CN104326986A - Preparation method and application of dichloropropenyl phenyl ether compound - Google Patents
Preparation method and application of dichloropropenyl phenyl ether compound Download PDFInfo
- Publication number
- CN104326986A CN104326986A CN201410526311.1A CN201410526311A CN104326986A CN 104326986 A CN104326986 A CN 104326986A CN 201410526311 A CN201410526311 A CN 201410526311A CN 104326986 A CN104326986 A CN 104326986A
- Authority
- CN
- China
- Prior art keywords
- compound
- general formula
- phenyl ether
- ether compound
- preparation
- 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.)
- Granted
Links
- IVKPGBHFEAJRDD-UHFFFAOYSA-N ClC(Cl)=CCOC(CC([Tl])=C1OCCCBr)C=C1Cl Chemical compound ClC(Cl)=CCOC(CC([Tl])=C1OCCCBr)C=C1Cl IVKPGBHFEAJRDD-UHFFFAOYSA-N 0.000 description 1
- WTUAWWLVVCGTRG-UHFFFAOYSA-N N#C/N=C1\SCCN1 Chemical compound N#C/N=C1\SCCN1 WTUAWWLVVCGTRG-UHFFFAOYSA-N 0.000 description 1
- JKMSGXSJCRGNMV-VRUNDCBJSA-O [NH2+]=C1SCCN1CCCOc(c(Cl)cc(OC/C=C(/Cl)\I)c1)c1Cl Chemical compound [NH2+]=C1SCCN1CCCOc(c(Cl)cc(OC/C=C(/Cl)\I)c1)c1Cl JKMSGXSJCRGNMV-VRUNDCBJSA-O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/44—Nitrogen atoms not forming part of a nitro radical
- C07D233/52—Nitrogen atoms not forming part of a nitro radical with hetero atoms directly attached to said nitrogen atoms
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/08—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
- C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
- C07D273/04—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D277/18—Nitrogen atoms
Abstract
The invention relates to a preparation method and application of a dichloropropenyl phenyl ether compound (I). The dichloropropenyl ether compound is obtained by condensation of a nitrogen-containing heterocyclic ring (II) and a dichloropropene-containing terminal brominated compound (III). The dichloropropenyl phenyl ether compound (I) has an effective control effect on harmful insects, and can be applied to preparation of insecticides for agriculture, gardening and other fields. (formula I).
Description
Technical field
The invention belongs to pesticide field, be specifically related to a kind of dichloropropylene base phenyl ether compound and its production and use.
Background technology
The control of insect is the core realm of pesticide science research all the time, and widely using of sterilant makes most insect obtain effective improvement.But along with the continuous expansion of sterilant application scale, the resistance problems of traditional pesticide species highlights day by day, add the continuous appearance of new disease and pest, the continuation of novel pesticide is researched and developed becomes inevitable choice.
Dichloropropylene is the active fragments of multiple sterilant, the pyridalyl of such as SUMITOMO CHEMICAL chemistry exploitation:
The nitrogenous nonaromatic heterocycles such as tetrahydroglyoxaline is also the Typical reactive fragment of sterilant, as Provado and Diacloden:
Above-mentioned two kinds of active fragmentss are carried out splicing and obtain dichloropropylene base phenyl ether compound by first, possess excellent desinsection, acaricidal activity.
Summary of the invention
The object of this invention is to provide, for various insect, there is excellent prevention effect, and efficiently, safety, an eco-friendly class dichloropropylene base phenyl ether compound, to meet Crop protection to efficient pesticides demand.
Another object of the present invention is to provide the preparation method of above-claimed cpd.
A further object of the invention is to provide above-claimed cpd and is preparing the purposes in sterilant.
The object of the invention reaches by following measures:
Dichloropropylene base phenyl ether compound of the present invention, is characterized in that the structure possessed as shown in formula I:
The preparation method of this dichloropropylene base phenyl ether compound, is characterized in that the chemical combination shown in formula I is by leading to
Compound shown in formula II and general formula III under acid binding agent effect in aprotic polar solvent condensation obtain:
Wherein, N-Het is:
Wherein acid binding agent is: pyridine, picoline, triethylamine, diisopropylethylamine (DIEA), 4-N, N-lutidine amine (DMAP), salt of wormwood and cesium carbonate.The consumption of acid binding agent is generally 1.5 ~ 10 times of compound molar weight shown in general formula II.
Wherein aprotic polar solvent is: DMF (DMF), N,N-dimethylacetamide (DMA), DMSO, dioxane, acetonitrile and hexamethylphosphoramide (HMPA).
Wherein the molar weight of general formula III compound is 0.9 ~ 1.9 times of general formula II compound molar weight.
General formula II compound reference literature (Journal of Organic Chemistry, 16,1395-1404,1951; Journal of Heterocyclic Chemistry, 24 (1), 275-278,1987; Synthetic Communications, 42 (13), 1950-1958,2012) method synthesis obtains;
The synthesis of general formula III compound reference literature (Pest Management Science, 69 (5), 635-641,2013) method obtains.
It is active that compound of Formula I has excellent control to insect, and thus compound of the present invention can be used as preparing sterilant, and then the plant such as protecting agriculture, gardening.Described insect has lepidoptera pest as bollworm, beet armyworm, small cabbage moth, cabbage caterpillar, Cnaphalocrocis medinali(rice leaf roller) and striped rice borer etc., homoptera pest is as leafhopper, plant hopper, earthworm worm, aleyrodid etc., Diptera pest as housefly, Liriomyza, mosquito class etc., the insect such as Orthoptera and Coleoptera etc.Certainly, the harmful organism that compound of the present invention can be prevented and treated is not limited to the scope of above-mentioned citing.
When being used as the sterilant in the fields such as agricultural, gardening when the compound of the present invention represented by general formula I, can be used alone, or use in the mode of insect-killing composition, as with formula I for activeconstituents, add that the conventional inert ingredient in this area is processed into aqueous emulsion, suspension agent, water dispersion granule, missible oil etc.
Conventional inert ingredient comprises: liquid vehicle, as water; Organic solvent is as toluene, dimethylbenzene, hexalin, methyl alcohol, butanols, ethylene glycol, acetone, dimethyl formamide, acetic acid, methyl-sulphoxide, animal and plant oil and lipid acid; Conventional superficiality agent, as emulsifying agent and dispersion agent, comprises anion surfactant, cats product, nonionogenic tenside and amphoterics.Other auxiliary agent, as wetting agent, thickening material etc.
When the compound of the present invention represented by general formula I is used as the activeconstituents in sterilant, the content in described sterilant can be selected in the scope of 0.1% to 99.5%, and can determine suitable active component content according to dosage form and application process.Usually, containing the activeconstituents described in 5% to 50% (weight percent, lower same) in aqueous emulsion, preferably its content is 10% to 40%; Containing the activeconstituents of 5% to 50% in suspension agent, preferably its content is 5% to 40%.
For Utilization of pesticides of the present invention, the application method commonly used can be selected, as cauline leaf spraying, used for ponds, soil treatment and seed treatment etc.Such as, when adopting cauline leaf spraying, as activeconstituents the compound represented by general formula I can working concentration scope be aqueous emulsion, suspension agent, water dispersion granule, the missible oil of 1 to 1000mg/L, preferably its concentration is 1 to 500mg/L.
Dichloropropylene base phenyl ether compound disclosed by the invention has excellent prevention effect to harmful insect, therefore can be used to the sterilant for the preparation of fields such as agricultural, gardening.
Embodiment
For the ease of to further understanding of the present invention, the embodiment provided below has done more detailed description to it.These embodiments only are not used for limiting scope of the present invention or implementation principle for describing.
Embodiment 1:
The synthesis of Compound I a (n=1, HN ?Het=
)
0.22g intermediate II a, 0.7g intermediate III a and 0.28g salt of wormwood are dissolved in 15mL acetonitrile, and slow temperature rising reflux reacts 16 hours, after being chilled to room temperature, filters, and collect filtrate, concentrating under reduced pressure obtains crude product, obtains final product Ia through column chromatography, yield 53%;
1h NMR (400MHz, CDCl
3) 8.10 (s, 1H, NH), 6.84 (s, 2H, Ar-H), 6.11 (t, J=6.4Hz, 1H, C=C
h), 4.59 (d, J=6.4Hz, 2H, CHC
h 2 o), 4.01 (t, J=6.0Hz, 2H, CH
2), 3.68-3.80 (m, 4H, 2 × CH
2), 3.66 (t, J=7.2Hz, 2H, CH
2), 2.10-2.14 (m, 2H, CH
2).
Embodiment 2:
The synthesis of compounds ib (n=1, HN ?Het=
)
0.2g intermediate II b, 0.7g intermediate III a and 1.01g diisopropylethylamine are dissolved in 15mL acetonitrile.Slow intensification stream reaction 20 hours, after being chilled to room temperature, concentrating under reduced pressure obtains crude product, obtains final product Ib through column chromatography, yield 61%;
1h NMR (400MHz, CDCl
3) 6.77 (s, 2H, Ar-H), 6.04 (t, J=6.4Hz, 1H, C=C
h), 4.52 (d, J=6.4Hz, 2H, CHC
h 2o), 3.91-3.96 (m, 4H, 2 × CH
2), 3.68 (t, J=7.2Hz, 2H, CH
2), 3.34 (t, J=7.6Hz, 2H, CH
2), 2.03-2.09 (m, 2H, CH
2).
Embodiment 3:
The synthesis of Compound I c (n=1, HN ?Het=
)
0.25g intermediate II c, 0.82g intermediate III a and 1.09g cesium carbonate are suspended in 15mL N,N-dimethylacetamide.Slowly be warming up to 90 DEG C of reactions 12 hours, after being chilled to room temperature, filter, collect filtrate, concentrating under reduced pressure obtains crude product, obtains final product Ic through column chromatography, yield 49%;
1h NMR (400MHz, CDCl
3) 6.77 (s, 2H, Ar-H), 6.04 (t, J=6.4Hz, 1H, C=C
h), 4.52 (d, J=6.0Hz, 2H, CHC
h 2 o), 4.41 (s, 2H, CH
2), 4.29 (s, 2H, CH
2), 3.92 (t, J=5.2Hz, 2H, CH
2), 3.67 (t, J=7.2Hz, 2H, CH
2), 2.97 (s, 3H, N-CH
3), 2.78-2.85 (m, 2H, CH
2), 2.04-2.13 (m, 2H, CH
2), 1.13 (t, J=7.2Hz, 3H, CH
3).
Embodiment 4:
The synthesis of Compound I d (n=1, HN ?Het=
)
0.25g intermediate II c, 0.87g intermediate III a and 2.65g pyridine are dissolved in 15mL1,4-dioxane.Slowly rise to 90 DEG C, react 18 hours, after being chilled to room temperature, concentrating under reduced pressure obtains crude product, obtains final product Id through column chromatography, yield 42%;
1h NMR (400MHz, CDCl
3) 6.77 (s, 2H, Ar-H), 6.04 (t, J=6.4Hz, 1H, C=C
h), 4.52 (d, J=6.4Hz, 2H, CHC
h 2 o), 4.39 (s, 2H, CH
2), 4.28 (s, 2H, CH
2), 3.92 (t, J=6.0Hz, 2H, CH
2), 3.66 (t, J=7.2Hz, 2H, CH
2), 2.97 (s, 3H, N-CH
3), 2.70 (t, J=7.2Hz, 2H, CH
2), 2.01-2.06 (m, 2H, CH
2), 1.48-1.53 (m, 2H, CH
2), 0.90 (t, J=7.2Hz, 3H, CH
3).
Embodiment 5:
The synthesis of Compound I e (n=2, HN ?Het=
)
0.23g intermediate II e, 0.98g intermediate III b and 1.26g cesium carbonate are dissolved in 15mL acetonitrile.Slow temperature rising reflux reacts 15 hours, after being chilled to room temperature, and concentrating under reduced pressure obtains crude product, obtains final product Ie through column chromatography, yield 38%;
1h NMR (400MHz, CDCl
3) 8.09 (s, 1H, NH), 6.84 (s, 2H, Ar-H), 6.12 (t, J=6.4Hz, 1H, C=C
h), 4.59 (d, J=6.0Hz, 2H, CHC
h 2 o), 3.97 (t, J=5.6Hz, 2H, CH
2), 3.76-3.82 (m, 2H, CH
2), 3.65-3.69 (m, 2H, CH
2), 3.46 (t, J=7.2Hz, 2H, CH
2), 1.82-1.89 (m, 4H, 2 × CH
2).
Embodiment 6:
The synthesis of Compound I f (n=2, HN ?Het=
)
By 0.20g intermediate II f, 0.68g intermediate III b and 0.76g4-N, N-lutidine amine is dissolved in 15mLDMF.Slowly be warming up to 85 DEG C, react 12 hours, after being chilled to room temperature, concentrating under reduced pressure obtains crude product, obtains final product If through column chromatography, yield 45%;
1h NMR (400MHz, CDCl
3) 6.84 (s, 2H, Ar-H), 6.12 (t, J=6.4Hz, 1H, C=C
h), 4.94 (s, 2H, CH
2), 4.90 (s, 2H, CH
2), 4.58 (d, J=6.4Hz, 2H, CHC
h 2 o), 3.96 (t, J=6.0Hz, 2H, CH
2), 3.61 (t, J=7.2Hz, 2H, CH
2), 3.03 (s, 3H, N-CH
3), 1.82-1.95 (m, 4H, 2 × CH
2).
Embodiment 7:
The synthesis of Compound Ig per (n=4, HN ?Het=
)
0.20g intermediate II g, 0.97g intermediate III c and 1.58g diisopropylethylamine are dissolved in 20mL methyl-sulphoxide.Slowly be warming up to 80 DEG C, react 18 hours, after being chilled to room temperature, concentrating under reduced pressure obtains crude product, obtains final product Ig through column chromatography, yield 46%;
1h NMR (400MHz, CDCl
3) 8.08 (s, 1H, NH), 6.84 (s, 2H, Ar-H), 6.12 (t, J=6.4Hz, 1H, C=C
h), 4.58 (d, J=6.4Hz, 2H, CHC
h 2 o), 3.95 (t, J=6.4Hz, 2H, CH
2), 3.76-3.80 (m, 2H, CH
2), 3.60-3.65 (m, 2H, CH
2), 3.37 (t, J=7.2Hz, 2H, CH
2), 1.79-1.86 (m, 2H, CH
2), 1.54-1.66 (m, 4H, 2 × CH
2), 1.39-1.45 (m, 2H, CH
2).
Embodiment 8:
Sample screens the insecticidal activity of mythimna separata
Adopt the leaf dipping method that international resistance Action Committee (IRAC) proposes.Supply examination target to be mythimna separata, naturally dry in the shade after fully infiltrating in the liquid prepared by appropriate leaf of Semen Maydis, put into the culture dish being lined with filter paper, connect mythimna separata 3 larva in mid-term in age 10/ware, be placed in 24-27 DEG C of observation indoor cultivation, 2d " Invest, Then Investigate " result.Touch polypide with writing brush, be reactionlessly considered as dead worm.Initial trial concentration 500 μ g/mL (liquid of other concentration can be diluted by the liquid of 500 μ g/mL and obtain).
Embodiment 9:
Sample screens the insecticidal activity of carmine spider mite
Adopt the spray method that international resistance Action Committee (IRAC) proposes.Examination target is supplied to be carmine spider mite.The Broad Bean Leaves being about to be connected to carmine spider mite is sprayed process under Potter spray tower, and after process, carmine spider mite is placed in 24 ~ 27 DEG C and observes indoor cultivation, 48h " Invest, Then Investigate " result.Touch polypide with writing brush, be reactionlessly considered as dead worm.Initial trial concentration 500 μ g/mL (liquid of other concentration can be diluted by the liquid of 500 μ g/mL and obtain).
The insecticidal activity data (Mortality, %) of table 1.Ia-Ie
Insecticidal activity test result shows, and partial target thing shows good mythimna separate, and when test concentrations is 500 μ g/mL, wherein chemical compounds I a, I b, I c, I e and the prevention effect of I g to mythimna separata are 100%; When test concentrations is 500 μ g/mL, wherein chemical compounds I a-I g does not all possess restraining effect to carmine spider mite.Above data show, in nitrogenous activity unit, introduce the dichloropropylene active fragments with different carbon chain structure, some target compound of gained presents good inhibition to mythimna separata, and part of compounds can be used as agricultural chemicals guide and does research deep further.
Claims (7)
1. a dichloropropylene base phenyl ether compound, is characterized in that the structure possessed as shown in formula I:
。
2. a preparation method for dichloropropylene base phenyl ether compound, it is characterized in that the compound shown in formula I by the compound shown in general formula II and general formula III under acid binding agent effect in aprotic polar solvent condensation obtain:
Wherein, N-Het is:
。
3. the preparation method as shown in claim 2, is characterized in that, wherein acid binding agent is: pyridine, picoline, triethylamine, diisopropylethylamine (DIEA), 4-N, N-lutidine amine (DMAP), salt of wormwood and cesium carbonate; The consumption of affiliated acid binding agent is generally 1.5 ~ 10 times of compound molar weight shown in general formula II.
4. the preparation method as shown in claim 2, is characterized in that: wherein aprotic polar solvent is: DMF (DMF), N,N-dimethylacetamide (DMA), DMSO, dioxane, acetonitrile and hexamethylphosphoramide (HMPA).
5. the synthetic method as shown in claim 2, wherein the molar weight of general formula III compound is 0.9 ~ 1.9 times of general formula II compound molar weight.
6. dichloropropylene base phenyl ether compound as claimed in claim 1 is preparing the purposes in sterilant, it is characterized in that: this compound is used alone; Or use in the mode of insect-killing composition, namely with formula I for activeconstituents, add that the conventional inert ingredient in this area is processed into aqueous emulsion, suspension agent, water dispersion granule, missible oil etc.
7. pyridine phenyl ether compound as claimed in claim 6 is preparing the purposes in sterilant, it is characterized in that: when the compound of the present invention represented by general formula I is used as the activeconstituents in sterilant, the content in described sterilant is selected in the scope of 0.1% to 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410526311.1A CN104326986B (en) | 2014-10-08 | 2014-10-08 | Preparation method and the application thereof of dichloropropylene base phenyl ether compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410526311.1A CN104326986B (en) | 2014-10-08 | 2014-10-08 | Preparation method and the application thereof of dichloropropylene base phenyl ether compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104326986A true CN104326986A (en) | 2015-02-04 |
| CN104326986B CN104326986B (en) | 2016-05-04 |
Family
ID=52401808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410526311.1A Expired - Fee Related CN104326986B (en) | 2014-10-08 | 2014-10-08 | Preparation method and the application thereof of dichloropropylene base phenyl ether compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104326986B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005112941A2 (en) * | 2004-05-18 | 2005-12-01 | Bayer Cropscience Ag | Substituted cyclic urea derivatives |
| WO2010060379A1 (en) * | 2008-11-28 | 2010-06-03 | 中国中化集团公司 | Ether compounds with nitrogen-containing 5-member heterocycle and the uses thereof |
| CN101747306A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Substituent ether compound and application thereof |
| CN101921228A (en) * | 2009-06-15 | 2010-12-22 | 中国中化股份有限公司 | Piperazine-contained propylene ether dihalide compound and applications thereof |
| CN102464621A (en) * | 2010-11-19 | 2012-05-23 | 中国中化股份有限公司 | Ether compound containing pyrimidine rings and application thereof |
-
2014
- 2014-10-08 CN CN201410526311.1A patent/CN104326986B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005112941A2 (en) * | 2004-05-18 | 2005-12-01 | Bayer Cropscience Ag | Substituted cyclic urea derivatives |
| WO2010060379A1 (en) * | 2008-11-28 | 2010-06-03 | 中国中化集团公司 | Ether compounds with nitrogen-containing 5-member heterocycle and the uses thereof |
| CN101747306A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Substituent ether compound and application thereof |
| CN101921228A (en) * | 2009-06-15 | 2010-12-22 | 中国中化股份有限公司 | Piperazine-contained propylene ether dihalide compound and applications thereof |
| CN102464621A (en) * | 2010-11-19 | 2012-05-23 | 中国中化股份有限公司 | Ether compound containing pyrimidine rings and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104326986B (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110092776B (en) | Pyrazole oxime ester compound containing pyridine-difluoride pyrazole structure and preparation method and application thereof | |
| CN104892591B (en) | The preparation method and application of the pyrazoles oxime compound of the oxadiazole heterocycle structure containing 3 aryl 1,2,4 | |
| CN110128409B (en) | Preparation and application of difluoromethylpyrazole oxime derivative containing pyridine bipyrazole structure | |
| CN110407828B (en) | Pyrazole-5-amide derivative containing oxazole structure and preparation method and application thereof | |
| CN104193727A (en) | Preparation and application of pyrazole oxime ether compound containing trifluoro methyl pyridine | |
| CN110845487B (en) | 3- (triazole biphenyl methoxyl) pyrazole amide compound containing isoxazole structure and preparation method and application thereof | |
| CN110407831B (en) | Preparation and application of pyrazole oxime ester derivative containing N- (3-chloropyridine-2-yl) pyrazole structure | |
| CN104557710B (en) | The preparation and application of the pyrazoles oxime compound of the pyrrazole structure containing multi-substituent | |
| CN104119316B (en) | Pyridine phenyl ether compound and Synthesis and applications thereof | |
| CN106243039B (en) | Preparation method and application of pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure | |
| CN110437221B (en) | Pyrazole derivative containing aryloxy methyl oxadiazole unit and preparation method and application thereof | |
| CN109879867B (en) | Preparation and application of pyrazole oxime ether compound containing 5-aryl oxazole structure | |
| CN104151309B (en) | Preparation and application containing 1,3,4 thiadiazoles Pyrazole Oxime Esters | |
| CN109553605B (en) | Pyrazole amide compound containing tetrazole biphenyl structure and preparation method and application thereof | |
| CN106432081A (en) | Preparation method and application of pyrazole oxime ether compound containing 4-Cl-3-ethyl-1-methylpyrazole structure | |
| CN110407813B (en) | Pyrazole oxime compound containing 1- (3-chloropyridine-2-yl) pyrazole structure and preparation method and application thereof | |
| CN104193683A (en) | Pyrazole oxime derivative containing dichloropropene as well as preparation method and application method of derivative | |
| CN110305115A (en) | The preparation and application of pyrazoles 9 oxime derivate of the one kind containing 1- (6- chloropyrazine -2- base) -3- methoxyl group pyrazoles unit | |
| CN105884744A (en) | Preparation and application of pyrazole oxime ester compound containing 2-chloropyridine structure | |
| CN109535154B (en) | Pyrazole amide compound containing 4-arylthiazole structure and preparation method and application thereof | |
| US20220267297A1 (en) | 2-substituted imidazolidine derivative containing aryl bipyridyloxy structure and preparation method and use thereof | |
| CN109879868B (en) | Preparation and application of pyrazole amide compound containing 2-aryl oxazole structure | |
| CN106349223B (en) | The preparation method and application of the pyrazoles oxime ether compound of the sulfide based structural containing pyrimidine | |
| CN104326986A (en) | Preparation method and application of dichloropropenyl phenyl ether compound | |
| CN104592220A (en) | Preparation and application of 1,3,4-thiadiazole-methyl phenyl ether compound |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160504 Termination date: 20161008 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |