CN101747198A - Method for preparing trans-pyrethroid and application of trans-pyrethroid - Google Patents
Method for preparing trans-pyrethroid and application of trans-pyrethroid Download PDFInfo
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- CN101747198A CN101747198A CN200910215697A CN200910215697A CN101747198A CN 101747198 A CN101747198 A CN 101747198A CN 200910215697 A CN200910215697 A CN 200910215697A CN 200910215697 A CN200910215697 A CN 200910215697A CN 101747198 A CN101747198 A CN 101747198A
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- dichloroethylene
- carboxylic acid
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- 239000002728 pyrethroid Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- YFHZSPDQKWFAPH-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methanol Chemical compound COCC1=C(F)C(F)=C(CO)C(F)=C1F YFHZSPDQKWFAPH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 68
- 241000238631 Hexapoda Species 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003380 propellant Substances 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 17
- 241000607479 Yersinia pestis Species 0.000 claims description 16
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- 239000003814 drug Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical group CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
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- 238000009472 formulation Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
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- 241000257303 Hymenoptera Species 0.000 abstract description 2
- 229940126062 Compound A Drugs 0.000 abstract 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 2
- GNSXRPHKECXUEQ-NXEZZACHSA-N 1-[[(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropyl]methyl]-2,3,5,6-tetrafluoro-4-(methoxymethyl)benzene Chemical compound FC1=C(C[C@H]2C([C@@H]2C=C(Cl)Cl)(C)C)C(=C(C(=C1F)COC)F)F GNSXRPHKECXUEQ-NXEZZACHSA-N 0.000 abstract 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 230000000749 insecticidal effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000257159 Musca domestica Species 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 231100000053 low toxicity Toxicity 0.000 description 4
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- 239000005946 Cypermethrin Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
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- 241001465754 Metazoa Species 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a method for preparing trans-pyrethroid and application of the trans-pyrethroid. The chemical name of the trans-pyrethroid is (1R)-2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane. (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane is used as a raw material, undergoes acid chloride reaction, and then is catalytically synthesized into a compound A together with 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol in the presence of a high-efficiency catalyst. The process has the characteristics of simple process route, safety and reliability, high quality and yield, less emission of the three wastes, and the like. The invention also provides application of the compound A in sanitary pesticide products for controlling flies, ants, louses, and the like.
Description
Technical field: the present invention relates to a kind of compound of organic insecticide class, is a kind of of pyrethroid, a kind of preparation method of trans pyrethroid and application thereof specifically.
Background technology: pyrethroid coumpound is used to prevent and treat mosquito, and has higher insecticidal activity, and this is a well known fact.U.S. Pat 4370346 discloses this compounds first and has been widely used in pest control.But its structure is the racemize structural compounds.And Chinese patent CN1669429 has related to the preventive and therapeutic effect of this compounds aspect part household sanitary insect pest.Yet to the further drug efficacy study of this compound different optical structure goodbye report not.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.Quite be necessary and should advocate.
General esterification process is synthetic pyrethroid series products under catalyst action with acid and alcohol, and reaction is incomplete, and by product is many, and " three wastes " amount is big, and it is difficult to separate, and yield and quality product are not high; The method for preparing the chrysanthemum esters product that CN101348436A adopts is to take " the pyridine method is synthetic " operational path to carry out large-scale production.This operational path is through secular application and development, ripe relatively, good product quality, need to use hexahydropyridine as acid binding agent but produce, this material breath malodor is dangerous big, and temperature of reaction is lower, generally need maintain 0～5 ℃ and react, shortcoming such as freezing energy consumption is bigger, and pyridine aftertreatment recovery process is loaded down with trivial details
Summary of the invention: the present invention under above-mentioned technical background, furthers investigate pyrethroid compound and preparation method thereof just.The contriver has carried out a large amount of investigations of groping, carried out improving research on the basis of existing technology, the different process route is carried out screening and optimizing and N-Methylimidazole and Tetramethyl Ethylene Diamine are made catalyzer being used in the synthetic aspect of pyrethroid, obtained comparatively ideal effect.Experimental data has confirmed the preparation method of compound structure (A), and this compound is in the ability of knocking down, kill capability and stability be convenient to index such as applications, finally obtained a kind ofly efficiently synthesizing the method for this compound and being the pesticide product of activeconstituents with this compound.
The invention provides a kind of simple preparation (1R)-2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-trans-3-(2, the 2-dichloroethylene)-2, the method of 2-dimethyl cyclopropane carboxylic acid ester, by the use of effective catalyst, optimized test effect, catalyst levels is few, easy easily than other method, economical and easily realize industrialization.
Purpose of the present invention: the 1st, preferred a kind of pyrethroid coumpound, it has the optically active body of greater activity and security, especially fly, ant or louse 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 preparation of compositions method, and in the application in domestic hygiene medication field.
The respective compound preparation method that the present invention also provides described structure to satisfy formula (A), promptly described compound can be prepared by following steps:
1) with (1R)-trans-3-(2, the 2-dichloroethylene)-2, the 2-dimethyl cyclopropane carboxylic acid carries out the effect of chloride with phosphorus trichloride or sulfur oxychloride in organic solvent, obtains (1R)-trans-3-(2 through acyl chloride reaction, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides; Described (1R)-trans-3-(2, the 2-dichloroethylene)-2, the mol ratio of 2-dimethyl cyclopropane carboxylic acid and phosphorus trichloride or sulfur oxychloride is 1～3: 1;
2) (1R) that step 1) is obtained-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides and 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol is under the effective catalyst effect, carry out catalytic esterification with alkaline acid binding agent and organic solvent, the synthetic pyrethroid compound that described structure satisfies (A), wherein (1R)-trans-3-(2 of obtaining, the 2-dichloroethylene)-2, the 2-dimethyl cyclopropane carboxylic acid is trans with 2,3,5, the mol ratio of 6-tetrafluoro-4-methoxymethyl benzylalcohol is 0.5～3: 1, more is optimized for 1～2: 1
Above-mentioned steps 1) described organic solvent is benzene,toluene,xylene or normal hexane;
Above-mentioned steps 2) described alkaline acid binding agent agent is selected from the carbonate of Li, Na or K, and described organic solvent is selected from benzene, the ethylene glycol organic solvent;
Above-mentioned steps 2) described effective catalyst is selected the N-Methylimidazole for use, Tetramethyl Ethylene Diamine or two kinds of catalyzer use together, the used molar weight of catalyzer with (1R)-trans-3-(2, the 2-dichloroethylene)-2,0.01～0.3: 1 of 2-dimethyl cyclopropane carboxylic acid acyl chlorides mol ratio more is optimized for 0.05～0.1: 1.
A kind of trans pyrethroid compound of the present invention, its chemical name is (1R)-2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester.The chrysanthemumic acid of compound shown in the formula (A) partly is (1R)-trans-3-(2, the 2-dichloroethylene)-2,1 carbon atom steric configuration on the triatomic ring of 2-dimethyl cyclopropane carboxylic acid part is the R configuration, be that described compound is (1R)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid.Described compound chrysanthemumic acid partly is (1R)-trans-3-(2, the 2-dichloroethylene)-2, on the triatomic ring of 2-dimethyl cyclopropane carboxylic acid part 1,3 carbon atom relative configurations are trans, be that described compound is: (1R)-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid.
Adopt this method to improve esterification reaction rate greatly, the reaction conditions gentleness, the esterification yield height, catalytic efficiency is good, has reduced three waste discharge, has reduced production energy consumption, has objective industrialization development prospect.
The present invention has saturated vapor pressure preferably to structure (A), still can stablize under normal temperature and high temperature and continue volatilization, drug effect is better, can effectively reduce pyrethroid toxicity and biotic resistance simultaneously, the activity of pyrethroid there is the compound of enhancement structural safety, people and animals is stimulated little.
Said structure formula (A) compound is used in the application that removes sanitary insect pest aspects such as killing fly, ant, louse good effect.Described sanitary insect pest is fly, ant, louse.
Described structure satisfies the compound of (A) as former medicine, is prepared into various forms of sterilants according to ordinary method, is used for killing except that fly, ant, louse.
The application of described a kind of trans pyrethroid compound, it is characterized in that: the compound that satisfies (A) with described structure is as former medicine, be prepared into various forms of sterilant formulations according to ordinary method, contain the conventional inert support of 0.001～100w/w% pyrethroid compound (A) and surplus in the described pest control reagent.
Described various forms of sterilant comprises insect aerosol or propellant.
Described application is that described pest control agent administration is assembled ground in insect or insect.
Embodiment: followingly the present invention is described, but the present invention not only is confined to following embodiment with some concrete examples:
The applicant has invented a kind of preparation method of pyrethroid compound, this compound is with (1R)-trans-3-(2, the 2-dichloroethylene)-2, and the 2-dimethyl cyclopropane carboxylic acid is a raw material, and then obtain (1R)-2 by chloride, esterification, 3,5,6-tetrafluoro-4-methoxymethyl benzyl-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester, this technology has the advantages that operational path is simple, safe and reliable, mass yield is high, cost is low, is fit to very much suitability for industrialized production.The present invention has also adopted new effective catalyst simultaneously, and catalyst levels is low, and compound is used in the application that removes sanitary insect pest aspects such as killing fly, ant, louse good effect.
Preparation embodiment 1:(1R)-and trans-3-(2, the 2-dichloroethylene)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid acyl chlorides.
In the four-hole bottle of a 500ml, drop into (1R)-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid 104.1g, be dissolved in 300ml toluene, stir, be warming up to 40～60 ℃, drip SOCl265.0g, drip off in 2 hours, be warming up to 65 ℃ again, be 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 (1R)-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 107.5g, content 96.4%, yield 91.7%.
Preparation embodiment 2:(1R)-2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester synthetic.
In the four-hole reaction flask of a 1000ml, drop into 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol 124.5g, Tetramethyl Ethylene Diamine 2.1g, N-Methylimidazole 2.7g is dissolved in 400ml toluene, soda ash 80g, acid binding agent water 100g, stir, 35 ℃ drip (1R)-trans-3-(2, the 2-dichloroethylene)-2 down, 2-dimethyl cyclopropane carboxylic acid acyl chlorides 138.2g, 35 ℃ of insulation reaction 1 hour again 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 (1R)-2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 202.8g, and content is 96.8%, and yield is 94.6%.Structure is identified as follows:
The IR infrared spectrum shows vc=o 1710cm
-1The strong absorption peak and the v-c-o-c-1195cm at place
-1And 1170cm
-1Two strong spike products in have ester group; At 2950cm
-1About with 1400cm
-1About characteristic peak v-
CH3, v-
CH2-existence.3075cm-1 and 3025cm
-1It is that the stretching vibration of v-c=c-causes 1685cm that two strong and spikes are arranged
-1Individual medium tenacity spike v-c=c-characteristic peak is arranged, other 840～750cm
-1Strong peak is v-c=c-flexural vibration, v
C-C1Vibration absorption peak; GC/MS shows that this compound molecular weight is 415.2; NMR (
1H, CDCl
3) δ: 5.73 (d, 1H); 5.38 (s, 2H); 4.68 (s, 2H); 3.33 (s, 3H); 1.52 (t, 1H); 1.06 (d, 1H); 0.99 (s, 6H). (
13C, CDCl
3) δ: 171.0,135.5,134.2,127.8,122.7,117.5,113.0,64.0,58.2,55.2,32.8,28.3,25.6,23.3.
Above spectrogram proves that jointly this compound is: (1R)-2,3,5, and 6-tetrafluoro-4-methoxymethyl benzyl-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
17H
16Cl
2F
4O
3Product is a faint yellow solid.
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 household sanitary insect pests such as fly, ant, louse is had efficient, the low toxicity of high ability of knocking down and kill capability, is applicable to domestic sanitary product field and is 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, whole process can be reacted under normal temperature or slightly heated condition, adopt effective catalyst and control feeding mode can effectively control the acyl chlorides hydrolysis simultaneously, energy consumption consumes low, therefore, above-mentioned synthesis technique is a kind of operational path and the preparation method with wide prospects for commercial application in this area.
Therefore, the present invention also provide a kind of containing (A) structure the desinsection of pyrethroid compound with composition (sterilant), the composition of said composition comprises the compound (active compound component) 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 fly, ant, louse class pest extremely.Described composition can be various forms of sterilants, comprises aerial fog pesticide or propellant 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) 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 fly, ant, louse contact.
(2) propellant:
Described desinsection propellant is characterized in that described desinsection propellant is installed in the propellant jar, and this desinsection propellant is made up of pyrethroid, water kind solvent and aerosol propellant, and wherein: the volume percent of desinsection propellant is: 0.01%～0.5%; The volume percent of water kind solvent is: 94%～98%; And be enough to compress and the aerosol propellant of the amount of the mixed solution formed by pyrethroid and alcoholic solvent of atomizing.During use this propellant jar is aimed at the dispenser place, be used for pushing the can body of propellant jar, the nozzle valve on the propellant jar is opened, and the mixed solution that highly compressed pyrethroid and water kind solvent are formed disperses to enter into the dispenser place fully.With the effect that can reach quick kill pests after insects such as fly, ant, louse 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 compound (A) uses lower ratio, therefore, compound of the present invention and the advantage that contains the sterilant of this compound are: the consumption that has reduced active insecticide 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 fly, ant, louse.
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 preparation method that the efficient catalytic synthetic pyrethroid compound of independent intellectual property right is arranged of independent studies exploitation, requirement to this compound should be the active insecticidal components that can be used as in the high-efficient low toxicity insecticide of domestic hygiene fly-killing, ant, louse, 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.
Embodiment 1, kerosene, propellent, casting resin with 0.15 weight part compd A (activeconstituents) and 48.85 weight parts under heating 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 0.03w/w%.
Embodiment 2, kerosene, propellent, filling with 0.15 weight part Es-esbiothrin (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 0.03w/w%.
Application Example 1 of the present invention and 2 is carried out efficacy testing to insect according to GB13917.2-2009, adopt the drum device.Detailed process is as follows: will be for (housefly Musca domestica30 of examination insect; the 3rd day～the 4th day the adult in back sprouts wings; female; male half and half); put into cylinder; after waiting to try worm recovery normal activity; metered injection from insect aerosol jar of the present invention (1.0 ± 0.1g), clog circular hole with plug immediately, extract baffle plate behind the 1min out the examination worm is contacted 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; recover feeding standard; feed with 5% syrup cotton balls, 24h checks dead borer population, does not knock down the examination worm by the worm that lives.Testing time is 3 times, the calculating of averaging.Indicator gauge 1 as a result.
The insect aerosol of table 1 The compounds of this invention preparation is to the insect killing effect of housefly
| Numbering | Insect | ??KT 50(fly) |
| Compd A | Housefly | ??2′34″ |
| The Es-esbiothrin | Housefly | ??5′02″ |
The result shows: the aerosol of The compounds of this invention A preparation has good insect killing effect to fly.
The above results shows, herein Fa Ming chemicals (A) 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, helped being used in enormous quantities the application of domestic hygiene preparation.
Embodiment 3, with 0.2% weight part compd A (activeconstituents) and solvent 1%, emulsifying agent 3%, essence 0.1%, suds suppressor 0.03%, water adds to 100% to be mixed, and is made into water dilution type propellant it is inserted in the aerosol jar that control valve is housed, and wherein contains active compound component 0.2w/w%.
Embodiment 4, with 0.5% weight part effective cypermethrin (activeconstituents) and solvent 1%, emulsifying agent 3%, essence 0.1%, suds suppressor 0.03%, water adds to 100% to be mixed, be made into water dilution type propellant it is inserted in the aerosol jar that control valve is housed, wherein contain active compound component 0.5w/w%.
Application Example 3 of the present invention is carried out efficacy testing to insect according to GB13917.1-2009, adopt the cannon spray head device, place on the carriage.Detailed process is as follows: will be for examination insect (30 of housefly Muscadomestica, the 3rd day～the 4th day adult after sprouting wings, female, hero half and half) (50 of the worker ants more than the monomorium pharaonis Monomorium pharaonis, 3 ages in days, be released to ware mouth inwall one circle Vaseline band earlier, at the bottom of the ware.Put into cannon spray head, worm to be tried is lined with white filter paper, and diameter is in the culture dish of 90mm, and ware is placed central authorities at the bottom of the cartouche, and cannon spray head is inverted), recover normal activity after, with the quantitative (1.43mL/m of desinsection propellant of the present invention
3) dosage moves in the little grass tube with micropipet, starts air compressor, adjusts pressure to 9.8 * 10 by reducing valve
4Pa places the little grass tube of propellant to be measured in the entry needle of shower nozzle below, opens air valve spray medicine.Sprayed medicine, timing immediately, and opening entry, write down down and out examination borer population at regular intervals, will all be transferred in the dependent insect cage of cleaning behind the 20min, recover feeding standard for the examination worm, feed with 5% syrup cotton balls, 24h checks dead borer population, does not knock down the examination worm by the worm that lives.Testing time is 3 times, the calculating of averaging.Indicator gauge 2 as a result.
The diluent water type propellant of table 2 The compounds of this invention preparation is to the insect killing effect of housefly, ant
| Numbering | The examination worm | ??KT 50(fly/cockroach)/min | Mortality ratio/% |
| Compd A | Housefly | ??3′56″ | ?100 |
| Effective cypermethrin | Housefly | ??4′50″ | ?98.0 |
| Compd A | Ant | ??-- | ?100 |
| Effective cypermethrin | Ant | ??-- | ?96.0 |
Claims (9)
1. the preparation method of a trans pyrethroid, its feature may further comprise the steps successively:
1) with (1R)-trans-3-(2, the 2-dichloroethylene)-2, the 2-dimethyl cyclopropane carboxylic acid carries out the effect of chloride with phosphorus trichloride or sulfur oxychloride in organic solvent, obtains (1R)-trans-3-(2 through acyl chloride reaction, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides; Described (1R)-trans-3-(2, the 2-dichloroethylene)-2, the mol ratio of 2-dimethyl cyclopropane carboxylic acid and phosphorus trichloride or sulfur oxychloride is 1～3: 1;
2) (1R) that step 1) is obtained-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides and 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol is under the effective catalyst effect, carry out catalytic esterification with alkaline acid binding agent and organic solvent, the synthetic trans pyrethroid compound that described structure satisfies (A), wherein (1R)-trans-3-(2 of obtaining, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides and 2,3,5, the mol ratio of 6-tetrafluoro-4-methoxymethyl benzylalcohol is 0.5～3: 1, more is optimized for 1～2: 1
2. the preparation method of a kind of trans pyrethroid compound according to claim 1, it is characterized in that: the described organic solvent of step 1) is benzene,toluene,xylene or normal hexane; Step 2) described alkaline acid binding agent agent is selected from the carbonate of Li, Na or K, and described organic solvent is selected from benzene, the ethylene glycol organic solvent.
3. the preparation method of a kind of trans pyrethroid compound according to claim 1, it is characterized in that: step 2) described effective catalyst selects the N-Methylimidazole for use, Tetramethyl Ethylene Diamine or two kinds of catalyzer use together, the used molar weight of catalyzer with (1R)-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides mol ratio is 0.01～0.3: 1, more is optimized for 0.05～0.1: 1.
4. the trans pyrethroid compound of the described preparation method of claim 1 preparation, it is characterized in that: 1 carbon atom steric configuration on the chrysanthemumic acid part triatomic ring of compound shown in the formula (A) is the R configuration, be that described compound is (1R)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid; 1,3 carbon atom relative configuration is trans on the described compound chrysanthemumic acid part triatomic ring, and promptly described compound is: (1R)-trans-3-(2, the 2-dichloroethylene)-2, the 2-dimethyl cyclopropane carboxylic acid; Described a kind of trans pyrethroid compound (A) full name is: (1R)-2,3,5, and 6-tetrafluoro-4-methoxymethyl benzyl-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester.
5. according to the application of the described a kind of trans pyrethroid compound of claim 4, it is characterized in that preventing and treating the application of sanitary insect pest aspect.
6. the application of a kind of trans pyrethroid compound according to claim 4 is characterized in that: described sanitary insect pest is sanitary insect pests such as fly, ant or louse.
7. the application of a kind of trans pyrethroid compound according to claim 4, it is characterized in that: the compound that satisfies (A) with described structure is as former medicine, be prepared into various forms of sterilant formulations according to ordinary method, contain the conventional inert support of 0.001～100w/w% pyrethroid compound (A) and surplus in the described pest control reagent.
8. the described application of claim 7 is characterized in that: the form of described control reagent comprises insect aerosol, propellant.
9. the described application of claim 7 is characterized in that: described application is that described pest control agent administration is assembled ground in insect or insect.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102283240A (en) * | 2011-06-29 | 2011-12-21 | 贵阳柏丝特化工有限公司 | Pesticide composition |
| CN102826993A (en) * | 2012-08-27 | 2012-12-19 | 安徽常泰化工有限公司 | Method for preparing cis-Z-3-(2-chloro-3,3,3-triflulo-1-propenyl)-2,2-dimethyl cyclopropane carbonyl chloride |
| CN104628570A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Clean production method of meperfluthrin |
| CN104628571A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Meperfluthrin production method with clean synthetic process |
| CN109776327A (en) * | 2019-02-27 | 2019-05-21 | 黄山学院 | Permethrin compound, preparation method and application thereof |
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2009
- 2009-12-30 CN CN200910215697A patent/CN101747198A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102283240A (en) * | 2011-06-29 | 2011-12-21 | 贵阳柏丝特化工有限公司 | Pesticide composition |
| CN102826993A (en) * | 2012-08-27 | 2012-12-19 | 安徽常泰化工有限公司 | Method for preparing cis-Z-3-(2-chloro-3,3,3-triflulo-1-propenyl)-2,2-dimethyl cyclopropane carbonyl chloride |
| CN104628570A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Clean production method of meperfluthrin |
| CN104628571A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Meperfluthrin production method with clean synthetic process |
| CN104628570B (en) * | 2013-11-15 | 2017-08-08 | 江苏扬农化工股份有限公司 | A kind of clean method for producing of fluorine chlorine ether chrysanthemum ester |
| CN109776327A (en) * | 2019-02-27 | 2019-05-21 | 黄山学院 | Permethrin compound, preparation method and application thereof |
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