CN106432081A - Preparation method and application of pyrazole oxime ether compound containing 4-Cl-3-ethyl-1-methylpyrazole structure - Google Patents
Preparation method and application of pyrazole oxime ether compound containing 4-Cl-3-ethyl-1-methylpyrazole structure Download PDFInfo
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- CN106432081A CN106432081A CN201610594091.5A CN201610594091A CN106432081A CN 106432081 A CN106432081 A CN 106432081A CN 201610594091 A CN201610594091 A CN 201610594091A CN 106432081 A CN106432081 A CN 106432081A
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- ethyl
- methylpyrazole
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- oxime ether
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- 0 CCc1n[n](C)c(C(NCc(cc2)ccc2Oc2ccc(C)cc2)=*)c1Cl Chemical compound CCc1n[n](C)c(C(NCc(cc2)ccc2Oc2ccc(C)cc2)=*)c1Cl 0.000 description 1
- RJIXMRGJBHLKHR-OVCLIPMQSA-N Cc1n[n](C)c(Cc(cc2)ccc2Cl)c1/C=N/O Chemical compound Cc1n[n](C)c(Cc(cc2)ccc2Cl)c1/C=N/O RJIXMRGJBHLKHR-OVCLIPMQSA-N 0.000 description 1
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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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- 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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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a pyrazole oxime ether compound (I) containing a 4-Cl-3-ethyl-1-methylpyrazole structure, a preparation method thereof and the application thereof. The pyrazole oxime ether compound (I) is prepared through the condensation reaction of pyrazole oxime (II) and 4-Cl-5-methyl chloride-3-ethyl-1-methylpyrazole (III). The pyrazole oxime ether compound (I) containing the 4-Cl-3-ethyl-1-methylpyrazole structure has the control effect on harmful insects. The above compound can be used for preparing pesticides in the fields of agriculture, gardening and the like.
Description
Technical field
The invention belongs to pesticide field, and in particular to a kind of pyrazoles oxime ether containing the chloro- 3- ethyl -1- methylpyrazole structure of 4-
Compound and its production and use.
Background technology
The preventing and treating of insect is the core realm of pesticide science research all the time, the widely using so that most evil of insecticide
Worm has obtained effective improvement.But the continuous expansion with insecticide application scale, the resistance problems of traditional pesticide species are increasingly
Highlight, add the emergence of new pest and disease damage so that the continuation research and development of novel pesticide becomes inevitable choice.
Pyrazoles oxime compound is the important nitrogen-containing heterocycle compound of a class, and its representation compound such as fenpyroximate, in pesticide
Play an important role in terms of the parasite killing in field.
There are some researchs to report pyrazoles oxime derivatives in recent years and there is good insecticidal effect, the research such as such as Dai is sent out
Existing compound A and B shows killing activity to acarid, diamondback moth etc..When test concentrations are 200 μ g/mL, compound A and B pair
The prevention effect of acarid is respectively 95% and 90%；Compound A and B is respectively 100% and 86% to the prevention effect of diamondback moth
(Chin.Chem.Lett.2014,25,1014-1016)；The pyrazoles 9 oxime derivate C containing pyridine heterocycle structure of the reports such as Fu and D
There is good inhibiting effect to aphid, acarid, compound C when proof load is for 10mg/L, the kill rate to Tetranychus urticae
For 95%, compound D when proof load is for 50mg/L, be 89% to the kill rate of aphid (Pest Manage.Sci.2014,
70,1207-1214).
Pyrazole ring is widely used in terms of agricultural production, and pyrazole compound has parasite killing, mite killing isoreactivity, pyrazole ring knot
Structure is widely incorporated in pesticide molecule design, the pyrazole heterocycle class insecticidal/acaricidal agent azoles of such as Mitsubishi chemical company exploitation
Insect amide, to aphid, Prodenia litura etc. with excellent killing activity.
Therefore, in order to find the heterocyclic pesticide having compared with high bioactivity, with pyrazoles oxime ring as skeleton, reasonably by pyrazoles
Oxime is stitched together with substituted pyrazolecarboxylic heterocyclic units, is therefrom expected to obtain the noval chemical compound with insecticidal activity.
Content of the invention
It is an object of the invention to provide for various insects there is excellent prevention effect, and efficiently, safe, eco-friendly
Azoles oxime ether compound of one class containing the chloro- 3- ethyl -1- methylpyrazole structure of 4-, to meet crop protection to efficient pesticides need
Ask.
It is a further object of the present invention to provide the preparation method of above-claimed cpd.
It is a still further object of the present invention to provide purposes of the above-claimed cpd in terms of insecticide is prepared.
The object of the invention can be reached by following measures：
Pyrazoles oxime ether compound containing the chloro- 3- ethyl -1- methylpyrazole structure of 4- of the present invention, it is characterised in that tool
Standby such as structure：
4. structure：
Such pyrazoles oxime ether compound preparation method containing the chloro- 3- ethyl -1- methylpyrazole heterocycle of 4-, it is characterised in that change
I a～I h of compound can be obtained by following being synthesized：
Wherein, intermediate II a～II h can refer to document (J.Agric.Food Chem.2008,56,10805-10810)
Method synthesis obtain；Intermediate III synthesis reference literature report conventional method (J.Agric.Food Chem.2012,
60,1470-1479).
Compound of Formula I has excellent preventing and treating activity to insecticide, thus the compound of the present invention can be used as preparing parasite killing
Agent, and then the plant such as protecting agriculture, gardening.Described insecticide has mythimna separata, planthopper and aphid etc..Certainly, the chemical combination of the present invention
The harmful organism that thing can be prevented and treated is not limited to the scope of the example above.
When the compound of the present invention for being represented by formula I is used as the insecticide in the field such as agricultural, gardening, individually can make
With, or used in the way of Pesticidal combination, such as with Formulas I as active component, add insecticides adjuvant commonly used in the art and be processed into
Aqueous emulsion, suspending agent, water dispersion granule, cream etc..
Conventional insecticides adjuvant includes:Liquid-carrier, such as water；Organic solvent such as toluene, dimethylbenzene, Hexalin, methanol, fourth
Alcohol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and plant oil and fatty acid；Conventional superficiality agent
As emulsifying agent and dispersant, including anion surfactant, cationic surfactant, nonionic surfactant and both sexes
Surfactant；Other auxiliary agents, such as wetting agent, thickening agent etc..
When the compound of the present invention for being represented by formula I is used as the active component in insecticide, in the insecticide
Content can be selected in the range of 0.1% to 99.5%, and can determine appropriate work according to dosage form and application process
Property component content.Generally, in aqueous emulsion containing the active component described in 5% to 50% (percentage by weight, similarly hereinafter), preferably its
Content is 10% to 40%；The active component containing 5% to 50% in suspending agent, preferably its content are 5% to 40%.
For the use of the insecticide of the present invention, conventional application method is may be selected, such as stem and leaf spraying, used for ponds, native
Earth process and seed treatment etc..For example, when using stem and leaf spraying, as the compound that represented by formula I of active component
Can concentration scope be the aqueous emulsion of 1 to 1000 μ g/mL, suspending agent, water dispersion granule, cream, preferably its concentration be 1 to
500μg/mL.
Pyrazole Oxime Esters containing the chloro- 3- ethyl -1- methylpyrazole heterocycle structure of 4- disclosed by the invention are to harmful
Insecticide shows excellent prevention effect, therefore can be used to prepare the insecticide for fields such as agricultural, gardening.
Specific embodiment
For the ease of further appreciating that to the present invention, examples provided below has done more detailed description to which.This
A little embodiments are not used for limiting the scope of the present invention or implementation principle only for narration.
Embodiment 1：
4mmol compound ii a is dissolved in 20mL acetonitrile, 8mmol Anhydrous potassium carbonate and III 6mmol of intermediate is subsequently added,
Temperature rising reflux reacts 12 hours.Reactant liquor is cooled to after room temperature, sucking filtration, solid is filtered off, mother solution vacuum rotary steam is to doing, and gained is residual
Excess obtains target compound Ia through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3):δ 7.71 (s, 1H, CH=N),
7.07-7.11(m,1H,Ar-H),6.67-6.99(m,3H,Ar-H),4.96(s,2H,CH2),3.90(s,3H,OCH3),3.78
(s,3H,N-CH3),3.61(s,3H,N-CH3), 2.61 (q, J=7.6Hz, 2H, CH2),2.34(s,3H,CH3),1.22(t,J
=7.6Hz, 3H, CH3).
Embodiment 2：
10mmol compound ii b is dissolved in 30mL acetonitrile, is subsequently added 15mmol Anhydrous potassium carbonate and intermediate III
13mmol, temperature rising reflux reacts 16 hours.Reactant liquor is cooled to after room temperature, sucking filtration, solid is filtered off, mother solution vacuum rotary steam is extremely
Dry, gained residue obtains target compound Ib through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3):δ7.73(s,1H,
), CH=N 6.82 (s, 4H, Ar-H), 4.98 (s, 2H, CH2),3.79(s,3H,OCH3),3.78(s,3H,N-CH3),3.59(s,
3H,N-CH3), 2.62 (q, J=7.6Hz, 2H, CH2),2.35(s,3H,CH3), 1.22 (t, J=7.6Hz, 3H, CH3).
Embodiment 3：
6mmol compound ii c is dissolved in the DMF of 25mL drying, is subsequently added 10mmol Anhydrous potassium carbonate and intermediate III
9mmol, is warming up to 85 DEG C, reacts 18 hours.Reactant liquor is cooled to after room temperature, is poured in 80mL water, is extracted with ethyl acetate,
Anhydrous sodium sulfate drying, column chromatographic isolation and purification obtains target compound Ic.1H NMR(400MHz,CDCl3):δ7.76(s,1H,
), CH=N 7.18 (d, J=8.8Hz, 2H, Ar-H), 6.90 (d, J=9.2Hz, 2H, Ar-H), 4.95 (s, 2H, CH2),3.78
(s,3H,N-CH3),3.60(s,3H,N-CH3), 2.61 (q, J=7.6Hz, 2H, CH2),2.35(s,3H,CH3),1.22(t,J
=7.6Hz, 3H, CH3).
Embodiment 4：
8mmol compound ii d is dissolved in the DMF of 30mL drying, is subsequently added 20mmol Anhydrous potassium carbonate and intermediate III
10mmol, is warming up to 85 DEG C, reacts 17 hours.Reactant liquor is cooled to after room temperature and is poured in 80mL water, be extracted with ethyl acetate,
Anhydrous sodium sulfate drying, column chromatographic isolation and purification obtains target compound Id.1H NMR(400MHz,CDCl3):δ7.69(s,1H,
), CH=N 7.23 (d, J=7.2Hz, 1H, Ar-H), 6.99-7.10 (m, 2H, Ar-H), 6.52 (d, J=8.0Hz, 1H, Ar-
H),4.96(s,2H,CH2),3.76(s,3H,N-CH3),3.58(s,3H,N-CH3), 2.61 (q, J=7.6Hz, 2H, CH2),
2.38(s,3H,CH3),2.36(s,3H,CH3), 1.22 (t, J=7.6Hz, 3H, CH3).
Embodiment 5：
5mmol compound ii e is dissolved in the DMSO of 25mL drying, is subsequently added 10mmol natrium carbonicum calcinatum and intermediate III
7mmol, is warming up to 90 DEG C, reacts 20 hours.Reactant liquor is cooled to after room temperature and is poured in 80mL water, be extracted with ethyl acetate,
Anhydrous sodium sulfate drying, column chromatographic isolation and purification obtains target compound Ie.1H NMR(400MHz,CDCl3):δ7.75(s,1H,
), CH=N 7.28 (d, J=9.2Hz, 2H, Ar-H), 6.83 (d, J=8.8Hz, 2H, Ar-H), 4.96 (s, 2H, CH2),3.78
(s,3H,N-CH3),3.59(s,3H,N-CH3), 2.62 (q, J=7.6Hz, 2H, CH2),2.35(s,3H,CH3),1.22(t,J
=7.6Hz, 3H, CH3).
Embodiment 6：
10mmol compound ii f is dissolved in 25mL acetonitrile, is subsequently added 20mmol natrium carbonicum calcinatum and intermediate III
11mmol, temperature rising reflux reacts 18 hours.Reactant liquor is cooled to after room temperature, sucking filtration, solid is filtered off, mother solution vacuum rotary steam is extremely
Dry, gained residue obtains target compound If through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3):δ7.75(s,1H,
), CH=N 7.42 (d, J=9.2Hz, 2H, Ar-H), 6.77 (d, J=8.8Hz, 2H, Ar-H), 4.96 (s, 2H, CH2),3.78
(s,3H,N-CH3),3.59(s,3H,N-CH3), 2.62 (q, J=7.6Hz, 2H, CH2),2.35(s,3H,CH3),1.22(t,J
=7.6Hz, 3H, CH3).
Embodiment 7：
4mmol compound ii g is dissolved in 30mL acetonitrile, 9mmol Carbon Dioxide caesium and III 6mmol of intermediate is subsequently added,
Temperature rising reflux reacts 21 hours.Reactant liquor is cooled to after room temperature, sucking filtration, solid is filtered off, mother solution vacuum rotary steam is to doing, and gained is residual
Excess obtains target compound Ig through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3):δ 7.77 (s, 1H, CH=N),
6.94-6.98(m,2H,Ar-H),6.50-6.53(m,1H,Ar-H),4.95(s,2H,CH2),3.79(s,3H,N-CH3),3.65
(s,3H,N-CH3), 2.61 (q, J=7.6Hz, 2H, CH2),2.34(s,3H,CH3), 1.22 (t, J=7.6Hz, 3H, CH3).
Embodiment 8：
10mmol compound ii h is dissolved in 25mL acetonitrile, is subsequently added 18mmol Anhydrous potassium carbonate and intermediate III
13mmol, temperature rising reflux reacts 16 hours.Reactant liquor is cooled to after room temperature, sucking filtration, solid is filtered off, mother solution vacuum rotary steam is extremely
Dry, gained residue obtains target compound Ih through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3):δ7.74(s,1H,
), CH=N 7.12-7.47 (m, 2H, Ar-H), 6.61 (d, J=8.8Hz, 1H, Ar-H), 4.95 (s, 2H, CH2),3.78(s,
3H,N-CH3),3.62(s,3H,N-CH3), 2.62 (q, J=7.6Hz, 2H, CH2),2.34(s,3H,CH3), 1.22 (t, J=
7.6Hz,3H,CH3).
Embodiment 9：
Sample is screened to the insecticidal activity of mythimna separata
The leaf dipping method for being proposed using international resistance Action Committee (IRAC)：It is mythimna separata for trying target, will Semen Maydiss in right amount
Leaf is dried in the shade after fully infiltrating in the medicinal liquid for preparing naturally, is put into and is lined with the culture dish of filter paper, connects mythimna separata 3 age mid-term larva 10
Head/ware, is placed in 24-27 DEG C of observation indoor cultivation, survey result after 2d.Polypide is touched with brush pen, reactionless is considered as dead worm.Test
500 μ g/mL of concentration (medicinal liquid of other concentration can be diluted by the medicinal liquid of 500 μ g/mL and obtain).
Embodiment 10：
Sample is screened to the insecticidal activity of aphid and brown paddy plant hopper
The nebulization for being proposed using international resistance Action Committee (IRAC)：It is aphid and Brown Planthopper for trying target,
I.e. respectively by the Broad Bean Leaves for being connected to aphid and the rice seedlings that are connected to brown paddy plant hopper under the Potter spray tower spraying treatment, after process
Tetranychus cinnabarinus and brown paddy plant hopper are placed in 24-27 DEG C of observation indoor cultivation, and aphid is placed in 20-22 DEG C of observation indoor cultivation, investigates after 48h
As a result.Polypide is touched with brush pen, reactionless is considered as dead worm.(medicinal liquid of other concentration can be by 500 μ g/ for 500 μ g/mL of experimental concentration
The medicinal liquid of mL dilutes and obtains).
Insecticidal activity test result shows, all compounds all show preferable insecticidal activity.It is 500 in proof load
During μ g/mL (table 1), compounds I a, I f, I g and I h are respectively 100%, 80%, 80% and 80% to the killing effect of mythimna separata；Change
I a of compound, I b, I c, I e, I f and I g are respectively 100%, 80%, 80%, 100%, 70% and 80% to the killing effect of aphid；
I b, I d and I f are respectively 80%, 80% and 80% to the suppression ratio of brown paddy plant hopper.
The insecticidal activity data of table 1.Ia-Ih
Above experimental data shows, substituted pyrazolecarboxylic heterocycle and pyrazoles oxime activity unit is reasonably combined, is obtained
New compound shows good biological activity, and wherein compounds I a and I f is optional as parasite killing guide, makees further structure and spreads out
Raw and structure activity study.Above experimental data is to continue to be engaged in MOLECULE DESIGN, the synthesis of novel pyrazole oxime compound from now on
Important structure choice pattern and test basis are provided with bioactivity research.
Claims (3)
1. a kind of pyrazoles oxime ether compound containing the chloro- 3- ethyl -1- methylpyrazole structure of 4-, it is characterised in that possess following knot
Structure：
2. a kind of preparation method of the pyrazoles oxime ether compound containing the chloro- 3- ethyl -1- methylpyrazole structure of 4-, it is characterised in that power
Compounds I a～1h shown in sharp claim 1 is obtained by being synthesized as follows：
3. purposes of the compound as shown in claim 1 in terms of insecticide is prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092776A (en) * | 2019-04-30 | 2019-08-06 | 南通大学 | The pyrazoles oxime ester compound and its preparation method and application of the connection polyfluoro pyrrazole structure containing pyridine |
| CN110105334A (en) * | 2019-04-30 | 2019-08-09 | 南通大学 | The preparation and application of pyrazol oxime ether derivatives containing 1- (3- chloropyridine -2- base) -3- trifluoromethyl pyrazol structure |
| CN110128410A (en) * | 2019-04-30 | 2019-08-16 | 南通大学 | Pyrazole Oxime Esters of the structure containing difluoromethyl pyrazole and its preparation method and application |
| CN110357820A (en) * | 2019-08-14 | 2019-10-22 | 南通大学 | A kind of pyrazoles oxime ether compound of -3- of methyl containing 1- substituted phenyl pyrazole structure and its preparation method and application |
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| CN104151308A (en) * | 2014-07-03 | 2014-11-19 | 南通大学 | Preparation method and application of 1,2,3-thiadiazole pyrazole oxime ether compounds |
| CN104557710A (en) * | 2014-12-25 | 2015-04-29 | 南通大学 | Preparation and application of pyrazole oxime compound containing multi-substituent pyrazole structure |
| CN105712932A (en) * | 2016-03-08 | 2016-06-29 | 南通大学 | Preparation and application of pyrazole oxime ether compound with 1-methyl-3-aryl-4-chloropyrazole structure |
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| EP0707000A1 (en) * | 1993-06-29 | 1996-04-17 | Nissan Chemical Industries, Limited | Aldoxime derivative and agrohorticultural bactericide |
| CN104151308A (en) * | 2014-07-03 | 2014-11-19 | 南通大学 | Preparation method and application of 1,2,3-thiadiazole pyrazole oxime ether compounds |
| CN104557710A (en) * | 2014-12-25 | 2015-04-29 | 南通大学 | Preparation and application of pyrazole oxime compound containing multi-substituent pyrazole structure |
| CN105712932A (en) * | 2016-03-08 | 2016-06-29 | 南通大学 | Preparation and application of pyrazole oxime ether compound with 1-methyl-3-aryl-4-chloropyrazole structure |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092776A (en) * | 2019-04-30 | 2019-08-06 | 南通大学 | The pyrazoles oxime ester compound and its preparation method and application of the connection polyfluoro pyrrazole structure containing pyridine |
| CN110105334A (en) * | 2019-04-30 | 2019-08-09 | 南通大学 | The preparation and application of pyrazol oxime ether derivatives containing 1- (3- chloropyridine -2- base) -3- trifluoromethyl pyrazol structure |
| CN110128410A (en) * | 2019-04-30 | 2019-08-16 | 南通大学 | Pyrazole Oxime Esters of the structure containing difluoromethyl pyrazole and its preparation method and application |
| CN110092776B (en) * | 2019-04-30 | 2021-09-07 | 南通大学 | Pyrazole oxime ester compound containing pyridine-difluoride pyrazole structure and preparation method and application thereof |
| CN110357820A (en) * | 2019-08-14 | 2019-10-22 | 南通大学 | A kind of pyrazoles oxime ether compound of -3- of methyl containing 1- substituted phenyl pyrazole structure and its preparation method and application |
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