CN101880260A - Insecticidal ester compound and preparation and application thereof - Google Patents
Insecticidal ester compound and preparation and application thereof Download PDFInfo
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- CN101880260A CN101880260A CN 201010191720 CN201010191720A CN101880260A CN 101880260 A CN101880260 A CN 101880260A CN 201010191720 CN201010191720 CN 201010191720 CN 201010191720 A CN201010191720 A CN 201010191720A CN 101880260 A CN101880260 A CN 101880260A
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Abstract
The invention discloses an insecticidal ester compound and preparation and application thereof. The compound has a structural general formula (Y) shown in the specifications, wherein X is radicals expressed by 3,3,3-trifluoro-1-propinyl (I) and 1-propenyl (II). The invention also relates to effective agents taking the insecticidal ester compound as an active ingredient for controlling harmful insects, intermediates for manufacturing the ester compound and a method for producing the intermediates. The insecticidal ester compound expressed by the formula (Y) has the advantages of high activity for controlling household pests, lower toxicity, structural safety, low toxicity of raw pesticides and low dosage.
Description
Technical field
The invention provides a kind of compound and synthetic method thereof and application, this compound belongs to the compound of organic insecticide class, is a kind of of pyrethroid.A kind of insecticidal ester compound and its production and application specifically.
Background technology
Sterilant is the clear and definite commodity of a kind of purposes, home-use sterilant wherein mainly plays the compound of insecticidal activity, for example, along with Tetramethrin, allethrin, permethrin etc. constantly are widely used, the index of weighing these compounds for a long time mainly concentrates on the power of knocking down and lethality two aspects.Though and have the higher power of knocking down as the Tetramethrin of family's sterilant, allethrin, permethrin etc., toxicity is big, consumption is not ideal enough greatly, and the part insect produced resistance, cost is high.The compound of other similar functions, as Deltamethrin etc., its lethality is better, but the ability of knocking down, pungency, security are undesirable again etc., make human consumer and dealer resist.
In environmental protection is under the megatrend of prerequisite, and more and more higher to environmental requirement people, it is more and more stronger that environmental consciousness becomes, and uses the drug activity of agricultural chemicals, sterilant more and more to pay attention to it.Therefore research and develop the pyrethroid product of new and effective low toxicity, the synthesis technique that a technology is simple, be easy to suitability for industrialized production is provided, the synthetic product compound that obtains is become a kind of mosquito, fly, cockroach, louse or acarid etc. are had the high ability of knocking down, the sterilant that higher kill capability is also arranged simultaneously, this has been the inexorable trend of domestic sanitary product and domestic pesticide development.
The pyrethroid coumpound of cyclopropane carboxylic ester can be used to prevent and treat mosquito, and has higher insecticidal activity, is widely known by the people.U.S. Pat 4370346 discloses this compounds first and has been widely used in pest control.But still exist toxicity higher, people and animals are had the obvious stimulation effect, and environmental pollution is big in the production process.
Summary of the invention
The present invention under above-mentioned technical background, furthers investigate such cyclopropanecarboxylcompound compound of different structure and conception just, proposed the brand-new compound that biological activity is higher than pyrethroid compound in the prior art far away.The contriver has carried out a large amount of investigations of groping, carried out improving research on the basis of existing technology, investigated the ability of knocking down, kill capability and stability and be convenient to index such as application with detailed experimental data, finally obtained a kind of insecticidal ester compound and be the pesticide product of activeconstituents with this compound.When [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl alcohol is as in the pyrethroid during alcohol moiety structure, the compound of preparation is used for the control of sanitary insect pest, have enough securities and biological drug effect, reduce the use of the higher cis body of toxicity simultaneously, reduced problems such as biotic resistance.
The X that provides in the mutual-through type of the present invention (Y) has partly carried out optimizing screening, optimize and have suitable saturated vapor pressure, under normal temperature and high temperature, still can stablize and continue volatilization, drug effect is better, simultaneously can effectively reduce pyrethroid toxicity and biotic resistance, the activity of pyrethroid there is the compound of enhancement structural safety, people and animals is stimulated little.
The invention provides a kind of simple method for preparing carboxylic acid chloride, obviously increase by handling content, easy easily than other method, economical and easily realize industrialization.
Purpose of the present invention: the 1st, preferred a kind of insecticidal ester compound has the optically active body of greater activity and security, especially mosquito, fly, cockroach, louse or acarid etc. is had the insecticidal activity of efficient, the low toxicity of high ability of knocking down and kill capability; The 2nd, the synthesis preparation method of this compound; The 3rd, the desinsection of above-claimed cpd with composition (promptly contain compound (X1) and (X2), for base material) the preparation method, and in the application in domestic hygiene medication field.
The objective of the invention is to be achieved through the following technical solutions:
A kind of insecticidal ester compound that provides with general formula (Y):
Wherein X is (I) 3,3,3-three fluoro-1-proyls or (II) 1-propenyl.
(Ⅰ)F
3C-C≡c-；
When X is (I) 3,3,3-three fluoro-1 proyl, compound (X1) are [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester;
When X is (II) 1-propenyl, compound (X2) is [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
Comprise in the The compounds of this invention general formula (Y) 1,3 chiral carbon atom of cyclopropane have optics optically active isomer R S, at cyclopropane ring, also exist on two keys cis trans and Z the E geometrical isomer; The compounds of this invention comprises that all have the active optical isomer of pest control, geometrical isomer and composition thereof.
The respective compound preparation method that the present invention also provides described structure to satisfy formula (Y), promptly described compound can be prepared by following steps:
1) be 3-(3 with corresponding chrysanthemumic acid, 3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid or 3-(1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid obtains 3-(3 through acyl chloride reaction under the effect of chloride reagent, 3,3-three fluoro-1-proyls)-2,2-dimethylcyclopropane acyl chlorides or 3-(1-propenyl)-2,2-dimethylcyclopropane acyl chlorides; The mol ratio of described chrysanthemumic acid and chloride reagent is 1～3: 1;
2) acyl chlorides that step 1) is obtained is respectively with [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl alcohol carries out esterification under the condition that organic solvent neutral and alkali catalyzer exists synthetic, obtain the pyrethroid compound that described structure satisfies (Y), wherein carboxylic acid chloride is 0.5～3: 1 with the mol ratio of [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl alcohol.
The described organic solvent of esterification is selected from benzene, and toluene, pyridine carry out in ethylene glycol, dimethylbenzene, the cyclohexanes organic solvent, and the alkaline reagentss such as methylate, ethylate, acetate, oxide compound or oxyhydroxide that add Li, Na or K are as acid binding agent.
The described chloride reagent of step 1) is selected from a kind of in phosphorus trichloride or the sulfur oxychloride.
All can obtain industrialization product according to above-mentioned preparation method's compounds X 1, X2.
Above-mentioned general formula (Y) respective compound and composition thereof is used in the application that removes sanitary insect pest aspects such as killing mosquitos and flies, cockroach, louse or acarid good effect.Described sanitary insect pest is mosquitos and flies, cockroach, louse or acarid.
Described structure satisfies the compound of (Y) as former medicine, is prepared into various forms of sterilants according to ordinary method, is used for killing except that mosquito, fly, cockroach, louse or acarid.
Described various forms of sterilant comprises coiled mosquito-repellent incense, electric mosquito repellent tablet, electric liquid device or insect aerosol.
Embodiment
Below in conjunction with embodiment the present invention is described, but the present invention not only is confined to following practical range.
Preparation embodiment 1:3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid's chloride
In the four-hole bottle of a 500ml, drop into 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid 103.2g is dissolved in 300ml toluene, stirs, and is warming up to 40～60 ℃, drips SOCl
271g dripped off in 2 hours, was warming up to 65 ℃ again, was incubated 1 hour.Be heated to 80 ℃ of desolventizing toluene under the 0.06Mpa negative pressure, 60～75 ℃ of cuts are collected in rectifying under the 0.08Mpa negative pressure again, obtain 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 107.4g, content 91.2%, yield 86.7%.
Preparation embodiment 2:3-(1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid's chloride
In the four-hole bottle of a 500ml, drop into 3-(1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 154.2g is dissolved in 300ml toluene, stirs, and is warming up to 40～60 ℃, drips SOCl
271g dripped off in 2 hours, was warming up to 65 ℃ again, was incubated 1 hour.Be heated to 80 ℃ of desolventizing toluene under the 0.06Mpa negative pressure, 60～75 ℃ of cuts are collected in rectifying under the 0.08Mpa negative pressure again, obtain 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 167.3g, content 94.3%, yield 91.7%.
Preparation embodiment 3:[2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester (compounds X 1) synthetic
In the four-hole reaction flask of a 1000ml, drop into [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl alcohol 84g, pyridine 5g0 is dissolved in 400ml toluene, stir, 5～10 ℃ drip 3-(3,3,3-three fluoro-1-proyls)-2 down, 2-dimethyl cyclopropane carboxylic acid acyl chlorides 110.0g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 300ml 10% hydrochloric acid, use 300ml 10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 171.3g, and content is 91.2%, and yield is 87.7%.Structure is identified as follows:
GC/MS shows that this compound molecular weight is 356.3; NMR (
1H, CDCl
3) δ: 5.98 (s, 2H); 4.10 (s, 2H); 3.85 (s, 2H); 3.03 (s, 1H); 1.82 (d, 1H); 1.06 (d, 1H); 0.99 (s, 6H).
Above spectrogram proves that this compound is: [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
16H
15N
2F
3O
4Product is a weak yellow liquid.
Preparation embodiment 4:[2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compounds X 2) synthetic
In the four-hole reaction flask of a 1000ml, drop into [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl alcohol 44.3g, pyridine 25g, be dissolved in 400ml toluene, stir, 5～10 ℃ drip 2 down, 2-dimethyl-3-(1-propenyl)) cyclopropane carboxylic acid isoxazolecarboxylic acid 45.2g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 300ml 10% hydrochloric acid, use 300ml10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 68.5g, content is 93.4%, and yield is 82.0%.Structure is identified as follows:
GC/MS shows that this compound molecular weight is 304.NMR(
1H，CDCl
3)δ：5.98(s，2H)；5.45(m，1H)；5.08(t，1H)；4.03(s，2H)；3.94(s，2H)；3.05(s，1H)；2.10(d，3H)；1.51(t，1H)；1.06(d，1H)；0.98(s，6H).
Above spectrogram proves that this compound is: [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
16H
22N
2O
4Product is a light yellow viscous liquid.
Above-claimed cpd can reduce the dose that need use under the prerequisite that does not reduce drug effect, thereby reduces the toxicity to non-target organism, improves security, reduces the left drug environmental pollution.
Above-claimed cpd of the present invention has the insecticidal activity that mosquito, fly, cockroach, louse or acarid etc. is had efficient, the low toxicity of high ability of knocking down and kill capability, is applicable to domestic sanitary product field and can be used as domestic pesticide.
Above-mentioned synthesis technique of the present invention can satisfy the goal of the invention requirement, technological process is convenient to control, other synthesis techniques are safer relatively for processing condition, and this raw materials technology, operational path and refuse etc. are handled all simple, therefore, above-mentioned synthesis technique is a kind of operational path and the preparation method with wide prospects for commercial application in this area.
Above-claimed cpd of the present invention has the insecticidal activity that mosquitos and flies, cockroach, louse or acarid etc. is had efficient, the low toxicity of high ability of knocking down and kill capability, is applicable to domestic sanitary product field and can be used as domestic pesticide.
Therefore, the present invention also provides a kind of desinsection composition (sterilant) that contains the pyrethroid compound of general formula (Y) structure, the composition of said composition comprises (active compound component) of the compound (1-2) that accounts for said composition gross weight 0.001-5%wt, preferred this active compound component content 0.005-5%wt, more preferably 0.01%-3%wt also contains the sterilant auxiliary material of this area routine in the composition.
For the ease of using, carry and store, insect-killing composition of the present invention is preferably the product of liquid state, solid-state or aerosol form.That is, compound of the present invention can be prepared into composition according to ordinary method as active insecticidal components, and promptly sterilant is used for removing mosquito, fly, cockroach, louse or acarid class pest extremely.Described composition can be various forms of sterilants, comprises disc type insecticidal incense, electric mosquito repellent tablet, vaporizer mosquito liquid or aerosol etc.
Below be that activeconstituents is prepared into composition to the compound of structure of the present invention, said composition comprises the various forms sterilant, and to this compound the detailed description of character of giving an example of the application in sterilant, but do not belong to limit for example:
(1) disc type sterilant (mosquito-repellent incense):
Described disc type disinsecting mosquito repellant incense made is mixed with compound of the present invention to join in the base material behind the liquid form and makes through this area ordinary method, and wherein the content of compound of the present invention is 0.03-0.2w/w%.
Specific embodiment can be following prepared: above-mentioned solvent adds active compound component and adds water when preparation base material (mosquito-repellent incense blank), be mixed to and form the disc type insecticidal incense that contains this active compound component about 0.03-0.2w/w% of concentration in product, oven dry then in the base material.In a preferred embodiment of the invention, use about 10-15cm of diameter and thickness to make two line mosquito-repellent incenses of suit as the conventional coil shape base material of 3-5mm usually.
The disc type sterilant that more than obtains can adopt ordinary method to use.That is, light disc type sterilant of the present invention near (for example dwelling house, office, stock barn) or its in the habitat of insect.Compound of the present invention is in burning or temperature can access volatilization during at 40～160 ℃ of states at product, after airborne effective constituent reached certain concentration, promptly insects such as mosquitos and flies, cockroach, louse or acarid being produced stimulated, expels, benumbs, knocks down and lethal effect.
(2) electric mosquito repellent tablet:
Described electric mosquito repellent tablet is that the solution that will contain The compounds of this invention drips and/or be coated in the product that makes on the carrier, and it is main base material that this carrier also can be porosity; The content that adds The compounds of this invention in unit (sheet) anti-mosquito incense sheet generally is no more than 30mg, and for example according to the different in kind of active compound component, its content can be 1-20mg/ sheet or composite with other chemicals, makes the mosquito sheet.
The carrier of above-mentioned electric mosquito repellent tablet or porosity are that main base material comprises paper pulp, asbestos, synthetic porous resin, porous, inorganic powder, glass fibre, sulphur thing powder or porous ceramic material; The size of this carrier has determined the size of electric mosquito repellent flake products, and in order to use factors such as convenient, carrier and this product are generally long 30-35mm, wide 20-22mm, the flap of thick 1.5-2mm.From the viewpoint of absorptivity and reservation insecticidal active ingredient, carrier preferably is in natural fiber material.In a preferred embodiment of the invention, this carrier is the sheet material that contains the paper pulp fiber of the cotton fibre of 50%wt and 50%wt.
When near the habitat of insect or its, using electric mosquito repellent tablet of the present invention,, make that the active compound component in the electric mosquito repellent tablet slowly discharges, it is diffusing to wave by the certain temperature of electric heating panel control.After spatial effective constituent reached certain concentration, just can produce sanitary insect pests such as mosquitos and flies, cockroach, louse or acarids stimulate, expel, benumb, knock down and lethal effect, thereby reaches insecticidal effect.
(3) vaporizer mosquito liquid:
Described vaporizer mosquito liquid is that The compounds of this invention is dissolved in the aliphatic hydrocarbon, the aliphatic hydrocarbon of the preferred C12-19 component of this aliphatic hydrocarbon, the antioxidant, the 0.1-1% spices that add 0.1-0.5% then, be mixed with compound of the present invention and in product mosquito-repellent incense liquid, account for the solution of 0.1-3%wt greatly, significantly reduce than conventional formulation dosage.
Vaporizer mosquito liquid is generally used with Electric heating, and this product is also referred to as electric liquid device.Electric liquid device is used principle: by the wicking action of carrier plug, mosquito-repellent incense liquid is taken to the top of new edition from the bottom of plug, under the heat effect of electric heater, activeconstituents slowly discharges, and can produce insecticidal action when spatial effective active composition reaches certain concentration.
(4) insect aerosol:
Described insect aerosol is 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 to be packed into have in the container of control valve, and under pressure, in jar, add propellent by this control valve and make, the preferred liquefied petroleum gas (LPG) of this propelling agent, third butane, carbonic acid gas, dme or pressurized air, the content of active compound component generally is no more than 0.8w/w% in the aerosol, for example can be 0.001-0.5w/w%.
During use, opening controlling valve, under the pressure effect of propelling agent, produce high velocity air in the container of aerosol, the compound soup that wherein contains activeconstituents is disperseed, atomizes, form small liquid particle and be suspended in the air, with the effect that can reach quick kill pests after insects such as mosquitos and flies, cockroach, louse or acarid contact.
Compared to the sterilant that has insecticidal action on the market at present, the activeconstituents that plays insecticidal action in the above-mentioned insect-killing composition of the present invention is that (X1～X4) uses lower ratio to compound, therefore, compound of the present invention and the advantage that contains the sterilant of this compound are: the consumption that has reduced insecticidal activating agent when having guaranteed insecticidal effect efficiently.
The present invention also provides the above-mentioned application of composition in desinsection, expelling parasite, and " worm " of the present invention comprises the healthy insects of harm humans and animals such as mosquitos and flies, cockroach, louse or acarid.
Study on the stability: many batches of products have been carried out study on the stability, and the sampling analysis result does not see mass discrepancy, in reasonable range.
Above-mentioned experiment is the part of numerous effect experiment of the present invention, more experimental data since length limit and owe temporarily to give.
The objective of the invention is to a kind of efficient chloride fluorine cyclopropanecarboxylcompound compound that independent intellectual property right is arranged of independent studies exploitation, and the preparation method that this compound is provided, to the requirement of this compound should be can be used as that domestic hygiene kills flies and mosquitoes, active insecticidal components in the high-efficient low toxicity insecticide of cockroach, louse or acarid, and require the synthesis technique of its this compound and yield that industrial production method can improve product and reduce production cost, simply, safety, be easy to industrialization promotion, reduce dosage, improve the product quality degree.
Application Example 1
The water and the hybrid shaping that add 120 weight parts in the mixture of W-Gum, carbon dust and the wood powder (1: 2～6: 3～5) of 99.9 weight parts, oven dry forms the incense coil base material then.The compound (X1) for preparing the method preparation of example 4 is dissolved into concentration in kerosene be 0.3-0.5w/v% solution.Evenly drip the above-mentioned solution of 6ml on above-mentioned incense coil base material, placement got final product in about 2～5 hours under the room temperature, obtained a cover and had 0.06w/w% compound (1) coiled mosquito-repellent incense (a).
Application Example 2
The water and the hybrid shaping that add 120 weight parts in the mixture of W-Gum, carbon dust and the wood powder (1: 2～6: 3～5) of 99.9 weight parts, oven dry forms the incense coil base material then.The compound (X2) for preparing the method preparation of example 5 is dissolved into concentration in kerosene be 0.3-0.5w/v% solution.Evenly drip the above-mentioned solution of 6ml on above-mentioned incense coil base material, placement got final product in about 2～5 hours under the room temperature, obtained a cover and had 0.06w/w% compound (2) coiled mosquito-repellent incense (b).
Application Example 3
The water and the hybrid shaping that add 120 weight parts in the mixture of W-Gum, carbon dust and the wood powder (1: 2～6: 3～5) of 99.9 weight parts, oven dry forms line spices shape line spices base material then.
Preparation Es-allethrin is dissolved into concentration in kerosene be 0.3-0.5w/v% solution.
Evenly drip the above-mentioned solution of 6ml on above-mentioned mosquito-repellent incense base material, placement got final product in about 2～5 hours under the room temperature, obtained a cover and had 0.6w/w%Es-allethrin coiled mosquito-repellent incense (c).
The coiled mosquito-repellent incense of Application Example 1-3 is carried out kill mosquito evaluation of pesticide effectiveness contrast according to GB13917.4-92, and the examination worm is a culex pipiens pollens; Detailed process is to draw 20 examination mosquitos with mosquito sucking tube, puts into airtight drum test set, appoints and gets 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, will all be transferred in the dependent insect cage of cleaning behind the 20min 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
| Sequence number | Effective constituent | Concentration w/w% | ??KT 50(min) |
| Implement 1 | Compound (1) | ??0.06 | ??3′46″ |
| Implement 2 | Compound (2) | ??0.06 | ??3′55″ |
| Implement 3 | The Es-allethrin | ??0.60 | ??4′43″ |
The result shows, general formula is that the relative effectivenes of compound of (Y) is at more than 20 times of Es-allethrin.Significantly better than allethrin, transfluthrin, the alkynes third chrysanthemum ester, tetrafluoro.
Application Example 4
With the solution impregnating carrier porous pad that contains 4mg compounds X 1 arbitrary compound and 15mg BHT (2,6 di tert butyl 4 methyl phenol) (cotton fibre: about 1: 1 of paper pulp fiber), placed 3 days under the room temperature, make electric mosquito repellent tablet.
Application Example 5
With the solution impregnating carrier porous pad that contains 4mg compounds X 2 arbitrary compounds and 15mg BHT (2,6 di tert butyl 4 methyl phenol) (cotton fibre: about 1: 1 of paper pulp fiber), placed 3 days under the room temperature, make electric mosquito repellent tablet.
The alkynes third chrysanthemum ester electric mosquito repellent tablet of application example 4-5 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.Specific as follows: with electric mosquito repellent tablet sample energising preheating 1h, 2h, 4h, 6h, 8h.Draw 20 female culex pipiens pollens with mosquito sucking tube, put into airtight drum test set, accurate smoked kill 1min, timing has simultaneously been smoked back segment power supply, and has been removed the electric mosquito repellent tablet device, notes 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 effect of the alkynes third chrysanthemum ester electric mat are relatively
The result shows: with The compounds of this invention (Y) be the electric mat relative effectivenes for preparing of former medicine 3～4 times at the alkynes third chrysanthemum ester anti-mosquito incense sheet.
Embodiment 6
With 0.4 part of compounds X 1 (as activeconstituents) and 0.3 part of BHT, the aliphatic hydrocarbon Hybrid Heating of the C14 of surplus is prepared into vaporizer mosquito liquid.This vaporizer mosquito liquid can be become electric liquid device, wherein containing active compound component is 0.4w/w%.
Embodiment 7
With 0.4 part of compounds X 2 (as activeconstituents) and 0.3 part of BHT, the aliphatic hydrocarbon Hybrid Heating of the C14 of surplus is prepared into vaporizer mosquito liquid.This vaporizer mosquito liquid can be become electric liquid device, wherein containing active compound component is 0.4w/w%.
The alkynes third chrysanthemum ester vaporizer mosquito liquid of Application Example 6,7 of the present invention and 1% is carried out evaluation of pesticide effectiveness contrast according to GB13917.6-92, adopt airtight drum device.With vaporizer mosquito liquid sample energising 2h, 36h, 84h, 168h, draw 20 female culex pipiens pollens with mosquito sucking tube, put into device, accurate smoked kill 1min, timing simultaneously, smoked object for appreciation is complete cuts off the electricity supply, and removes the vaporizer mosquito liquid device, and record is at regular intervals gone down to such an extent that be examination mosquito number.The results are shown in Table 3:
The vaporizer mosquito liquid of table 3. The compounds of this invention preparation and the alkynes third chrysanthemum ester vaporizer mosquito liquid effect are relatively
The result shows: The compounds of this invention X1, X2 are that the relative effectivenes of vaporizer mosquito liquid of former medicine preparation is about 3 times of the alkynes third chrysanthemum ester vaporizer mosquito liquid.
Embodiment 8
Kerosene, propellent, filling with 0.15 weight part compounds X 1 (activeconstituents) and 48.85 weight parts under heating merely mix, it is inserted in the aerosol jar that control valve is housed, and inject third butane by this control valve and obtain insect aerosol adding to depress, wherein contain active compound component 0.02w/w%.
Application Example 8 of the present invention is carried out efficacy testing to insect according to GB13917.2-92, adopt 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 from insect aerosol jar of the present invention; extracting baffle plate behind the 1min out makes the examination worm contact with medicament; timing immediately; and opening entry, writing down down and out examination borer population at regular intervals, will all be transferred in the dependent insect cage of cleaning behind the 20min for the examination worm.Indicator gauge 4 as a result.
The insect aerosol of table 4 The compounds of this invention preparation is to the insect killing effect of fly, cockroach
| Numbering | Insect | ??KT 50(fly/cockroach) |
| Compounds X 1 | Fly | ??3′34″ |
| Compounds X 1 | Cockroach | ??4′50″ |
The result shows: The compounds of this invention X1, the aerosol of X2 preparation has good insect killing effect to fly, cockroach.
The above results shows, herein Fa Ming chemicals (Y) be have structural safety, former medicine toxicity is low, usage quantity is low, is to be applied to the lower raw insecticide medicine of sterilant consumption, dosage is also lacked than traditional old kind.These compound tests of pesticide effectiveness show to have excellent insecticidal activity, knock down soon, and the lethality rate height, vapour pressure is suitable, KT under low concentration
50(min) at 2～4 minutes, mortality ratio 100% in 24 hours, can stablize to continue volatilization under normal temperature or heated condition, and toxicity is low about 3～8 times with respect to the cis product simultaneously, helps being used in enormous quantities the application of domestic hygiene preparation.
Compound of the present invention is at same KT
50The index prerequisite under, by experiment in batches, to compare its concentration in product low 10～30 times with similar chrysanthemum esters product.The content that more experiment showed, The compounds of this invention is when 0.01～0.6% concentration, and the sterilant effect that is applied to different dosage form all is better than existing kind.
Claims (9)
1. insecticidal ester compound is characterized in that being represented by following general formula (Y):
Wherein X is (I) 3,3,3-three fluoro-1 proyl, F
3C-C ≡ C-; (II) 1-propenyl,
2. a kind of insecticidal ester compound according to claim 1, it is characterized in that cyclopropane 1 in the The compounds of this invention general formula (Y), 3 chiral carbon atoms have optics optically active isomer R S, at cyclopropane ring, also exist on two keys cis trans and Z the E geometrical isomer; The compounds of this invention comprises that all have the active optical isomer of pest control, geometrical isomer and composition thereof.
When X is (I) 3,3,3-three fluoro-1 proyl, compound (X1) are [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester;
When X is (II) 1-propenyl, compound (X2) is [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
3. according to the preparation method of claim 1 or 2 described a kind of insecticidal ester compounds, its feature may further comprise the steps successively:
1) with corresponding chrysanthemumic acid under the effect of chloride reagent, obtain 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethylcyclopropane acyl chlorides or 3-(1-propenyl)-2,2-dimethylcyclopropane acyl chlorides through acyl chloride reaction; The mol ratio of described chrysanthemumic acid and chloride reagent is 1～3: 1;
2) acyl chlorides that step 1) is obtained is respectively with [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl alcohol carries out esterification under the condition that organic solvent neutral and alkali catalyzer exists synthetic, obtain the pyrethroid compound that described structure satisfies (Y), wherein carboxylic acid chloride is 0.5～3: 1 with the mol ratio of [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl alcohol.
4. the preparation method of a kind of insecticidal ester compound according to claim 3, it is characterized in that: the described isomerization basic catalyst of step 1) is selected from methylate, ethylate, acetate, oxide compound or the oxyhydroxide of Li, Na or K, described organic solvent is selected from benzene, toluene, pyridine, ethylene glycol, dimethylbenzene, cyclohexanes organic solvent.
5. the preparation method of a kind of insecticidal ester compound according to claim 3 is characterized in that: step 2) described chloride reagent is selected from a kind of in phosphorus trichloride or the sulfur oxychloride.
6. according to the application of claim 1 or 2 described a kind of insecticidal ester compounds, its feature is in the application that is to prevent and treat aspect the sanitary insect pest.
7. the application of a kind of insecticidal ester compound according to claim 6 is characterized in that: described sanitary insect pest is mosquito, fly, cockroach, louse or acarid.
8. the application of a kind of insecticidal ester compound according to claim 7, it is characterized in that: the compound that satisfies (Y) with described structure is as former medicine, be prepared into various forms of sterilants according to ordinary method, be used for killing except that mosquito, fly, cockroach, louse or acarid.
9. the application of a kind of insecticidal ester compound according to claim 8 is characterized in that: described various forms of sterilants comprise coiled mosquito-repellent incense, electric mosquito repellent tablet, electric liquid device or insect aerosol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086154A (en) * | 2010-12-18 | 2011-06-08 | 浙江大学 | Pyrethroid intermediate and synthesis method thereof |
| CN109651145A (en) * | 2019-01-17 | 2019-04-19 | 江苏春江润田农化有限公司 | The synthetic method of trifluoro ynoic acid methyl ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176189A (en) * | 1977-06-20 | 1979-11-27 | Sumitomo Chemical Company, Limited | Insecticidal and acaricidal hydantoin N-methylol esters |
| CN1284055A (en) * | 1997-12-22 | 2001-02-14 | 阿温提斯作物科学有限公司 | Derivatives of 2,2-dimethyl 3-(2-fluoro vinyl) cyclopropane carboxylic acid, their prepn process and use as pesticides |
-
2010
- 2010-06-04 CN CN 201010191720 patent/CN101880260A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176189A (en) * | 1977-06-20 | 1979-11-27 | Sumitomo Chemical Company, Limited | Insecticidal and acaricidal hydantoin N-methylol esters |
| CN1284055A (en) * | 1997-12-22 | 2001-02-14 | 阿温提斯作物科学有限公司 | Derivatives of 2,2-dimethyl 3-(2-fluoro vinyl) cyclopropane carboxylic acid, their prepn process and use as pesticides |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086154A (en) * | 2010-12-18 | 2011-06-08 | 浙江大学 | Pyrethroid intermediate and synthesis method thereof |
| CN109651145A (en) * | 2019-01-17 | 2019-04-19 | 江苏春江润田农化有限公司 | The synthetic method of trifluoro ynoic acid methyl ester |
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