CN102267950B - Oxime ether dichloro-allyl ether compounds with insecticidal activity - Google Patents
Oxime ether dichloro-allyl ether compounds with insecticidal activity Download PDFInfo
- Publication number
- CN102267950B CN102267950B CN 201110163149 CN201110163149A CN102267950B CN 102267950 B CN102267950 B CN 102267950B CN 201110163149 CN201110163149 CN 201110163149 CN 201110163149 A CN201110163149 A CN 201110163149A CN 102267950 B CN102267950 B CN 102267950B
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- alkyl
- allyl ether
- ether compounds
- 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.)
- Active
Links
Abstract
The invention discloses oxime ether dichloro-allyl ether compounds (shown in a general formula (I)) with insecticidal activity, a preparation method thereof, an insecticide composition containing the compounds and a method for controlling pests by using the compounds, wherein R, R<1>, n and B are defined in the specification.
Description
The application is for dividing an application
The applying date of original application is: on August 12nd, 2008
Application number is: 200810032058.9
Denomination of invention is: the nitrogen heterocyclic ring dichloro allyl ether compounds of tool insecticidal activity
Technical field
The present invention relates to some and have the bioactive oxime ether of desinsection dichloro allyl ether compounds and its composition, in agricultural and non-agricultural environment, come the method for pest control and their preparation method with them.
Background technology
The control of insect is extremely important in the process that realizes high-efficiency agriculture.The simultaneously control of insect is in forest, chamber crop, ornamental plant, nursery crop, storing food and fiber product, domestic animal, family, and also is important in public health and the animal health.Although existing a lot of pest control agents on the market still need more efficient, safety, economy and the new compound with different modes of action.
SUMITOMO CHEMICAL company discloses the dichloropropylene compound i with insecticidal activity at JP 09194418 among the US 5922880, and has therefrom found the Pyridalyl new pesticides shown in the formula ii, and its trade name is S-1812:
Compound i i has very high susceptibility to lepidoptera pest, also can be mixed with various medicaments, plays synergism.
Have in the bioactive compound process of desinsection designing and synthesizing, we find that the oxime ether dichloropropylene compound that contains 2-alcoxyl (sulphur) yl pyrimidines-4-has good insecticidal activity.Has the bioactive new compound of excellent desinsection for designing and synthesizing, we design and synthesize the oxime ether dichloro allyl ether compounds with the tool insecticidal activity shown in the formula (I) that has no bibliographical information with among the Pyridalyl shown in 2-alcoxyl (sulphur) yl pyrimidines-4-and the oxime ether structure drawing-in system ii.
Summary of the invention
The invention provides oxime ether dichloro allyl ether compounds and all isomer thereof shown in the formula (I):
Wherein
N is 1,2,3 or 4;
R is H or halogen;
R
1H, C
1~ C
6Alkyl, C
1~ C
6Haloalkyl;
B is B-1, B-2 or B-3;
R
2H, halogen, C
1~ C
6Alkyl, C
1~ C
6Haloalkyl;
R
3C
1~ C
6Alkyl, C
1~ C
6Haloalkyl;
R
4R
1Halogen, C
1~ C
6Alkyl, C
1~ C
6Haloalkyl;
X is O, S, SO or SO
2
In the definition of top formula (I), no matter the separately use or be used in the compound word of used term represents following substituting group:
Halogen: refer to fluorine, chlorine, bromine, iodine;
Alkyl: refer to the straight or branched alkyl;
Haloalkyl: refer to the straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom.
Compound of the present invention can one or more steric isomers form exist.Various isomer comprise enantiomorph, diastereomer, geometrical isomer.
The invention still further relates to a kind of formula that contains biologic effective dose (I) compound and at least a other composition that is selected from tensio-active agent, solid diluent and liquid diluent of pest control.
The invention still further relates to a kind of formula that contains biologic effective dose (I) compound and at least a other bioactive compounds of significant quantity or the composition of preparation of pest control.
The invention still further relates to a kind of method of pest control, comprise formula (I) compound contact insect or its environment with biologic effective dose.Also relate to simultaneously a kind of like this insect pest control method, insect or its environment are with formula (I) compound of biologic effective dose or contain at least a other compound of formula (I) compound and biologic effective dose or the mixture of preparation contacts pest control.
Formula of the present invention (I) compound has broad spectrum activity: the compound that has can be used for preventing and treating on the various crops the various harmful insects such as mythimna separata, small cabbage moth, prodenia litura, beet armyworm, leafhopper, aphid; The compound that has can be used for preventing and treating on the various crops the various mite classes such as cotton spider mites, tangerine Panonychus citri, and the compound that has has very high biological activity so that just can obtain good effect under very low dosage.
In view of economy and the biological activity of compound, preferred compound is:
Preferred formula (I) compound, wherein n is 3; R is H; R
1H, methyl; B is 2-(C
1~ C
4Alkoxyl group)-6-trifluoromethyl pyrimidine-4-is basic, 2-(C
1~ C
4Alkylthio)-6-trifluoromethyl pyrimidine-4-is basic, 6-halogen quinoline-2-is basic, 3-fluoro-5-chloropyridine-2-base.
Particularly preferred formula (I) compound, wherein n is 3; R is H; R
1It is methyl; B is 2-oxyethyl group-6-trifluoromethyl pyrimidine-4-base.
The preferred composition of the present invention is the composition that contains above-mentioned preferred compound.Preferred method is to use the method for above-mentioned preferred compound.
Can the present invention be described with the compound of listing in the following table 1.But do not limit the present invention.Among the present invention the fusing point of giving all not calibrated, all compounds all can be observed its molecular ion peak in the table 1 in LC-MS (APCI, Pos) (Agilent 1100Series LC/MSD).Compound in the table 1
1H NMR (Varian INOVA-300spectrometer using tetramethylsilane (TMS) marks in doing) data see Table 2.
Table 1
Table 2
Compound shown in the formula of the present invention (I) can obtain by reaction formula 1-1 or the reaction formula 1-2 shown in following, (II) among the reaction formula 1-1 can obtain by the reaction formula 2 shown in following, (III) in the reaction formula 1 can obtain by the reaction formula 3 shown in following, and (IV) among the reaction formula 1-2 can obtain by the reaction formula 4 shown in following.All such as front restriction, L is leavings group to substituting group wherein, such as bromine etc. except specializing.
Reaction formula 1-1:
Reaction formula 1-2:
Reaction formula 2:
Reaction formula 3:
Reaction formula 4:
The compound of formula (I) can prepare (reaction formula 1-1) like this: at suitable solvent such as N, in the dinethylformamide (DMF), in 10～100 ℃, with suitable alkali such as salt of wormwood, potassium hydroxide, sodium bicarbonate, yellow soda ash, sodium-hydroxide treatment formula (II) and compound (III).
The compound of formula (I) can also prepare (reaction formula 1-2) like this: in suitable solvent such as normal hexane, in room temperature to the solvent refluxing temperature, with suitable alkali such as salt of wormwood, potassium hydroxide, sodium bicarbonate, yellow soda ash, sodium-hydroxide treatment formula (IV) and compound (V).
The compound of formula (II) can prepare (reaction formula 2) like this: in suitable solvent such as methyl alcohol or ethanol, in room temperature to the solvent refluxing temperature, obtain the compound of formula (XI) with the compound of suitable alkali such as salt of wormwood, potassium hydroxide, sodium bicarbonate, yellow soda ash and/or sodium-hydroxide treatment formula (IX) and formula (X), and then in suitable another solvent such as tetracol phenixin, with t-butyl hypochlorate it is carried out the compound that chlorination reaction obtains formula (II).
The compound of formula (III) can prepare according to several different methods, the method of reaction formula 3 is included in suitable alkali such as salt of wormwood, potassium hydroxide, sodium bicarbonate, yellow soda ash and/or sodium hydroxide exist lower, at solvent-free or suitable solvent such as N, in the dinethylformamide (DMF), arrive under the solvent refluxing temperature formula (XII) and (XIII) reaction in room temperature.
The compound of formula (IV) can prepare according to the method for reaction formula 4, namely in suitable solvent such as DMF (DMF), processes the compound of formula (II) and formula (XIII) with suitable salt such as anhydrous potassium sulfate.
The synthetic method of above-claimed cpd has more detailed elaboration in the following embodiments.
Formula provided by the invention (I) compound has biological activity and the compound that has has good biological activity. particularly aspect the preventing and treating of agricultural, gardening, flowers and sanitary insect pest, show high reactivity.Harmful organism described here include but not limited to this:
Harmful insect: Orthoptera such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as leafhopper, plant hopper, aphid, lepidopteran such as oriental armyworm, prodenia litura, small cabbage moth, beet armyworm, cabbage looper, cabbage caterpillar, Hymenoptera such as sawfly larva, Diptera such as yellow-fever mosquito, culex, fly;
Pest mite class: acarina such as tangerine Panonychus citri, cotton spider mites, T.urticae Koch;
Formula provided by the invention (I) compound is effective for Control pests and mite.Usually use formula (I) compound of 10～5000ppm, it is dispersed in water or other the aqueous carrier, impose in the soil of plant, crop or plant growth, can prevent effectively that crop from suffering the infringement of worm and/or mite.
When using formula of the present invention (I) compound separately, be that effectively they also can use with the other biological chemical substance to control worm and/or mite, these biochemicals comprise other sterilants, nematocides and miticide.Such as formula of the present invention (I) the compound sterilants such as macrolide, γ-aminobutyric acid (GABA) antagonist, desinsection ureas and neotonin analoglike thing of organic phosphates, pyrethroid, amino formate, class nicotinoids, neural sodium channel blockers, desinsection effectively, the miticides such as aramite, propargite, methamidophos, fenpyroximate, hexythiazox and pyridaben cooperate or mix use together.
With (I) provided by the invention compound, Agrotechnical formulation as effective ingredient, can make desirable any formulation such as the compressing grains done, easily flow mixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate, pulvis, powdery enriched material, microemulsion, suspension agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable auxiliary agent comprises carrier (thinner) and other auxiliary such as spreader-sticker, emulsifying agent, wetting agent, dispersion agent, tackiness agent and decomposition agent.Contain in these preparations with the compounds of this invention inertia, that the acceptable solid of pharmacology or liquid diluent have mixed.
For example: wettable powder of the present invention, pulvis and powder enriched material, can be by with formula (I) compound of weight about 5～30%, mill together and prepare with the solid anion surfactant of weight about 5～30%.The dioctyl ester that a kind of suitable anion surfactant is sodium sulfosuccinate.The also inert solid diluent of operating weight 40%～90% in these preparations is such as talcum, kaolin, diatomite, Wingdale, silicate etc.
The preparation of compressing grains is that then the mixture recompression is about 10～100 orders (1.676～0.152mm) size or larger particles with the milling together such as 5～30 parts of formula (I) compounds and solid surfactant and about 40～90 parts gypsum of about equivalent.
Employed solid surfactant not only has the dioctyl phenyl ester of the sodium sulfosuccinate of negatively charged ion in the present invention's prescription, also has the block polymer of non-ionic type oxyethane and propylene oxide.
Easily flowing agent can be used with the aqueous solution on the spot.
Formula (I) solid preparation can be combined with other sterilant, can use as multicomponent mixture, perhaps sequentially uses.
In like manner, the liquid preparation of formula (I) also can be combined with other sterilant, can mix in container or use successively respectively in the liquid spray mode.Effective formula (I) compound that should contain the 50～5000ppm that has an appointment in the spray liquid agent prescription of the present invention.
The example of composition of the present invention also can be wettable powder, pulvis, granule and liquor, emulsible enriching agent, emulsion, suspension enriching agent, aerosol and smoke substance.Wettable powder contains 15,25,50 weight activeconstituentss usually, and usually except solid inert carrier, also contains 3～10% weight fraction powders, can add in case of necessity 0～10% weight stablizer and/or other additive such as permeate agent and tackiness agent.Pulvis may be molded to the pulvis enriching agent that has the composition similar to wettable powder but do not have dispersion agent usually.(1.676～0.152mm) sizes, and available agglomerating or implantttion technique preparation are made and had 10～100 orders to granula usually.Usually, granula contains the activeconstituents of 0.5～50% weight and 0～10% weight additive such as stablizer, tensio-active agent, slowly-releasing modifying agent.Outside but emulsion concentrate desolventizes, can contain cosolvent in case of necessity, 1～50%W/V activeconstituents, other additive of 2～20%W/V emulsifying agent and 0～20%W/V such as stablizer, permeate agent and corrosion inhibitor, suspension enriching agent contain the activeconstituents of 10～75% weight, the dispersion agent of 0.5～15% weight, other additive such as defoamer, corrosion inhibitor, stablizer, permeate agent and the tackiness agent of 0.1～10% weight usually.
Water dispersant and emulsion, for example by dilute with water according to the composition that wettable powder of the present invention or enriched material obtain, also list scope of the present invention in.Indication emulsion comprises two kinds of water-in-oil and oil-in-waters.
The invention will be further described below in conjunction with embodiment, and the yield among the embodiment is all without optimization.
Embodiment
Embodiment 1
Steps A: 2-methoxyl group-4-hydroxyl-6-trifluoromethyl pyrimidine (01-A) synthetic
In the 100ml there-necked flask of cyanamide 1.00g adding with dry prolong, stir the methanol solution 5.00g of the lower HCl of adding.Slowly be warming up to 25-80 ℃ of reaction after 2-6 hour, after being cooled to about 10 ℃, ice-water bath drips trifluoroacetic ethyl acetoacetate 3.50g, dropwise with 20% NaOH solution and regulate pH value to 14, whole process control temp finishes and is warming up to backflow below 30 ℃, reacts the precipitation that reduces pressure after 5 ~ 6 hours, it is acid adding 20 gram water adjust pHs, to separating out the amount of solid maximum, dry to get the thick about 3.0g of product, content 96%(HPLC).
Synthesizing of step B:2-methoxyl group-4-chloro-6-trifluoromethyl pyrimidine (01-B)
In there-necked flask, add 3.88g (20mmol) 2-methoxyl group-4-hydroxyl-6-trifluoromethyl pyrimidine and 9.20g (60mmol) phosphorus oxychloride, slowly drip 3.03g(30mmol after ice bath is cooled to 0 ℃) triethylamine, dropwise, keep 0 ℃ of reaction 1hr.Then reaction mixture is poured in the frozen water, the NaOH aqueous solution with 25% is regulated pH value to 5 ~ 6, filters the solid of separating out, and with 50ml water washing filter cake, gets white solid 3.76g, content 95%(HPLC after the drying).
Synthesizing of step C:4-(3-bromine propoxy-)-2-methoxyl group-6-trifluoromethyl pyrimidine (01-C)
In the 100ml there-necked flask of dry prolong is housed, add 3.25g 2-methylthio group-4-chloro-6-trifluoromethyl pyrimidine, the 2.75g3-bromopropyl alcohol, 2.75g salt of wormwood and 20ml DMF, room temperature reaction 8 hours reacts complete, in the impouring water, washing, ethyl acetate extraction, anhydrous sodium sulfate drying, solvent is sloughed in decompression, get the 5.20g title compound, content 82%(HPLC).
Step D:4-hydroxyl-acetophenone oxime-O-(3,3-two chloroallyloxyaminos) ether (01-F) is synthetic
In the 100ml there-necked flask of prolong is housed, add 5.4g 4-hydroxyacetophenone (01-D), 7.8g 3,3-dichloro allyl oxygen amine hydrochlorate (01-E), 50ml ethanol, room temperature drips the aqueous sodium hydroxide solution of 10.0g 20%, dropwise and be warming up to 60 ℃ of reactions 5 hours, after reacting completely, react complete, in the impouring water, washing, ethyl acetate extraction, anhydrous sodium sulfate drying, solvent is sloughed in decompression, gets the 9.8g yellow solid, content 95%(HPLC), yield 90%.
Step e: 4-hydroxyl-2,6-dichloroacetophenone oxime-O-(3,3-two chloroallyloxyaminos) ether (01-G) is synthetic
In the 100ml there-necked flask of dry prolong is housed, add 2.3g (01-F), the 20ml tetracol phenixin drips the 2.7g t-butyl hypochlorate below 0 ℃, dropwised room temperature reaction 2～6 hours, in the impouring water, washing, ethyl acetate extraction, anhydrous sodium sulfate drying, solvent is sloughed in decompression, gets the 2.8g yellow solid, yield 91%.
Step F: 4-(3-(2,6-, two chloro-4-(1-(3,3-dichloro allyl oxygen imido grpup) ethyl) phenoxy group) propoxy--2-methoxyl group-6-(trifluoromethyl) pyrimidine (01)
In the 100ml there-necked flask of dry prolong is housed, add 3.2g(01-C), 3.2g (01-G), 1.3g salt of wormwood and 20mlDMF, room temperature reaction 10～20 hours, in the impouring water, washing, ethyl acetate extraction, anhydrous sodium sulfate drying, solvent is sloughed in decompression, gets the 5.7g yellow liquid, (sherwood oil: the title compound of purifying to get of ethyl acetate=100:1), confirm through mass spectrum and nuclear-magnetism by structure through column chromatography for target compound.
Embodiment 2
Preparation suspension agent: first 2～6% wetting dispersing agent is diluted in 4～10% the frostproofer, and in this solution, slowly add a certain amount of water, then under the high speed shear cutter stirs, add successively 5～80% formula provided by the invention (I) active compound, 0.01～0.05% sanitas, 0.01～0.05% defoamer and thickening material etc.Mill in the last impouring sand mill, add again solvent to volume.Be diluted with water to required any concentration during use.
Embodiment 3
First with 5 parts of suitable tensio-active agents such as naphthalenesulfonic acid-formaldehyde condensate, the sodium dibutyl naphthalene sulfonate formaldehyde condensation products is diluted in 5 parts of suitable frostproofers such as ethylene glycol, in the glycerol, and in this solution, slowly add entry, (3-(2 to add successively 10 parts of compound 4-provided by the invention under rapid stirring, 6-two chloro-4-(3,3-two chloroallyloxyaminos) phenoxy group) propoxy--2-methoxyl group-6-(trifluoromethyl) pyrimidine and other suitable auxiliary agent such as sanitas (phenylformic acid or formaldehyde etc.), defoamer (organic silicone) and thickening material (xanthan gum or carboxymethyl cellulose etc.), finish and rear it is milled, add at last residual solvent to volume.
Embodiment 4
The concentrated floating agent of preparation: water, tensio-active agent, antifreezing agent, defoamer, thickening material and the sanitas with certain proportioning mixes composition homogeneous water first, then formula provided by the invention (I) compound, suitable solvent and emulsifying agent, co-emulsifier mixed making it become even oil phase.At last under high-speed stirring with the even oil phase emulsifiable concentrates that namely can be made into mixed with water.Be diluted with water to required any concentration during use.
Institute's synthetic compound is carried out desinsection and Acaricidal Activity, now listed the experimental result of part of compounds.
The Insecticidal Activity of 5 pairs of rice green leafhoppers of embodiment (Nephotettix cincticeps)
Will be by missible oil or the wettable powder of the oxime ether dichloro allyl ether compounds provided by the invention of above-mentioned Agrotechnical formulation embodiment method preparation, dilute with water is made into the pesticidal solutions of predetermined concentration, choosing two core rice seedlings soaks into the liquid, take out after 5 seconds and dry, place Boiling tube, then every pipe 20 strains introduce 20 or above rice green leafhopper nymph in 5 age, the mouth of pipe is placed under the greenhouse experiment with white gauze wrapping, checks survival and dead borer population after 24 hours.Experiment repeats 3 times.Results averaged.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and mortality ratio 100%～90% is the A level, and mortality ratio 90%～70% is the B level, and mortality ratio 70%～50% is the C level, and mortality ratio 0%～50% is the D level.It is active that compound 02 shows the A level.
The Insecticidal Activity of 6 pairs of bean aphids of embodiment (Aphis fabae)
Will be by missible oil or the wettable powder of the oxime ether dichloro allyl ether compounds provided by the invention of above-mentioned Agrotechnical formulation embodiment method preparation, dilute with water is made into the pesticidal solutions of predetermined concentration, bean aphid is connected on the bean seedlings that just have been unearthed, every strain connects more than 20, then bean seedlings is dipped in the liquid together with the examination worm, takes out after 5 seconds, suck unnecessary liquid, insert in the sponge of suction, cover with glass-tube, check survival and dead borer population after 24 hours.Repeat results averaged 3 times.Active relatively blank is divided into A, B, C, D level Four in per-cent, and mortality ratio 100%～90% is the A level, and mortality ratio 90%～70% is the B level, and mortality ratio 70%～50% is the C level, and mortality ratio 0%～50% is the D level.Compound 02 performance B level is active.
Claims (6)
1. have an oxime ether dichloro allyl ether compounds of insecticidal activity, it is characterized in that: with formula (I) expression oxime ether dichloro allyl ether compounds:
Wherein
N is 1,2,3 or 4;
R is H or halogen;
R
1H, C
1～C
6Alkyl, C
1～C
6Haloalkyl;
B is
R
2H, halogen, C
1～C
6Alkyl, C
1～C
6Haloalkyl;
R
3C
1～C
6Alkyl, C
1～C
6Haloalkyl;
In the definition of top formula (I), no matter the separately use or be used in the compound word of used term represents following substituting group:
Halogen: refer to fluorine, chlorine, bromine, iodine;
Alkyl: refer to the straight or branched alkyl;
Haloalkyl: refer to the straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom.
2. the oxime ether dichloro allyl ether compounds of tool insecticidal activity according to claim 1 is characterized in that preferred compound is:
N is 3 in formula (I); R is H; B is 2-(C
1～C
4Alkoxyl group)-formula (I) compound during 6-trifluoromethyl pyrimidine-4-base.
3. the oxime ether dichloro allyl ether compounds of tool insecticidal activity according to claim 1 and 2 is characterized in that particularly preferred compound is:
The compound of formula (I), wherein n is 3; R is H; B is 2-oxyethyl group-6-trifluoromethyl pyrimidine-4-base.
4. according to claim 1 and 2, the preparation method of the oxime ether dichloro allyl ether compounds of 3 described tool insecticidal activities, it is characterized in that at solvent N, in the dinethylformamide (DMF), in 10-100 ℃, compound with any one processing formula (II) in salt of wormwood, potassium hydroxide, sodium hydroxide, sodium bicarbonate or the yellow soda ash and formula (III) obtains formula (I) compound, and reaction formula is as follows:
R in the formula
1, R, n, B have claim 1 or 2,3 to definition, L is the leavings group chlorine or bromine.
5. according to claim 1 and 2, the preparation method of the oxime ether dichloro allyl ether compounds of 3 described tool insecticidal activities, it is characterized in that in the solvent normal hexane, in room temperature to the solvent refluxing temperature, compound with any one processing formula (IV) in salt of wormwood, potassium hydroxide, sodium hydroxide, sodium bicarbonate or the yellow soda ash and formula (V) obtains formula (I) compound, and reaction formula is as follows:
R in the formula
1, R, n, B have claim 1 or 2,3 to definition, L is the leavings group chlorine or bromine.
6. according to claim 1 and 2, the purposes of the oxime ether dichloro allyl ether compounds of 3 described tool insecticidal activities in preparing the medicine that insect is had prevention effect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110163149 CN102267950B (en) | 2008-08-12 | 2008-08-12 | Oxime ether dichloro-allyl ether compounds with insecticidal activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110163149 CN102267950B (en) | 2008-08-12 | 2008-08-12 | Oxime ether dichloro-allyl ether compounds with insecticidal activity |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100320589A Division CN101337940B (en) | 2008-08-12 | 2008-08-12 | Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102267950A CN102267950A (en) | 2011-12-07 |
| CN102267950B true CN102267950B (en) | 2013-03-13 |
Family
ID=45050432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110163149 Active CN102267950B (en) | 2008-08-12 | 2008-08-12 | Oxime ether dichloro-allyl ether compounds with insecticidal activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102267950B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761499A (en) * | 2015-02-28 | 2015-07-08 | 南通大学 | 1, 1-dichloropropene ether compound containing N-substituent-3-methylpyrazole oxime unit structure, preparation method and application thereof |
| CN113527200B (en) * | 2021-05-27 | 2022-12-02 | 北京斯利安药业有限公司 | Preparation method of cloquinadol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169147A (en) * | 1994-10-14 | 1997-12-31 | 住友化学工业株式会社 | Dihalopropene compounds, insecticidal/acaricidal agent contg. same, and intermediates |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09194418A (en) * | 1996-01-18 | 1997-07-29 | Sumitomo Chem Co Ltd | Dihalopropene compound, its use and its production intermediate |
| JP2003231672A (en) * | 2001-08-03 | 2003-08-19 | Nissan Chem Ind Ltd | Oxime type compound or its salts and bactericide for agriculture and horticulture |
-
2008
- 2008-08-12 CN CN 201110163149 patent/CN102267950B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169147A (en) * | 1994-10-14 | 1997-12-31 | 住友化学工业株式会社 | Dihalopropene compounds, insecticidal/acaricidal agent contg. same, and intermediates |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2003-231672A 2003.08.19 |
| JP特开平9-194418A 1997.07.29 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102267950A (en) | 2011-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101337940B (en) | Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity | |
| EP2229814B1 (en) | Fungicidal Compositions | |
| CN101337959B (en) | 2-amino-N-oxybenzamidecompounds with insecticidal activity | |
| CN104886079B (en) | 1,2,3-thiadiazoles-5-formamidine poly-heterocyclic compounds is as acaricidal purposes | |
| CN101928271B (en) | 3-o-methylphenyl-2-oxo-1-oxaspiro[4,4]-n-3-ene-4-alcohol and derivatives thereof | |
| WO2009116151A1 (en) | 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivatives and herbicides containing the derivatives as the active ingredient | |
| CN101885703A (en) | N-oxyaryloxyphenoxy carboxylic acid amide compound with bioactivity and preparation method thereof | |
| CN105315199A (en) | N-pyridine aryloxyphenoxy carboxylic acid derivatives, preparation method and applications thereof | |
| CN101928272A (en) | 3-o-methylphenyl-2-oxo-1-oxaspiro[4,5]-decyl-3-alkene-4-ol derivative | |
| CN103242225B (en) | Picolinate amino pyridine compound and preparation method thereof | |
| JPS605585B2 (en) | 2,5'-bistrifluoromethyl-2'-chloro-4,6-dinitrodiphenylamine and its production method, and insecticide, acaricide, or fungicide compositions containing the compound as an active ingredient | |
| KR910001130B1 (en) | Process for preparing benzotriazoles | |
| CN100579962C (en) | Aryl pyrrole compounds with insecticidal, miticidal and fungicidal bioactivities and process for preparing same | |
| CN102267950B (en) | Oxime ether dichloro-allyl ether compounds with insecticidal activity | |
| JP4864269B2 (en) | 3-thiomethylpyrazole as a pesticide | |
| WO2019228289A1 (en) | Substituted oxadiazole compound and application thereof | |
| CN105777580A (en) | Acyl acetonitrile compound and preparation method and application thereof | |
| JPH07330518A (en) | Insecticidal and acaricidal agent | |
| JPH09505320A (en) | Pyrimidinyl aryl ketone oxime | |
| CN107840825A (en) | Seven fluorine isopropyl quinoline class compounds and preparation method and application | |
| CN109824603B (en) | Pyrimidinamine compound, preparation method and application thereof | |
| KR930009824B1 (en) | Pyridazinonn derivatives | |
| CN101323584B (en) | Oxime ether aryl pyrrole compounds having insecticidal, acaricidal and antifungal bioactivity | |
| CN105254558A (en) | Dichloroallyl ether compound, preparation method and applications thereof | |
| CN101362720A (en) | Pyrazole methanol esters compounds, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HUNAN CHEMICAL ENGINEERING INST. Free format text: FORMER OWNER: CHINA PESTICIDE DISCOVERY ENGINEERING TECHNICAL RESEARCH CENTRE Effective date: 20130926 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130926 Address after: 410007 Changsha Furong Road, Hunan, No. two, No. 251 Patentee after: Hunan Chemical Engineering Inst. Address before: 410007 No. 551 Changsha Avenue, Yuhua District, Hunan, Changsha Patentee before: China Pesticide Discovery Engineering Technical Research Centre |