CN110003184A - The preparation and application of pyrazoles oxime derivatives of the one kind containing 1,2,4- triazole structures - Google Patents
The preparation and application of pyrazoles oxime derivatives of the one kind containing 1,2,4- triazole structures Download PDFInfo
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- CN110003184A CN110003184A CN201910104423.0A CN201910104423A CN110003184A CN 110003184 A CN110003184 A CN 110003184A CN 201910104423 A CN201910104423 A CN 201910104423A CN 110003184 A CN110003184 A CN 110003184A
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- Prior art keywords
- triazole
- compound
- oxime derivatives
- pyrazoles oxime
- insecticide
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Classifications
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The present invention relates to the preparations and application of a kind of pyrazoles oxime derivatives (I) containing 1,2,4- triazole structures.It is condensed to yield with 1,2,4- triazole Biphenylmethyl chlorine (II) with pyrazoles oxime (III).The pyrazoles oxime derivatives for containing 1,2,4- triazole structures have effective control efficiency to harmful insect, which is used to prepare the insecticide in the fields such as agricultural, gardening.
Description
Technical field
The present invention relates to chemical pesticide fields, and in particular to one kind contains the pyrazoles oxime derivatives of 1,2,4- triazole structures
Preparation and application.
Background technique
Prevention and treatment and inhibition insect pest are the core contents of pesticide science research field.Various types of insecticides are widely used
Insect pest is set to be constantly in controllable state.But the scale used with insecticide constantly expands and uses the gradually increasing of time
Long, pest starts to develop drug resistance to traditional pesticide gradually or even cross-resistance.In addition as new insect pest constantly goes out
It is existing, so that the research and development that continues of novel pesticide becomes inevitable choice.
Nitrogen-containing heterocycle compound is widely used in terms of agricultural production, and pyrazoles oxime compound is as a kind of important nitrogenous
Heterocyclic compound has excellent desinsection, mite killing isoreactivity, and wherein typicalness compound has fenpyroximate, in killing for pesticide field
It plays an important role in terms of worm.
In recent years, there are some researchs to report pyrazoles oxime derivatives and show good insecticidal action.Such as Dai synthesis
The pyrazoles oxime compound A and B containing 1,3,4- thiadiazoles heterocycle structures to show excellent desinsection to aphid, diamondback moth etc. living
Property, when proof load is 100 μ g/mL, compound A and B is 100% to the killing activity of aphid；Compound A and B are to small
The killing rate of diamond-back moth are respectively 60% and 100% (Bioorg.Med.Chem.Lett.2016,26,3818-3821).
1,2,4- triazole compound is also a kind of important nitrogen-containing heterocycle compound, has good bioactivity,
It has a wide range of applications in agricultural production.
Therefore, in order to further find the compound with excellent bioactivity from pyrazoles oxime derivatives, using work
1,2,4- triazole group, is reasonably engaged togather, the invention discloses one by property group joining method with pyrazoles oxime skeleton
Class has the pyrazoles oxime derivatives containing 1,2,4- triazole structures of agricultural insecticidal application value.
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
One kind contains the pyrazoles oxime derivatives of 1,2,4- triazole structures, to meet crop protection to efficient pesticides demand.
It is a further object of the present invention to provide the preparation methods of above compound.
A further object of the present invention is to provide purposes of the above compound in terms of preparing insecticide.
In order to solve the above technical problems, the first aspect of the present invention provides a kind of pyrazoles oxime for containing 1,2,4- triazole structures
Analog derivative, with general formula I,
Preferably, the pyrazoles oxime derivatives containing 1,2,4- triazole structures have the following structure:
The present invention provides the preparation method of the above-mentioned pyrazoles oxime derivatives for containing 1,2,4- triazole structures, it is characterised in that
Include the following steps:
Compound III is dissolved in organic solvent, acid binding agent is added, then intermediate II, finally heated one section of reaction is being added
Time filters after being cooled to room temperature reaction solution, and mother liquor is concentrated under reduced pressure, and gained residue obtains target through column chromatographic isolation and purification
Compound,
Wherein, R:Br；F；OCF3；CH3；3,5-F2。
Preferably, the acid binding agent is selected from cesium carbonate, 4-dimethylaminopyridine (DMAP), potassium carbonate, sodium carbonate, three second
Amine；The organic solvent is selected from n,N-Dimethylformamide (DMF), 2- butanone, acetonitrile, acetone, tetrahydrofuran (THF).Heating
Reaction temperature is 35 DEG C~105 DEG C, and the reaction time is 10 hours~26 hours.
Preferably, the preparation method of the pyrazoles oxime derivatives containing 1,2,4- triazole structures, includes the following steps:
Wherein, intermediate 1,2,4- triazole diphenylmethyl chlorine can refer to document (J.Med.Chem.1998,41,
2390-2410；Chin.Chem.Lett.2014,25,1014-1016 method) synthesizes to obtain；The synthesis of intermediate pyrazole oxime
The conventional method (Bioorg.Med.Chem.Lett.2016,26,4504-4507) of reference literature report.
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 pyrazoles oxime derivatives of the triazole structure disclosed by the invention containing 1,2,4- prevent harmful insect with excellent
Effect is controlled, 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 compound III a is dissolved in 30mL DMF, 6mmol cesium carbonate is then added, is added thereto under room temperature
Intermediate II 5mmol, finishes, and is heated to 105 DEG C, reacts 18 hours.Reaction solution is cooled to room temperature, is filtered, mother liquor decompression is dense
Contracting, gained residue obtain target compound Ia through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3):δ8.59(s,1H,
), Triazole-H 8.12 (s, 1H, Triazole-H), 7.82 (s, 1H, CH=N), 7.63 (d, J=8.4Hz, 2H, Ar-H),
7.37~7.41 (m, 4H, Ar-H), 6.76 (d, J=9.2Hz, 2H, Ar-H), 5.01 (s, 2H, CH2),3.60(s,3H,CH3),
2.34(s,3H,CH3).
Embodiment 2:
5mmol compound III b is dissolved in 25mL 2- butanone, 15mmol 4-dimethylaminopyridine (DMAP) then is added,
Intermediate II 4mmol is added thereto under room temperature, finishes, temperature rising reflux, reacts 12 hours.Reaction solution is cooled to room
Temperature filters, and mother liquor is concentrated under reduced pressure, and gained residue obtains target compound Ib through column chromatographic isolation and purification；1H NMR(400MHz,
CDCl3): δ 8.56 (s, 1H, Triazole-H), 8.11 (s, 1H, Triazole-H), 7.82 (s, 1H, CH=N), 7.62 (d, J
=8.4Hz, 2H, Ar-H), 7.41 (d, J=8.4Hz, 2H, Ar-H), 6.99~7.19 (m, 3H, Ar-H), 6.73~6.77 (m,
1H,Ar-H),5.01(s,2H,CH2),3.65(s,3H,CH3),2.34(s,3H,CH3).
Embodiment 3:
6mmol compound III c is dissolved in 30mL acetonitrile, 20mmol potassium carbonate is then added, is added thereto under room temperature
Enter intermediate II 8mmol, finish, temperature rising reflux reacts 10 hours.Reaction solution is cooled to room temperature, is filtered, mother liquor decompression is dense
Contracting, gained residue obtain target compound Ic through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3):δ8.58(s,1H,
), Triazole-H 8.12 (s, 1H, Triazole-H), 7.83 (s, 1H, CH=N), 7.63 (d, J=8.4Hz, 2H, Ar-H),
7.41 (d, J=8.4Hz, 2H, Ar-H), 7.16 (d, J=8.8Hz, 2H, Ar-H), 6.89 (d, J=8.8Hz, 2H, Ar-H),
5.00(s,2H,CH2),3.62(s,3H,CH3),2.35(s,3H,CH3).
Embodiment 4:
8mmol compound III d is dissolved in 30mL acetone, under room temperature thereto be added 10mmol intermediate II and
16mmol sodium carbonate, finishes, and is warming up to 35 DEG C, reacts 16 hours.Stop reaction, by reaction solution vacuum rotary steam to doing, gained is residual
Excess obtains target compound Id through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3):δ8.57(s,1H,Triazole-
), H 8.11 (s, 1H, Triazole-H), 7.82 (s, 1H, CH=N), 7.62 (d, J=8.4Hz, 2H, Ar-H), 7.43 (d, J=
8.0Hz, 2H, Ar-H), 6.76~7.10 (m, 4H, Ar-H), 5.05 (s, 2H, CH2),3.59(s,3H,CH3),2.36(s,3H,
CH3),2.30(s,3H,CH3).
Embodiment 5:
10mmol compound III e is dissolved in 30mL tetrahydrofuran, 13mmol intermediate II is added thereto under room temperature
And 22mmol triethylamine, it finishes, reacts at room temperature 26 hours.Stop reaction, by reaction solution vacuum rotary steam to dry, gained residue warp
Column chromatographic isolation and purification obtains target compound Ie；1H NMR(400MHz,CDCl3):δ8.56(s,1H,Triazole-H),8.12
(s, 1H, Triazole-H), 7.85 (s, 1H, CH=N), 7.62 (d, J=8.4Hz, 2H, Ar-H), 7.40 (d, J=8.4Hz,
2H, Ar-H), 6.40~6.56 (m, 3H, Ar-H), 5.02 (s, 2H, CH2),3.61(s,3H,CH3),2.35(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 3d.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Test
500 μ g/mL of concentration.
Embodiment 15:
Sample screens the insecticidal activity of aphid
The spray-on process for using international resistance Action Committee (IRAC) to propose: for examination target for aphid, i.e., aphid will be connected to
Broad Bean Leaves under Potter spray tower spraying treatment, aphid is placed in 20-22 DEG C of observation ward and cultivates after processing, adjusts after 48h
Come to an end fruit.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.500 μ g/mL of experimental concentration.
Insecticidal activity test result shows that all compounds all show preferable insecticidal activity.It is 500 in test concentrations
When μ g/mL (table 1), the e of chemical compounds I a~I is 100% to the killing effect of mythimna separata；The e of chemical compounds I a~I is living to the desinsection of aphid
Property is respectively 100%, 60%, 100%, 100% and 100%.
The preliminary insecticidal activity data of table 1.Ia-Ie
The above experimental data shows reasonably to be spliced 1,2,4- triazole heterocyclic structure and pyrazoles oxime skeleton, obtains
To new compound show good biological activity, these experimental datas are simultaneously also to continue to be engaged in novel pyrazole oximes from now on
The molecule synthesis and bioactivity research of derivative provide important structure choice mode and theoretical foundation.
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. the pyrazoles oxime derivatives (I) that one kind contains 1,2,4- triazole structures, it is characterised in that structure are as follows:
2. a kind of preparation method of the pyrazoles oxime derivatives containing 1,2,4- triazole structures as described in claim 1, special
Sign is that method is as follows:
3. the pyrazoles oxime derivatives I containing 1,2,4- triazole structures is in terms of preparing insecticide as described in claim 1
Purposes, it is characterised in that: the compound is used alone；Or using compound I in claim 1 as active constituent, in addition this field
Common insecticides adjuvant be processed into aqueous emulsion, suspending agent, water dispersion granule, missible oil the mode of Pesticidal combination use.
4. the pyrazoles oxime derivatives I containing 1,2,4- triazole structures is in terms of preparing insecticide as claimed in claim 3
Purposes, it is characterised in that: when compound I is used as the active constituent of insecticide, content in the insecticide can 0.1% to
It is selected in the range of 99.5%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357872A (en) * | 2019-08-14 | 2019-10-22 | 南通大学 | A kind of pyrazoles oxime compound and its preparation method and application of the structure of substituted-phenyl containing thiazole |
| CN111269225A (en) * | 2020-03-25 | 2020-06-12 | 南通大学 | Pyrazole derivative containing pyridyl pyrazole structural unit and preparation method and application thereof |
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| CN111269225A (en) * | 2020-03-25 | 2020-06-12 | 南通大学 | Pyrazole derivative containing pyridyl pyrazole structural unit and preparation method and application thereof |
| CN111269225B (en) * | 2020-03-25 | 2022-12-27 | 南通大学 | Pyrazole derivative containing pyridyl pyrazole structural unit and preparation method and application thereof |
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Application publication date: 20190712 |