),3.45～3.39(m,8H),3.06～3.01(m,2H),1.42～1.36(m,2H),1.30～1.25(m,2H),0.89～0.85(t,3H).
Biological activity assay
Example 3 acaricidal Activity assay
Example 3 acaricidal Activity assay
The acarid killing activity is measured by adopting an immersion method and a method for statistically correcting the mortality of pests. The specific process is as follows: the test reagents are respectively diluted to required concentration according to effective components, 50mL of liquid medicine is respectively absorbed under aseptic condition and injected into a culture dish, and then the test reagents are respectively immersed into the leaves of cinnabar mite eggs (a group in which the mite eggs are normally raised according to an indoor standardized method), and a flat plate added with 50mL of sterilized water is used as a blank control. Spirodiclofen was used as a comparative drug. The petri dish was placed in a 24 + -1 deg.C incubator. And after 48h, investigating and counting the mortality. Each experiment was repeated 3 times and the average was taken.
TABLE 1 acaricidal Activity test results for Compound I
According to the test results in table 1, it can be known that the acaricidal activity of the obtained series of compound I of the present invention is significantly higher than that of spirodiclofen at the same dosage. The killing rate of the mite eggs still reaches over 90 percent at a low concentration of 1 ppm.
Claims (2)
1. The application of a compound shown in the formula I in preventing and controlling agricultural and forestry acarid damage is disclosed, wherein the structural formula of the compound shown in the formula I is as follows:
2. an acaricidal composition comprising a compound of formula I as an active ingredient and an agriculturally or forestry acceptable carrier, said compound of formula I having the structural formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810587098.3A CN108640871B (en) | 2018-06-06 | 2018-06-06 | Fluorine-containing pyridine piperazine urea compound and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810587098.3A CN108640871B (en) | 2018-06-06 | 2018-06-06 | Fluorine-containing pyridine piperazine urea compound and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108640871A CN108640871A (en) | 2018-10-12 |
| CN108640871B true CN108640871B (en) | 2020-03-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810587098.3A Active CN108640871B (en) | 2018-06-06 | 2018-06-06 | Fluorine-containing pyridine piperazine urea compound and application thereof |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109336882B (en) * | 2018-11-07 | 2021-08-17 | 青岛科技大学 | Fluorine-containing pyridine acyl piperazine compound and application thereof |
| CN115806512A (en) * | 2021-09-15 | 2023-03-17 | 张建勋 | Fluorine-containing acaricide and preparation method thereof |
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