CN100584817C - Pyrethroid compound and uses - Google Patents
Pyrethroid compound and uses Download PDFInfo
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- CN100584817C CN100584817C CN200810167598A CN200810167598A CN100584817C CN 100584817 C CN100584817 C CN 100584817C CN 200810167598 A CN200810167598 A CN 200810167598A CN 200810167598 A CN200810167598 A CN 200810167598A CN 100584817 C CN100584817 C CN 100584817C
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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Abstract
The invention relates to pyrethroid compounds, preparation methods and applications in sanitary insecticidal products thereof. The general formula for the compounds is (A), wherein R1 is methyl, methoxymethyl (-CH2OCH3) or H atoms, and R2 is -CF3 or -COOCH (CF3)2. Experiments prove that the compounds with the general formula (A) have excellent effects in preventing and controlling mosquitoes, flies, German cockroaches and other sanitary pests.
Description
Technical field
The present invention relates to pyrethroid compound, with and preparation method thereof with the application in control sanitary insect pest field.
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 to some traditional pyrethroid products (as esbiothrin) etc., and the former dose of pyrethroid that needs 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):
R wherein
1Be methyl, methoxymethyl (CH
2OC
3H) or the H atom, R
2For-CF
3Or
When R1 is a methyl, R2 is-CF
3The time be compound (1) 2,3,5,6-tetrafluoro-4-methyl-benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound
When R1 is a methyl, R2 is-COOCH (CF
3)
2The time be compound (2) 2,3,5,6-tetrafluoro-4-methyl-benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound
When R1 is a methoxymethyl, R2 is-CF
3The time be compound (3) 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound
When R1 is a methoxymethyl, R2 is-COOCH (CF
3)
2The time be compound (4) 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound
When R1 is H, R2 is-CF
3The time be compound (5) 2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound
When R1 is H, R2 is-COOCH (CF
3)
2The time be compound (6) 2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound
Comprise any steric isomer that meets (A) formula in the compound of the present invention with insecticidal activity.
The preparation method that the present invention also provides described structure to satisfy the compound of formula (A), promptly described compound can be prepared by following steps:
With structural formula is the chrysanthemumic acid acyl chlorides of (Y) and the tetrafluorobenzyl alcohol esterification preparation that structural formula is (X).
Esterification can be carried out in organic solvents such as toluene, dimethylbenzene, hexanaphthene, and the mol ratio of chrysanthemumic acid acyl chlorides and tetrafluorobenzyl alcohol is 0.8: 1-1.5: 1, add pyridine as acid binding agent.
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 according to ordinary method, be used for remove killing mosquito, fly or Groton bug.
Described various forms of sterilant comprises coiled mosquito-repellent 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 coiled mosquito-repellent incense
Described coiled mosquito-repellent 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 0.01-3.0w/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 add water and admix in the coiled mosquito-repellent incense base material when preparation base material (fragrant base), forms the coiled mosquito-repellent 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 coiled mosquito-repellent 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 coiled mosquito-repellent 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 coiled mosquito-repellent incense that more than obtains can ordinary method use.That is, light coiled mosquito-repellent incense of the present invention near (for example dwelling house, office, stock barn) or its in the habitat of insect.The burning of coiled mosquito-repellent 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 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, many inorganic powders, 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 new edition 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.Carry out efficacy testing with traditional hygienic insecticide esbiothrin, the result shows that the drug effect of compound (3), (4) is at more than 10 times of esbiothrin.
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 1:2,3,5,6-tetrafluoro-4-methyl-benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound compound (1) synthetic
In the four-hole bottle of a 2000ml, drop into 2,3,5, the 6-tetrafluoro is to methylbenzyl alcohol 97.0g (0.5mol), and pyridine 50.0g is dissolved in 800ml toluene, throw to finish and stir, 0-5 ℃ drips 2 down, and 2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 135.9g (0.6mol) drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution once, use 400ml 5%NaHCO again
3Washing once divides oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purifies solvent toluene, obtains compound 2,3,5,6-tetrafluoro-4-methyl-benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound, weight 188.7g, content are 97.8%, yield 96.1%.The molecular formula of this compound: C
17H
15F
7O
2Molecular weight: 384, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.51 (m, 2H); 2.35 (s, 3H); 5.34 (m, 2H); 5.93 (d, 1H); 5.70 (s, 1H).
Preparation embodiment 2:2,3,5,6-tetrafluoro-4-methyl-benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound compound (2) synthetic
In the four-hole bottle of a 2000ml, drop into 2,3,5, the 6-tetrafluoro is to methylbenzyl alcohol 97.0g (0.5mol), and pyridine 50.0g is dissolved in 800ml toluene, throw to finish and stir, 0-5 ℃ drips 2 down, and 2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropane carboxylic acid isoxazolecarboxylic acid 211.5g (0.6mol) drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution once, use 400ml5%NaHCO again
3Washing once, divide oil-yielding stratum under the 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent toluene, obtain compound 2,3,5,6-tetrafluoro-4-methyl-benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound, weight 250.3g, content are 96.9%, yield 95.1%.The molecular formula of this compound: C
20H
16F
10O
4Molecular weight: 510, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.51 (m, 2H); 2.35 (s, 3H); 5.34 (m, 2H); 6.44 (d, 1H); 6.14 (s, 1H); 3.98 (s, 1H).
Preparation embodiment 3:2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound compound (3) synthetic
In the four-hole bottle of a 2000ml, drop into 2,3,5, the 6-tetrafluoro is to methoxyl methyl phenylcarbinol 112.0g (0.5mol), and pyridine 50.0g is dissolved in 800ml toluene, throw to finish and stir, 0-5 ℃ drips 2 down, and 2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 135.9g (0.6mol) drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution once, use 400ml 5%NaHCO again
3Washing once divides oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purifies solvent toluene, obtains compound 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound, weight 205.7g, content are 97.5%, yield 96.9%.The molecular formula of this compound: C
18H
17F
7O
3Molecular weight: 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.51 (m, 2H); 3.24 (s, 3H); 4.63 (s, 2H); 5.34 (m, 2H); 5.93 (d, 1H); 5.70 (s, 1H).
Preparation embodiment 4:2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound compound (4) synthetic
In the four-hole bottle of a 2000ml, drop into 2,3,5, the 6-tetrafluoro is to methoxyl methyl phenylcarbinol 112.0g (0.5mol), and pyridine 50.0g is dissolved in 800ml toluene, throw to finish and stir, 0-5 ℃ drips 2 down, and 2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropane carboxylic acid isoxazolecarboxylic acid 211.5g (0.6mol) drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution once, use 400ml5%NaHCO again
3Washing once, divide oil-yielding stratum under the 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent toluene, obtain compound 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound, weight 280.2g, content are 97.2%, yield 96.7%.The molecular formula of this compound: C
21H
18F
10O
5Molecular weight: 540, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.51 (m, 2H); 3.24 (s, 3H); 4.63 (s, 2H); 5.34 (m, 2H); 6.44 (d, 1H); 6.14 (s, 1H); 3.98 (s, 1H).
Preparation embodiment 5:2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound compound (5) synthetic
In the four-hole bottle of a 2000ml, drop into 2,3,5,6-tetrafluorobenzyl alcohol 90.0g (0.5mol), pyridine 50.0g is dissolved in 800ml toluene, throw to finish and stir, 0-5 ℃ drips 2 down, and 2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 135.9g (0.6mol) drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution once, use 400ml 5%NaHCO again
3Washing once divides oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purifies solvent toluene, obtains compound 2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound, weight 182.7g, content are 98.2%, yield 97.5%.The molecular formula of this compound: C
16H
13F
7O
2Molecular weight: 370, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.51 (m, 2H); 6.57 (s, 1H); 5.34 (m, 2H); 5.93 (d, 1H); 5.70 (s, 1H).
Preparation embodiment 6:2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound compound (6) synthetic
In the four-hole bottle of a 2000ml, drop into 2,3,5,6-tetrafluorobenzyl alcohol 90.0g (0.5mol), pyridine 50.0g is dissolved in 800ml toluene, throw to finish and stir, 0-5 ℃ drips 2 down, and 2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropane carboxylic acid isoxazolecarboxylic acid 211.5g (0.6mol) drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution once, use 400ml 5%NaHCO again
3Washing once, divide oil-yielding stratum under the 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent toluene, obtain compound 2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound, weight 244.7g, content are 97.7%, yield 96.4%.The molecular formula of this compound: C
19H
14F
10O
4Molecular weight: 496, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.51 (m, 2H); 3.24 (s, 3H); 6.57 (s, 1H); 6.44 (d, 1H); 6.14 (s, 1H); 3.98 (s, 1H).
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 99.92 weight parts and be shaped, oven dry forms line spices shape mosquito-repellent incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound (1) 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 coiled mosquito-repellent incense I that a cover has 0.08w/w% compound (1) with 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 99.92 weight parts and be shaped, oven dry forms line spices shape mosquito-repellent incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound (2) 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 coiled mosquito-repellent incense II that a cover has 0.08w/w% compound (2) with 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 99.92 weight parts and be shaped, oven dry forms line spices shape mosquito-repellent incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound (3) 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 coiled mosquito-repellent incense III that a cover has 0.08w/w% compound (3) with 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 99.92 weight parts and be shaped, oven dry forms line spices shape mosquito-repellent incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound (4) 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 coiled mosquito-repellent incense IV that a cover has 0.08w/w% compound (4) with 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 99.92 weight parts and be shaped, oven dry forms line spices shape mosquito-repellent incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound (5) 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 coiled mosquito-repellent incense V that a cover has 0.08w/w% compound (5) with 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 99.92 weight parts and be shaped, oven dry forms line spices shape mosquito-repellent incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound (6) 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 coiled mosquito-repellent incense VI that a cover has 0.08w/w% compound (6) with micro-syringe.
Application Example 7
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 99.2 weight parts and be shaped, oven dry forms line spices shape mosquito-repellent incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 4.0w/v% solution of preparation Es-esbiothrin 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 coiled mosquito-repellent incense VII that a cover has the 0.8w/w%Es-esbiothrin with micro-syringe.
Application Example 8
The coiled mosquito-repellent incense of Application Example 1-7 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) | 0.08 | 7.68 | 100 |
| Mosquito-repellent incense II | Compound (2) | 0.08 | 8.20 | 100 |
| Mosquito-repellent incense III | Compound (3) | 0.08 | 5.16 | 100 |
| Mosquito-repellent incense IV | Compound (4) | 0.08 | 5.33 | 100 |
| Mosquito-repellent incense V | Compound (5) | 0.08 | 9.87 | 100 |
| Mosquito-repellent incense VI | Compound (6) | 0.08 | 10.21 | 100 |
| Mosquito-repellent incense VII | The Es-esbiothrin | 0.8 | 5.47 | 100 |
The result shows that the relative effectivenes of compound (3) and (4) is at more than 10 times of Es-esbiothrin.
Application Example 9
With containing 2mg compound (3), 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 10
With containing 2mg compound (4), 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 11
With 0.2 part of compound (3) 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 compd A l0.2w/w%.
Application Example 12
With 0.2 part of compound (4) 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 compd A l0.2w/w%.
Application Example 13
Kerosene with 0.3 weight part compound (3) 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 compd A l0.3w/w% to obtain a kind of insect aerosol by this valve.
Application Example 14
The alkynes third chrysanthemum ester electric mosquito repellent tablet of Application Example 9,10 of the present invention and at present the most frequently used 10mg/ sheet is carried out evaluation of pesticide effectiveness contrast to mosquito 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 the alkynes third chrysanthemum ester electric mat effect
The result shows: with The compounds of this invention (3), (4) be that the relative effectivenes of the electric mat for preparing of former medicine is at more than 5 times of the alkynes third chrysanthemum ester chrysanthemum ester anti-mosquito incense sheet.
Application Example 15
The alkynes third chrysanthemum ester electric liquid device of Application Example 11,12 of the present invention and at present the most frequently used 1% 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 of table 3. The compounds of this invention preparation and the comparison of the alkynes third chrysanthemum ester vaporizer mosquito liquid effect
The result shows: The compounds of this invention (3), (4) be that the relative effectivenes of the vaporizer mosquito liquid for preparing of former medicine is at more than 5 times of the alkynes third chrysanthemum ester chrysanthemum ester vaporizer mosquito liquid.
Application Example 16
Application Example 13 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 | 5.75 minute | 100％ |
| Fly | 7.32 minute | 100％ |
| Groton bug | 6.24 minute | 100％(72h) |
The result shows: the aerosol of The compounds of this invention (3) preparation is to mosquito, and fly, Groton bug have good insect killing effect.
Claims (4)
1. pyrethroid compound, it is selected from:
2,3,5,6-tetrafluoro-4-methyl-benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound
2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-2,2-dimethyl-3-(3,3,3-three fluoro-propenyl) cyclopropanecarboxylcompound
2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound
Or
2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(2,2,2-three fluoro-1-trifluoromethyl oxyethyl group formyls) vinyl cyclopropanecarboxylcompound
2. the application of pyrethroid compound according to claim 1 aspect the control sanitary insect pest.
3. the application of pyrethroid compound according to claim 2 is characterized in that: described sanitary insect pest is mosquito, fly or Groton bug.
4. the application of pyrethroid compound according to claim 3, it is characterized in that: with the described compound of claim 1 as former medicine, be prepared into coiled mosquito-repellent incense, electric mosquito repellent tablet, electric liquid device or insect aerosol, be used for removing mosquito, fly or Groton bug extremely.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810167598A CN100584817C (en) | 2008-10-14 | 2008-10-14 | Pyrethroid compound and uses |
| PCT/CN2009/070767 WO2010043121A1 (en) | 2008-10-14 | 2009-03-13 | Pyrethroid compounds and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810167598A CN100584817C (en) | 2008-10-14 | 2008-10-14 | Pyrethroid compound and uses |
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| WO (1) | WO2010043121A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100584817C (en) * | 2008-10-14 | 2010-01-27 | 江苏扬农化工股份有限公司 | Pyrethroid compound and uses |
| CN101367730A (en) * | 2008-10-16 | 2009-02-18 | 贵阳柏丝特化工有限公司 | Pyrethroid and synthesis thereof |
| US8629296B2 (en) | 2009-05-21 | 2014-01-14 | Jiangsu Yangnong Chemical Co., Ltd. | Pyrethroid compound, preparation process and use thereof |
| CN101632377B (en) * | 2009-06-05 | 2013-01-30 | 江苏扬农化工股份有限公司 | Electrothermal pesticide tablet |
| CN102835416A (en) * | 2009-06-04 | 2012-12-26 | 江苏扬农化工股份有限公司 | Electric warming disinfestation tablets |
| CN101632381B (en) * | 2009-06-04 | 2013-07-03 | 江苏扬农化工股份有限公司 | Pesticide aerosol |
| CN101637178B (en) * | 2009-06-05 | 2013-01-30 | 江苏扬农化工股份有限公司 | Pesticide spray |
| CN101665433B (en) * | 2009-06-05 | 2013-02-13 | 江苏扬农化工股份有限公司 | New pyrethroid compound and preparation method and application |
| CN101637180B (en) * | 2009-06-05 | 2012-11-28 | 江苏扬农化工股份有限公司 | Insecticidal incense |
| CN104082334A (en) * | 2009-06-05 | 2014-10-08 | 江苏扬农化工股份有限公司 | Winged insect repelling patch |
| CN104126603B (en) * | 2009-06-05 | 2016-06-15 | 江苏扬农化工股份有限公司 | A kind of the method for control of Pest control repellant and insect |
| CN101637179A (en) * | 2009-06-05 | 2010-02-03 | 江苏扬农化工股份有限公司 | Electrothermal insecticidal liquid |
| CN104068042A (en) * | 2009-07-01 | 2014-10-01 | 江苏扬农化工股份有限公司 | Mosquito control agent and preparation method and application of mosquito control agent |
| CN104788315B (en) * | 2010-01-21 | 2018-03-23 | 江苏扬农化工股份有限公司 | Ester compounds available for desinsection |
| CN102283239A (en) * | 2010-06-17 | 2011-12-21 | 茅燕菊 | Insecticide |
| CN102153474B (en) * | 2011-02-14 | 2013-11-13 | 江苏扬农化工股份有限公司 | Ester compound for preventing and controlling animal parasites, and preparation method and application thereof |
| TWI663151B (en) * | 2016-05-31 | 2019-06-21 | 日商大日本除蟲菊股份有限公司 | Ester compounds and use thereof |
| CN108264468A (en) * | 2016-12-30 | 2018-07-10 | 江苏扬农化工股份有限公司 | A kind of Pesticidal compound with diether linkage structure |
| CN107251911A (en) * | 2017-07-27 | 2017-10-17 | 浙江泽源植物科技有限公司 | A kind of preparation method using fennel seeds stalk as the smokeless mosquito-repellent incense of primary raw material |
| CN109907067A (en) * | 2017-12-12 | 2019-06-21 | 江苏扬农化工股份有限公司 | It can be used for the ester compounds of desinsection |
| CN109988068A (en) * | 2017-12-29 | 2019-07-09 | 江苏扬农化工股份有限公司 | A kind of pyrethroid compound of single spatial configuration |
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| CN1648119A (en) * | 2004-01-20 | 2005-08-03 | 江苏扬农化工股份有限公司 | Several new pyrethroid compounds |
| CN100584817C (en) * | 2008-10-14 | 2010-01-27 | 江苏扬农化工股份有限公司 | Pyrethroid compound and uses |
| CN101367722B (en) * | 2008-10-16 | 2011-12-07 | 贵阳柏丝特化工有限公司 | Preparation of pyrethroid midbody |
| CN101367730A (en) * | 2008-10-16 | 2009-02-18 | 贵阳柏丝特化工有限公司 | Pyrethroid and synthesis thereof |
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| CN101381306A (en) | 2009-03-11 |
| WO2010043121A9 (en) | 2010-07-01 |
| WO2010043121A1 (en) | 2010-04-22 |
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