CN101638367B - Novel pyrethroid compounds derived from tefluthrin - Google Patents
Novel pyrethroid compounds derived from tefluthrin Download PDFInfo
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- CN101638367B CN101638367B CN2008100211492A CN200810021149A CN101638367B CN 101638367 B CN101638367 B CN 101638367B CN 2008100211492 A CN2008100211492 A CN 2008100211492A CN 200810021149 A CN200810021149 A CN 200810021149A CN 101638367 B CN101638367 B CN 101638367B
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- CN
- China
- Prior art keywords
- propenyl
- fluoro
- carboxylic acid
- cyclopropane carboxylic
- dimethyl cyclopropane
- 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.)
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- 239000002728 pyrethroid Substances 0.000 title claims abstract description 19
- ZFHGXWPMULPQSE-SZGBIDFHSA-N (Z)-(1S)-cis-tefluthrin Chemical compound FC1=C(F)C(C)=C(F)C(F)=C1COC(=O)[C@@H]1C(C)(C)[C@@H]1\C=C(/Cl)C(F)(F)F ZFHGXWPMULPQSE-SZGBIDFHSA-N 0.000 title description 5
- 239000005939 Tefluthrin Substances 0.000 title description 5
- 241000238631 Hexapoda Species 0.000 abstract description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 2
- 230000002147 killing effect Effects 0.000 abstract 1
- 230000003405 preventing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 238000005554 pickling Methods 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 241000723353 Chrysanthemum Species 0.000 description 4
- 235000007516 Chrysanthemum Nutrition 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 241000257159 Musca domestica Species 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000256059 Culex pipiens Species 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000000857 drug effect Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 1
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical group CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Abstract
The invention relates to novel pyrethroid compounds shown in a general formula (I), which have good insect expelling, killing and preventing activity, and can be used surely. In the formula, when X is -H group, R can be -H, -CH3, -OCH3 and -CH2OCH3 group; and when the X is -Cl group, the R can be -H, -OCH3, -CH2OCH3 group.
Description
Technical field
The present invention relates to some new new pyrethroid compounds and preparation method thereof.
Background technology
Pyrethroid is an analoglike natural pyrethrum structure artificial synthetic sterilant, and, low toxicity efficient with it, easily degraded, the characteristics that environment compatibility is good have occupied domestic sanitary desinsection market and part agricultural chemicals market substantially.Wherein tefluthrin is first pyrethroid insectide that is used for soil, can keep longer residual effect to soil pests, and unlikelyly causing extended residual danger, but shortcoming is that high relatively poison and desinsection drug effect are still not high enough relatively, has limited its use in the family expenses hygienic insecticide.
The applicant compares research by some the new pyrethroid compounds to the configuration of tefluthrin, drug effect, vapour pressure etc. and recent development, some new compounds have been synthesized, the preliminary test of pesticide effectiveness of these compounds shows to have strong insecticidal action, and its lethality rate height, vapour pressure also have raising and can stablize lasting volatilization toxicity decline simultaneously at normal temperatures.The application of pyrethroid has been widened in the invention of these compounds, and has enlarged the pyrethroid family member.
Summary of the invention
The present invention relates to the pyrethroid compounds of following general formula (I) expression, have expelling parasite preferably, desinsection, insect protected activity, and confirm and to use.
R in the formula
When X is-H when base, R can be-H in the formula ,-CH
3,-OCH
3,-CH
2OCH
3Base;
When X is-Cl when base, R can be-H in the formula ,-OCH
3,-CH
2OCH
3Base.
1. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound chemistry name is called: 3-(3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid-2,3,5,6-tetrafluoro-4-methoxyl methyl carbobenzoxy ester is called for short: inclined to one side seven fluorine s; Molecular formula is: C
18H
17F
7O
3Molecular weight is: 414.1; Structural formula is:
2. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound chemistry name is called: 3-(3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid-2,3,5,6-tetrafluoro-4-methoxy benzyl ester is called for short: inclined to one side seven fluorine methoxy chrysanthemum esters; Molecular formula is: C
17H
15F
7O
3Molecular weight is: 400.1; Structural formula is:
3. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound chemistry name is called: 3-(3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid-2,3,5,6-tetrafluoro-4-methyl benzyl ester is called for short: inclined to one side tefluthrin; Molecular formula is: molecular formula is: C
17H
15F
7O
2Molecular weight is: 384.1; Structural formula is:
4. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound chemistry name is called: 3-(3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid-2,3,5, the 6-ptfe benzyl, be called for short: inclined to one side seven fluorine remove first chrysanthemum ester; Molecular formula is: molecular formula is: C
16H
13F
7O
2Molecular weight is: 370.1; Structural formula is:
5. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound chemistry name is called: 3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5,6-tetrafluoro-4-methoxyl methyl carbobenzoxy ester is called for short: seven fluorine s; Molecular formula is: C
18H
17ClF
7O
3Molecular weight is: 448.6; Structural formula is as follows:
6. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound chemistry name is called: 3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid-2,3,5,6-tetrafluoro-4-methoxy benzyl ester is called for short: seven fluorine methoxy chrysanthemum esters; Molecular formula is: C
17H
15ClF
7O
3Molecular weight is: 434.6; Structural formula is as follows:
7. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound chemistry name is called: 3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid-2,3,5,6-tetrafluoro-4-methyl benzyl ester, be called for short: seven fluorine remove first chrysanthemum ester; Molecular formula is: C
16H
13ClF
7O
2Molecular weight is: 404.6; Structural formula is as follows:
8. the pyrethroid compound of above-mentioned formula (I) is characterized in that this compound its preparation method is by 3-(3,3,3-three fluoro-1-propenyl)-2, and (R is-H-CH to 2-dimethyl cyclopropane carboxylic acid acyl chlorides with the alcohol of being represented by general formula R-OH
3,-OCH
3-CH
2OCH
3Basic) or 3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2, (R is-H-OCH to 2-dimethyl cyclopropane carboxylic acid acyl chlorides with the alcohol of being represented by general formula R-OH
3,-CH
2OCH
3Base) esterification is synthetic, and esterification is carried out in the presence of pyridine.
Specific implementation method
Synthesizing of embodiment 1 compound (1)
3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 23.2g is added in the dropping funnel, adds toluene 110g, pyridine 9.5g, 2,3 in the four-hole reaction flask of 500ml, 5,6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.9g stirs and makes dissolving fully, drips 3-(3 under 10-15 ℃ of temperature condition, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides drips 1hr and finishes insulation continuation stirring reaction 0.5-1hr.Add 5% hydrochloric acid soln and carry out pickling, divide the phase of anhydrating, oil reservoir 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with deionized water again.Oil reservoir after the washing is sloughed toluene and is obtained compound (1): 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5, and 6-tetrafluoro-4-methoxyl methyl carbobenzoxy ester, weight is 41.5g, and content is 95.2%, and yield is 95.4%.
Synthesizing of embodiment 2 compounds (2)
3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 23.2g is added in the dropping funnel, adds toluene 110g, pyridine 9.5g, 2,3 in the four-hole reaction flask of 500ml, 5,6-tetrafluoro-4-methoxyl group benzylalcohol 21.4g stirs and makes dissolving fully, drips 3-(3 under 10-15 ℃ of temperature condition, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides drips 1hr and finishes insulation continuation stirring reaction 0.5-1hr.Add 5% hydrochloric acid soln and carry out pickling, divide the phase of anhydrating, oil reservoir 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with deionized water again.Oil reservoir after the washing is sloughed toluene and is obtained compound (1): 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5, and 6-tetrafluoro-4-methoxy benzyl ester, weight is 39.9g, and content is 95.5%, and yield is 95.2%.
Synthesizing of embodiment 3 compounds (3)
3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 23.2g is added in the dropping funnel, adds toluene 110g, pyridine 9.5g, 2,3 in the four-hole reaction flask of 500ml, 5,6-tetrafluoro-4-xylyl alcohol 19.8g stirs and makes dissolving fully, drips 3-(3 under 10-15 ℃ of temperature condition, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides drips 1hr and finishes insulation continuation stirring reaction 0.5-1hr.Add 5% hydrochloric acid soln and carry out pickling, divide the phase of anhydrating, oil reservoir 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with deionized water again.Oil reservoir after the washing is sloughed toluene and is obtained compound (1): 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5, and 6-tetrafluoro-4-methyl benzyl ester, weight is 38.2g, and content is 96.1%, and yield is 95.6%.
Synthesizing of embodiment 4 compounds (4)
3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 23.2g is added in the dropping funnel, adds toluene 110g, pyridine 9.5g, 2,3 in the four-hole reaction flask of 500ml, 5,6-tetrafluorobenzyl alcohol 18.4g stirs and makes dissolving fully, drips 3-(3 under 10-15 ℃ of temperature condition, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides drips 1hr and finishes insulation continuation stirring reaction 0.5-1hr.Add 5% hydrochloric acid soln and carry out pickling, divide the phase of anhydrating, oil reservoir 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with deionized water again.Oil reservoir after the washing is sloughed toluene and is obtained compound (1): 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5, and the 6-ptfe benzyl, weight is 36.9g, and content is 95.9%, and yield is 95.6%.
Synthesizing of embodiment 5 compounds (5)
3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 26.0g is added in the dropping funnel, adds toluene 110g, pyridine 9.5g, 2,3 in the four-hole reaction flask of 500ml, 5,6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.9g stirs and makes dissolving fully, drips 3-(2-chloro-3 under 10-15 ℃ of temperature condition, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides drips 1hr and finishes insulation continuation stirring reaction 0.5-1hr.Add 5% hydrochloric acid soln and carry out pickling, divide the phase of anhydrating, oil reservoir 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with deionized water again.Oil reservoir after the washing is sloughed toluene and is obtained compound (1): 3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5, and 6-tetrafluoro-4-methoxyl methyl carbobenzoxy ester, weight is 44.6g, and content is 96.5%, and yield is 95.9%.
Synthesizing of embodiment 6 compounds (6)
3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 26.0g is added in the dropping funnel, adds toluene 110g, pyridine 9.5g, 2,3 in the four-hole reaction flask of 500ml, 5,6-tetrafluoro-4-methoxyl group benzylalcohol 22.9g stirs and makes dissolving fully, drips 3-(2-chloro-3 under 10-15 ℃ of temperature condition, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides drips 1hr and finishes insulation continuation stirring reaction 0.5-1hr.Add 5% hydrochloric acid soln and carry out pickling, divide the phase of anhydrating, oil reservoir 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with deionized water again.Oil reservoir after the washing is sloughed toluene and is obtained compound (1): 3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5, and 6-tetrafluoro-4-methoxy benzyl ester, weight is 43.4g, and content is 96.4%, and yield is 96.3%.
Synthesizing of embodiment 7 compounds (7)
3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 26.0g is added in the dropping funnel, adds toluene 110g, pyridine 9.5g, 2,3 in the four-hole reaction flask of 500ml, 5,6-tetrafluorobenzyl alcohol 22.9g stirs and makes dissolving fully, drips 3-(2-chloro-3 under 10-15 ℃ of temperature condition, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides drips 1hr and finishes insulation continuation stirring reaction 0.5-1hr.Add 5% hydrochloric acid soln and carry out pickling, divide the phase of anhydrating, oil reservoir 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with deionized water again.Oil reservoir after the washing is sloughed toluene and is obtained compound (1): 3-(2-chloro-3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-2,3,5, and the 6-ptfe benzyl, weight is 40.3g, and content is 96.6%, and yield is 96.2%.
Concrete Application Example is as follows:
Embodiment 8
The ethanol solution of different concns is respectively made in compound (1), (2), (3), (4), (5), (6), (7), this solution is added in aerosol jar, pour a certain amount of propellent again, make the aerosol of 7 different concns.
Effect example 1
By the method for stipulating among GB13917.1-92 and the GB/T17322.1-1998 with the aerosol sample using dosage 1.43ml/m for preparing with each compound among the embodiment 8
3Culex pipiens pollens, housefly are carried out direct spray testing, using dosage 7.14ml/m
3Groton bug is carried out direct spray testing, and the test triplicate also calculates KT respectively
50, observe behind the 24hr and calculate mortality ratio, establish blank simultaneously, result such as following table:
As seen from the experiment, compound (1) (2) (3) (4) (5) (6) (7) is directly sprayed to culex pipiens pollens, housefly, Groton bug: compound (1) (2) (5) (6) is all stronger to culex pipiens pollens, housefly, the Groton bug activity that causes death, and knocks down active general; Compound (3) (4) (7) is all stronger to culex pipiens pollens, housefly, the Groton bug activity that causes death, and knocks down active relatively poor; Simultaneously, as can be known, compound (1) (2) (5) (6) has extraordinary drug effect from working concentration and effect comparison.
Claims (1)
1. the pyrethroid compound represented of following formula
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| CN2008100211492A CN101638367B (en) | 2008-07-28 | 2008-07-28 | Novel pyrethroid compounds derived from tefluthrin |
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|---|---|---|---|
| CN2008100211492A CN101638367B (en) | 2008-07-28 | 2008-07-28 | Novel pyrethroid compounds derived from tefluthrin |
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| CN101638367B true CN101638367B (en) | 2011-02-02 |
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|---|---|---|---|---|
| CN104430488A (en) * | 2014-11-25 | 2015-03-25 | 贵阳中精科技有限公司 | Insect aerosol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4370346A (en) * | 1979-12-21 | 1983-01-25 | Imperial Chemical Industries Plc | Halogenated esters |
| US4405640A (en) * | 1979-12-21 | 1983-09-20 | Imperial Chemical Industries Plc | Substituted fluorobenzyl cyclopropane carboxylates useful as insecticides |
| JP2002249464A (en) * | 2001-02-22 | 2002-09-06 | Sumitomo Chem Co Ltd | Ester compound and harmful organism preventive agent containing the same as active ingredient |
-
2008
- 2008-07-28 CN CN2008100211492A patent/CN101638367B/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4370346A (en) * | 1979-12-21 | 1983-01-25 | Imperial Chemical Industries Plc | Halogenated esters |
| US4405640A (en) * | 1979-12-21 | 1983-09-20 | Imperial Chemical Industries Plc | Substituted fluorobenzyl cyclopropane carboxylates useful as insecticides |
| JP2002249464A (en) * | 2001-02-22 | 2002-09-06 | Sumitomo Chem Co Ltd | Ester compound and harmful organism preventive agent containing the same as active ingredient |
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|---|---|
| CN101638367A (en) | 2010-02-03 |
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