CN104557710B - The preparation and application of the pyrazoles oxime compound of the pyrrazole structure containing multi-substituent - Google Patents
The preparation and application of the pyrazoles oxime compound of the pyrrazole structure containing multi-substituent Download PDFInfo
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- CN104557710B CN104557710B CN201410820503.3A CN201410820503A CN104557710B CN 104557710 B CN104557710 B CN 104557710B CN 201410820503 A CN201410820503 A CN 201410820503A CN 104557710 B CN104557710 B CN 104557710B
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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
Abstract
The present invention relates to the preparation and application of a kind of pyrazoles oxime compound (I) of pyrrazole structure containing multi-substituent.It is condensed to yield with the oxime of hydroxyl containing pyrazoles (II) and methyl bromide (chlorine) intermediate (III) of 1,3 dimethyl, 5 aryloxy group pyrazoles 4.The pyrazoles oxime compound I of the pyrrazole structure containing multi-substituent has effective prevention effect to harmful insect, and the compound can be used for the insecticide for preparing the fields such as agricultural, gardening.
Description
Technical field
The invention belongs to pesticide field, and in particular to a kind of pyrazoles oxime compound of pyrrazole structure containing multi-substituent and its
Preparation method and purposes.
Background technology
The preventing and treating of insect is the key areas of pesticide science research all the time, and insecticide is widely used so that most of
Insect obtains effectively preventing.
Pyrazoles oximes structure is a kind of common biocidal activity fragment, wherein representative compound fenpyroximate, and it is available
To prevent and treat a variety of phytophagous mites, such as red spider, fistula mite, leeched line mite.
With the extensive use of fenpyroximate, the resistance to the action of a drug is generated to fenpyroximate with country, some insects in some areas, together
When, new insect pest continuously emerges again, and this causes the research and development that continues of novel pesticide to turn into inevitable choice.
By the way that by the combination of multi-substituent pyrazole heterocycle group and pyrazoles oxime, being expected to obtain has the new of insecticidal activity
Compound.
The content of the invention
It is an object of the invention to provide there is excellent prevention effect for various insects, and efficiently, it is safe, environment-friendly
The pyrazoles oxime compound of a kind of pyrrazole structure containing multi-substituent, to meet crop protection to efficient pesticides demand.
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：
The pyrazoles oxime compound of the pyrrazole structure of the present invention containing multi-substituent, it is characterised in that possess such as the institute of formula I
The structure shown：
Wherein, the position of substitution represents with 2~4 or 2 '~4 ' on phenyl ring；
R1(or R2) it is H, Cl, Br, F, I, CH3, OCH3Or OCF3In a kind of group monosubstituted base, or appoint to be above-mentioned
Two kinds of groups of meaning form disubstituted；
R1(or R2) the position of substitution on phenyl ring can be in 2 (2 ') positions or 3 (3 ') positions or 4 (4 ') positions.
The pyrazoles oxime compound preparation method of such pyrrazole structure containing multi-substituent, it is characterised in that shown in formula I
Compound is by formula II and 1,3- dimethyl -5- aryloxy group-pyrazoles -4- methyl bromides (chlorine) intermediate (III) under acid binding agent effect
It is condensed to yield in aprotic polar solvent：
Wherein, the position of substitution represents with 2~4 or 2 '~4 ' on phenyl ring；
R1(or R2) it is H, Cl, Br, F, I, CH3, OCH3Or OCF3In a kind of group monosubstituted base, or appoint to be above-mentioned
Two kinds of groups of meaning form disubstituted；
R1(or R2) the position of substitution on phenyl ring can be in 2 (2 ') positions or 3 (3 ') positions or 4 (4 ') positions.
Acid binding agent is：Pyridine, sodium acid carbonate, triethylamine, diisopropylethylamine (DIEA), 4-N, N- lutidines
(DMAP), sodium carbonate, potassium carbonate and cesium carbonate；The dosage of acid binding agent be usually compound mole shown in formula II 1.2~
15 times.
Wherein aprotic polar solvent is：DMF (DMF), DMA (DMA),
DMSO, Isosorbide-5-Nitrae-dioxane, acetonitrile and hexamethyl phosphoramide (HMPA).
Wherein the mole of compound III is 0.95~1.6 times of the compound mole of formula II.
The compound reference literature of formula II (Eur.J.Med.Chem., (2013) 60,376-385；
Bioorg.Med.Chem.Lett., 2005 (15), 3307-3312.) method synthesize to obtain；
Compound of Formula I has excellent preventing and treating 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.Described insect has mythimna separata, Tetranychus cinnabarinus etc..Certainly, compound of the invention can
The harmful organism of preventing and treating is not limited to the scope of the example above.
When the compound of the invention represented by 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 component, it is processed into plus insecticides adjuvant commonly used in the art
Aqueous emulsion, suspending agent, water dispersion granule, missible oil etc..
Conventional 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 aliphatic acid；Conventional superficiality agent
Such as emulsifying agent and dispersant, including anion surfactant, cationic surfactant, nonionic surfactant and both sexes
Surfactant；Other auxiliary agents, such as wetting agent, thickener.
When the compound of the invention 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 appropriate work can be determined 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%；Containing 5% to 50% active component in suspending agent, preferably its content is 5% to 40%.
Use for the insecticide of the present invention, conventional application method may be selected, such as cauline leaf spraying, used for ponds, native
Earth processing and seed treatment etc..For example, when using cauline leaf spraying, the compound that is represented by formula I as active component
Aqueous emulsion, suspending agent, water dispersion granule, the missible oil that concentration range is 1 to 1000 μ g/mL can be used.
The pyrazoles oxime compound of the pyrrazole structure disclosed by the invention containing multi-substituent has excellent anti-to harmful insect
Effect is controlled, therefore can be used to prepare the insecticide for fields such as agricultural, gardening.
Embodiment
For the ease of being further appreciated that to the present invention, examples provided below has done more detailed description to it.This
A little embodiments are only not used for limiting the scope of the present invention or implementation principle for narration.
Embodiment 1：
Chemical compounds I a synthesis (X=Cl, R1=H, R2=4-Cl)
Pyrazoles oxime intermediate II a 5mmol, 1,3- dimethyl -5- phenoxy groups-pyrazoles -4- methyl chlorides are added in reaction bulb
6mmol the and 25mL acetonitriles of intermediate III, put into 9mmol potassium carbonate thereto under stirring, the mixture of gained is heated to reflux into 12
Hour.Stop heating.Filtering, by mother liquor concentrations to doing, silica gel mixed sample dress post separation purifies to obtain a of object I.1H NMR
(400MHz,CDCl3):δ 7.61 (s, 1H, CH=N), 7.30-7.34 (m, 2H, ArH), 7.09-7.20 (m, 3H, ArH), 6.89
(d, J=8.0Hz, 2H, Ar-H), 6.83 (d, J=8.0Hz, 2H, Ar-H), 4.67 (s, 2H, CH2),3.60(s,3H,N-CH3),
3.55(s,3H,N-CH3),2.36(s,3H,CH3),2.25(s,3H,CH3).
Embodiment 2：
Chemical compounds I b synthesis (reference compound Ia synthesis, wherein X=Cl, R1=4-Cl, R2=4-Cl)
Pyrazoles oxime intermediate II b 4mmol, 13- dimethyl -5- phenoxy groups-pyrazoles -4- methyl chlorides are added in reaction bulb
4.4mmol the and 15mL DMF of intermediate III, put into 5mmol cesium carbonates, the mixture of gained are heated to reflux thereto under stirring
12 hours.Stop heating.Filtering, by mother liquor concentrations to doing, chromatographic column separating-purifying obtains the b of object I.1H NMR(400MHz,
CDCl3):δ 7.59 (s, 1H, CH=N), 7.27 (d, J=8.0Hz, 2H, Ar-H), 7.19 (d, J=8.0Hz, 2H, Ar-H),
6.82 (d, J=8.0Hz, 4H, Ar-H), 4.65 (s, 2H, CH2),3.59(s,3H,N-CH3),3.55(s,3H,N-CH3),2.33
(s,3H,CH3),2.24(s,3H,CH3).
Embodiment 3：
Chemical compounds I c synthesis (reference compound Ia synthesis, wherein X=Br, R1=3-F, R2=4-Cl)
Pyrazoles oxime intermediate II c 3mmol, 1,3- dimethyl -5- phenoxy groups-pyrazoles -4- methyl bromides are added in reaction bulb
The 4.4mmol of intermediate III and 25mL1,4- dioxane, 18mmol 4-N, TMSDMA N dimethylamine yl pyridines are put under stirring thereto
(DMAP) mixture of gained, is heated into 80 DEG C to react 19 hours.Stop heating.Filtering, concentrates the filtrate to dry, chromatographic column
Separating-purifying obtains the c of object I.1H NMR(400MHz,CDCl3):δ 7.60 (s, 1H, CH=N), 7.20 (d, J=8.0Hz,
2H,Ar-H),6.98-7.02(m,2H,Ar-H),6.82-6.87(m,4H,Ar-H),4.67(s,2H,CH2),3.60(s,3H,
N-CH3),3.56(s,3H,N-CH3),2.35(s,3H,CH3),2.26(s,3H,CH3).
Embodiment 4：
Chemical compounds I d synthesis (reference compound Ia synthesis, wherein X=Br, R1=4-OCF3,R2=4-Cl)
Pyrazoles oxime intermediate II d 2mmol, 1,3- dimethyl -5- phenoxy groups-pyrazoles -4- methyl bromides are added in reaction bulb
3mmol the and 15mL DMAs of intermediate III, put into 5mmol potassium carbonate thereto under stirring, by the mixing of gained
Thing is to slowly warm up to 80 DEG C and reacted 16 hours, after being cooled to room temperature, filtering, collects filtrate, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography
Final product Id.1H NMR(400MHz,CDCl3):δ 7.61 (s, 1H, CH=N), 7.17-7.21 (m, 4H, ArH), 6.90 (d, J
=12.0Hz, 2H, Ar-H), 6.83 (d, J=8.0Hz, 2H, Ar-H), 4.64 (s, 2H, CH2),3.61(s,3H,N-CH3),
3.56(s,3H,N-CH3),2.34(s,3H,CH3),2.24(s,3H,CH3).
Embodiment 5：
Chemical compounds I e synthesis (reference compound Ia synthesis, wherein X=Br, R1=2-Cl, R2=2,4-Cl2)
Pyrazoles oxime intermediate II e 4mmol, 1,3- dimethyl -5- phenoxy groups-pyrazoles -4- methyl bromides are added in reaction bulb
5.6mmol the and 20mL DMSO of intermediate III, put into 6mmol potassium carbonate thereto under stirring, the mixture of gained is heated into 80
DEG C reaction 18 hours, stop heating.Filtering, by mother liquor concentrations to doing, silica gel mixed sample dress post separation purifies to obtain the e of object I.1H
NMR(400MHz,CDCl3):δ 7.56 (s, 1H, CH=N), 7.46 (d, J=8.0Hz, 1H, Ar-H), 7.40 (s, 1H, ArH),
7.00-7.18(m,3H,Ar-H),6.66-6.71(m,2H,Ar-H),4.64(s,2H,CH2),3.63(s,3H,N-CH3),3.58
(s,3H,N-CH3),2.34(s,3H,CH3),2.23(s,3H,CH3).
Embodiment 6：
Chemical compounds I f synthesis (reference compound Ia synthesis, wherein X=Br, R1=2-F, R2=2,4-Cl2)
Pyrazoles oxime intermediate II f 6mmol, 1,3- dimethyl -5- phenoxy groups-pyrazoles -4- methyl bromides are added in reaction bulb
8mmol the and 30mL Isosorbide-5-Nitraes of intermediate III-dioxane, put into 18mmol pyridines, the mixture of gained are added thereto under stirring
Hot to 85 DEG C are reacted 13 hours, stop heating.Filtering, by mother liquor concentrations to doing, silica gel mixed sample dress post separation purifies to obtain target
The f of thing I.1H NMR(400MHz,CDCl3):δ 7.57 (s, 1H, CH=N), 7.40 (s, 1H, ArH), 7.16-7.20 (m, 1H, Ar-
H),6.98-7.09(m,3H,Ar-H),6.68-6.77(m,2H,Ar-H),4.62(s,2H,CH2),3.65(s,3H,N-CH3),
3.57(s,3H,N-CH3),2.32(s,3H,CH3),2.23(s,3H,CH3).
Embodiment 7：
Sample screens to the insecticidal activity of Tetranychus cinnabarinus
The spray-on process proposed using international resistance Action Committee (IRAC).It is Tetranychus cinnabarinus for examination target.It will be connected to
The Broad Bean Leaves of Tetranychus cinnabarinus spraying treatment under Potter spray towers, Tetranychus cinnabarinus is placed in 24~27 DEG C of observation ward after processing
Cultivate, investigation result after 48h.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.The μ g/mL of initial trial concentration 500 are (other dense
The decoction of degree can be diluted and be obtained by 500 μ g/mL decoction).
Embodiment 8：
Sample screens to the insecticidal activity of mythimna separata
The leaf dipping method proposed using international resistance Action Committee (IRAC).It is mythimna separata for examination target, will appropriate corn
Leaf dries in the shade naturally after fully being infiltrated in the decoction prepared, is put into the culture dish for being lined with filter paper, connects mythimna separata 3 age mid-term larva 10
Head/ware, it 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.Initially
The μ g/mL of experimental concentration 500 (decoction of other concentration can be diluted and be obtained by 500 μ g/mL decoction).
Table 1.Ia-If insecticidal activity data (Mortality, %)
Insecticidal activity test result shows that partial target thing shows good killing activity to Tetranychus cinnabarinus, works as test
When concentration is 500 μ g/mL, wherein chemical compounds I b is to the prevention effect of Tetranychus cinnabarinus up to 75%；When test concentrations are 500 μ g/mL
When, wherein chemical compounds I f shows certain inhibitory action to mythimna separata.Data above shows, is introduced in pyrazoles oxime cellular construction
With multi-substituent pyrazoles active fragment, some objects of gained show inhibition, partization to Tetranychus cinnabarinus, mythimna separata
Compound can make further in-depth study as agricultural chemicals guide.
Claims (4)
1. the pyrazoles oxime compound of a kind of pyrrazole structure containing multi-substituent, it is characterised in that structure is：
2. a kind of preparation method of the pyrazoles oxime compound of pyrrazole structure containing multi-substituent as claimed in claim 1, it is special
Sign is that method is as follows：
3. use of the pyrazoles oxime compound of the pyrrazole structure containing multi-substituent in terms of insecticide is prepared as claimed in claim 1
On the way, it is characterised in that：The compound is used alone；Or using compound in claim 1 as active component, plus commonly used in the art
Insecticides adjuvant be processed into aqueous emulsion, suspending agent, water dispersion granule, the mode of Pesticidal combination of missible oil and use.
4. use of the pyrazoles oxime compound of the pyrrazole structure containing multi-substituent in terms of insecticide is prepared as claimed in claim 3
On the way, it is characterised in that：When compound described in claim 1 is used as the active component of insecticide, containing in the insecticide
Amount is selected in the range of 0.1% to 99.5%.
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| CN105753856B (en) * | 2016-03-08 | 2019-01-22 | 南通大学 | A kind of preparation and application of the difluoromethyl pyrazole class compound of the structure of oxadiazoles containing 1,3,4- |
| CN106432081B (en) * | 2016-07-26 | 2020-03-31 | 南通大学 | Preparation method and application of pyrazole oxime ether compound containing 4-chloro-3-ethyl-1-methylpyrazole structure |
| CN106243039B (en) * | 2016-07-29 | 2020-03-31 | 南通大学 | Preparation method and application of pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure |
| CN106432216B (en) * | 2016-08-01 | 2019-09-20 | 南通大学 | The preparation method and application of the pyrazol acid amide compounds of the isoxazole structure of aryl containing 5- |
| CN106946782B (en) * | 2017-02-08 | 2019-09-24 | 南通大学 | Pyrazole Oxime Esters of the biphenyl structures containing pyrazoles and its preparation method and application |
| 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 |
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| EP0361827A1 (en) * | 1988-09-29 | 1990-04-04 | Sumitomo Chemical Company, Limited | Pyrazole compounds, method for production thereof, use thereof and intermediates for production thereof |
| EP0391685A1 (en) * | 1989-04-07 | 1990-10-10 | Ube Industries, Ltd. | Pyrazoleoxime derivatives and insecticides, acaricides and fungicides |
| WO2006000311A1 (en) * | 2004-06-26 | 2006-01-05 | Merial Ltd. | 1-arylpyrazole derivatives pesticidal agents |
| CN1844103A (en) * | 2006-03-22 | 2006-10-11 | 南开大学 | Pyrazol oxime ether derivatives and preparation process and use thereof |
| CN104193683A (en) * | 2014-07-25 | 2014-12-10 | 南通大学 | Pyrazole oxime derivative containing dichloropropene as well as preparation method and application method of derivative |
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| EP0361827A1 (en) * | 1988-09-29 | 1990-04-04 | Sumitomo Chemical Company, Limited | Pyrazole compounds, method for production thereof, use thereof and intermediates for production thereof |
| EP0391685A1 (en) * | 1989-04-07 | 1990-10-10 | Ube Industries, Ltd. | Pyrazoleoxime derivatives and insecticides, acaricides and fungicides |
| WO2006000311A1 (en) * | 2004-06-26 | 2006-01-05 | Merial Ltd. | 1-arylpyrazole derivatives pesticidal agents |
| CN1844103A (en) * | 2006-03-22 | 2006-10-11 | 南开大学 | Pyrazol oxime ether derivatives and preparation process and use thereof |
| CN104193683A (en) * | 2014-07-25 | 2014-12-10 | 南通大学 | Pyrazole oxime derivative containing dichloropropene as well as preparation method and application method of derivative |
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