CN1398515A - N-phenyl pyrazole derivative pesticide - Google Patents
N-phenyl pyrazole derivative pesticide Download PDFInfo
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- CN1398515A CN1398515A CN02128312A CN02128312A CN1398515A CN 1398515 A CN1398515 A CN 1398515A CN 02128312 A CN02128312 A CN 02128312A CN 02128312 A CN02128312 A CN 02128312A CN 1398515 A CN1398515 A CN 1398515A
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- CN
- China
- Prior art keywords
- compound
- pyrazole derivative
- pesticide
- add
- phenyl pyrazole
- 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
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- 239000000575 pesticide Substances 0.000 title claims abstract description 13
- WITMXBRCQWOZPX-UHFFFAOYSA-N 1-phenylpyrazole Chemical class C1=CC=NN1C1=CC=CC=C1 WITMXBRCQWOZPX-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000002917 insecticide Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 241000607479 Yersinia pestis Species 0.000 abstract 1
- 230000002147 killing effect Effects 0.000 abstract 1
- 230000000361 pesticidal effect Effects 0.000 abstract 1
- 230000003405 preventing effect Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 150000003217 pyrazoles Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- -1 acetylamino, chloro acetylamino Chemical group 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 4
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229940029273 trichloroacetaldehyde Drugs 0.000 description 2
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241001179564 Melanaphis sacchari Species 0.000 description 1
- 241000409991 Mythimna separata Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000073 carbamate insecticide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000002584 immunomodulator Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
- GWBNYWVYPASUBM-UHFFFAOYSA-N trifluoromethanesulfinyl chloride Chemical compound FC(F)(F)S(Cl)=O GWBNYWVYPASUBM-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- 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
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
N-phenyl pyrazole derivative pesticide includes mainly six kinds of pesticides with N-phenyl pyrazole derivative, which has excellent and wide-spectrum pest preventing and killing effect. Compared with similar product, the present invention has higher pesticidal effect.
Description
Technical field the present invention relates to the pyrazoles agricultural chemical insecticide.
Background technology French Luo Na-Rhone-Poulenc in 1989 has developed the pyrazoles broad spectrum pesticide, its commodity are called " Regent ", this compound is a kind of broad spectrum pesticide that many insects is had excellent preventive effect, for example:, all demonstrated high susceptibility to insects such as Semiptera, Lepidoptera, thrips, coleoptera and insect that cyclopentadiene, chrysanthemum ester class, carbamate insecticide have been developed immunity to drugs.The molecular structural formula of commodity " Regent " by name is:
1999 Nian Luona companies apply for a patent US 5,916, and 618 have also introduced the synthetic of a series of Regent derivatives, and main amino on heterocycle is substituted by acetylamino, chloro acetylamino.The trifluoromethyl sulphinyl base is derived and is compounds such as trifluoromethyl sulfonyl, trifluoromethylthio.
2000, the compound of following structure is arranged in the U.S. Pat 6,015,910 of French Luo Na company application:
Some characteristic of this compound have surpassed " Regent ".To cotten aphid systemic activity LC
50=0.21ppm, and Regent is 11.3ppm; To sorghum aphid systemic activity LC
50=0.6ppm, and Regent＞20ppm.
At present, more and more Yan Ge environmental requirement, make China old farmer medicine kind, particularly some pesticide species like a fish out of water and poisonous to the person poultry safety (for example: high malicious organophosphorous pesticide) be eliminated unavoidably, just must develop and have the pesticide new variety that activity is high, Environmental compatibility is good, the mode of action is novel, improve the development level of China's pesticide industry and the chemical control level of crops, solve the update of pesticide species, reduce pressure environment.
Summary of the invention highly effective pesticide insecticide of the present invention is the N-phenylpyrazole derivatives, and it has following general structure:
In the formula:
-CH
2CCl
3,
Or-N (COOC
2H
5)
2
R
2=-C
2H
5,-OC
2H
5Or-OCF
3
The noval chemical compound that has specifically synthesized following structure:
The synthetic method of the compound of above-mentioned new construction is as follows:
(1) 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles is synthetic
This reaction is by 2, and the 6-dichlor-4-trifluoromethyl aniline generates diazol with natrium nitrosum, sulfuric acid reaction earlier, and then, again with 2, the reaction of 3-dicyano ethyl propanoate generates end product through the ammoniacal liquor closed loop.Then:
(2) compound (1) is synthetic:
Above-mentioned being reflected in the tetrahydrofuran solvent through back flow reaction, made acid binding agent with sodium hydride, can make compound (I).
(3) 5-amino-3-cyano group-1-(2,6 dichlor-4-trifluoromethyl phenyl)-4-ethylmercapto group pyrazoles is synthetic:
Reaction generates sulfocyanic ester compound by 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles and sodium sulfocynanate reaction.
(4) compound (II) is synthetic:
Be reflected in the tetrahydrofuran solvent,, make acid binding agent, can make compound (II) with sodium hydride through back flow reaction.
(5) compound (III) is synthetic:
(6) compound (IV) is synthetic:
Reaction is carried out in two steps, at first, and trichloroacetaldehyde, in the presence of the catalyzer p-methyl benzenesulfonic acid, in toluene solvant, reflux, obtain amino substituent, then, make compound (IV) through sodium borohydride reduction.
Agricultural insecticide immunomodulator compounds of the present invention is compared with external commodity Regent, has identical or higher insecticidal effect.Be example with compound (I), (VI) now, test result is as follows:
Table is to 72 hours drug effect contrast tests of mythimna separata three class larvas result
| Medicament | Concentration (ppm) | For examination borer population (head) | Dead worm (head) | Corrected mortality (%) |
| Compound (I) | ????5 ????1 ????0.2 | ????45 ????45 ????42 | ????45 ????43 ????3 | ????100.0 ????95.6 ????7.1 |
| Compound (VI) | ????5 ????1 ????0.2 | ????45 ????45 ????44 | ????45 ????45 ????23 | ????100.0 ????100.0 ????52.3 |
| ????Regent | ????10 ????5 ????1 | ????45 ????49 ????45 | ????44 ????38 ????6 | ????97.8 ????77.6 ????13.4 |
Embodiment
Embodiment 1
95g Regent is dissolved in the 100ml oxolane, add 2.5g methylallyl chloride, 1g sodium hydride, reflux after 22 hours, add the 200ml ethyl acetate extraction, oil reservoir is through 2 * 100ml washing, precipitation, the residual thing of still is recrystallized through 30g toluene, get 1.5g compound (I), fusing point: 172-174 ℃, structure is confirmed through H-NMR.
Embodiment 2
2g 5-amino-3-cyano group-1-(2,6 dichlor-4-trifluoromethyl phenyl)-4-ethylmercapto group pyrazoles is dissolved in the 60ml oxolane, adds the 0.5g sodium hydride, the 1g methylallyl chloride, back flow reaction 8 hours, reduce to room temperature after, add the 100ml ethyl acetate extraction, oil reservoir is through washing two times, the decompression precipitation, still is residual through column chromatography (hexane: ethyl acetate=2: 1), obtain 0.5g compound (II), fusing point: 123-125 ℃, structure is confirmed through H-NMR.
Embodiment 3
2.5g 5-amino-3-cyano group-1-(2,6 dichlor-4-trifluoromethyl phenyl)-4-ethoxy sulfenyl pyrazoles is dissolved in the 100ml oxolane, adds the 0.5g sodium hydride, the 1g methylallyl chloride, temperature rising reflux reaction 4 hours is after the cooling, add the 100ml ethyl acetate extraction, oil reservoir is through washing the decompression precipitation two times, the residual thing of still is through column chromatography (hexane: ethyl acetate=2: 1), obtain the 0.5g product,, get 0.1g compound (III) again through recrystallization, fusing point: 140～144 ℃, structure is confirmed through H-NMR.
Embodiment 4
With 5g 5-amino-3-cyano group-1-(2,6 dichlor-4-trifluoromethyl phenyl)-4-ethoxy sulfenyl pyrazoles, 150ml toluene, 1g p-methyl benzenesulfonic acid, 3.5g trichloroacetaldehyde put into reaction bulb, reflux after 5 hours, cooling adds 200ml washing two times, the decompression precipitation, get the residual thing of 6.5g still, with it and 1.2g sodium borohydride, 100ml methyl alcohol, put into reaction bulb, reaction is 2 hours under the room temperature.Add hydrochloric acid neutralization, add the dilution of 200ml water after, use the 100ml ethyl acetate extraction, oil reservoir is through 2 * 200ml washing, precipitation, the residual thing of still gets compound (IV) behind 50ml toluene recrystallization, molten point: 158-164 ℃, product is confirmed structure through H-NMR.
Embodiment 5
After will diluting with acetate by the nitrosyl sulfuric acid of 7g natrium nitrosum and the preparation of the 27.5ml concentrated sulfuric acid, add 21.2g2 to it, the 50ml acetic acid solution of 6-dichlor-4-trifluoromethyl aniline, this mixture is warming up to 55 ℃, reacted 20 minutes, with its impouring 14.0g 2, the acetate of 6-dicyano ethyl propanoate, in the agitating solution of water, after 15 minutes, add the 200ml water stratification, use the dichloromethane extraction water layer, oil reservoir and the reaction of 20ml ammoniacal liquor 2 hours are through conventional post processing, obtain 22g 5-amino-3-cyano group-1-(2,6 dichlor-4-trifluoromethyl phenyl) pyrazoles, molten some 140-142 ℃, structure is confirmed through H-NMR.
Embodiment 6
In reaction bulb, add 50ml toluene, 16.6g 5-amino-3-cyano group-1-(2,6 dichlor-4-trifluoromethyl phenyl) pyrazoles, catalyzer, stirring is cooled to 5 ℃, add the 10.9g trifluoromethyl sulphinyl chlorine, 5 ℃ of reactions 1 hour, 50 ℃ of reactions 8 hours, be chilled to room temperature, add 100ml water, filter, washing, get 19.7g product Regent, molten some 196-198 ℃.
Embodiment 7
The 4.05g sodium sulfocyanate is dissolved in the 75ml methyl alcohol, be cooled to-78 ℃, splash into the 10ml methanol solution of 3g bromine to it, after dropwising, splash into 5g 5-amino-3-cyano group-1-(2 at uniform temp, 6 dichlor-4-trifluoromethyl phenyl) the 50ml methanol solution of pyrazoles, after reaction finishes, add 250ml water, filter, oven dry obtains intermediate and replaces thiocyanates.This intermediate of 3.1g is dissolved in the 50ml industrial alcohol, add the 10ml aqueous solution of iodoethane and 0.92g potassium hydroxide in-7 ℃ to it, after having reacted, add 180ml water, filter, get product 5-amino-3-cyano group-1-(2,6 dichlor-4-trifluoromethyl phenyl)-4-trifluoro ethylmercapto group pyrazoles, fusing point: 159-163 ℃.
Claims (2)
1, a class formation is the N-phenyl pyrazole derivative pesticide, it is characterized in that this insecticide has following general structure:
In the formula:
-CH
2CCl
3,
Or-N (COOC
2H
5)
2R
2=-C
2H
5,-OC
2H
5Or-OCF
3
2,, it is characterized in that the concrete structure of insecticide is according to the described insecticide of claim 1:
Six N-phenylpyrazole derivatives.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021283125A CN1204123C (en) | 2002-07-30 | 2002-07-30 | N-phenyl pyrazole derivative pesticide |
| PCT/CN2003/000343 WO2004010785A1 (en) | 2002-07-30 | 2003-05-12 | A series of n-phenylpyrazole derivatives insecticide compounds |
| KR1020047021516A KR100603690B1 (en) | 2002-07-30 | 2003-05-12 | A series of n-phenylpyrazole derivatives insecticide compounds |
| JP2004523726A JP2005534683A (en) | 2002-07-30 | 2003-05-12 | A series of n-phenylpyrazole derivatives insecticide compounds |
| AU2003242089A AU2003242089A1 (en) | 2002-07-30 | 2003-05-12 | A series of n-phenylpyrazole derivatives insecticide compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021283125A CN1204123C (en) | 2002-07-30 | 2002-07-30 | N-phenyl pyrazole derivative pesticide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1398515A true CN1398515A (en) | 2003-02-26 |
| CN1204123C CN1204123C (en) | 2005-06-01 |
Family
ID=4745954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021283125A Expired - Lifetime CN1204123C (en) | 2002-07-30 | 2002-07-30 | N-phenyl pyrazole derivative pesticide |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2005534683A (en) |
| KR (1) | KR100603690B1 (en) |
| CN (1) | CN1204123C (en) |
| AU (1) | AU2003242089A1 (en) |
| WO (1) | WO2004010785A1 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100593540C (en) * | 2007-09-30 | 2010-03-10 | 浙江工业大学 | A kind of preparation method of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazole |
| CN1915977B (en) * | 2005-08-18 | 2010-04-07 | 李坚 | Chlorine-fipronil, prepartion and application |
| CN102206184A (en) * | 2010-03-29 | 2011-10-05 | 南开大学 | 3-cyano-1-(2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivative insecticide |
| WO2011137697A1 (en) * | 2010-05-07 | 2011-11-10 | 湖南化工研究院 | N-phenyl-5-substituted aminopyrazole preparations and application thereof for controlling coleoptera pests |
| CN102250008A (en) * | 2010-05-17 | 2011-11-23 | 温州大学 | Preparation method of 5-amino-3-cyano-4-ethylthio-1-(2,6-dichloro-4-trifluoromethylphenyl) pyrazole |
| CN101444221B (en) * | 2008-12-27 | 2011-11-30 | 东莞市瑞德丰生物科技有限公司 | Composite containing oxadiazines and pyrromonazole pesticide |
| CN101491251B (en) * | 2009-02-23 | 2012-08-08 | 深圳诺普信农化股份有限公司 | Pesticide combination and use thereof |
| CN104642401A (en) * | 2015-02-03 | 2015-05-27 | 沈阳农业大学 | Flufiprole oily agent for preventing and controlling locusts and preparation method thereof |
| CN104855399A (en) * | 2015-05-02 | 2015-08-26 | 广东中迅农科股份有限公司 | Insecticidal combination containing butene-fipronil and fluorine benzene worm amide |
| CN106187896A (en) * | 2016-07-19 | 2016-12-07 | 中南民族大学 | Ultrasonic atomization microwave radiation integration system is for the single or multiple alkyl derivative of arylpyrazole |
| CN106305758A (en) * | 2015-06-23 | 2017-01-11 | 沈阳中化农药化工研发有限公司 | Synergistic and compounded pest and mite killing composition |
| CN111072568A (en) * | 2019-12-26 | 2020-04-28 | 华东理工大学 | Phenylpyrazole compounds containing azo structure and preparation method and application thereof |
| CN114105877A (en) * | 2021-06-30 | 2022-03-01 | 浙江美诺华药物化学有限公司 | Preparation method of fipronil intermediate and method for preparing fipronil by using fipronil intermediate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104522036B (en) * | 2014-12-19 | 2017-02-01 | 湖南化工研究院有限公司 | Insecticidal composition used for preventing and controlling lepidoptera pests and homoptera pests |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547974A (en) * | 1985-12-20 | 1996-08-20 | Rhone-Poulenc Agriculture Ltd. | Derivatives of N-phenylpyrazoles |
| GB8531485D0 (en) * | 1985-12-20 | 1986-02-05 | May & Baker Ltd | Compositions of matter |
| GB8713768D0 (en) * | 1987-06-12 | 1987-07-15 | May & Baker Ltd | Compositions of matter |
| FR2696906B1 (en) * | 1992-10-20 | 1996-09-20 | Rhone Poulenc Agrochimie | PROCESS FOR THE AGROCHEMICAL TREATMENT OF RICE AND SEEDS THUS PROCESSED. |
| US5614182A (en) * | 1995-04-10 | 1997-03-25 | Rhone-Poulenc Inc. | Methods of attracting and combatting insects |
| FR2735952B1 (en) * | 1995-06-29 | 1997-08-01 | Rhone Poulenc Agrochimie | METHOD FOR CONTROLLING A POPULATION OF SOCIAL INSECTS |
| FR2739255B1 (en) * | 1995-09-29 | 1998-09-04 | Rhone Merieux | PEST CONTROL COMPOSITION FOR THE TREATMENT AND PROTECTION OF PETS |
| SE517612C2 (en) * | 1995-12-20 | 2002-06-25 | Rhone Poulenc Agrochimie | Use of 5-amino-4-ethylsulfinyl-1-arylpyrazole compounds as pesticides |
| FR2750861B1 (en) * | 1996-07-11 | 1998-12-24 | Rhone Merieux | PROCESSES FOR REMOVING PARASITES, ESPECIALLY VERTEBRATE ECTOPARASITES, ESPECIALLY MAMMALS AND COMPOSITIONS FOR CARRYING OUT THIS PROCESS |
| EP0839809A1 (en) * | 1996-11-01 | 1998-05-06 | Rhone-Poulenc Agrochimie | Pesticidal 1-arylpyrazole-5-sulfinilimine derivatives |
| FR2761232B1 (en) * | 1997-03-26 | 2000-03-10 | Rhone Merieux | PROCESS AND MEANS FOR ERADICATION OF CHIPS IN PREMISES LIVED BY SMALL MAMMALS |
| JP4336906B2 (en) * | 1997-04-07 | 2009-09-30 | 日本農薬株式会社 | Pyrazole derivatives, process for producing the same, intermediates, and pest control agents containing the same as active ingredients |
| DK0976737T3 (en) * | 1997-04-07 | 2009-07-20 | Nihon Nohyaku Co Ltd | Pyrazole derivatives, processes for their preparation, intermediates and pesticides containing these as active ingredient |
-
2002
- 2002-07-30 CN CNB021283125A patent/CN1204123C/en not_active Expired - Lifetime
-
2003
- 2003-05-12 AU AU2003242089A patent/AU2003242089A1/en not_active Abandoned
- 2003-05-12 WO PCT/CN2003/000343 patent/WO2004010785A1/en active Application Filing
- 2003-05-12 JP JP2004523726A patent/JP2005534683A/en active Pending
- 2003-05-12 KR KR1020047021516A patent/KR100603690B1/en not_active IP Right Cessation
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| CN1915977B (en) * | 2005-08-18 | 2010-04-07 | 李坚 | Chlorine-fipronil, prepartion and application |
| CN100593540C (en) * | 2007-09-30 | 2010-03-10 | 浙江工业大学 | A kind of preparation method of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazole |
| CN101444221B (en) * | 2008-12-27 | 2011-11-30 | 东莞市瑞德丰生物科技有限公司 | Composite containing oxadiazines and pyrromonazole pesticide |
| CN101491251B (en) * | 2009-02-23 | 2012-08-08 | 深圳诺普信农化股份有限公司 | Pesticide combination and use thereof |
| CN102206184A (en) * | 2010-03-29 | 2011-10-05 | 南开大学 | 3-cyano-1-(2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivative insecticide |
| WO2011120312A1 (en) * | 2010-03-29 | 2011-10-06 | 南开大学 | 3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazole derivatives as insecticides |
| CN102206184B (en) * | 2010-03-29 | 2013-07-10 | 南开大学 | 3-cyano-1-(2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivative insecticide |
| WO2011137697A1 (en) * | 2010-05-07 | 2011-11-10 | 湖南化工研究院 | N-phenyl-5-substituted aminopyrazole preparations and application thereof for controlling coleoptera pests |
| CN102250008A (en) * | 2010-05-17 | 2011-11-23 | 温州大学 | Preparation method of 5-amino-3-cyano-4-ethylthio-1-(2,6-dichloro-4-trifluoromethylphenyl) pyrazole |
| CN104642401A (en) * | 2015-02-03 | 2015-05-27 | 沈阳农业大学 | Flufiprole oily agent for preventing and controlling locusts and preparation method thereof |
| CN104855399A (en) * | 2015-05-02 | 2015-08-26 | 广东中迅农科股份有限公司 | Insecticidal combination containing butene-fipronil and fluorine benzene worm amide |
| CN104855399B (en) * | 2015-05-02 | 2018-06-19 | 广东中迅农科股份有限公司 | A kind of Pesticidal combination containing butene-fipronil and fluorobenzene insect amide |
| CN106305758A (en) * | 2015-06-23 | 2017-01-11 | 沈阳中化农药化工研发有限公司 | Synergistic and compounded pest and mite killing composition |
| CN106187896A (en) * | 2016-07-19 | 2016-12-07 | 中南民族大学 | Ultrasonic atomization microwave radiation integration system is for the single or multiple alkyl derivative of arylpyrazole |
| CN111072568A (en) * | 2019-12-26 | 2020-04-28 | 华东理工大学 | Phenylpyrazole compounds containing azo structure and preparation method and application thereof |
| CN111072568B (en) * | 2019-12-26 | 2024-07-23 | 华东理工大学 | Phenyl pyrazole compound containing azo structure, and preparation method and application thereof |
| CN114105877A (en) * | 2021-06-30 | 2022-03-01 | 浙江美诺华药物化学有限公司 | Preparation method of fipronil intermediate and method for preparing fipronil by using fipronil intermediate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1204123C (en) | 2005-06-01 |
| KR100603690B1 (en) | 2006-07-20 |
| KR20050016663A (en) | 2005-02-21 |
| JP2005534683A (en) | 2005-11-17 |
| WO2004010785A1 (en) | 2004-02-05 |
| AU2003242089A1 (en) | 2004-02-16 |
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