CN110128409A - The preparation and application of the difluoromethyl pyrazole 9 oxime derivate of the connection pyrrazole structure containing pyridine - Google Patents
The preparation and application of the difluoromethyl pyrazole 9 oxime derivate of the connection pyrrazole structure containing pyridine Download PDFInfo
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- CN110128409A CN110128409A CN201910361413.5A CN201910361413A CN110128409A CN 110128409 A CN110128409 A CN 110128409A CN 201910361413 A CN201910361413 A CN 201910361413A CN 110128409 A CN110128409 A CN 110128409A
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- connection
- structure containing
- containing pyridine
- pyrazole
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
Abstract
The present invention relates to the preparations and application of a kind of difluoromethyl pyrazole 9 oxime derivate (I) of connection pyrrazole structure containing pyridine.It is condensed to yield by pyridine connection pyrazol formyl chloride (II) with difluoromethyl pyrazole oxime (III).The difluoromethyl pyrazole 9 oxime derivate of the connection pyrrazole structure containing pyridine has effective control efficiency to harmful insect, which can be used for preparing the insecticide in the fields such as agricultural, gardening.
Description
Technical field
The present invention relates to chemical pesticide fields, and in particular to it is a kind of containing pyridine connection pyrrazole structure difluoromethyl pyrazole oxime spread out
The preparation and application of biology.
Background technique
The prevention and treatment of pest is the core realm of pesticide science research all the time, and insecticide is widely used so that most evils
Worm has obtained effective improvement.But with the continuous expansion of insecticide application scale, the resistance problems of traditional pesticide species are increasingly
It highlights, in addition the emergence of new pest and disease damage, so that the research and development that continues of novel pesticide becomes inevitable choice.
Pyrazoles oxime compound has a wide range of applications in pesticide field, and wherein representative compound has fenpyroximate:
Pyrazole ring is the Typical reactive segment in drug molecule and pesticide molecule, can effectively change the physics and chemistry of compound
Property, and the compound containing pyrazole ring has stronger physiological activity in vivo.
Therefore, in order to further find the compound with excellent bioactivity from pyrazoles oxime derivatives, using work
Property group joining method, reasonably pyrazole group is linked together with pyrazoles oxime skeleton, the invention discloses one kind have agriculture
With the difluoromethyl pyrazole 9 oxime derivate for the connection pyrrazole structure containing pyridine that pesticidal applications are worth.
Summary of the invention
It is and efficient, safe, environmental-friendly the object of the present invention is to provide there is excellent control efficiency for various pests
The difluoromethyl pyrazole 9 oxime derivate of one kind connection pyrrazole structure containing pyridine, to meet crop protection to efficient pesticides demand.
A further object of the present invention is to provide purposes of the above compound in terms of preparing insecticide.
It is a further object of the present invention to provide the preparation methods of above compound.
In order to solve the above technical problems, the first aspect of the present invention provides a kind of difluoromethyl of connection pyrrazole structure containing pyridine
Pyrazoles 9 oxime derivate, with general formula I,
Preferably, the difluoromethyl pyrazole 9 oxime derivate of the connection pyrrazole structure containing pyridine has the following structure:
The second aspect of the present invention provides the preparation of the difluoromethyl pyrazole 9 oxime derivate of the above-mentioned connection pyrrazole structure containing pyridine
Method comprising following steps:
Compound III is dissolved in organic solvent, acid binding agent is added, then in the mixing that intermediate II and a small amount of solvent is added
Liquid, for a period of time, mother liquor is concentrated under reduced pressure final reaction, and gained residue isolates and purifies to obtain target compound,
Preferably, the acid binding agent is selected from triethylamine, and pyridine, sodium acetate, sodium bicarbonate, the solvent is selected from N, N- diformazan
Base formamide (DMF), methylene chloride, chloroform, acetonitrile, tetrahydrofuran (THF), reaction temperature are 0 DEG C~90 DEG C, when reaction
Between be 8 hours~26 hours.
Preferably, containing pyridine connection pyrrazole structure difluoromethyl pyrazole 9 oxime derivate the preparation method is as follows:
Wherein, intermediate pyridine connection pyrazol formyl chloride synthesis reference literature report conventional method (organic chemistry,
2011,31,1943-1948)；The conventional method of the synthesis reference literature report of difluoromethyl pyrazole oxime intermediate
(J.Agric.Food Chem.2008,56,10805-10810)。
Compound of Formula I has excellent prevention and treatment activity to insect, thus the compound of the present invention can be used as preparing desinsection
Agent, and then protect the plants such as agricultural, gardening.The insect include lepidoptera pest for example bollworm, beet armyworm, diamondback moth,
Cabbage caterpillar, rice leaf roller and striped rice borer etc.；Homoptera pest such as leafhopper, plant hopper, earthworm worm, aleyrodid, the scale insect of Psyllidae etc.；
Diptera pest such as housefly, Liriomyza, mosquito class etc.；The locust etc. of Orthoptera, longicorn, chafer, weevil, bean weevil of coleoptera etc.
Pest etc.；The stinkbug etc. of Semiptera.Certainly, the harmful organism that the compound of the present invention can prevent and treat is not limited to the range of the example above.
When the compound of the present invention indicated by general formula I is used as the insecticide in the fields such as agricultural, gardening, can individually make
With, or used in a manner of Pesticidal combination, such as using Formulas I as active constituent, in addition insecticides adjuvant commonly used in the art is processed into
Aqueous emulsion, suspending agent, water dispersion granule, missible oil etc..
Common insecticides adjuvant includes: liquid-carrier, such as water；Organic solvent such as toluene, dimethylbenzene, cyclohexanol, methanol, fourth
Alcohol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and plant oil and fatty acid；Common surface agent is such as
Emulsifier and dispersing agent, including anionic surfactant, cationic surfactant, nonionic surfactant and both sexes table
Face activating agent；Other auxiliary agents, such as wetting agent, thickener.
When being used as the active constituent in insecticide by the compound of the present invention that general formula I is indicated, in the insecticide
Content is selected in the range of 0.1% to 99.5%, and can determine activity appropriate according to dosage form and method of administration
Component content.In general, preferably it contains containing active constituent described in 5% to 50% (weight percent, similarly hereinafter) in aqueous emulsion
Amount is 10% to 40%；In suspending agent containing 5% to 50% active constituent, preferably its content be 5% to 40%.
Common application method may be selected in use for insecticide of the invention, as cauline leaf is spraying, used for ponds, native
Earth processing and seed treatment etc..For example, when spraying using cauline leaf, the compound indicated by general formula I as active constituent
Can be used concentration range be 1 to 1000 μ g/mL aqueous emulsion, suspending agent, water dispersion granule, missible oil, preferably its concentration be 1 to
500μg/mL。
The difluoromethyl pyrazole 9 oxime derivate of the connection pyrrazole structure disclosed by the invention containing pyridine has harmful insect excellent
Control efficiency, therefore can be used to prepare the insecticide for fields such as agricultural, gardening.
Specific embodiment
Above scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.Implementation condition used in the examples can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1:
4mmol IIIa, 1mL triethylamine and 20mL n,N-Dimethylformamide (DMF) are added in 50mL round-bottomed flask,
Under ice bath stirring, the mixed solution of II a and the 2mL DMF of 6mmol is slowly added dropwise thereto.Drop finishes, and is heated to 90 DEG C, reaction 8
Hour.Decompression boils off solvent, and residue obtains I a of target compound through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3)
δ:8.54(dd,J1=4.8Hz, J2=1.6Hz, 1H, Py-H), 8.26 (s, 1H, CH=N), 8.23 (s, 1H, Pyrazole-H),
7.98(dd,J1=8.4Hz, J2=1.6Hz, 1H, Py-H), 7.50~7.53 (m, 1H, Py-H), 7.33 (d, J=9.2Hz, 2H,
), Ar-H 6.78~7.04 (m, 3H, Ar-H and CHF2),3.78(s,3H,CH3).
Embodiment 2:
In 50mL round-bottomed flask, 3mmol IIIb, 2mL pyridine and 25mL methylene chloride is added.Under ice bath stirring, Xiang Qi
In be slowly added dropwise 4.5mmol II a and 2mL methylene chloride mixed solution.Drop finishes, and continues ice bath stirring 12 hours.Decompression is steamed
Solvent is removed, residue obtains I b of target compound through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3)δ:8.51(dd,J1
=4.8Hz, J2=1.6Hz, 1H, Py-H), 8.10 (s, 1H, CH=N), 7.94 (dd, J1=8.0Hz, J2=1.6Hz, 1H, Py-
), H 7.46~7.49 (m, 1H, Py-H), 7.28 (s, 1H, Pyrazole-H), 7.25 (d, J=9.2Hz, 1H, Ar-H), 7.13
~7.15 (m, 1H, Ar-H), 6.70~6.96 (m, 3H, Ar-H and CHF2),3.75(s,3H,CH3).
Embodiment 3:
In 100mL round-bottomed flask, 6mmol IIIc, 12mmol sodium acetate and 30mL chloroform is added.It is stirred at room temperature
Under, the mixed solution of the IIa and 3mL chloroform of 8mmol is slowly added dropwise thereto.Drop finishes, and continues to be stirred at room temperature 26 hours.Subtract
Pressure boils off solvent, and residue obtains I c of target compound through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3)δ:8.51
(dd,J1=4.8Hz, J2=1.6Hz, 1H, Py-H), 8.02 (s, 1H, CH=N), 7.94 (dd, J1=8.0Hz, J2=1.6Hz,
1H, Py-H), 7.47~7.50 (m, 1H, Py-H), 7.26 (s, 1H, Pyrazole-H), 7.04~7.20 (m, 3H, Ar-H),
6.68~6.99 (m, 2H, Ar-H and CHF2),3.81(s,3H,CH3).
Embodiment 4:
In 50mL round-bottomed flask, 3mmol IIId, 2mL triethylamine and 20mL tetrahydrofuran (THF), ice bath stirring is added
Under, the mixed solution of II b and the 2mL THF of 4.5mmol is slowly added dropwise thereto.Drop finishes, and continues ice bath and reacts 10 hours.Subtract
Pressure boils off solvent, and residue obtains I d of target compound through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3)δ:8.51
(dd,J1=4.8Hz, J2=1.6Hz, 1H, Py-H), 8.08 (s, 1H, CH=N), 7.93 (dd, J1=8.0Hz, J2=1.2Hz,
1H, Py-H), 7.45~7.48 (m, 1H, Py-H), 7.25 (s, 1H, Pyrazole-H), 6.64~7.04 (m, 6H, Ar-H and
CHF2),3.76(s,3H,CH3).
Embodiment 5:
In 100mL round-bottomed flask, 8mmol IIIe, 16mmol sodium bicarbonate and 40mL acetonitrile is added.Under ice bath stirring,
The mixed liquor of II b and the 4mL acetonitrile of 10mmol is slowly added dropwise thereto.Drop finishes, and heating reflux reaction 20 hours.Decompression boils off
Solvent, residue obtain I e of target compound through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3)δ:8.52(dd,J1=
4.8Hz,J2=1.6Hz, 1H, Py-H), 8.10 (s, 1H, CH=N), 7.94 (dd, J1=8.4Hz, J2=1.6Hz, 1H, Py-
), H 7.62 (d, J=8.8Hz, 2H, Ar-H), 7.45~7.48 (m, 1H, Py-H), 7.26 (s, 1H, Pyrazole-H), 6.64
~6.96 (m, 4H, Ar-H and CHF2),3.74(s,3H,CH3).
Embodiment 6:
Sample screens the insecticidal activity of mythimna separata
The leaf dipping method for using international resistance Action Committee (IRAC) to propose: for examination target for mythimna separata, i.e., by appropriate corn
Leaf dries in the shade naturally after sufficiently infiltrating in the medical fluid prepared, is put into the culture dish for being lined with filter paper, connects mythimna separata 3 age mid-term larva 10
Head/ware is placed in 24-27 DEG C of observation ward and cultivates, investigation result after 2d.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Test
500 μ g/mL of concentration.
Insecticidal activity test result shows that all compounds show preferable mythimna separate.It is in proof load
When 500 μ g/mL (table 1), the e of chemical compounds I a~I is respectively 100%, 100%, 100% to the killing effect of mythimna separata, 100% He
100%.
The insecticidal activity data of table 1.Ia-Ie
The above experimental data shows that pyridine, which is joined pyrazole structural unit, reasonably to be combined with pyrazoles oxime activity unit one
It rises, obtained noval chemical compound shows good bioactivity, and the type compound is optional to be used as desinsection guide, makees further
Structure derivative and structure activity study.These experimental datas are also to continue to be engaged in the molecule of novel pyrazole oxime compound from now on to set
Meter, synthesis provide important theoretical foundation with bioactivity research.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel only illustrate the present invention it should be appreciated that the present invention is not limited by examples detailed above described in examples detailed above and specification
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its is equal
Object defines.
Claims (4)
1. a kind of difluoromethyl pyrazole 9 oxime derivate (I) of the connection pyrrazole structure containing pyridine, it is characterised in that have such as flowering structure:
2. a kind of preparation method of the difluoromethyl pyrazole 9 oxime derivate I of the connection pyrrazole structure containing pyridine as described in claim 1,
It is characterized in that method is as follows:
3. the difluoromethyl pyrazole 9 oxime derivate I of the connection pyrrazole structure containing pyridine is preparing insecticide side as described in claim 1
The purposes in face, it is characterised in that: the compound is used alone；Or using compound I in claim 1 as active constituent, in addition this
The common insecticides adjuvant in field be processed into aqueous emulsion, suspending agent, water dispersion granule, missible oil the mode of Pesticidal combination make
With.
4. the difluoromethyl pyrazole 9 oxime derivate I of the connection pyrrazole structure containing pyridine is preparing insecticide side as claimed in claim 3
The purposes in face, it is characterised in that: when compound I is used as the active constituent in insecticide, content in the insecticide can be
It is selected in the range of 0.1% to 99.5%.
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Cited By (7)
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| CN110305115A (en) * | 2019-08-19 | 2019-10-08 | 南通大学 | The preparation and application of pyrazoles 9 oxime derivate of the one kind containing 1- (6- chloropyrazine -2- base) -3- methoxyl group pyrazoles unit |
| CN110746356A (en) * | 2019-11-28 | 2020-02-04 | 南通大学 | Preparation method and application of difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure |
| CN110804040A (en) * | 2019-11-25 | 2020-02-18 | 南通大学 | Preparation method and application of pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl |
| CN110845412A (en) * | 2019-11-28 | 2020-02-28 | 南通大学 | Preparation and application of pyrazole oxime compound containing 1-methyl-3-difluoromethyl-5-chloropyrazole unit |
| CN110845478A (en) * | 2019-11-25 | 2020-02-28 | 南通大学 | Preparation and use of pyrazole formyloxime derivatives containing 1-substituted pyridyl-3-trifluoromethylpyrazole units |
| CN111518079A (en) * | 2020-06-04 | 2020-08-11 | 南通大学 | Preparation and application of pyrazole derivative containing N-pyridyl-3-pyrazolophenylmethoxypyrazole unit |
| CN111925359A (en) * | 2020-08-31 | 2020-11-13 | 南通大学 | Preparation method and application of pyrazole derivative containing 1, 3-disubstituted pyrazole group |
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| CN110305115A (en) * | 2019-08-19 | 2019-10-08 | 南通大学 | The preparation and application of pyrazoles 9 oxime derivate of the one kind containing 1- (6- chloropyrazine -2- base) -3- methoxyl group pyrazoles unit |
| CN110804040A (en) * | 2019-11-25 | 2020-02-18 | 南通大学 | Preparation method and application of pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl |
| CN110845478A (en) * | 2019-11-25 | 2020-02-28 | 南通大学 | Preparation and use of pyrazole formyloxime derivatives containing 1-substituted pyridyl-3-trifluoromethylpyrazole units |
| CN110746356A (en) * | 2019-11-28 | 2020-02-04 | 南通大学 | Preparation method and application of difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure |
| CN110845412A (en) * | 2019-11-28 | 2020-02-28 | 南通大学 | Preparation and application of pyrazole oxime compound containing 1-methyl-3-difluoromethyl-5-chloropyrazole unit |
| CN110746356B (en) * | 2019-11-28 | 2021-06-29 | 南通大学 | Preparation method and application of difluoromethyl pyrazole oxime ester containing 3-trifluoromethyl-5-chloropyrazole structure |
| CN110845412B (en) * | 2019-11-28 | 2021-11-23 | 南通大学 | Preparation and application of pyrazole oxime compound containing 1-methyl-3-difluoromethyl-5-chloropyrazole unit |
| CN111518079A (en) * | 2020-06-04 | 2020-08-11 | 南通大学 | Preparation and application of pyrazole derivative containing N-pyridyl-3-pyrazolophenylmethoxypyrazole unit |
| CN111518079B (en) * | 2020-06-04 | 2022-07-12 | 南通大学 | Preparation and application of pyrazole derivative containing N-pyridyl-3-pyrazolophenylmethoxypyrazole unit |
| CN111925359A (en) * | 2020-08-31 | 2020-11-13 | 南通大学 | Preparation method and application of pyrazole derivative containing 1, 3-disubstituted pyrazole group |
| CN111925359B (en) * | 2020-08-31 | 2022-07-12 | 南通大学 | Preparation method and application of pyrazole derivative containing 1, 3-disubstituted pyrazole group |
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