CN101580471B - Pyrethroid compound, preparation method and application thereof - Google Patents
Pyrethroid compound, preparation method and application thereof Download PDFInfo
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- CN101580471B CN101580471B CN 200810097823 CN200810097823A CN101580471B CN 101580471 B CN101580471 B CN 101580471B CN 200810097823 CN200810097823 CN 200810097823 CN 200810097823 A CN200810097823 A CN 200810097823A CN 101580471 B CN101580471 B CN 101580471B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002728 pyrethroid Substances 0.000 title claims abstract description 24
- 230000000749 insecticidal effect Effects 0.000 claims abstract description 25
- 230000003287 optical effect Effects 0.000 claims abstract description 12
- 241000255925 Diptera Species 0.000 claims description 42
- 239000000077 insect repellent Substances 0.000 claims description 29
- 241000238631 Hexapoda Species 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 235000013599 spices Nutrition 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000000443 aerosol Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000003814 drug Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- 230000002147 killing effect Effects 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
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- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 230000001442 anti-mosquito Effects 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 13
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229940126062 Compound A Drugs 0.000 abstract 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 241000607479 Yersinia pestis Species 0.000 description 11
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- -1 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl Chemical group 0.000 description 5
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- 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 4
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- XEBGWKNWNKCQHU-UHFFFAOYSA-N 1-methoxy-1-phenylethanol Chemical compound COC(C)(O)C1=CC=CC=C1 XEBGWKNWNKCQHU-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 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 3
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000005611 electricity Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 241000256059 Culex pipiens Species 0.000 description 1
- 208000000655 Distemper Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 240000004460 Tanacetum coccineum 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 compound 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
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940015367 pyrethrum Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a pyrethroid compound A which has a structural formula below, wherein R1 and R2 are respectively the same or different halogens, and the pyrethroid compound is a d-trans single optical active isomer. The pyrethroid compound has more obvious effect of desinsection compared with a racemic compound or other compounds of the same class of the prior art. The invention also provides a preparation method and application in sanitary insecticidal products of the pyrethroid compound A.
Description
Technical field
The present invention relates to a kind of pyrethroid compound, relate in particular to a kind of pyrethroid compound of single optical activity.
Background technology
Pyrethroid coumpound can be used to prevent and treat mosquito, and has higher insecticidal activity, and this is widely known by the people, and U.S. Pat 4370346 discloses first and met following structural formula in this compounds,
And R
1And R
2Racemoid when being chlorine simultaneously, and publication number is to mention once that this racemoid can be used for controlling sanitary insect pest in the Chinese patent of CN1669429, CN1669419.Yet the drug efficacy study about this compound different optical isomer component does not but appear in the newspapers.Along with people's is increasingly high to environmental requirement, and the high biological activity of agricultural chemicals more and more causes people's attention.Pyrethroid has 2～8 optical isomers usually, and biological activity is widely different between each isomer, therefore needs the most highly active isomer of research preparation.See from the angle of environmental protection, use highly active single optical isomer can under the prerequisite that does not reduce drug effect, reduce the dose that to use, thereby reduce toxicity, improve security, reduce the left drug environmental pollution non-target organism.
The present invention is just under above-mentioned technical background; Pyrethroid compound to the different optical isomer is furtherd investigate; Propose biological activity and exceeded the single optical activity body compound of pyrethroid compound in the prior art far away, and proposed the preparation method and its application aspect desinsection of this compound.
Summary of the invention
The object of the invention just provides a kind of new pyrethroid coumpound, and this compound is the single optical activity body, and the present invention simultaneously also provides the preparation method and its application aspect pest control of this compound.
The objective of the invention is to realize through following technical scheme:
A kind of pyrethroid compound is provided, for structure satisfies the compd A of following formula,
R wherein
1And R
2Be respectively halogen identical or inequality, it is characterized in that: said compd A is the trans single optical activity isomer of dextrorotation.
Said R1 preferably is respectively fluorine, a chlorine or bromine identical or inequality with R2; Further preferably be fluorine, chlorine or bromine simultaneously.
When R1 and R2 were chlorine simultaneously, compd A was 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R1 and R2 were bromine simultaneously, compd A was 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R1 be chlorine, when R2 is bromine, compd A is 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2-chlorine 2-bromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
The present invention also provides the preparation method of said compd A, and promptly said compd A is by 2,3.5, and the trans dihalo-chrysanthemic acid esterification of acyl chloride of dextrorotation that pure and mild described R1 of 6-tetrafluoro-4-methoxyl methyl carbobenzoxy and R2 are corresponding obtains.Wherein, the trans dihalo-chrysanthemic acid acyl chlorides of dextrorotation that said R1 and R2 are corresponding is obtained through acyl chloride reaction by R1 and the corresponding dihalo-chrysanthemic acid of R2; The reagent of said chloride is selected from a kind of in phosphorus trichloride, sulfur oxychloride, the TRIPHOSGENE 99.5.
The present invention also provides described compd A in the application of remove killing aspect mosquito, fly or the Groton bug.
The above-mentioned application of said compd A, be with said compd A as former medicine, be prepared into various forms of sterilants according to ordinary method, be used for remove killing mosquito, fly or Groton bug.
Said various forms of sterilant comprises disc type insecticidal incense, electric mosquito repellent tablet, electric liquid device or insect aerosol etc.
Below be former medicine in preparation various forms sterilant to said compd A application is described in detail:
(1) preparation disc type insecticidal incense
Described disc type insecticidal incense is mixed with compd A to join behind the liquid form and processes in the base material, and wherein the content of compd A is 0.01～1.0w/w%.
The liquid form that said compd A is mixed with is missible oil or is the solution of solvent with the hydro carbons.
Said missible oil can add water and admix in the disc type insecticidal incense base material when preparation base material (fragrant base), forms the disc type insecticidal incense that contains above-mentioned concentration compd A, then oven dry.Also contain tensio-active agent and other auxiliary agents in the said missible oil; The instance of said tensio-active agent comprises one or more mixtures in alkyl-sulphate, AS, alkylaryl sulphonate, polyoxyalkylene alkyl, polyoxyalkylene alkyl aryl ether, polyoxyalkylene styryl phenyl ether, polyol ethers or the sugar alcohol derivant; The instance of said other auxiliary agents comprises one or more the mixture in perfume compound, tinting material or the sterilant.
Said is that the solution of solvent can spray on the disc type insecticidal incense base material with the hydro carbons, forms the disc type insecticidal incense that contains above-mentioned concentration compd A.Said varsol preferably has the saturated hydrocarbons solvent of 150～350 ℃ of boiling points, and instance comprises straight chain hydrocarbon, branched-chain hydrocarbon, cycloaliphates or their mixture.
The base material of said disc type insecticidal incense is made up of one or more inflammable substances and one or more tackiness agents, and wherein the weight ratio of inflammable substance and tackiness agent is 90: 10 to 99.9: 0.1.The instance of inflammable substance comprises the plant drymeal that is selected from wood powder, pyrethrum extraction powder, citrus peel meal, palm oil-bound distemper, coconut shell powder or walnut parting, or is selected from the carbon dust of wood charcoal powder, activity charcoal powder or coal dust, or their mixture; The instance of tackiness agent comprises the Tabu powder, is selected from tapioca(flour), the polymkeric substance of starch, casein, methylcellulose gum, CMC 99.5 or Z 150PH of W-Gum or wheat starch and composition thereof.
Said disc type insecticidal incense base material normally through mixing inflammable substance and tackiness agent, is mediated with water, moulding and oven dry preparation.The shape of disc type insecticidal incense base material is restriction not, can be plate-like or strip.The present invention uses about 12cm of diameter and the thickness conventional coil shape base material as 3-5mm usually in two line spices of a cover.
The disc type insecticidal incense that more than obtains can ordinary method be used.That is, light disc type insecticidal incense of the present invention near (for example dwelling house, office, stock barn) or its in the habitat of insect.The burning of disc type insecticidal incense can make the ester cpds volatilization of formula (A); After airborne effective constituent reaches certain concentration; To mosquito, fly, sanitary insect pests such as Groton bug produce to be stimulated, drives, benumbs, knocks down and lethal effect; Thereby reach mosquito, fly, the control of sanitary insect pests such as Groton bug.
(2) preparation electric mosquito repellent tablet
Said electric mosquito repellent tablet is the solution that contains compd A to be dripped and/or is coated on the porosity base material make, and the content of compd A is the 1-20mg/ sheet in the said anti-mosquito incense sheet.Also contain the additive that is selected from inhibitor, stifling regulator, spices or dyestuff in the said solution that contains compd A.
The instance of the porous substrate of said electric mosquito repellent tablet comprises paper pulp, asbestos, synthetic porous resin, porous, inorganic powder, spun glass, sulphur thing powder or porous ceramic material; Said porous substrate is long 30-35mm, wide 20-22mm, the sheet of thick 1.5-2mm.An example that is used for porous pad of the present invention is the sheet of paper pulp fiber that contains cotton fibre and 50% weight of 50% weight, sees from absorptivity and the viewpoint that keeps insecticidal active ingredient, preferably uses the natural fiber material film-making.
When using electric mosquito repellent tablet of the present invention near (for example dwelling house, office, stock barn) or its in the habitat of insect, through the certain temperature of electric heating panel control, the medicine that floods in the sheet just begin slowly wave diffusing.After spatial effective constituent reaches certain concentration, just can be to mosquito, fly, sanitary insect pests such as Groton bug produce to be stimulated, drives, benumbs, knocks down and lethal effect, thereby reaches mosquito, fly, the control of sanitary insect pests such as Groton bug.
(3) preparation electric liquid device
Said electric liquid device is that compd A is dissolved in the aliphatic hydrocarbon, adds the inhibitor of 0.1-0.5% then, and 0.1-1% spices is mixed with the solution that contains the 0.1-2% compd A and obtains; The aliphatic hydrocarbon of the preferred C14 component of said aliphatic hydrocarbon.
Electric liquid device liquid is through the wicking action of plug, takes mosquito-repellent incense liquid the top of new edition to from the bottom of plug, under the electrically heated effect of ring heater; After making spatial effective constituent reach certain concentration; Just can be to mosquito, fly, sanitary insect pests such as Groton bug produce to be stimulated, drives, benumbs, knocks down and lethal effect; Thereby reach mosquito, fly, the control of sanitary insect pests such as Groton bug.
(4) preparation insect aerosol
Said insect aerosol be with compd A, kerosene and synergistic agent, perfume compound, the sterilant according to circumstances selected under room temperature or heating condition, mixes one of the compsn adding of getting up be equipped with a valve jar in; And under pressure, in jar, add propelling agent through this valve and make, the content of compd A is 0.001～0.5w/w% in the final composition; Said propelling agent accounts for 20～60% of composition total weight; Preferred LPG liquefied petroleum gas, third butane, dme or pressurized air, further preferred third butane.
When insect aerosol of the present invention was used in the habitat of insect, by-pass valve control was opened, under the pressure effect of propelling agent; Produce high velocity air, jar is included the soup aerosol dispersion of effective constituent and the gasification of propelling agent, the small liquid pearl that contains effective insecticidal constituent of formation is suspended in the air; With mosquito; Fly, sanitary insect pests such as Groton bug contact, and reach the purpose of quick kill pests.
The inventor finds in the research process to the pyrethroid optical isomer; Single optical isomer of the present invention has than its raceme compound of the prior art and has higher insecticidal activity; Through further exploring; The contriver finds that the compound that this structural formula is represented all has very high insecticidal activity when R1 in the aforementioned structural formula and R2 are chlorine or bromine identical or inequality.
Based on above-mentioned achievement in research, the present invention proposes compd A and killing mosquito, fly, the application of sanitary insect pest aspects such as Groton bug, and concrete application mode has been proposed.Through experiment; Proved compound according to the invention and housefly, culex pipiens pollens, Groton bug etc. have been had remarkable prevention effect with its various sterilants for former medicine preparation; And the insecticidal activity of this optically active individual isomer is far above similar raceme; Carry out efficacy testing with hygienic insecticide esbiothrin commonly used at present in addition, the result shows that the drug effect of this compounds is at more than 10～20 times of esbiothrin.As replacing esbiothrin with this compounds, reach same effect, its dosage only needs about 5～10% of esbiothrin, has alleviated the pollution to environment greatly.
Embodiment
Below with form illustrated in detail technical scheme of the present invention and the effect of embodiment, but the present invention is not limited to following examples.
Preparation embodiment 1.
2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester (compound I) synthetic:
In the four-hole bottle of a 2000ml, drop into tetrafluoro to methoxyl methyl phenylcarbinol 112.0g, pyridine 38.0g; Be dissolved in 800ml toluene; Throw to finish and stir, 0～5 ℃ drips (R)-2 down, and 2-dimethyl--3-trans-(2; The 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 114.0g drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution, use 400ml 5%NaHCO again
3Washing, oil reservoir is heated to 100 ℃ and purifies solvent toluene under the 10mmHg negative pressure, obtain compound 2; 3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R; 3S)-and 3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester faint yellow solid; Weight 203.3g, content are 97.8%, yield 95.8%.The molecular formula of this compound: C
17H
17Cl
2F
4O
3Molecular weight: 416.2; Optically-active [α]=-9.32; Dissolve in organic solvents such as toluene, benzene, YLENE, the infrared signature absorption peak is 3600-3100,2950,1510,1260,1180,1050, and 870cm
-1Nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.15-1.38 (m, 6H); 1.55-2.33 (m, 2H); 4.10 (d, 3H); 5.19 (m, 2H; 6.22 (d, 1H).
Preparation embodiment 2.
2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound I I) synthetic:
56.0g tetrafluoro drops in the 1000ml four-hole bottle methoxyl methyl phenylcarbinol, pyridine 25g, 400ml toluene; Throw Bi Changwen and stirred 15 minutes down, drip (R)-2 down at 0～5 ℃, 2-dimethyl--3-trans-(2; The 2-dibromo vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 79.4g; Drip complete 10 ℃ and be incubated 1 hour down, oil reservoir is used 100ml 5%NaHCO again with 150ml 5% salt acid elution
3Washing, washing is to neutral again.Oil reservoir negative pressure piptonychia benzene, temperature is 100 ℃ eventually, and absolute pressure 10mmHg obtains compound 2,3; 5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dibromo vinyl)-2; 2-dimethyl cyclopropane carboxylic acid ester is a pale solid, and weight 125.1g, content are 97.1%, and yield is 96.2%.
Preparation embodiment 3.
2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2-chloro-2-bromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound III) synthetic:
Tetrafluoro drops in the four-hole bottle of 2000ml methoxyl methyl phenylcarbinol 112.0g, pyridine 50.0g, 800ml toluene; Stirring and dissolving, under 0～5 ℃ to wherein drip (R)-2-chloro-2-bromo-3-trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 136.2g; Drip and finish; 10 ℃ of insulation reaction 4 hours are used 5% chlorohydric acid pickling, 5%NaHCO
3Solution washing is carried out twice washing with oil reservoir with ionized water 200ml again.Oil reservoir negative pressure piptonychia benzene, temperature is 100 ℃ eventually, and absolute pressure 10mmHg obtains compound 2; 3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2-chlorine 2-bromo vinyl)-2; 2-dimethyl cyclopropane carboxylic acid ester is a pearl look solid, and weight 229.8g, content are 98.2%, and yield is 98.1%.
Application implementation example 1
Compound of the present invention (compound I) and at present the most frequently used d-allethrin are carried out evaluation of pesticide effectiveness contrast according to GB13917.4-92, compound I 0.028g is dissolved in 1g kerosene, drop to the blank mosquito-repellent incense blank of 35g is processed 0.08% compound I mosquito-repellent incense; Process 0.8% dextrorotation propylene mosquito-repellent incense 0.28 d-allethrin is dissolved in the same drop of 1g kerosene to the blank mosquito-repellent incense blank of 35g, respectively two kinds of mosquito-repellent incenses are carried out efficacy testing, detailed process is to draw 20 female culex pipiens fatigans with mosquito sucking tube; Put into airtight drum test set; Appoint and get one section of mosquito-repellent incense to be tested, put to mosquito coil frame the igniting mosquito-repellent incense timing; Remove mosquito-repellent incense behind the 1min; Write down down and out examination mosquito number at set intervals, will all supply to try in the dependent insect cage that mosquito is transferred to cleaning the dead examination of inspection mosquito number behind the 24hr behind the 20min.
Experimental result is seen table 1:
The comparison of table 1. The compounds of this invention and d-allethrin effect exterminating mosquito
The result shows that the relative effectivenes of compound I is at more than 10 times of d-allethrin.
Application implementation example 2
With compound I of the present invention and compound (±) 2; 3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(2; The 2-dichloroethylene)-2; 2-dimethyl cyclopropane carboxylic acid ester (the DL body that compound I does not split) is processed 0.08% mosquito-repellent incense respectively with application implementation example 1 same method, carries out the evaluation of pesticide effectiveness according to GB13917.4-92, and the result is as shown in table 2:
The comparison of table 2. The compounds of this invention and its raceme effect exterminating mosquito
The result shows: the relative reactivity of the trans body compound I of the single dextrorotation of the present invention is 1.7 times of DL body.
Application implementation example 3
In the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.92 weight parts, add the water of 120 weight parts and mediate and be shaped, oven dry forms line spices shape line spices base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound I in kerosene.
On this cover line spices base material, evenly drip the above-mentioned solution of 4ml, at room temperature place 3 hours then to obtain the disc type insecticidal incense that a cover has the 0.04w/w% compound I with micro-syringe.
Application implementation example 4
In the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.92 weight parts, add the water of 120 weight parts and mediate and be shaped, oven dry forms line spices shape line spices base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound I I in kerosene.
On this cover line spices base material, evenly drip the above-mentioned solution of 8ml, at room temperature place then and had the disc type insecticidal incense of 0.08w/w% compound I I to obtain a cover in 3 hours with micro-syringe.
Application implementation example 5
In the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.92 weight parts, add the water of 120 weight parts and mediate and be shaped, oven dry forms line spices shape line spices base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation compound III in kerosene.
On this cover line spices base material, evenly drip the above-mentioned solution of 8ml, at room temperature place 3 hours then to obtain the disc type insecticidal incense that a cover has the 0.16w/w% compound III with micro-syringe.
Application implementation example 6
With containing the 2mg compound I, the long 35mm of preparation dipping of 15mg BHT (2,6 di tert butyl 4 methyl phenol) and 0.5mg dyestuff; Wide 22mm, the porous pad of thick 2mm (cotton fibre: 50% weight percent, paper pulp fiber: 50% weight percent); Room temperature held 3 days makes electric mosquito repellent tablet.
Application implementation example 7
With 0.5 part of compound I and 0.3 part of BHT, 0.3 part spices, 98.9 parts n-tetradecane lump together and are prepared into mosquito liquid under heating.Can becomes electric liquid device then, wherein contains compound I 0.5w/w%.
Application implementation example 8
Kerosene with 0.3 weight part compound I and 59.7 weight parts under heating mixes a kind of pesticide preparation of preparation.The preparation that obtains is put into the aerosol jar, on jar a valve is housed, and inject 40.0 weight parts, third butane adding to depress,, wherein contain compound I 0.3w/w% to obtain a kind of insect aerosol through this valve.
Application implementation example 9
With 4,5 and 6 preparations of application implementation of the present invention example be that the coiled mosquito-repellent incense of former medicine carries out the evaluation of pesticide effectiveness contrast to mosquito with at present the most frequently used 0.8% d-allethrin mosquito-repellent incense according to GB13917.4-92 with The compounds of this invention, respectively four kinds of mosquito-repellent incenses are carried out efficacy testing, detailed process be with 20 female culex pipiens fatigans of mosquito sucking tube absorption; Put into airtight drum test set; Appoint and get one section of mosquito-repellent incense to be tested, put to mosquito coil frame the igniting mosquito-repellent incense timing; Remove mosquito-repellent incense behind the 1min; Write down down and out examination mosquito number at regular intervals, will all supply to try in the dependent insect cage that mosquito is transferred to cleaning the dead examination of inspection mosquito number behind the 24h behind the 20min.The result sees table 3:
The coiled mosquito-repellent incense of table 3. The compounds of this invention preparation and the comparison of d-allethrin mosquito-repellent incense effect exterminating mosquito
The result shows: the relative effectivenes of compound I is at more than 20 times of d-allethrin, and the relative effectivenes of compound I I is at 10 times of d-allethrin, and the relative effectivenes of compound III is at more than 5 times of d-allethrin.
Application implementation example 10
The alkynes third chrysanthemum ester electric mosquito repellent tablet of application implementation of the present invention example 7 and at present the most frequently used 10mg/ sheet is carried out the evaluation of pesticide effectiveness contrast to mosquito according to GB13917.5-92, adopt airtight drum device.Detailed process is following.With electric mosquito repellent tablet sample energising preheating 1h, 2h, 4h, 6h; 8h draws 20 female culex pipiens fatigans with mosquito sucking tube, puts into airtight drum test set, accurately smoked kill 1min; Clock simultaneously, cut off the electricity supply after smoking, and remove the electric mosquito repellent tablet device, write down down and out examination mosquito number at regular intervals.The result sees table 4:
The electric mat of table 4. The compounds of this invention preparation and the comparison of the alkynes third chrysanthemum ester electric mat effect exterminating mosquito
The result shows: the relative effectivenes of electric mat that with The compounds of this invention I is former medicine preparation is at more than 5 times of the alkynes third chrysanthemum ester chrysanthemum ester anti-mosquito incense sheet.
Application implementation example 11
Application implementation of the present invention example 8 and at present the most frequently used 1% the alkynes third chrysanthemum ester electric liquid device are carried out evaluation of pesticide effectiveness contrast according to GB13917.6-92, adopt airtight drum device.Detailed process is following: with electric liquid device sample energising 2h, 36h, 84h; 168h, 336h draws 20 female culex pipiens fatigans with mosquito sucking tube; Put into airtight drum test set, accurately smoked kill 1min clocks simultaneously; Cut off the electricity supply after smoked, and remove the electric liquid device device, write down down and out examination mosquito number at regular intervals.The result sees table 5:
The vaporizer mosquito liquid of table 5. The compounds of this invention preparation and the comparison of the alkynes third chrysanthemum ester vaporizer mosquito liquid effect exterminating mosquito
The result shows: The compounds of this invention I is that the relative effectivenes of vaporizer mosquito liquid of former medicine preparation is at more than 5 times of the alkynes third chrysanthemum ester chrysanthemum ester vaporizer mosquito liquid.
Application implementation example 12
Application implementation of the present invention example 9 is carried out mosquito according to GB13917.2-92, fly, the efficacy testing of Groton bug adopts airtight drum device.Detailed process is following: will supply the examination insect to put into cylinder, and after waiting to try worm and recovering normal activity, metered injection 1g medicament from insect aerosol jar of the present invention; Extracting baffle plate behind the 1min out makes the examination worm contact with medicament; Down and out examination borer population is write down in timing immediately, and opening entry at regular intervals; To all supply to try in the dependent insect cage that worm is transferred to cleaning the dead examination of inspection borer population behind the 24h behind the 20min.Wherein Groton bug is checked the 72h mortality ratio.The result sees table 6:
The insect aerosol of table 6. The compounds of this invention preparation is to mosquito, fly, the insect killing effect of Groton bug
The result shows: the aerosol of The compounds of this invention I preparation is to mosquito, and fly, Groton bug have good insect killing effect.
Claims (9)
1. pyrethroid compound, for structure satisfies the compd A of following formula,
R wherein
1And R
2Be respectively chlorine or bromine identical or inequality, it is characterized in that: said compd A is the trans single optical activity isomer of dextrorotation.
2. the described pyrethroid compound of claim 1 is characterized in that: described R1 and R2 are chlorine or bromine simultaneously.
3. the preparation method of the described pyrethroid compound of claim 1 is characterized in that: said compd A is by 2,3,5, and the trans dihalo-chrysanthemic acid esterification of acyl chloride of dextrorotation that pure and mild described R1 of 6-tetrafluoro-4-methoxyl methyl carbobenzoxy and R2 are corresponding obtains.
4. the described pyrethroid compound of claim 1 is in the application of remove killing aspect mosquito, fly or the Groton bug.
5. the application of the described pyrethroid compound of claim 4 is characterized in that: as former medicine, be prepared into various forms of sterilants according to ordinary method with said compd A, be used for removing mosquito, fly or Groton bug extremely; Said various forms of sterilant comprises disc type insecticidal incense, electric mosquito repellent tablet, electric liquid device or insect aerosol.
6. the application of the described pyrethroid compound of claim 5 is characterized in that: described disc type insecticidal incense is mixed with compd A to join in the base material behind the liquid form and processes, and wherein the content of compd A is 0.01-1.0w/w%;
The liquid form that said compd A is mixed with is missible oil or is the solution of solvent with the hydro carbons;
Described base material is made up of one or more inflammable substances and one or more tackiness agents, and wherein the weight ratio of inflammable substance and tackiness agent is 90: 10 to 99.9: 0.1.
7. the application of the described pyrethroid compound of claim 5 is characterized in that: said electric mosquito repellent tablet is the solution that contains compd A to be dripped and/or is coated on the porosity base material make, and the content of compd A is the 1-20mg/ sheet in the said anti-mosquito incense sheet; Said porous substrate comprises paper pulp, asbestos, synthetic porous resin, porous, inorganic powder, spun glass or porous ceramic material; Said porous substrate is long 30-35mm, wide 20-22mm, the sheet of thick 1.5-2mm; Also contain the additive that is selected from inhibitor, stifling regulator, spices or dyestuff in the said solution that contains compd A.
8. the application of the described pyrethroid compound of claim 5; It is characterized in that: said electric liquid device is that compd A is dissolved in the aliphatic hydrocarbon; The inhibitor that adds 0.1-0.5% then, 0.1-1% spices is mixed with the solution that contains the 0.1-2% compd A and obtains; Said aliphatic hydrocarbon is the aliphatic hydrocarbon of C14 component.
9. the application of the described pyrethroid compound of claim 4; It is characterized in that: said insect aerosol be with compd A, kerosene and synergistic agent, perfume compound, the sterilant according to circumstances selected under room temperature or heating condition, mixes one of the compsn adding of getting up be equipped with a valve jar in; And under pressure, in jar, add propelling agent through this valve and make, wherein the content of compd A is 0.001-0.5w/w%; Said propelling agent accounts for 20～60% of composition total weight, is selected from LPG liquefied petroleum gas, third butane, dme or pressurized air.
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| CN101524084B (en) * | 2009-04-30 | 2012-11-07 | 江苏扬农化工股份有限公司 | Muscicide incense and preparation method 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 |
| 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 |
| CN104351174A (en) * | 2012-10-18 | 2015-02-18 | 江苏扬农化工股份有限公司 | Insecticide spray |
| CN102870773A (en) * | 2012-10-18 | 2013-01-16 | 江苏扬农化工股份有限公司 | Pesticidal spray |
| CN104628571A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Meperfluthrin production method with clean synthetic process |
| CN104628570B (en) * | 2013-11-15 | 2017-08-08 | 江苏扬农化工股份有限公司 | A kind of clean method for producing of fluorine chlorine ether chrysanthemum ester |
| MY183491A (en) * | 2013-12-30 | 2021-02-22 | Shogun Organics Ltd | Insecticide compound and the compositions thereof |
| WO2018050213A1 (en) | 2016-09-14 | 2018-03-22 | Endura S.P.A. | Improved process for the preparation of pyrethroids |
| CN108250079A (en) * | 2016-12-29 | 2018-07-06 | 江苏扬农化工股份有限公司 | A kind of pyrethroid compound containing difluoro chrysanthemumic acid structure |
| CN108250078A (en) * | 2016-12-29 | 2018-07-06 | 江苏扬农化工股份有限公司 | A kind of pyrethroid compound |
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