CN101492393A - Pyrethroid compounds, preparation and use thereof - Google Patents
Pyrethroid compounds, preparation and use thereof Download PDFInfo
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- CN101492393A CN101492393A CNA2009101188750A CN200910118875A CN101492393A CN 101492393 A CN101492393 A CN 101492393A CN A2009101188750 A CNA2009101188750 A CN A2009101188750A CN 200910118875 A CN200910118875 A CN 200910118875A CN 101492393 A CN101492393 A CN 101492393A
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Abstract
The invention relates to pyrethroid compounds with general formula of (A), or stereochemical isomers thereof, or a mixture of the stereochemical isomers and a preparation method of the compounds and the application thereof in hygiene insecticidal products. In the formula (A), R refers to F atom or H atom, and Z is cyano (-CN) or H atom. Experiments show that the compounds have good effects on preventing sanitary insect pests of mosquitoes, flies, German cockroaches, etc.
Description
Technical field
The present invention relates to pyrethroid compound, relate in particular to a kind of compound that 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 the formula: R is F atom or H atom, Z be cyano group (CN) or the H atom.)
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.Because it has efficiently, low toxicity, low residue, environment compatibility are good, obtained application widely in the prevention and control field of sanitary insect pest.But growth along with duration of service, mosquitos and flies has produced certain resistance (Gao Xiwu 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 needs to add in products such as mosquito-repellent incense or aerosol for prevention effect same before reaching has increased greatly.This has not only improved production cost, has also increased the weight of environmental pressure.
The present invention has formed the fluorine-containing pyrethroid compound of a series of novelties by the structure of modification to traditional pyrethroid acid, alcohol moiety.The preliminary test of pesticide effectiveness of these compounds shows to have excellent insecticidal activity, knocks down soon, and lethality rate height, vapour pressure height can be stablized at normal temperatures and continue volatilization, are fit to production health pesticide preparation product.Owing to the introducing of fluorine element, also greatly reduce the resistance risk of insect simultaneously.
Summary of the invention
Purpose of the present invention just provides a kind of pyrethroid compound of novelty, and the application on sanitary insect pests such as control mosquito, fly, Groton bug.The objective of the invention is to be achieved through the following technical solutions:
The pyrethroid compound that provides with general formula (A):
Wherein: R is F atom or H atom, Z be cyano group (CN) or the H atom.
Work as R=F, Z=-CN is compound (1): alpha-cyano-3-phenoxy group-4-fluoro-benzyl-2,2-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;
Compound (2)
Work as R=F, Z=H is compound (3): 3-phenoxy group-4-fluoro-benzyl-2,2-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 during partly for the trans individual isomer of dextrorotation be compound alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound; When R1 is R=H, Z=-CN and chrysanthemumic acid during partly for the trans individual isomer of dextrorotation be compound alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
Compound of the present invention comprises pyrethroid compound or its three-dimensional chemical isomer that provides with general formula (A), or the mixture of these steric isomers.
The preparation method that the present invention also provides described structure to satisfy the compound of formula (A), with reference to CN1303846A, the preparation method of chrysanthemum ester compound among the CN101100445A, The compounds of this invention (A) can be prepared by following steps:
With structural formula is the chrysanthemumic acid acyl chlorides of (X) and structural formula for the pure direct esterification of (Y) or preparation prepare structural formula for the aldehyde esterification in the presence of NaCN for (Z) of the chrysanthemumic acid acyl chlorides of (X) and structural formula, and the definition of R is the same in the formula.
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 in the reaction as acid binding agent, temperature of reaction 0-25 ℃.
The present invention also provides described compound in the application of remove killing aspect the sanitary insect pests such as mosquito, fly or Groton bug.
The above-mentioned application of described compound be with described compound (A) as former medicine, be prepared into various forms of sterilants, be used for remove killing mosquito, fly or Groton bug.
Described various forms of sterilant comprises disc type insecticidal incense, electric mosquito repellent tablet, electric liquid device or insect aerosol etc.
Below described structure is satisfied (A) The compounds of this invention be that the application of former medicine in preparation various forms sterilant is described in detail:
(1) preparation disc type insecticidal incense
Described disc type insecticidal incense is mixed with compound of the present invention to join behind the liquid form and makes in the base material, 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 is the solution of solvent with kerosene.
Described missible oil can be sprayed onto on the base material (fragrant base), forms the disc type insecticidal incense of the The compounds of this invention that contains above-mentioned concentration, then oven dry.Also contain tensio-active agent and other auxiliary agents in the described missible oil; 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 the sugar alcohol derivant; The example of described other auxiliary agents comprises one or more the mixture in perfume compound, tinting material or the 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 of starch, casein, methylcellulose gum, carboxymethyl cellulose or polyvinyl alcohol of being selected from 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 and oven dry preparation.The shape of coiled mosquito-repellent incense base material can be plate-like or strip without limits.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
Described electric mosquito repellent tablet is will contain the solution dropping of The compounds of this invention and/or be coated on the porosity base material to make, and the content of The compounds of this invention is the 0.1-20mg/ sheet in the described anti-mosquito incense sheet.Also contain the additive that is selected from antioxidant, stifling conditioning agent, spices or dyestuff in the described solution that contains compound (A).
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 ceramic material; Described 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 that contains the paper pulp fiber of the cotton fibre of 50% weight and 50% weight, from absorptivity with keep the viewpoint of 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, by 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
Described electric liquid device is that The compounds of this invention is dissolved in the aliphatic hydrocarbon, adds the antioxidant of 0.1-0.5% then, 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, 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
Described insect aerosol is that the composition that compound of the present invention, kerosene and synergistic agent, perfume compound, the sterilant according to circumstances selected mix under room temperature or heating condition is added in the jar that a valve is housed, and under pressure, in jar, add propelling agent by this valve and make, the content of The compounds of this invention is 0.001-0.5w/w% in the final composition; Described propelling agent accounts for the 20-60% of composition total weight; Preferred liquefied petroleum gas (LPG), third butane, dme or pressurized air, further preferred third butane.
When insect aerosol of the present invention is used in the habitat of insect, by-pass valve control is 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.
Based on above-mentioned achievement in research, the present invention proposes compound of the present invention 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 of the present invention and housefly, culex pipiens pollens, Groton bug etc. have been had remarkable prevention effect with its various sterilants for former medicine preparation.
Embodiment
Explain technical scheme of the present invention and effect in detail with the form of embodiment below, but the present invention is not limited to following examples.
Preparation embodiment 1: compound (1) alpha-cyano-3-phenoxy group-4-fluoro-benzyl-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 the 80ml hexanaphthene, be added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, throw to finish stir 10min, 10-20 ℃ slowly drips 2 in following 2 hours, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum under the 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent, obtain compound alpha-cyano-3-phenoxy group-4-fluoro-benzyl-2,2-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 the chrysanthemumic acid ring-H); (6.25 s, 1H, benzyl α H); 6.83-6.89 (m, 3H); 6.92-7.22 (m, 5H).
Preparation embodiment 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 the 80ml hexanaphthene, be added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, add the 0.5g Tetrabutyl amonium bromide again, throw to finish and stir 10min, 10-20 ℃ slowly drips 2 in following 2 hours, and 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum under the 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 the chrysanthemumic acid ring-H); (6.25 s, 1H, benzyl α H); 6.85-7.15 (m, 4H); 6.92-7.22 (m, 5H).
Preparation embodiment 3: compound (3) 3-phenoxy group-4-fluoro-benzyl-2,2-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, 10-20 ℃ slowly drips 2 in following 2 hours, and 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum under the 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent toluene, obtain compound 3-phenoxy group-4-fluoro-benzyl-2,2-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 the chrysanthemumic acid ring-H); (5.34 s, 2H, benzyl α H); 6.83-6.89 (m, 3H); 6.92-7.22 (m, 5H).
Preparation embodiment 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, 10-20 ℃ slowly drips 2 in following 2 hours, and 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum under the 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 the chrysanthemumic acid ring-H); (5.34 s, 2H, benzyl α H); 6.85-7.15 (m, 4H); 6.92-7.22 (m, 5H).
Preparation embodiment 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 the 80ml hexanaphthene, be added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, throw to finish and stir 10min, 10-20 ℃ slowly drips (1R in following 2 hours, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum under the 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 the 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 embodiment 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 is dissolved in the 80ml hexanaphthene, is added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, add the 0.5g Tetrabutyl amonium bromide again, throw to finish stir 10min, 10-20 ℃ slowly drip in following 2 hours (1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum under the 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 the 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
Add 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 and be shaped, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation compound (1) in kerosene.
On this cover incense coil base material,, at room temperature place 3 hours then to obtain the disc type insecticidal incense I that a cover has 0.04w/w% compound (1) with the above-mentioned solution of the even Dropwise 5 ml of micro-syringe.
Application Example 2
Add 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 and be shaped, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation compound (2) in kerosene.
On this cover incense coil base material,, at room temperature place 3 hours then to obtain the disc type insecticidal incense II that a cover has 0.04w/w% compound (2) with the above-mentioned solution of the even Dropwise 5 ml of micro-syringe.
Application Example 3
Add 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 and be shaped, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation compound (3) in kerosene.
On this cover incense coil base material,, at room temperature place 3 hours then to obtain the disc type insecticidal incense III that a cover has 0.04w/w% compound (3) with the above-mentioned solution of the even Dropwise 5 ml of micro-syringe.
Application Example 4
Add 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 and be shaped, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation compound (4) in kerosene.
On this cover incense coil base material,, at room temperature place 3 hours then to obtain the disc type insecticidal incense IV that a cover has 0.04w/w% compound (4) with the above-mentioned solution of the even Dropwise 5 ml of micro-syringe.
Application Example 5
Add 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 and be shaped, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation compound (5) in kerosene.
On this cover incense coil base material,, at room temperature place 3 hours then to obtain the disc type insecticidal incense V that a cover has 0.04w/w% compound (5) with the above-mentioned solution of the even Dropwise 5 ml of micro-syringe.
Application Example 6
Add 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 and be shaped, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation compound (6) in kerosene.
On this cover incense coil base material,, at room temperature place 3 hours then to obtain the disc type insecticidal incense VI that a cover has 0.04w/w% compound (6) with the above-mentioned solution of the even Dropwise 5 ml of micro-syringe.
Reference example 1
Add 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 and be shaped, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.8w/v% solution of preparation tetrafluoro in kerosene.
On this cover incense coil base material,, at room temperature place 3 hours then to obtain the disc type insecticidal incense VII that a cover has 0.04w/w% tetrafluoro with the above-mentioned solution of the even Dropwise 5 ml of micro-syringe.
Give birth to and survey embodiment 1
With 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 the examination worm is a culex pipiens pollens, and the 2-3 days female mosquitos of not sucking blood in back sprout 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, remove mosquito-repellent incense behind the 1min, write down down and out examination mosquito number at set intervals, to all be transferred in the dependent insect cage of cleaning behind the 20min, check dead examination mosquito number behind the 24h for the examination mosquito.
Experimental result sees 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 | Tetrafluoro | 0.04 | 8.47 | 95 |
The result shows that the relative effectivenes of compound (1) is at 1.3 times of tetrafluoro, and the relative effectivenes of the compound of individual isomer (5) is more at more than 1.8 times of tetrafluoro.
Application Example 7
With containing 1mg compound (1), 15mg BHT (2, the 6-di-tert-butyl-4-methy phenol) and the long 35mm of the preparation of 0.5mg dyestuff dipping, wide 22mm, the porous pad of thick 2mm (cotton fibre: 50% weight percent, paper pulp fiber: 50% weight percent), placed 3 days under the room temperature, make electric mosquito repellent tablet.
Application Example 8
With containing 1mg compound (5), 15mg BHT (2, the 6-di-tert-butyl-4-methy phenol) and the long 35mm of the preparation of 0.5mg dyestuff dipping, wide 22mm, the porous pad of thick 2mm (cotton fibre: 50% weight percent, paper pulp fiber: 50% weight percent), placed 3 days under the room temperature, make electric mosquito repellent tablet.
Reference example 2
With containing 1mg tetrafluoro, 15mg BHT (2, the 6-di-tert-butyl-4-methy phenol) and the long 35mm of the preparation of 0.5mg dyestuff dipping, wide 22mm, the porous pad of thick 2mm (cotton fibre: 50% weight percent, paper pulp fiber: 50% weight percent), placed 3 days under the room temperature, make electric mosquito repellent tablet.
Give birth to and survey embodiment 2
With Application Example 7,8 of the present invention, reach reference example 2 and carry out the evaluation of pesticide effectiveness of mosquito is contrasted according to GB13917.5-92, adopt airtight drum device.Detailed process is as follows.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 results are shown in Table 2:
The electric mat of table 2. The compounds of this invention preparation and the comparison of tetrafluoro electric mat effect
The result shows: with The compounds of this invention (1) be the electric mat relative effectivenes for preparing of former medicine 1.3 times at tetrafluoro, and the relative effectivenes of the compound of individual isomer (5) is more at more than 1.8 times of tetrafluoro.
Application Example 9
With 0.2 part of compound (1) and 0.3 part of BHT, 0.3 part spices, 99.2 parts n-tetradecane lump together and are prepared into mosquito liquid under heating.Can becomes electric liquid device then, wherein contains compound (1) 0.2w/w%.
Give birth to and survey embodiment 3
Application Example 9 of the present invention is carried out evaluation of pesticide effectiveness contrast according to GB13917.6-92, adopt airtight drum device.Detailed process is as follows: with 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, 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 results are shown in Table 3:
The vaporizer mosquito liquid insecticidal effect statistics of table 3. The compounds of this invention preparation
The result shows: the electric liquid device of The compounds of this invention (1) preparation has good prevention effect to mosquito
Application Example 10
Kerosene with 0.3 weight part compound (1) 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 (1) 0.3w/w% to obtain a kind of insect aerosol by this valve.
Give birth to and survey embodiment 4
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 the examination insect; after waiting to try worm recovery 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 be transferred in the dependent insect cage of cleaning behind the 20min, check dead examination borer population behind the 24h for the examination worm.Wherein Groton bug is checked the 72h mortality ratio.The results are shown in Table 4:
The insect aerosol of table 4. The compounds of this invention preparation 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) |
The result shows: the aerosol of The compounds of this invention (1) preparation is to mosquito, and fly, Groton bug have good insect killing effect.
Claims (7)
1, a kind of compound that meets following formula (A), or its three-dimensional chemical isomer, or the mixture of these steric isomers:
Wherein: R is F atom or H atom, Z be cyano group (CN) or the H atom.
2, the compound of a kind of formula as claimed in claim 1 (A) or its three-dimensional chemical isomer, or the mixture of these steric isomers is characterized in that described compound is selected from:
Compound (1): alpha-cyano-3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound (R=F, Z=-CN);
Compound (2): alpha-cyano-3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound (R=H, Z=-CN);
Compound (3): 3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound (R=F, Z=H);
Compound (4): 3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound (R=H, Z=H).
3, the compound of a kind of formula as claimed in claim 1 (A) or its three-dimensional chemical isomer, or the mixture of these steric isomers, it is characterized in that: described three-dimensional chemical isomer is selected from:
Compound (5) alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound;
Compound (6) alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
4, the compound of the described a kind of formula of claim 1 (A) or its three-dimensional chemical isomer, or the preparation process of mixture of these steric isomers is characterized in that and can be prepared by following steps:
With structural formula is the chrysanthemumic acid acyl chlorides of (X) and structural formula for the pure direct esterification of (Y) or preparation prepare structural formula for the aldehyde esterification in the presence of NaCN for (Z) of the chrysanthemumic acid acyl chlorides of (X) and structural formula, and R is F atom or H atom in the formula;
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 in the reaction as acid binding agent, temperature of reaction 0-25 ℃.
5, the described a kind of compound that meets formula (A) of claim 1, or its three-dimensional chemical isomer, or the application of the mixture of these steric isomers aspect the control sanitary insect pest.
6, application as claimed in claim 5 is characterized in that: described sanitary insect pest is mosquito, fly or Groton bug.
7, application as claimed in claim 5 is characterized in that: the compound that satisfies (A) formula with described structure is prepared into various forms of sterilants as former medicine, is used for removing killing mosquito, fly or Groton bug.
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| CN108003021A (en) * | 2017-12-01 | 2018-05-08 | 广州市禾基生物科技有限公司 | A kind of preparation method of low polarity grease |
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeling pyrethroid |
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| US4328237A (en) * | 1978-02-28 | 1982-05-04 | Montedison S.P.A. | Pyrethroids |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| CN100500649C (en) * | 2007-08-03 | 2009-06-17 | 华东师范大学 | Monohalogenated pyrethric acid alpha-cyano-4-fluoro-3-phenoxybenzyl ester and its preparation method and use |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108003021A (en) * | 2017-12-01 | 2018-05-08 | 广州市禾基生物科技有限公司 | A kind of preparation method of low polarity grease |
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeling pyrethroid |
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