CN102633684B - Pyrethroid compound, preparation method and application thereof - Google Patents
Pyrethroid compound, preparation method and application thereof Download PDFInfo
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- CN102633684B CN102633684B CN201210064535.6A CN201210064535A CN102633684B CN 102633684 B CN102633684 B CN 102633684B CN 201210064535 A CN201210064535 A CN 201210064535A CN 102633684 B CN102633684 B CN 102633684B
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- 0 CC(C)([C@@]1C=CC(F)(F)F)C1C(OC(*)c1cc(Oc2ccccc2)c(*)cc1)=O Chemical compound CC(C)([C@@]1C=CC(F)(F)F)C1C(OC(*)c1cc(Oc2ccccc2)c(*)cc1)=O 0.000 description 1
Abstract
The invention relates to a pyrethroid compound shown in a general formula (A), or stereochemistry isomers of the pyrethroid compound, or a mixture of the stereochemistry isomers, a preparation method of the compounds, and the application of the compounds in hygienic insecticide products. In the formula (A), R is F atom or H atom, and Z is cyanogroup (-CH) or H atom. The experiment proves that the compound has good control effect for sanitary insect pests such as mosquitoes, flies, german cockroaches and the like.
Description
The application is to be the divisional application that March 4, application number in 2009 are 200910118875.0, denomination of invention is " a kind of pyrethroid compound and its preparation method and application " applying date.
Technical field
The present invention relates to pyrethroid compound, relate in particular to the compound that one meets following formula (A), or its three-dimensional chemical isomer, or the mixture of these steric isomers with and preparation method thereof with the application in control sanitary insect pest field.
(in formula: R is F atom or H atom, Z is cyano group (CN) or H atom.)
Background technology
Pyrethroid coumpound can be for mosquito control, and has higher insecticidal activity, and this is widely known by the people.Because it has efficiently, low toxicity, low residue, environment compatibility be good, be widely used in the prevention and control field of sanitary insect pest.But along with the growth of duration of service, mosquitos and flies has produced certain resistance (Ghosh force etc. to some traditional pyrethroid products (as esbiothrin) etc., Chinese media biology and control magazine, 2004,15 (2), 105) the former dose of pyrethroid that, need add in the product such as mosquito-repellent incense or aerosol for same prevention effect before reaching has increased greatly.This has not only improved production cost, has also increased the weight of environmental pressure.
The present invention, by the structure of modification to traditional pyrethroid acid, alcohol moiety, has formed the fluorine-containing pyrethroid compound of series of novel.The preliminary test of pesticide effectiveness of these compounds shows to have good insecticidal activity, knocks down soon, and lethality rate is high, and vapour pressure height can be stablized at normal temperatures and continue volatilization, is applicable to production health pesticide preparation product.Due to the introducing of fluorine element, also greatly reduce the resistance risk of insect simultaneously.
Summary of the invention
Object of the present invention is just to provide a kind of pyrethroid compound of novelty, and in the application preventing and treating on the sanitary insect pests such as mosquito, fly, Groton bug.The object of the invention is to be achieved through the following technical solutions:
The pyrethroid compound providing with general formula (A):
Wherein: R is F atom or H atom, Z is cyano group (CN) or H atom.
Work as R=F, Z=-CN is compound (1): fluoro-benzyl-2 of alpha-cyano-3-phenoxy group-4-, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound;
Work as R=H, Z=-CN is compound (2): alpha-cyano-3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound;
Work as R=F, Z=H is compound (3): fluoro-benzyl-2 of 3-phenoxy group-4-, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound;
Work as R=H, Z=H is compound (4): 3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
When R1 is R=F, Z=-CN and chrysanthemumic acid part are compound alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2 while being the trans individual isomer of dextrorotation, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound; When R1 is R=H, Z=-CN and chrysanthemumic acid part are compound alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2 while being the trans individual isomer of dextrorotation, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
Compound of the present invention comprises the pyrethroid compound or its three-dimensional chemical isomer that provide with general formula (A), or the mixture of these steric isomers.
The preparation method that the present invention also provides described structure to meet the compound of formula (A), with reference to CN1303846A, the preparation method of chrysanthemum ester compound in CN101100445A, the compounds of this invention (A) can be prepared by following steps:
Be aldehyde esterification preparation under NaCN exists that the alcohol direct esterification that is (Y) of the chrysanthemumic acid acyl chlorides of (X) and structural formula or the preparation chrysanthemumic acid acyl chlorides that is (X) by structural formula and structural formula are (Z) by structural formula, in formula, the definition of R is the same.
Esterification can be carried out at organic solvents such as toluene, dimethylbenzene, hexanaphthenes, and the mol ratio of chrysanthemumic acid acyl chlorides and alcohol or aldehyde is 0.8: 1-1.5: 1, and the mol ratio of aldehyde and NaCN is 1: 1, adds pyridine as acid binding agent in reaction, temperature of reaction 0-25 ℃.
The present invention also provides described compound in the application except killing aspect the sanitary insect pests such as mosquito, fly or Groton bug.
The above-mentioned application of described compound is using described compound (A) as former medicine, is prepared into various forms of sterilants, kills mosquito, fly or Groton bug for removing.
Described various forms of sterilant comprises disc type insecticidal incense, electric mosquito repellent tablet, electric liquid device or insect aerosol etc.
Be that former medicine is described in detail in the application of preparing in various forms sterilant to the compounds of this invention of described structure satisfied (A) below:
(1) prepare disc type insecticidal incense
Described disc type insecticidal incense is mixed with compound of the present invention after liquid form and joins in base material and make, and wherein the content of the compounds of this invention is 0.005-3.0w/w%.
The liquid form that compound of the present invention is mixed with is missible oil or the solution take kerosene as solvent.
It is upper that described missible oil can be sprayed onto base material (fragrant base), forms the disc type insecticidal incense of the compounds of this invention that contains above-mentioned concentration, then dries.In described missible oil, also contain tensio-active agent and other auxiliary agents; The example of described tensio-active agent comprises one or more mixtures in alkyl-sulphate, alkylsulfonate, alkylaryl sulphonate, polyoxyalkylene alkyl, polyoxyalkylene alkyl aryl ether, polyoxyalkylene styryl phenyl ether, polyol ethers or sugar alcohol derivant; The example of described other auxiliary agents comprises one or more the mixture in perfume compound, tinting material or sterilant.
The base material of described 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 example 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 example of tackiness agent comprises the polymkeric substance that is selected from starch, casein, methylcellulose gum, carboxymethyl cellulose or polyvinyl alcohol of tapioca (flour), W-Gum or wheat starch and composition thereof.
Described disc type insecticidal incense base material normally, by mixing inflammable substance and tackiness agent, is mediated with water, moulding oven dry preparation.The shape of coiled mosquito-repellent incense base material does not limit, and can be plate-like or strip.The present invention conventionally uses the conventional coil shape base material that diameter 12cm and thickness are 3-5mm in two a set of line spices.
The disc type insecticidal incense more than obtaining can ordinary method be used., for example, near the habitat of insect (house, office, stock barn) or its, light disc type insecticidal incense of the present invention.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, the 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 the sanitary insect pests such as Groton bug.
(2) prepare electric mosquito repellent tablet
Described electric mosquito repellent tablet is the solution that contains the compounds of this invention to be dripped and/or is coated on porosity base material make, and in described anti-mosquito incense sheet, the content of the compounds of this invention is 0.1-20mg/ sheet.In the described solution that contains compound (A), also contain the additive that is selected from antioxidant, stifling conditioning agent, spices or dyestuff.
The example of the porous substrate of described electric mosquito repellent tablet comprises paper pulp, asbestos, synthetic porous resin, porous, inorganic powder, glass fibre, sulphur thing powder or porous porcelain material; Described porous substrate is long 30-35mm, wide 20-22mm, the sheet of thick 1.5-2mm.Be the sheet containing the cotton fibre of 50% weight and the paper pulp fiber of 50% weight for an example of porous pad of the present invention, from the viewpoint of absorptivity and reservation insecticidal active ingredient, preferably use natural fiber material film-making.
While using electric mosquito repellent tablet of the present invention for example, in the habitat of insect (house, office, stock barn) or near it, by the certain temperature of electric heating panel control, waving that the medicine flooding in sheet just starts to blow slowly is loose.After the effective constituent in space reaches certain concentration, just can be to mosquito, fly, the sanitary insect pests such as Groton bug produce to be stimulated, drives, benumbs, knocks down and lethal effect, thereby reaches to mosquito, fly the control of the sanitary insect pests such as Groton bug.
(3) prepare electric liquid device
Described electric liquid device is that the compounds of this invention is dissolved in aliphatic hydrocarbon, then adds the antioxidant of 0.1-0.5%, and 0.1-1% spices is mixed with the solution that contains 0.1-2% compound of the present invention and obtains; The aliphatic hydrocarbon of the preferred C14 component of described aliphatic hydrocarbon.
Electric liquid device liquid is by the wicking action of plug, mosquito-repellent incense liquid is taken to the top of plug from the bottom of plug, under the electrically heated effect of ring heater, the effective constituent in space is reached after certain concentration, just can be to mosquito, fly, the 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 the sanitary insect pests such as Groton bug.
(4) prepare insect aerosol
Described insect aerosol is by compound of the present invention, kerosene and the composition that mixes under room temperature or heating condition of synergistic agent, perfume compound, the sterilant according to circumstances selected adds in a tank that a valve is housed, and under pressure, in tank, adding propelling agent to make by this valve, in final composition, the content of the compounds of this invention is 0.001-0.5w/w%; Described propelling agent accounts for the 20-60% of composition total weight; Preferably liquefied petroleum gas (LPG), the third butane, dme or pressurized air, further preferred the third butane.
In the time that the habitat of insect is used insect aerosol of the present invention, by-pass valve control is opened, under the pressure-acting of propelling agent, produce high velocity air, tank is included to the liquid aerosol dispersion of effective constituent and the gasification of propelling agent, the small liquid pearl containing effective insecticidal constituent of formation is suspended in air, with mosquito, fly, the sanitary insect pests such as Groton bug contact, and reach the object of quick kill pests.
Based on above-mentioned achievement in research, the present invention proposes compound of the present invention and killing mosquito, fly, the application of the sanitary insect pest aspects such as Groton bug, and concrete application mode has been proposed.Through experiment, prove compound of the present invention and the various sterilants prepared take it as former medicine have significant prevention effect to housefly, culex pipiens pollens, Groton bug etc.
Embodiment
Explain in detail technical scheme of the present invention and effect by the form of embodiment below, but the present invention is not limited to following examples.
Preparation Example 1: fluoro-benzyl-2 of compound (1) alpha-cyano-3-phenoxy group-4-, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 4-fluoro-3-phenoxy benzaldehyde 10.8g (0.05mol), pyridine 5g, be dissolved in 80ml hexanaphthene, be added dropwise to the saturated aqueous solution containing 2.45g (0.05mol) NaCN, throw to finish and stir 10min, in 2 hours, slowly drip 2 at 10-20 ℃, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol), drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase is washed once with 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt are each successively, divide oil-yielding stratum under 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent, obtain fluoro-benzyl-2 of compound alpha-cyano-3-phenoxy group-4-, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 20.2, content 94.3%, yield 88.1% (in aldehyde).The molecular formula of this compound: C
23h
18f
4nO
3, molecular weight: 432.4, nuclear magnetic resonance spectrum (
1h (ppm) CDCl
3) 5.93 (m, 1H); 5.70 (m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on chrysanthemumic acid ring-H); 6.25 (s, 1H, benzyl α H); 6.83-6.89 (m, 3H); 6.92-7.22 (m, 5H).
Preparation Example 2: compound (2) alpha-cyano-3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 3-phenoxy benzaldehyde 9.9g (0.05mol), pyridine 5g, be dissolved in 80ml hexanaphthene, be added dropwise to the saturated aqueous solution containing 2.45g (0.05mol) NaCN, then add 0.5g Tetrabutyl amonium bromide, throw to finish and stir 10min, at 10-20 ℃, in 2 hours, slowly drip 2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol), drip 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase is washed once with 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt are each successively, divide oil-yielding stratum under 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent, obtain compound alpha-cyano-3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 19.85, content 95.2%, yield 90.0% (in aldehyde).The molecular formula of this compound: C
23h
19f
3nO
3, molecular weight: 414.4, nuclear magnetic resonance spectrum (
1h (ppm) CDCl
3) 5.93 (m, 1H); 5.70 (m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on chrysanthemumic acid ring-H); 6.25 (s, 1H, benzyl α H); 6.85-7.15 (m, 4H); 6.92-7.22 (m, 5H).
Preparation Example 3: fluoro-benzyl-2 of compound (3) 3-phenoxy group-4-, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 4-fluoro-3-phenoxy benzenemethanol 10.9g (0.05mol), pyridine 5g, be dissolved in 80ml toluene, throw to finish and stir, at 10-20 ℃, in 2 hours, slowly drip 2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol), drip 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase is washed once with 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt are each successively, divide oil-yielding stratum under 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent toluene, obtain fluoro-benzyl-2 of compound 3-phenoxy group-4-, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 18.82, content 96.9%, yield 89.9% (in aldehyde).The molecular formula of this compound: C
22h
20F
4o
3, molecular weight: 408.3, nuclear magnetic resonance spectrum (
1h (ppm) CDCl
3) 5.93 (m, 1H); 5.70 (m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on chrysanthemumic acid ring-H); 5.34 (s, 2H, benzyl α H); 6.83-6.89 (m, 3H); 6.92-7.22 (m, 5H).
Preparation Example 4: compound (4) 3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 3-phenoxy benzenemethanol 10.2g (0.05mol), pyridine 5g, be dissolved in 80ml toluene, throw to finish and stir, at 10-20 ℃, in 2 hours, slowly drip 2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol), drip 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase is washed once with 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt are each successively, divide oil-yielding stratum under 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent toluene, obtain compound 3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 18.45, content 97.3%, yield 91.9% (in aldehyde).The molecular formula of this compound: C
22h
21f
3o
3, molecular weight: 390.4, nuclear magnetic resonance spectrum (
1h (ppm) CDCl
3) 5.93 (m, 1H); 5.70 (m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on chrysanthemumic acid ring-H); 5.34 (s, 2H, benzyl α H); 6.85-7.15 (m, 4H); 6.92-7.22 (m, 5H).
Preparation Example 5: compound (5) alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 4-fluoro-3-phenoxy benzaldehyde 10.8g (0.05mol), pyridine 5g, be dissolved in 80ml hexanaphthene, be added dropwise to the saturated aqueous solution containing 2.45g (0.05mol) NaCN, throw to finish and stir 10min, at 10-20 ℃, in 2 hours, slowly drip (1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol), drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase is washed once with 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt are each successively, divide oil-yielding stratum under 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent, obtain compound alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 19.9, content 94.9%, yield 88.3% (in aldehyde).The molecular formula of this compound: C
23h
18f
4nO
3, molecular weight: 432.4, nuclear magnetic resonance spectrum (
1h (ppm) CDCl
3) 5.93 (m, 1H); 5.70 (m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on chrysanthemumic acid ring-H); 6.25 (s, 1H, benzyl α H); 6.83-6.89 (m, 3H); 6.92-7.22 (m, 5H), ee value 90%.
Preparation Example 6: compound (6) alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 3-phenoxy benzaldehyde 9.9g (0.05mol), pyridine 5g, be dissolved in 80ml hexanaphthene, be added dropwise to the saturated aqueous solution containing 2.45g (0.05mol) NaCN, add again 0.5g Tetrabutyl amonium bromide, throw to finish and stir 10min, at 10-20 ℃, in 2 hours, slowly drip (1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol), drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase is washed once with 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt are each successively, divide oil-yielding stratum under 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent, obtain compound alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 19.33, content 94.8%, yield 89.2% (in aldehyde).The molecular formula of this compound: C
23h
19f
3nO
3, molecular weight: 414.4, nuclear magnetic resonance spectrum (
1h (ppm) CDCl
3) 5.93 (m, 1H); 5.70 (m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on chrysanthemumic acid ring-H); 6.25 (s, 1H, benzyl α H); 6.85-7.15 (m, 4H); 6.92-7.22 (m, 5H), ee value 90%.
Application Example 1
Be shaped to adding the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts, then dry and form plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, prepare the 0.8w/v% solution of compound (1) in kerosene.
On this cover plate perfume base material, evenly drip the above-mentioned solution of 5ml with micro-syringe, then at room temperature place 3 hours to obtain the disc type insecticidal incense I of a set of 0.04w/w% of having compound (1).
Application Example 2
Be shaped to adding the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts, then dry and form plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, prepare the 0.8w/v% solution of compound (2) in kerosene.
On this cover plate perfume base material, evenly drip the above-mentioned solution of 5ml with micro-syringe, then at room temperature place 3 hours to obtain the disc type insecticidal incense II of a set of 0.04w/w% of having compound (2).
Application Example 3
Be shaped to adding the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts, then dry and form plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, prepare the 0.8w/v% solution of compound (3) in kerosene.
On this cover plate perfume base material, evenly drip the above-mentioned solution of 5ml with micro-syringe, then at room temperature place 3 hours to obtain the disc type insecticidal incense III of a set of 0.04w/w% of having compound (3).
Application Example 4
Be shaped to adding the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts, then dry and form plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, prepare the 0.8w/v% solution of compound (4) in kerosene.
On this cover plate perfume base material, evenly drip the above-mentioned solution of 5ml with micro-syringe, then at room temperature place 3 hours to obtain the disc type insecticidal incense IV of a set of 0.04w/w% of having compound (4).
Application Example 5
Be shaped to adding the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts, then dry and form plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, prepare the 0.8w/v% solution of compound (5) in kerosene.
On this cover plate perfume base material, evenly drip the above-mentioned solution of 5ml with micro-syringe, then at room temperature place 3 hours to obtain the disc type insecticidal incense V of a set of 0.04w/w% of having compound (5).
Application Example 6
Be shaped to adding the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts, then dry and form plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, prepare the 0.8w/v% solution of compound (6) in kerosene.
On this cover plate perfume base material, evenly drip the above-mentioned solution of 5ml with micro-syringe, then at room temperature place 3 hours to obtain the disc type insecticidal incense VI of a set of 0.04w/w% of having compound (6).
Reference example 1
Be shaped to adding the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts, then dry and form plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, prepare the 0.8w/v% solution of dimefluthrin in kerosene.
On this cover plate perfume base material, evenly drip the above-mentioned solution of 5ml with micro-syringe, then at room temperature place 3 hours to obtain the disc type insecticidal incense VII of a set of 0.04w/w% of having dimefluthrin.
The raw embodiment 1 that surveys
By Application Example 1-6, the disc type insecticidal incense of reference example 1 is carried out kill mosquito evaluation of pesticide effectiveness contrast according to GB13917.4-92, and examination worm is culex pipiens pollens, the female mosquito of not sucking blood for 2-3 days after sprouting wings; Detailed process is to draw 20 examination mosquitos with mosquito sucking tube, put into airtight drum test set, appoint and get one section of tested mosquito-repellent incense, put to fragrant frame, light timing, after 1min, remove mosquito-repellent incense, record at set intervals down and out examination mosquito number, after 20min, will all be transferred in clean dependent insect cage for examination mosquito, after 24h, check dead examination mosquito number.
Experimental result is in table 1:
The comparison of table 1. the compounds of this invention and control compounds effect exterminating mosquito
| Mosquito-repellent incense | Effective constituent | Concentration w/w% | KT50(min) | 24h mortality ratio (%) |
| Mosquito-repellent incense I | Compound (1) | 0.04 | 6.65 | 100 |
| Mosquito-repellent incense II | Compound (2) | 0.04 | 8.55 | 90 |
| Mosquito-repellent incense III | Compound (3) | 0.04 | 10.25 | 80 |
| Mosquito-repellent incense IV | Compound (4) | 0.04 | 12.33 | 75 |
| Mosquito-repellent incense V | Compound (5) | 0.04 | 5.03 | 100 |
| Mosquito-repellent incense VI | Compound (6) | 0.04 | 8.12 | 95 |
| Mosquito-repellent incense VII | Dimefluthrin | 0.04 | 8.47 | 95 |
Result demonstration, the relative effectivenes of compound (1) is at 1.3 times of dimefluthrin, and the relative effectivenes of the compound of individual isomer (5) is more at the more than 1.8 times of dimefluthrin.
Application Example 7
With containing 1mg compound (1), 15mg BHT (2,6-di-tert-butyl-4-methy phenol) and the long 35mm of preparation dipping of 0.5mg dyestuff, wide 22mm, porous pad (the cotton fibre: 50% weight percent of thick 2mm, paper pulp fiber: 50% weight percent), under room temperature, place 3 days, make electric mosquito repellent tablet.
Application Example 8
With containing 1mg compound (5), 15mg BHT (2,6-di-tert-butyl-4-methy phenol) and the long 35mm of preparation dipping of 0.5mg dyestuff, wide 22mm, porous pad (the cotton fibre: 50% weight percent of thick 2mm, paper pulp fiber: 50% weight percent), under room temperature, place 3 days, make electric mosquito repellent tablet.
Reference example 2
With containing 1mg dimefluthrin, 15mg BHT (2,6-di-tert-butyl-4-methy phenol) and the long 35mm of preparation dipping of 0.5mg dyestuff, wide 22mm, porous pad (the cotton fibre: 50% weight percent of thick 2mm, paper pulp fiber: 50% weight percent), under room temperature, place 3 days, make electric mosquito repellent tablet.
The raw embodiment 2 that surveys
By Application Example 7,8 of the present invention, and reference example 2 carries out the evaluation of pesticide effectiveness contrast to mosquito according to GB13917.5-92, adopts airtight drum device.Detailed process is as follows.By 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, after smoking, cut off the electricity supply, and remove electric mosquito repellent sheet devices, record at regular intervals down and out examination mosquito number.The results are shown in Table 2:
The comparison of electric mat prepared by table 2. the compounds of this invention and dimefluthrin electric mat effect
Result shows: the electric mat relative effectivenes of preparing take the compounds of this invention (1) as former medicine is at 1.3 times of dimefluthrin, and the relative effectivenes of the compound of individual isomer (5) is more at the more than 1.8 times of dimefluthrin.
Application Example 9
Heating under by 0.2 part of compound (1) and 0.3 part of BHT, the spices of 0.3 part, the n-tetradecane of 99.2 parts is combined and is prepared into mosquito liquid.Then filling one-tenth electric liquid device, wherein containing compound (1) 0.2w/w%.
The raw embodiment 3 that surveys
Application Example 9 of the present invention is carried out to evaluation of pesticide effectiveness contrast according to GB13917.6-92, adopt airtight drum device.Detailed process is as follows: by electric liquid device sample energising 2h, 36h, 84h, 168h, 336h, draw 20 female culex pipiens fatigans with mosquito sucking tube, put into airtight drum test set, accurately smoked kill 1min, clock simultaneously, after smoked, cut off the electricity supply, and remove electric liquid device device, record at regular intervals down and out examination mosquito number.The results are shown in Table 3:
Vaporizer mosquito liquid insecticidal effect statistics prepared by table 3. the compounds of this invention
Result shows: electric liquid device prepared by the compounds of this invention (1) has good prevention effect to mosquito
Application Example 10
The kerosene of 0.3 weight part compound (1) and 59.7 weight parts is mixed to a kind of pesticide preparation of preparation under heating.The preparation obtaining is put into inhalator jar, a valve is housed on tank, and inject 40.0 weight part the third butane adding to depress by this valve, to obtain a kind of insect aerosol, wherein containing compound (1) 0.3w/w%.
The raw embodiment 4 that surveys
Application Example 10 of the present invention is carried out mosquito according to GB13917.2-92, fly, the efficacy testing of Groton bug, adopts airtight drum device.Detailed process is as follows: will put into cylinder for examination insect; recover after normal activity wait trying worm; metered injection 1g medicament from insect aerosol tank of the present invention; after 1min, extracting baffle plate out makes to try worm and contacts with medicament; timing immediately, and start record, record at regular intervals down and out examination borer population; after 20min, will all be transferred in clean dependent insect cage for examination worm, after 24h, check dead examination borer population.Wherein Groton bug check 72h mortality ratio.The results are shown in Table 4:
Insect aerosol prepared by table 4. the compounds of this invention is to mosquito, fly, the insect killing effect of Groton bug
| Insect | KT50 (mosquito/fly/cockroach) | 24 hours mortality ratio |
| Mosquito | 6.22 minute | 100％ |
| Fly | 7.58 minute | 100％ |
| Groton bug | 5.96 minute | 100％(72h) |
Result shows: aerosol prepared by the compounds of this invention (1) is to mosquito, fly, and Groton bug has good insect killing effect.
Claims (5)
1. a compound, is characterized in that: described compound is alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
2. the preparation method of compound claimed in claim 1, is characterized in that being prepared by following steps:
Be aldehyde esterification preparation under NaCN exists that the alcohol direct esterification that is (Y) of the chrysanthemumic acid acyl chlorides of (X) and structural formula or the chrysanthemumic acid acyl chlorides that is (X) by structural formula and structural formula are (Z) by structural formula, in formula, R is H atom;
Esterification is carried out at organic solvents such as toluene, dimethylbenzene, hexanaphthenes, and the mol ratio of chrysanthemumic acid acyl chlorides and alcohol or aldehyde is 0.8:1-1.5:1, and the mol ratio of aldehyde and NaCN is 1:1, adds pyridine as acid binding agent in reaction, temperature of reaction 0-25 ℃.
3. the application of compound claimed in claim 1 aspect control sanitary insect pest.
4. application as claimed in claim 3, is characterized in that: described sanitary insect pest is mosquito, fly or Groton bug.
5. application as claimed in claim 3, is characterized in that: using described compound as former medicine, be prepared into various forms of sterilants, kill mosquito, fly or Groton bug for removing.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258202A (en) * | 1978-02-28 | 1981-03-24 | Montedison S.P.A. | Cyclopropanecarboxylic acids and esters |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258202A (en) * | 1978-02-28 | 1981-03-24 | Montedison S.P.A. | Cyclopropanecarboxylic acids and esters |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
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