CN109879867A - A kind of preparation and application of the Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure - Google Patents
A kind of preparation and application of the Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure Download PDFInfo
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- CN109879867A CN109879867A CN201910169236.0A CN201910169236A CN109879867A CN 109879867 A CN109879867 A CN 109879867A CN 201910169236 A CN201910169236 A CN 201910169236A CN 109879867 A CN109879867 A CN 109879867A
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- oxazole
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- oxime esters
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- pyrazole oxime
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Abstract
The present invention relates to the preparations and application of a kind of Pyrazole Oxime Esters (I) of the oxazole of aryl containing 5- structure.It is condensed to yield with 5- aryl oxazole -2- methyl chloride (II) and pyrazoles oxime (III).The Pyrazole Oxime Esters of the oxazole of aryl containing the 5- structure 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 a kind of Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure
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 Pyrazole Oxime Esters important contain as a kind of
Nitrogen heterocyclic has excellent desinsection, mite killing isoreactivity, and wherein typicalness compound has fenpyroximate, in pesticide field
It plays an important role in terms of desinsection.
In recent years, there are some researchs to report Pyrazole Oxime Esters and show good insecticidal action.Such as Dai is closed
At the Pyrazole Oxime Esters A and B of the heterocycle structure containing thiadiazoles 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).
Disliking azole compounds is also a kind of important nitrogen-containing heterocycle compound, has good bioactivity, raw in agricultural
It has a wide range of applications in production.
Therefore, it in order to further find the compound with excellent bioactivity from Pyrazole Oxime Esters, uses
Oxazole group and pyrazoles oxime skeleton are reasonably engaged togather by active group joining method, and the invention discloses one kind to have
The Pyrazole Oxime Esters of the oxazole structure of aryl containing 5- 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
The Pyrazole Oxime Esters of one kind oxazole structure of aryl containing 5-, 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 ether of the oxazole of aryl containing 5- structure
Class compound, with general formula I,
Preferably, the Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure have the following structure:
The present invention provides the preparation method of the Pyrazole Oxime Esters of the above-mentioned oxazole of aryl containing 5- structure, 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, R1:F；Cl；R2:Cl；Br；OCH3。
Preferably, the acid binding agent is selected from cesium carbonate, 4-dimethylaminopyridine (DMAP), sodium bicarbonate, potassium carbonate, N, N-
Diisopropylethylamine (DIEA)；The organic solvent is selected from n,N-Dimethylformamide (DMF), 2- butanone, acetonitrile, acetone.Add
Thermal response temperature is 35 DEG C~120 DEG C, and the reaction time is 9 hours~28 hours.
Preferably, the preparation method of the Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure, includes the following steps:
Wherein, intermediate substituted-phenyl connection oxazole methyl chloride can refer to the side of document (Molecules, 2017,22,1925)
Method synthesizes to obtain；The conventional method of the synthesis reference literature report of intermediate pyrazole oxime
(Bioorg.Med.Chem.Lett.2016,26,4504–4507)。
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 Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure disclosed by the invention 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:
5mmol compound III a is dissolved in 30mL DMF, 15mmol 4-dimethylaminopyridine (DMAP) then is added, room temperature
Under the conditions of intermediate II a 4mmol is added thereto, finish, be heated to 120 DEG C, react 28 hours.Reaction solution is cooled to room
Temperature filters, and mother liquor is concentrated under reduced pressure, and gained residue obtains target compound Ia through column chromatographic isolation and purification；1H NMR(400MHz,
CDCl3): δ 7.85 (s, 1H, CH=N), 7.59~7.62 (m, 2H, Ar-H), 7.25 (s, 1H, Oxazole-H), 7.04~
7.23 (m, 4H, Ar-H), 6.90 (s, 1H, Ar-H), 6.75~6.78 (m, 1H, Ar-H), 5.10 (s, 2H, CH2),3.63(s,
3H,CH3),2.38(s,3H,CH3).
Embodiment 2:
5mmol compound III b is dissolved in 25mL 2- butanone, 15mmol sodium bicarbonate is then added, under room temperature to it
Middle addition intermediate II a 6mmol, finishes, and is heated to 35 DEG C, reacts 15 hours.Reaction solution is cooled to room temperature, is filtered, mother liquor
It is concentrated under reduced pressure, gained residue obtains target compound Ib through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3):δ7.85
(s, 1H, CH=N), 7.59~7.62 (m, 2H, Ar-H), 7.21~7.24 (m, 3H, Ar-H and Oxazole-H), 7.09~
7.13 (m, 2H, Ar-H), 6.81 (d, J=9.2Hz, 2H, Ar-H), 5.09 (s, 2H, CH2),3.59(s,3H,CH3),2.34(s,
3H,CH3).
Embodiment 3:
4mmol compound III c is dissolved in 30mL acetonitrile, 8mmol potassium carbonate is then added, is added thereto under room temperature
Intermediate II a 5mmol, finishes, and temperature rising reflux 9 hours.Reaction solution is cooled to room temperature, is filtered, mother liquor is concentrated under reduced pressure, gained
Residue obtains target compound Ic through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3): δ 7.85 (s, 1H, CH=N),
7.59~7.62 (m, 2H, Ar-H), 7.37 (d, J=8.8Hz, 2H, Ar-H), 7.24 (s, 1H, Oxazole-H), 7.09~
7.14 (m, 2H, Ar-H), 6.75 (d, J=9.2Hz, 2H, Ar-H), 5.08 (s, 2H, CH2),3.58(s,3H,CH3),2.34(s,
3H,CH3).
Embodiment 4:
5mmol compound III d is dissolved in 30mL acetone, under room temperature thereto be added 8mmol intermediate II b and
20mmol n,N-diisopropylethylamine (DIEA), finishes, and is heated to reflux 18 hours.Stop reaction, extremely by reaction solution vacuum rotary steam
Dry, gained residue obtains target compound Id through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3):δ7.74(s,1H,CH
=N), 7.49 (d, J=8.8Hz, 2H, Ar-H), 7.31 (d, J=8.4Hz, 2H, Ar-H), 7.22 (s, 1H, Oxazole-H),
6.74(s,4H,Ar-H),5.04(s,2H,CH2),3.68(s,3H,OCH3),3.53(s,3H,N-CH3),2.28(s,3H,
CH3).
Embodiment 5:
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 6:
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 d of chemical compounds I a~I is respectively 90%, 100%, 100% and 100% to the killing effect of mythimna separata；Compound
The d of I a~I is 100% to the insecticidal activity of aphid.
The preliminary insecticidal activity data of table 1.Ia-Id
The above experimental data shows reasonably to splice oxazole heterocycle structure and pyrazoles oxime skeleton, and what is obtained is novel
Compound shows that good biological activity, these experimental datas are also to continue to be engaged in novel pyrazole oximido ether compound from now on simultaneously
Molecule synthesis and bioactivity research 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. a kind of Pyrazole Oxime Esters (I) of the oxazole of aryl containing 5- structure, it is characterised in that structure are as follows:
2. a kind of preparation method of the Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure as described in claim 1, special
Sign is that method is as follows:
3. the Pyrazole Oxime Esters I of the oxazole of aryl containing 5- structure 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 Pyrazole Oxime Esters I of the oxazole of aryl containing 5- structure 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 (3)
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| 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 |
| CN110407828A (en) * | 2019-08-19 | 2019-11-05 | 南通大学 | A kind of pyrazoles -5- amide derivatives of the structure containing oxazole and its preparation method and application |
| CN110437221A (en) * | 2019-08-27 | 2019-11-12 | 南通大学 | The pyrazole derivatives and its preparation method and application of the oxadiazoles unit of methyl containing aryloxy group |
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Cited By (5)
| 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 |
| CN110407828A (en) * | 2019-08-19 | 2019-11-05 | 南通大学 | A kind of pyrazoles -5- amide derivatives of the structure containing oxazole and its preparation method and application |
| CN110407828B (en) * | 2019-08-19 | 2022-03-08 | 南通大学 | Pyrazole-5-amide derivative containing oxazole structure and preparation method and application thereof |
| CN110437221A (en) * | 2019-08-27 | 2019-11-12 | 南通大学 | The pyrazole derivatives and its preparation method and application of the oxadiazoles unit of methyl containing aryloxy group |
| CN110437221B (en) * | 2019-08-27 | 2021-11-16 | 南通大学 | Pyrazole derivative containing aryloxy methyl oxadiazole unit and preparation method and application thereof |
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