CN110357820A - A kind of pyrazoles oxime ether compound of -3- of methyl containing 1- substituted phenyl pyrazole structure and its preparation method and application - Google Patents
A kind of pyrazoles oxime ether compound of -3- of methyl containing 1- substituted phenyl pyrazole structure and its preparation method and application Download PDFInfo
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- CN110357820A CN110357820A CN201910748536.4A CN201910748536A CN110357820A CN 110357820 A CN110357820 A CN 110357820A CN 201910748536 A CN201910748536 A CN 201910748536A CN 110357820 A CN110357820 A CN 110357820A
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- substituted phenyl
- compound
- phenyl pyrazole
- oxime ether
- ether compound
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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
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
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- Organic Chemistry (AREA)
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- Dentistry (AREA)
- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract
The present invention relates to pyrazoles oxime ether compounds (I) of a kind of -3- of methyl containing 1- substituted phenyl pyrazole structure and its preparation method and application.It is condensed to yield by 1- methyl -3- substituted phenyl pyrazole methyl chloride (II) and pyrazoles hydroxyl oxime (III).The Pyrazole Oxime Esters of-the 3- of methyl containing the 1- substituted phenyl pyrazole structure have 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 a kind of pyrazoles of -3- of methyl containing 1- substituted phenyl pyrazole structure
Oxime ether compound and its preparation method and application.
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.
Substituted pyrazolecarboxylic class compound has wide spectrum biological activity, is widely used in pesticide and field of medicaments.
Pyrazole Oxime Esters are also a kind of important nitrogen-containing heterocycle compounds, and typicalness compound has fenpyroximate,
It is played an important role in terms of the desinsection of pesticide field.
Therefore, it in order to further find the compound with excellent bioactivity from Pyrazole Oxime Esters, uses
1- methyl -3- substituted phenyl pyrazole group and pyrazoles oxime skeleton are reasonably engaged togather by active group joining method, this hair
The bright pyrazoles oxime etherificate for disclosing a kind of -3- substituted phenyl pyrazole structure of methyl containing 1- with agricultural insecticidal application value is closed
Object.
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 pyrazoles oxime ether compound of one kind -3- substituted phenyl pyrazole structure of methyl containing 1-, to meet crop protection to efficient pesticides need
It asks.
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 -3- substituted phenyl pyrazole knot of methyl containing 1-
The pyrazoles oxime ether compound of structure, with general formula I,
Preferably, the pyrazoles oxime ether compound of -3- of methyl containing the 1- substituted phenyl pyrazole structure has the following structure:
The second aspect of the present invention provides the pyrazoles oxime ether compound of the above-mentioned -3- of methyl containing 1- substituted phenyl pyrazole structure
Preparation method comprising 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 isolates and purifies to obtain target compound,
Preferably, the acid binding agent is selected from sodium carbonate, potassium carbonate, cesium carbonate, potassium hydroxide, triethylamine, the solvent choosing
From acetonitrile, DMF, acetone, methanol.Reaction time is 8-20 hours.
Preferably, the pyrazoles oxime ether compound of -3- of methyl containing 1- substituted phenyl pyrazole structure the preparation method is as follows:
Wherein, 1- methyl -3- substituted phenyl pyrazole methyl chloromethylated intermediate can refer to document (J.Med.Chem.1998,41,
2390) method synthesizes to obtain；Conventional method (the J.Agric.Food of the synthesis reference literature report of pyrazoles oxime intermediate
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 pyrazoles oxime ether compound of -3- of methyl containing 1- substituted phenyl pyrazole structure disclosed by the invention 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 compound III a is dissolved in 30mL acetonitrile, 10mmol potassium carbonate is then added, is added thereto under room temperature
Enter 5mmol intermediate II a, finish, is heated to reflux 12 hours.Reaction solution is cooled to room temperature, is filtered, mother liquor is concentrated under reduced pressure, institute
It obtains residue and obtains target compound Ia through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3) δ: 7.79 (s, 1H, CH=N),
7.66~7.70 (m, 2H, Ar-H), 7.27 (s, 1H, Pyrazole-H), 7.08 (t, J=8.8Hz, 2H, Ar-H), 6.91~
6.96 (m, 1H, Ar-H), 6.73~6.81 (m, 2H, Ar-H), 4.89 (s, 2H, CH2),3.88(s,3H,N-CH3),3.66(s,
3H,N-CH3),2.35(s,3H,CH3).
Embodiment 2:
4mmol compound III b is dissolved in 20mL acetonitrile, under room temperature thereto be added intermediate II a 7mmol and
8mmol cesium carbonate.It finishes, heating reflux reaction 15 hours.Stop reaction, by reaction solution vacuum rotary steam to dry, gained residue
Target compound Ib is obtained through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3) δ: 7.79 (s, 1H, CH=N), 7.67~
7.71 (m, 2H, Ar-H), 7.26~7.28 (m, 3H, Ar-H and Pyrazole-H), 7.08 (t, J=8.8Hz, 2H, Ar-
), H 6.84 (d, J=9.2Hz, 2H, Ar-H), 4.91 (s, 2H, CH2),3.88(s,3H,N-CH3),3.61(s,3H,N-CH3),
2.39(s,3H,CH3).
Embodiment 3:
5mmol compound III c is dissolved in 20mL DMF, 5mmol intermediate II b and 1mL is added thereto under room temperature
Triethylamine finishes, and is warming up to 90 DEG C, reacts 16 hours.Stop reaction, by reaction solution vacuum rotary steam to dry, gained residue warp
Column chromatographic isolation and purification obtains target compound Ic；1H NMR(400MHz,CDCl3) δ: 7.76 (s, 1H, CH=N), 7.66 (d, J=
8.4Hz, 2H, Ar-H), 7.35 (d, J=8.8Hz, 2H, Ar-H), 7.26 (s, 1H, Pyrazole-H), 6.83 (s, 4H, Ar-
H),4.93(s,2H,CH2),3.88(s,3H,N-CH3),3.76(s,3H,OCH3),3.61(s,3H,N-CH3),2.39(s,3H,
CH3).
Embodiment 4:
5mmol compound III d is dissolved in 25mL methanol, under room temperature thereto be added 9mmol intermediate II b and
13mmol potassium hydroxide, finishes, and temperature rising reflux reacts 20 hours.Stop reaction, by reaction solution vacuum rotary steam to dry, gained remnants
Object obtains target compound Id through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3) δ: 7.77 (s, 1H, CH=N), 7.66
(d, J=8.4Hz, 2H, Ar-H), 7.35 (d, J=8.4Hz, 2H, Ar-H), 7.26 (s, 1H, Pyrazole-H), 6.99 (t, J
=8.4Hz, 2H, Ar-H), 6.84~6.88 (m, 2H, Ar-H), 4.92 (s, 2H, CH2),3.88(s,3H,N-CH3),3.62(s,
3H,N-CH3),2.38(s,3H,CH3).
Embodiment 5:
3mmol compound III e is dissolved in 25mL DMF, 8mmol sodium carbonate is then added, is added thereto under room temperature
Intermediate II b 4mmol, finishes, and is warming up to 110 DEG C, reacts 8 hours.Stop reaction, reaction solution is poured into and fills 100mL water
It in beaker, is extracted with ethyl acetate for several times, anhydrous sodium sulfate is dry, filters, and mother liquor vacuum rotary steam is to doing, and gained residue is through column
Chromatography purifies to obtain target compound Ie；1H NMR(400MHz,CDCl3) δ: 7.71 (s, 1H, CH=N), 7.57 (d, J=
8.8Hz, 2H, Ar-H), 7.38 (d, J=2.4Hz, 1H, Ar-H), 7.29 (d, J=8.8Hz, 2H, Ar-H), 7.19 (s, 1H,
), Pyrazole-H 7.04~7.07 (m, 1H, Ar-H), 6.57 (d, J=8.8Hz, 1H, Ar-H), 4.82 (s, 2H, CH2),
3.81(s,3H,N-CH3),3.57(s,3H,N-CH3),2.29(s,3H,CH3).
Embodiment 6:
6mmol compound III f is dissolved in 30mL acetone, 20mmol cesium carbonate is then added, is added thereto under room temperature
Enter intermediate II b 5mmol, finish, temperature rising reflux reacts 18 hours.Stop reaction, filters, mother liquor vacuum rotary steam to dry, gained
Residue obtains target compound If through column chromatographic isolation and purification；1H NMR(400MHz,CDCl3) δ: 7.78 (s, 1H, CH=N),
7.66 (d, J=8.4Hz, 2H, Ar-H), 7.41 (d, J=8.8Hz, 2H, Ar-H), 7.36 (d, J=8.4Hz, 2H, Ar-H),
7.26 (s, 1H, Pyrazole-H), 6.78 (d, J=9.2Hz, 2H, Ar-H), 4.91 (s, 2H, CH2),3.88(s,3H,N-
CH3),3.62(s,3H,N-CH3),2.39(s,3H,CH3).
Embodiment 7:
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 the f of chemical compounds I a~I shows excellent to kill mythimna separata effect.In test concentrations
When for 500 μ g/mL (table 1), the f of chemical compounds I a~I is respectively 100%, 100%, 100%, 100% to the insecticidal activity of mythimna separata,
100% and 100%.
The insecticidal activity data of table 1.Ia-If
The above experimental data shows 1- methyl -3- substituted phenyl pyrazole structural unit and pyrazoles oxime activity unit is reasonable
Ground is combined, and obtained noval chemical compound shows good bioactivity, and the type compound is optional first as desinsection
It leads, makees further structure derivative and structure activity study.These experimental datas are also to continue to be engaged in novel pyrazole oxime ethers from now on
MOLECULE DESIGN, synthesis and the bioactivity research of compound provide important 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 pyrazoles oxime ether compound I of -3- of methyl containing 1- substituted phenyl pyrazole structure, it is characterised in that structure are as follows:
2. a kind of preparation of the pyrazoles oxime ether compound I of -3- of methyl containing 1- substituted phenyl pyrazole structure as described in claim 1
Method, it is characterised in that method is as follows:
3. prepared by a kind of pyrazoles oxime ether compound I of -3- of methyl containing 1- substituted phenyl pyrazole structure as described in claim 1
Purposes in terms of insecticide, it is characterised in that: the compound is used alone；Or used in a manner of Pesticidal combination, i.e., to change
Conjunction object I is active constituent, in addition insecticides adjuvant commonly used in the art is processed into aqueous emulsion, suspending agent, water dispersion granule, cream
Oil.
4. prepared by a kind of pyrazoles oxime ether compound I of -3- of methyl containing 1- substituted phenyl pyrazole structure as claimed in claim 3
Purposes in terms of insecticide, it is characterised in that: when compound I is used as the active constituent in insecticide, in the insecticide
Content can be selected in the range of 0.1% to 99.5%.
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Cited By (1)
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