CN104151308B - Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters - Google Patents
Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters Download PDFInfo
- Publication number
- CN104151308B CN104151308B CN201410315416.2A CN201410315416A CN104151308B CN 104151308 B CN104151308 B CN 104151308B CN 201410315416 A CN201410315416 A CN 201410315416A CN 104151308 B CN104151308 B CN 104151308B
- Authority
- CN
- China
- Prior art keywords
- compound
- thiadiazoles
- oxime esters
- preparation
- pyrazole oxime
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- 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)
Abstract
The present invention relates to a kind of preparation and application for containing 1,2,3 thiadiazoles Pyrazole Oxime Esters (I).It is condensed to yield with the oxime of hydroxyl containing pyrazoles (II) with the thiadiazoles (III) of 5 chloromethyl of substitution 1,2,3 substituted.1,2, the 3 thiadiazoles Pyrazole Oxime Esters I that contain have 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 one kind contains 1,2,3- thiadiazoles Pyrazole Oxime Esters and preparation side
Method and purposes.
Background technology
The preventing and treating of insect 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
Highlight, plus the emergence of new pest and disease damage so that the research and development that continues of novel pesticide turns into inevitable choice.
Pyrazole ring and 1,2,3- Thiadiazoles are common in insecticide, acaricide and bactericide, are agricultural chemical compound designs
Active building block.Connecting to be expected to obtain with 1,2,3- Thiadiazoles by pyrazole ring by oxime ether has potential desinsection, sterilizes and kill
The compound of mite activity.
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
One kind contains 1,2,3- thiadiazoles Pyrazole Oxime Esters, 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：
It is of the present invention to contain 1,2,3- thiadiazoles Pyrazole Oxime Esters, it is characterised in that to possess as shown in formula I
Structure：
Wherein, the position of substitution represents with 2~4 on phenyl ring；
R1For H, Cl, Br, F, CH3, OCH3, NO2,CF3Or OCF3；
R2For methyl, ethyl, n-propyl, isopropyl orWherein, R3Selected from H, Cl, F, CH3, OCH3Or CF3)
The preparation method of 1,2, the 3- thiadiazoles Pyrazole Oxime Esters, it is characterised in that the compound shown in formula I
It is condensed to yield as the compound shown in formula II and general formula III under acid binding agent effect in aprotic polar solvent：
Wherein, the position of substitution represents with 2~4 on phenyl ring；
R1For H, Cl, Br, F, CH3, OCH3, NO2,CF3Or OCF3；
R2For methyl, ethyl, n-propyl, isopropyl orWherein, R3Selected from H, Cl, F, CH3, OCH3Or CF3)
Wherein acid binding agent is：Pyridine, picoline, triethylamine, diisopropylethylamine (DIEA), 4-N, N- lutidines
(DMAP), one kind in potassium carbonate or cesium carbonate.The dosage of acid binding agent be usually compound mole shown in formula II 1.5~
10 times.
Wherein aprotic polar solvent is：DMF (DMF), DMA (DMA),
One kind in DMSO, dioxane, acetonitrile or hexamethyl phosphoramide (HMPA).
Wherein the mole of general formula III compound is 0.9~1.9 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；
General formula III compound reference literature (Chinese invention patent：CN101891709) method synthesizes 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 lepidoptera pest such as bollworm, beet armyworm, diamondback moth, dish
Blue or green worm, rice leaf roller and striped rice borer etc., homoptera pest such as leafhopper, plant hopper, earthworm worm, aleyrodid etc., Diptera pest such as housefly,
Liriomyza, mosquito class etc., the insect such as Orthoptera and coleoptera etc..Certainly, the harmful organism that compound of the invention can prevent and treat is unlimited
In 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
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 thiadiazoles containing 1,2,3- disclosed by the invention have excellent preventing and treating effect to harmful insect
Fruit, 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：
Compound Ia synthesis (R in formula II1For 4-C (CH3)3, R in general formula III2For CH3)
In a reaction bulb, 5mmol compound iis, 5.5mmol compound IIIs, 10mmol Carbon Dioxides caesium and 60mL are added
DMF, it is heated to 90 DEG C of reaction 20h.Stop heating, cool down, filter, mother liquor is rotated to doing, and gained residue is with petroleum ether/acetic acid
Ethyl ester (V:V=15:1) it is eluent, target compound Ia, yield 71.4% is separated to obtain by silica gel column chromatography；1HNMR
(400MHz,CDCl3):δ 7.78 (s, 1H, CH=N), 7.31 (d, J=8.8Hz, 2H, Ar-H), 6.80 (d, J=8.4Hz, 2H,
Ar-H),5.22(s,2H,CH2),3.59(s,3H,N-CH3),2.65(s,3H,CH3),2.38(s,3H,CH3),1.30(s,
9H,-C(CH3)3).
Embodiment 2：
Compound Ib synthesis (R in formula II1For 4-OCF3, R in general formula III2For CH3)
In a reaction bulb, 5mmol compound iis, 9mmol compound IIIs, 10mmol DIPEA and 60mLDMSO are added,
It is heated to 90 DEG C of reaction 15h.Stop heating, cooling, mother liquor is rotated to doing, and gained residue is with petrol ether/ethyl acetate (V:V
=15:1) it is eluent, target compound Ib, yield 65.3% is separated to obtain by silica gel column chromatography；1H NMR(400MHz,
CDCl3):δ 7.80 (s, 1H, CH=N), 7.19 (d, J=8.4Hz, 2H, Ar-H), 6.91 (d, J=9.2Hz, 2H, Ar-H),
5.20(s,2H,CH2),3.63(s,3H,N-CH3),2.67(s,3H,CH3),2.39(s,3H,CH3).
Embodiment 3：
Compound Ic synthesis (R in formula II1For 4-F, R in general formula III2For CH3)
In a reaction bulb, 5mmol compound iis, 7.5mmol compound IIIs, 10mmol potassium carbonate and 60mL second are added
Nitrile, heating reflux reaction 20 hours.Stop heating, cool down, filtering, mother liquor is rotated to doing, and gained residue is with petroleum ether/acetic acid
Ethyl ester (V:V=25:1) it is eluent, target compound Ic, yield 60.5% is separated to obtain by silica gel column chromatography；1HNMR
(400MHz,CDCl3):δ 7.76 (s, 1H, CH=N), 6.96-7.00 (m, 2H, Ar-H), 6.82-6.85 (m, 2H, Ar-H),
5.20(s,2H,CH2),3.59(s,3H,N-CH3),2.64(s,3H,CH3),2.35(s,3H,CH3).
Embodiment 4：
Compound Id synthesis (R in formula II1For 3-F, R in general formula III2For CH3)
In a reaction bulb, 5mmol compound iis, 8mmol compound IIIs, 11mmol DMAP and 50mL acetonitriles are added, is added
Hot back flow reaction 18 hours.Stop heating, cool down, filtering, mother liquor is rotated to doing, and gained residue is with petrol ether/ethyl acetate
(V:V=15:1) it is eluent, target compound Id, yield 61.2% is separated to obtain by silica gel column chromatography；1HNMR(400MHz,
CDCl3):δ 7.80 (s, 1H, CH=N), 7.22-7.26 (m, 1H, Ar-H), 6.79-6.83 (m, 1H, Ar-H), 6.61-6.65
(m,2H,Ar-H),5.21(s,2H,CH2),3.60(s,3H,N-CH3),2.64(s,3H,CH3),2.37(s,3H,CH3).
Embodiment 5：
Compound Ie synthesis (R in formula II1For 3-Cl, R in general formula III2For CH3)
In a reaction bulb, 5mmol compound iis, 8mmol compound IIIs, 12mmol DIPEA and 50mL1,4- bis- are added
The ring of oxygen six, it is heated to 90 DEG C of reaction 20h.Stop heating, cooling, mother liquor is rotated to doing, and gained residue is with petroleum ether/acetic acid second
Ester (V:V=15:1) it is eluent, target compound Ie, yield 62.8% is separated to obtain by silica gel column chromatography；1H NMR
(400MHz,CDCl3):δ 7.77 (s, 1H, CH=N), 7.16-7.20 (m, 1H, Ar-H), 7.04 (d, J=7.6Hz, 1H, Ar-
), H 6.86 (s, 1H, Ar-H), 6.72 (d, J=8.0Hz, 1H, Ar-H), 5.17 (s, 2H, CH2),3.57(s,3H,N-CH3),
2.60(s,3H,CH3),2.33(s,3H,CH3).
Embodiment 6：
Compound If synthesis (R in formula II1For 4-I, R in general formula III2For CH3)
In a reaction bulb, 5mmol compound iis, 9mmol compound IIIs, 10mmol DMAP and 50mL DMF are added, is added
Hot to 90 DEG C reaction 16h.Stop heating, cooling, mother liquor is rotated to doing, and gained residue is with petrol ether/ethyl acetate (V:V=
20:1) it is eluent, target compound If, yield 64.6% is separated to obtain by silica gel column chromatography；1H NMR(400MHz,
CDCl3):δ 7.77 (s, 1H, CH=N), 7.58 (d, J=8.8Hz, 2H, Ar-H), 6.65 (d, J=8.8Hz, 2H, Ar-H),
5.19(s,2H,CH2),3.59(s,3H,N-CH3),2.65(s,3H,CH3),2.36(s,3H,CH3).
Embodiment 7：
Synthesis (the R in formula II of Compound Ig per1For 2-CH3, R in general formula III2For n-Pr)
In a reaction bulb, 5mmol compound iis, 7.5mmol compound IIIs, 10mmol Anhydrous potassium carbonates and 60mL are added
Acetonitrile, it is heated to the 20h that flows back.Stop heating, cool down, filter, mother liquor is rotated to doing, and gained residue is with petroleum ether/acetic acid second
Ester (V:V=15:1) it is eluent, target compound Ia is separated to obtain by silica gel column chromatography.Pale yellow oil, yield
54.6%,1H NMR(400MHz,CDCl3):δ 7.71 (s, 1H, CH=N), 7.22 (d, J=6.4Hz, 1H, Ar-H), 7.00~
7.11 (m, 2H, ArH), 6.53 (d, J=8.0Hz, 1H, Ar-H), 5.22 (s, 2H, CH2),3.60(s,3H,N-CH3),2.97
(t, J=7.2Hz, 2H, CH2),2.39(s,3H,CH3), 2.37 (s, 3H, CH3), 1.76~1.86 (m, 2H, CH2),0.98(t,
J=7.2Hz, 3H, CH3).
Embodiment 8：
Sample screens to the insecticidal activity of aphid
A certain amount of medicine is weighed, adds 1mL DMSO to dissolve, adds emulsifying agent TW-20 two to drip, be sufficiently stirred with glass bar, made
Its mutual phased soln, then after adding appropriate distilled water, be sufficiently stirred again, being made into 500 μ g/mL decoction, (decoction of other concentration can
Diluted by 500 μ g/mL decoction and obtained).Plant with aphid is impregnated 5 seconds in above-mentioned decoction, gets rid of unnecessary decoction,
Plant is inserted in water-absorbing sponge, and plant is covered with cloche, is sealed with gauze, is checked respectively for after 24 hours and 48 hours dead
Rate and the statistical correction death rate are died, each compound is repeated 3 times, and control only adds emulsifying agent and solvent, stirring into distilled water
Uniformly.
Embodiment 9：
Sample is to the acaricidal activity screening into mite
When the dwarf bean being for experiment is grown to two panels true leaf, selection growing way is relatively more neat, leaf area 5cm2Left and right, plant height
10cm or so plant connects worm, and every plant of worm amount control is at 120 or so.Connect worm and carry out chemicals treatment after 24 hours.Weigh certain
The medicine sample of amount adds 1mL acetone (or other suitable solvents) in 100mL beakers.Add two drop emulsifying agent TW-20, filled with glass bar
Point stirring, makes its mutual phased soln, then after adding distilled water, is sufficiently stirred again, is made into 200 μ g/mL decoction.Chemicals treatment uses
Plant infusion process, i.e., the plant with tetranychid is impregnated 5 seconds in above-mentioned decoction, after plant is taken out from decoction, gently trembled
It is dynamic, unnecessary decoction is got rid of, is then moved into water planting cylinder, is placed at room temperature.Result is checked respectively for after 24 hours and 48 hours.Often
Individual compound is repeated 3 times, and is averaged.
Embodiment 10：
Sample screens to the insecticidal activity of diamondback moth
The leaf dipping method proposed using international resistance Action Committee (IRAC).Weighed on assay balance 2mg medicines sample in
In 10mL small beakers, add 50 μ L dimethylformamides (pure to analyze) dissolving, add 10mL water that 200 μ g/mL decoctions are made.Use straight peen
Ophthalmology tweezers impregnate cabbage leaves, second time 2-3, get rid of extraction raffinate.1 tablet once, totally 3, each sample.By sample flag sequence
It is successively placed on processing paper.After decoction is dry, it is put into the straight type pipe for having markd 10cm length, accesses 2 age diamondback moth larvaes,
The mouth of pipe is covered with gauze.Test process is placed in standard process chamber, 48h inspection results (chitin inhibitor will be observed 4 days).
Table 1.Ia-Ig insecticidal activity data (Mortality, %)
Insecticidal activity test result shows that partial target thing shows good desinsection and acaricidal activity, works as test concentrations
For 200 μ g/mL when, its chemical compounds I a, I b, I c, I d, I e and I f are respectively 95,100,99,98 to the prevention effect of aphid,
100 and 95%；When test concentrations are 200 μ g/mL, its chemical compounds I a, I c and I e are fine to the inhibiting rate of diamondback moth, reach
100%；When test concentrations are 200 μ g/mL, its chemical compounds I b, I d and I f are to being respectively 80,80 Hes into the inhibiting rate of mite
90%.Data above shows, introduce substituted 1 in pyrazoles oxime activity unit structure, 2,3- thiadiazoles heterocyclic ring expansions its kill
Worm is composed, and part of compounds can be used as pesticide poullant to make further discussion and research.
Claims (4)
1. one kind contains 1,2,3- thiadiazoles Pyrazole Oxime Esters I, it is characterised in that structure is：
2. a kind of preparation method for containing 1,2,3- thiadiazoles Pyrazole Oxime Esters I as claimed in claim 1, its feature exist
It is as follows in method：
3. the Pyrazole Oxime Esters I of thiadiazoles containing 1,2,3- as claimed in claim 1 is in terms of diamondback moth medicine is killed in preparation
Purposes, it is characterised in that：The compound is used alone；Or so that compound I is active component in claim 1, plus ability
The conventional insecticides adjuvant in domain is processed into aqueous emulsion, suspending agent, water dispersion granule, the mode of Pesticidal combination of missible oil and used.
4. the Pyrazole Oxime Esters I of thiadiazoles containing 1,2,3- as claimed in claim 3 is in terms of diamondback moth medicine is killed in preparation
Purposes, it is characterised in that：When compound I described in claim 1 is used as killing the active component of diamondback moth medicine, it is described kill it is small
Content in diamond-back moth medicine is selected in the range of 0.1% to 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410315416.2A CN104151308B (en) | 2014-07-03 | 2014-07-03 | Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410315416.2A CN104151308B (en) | 2014-07-03 | 2014-07-03 | Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104151308A CN104151308A (en) | 2014-11-19 |
| CN104151308B true CN104151308B (en) | 2017-12-29 |
Family
ID=51876966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410315416.2A Expired - Fee Related CN104151308B (en) | 2014-07-03 | 2014-07-03 | Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151308B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2978066A1 (en) * | 2015-03-19 | 2016-09-22 | E I Du Pont De Nemours And Company | Fungicidal pyrazoles |
| 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 |
| CN110003184A (en) * | 2019-02-01 | 2019-07-12 | 南通大学 | The preparation and application of pyrazoles oxime derivatives of the one kind containing 1,2,4- triazole structures |
| CN109879867B (en) * | 2019-03-06 | 2022-03-01 | 南通大学 | Preparation and application of pyrazole oxime ether compound containing 5-aryl oxazole 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 |
| 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 |
| 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 |
| CN111635399B (en) * | 2020-07-01 | 2022-05-03 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108691A (en) * | 1985-12-27 | 1988-01-20 | 日本农药株式会社 | Pyrazole oxime derivatives, process for their preparation and their use |
| EP0707000A1 (en) * | 1993-06-29 | 1996-04-17 | Nissan Chemical Industries, Limited | Aldoxime derivative and agrohorticultural bactericide |
| CN1844103A (en) * | 2006-03-22 | 2006-10-11 | 南开大学 | Pyrazol oxime ether derivatives and preparation process and use thereof |
| CN102442966A (en) * | 2010-10-09 | 2012-05-09 | 南京工业大学 | N-substituted phenyl oxime ether compound containing heterocycle ketone as well as preparation and application to prevention and treatment of plant diseases and insect pests thereof |
-
2014
- 2014-07-03 CN CN201410315416.2A patent/CN104151308B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108691A (en) * | 1985-12-27 | 1988-01-20 | 日本农药株式会社 | Pyrazole oxime derivatives, process for their preparation and their use |
| EP0707000A1 (en) * | 1993-06-29 | 1996-04-17 | Nissan Chemical Industries, Limited | Aldoxime derivative and agrohorticultural bactericide |
| CN1844103A (en) * | 2006-03-22 | 2006-10-11 | 南开大学 | Pyrazol oxime ether derivatives and preparation process and use thereof |
| CN102442966A (en) * | 2010-10-09 | 2012-05-09 | 南京工业大学 | N-substituted phenyl oxime ether compound containing heterocycle ketone as well as preparation and application to prevention and treatment of plant diseases and insect pests thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104151308A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104151308B (en) | Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters | |
| CN104892591B (en) | The preparation method and application of the pyrazoles oxime compound of the oxadiazole heterocycle structure containing 3 aryl 1,2,4 | |
| CN107445947B (en) | One kind containing the pyrazoles oxime ether compound and its preparation method and application of 1,2,3- triazole biphenyl structures | |
| CN104193727B (en) | The preparation and application of Pyrazole Oxime Esters containing trifluoromethyl pyridine | |
| CN106432216B (en) | The preparation method and application of the pyrazol acid amide compounds of the isoxazole structure of aryl containing 5- | |
| CN110092776A (en) | The pyrazoles oxime ester compound and its preparation method and application of the connection polyfluoro pyrrazole structure containing pyridine | |
| CN106946782B (en) | Pyrazole Oxime Esters of the biphenyl structures containing pyrazoles and its preparation method and application | |
| CN104557710B (en) | The preparation and application of the pyrazoles oxime compound of the pyrrazole structure containing multi-substituent | |
| CN110407828A (en) | A kind of pyrazoles -5- amide derivatives of the structure containing oxazole and its preparation method and application | |
| CN110128409A (en) | The preparation and application of the difluoromethyl pyrazole 9 oxime derivate of the connection pyrrazole structure containing pyridine | |
| CN104151309B (en) | Preparation and application containing 1,3,4 thiadiazoles Pyrazole Oxime Esters | |
| CN110105334A (en) | The preparation and application of pyrazol oxime ether derivatives containing 1- (3- chloropyridine -2- base) -3- trifluoromethyl pyrazol structure | |
| CN109678845A (en) | Pyrazole amide analog derivative of the structure containing benzotriazole and its preparation method and application | |
| CN106243039B (en) | Preparation method and application of pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure | |
| CN110407831A (en) | - the 2- of chloropyridine containing N-(3- base) pyrrazole structure pyrazoles oxime ester derivative preparation and application | |
| CN106946856A (en) | Pyrazoles 9 oxime derivate of the biphenyl structures containing tetrazole and its production and use | |
| CN105693710B (en) | The preparation and application of pyrazoles oxime ether compound containing 5- (4- fluorophenyl) isoxazole structure | |
| CN109678846A (en) | Pyrazol acid amide compounds of the triazole structure containing 1,2,3- and its preparation method and application | |
| CN110437221A (en) | The pyrazole derivatives and its preparation method and application of the oxadiazoles unit of methyl containing aryloxy group | |
| CN109879867A (en) | A kind of preparation and application of the Pyrazole Oxime Esters of the oxazole of aryl containing 5- structure | |
| CN106432081A (en) | Preparation method and application of pyrazole oxime ether compound containing 4-Cl-3-ethyl-1-methylpyrazole structure | |
| CN109553605A (en) | Pyrazol acid amide compounds of the biphenyl structures containing tetrazole and its preparation method and application | |
| CN106866649B (en) | The preparation method and application of the pyrazol acid amide compounds of -1,3,4- oxadiazoles structure of aryl containing 5- | |
| CN108976221A (en) | Pyrazoles oxime ether compound of the biphenyl structures of oxadiazoles containing 1,3,4- and its preparation method and application | |
| CN109053713A (en) | Pyrazole Oxime Esters of the biphenyl structures containing oxazole and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171229 Termination date: 20180703 |