CN1115326C - Pyrethroids compounds and preparation method and application thereof - Google Patents
Pyrethroids compounds and preparation method and application thereof Download PDFInfo
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- CN1115326C CN1115326C CN99126022A CN99126022A CN1115326C CN 1115326 C CN1115326 C CN 1115326C CN 99126022 A CN99126022 A CN 99126022A CN 99126022 A CN99126022 A CN 99126022A CN 1115326 C CN1115326 C CN 1115326C
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- Prior art keywords
- compound
- dextrorotation
- trans
- propargyl
- dimethyl
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- -1 2, 2-dichlorovinyl Chemical group 0.000 claims abstract description 13
- 239000002728 pyrethroid Substances 0.000 claims abstract description 11
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- 241000723353 Chrysanthemum Species 0.000 claims description 8
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 abstract description 2
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 abstract description 2
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- VMVPLAJQLQHHMF-UHFFFAOYSA-N O1N=C(C=C1)C(=O)O.C1(CC1)C(=O)O Chemical compound O1N=C(C=C1)C(=O)O.C1(CC1)C(=O)O VMVPLAJQLQHHMF-UHFFFAOYSA-N 0.000 description 5
- 230000000857 drug effect Effects 0.000 description 5
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- SMKRKQBMYOFFMU-UHFFFAOYSA-N prallethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OC1C(C)=C(CC#C)C(=O)C1 SMKRKQBMYOFFMU-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000257159 Musca domestica Species 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 235000021050 feed intake Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 241001674044 Blattodea Species 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The present invention relates to a pyrethroid compound, a preparation method thereof and an application thereof. The chemical name of the pyrethroid compound is (+)-2, 2-dimethyl-3-trans-form(2, 2-dichlorovinyl) cyclopropane-carboxylic acid-(+)2-methyl-3-(2-propargyl)-4-ketocyclopentyl-2-alkenyl ester called d-propargyl chloride pyrethrin for short. The pyrethroid compound is a simple optical pure compound, and has the characteristics of low production cost, high disinsection effect and low environmental pollution.
Description
The present invention relates to a kind of pyrethroid coumpound and its production and application.
Pyrethroid is to copy natural pyrethrin to carry out structure of modification and the insecticides that obtains.In the existing agricultural chemicals in the world, has the chirality pesticide species and account for 25%, but the sales quota of single efficient isomer only is 7% in the market that as seen the development space in this field is very big.At present, pesticide research is deep into molecule stereoisomerism field gradually, and wherein the research and development of optical activity pyrethroid are taken the lead especially, different isomer, different its insecticidal activity differences of optical property are very big, and the high efficiency of optical activity product is self-evident.But since the preparation of single efficient isomer with separates very difficult, therefore single efficient isomer is considerably less at present, basically all be to adopt the active ingredient of various mixture of isomers as agricultural chemicals, product effectiveness is low with regard to having caused, problems such as cost is high, environmental pollution have to be solved for this.
The purpose of this invention is to provide a kind of new pyrethroid coumpound, this compound is single efficient isomer, the present invention simultaneously also provides a kind of simple synthetic method and the application of this compound, has that production cost is low, desinsection is renderd a service high, the little characteristics of environmental pollution.
Pyrethroid coumpound of the present invention, its chemical name is: (+)-2,2-dimethyl-3-trans (2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(+) 2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters, be called for short dextrorotation propargyl chloride chrysanthemum ester, structural formula is:
Compound of the present invention is a kind of single optical purity, molecular formula: C
17H
18Cl
2O
3, molecular weight 341, rerum natura: the red-brown transparent liquid, be soluble in most of organic solvents, be insoluble in water.
In pyrethroid coumpound,
C in the three carbocyclic ring chrysanthemumic acid
1And C
3And the C in the propine alcohol ketone
1Therefore all be chiral carbon atom, 8 isomer can be arranged, calculate 8 isomer the theoretical relative effectivenes of housefly is respectively: (1R, 3R, C
1S) body-100, (1S, 3S, C1R) body-0.50, (1R, 3R, C
1R) body-18.30, (1S, 3S, C
1S) body-4.80, (1R, 3S, C
1S) body-58.50, (1S, 3R, C
1R) body-3.42, (1R, 3S, C
1R) body-14.00, (1S, 3R, C
1S) body-7.30, compound of the present invention is (1R, 3R, C
1S) body, as seen its insecticidal activity is the highest, and it is used as sterilant, has very high desinsection and renders a service.Compound of the present invention can be used for the control of health such as mosquitos and flies, cockroach.
Compound its preparation method of the present invention is very simple, can be synthesized into by dextrorotation trans dichloro chrysanthemum acyl chlorides and dextrorotation propine alcohol ketone.Its synthesis step is followed successively by: 1, dextrorotation propine alcohol ketone and pyridine are dissolved in the solvent; 2, under 10-18 ℃ of temperature condition to wherein dripping the trans dichloro chrysanthemum of dextrorotation acyl chlorides, chemistry (+)-2 by name, 2-dimethyl-3-is trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid, drips 1hr and finishes; 3, continue to be warming up to 50-55 ℃ of stirring reaction 4hr; 4, aftertreatment.
Wherein aftertreatment can be taked following method: suction filtration → pickling → alkali cleaning → washing → precipitation.
In the synthetic method of The compounds of this invention, raw material dextrorotation propine alcohol ketone, pyridine, (+)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) weight ratio of cyclopropane carboxylic acid isoxazolecarboxylic acid is 1: 0.64: 1.53, used solvent is general organic solvent, as toluene, acetone etc., the ratio of the used quantity of solvent and the alcohol ketone of input is 0.026 a liter/gram; In aftertreatment, the filtrate of carrying out behind the suction filtration is carried out pickling earlier, and pickling can be adopted 10% hydrochloric acid soln, carries out alkali cleaning again, and alkali cleaning can be adopted 5% NaHCO
3Solution, after the alkali cleaning through the washing, slough solvent get final product compound of the present invention.
In addition, the present invention has also synthesized other two kinds of optical isomers:
1, compound (I): (+)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(±)-2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters is synthetic, is synthesized into by dextrorotation trans dichloro chrysanthemum acyl chlorides and propine alcohol ketone, and the preparation method is as follows:
In the four-hole boiling flask of a 250ml, drop into (±)-2-methyl-3-(2-propargyl)-ring penta-2-alkene-4-oxo-1-alcohol (being DL propine alcohol ketone) 3.00g, pyridine 2.10g, be dissolved in toluene 70ml, feed intake and finish to stir, under 10-18 ℃ of temperature condition to wherein dripping (+)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 4.60g drips 1hr and finishes, and heats up at 50-55 ℃ of stirring reaction 4hr.Carry out suction filtration then, add 10% hydrochloric acid soln 50ml and carry out the pickling layering in filtrate, oil reservoir is with 5% NaHCO
3Solution 50ml washs, and again oil reservoir is carried out twice washing with ionized water 50ml.Oil reservoir after the washing is sloughed toluene, compound (I): (+)-2,2-dimethyl-3-is trans-(2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(±)-2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters.Weight 6.73g, content are 96.03%, and yield is 94.76%.
2, compound (II): (±)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(+)-2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters is synthetic, is synthesized into by DL trans dichloro chrysanthemum acyl chlorides and dextrorotation propine alcohol ketone, and the preparation method is as follows:
In the four-hole boiling flask of a 250ml, drop into dextrorotation propine alcohol ketone 3.00g, pyridine 1.90g, be dissolved in toluene 80ml, feed intake and finish to stir, under 10-18 ℃ of temperature condition to wherein dripping (±)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 4.55g drips 1hr and finishes, and heats up and continues stirring reaction 4hr at 50-55 ℃.Carry out suction filtration then, add 10% hydrochloric acid soln 50ml and carry out the pickling layering in filtrate, oil reservoir is with 5% NaHCO
3Solution 50ml washs, and again oil reservoir is carried out twice washing with ionized water 50ml.Oil reservoir after the washing is sloughed toluene, gets Compound I I): (±)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(+)-2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters, weight is 6.79g, and content is 96.20%, and yield is 95.78%.
Compound of the present invention uses as sterilant, has following beneficial effect: 1, insecticidal effect height:
The drug effect of compound of the present invention (compound III) with Compound I, Compound I I and ETOC (silkworm restrains more) compared:
(1), specimen: the spray agent that Compound I, II, III, ETOC is made into suitable concn respectively with acetone.
(2), try worm: a, housefly, 4-5 age in days adult after sprouting wings;
B, German little butterfly, 2 age in week adult, female, male half and half.
(3), testing method: simulated field, carry out according to GB13917.8-92.
(4), test-results: see following table 1,2
Table 1 drug effect contrast (the examination worm is a housefly)
| Drug effect | Concentration (%) | KT50 | KT95 |
| Compound I | 0.01 | 2′00″ | 3′48″ |
| Compound I I | 0.01 | 2′45″ | 4′25″ |
| Compound III | 0.006 | 1′48″ | 4′03″ |
| ETOC | 0.021 | 2′06″ | 5′24″ |
Table 2 drug effect contrast (the examination worm is German little butterfly)
| Drug effect | Concentration (%) | KT50 | KT95 |
| Compound I | 0.01 | 1′06″ | 1′06″ |
| Compound I I | 0.01 | 1′30″ | 2′14″ |
| Compound III | 0.006 | 53″ | 58″ |
| ETOC | 0.025 | 1′00″ | 1′48″ |
Can find out that from above experimental result compound of the present invention has very high insecticidal activity.
2, production cost is low: because the high efficiency of product of the present invention must cause the reduction greatly of production cost, the mixture than using traditional various isomer uses compound of the present invention as sterilant, and cost can reduce about 35%-40%.
3, pollute little: because compound of the present invention is single optical purity,, does not exist in the mixture invalid body and poor efficiency body to enter environment and produce pollution problems, compliance with environmental protection requirements therefore than the mixture that uses traditional various isomer.
Below be embodiments of the invention:
Embodiment: compound III: (+)-2, the preparation of 2-dimethyl-3-trans (2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(+) 2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters
In the four-hole boiling flask of a 250ml, drop into dextrorotation propine alcohol ketone 3.00g, pyridine 1.90g, be dissolved in toluene 80ml, feed intake and finish to stir, under 10-18 ℃ of temperature condition to wherein dripping (+)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 4.60g drips 1hr and finishes, and continues to be warming up to 50-55 ℃ of stirring reaction 4hr.Carry out suction filtration then, add 10% hydrochloric acid soln 50ml and carry out pickling in filtrate, oil reservoir is with 5% NaHCO
3Solution 50ml washs, and again oil reservoir is carried out twice washing with ionized water 50ml.Oil reservoir after the washing is sloughed toluene, obtain compound III: (+)-2,2-dimethyl-3-trans (2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(+) 2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters, weight is 6.75g, and content is 97.31%, and yield is 96.31%.
Claims (3)
1, a kind of pyrethroid coumpound, its chemical name is: (+)-2,2-dimethyl-3-trans (2, the 2-dichloroethylene) cyclopropane-carboxylic acid-(+) 2-methyl-3-(2-propargyl)-4-oxo ring penta-2-alkenyl esters, be called for short dextrorotation propargyl chloride chrysanthemum ester, structural formula is:
It is characterized in that described compound is a kind of single optical purity.
2, the preparation method of compound as claimed in claim 1 is synthesized into by dextrorotation trans dichloro chrysanthemum acyl chlorides and dextrorotation propine alcohol ketone, it is characterized in that adopting following synthesis step: 1, dextrorotation propine alcohol ketone and pyridine are dissolved in the solvent; 2, under 10-18 ℃ of temperature condition to wherein dripping the trans dichloro chrysanthemum of dextrorotation acyl chlorides, drip 1hr and finish; 3, continue to be warming up to 50-55 ℃ of stirring reaction 4hr; 4, take following method: suction filtration → pickling → alkali cleaning → washing → precipitation carries out aftertreatment.
3, compound as claimed in claim 1 is as the application of sterilant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99126022A CN1115326C (en) | 1999-12-13 | 1999-12-13 | Pyrethroids compounds and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99126022A CN1115326C (en) | 1999-12-13 | 1999-12-13 | Pyrethroids compounds and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1303846A CN1303846A (en) | 2001-07-18 |
| CN1115326C true CN1115326C (en) | 2003-07-23 |
Family
ID=5284276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99126022A Expired - Lifetime CN1115326C (en) | 1999-12-13 | 1999-12-13 | Pyrethroids compounds and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1115326C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103960231A (en) * | 2011-08-16 | 2014-08-06 | 江苏扬农化工股份有限公司 | Long-acting insecticidal spray and application thereof |
| CN102349536A (en) * | 2011-08-16 | 2012-02-15 | 江苏扬农化工股份有限公司 | Long-acting insecticidal spraying agent and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2055822A (en) * | 1979-07-27 | 1981-03-11 | Sumitomo Chemical Co | Carboxylic ester compounds for use as insecticides |
-
1999
- 1999-12-13 CN CN99126022A patent/CN1115326C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2055822A (en) * | 1979-07-27 | 1981-03-11 | Sumitomo Chemical Co | Carboxylic ester compounds for use as insecticides |
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| CN1303846A (en) | 2001-07-18 |
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